% Encoding: UTF-8

@Article{Boyaciyan2018,
  author   = {D. Boyaciyan and P. Krause and R. von Klitzing},
  journal  = {Soft Matter},
  title    = {Making strong polyelectrolyte brushes pH-sensitive by incorporation of gold nanoparticles},
  year     = {2018},
  pages    = {4029--4039},
  volume   = {14},
  abstract = {Doping polymer brushes with gold nanoparticles (AuNPs) results in composite materials with colorimetric sensor properties. The present paper addresses the effect of electrostatic particle--particle interaction and the effect of the polymer brush type on particle assembly formation within the polymer matrix. The prospect for long-term use as colorimetric sensors is tested. Therefore, two different types of brushes of pH-insensitive polymers, non-ionic poly(N-isopropylacrylamide) (PNIPAM) and cationic poly-[2-(methacryloyloxy)ethyl] trimethylammonium chloride (PMETAC), are studied. After incubation of the non-ionic PNIPAM brush in an aqueous suspension of AuNPs with a pH-sensitive carboxylic acid capping, hydrogen binding led to attachment of the AuNPs, but they were easily detached at high pH due to loss of the hydrogen binding. In contrast, the anionic AuNPs adhere well to cationic PMETAC brushes even after post-treatment at low pH where the charge density of the AuNPs is strongly reduced. Therefore, the PMETAC/AuNP composites were further tested with respect to their stability against pH variations and their impact for colorimetric sensors. Although the neat PMETAC brush is not pH-sensitive, after embedding pH-sensitive AuNPs, the PMETAC/AuNP composite becomes pH-sensitive in a reversible manner. This is detectable by the reversible shift of the plasmon band and the reversible thickness change of the composites by exposing them to different pH.},
  doi      = {10.1039/C8SM00411K},
  file     = {:Boyaciyan2018 - Making Strong Polyelectrolyte Brushes PH Sensitive by Incorporation of Gold Nanoparticles.pdf:PDF},
  groups   = {All entries},
  keywords = {polyelectrolyte, pH, brush, strong},
}

@Article{Schmidt2008,
  author     = {Stephan Schmidt and Hubert Motschmann and Thomas Hellweg and Regine von Klitzing},
  journal    = {Polymer},
  title      = {Thermoresponsive surfaces by spin-coating of PNIPAM-co-PAA microgels: A combined AFM and ellipsometry study},
  year       = {2008},
  pages      = {749--756},
  volume     = {49},
  abstract   = {Thermosensitive coatings are fabricated by spin-coating of microgels consisting of the cross-linked copolymer poly(N-isopropyl acrylamideco-acrylic acid) (P(NIPAM-co-AA)) on silicon wafers. The microgels were synthesized with two different cross-linker molar ratios and the thin films were prepared at pH 2. At this pH the particles are negatively charged only due to the starter used for the polymerization. Scanning force microscopic (AFM) images indicate a dense packing of the particles and a strong flattening in the adsorbed state. This effect is stronger for microgels containing less cross-linker. Coatings consisting of these microgel particles show a reversible thermoresponsive swelling/shrinking in the region of the lower critical solution temperature (LCST) of NIPAM. For the ellipsometric study of this process a standard setup was modified in order to allow temperature dependent measurements of the optical thickness in a liquid cell. The temperature induced transition is sharper in the case of microgels with lower amount of cross-linker and smears out with increasing amount of cross-linker. No significant desorption of the particles occurs at pH 2, which was shown by AFM of the dried films before and after the ellipsometric measurements. In the dry state the average thickness of the prepared films is approximately 30 nm and a thickness of about 400 nm is reached in the swollen state.},
  file       = {:Schmidt2007 - Thermoresponsive Surfaces by Spin Coating of PNIPAM Co PAA Microgels_ a Combined AFM and Ellipsometry Study.pdf:PDF},
  groups     = {All entries},
  keywords   = {microgel, control parameter, thermoresponsive, AFM, ellipsometry},
  printed    = {printed},
  ranking    = {rank3},
  readstatus = {skimmed},
}

@Article{Han2018,
  author     = {Haoya Han and Li Li and Qingsong Yang and Yuchuan Tian and Yunwei Wang and Zhishuang Ye and Regine von Klitzing and Xuhong Guo},
  journal    = {Journal of Materials Science},
  title      = {Characterization of hollow silica-polyelectrolyte composite nanoparticles by small-angle X-ray scattering},
  year       = {2018},
  pages      = {3210--3224},
  volume     = {53},
  abstract   = {Hollow silica--polyelectrolyte composite nanoparticles were prepared using templates of spherical polyelectrolyte brushes which consist of a polystyrene (PS) core and a densely grafted linear poly(acrylic acid) shell. The obtained hollow particles were systematically studied by small-angle X-ray scattering (SAXS) in combination with other characterization methods such as transmission electron microscopy and dynamic light scattering. The hollow structure formed by dissolving the PS core was confirmed by the reduction of electron density to zero in the cavity through fitting SAXS data. SAXS revealed both the inward and outward expansions of the hollow silica--polyelectrolyte composite particles upon increasing pH from 3 to 9, while further increasing pH led to the partial dissolution of silica layer and even destruction of the hollow structure. SAXS was confirmed to be a unique and powerful characterization method to observe hollow silica nanoparticles, which should be ideal candidates for controlled drug delivery.},
  file       = {:Han2018 - Characterization of Hollow Silica Polyelectrolyte Composite Nanoparticles by Small Angle X Ray Scattering.pdf:PDF},
  groups     = {All entries},
  keywords   = {PAA, polystyrene, DLS, TEM, SAXS, X-ray, polyelectrolyte brush, spherical brush},
  printed    = {printed},
  ranking    = {rank2},
  readstatus = {skimmed},
}

@Article{Zeghal1999,
  author     = {Mehdi Zeghal and Bertrand Deloche and Philippe Auroy},
  journal    = {Macromolecules},
  title      = {Chain Segment Ordering in Swollen Polymer Brushes: Deuterium NMR Investigations},
  year       = {1999},
  pages      = {4947--4955},
  volume     = {32},
  abstract   = {The dynamics of deuterated poly(dimethylsiloxane) chains grafted on a solid substrate and immersed in various solvents is investigated using deuterium NMR. It is observed that the segment reorientations are uniaxial around the normal to the grafting plane. For layers of moderate grafting density, immersed in poor solvent, the anisotropy is homogeneous and characterized by a negative order parameter S. The segment orientational fluctuations are preferentially parallel to the grafting plane through the whole layer. This anisotropy, due to the squeezing of the chains, depends on the average concentration of the polymer layer. On the contrary, in good solvent, the average order parameter is positive, indicating that the segments are preferentially oriented perpendicularly to the grafting plane. In this regime, the distribution of order P(S) is broad and the chains are nonuniformly stretched.},
  comment    = {THE paper},
  file       = {:Zeghal1999 - Chain Segment Ordering in Swollen Polymer Brushes_ Deuterium NMR Investigations.pdf:PDF},
  groups     = {All entries},
  keywords   = {PDMS, NMR, key article, planar brush},
  printed    = {printed},
  ranking    = {rank4},
  readstatus = {read},
}

@Article{Lorthioir2002,
  author     = {C. Lorthioir and P. Auroy and B. Deloche and Y. Gallot},
  journal    = {European Physical Journal E: Soft Matter},
  title      = {Chain segment ordering in lamellar sublayers of block copolymers: A NMR study},
  year       = {2002},
  pages      = {261--266},
  volume     = {7},
  abstract   = {The chain segment dynamics in the bulk lamellar phase of polystyrene-polydimethylsiloxane (PS-PDMS) block copolymers has been probed by NMR. The experiments were performed on a PSPDMS diblock and on a PS-PDMS-PS triblock with twice the molecular weight. In the diblock, at room temperature, the PDMS block segments undergo uniaxial reorientations around the normal to the lamellae. In the triblock, the reorientational motions exhibit a lower degree of symmetry: deviations from a uniaxial dynamics are observed. Such a behaviour originates in the anchorage of both PDMS chain ends into the PS glassy layers.},
  comment    = {-Fluctuations around a symmetry axis along the layer normal
-In triblock copolymer: knots and other "defectes" induce a different local symmetry axis
-Distribution of order along the layer normal is wider than in e.g. grafted films of similar grafting density},
  file       = {:Lorthioir2002 - Chain Segment Ordering in Lamellar Sublayers of Block Copolymers_ a NMR Study.pdf:PDF},
  groups     = {All entries},
  keywords   = {block copolymer, NMR},
  printed    = {printed},
  ranking    = {rank4},
  readstatus = {read},
}

@Article{Jancelewicz2011,
  author     = {Mariusz Jancelewicz and Zbigniew Fojud and Wiktor Waszkowiak and Stefan Jurga},
  journal    = {European Polymer Journal},
  title      = {Local mobility in grafted polydimethylsiloxane melts},
  year       = {2011},
  pages      = {48--51},
  volume     = {47},
  abstract   = {Spin--lattice relaxation time constants, T1, were studied for low-molecular-weight linear and grafted polydimethylsiloxane over a wide temperature and frequency range. Quantitative evaluations of proton T1 measurements indicated two relaxation processes: anisotropic rotation of methyl groups around the Si--C bond (low temperature process) and motions of the PDMS side-chains connected with the glass transition (high temperature process). Additional analyses of the T1 relaxation dispersion profiles revealed specific local segment fluctuation times, which are characteristic of the coherent motions in the grafted polymer chains.},
  file       = {:Jancelewicz2011 - Local Mobility in Grafted Polydimethylsiloxane Melts.pdf:PDF},
  groups     = {All entries},
  keywords   = {PDMS, polymer melt, neutral brush, NMR, copolymer, silica surface},
  printed    = {printed},
  ranking    = {rank4},
  readstatus = {skimmed},
}

@Article{Sotta1999,
  author   = {P. Sotta and S. Valic and B. Deloche and D. Maring and H. W. Spiess},
  journal  = {Acta Polymerica},
  title    = {Effect of the diamagnetic susceptibility in NMR measurements in diblock copolymers},
  year     = {1999},
  pages    = {205--213},
  volume   = {50},
  abstract = {Symmetric diblock copolymers in the lamellar phase are studied by NMR. 2H NMR spectra obtained in macroscopically oriented monodomains show an absolute frequency shift of a few ppm, which depends of the orientation of the sample with respect to the magnetic field. This is interpreted as due to the anisotropy of the diamagnetic susceptibility, related to the lamellar structure itself rather than to an orientational order of polymer chain segments. The spectra obtained in both 2D 13C and 1H rotor-synchronized MAS experiments reflect the same effect. Specifically, we show that 1H rotor-synchronized MAS experiments allow us to discriminate unambiguously the effect of diamagnetic susceptibility anisotropy and the effect of molecular orientation.},
  file     = {:Sotta1999 - Effect of the Diamagnetic Susceptibility in NMR Measurements in Diblock Copolymers.pdf:PDF},
  groups   = {All entries},
  keywords = {block copolymer, NMR, susceptibility},
  printed  = {printed},
  ranking  = {rank4},
}

@Article{Zeghal1995,
  author   = {M. Zeghal and P. Auroy and B. Deloche},
  journal  = {Physical Review Letters},
  title    = {Local Uniaxial Order in a Grafted Polymer Melt via Deuterium NMR},
  year     = {1995},
  number   = {11},
  pages    = {2140--2143},
  volume   = {75},
  abstract = {Dynamics of end-grafted polymer chains on a solid substrate are investigated by deuterium NMR, which is sensitive to the anisotropy of molecular motions. The experiments are performed on a perdeuterated polydimethylsiloxane melt grafted on planar silica slides. The NMR spectra show clearly that chain segments undergo uniaxial reorientations around the normal to the interface. This local order reveals the existence of orientational correlations between chain segments. The corresponding degree of anisotropy is much higher than in other lamellar systems such as block copolymers.},
  comment  = {THE paper - the prequel},
  file     = {:Zeghal1995 - Local Uniaxial Order in a Grafted Polymer Melt Via Deuterium NMR.pdf:PDF},
  groups   = {All entries},
  keywords = {planar brush, PDMS, NMR},
  printed  = {printed},
  ranking  = {rank4},
}

@Article{CohenAddad1975,
  author   = {J. P. Cohen-Addad},
  journal  = {Journal of Chemical Physics},
  title    = {Method of measurement of nonzero average dipolar spin coupling in molten polymers},
  year     = {1975},
  pages    = {4880--4885},
  volume   = {63},
  abstract = {The present paper concerns a problem more general than that related to NMR studies of molten polymer systems. It aims at defining a method of measurement of the nonzero average dipolar spin coupling in the case where (i) spin-spin relaxation rates due to nucleus motion, (ii) field inhomogeneities, and (iii) chemical shifts are of the same order of magnitude as the nonzero average dipolar coupling, in frequency units. It is shown that by using pulse sequences giving rise to appropriate response functions of the transverse magnetization, contributions (i), (ii), and (iii) can be eliminated. As an example, the experimental determination of the nonzero average dipolar coupling is considered, using a cis-l,4-polybutadiene sample.},
  file     = {:Cohen-Addad1975 - Method of Measurement of Nonzero Average Dipolar Spin Coupling in Molten Polymers.pdf:PDF},
  groups   = {All entries},
  keywords = {NMR, polymer melt},
  printed  = {printed},
  ranking  = {rank2},
}

@Article{Lorthioir2003,
  author     = {C. Lorthioir and B. Deloche and Y. Gallot},
  journal    = {Europhysics Letters},
  title      = {Heterogeneity of the chain segment dynamics and ordering in lamellar layers of a symmetric triblock copolymer},
  year       = {2003},
  pages      = {746--752},
  volume     = {62},
  abstract   = {The segmental ordering within the sublayers of a lamellar polystyrene-polydimethylsiloxane-polystyrene triblock (PS-PDMS-PS) is examined by NMR. The carbon and deuterium NMR line shapes of the PDMS sequence (soft block) reveal clearly a wide distribution of segmental orientational order S in the lamellae and thus a distribution of constraints probed by the chains. It is observed that this distribution is mainly due to the coexistence of positive and negative S, resulting from a competitive ordering effect induced by the presence of glassy interfaces (S  0).},
  file       = {:Lorthioir2003 - Heterogeneity of the Chain Segment Dynamics and Ordering in Lamellar Layers of a Symmetric Triblock Copolymer.pdf:PDF},
  groups     = {All entries},
  keywords   = {PDMS, NMR, block copolymer},
  printed    = {printed},
  readstatus = {skimmed},
}

@Article{Fleischer1985,
  author   = {Gerald Fleischer and Dieter Geschke and J{\"{o}}rg K{\"{a}}rger and Wilfried Heink},
  journal  = {Journal of Magnetic Resonance},
  title    = {Peculiarities of Self-Diffusion Studies on Polymer Systems by the NMR Pulsed Field Gradient Technique},
  year     = {1985},
  pages    = {429--443},
  volume   = {65},
  abstract = {The measurement of polymer self-diffusion coefficients in solution and melt with the NMR pulsed field gradient technique demands special care because of the slow and generally complicated diffusion process. The echo attenuations are derived and discussed for the following special cases: (i) the macromolecules have a distribution of molar masses, (ii) the species undergo diffusion with two mechanisms, (iii) the diffusion is hindered. The effects of chemical exchange and inner gradients are also discussed. In all these cases deviations from an exponential echo attenuation with a time-dependent self-diffusion coefficient are to be expected, leading to a complication of the interpretation of the experimental data. Based on the mathematical expressions thus obtained and on measurements with a highly sophisticated NMR pulsed field gradient spectrometer, it is shown that the NMR selfdiffusion data of polymers in solution and melt so far reported are most likely the effect of mere Center-Of-ItUSS motions of the macromolecules.},
  file     = {:Fleischer1985 - Peculiarities of Self Diffusion Studies on Polymer Systems by the NMR Pulsed Field Gradient Technique.pdf:PDF},
  keywords = {diffusion, pfg diffusion, NMR, polymer melt},
  printed  = {printed},
  ranking  = {rank3},
}

@PhdThesis{Chasse2012a,
  author   = {Walter Chasse},
  school   = {Martin-Luther-Universit{\"{a}}t Halle-Wittenberg},
  title    = {Structure, Formation and Thermodynamic Properties of Polymer Networks as Studied by NMR},
  year     = {2012},
  month    = sep,
  type     = {phdthesis},
  abstract = {Contents
1. Introduction 1
2. Conceptual and Theoretical Background 8
2.1. Statistical Chain Conformation . . . . . . . . . . . . . . . . . . . . . . . 9
2.2. Thermodynamic Properties of Polymers in Solution . . . . . . . . . . . . 13
2.3. Polymer Dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.4. Residual Order in Polymer Networks . . . . . . . . . . . . . . . . . . . . 21
2.5. 1H Double-Quantum NMR . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3. Results and Discussion 32
3.1. Precise dipolar coupling constant distribution analysis in proton multiplequantum
NMR of elastomers . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.2. Cross-Link Density Estimation of PDMS Networks with Precise Consideration
of Networks Defects . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.3. Thermodynamics of Swollen Networks As Reected in Segmental Orientation
Correlations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.4. Real-Time Observation of Polymer Network Formation by Liquid and
Solid-State NMR Revealing Multistage Reaction Kinetics . . . . . . . . . 76
3.5. Solution Cross-linked Networks . . . . . . . . . . . . . . . . . . . . . . . 86
3.6. Partial Swelling of Networks . . . . . . . . . . . . . . . . . . . . . . . . . 92
4. Summary 102
A. Experimental Details 103
A.1. Poly(dimethylsiloxane) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
A.2. Sample Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
A.3. Sample Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
A.4. Equilibrium Swelling Experiments . . . . . . . . . . . . . . . . . . . . . . 108
A.5. Double-Quantum NMR Experiments . . . . . . . . . . . . . . . . . . . . 109
Bibliography 109},
  file     = {:2012 - Structure, Formation and Thermodynamic Properties of Polymer Networks As Studied by NMR.pdf:PDF},
  groups   = {All entries},
  keywords = {polymer network, NMR},
}

@Article{Chasse2012,
  author   = {Walter Chasse and Kay Saalw{\"{a}}chter and Jens-Uwe Sommer},
  journal  = {Macromolecules},
  title    = {Thermodynamics of Swollen Networks As Reflected in Segmental Orientation Correlations},
  year     = {2012},
  pages    = {5513--5523},
  volume   = {45},
  abstract = {We show that segmental orientation correlations, arising from network constraints and reflected in NMR observables such as the apparent proton residual dipolar coupling constant (RDCC), are sensitive to the thermodynamic state of a swollen network. The RDCC is proportional to a dynamic tensor order parameter of the network chain, which depends upon the fluctuation statistics of a network chain subject to swelling-induced stretching and excludedvolume interactions. The correlation of its value at swelling equilibrium with the corresponding degree of swelling for different networks directly reflects the value of the thermodynamic interaction parameter. A description of the phenomenon based on scaling theory allows for conclusions on the limited validity of the classical Flory-Rehner (FR) model for the goodsolvent case. Our study is supplemented by temperature-dependent swelling experiments of different PDMS networks in various solvents, analyzed via a novel construction of solvent-independent swelling master curves, which also emphasize deviations from the FR model for good solvents and further confirm previous reports on concentration- or cross-linking-dependent interaction parameters. We rationalize the failure of the FR model for the good-solvent case in terms of the ratio of the network correlation length and the thermal blob size.},
  file     = {:Chasse2012 - Thermodynamics of Swollen Networks As Reflected in Segmental Orientation Correlations.pdf:PDF},
  groups   = {All entries},
  keywords = {NMR, polymer network},
}

@Article{Tajouri2015,
  author   = {Tahar Tajouri and Mohamed Aymen Ben Mariem and Hubert Hommel},
  journal  = {Concepts in Magnetic Resonance Part A},
  title    = {"Pseudo solid" nuclear spin echo study of poly(ethylene oxide) grafted on silica. Comparison with magic-angle spinning technique results},
  year     = {2015},
  pages    = {306--317},
  volume   = {44A},
  abstract = {The polymer/solid interface of Poly (ethylene oxide) (PEO) grafted on silica is studied by 1H NMR. For grafted polymers, the dipolar interaction is an important factor in the spin--spin relaxation process. For this purpose, the part of the dipolar interaction that is not averaged to zero by the motion is used. The "pseudo solid" spin echo can indeed give an estimation of the nonzero average dipolar interactions. The appropriate pulse sequence permits a standard measurement of the average dipolar spin coupling involved in the transverse magnetization relaxation. The influence of some major parameters such as molecular weights of the chains, grafting ratios, and temperatures on the relaxation and ultimately on the concentration is followed by "pseudo solid" spin echo. The magic-angle spinning technique is also used. The sample rotation confirms by the narrowing of the central line and the appearance of side bands, the existence of a residual dipolar interaction which reveals the concentration of high monomer units at the surface. The study of the side bands permits to calculate the second moment as a function of temperature. A fair agreement is obtained by these two independent techniques: pseudo solid echo and magic-angle spinning.},
  file     = {:Tajouri2015 - _Pseudo Solid_ Nuclear Spin Echo Study of Poly(ethylene Oxide) Grafted on Silica. Comparison with Magic Angle Spinning Technique Results.pdf:PDF},
  groups   = {All entries},
  keywords = {pseudo-solid echo, NMR, silica, spherical brush},
  printed  = {printed},
  ranking  = {rank1},
}

@Article{Bertmer2006,
  author   = {Marko Bertmer and Dan E. Demco and Mingfei Wang and Claudiu Melian and Ramona I. Marcean-Chelcea and Radu Fechete and Maria Baias and Bernhard Bl{\"{u}}mich},
  journal  = {Chemical Physics Letters},
  title    = {Segmental dynamic heterogeneity of short-chain grafted-poly(dimethylsiloxane) by 1H spin-diffusion NMR},
  year     = {2006},
  pages    = {404--409},
  volume   = {431},
  abstract = {Segmental dynamic heterogeneity of short-chain grafted poly(dimethylsiloxane) (PDMS) on pyrogenic silica was investigated using 1H NMR spin-diffusion. A double-quantum dipolar filter was employed for selection of the interface (rigid) region. One-dimensional spin-diffusion equations were solved numerically for a space distribution of spin diffusivity D(x) of the mobile PDMS chains. The degree of heterogeneity can be quantified by the parameters of Gaussian and exponential diffusivity distribution functions which yield similar diffusivities. The rigid and mobile domain sizes and spin diffusivities were correlated with the PDMS chain length, the temperature, and 1H residual dipolar couplings.},
  file     = {:Bertmer2006 - Segmental Dynamic Heterogeneity of Short Chain Grafted Poly(dimethylsiloxane) by 1H Spin Diffusion NMR.pdf:PDF},
  groups   = {All entries},
  keywords = {NMR, PDMS, silica},
  printed  = {printed},
  ranking  = {rank3},
}

@Article{Litvinov2002,
  author   = {V. M. Litvinov and H. Bathel and J. Weis},
  journal  = {Macromolecules},
  title    = {Structure of a PDMS Layer Grafted onto a Silica Surface Studied by Means of DSC and Solid-State NMR},
  year     = {2002},
  pages    = {4356--4364},
  volume   = {35},
  abstract = {The structure of a poly(dimethylsiloxane) (PDMS) layer at the surface of hydrophilic silica has been studied by means of DSC, proton NMR T2 relaxation experiments, and 1H and 29Si NMR spectroscopy. The samples were prepared using (1) the adsorption of PDMS from a PDMS solution onto the silica surface followed by a thermal treatment and (2) mechanical mixing of PDMS with the silica followed by the separation of bound rubber. It was shown that these procedures caused the formation of chain loops chemically attached to the silica surface at both chain ends. The average length of the grafted chains varied from about four to eight Si-O bonds. The experiments provided information on the mobility of the grafted chains, which is related to the structure of the grafted layer. The grafted PDMS layer was found to consist of immobilized chain segments at the PDMS-silica interface and mobile chain portions outside the interface. The chain immobilization at the interface caused a substantial decrease in the heat capacity at Tg and suppressed crystallinity of the grafted PDMS. The interface fraction increased proportionally with a decreasing chain length. About four dimethylsiloxane pendant chain units next to the grafting site were immobilized due to chain anchoring to the silica surface. A small fraction of -SiO(CH3)2- chain units was immobilized as a result of physical adsorption at the silica surface. The fraction of physically adsorbed chain units appears to be proportional to the number of residual silanol groups at the silica surface. The mobility of the chain portions outside the interface was found to differ significantly in the various samples studied and to increase with an increasing average length of the grafted chains. The NMR method allowed us to make a distinction between a dense "brushlike" structure of the grafted layer containing grafted chains of a fairly uniform length and a layer containing a significant fraction of long chain loops outside the densely grafted layer. It was found that the structure of the grafted layer is to a great extent dependent on the grafting procedure employed.},
  file     = {:Litvinov2002 - Structure of a PDMS Layer Grafted onto a Silica Surface Studied by Means of DSC and Solid State NMR.pdf:PDF},
  groups   = {All entries},
  keywords = {NMR, DSC, PDMS, silica, spherical brush},
  printed  = {printed},
  ranking  = {rank3},
}

@Article{Valic1995,
  author     = {S. Valic and B. Deloche and Y. Gallot and A. Skoulios},
  journal    = {Polymer},
  title      = {Orientational diffusion of homopolymer chains in a lamellar structure of diblock copolymer: a deuterium n.m.r. study},
  year       = {1995},
  number     = {15},
  pages      = {3041--3044},
  volume     = {36},
  abstract   = {Chain dynamics in lamellar microdomains of polystyrene-polybutadiene (PS-PB) diblock copolymer is investigated by deuterium nuclear magnetic resonance (n.m.r.). The experiments are performed on perdeuterated PB homopolymer chains dissolved in the PB sublayers of a macroscopically oriented PS-PB sample. The n.m.r. spectra show that homopolymer chain segments undergo uniaxial reorientations around the direction normal to the layers. This local uniaxial order implies that the PB chains of the diblock are slightly elongated and that the segments between chains are correlated in orientation.},
  comment    = {Tracer Chains},
  file       = {:Valic1995 - Orientational Diffusion of Homopolymer Chains in a Lamellar Structure of Diblock Copolymer_ a Deuterium N.m.r. Study.pdf:PDF;:OrientationalDiffusionOfHomopolymerChainsInALamellarStructureOfDiblockCopolymer-ADeuteriumNMRStudy_ValicEtAl_Polymer1995.pdf:PDF},
  groups     = {All entries},
  keywords   = {NMR, block copolymer},
  printed    = {printed},
  ranking    = {rank2},
  readstatus = {read},
}

@Article{Collignon1981,
  author   = {J. Collignon and H. Sillescu and H. W. Spiess},
  journal  = {Colloid and Polymer Science},
  title    = {Pseudo-solid echoes of proton and deuteron NMR in polyethylene melts},
  year     = {1981},
  pages    = {220--226},
  volume   = {259},
  abstract = {A. Introduction
Cohen-Addad and coworkers (1-5) have discovered that the entanglement coupling in concentrated solutions and melts of high mol.wt. polymers gives rise to a solid like contribution in the 1H-NMR spectrum of the polymer that is caused by "nonzero average dipolar coupling". This residual coupling can be completely averaged by magic angle rotation or partly averaged by rather slow sample spinning in a conventional high-resolution NMR spectrometer (1-3), and it can be determined approximately by NMR pulse techniques (4-5). Since it is impossible to solve the multi-spin problem of 1H dipolar coupling, the authors have restricted their analysis of the NMR data to short times where the residual coupling is approximately static. The analysis of the corresponding 2D-NMR is much simpler since it is governed by the quadrupole coupling of the deuteron with the field gradient of a single C-D bond, and is thus a one spin I = 1 problem. Cohen-Addad and Vogin (4) have already solved this problem for the static dipolar coupling of a proton pair. In Section B, we discuss the extension of this theory to dynamic residual couplings (6). Applications to 2D- and 1H-NMR in molten deuterated (PED) and ordinary (PEH) polyethylenes as well as in PEH/PED mixtures are presented in subsequent sections.},
  file     = {:Collignon1981 - Pseudo Solid Echoes of Proton and Deuteron NMR in Polyethylene Melts.pdf:PDF},
  groups   = {All entries},
  keywords = {pseudo-solid echo, NMR, polymer melt, polyethylene},
  printed  = {printed},
}

@Article{Liff1993,
  author   = {Mark L. Liff},
  journal  = {Macromolecules},
  title    = {Obtaining More from the Chemical Shift Anisotropy of Elastic Polymer Networks: A Simple Model To Account for the Distribution of Chain Lengths in a Network},
  year     = {1993},
  pages    = {551--553},
  volume   = {26},
  abstract = {Information on details of the molecular structure of polymer networks, including parameters of irregularity such as the chain-length distribution, the number of dangling chains, and the deviation from uniformity in functionality of cross-links, is necessary for understanding the behavior of networks and developing an adequate theory.1$\cdot$2 It has been emphasized recently that there are relatively few experimental techniques for studying details of a polymer network structure.3 Among these few, nuclear magnetic resonance methods play an increasingly important role. The general features and peculiarities of NMR in polymer networks are now well understood. [4-18] Less progress has been achieved in NMR elucidation of details of a polymer network structure, such as deviation from an ideal network. A number of obstacles preclude a rigorous treatment of this problem. One problem inherent in using NMR line shape for network studies is the difficulty in accounting for dipole interactions of spins close to each other in space but nonadjacent on a chain. Investigation of line shapes governed by one-spin Hamiltonians circumvents this problem, and 2H NMR has proven to be very helpful. [14-18] However, since 2H NMR is limited to networks labeled with deuterium, it is evident that approaches based on other one-spin Hamiltonians, such as chemical shift anisotropy (CSA), are desirable.19,20 In this paper an attempt is made to use a simple model of a freely jointed chain to discuss the influence of irregularities of a network on a line shape governed by CSA.},
  file     = {:Liff1993 - Obtaining More from the Chemical Shift Anisotropy of Elastic Polymer Networks_ a Simple Model to Account for the Distribution of Chain Lengths in a Network.pdf:PDF},
  groups   = {All entries},
  keywords = {NMR, polymer network},
  printed  = {printed},
  ranking  = {rank2},
}

@Article{Guyonnet1989,
  author   = {R. Guyonnet and J. P. Cohen-Addad},
  journal  = {Macromolecules},
  title    = {Effects of Chain Stifness on NMR Properties. Wiener-Integral Description},
  year     = {1989},
  pages    = {135--142},
  volume   = {22},
  abstract = {This work deals with the description of stiffness effects upon the magnetization relaxation of nuclei attached to polymer chains, in a melt or in a gel. A Wiener-integral approach is used to calculate the residual energy of tensorial spin-spin interactions, taking chain stiffness effects into consideration. It is shown how the effect of chain length competes with that of stiffness. The distribution function of the residual energy existing along a chain segment is calculated in the case where a force is applied to chain ends. It is shown that the usual description of stiffness leads to a residual energy equivalent to that associated with an ideal chain. A local interaction is introduced to modify the residual energy. The case where a chain has fixed end points is considered to illustrate properties of gel systems.},
  file     = {:Guyonnet1989 - Effects of Chain Stifness on NMR Properties. Wiener Integral Description.pdf:PDF},
  groups   = {All entries},
  keywords = {NMR, polymer melt, microgel},
}

@Article{Schmit1989,
  author   = {C. Schmit and J. P. Cohen-Addad},
  journal  = {Macromolecules},
  title    = {NMR Approach to the Characterization of the Swelling Process of Polyethylene Networks},
  year     = {1989},
  pages    = {142--146},
  volume   = {22},
  abstract = {Statistical properties of irregular polyethylene networks of different cross-link densities were probed by determining their gel fraction and equilibrium swelling ratio and by measuring the magnetic relaxation of protons. Experimental results were in agreement with the description of the vulcanization of linear chains within a percolation framework leading to a G-1 dependence of the equilibrium swelling ratio Qm. A parametrized assay function was formed to fit the observed relaxation functions. The fit yielded the second and fourth moment behavior of the resonance line. Evidence for a two-step swelling behavior of the PE networks in the presence of a swelling agent (xylene) is given. The second moment of the relaxation functions observed in networks swollen at equilibrium was shown to be independent of the cross-link density. This result was assigned to the existence of a submolecule perceived from NMR with a size smaller than the average distance between cross-links in the polymer gel.},
  file     = {:Schmit1989 - NMR Approach to the Characterization of the Swelling Process of Polyethylene Networks.pdf:PDF},
  groups   = {All entries},
  keywords = {NMR, polymer network, swelling},
}

@Article{CohenAddad1989,
  author   = {J. P. Cohen-Addad},
  journal  = {Macromolecules},
  title    = {NMR and Gel Elasticity Interrelationship},
  year     = {1989},
  pages    = {147--151},
  volume   = {22},
  abstract = {This work deals with the spin-system response of nuclei attached to polymer chains in a gel. It is shown that elongation effects and internal fluctuations of chain segments are involved in the gel elasticity and in the relaxation of transverse magnetization, using a phantom network model. Effects of an affine deformation of chain segments on NMR properties are discussed considering a uniaxially strained network structure. The - l/ 2 dependence of the retractive force is contrasted to the 2 - l/ dependence of magnetic relaxation rates ( is the stretching ratio).},
  file     = {:Cohen-Addad1989 - NMR and Gel Elasticity Interrelationship.pdf:PDF},
  groups   = {All entries},
  keywords = {NMR, microgel},
}

@Article{Brereton1990,
  author   = {M. G. Brereton},
  journal  = {Macromolecules},
  title    = {NMR Transverse Relaxation Function Calculated for Constrained Polymer Chains: Application to Entanglements and Networks},
  year     = {1990},
  pages    = {1119--1131},
  volume   = {23},
  abstract = {A general method is presented for calculating the NMR transverse relaxation function due to dipolar interactions between a spin pair, rigidly attatched to a constrained polymer chain. The constraints considered are those restricting the dynamics of the end-to-end vector of an arbitrary group of consecutive polymer segments. A direct application is made to the motion of polymer chains, as perceived by NMR, in deformed cross-linked systems. The ability to handle this type of constraint enables a more general hierarchical chain structure to be created, where the dynamics on one scale can be quite different from those operating on another scale, so that entanglements as well as cross-linlfs can be included. General results are given for the relaxation function in a form that is shown to be dynamically scale invariant. The methods presented and in particular the incorporation of the constraints are entirely novel and lead to an exact calculation of the transverse NMR relaxation function. As a result the conditions under which the NMR relaxation is exponential or otherwise are clearly shown. The general results are explicitly illustrated by the case of a chain, consisting of two levels of structure, i.e., a small-scale structure with relatively fast (with respect to the NMR time) relaxation and a larger scale structure subjected to deformation and governed by slower dynamics.},
  file     = {:Brereton1990 - NMR Transverse Relaxation Function Calculated for Constrained Polymer Chains_ Application to Entanglements and Networks.pdf:PDF},
  groups   = {All entries},
  keywords = {NMR, polymer network},
}

@Article{CohenAddad1974,
  author   = {J. P. Cohen-Addad and R. Vogin},
  journal  = {Physical Review Letters},
  title    = {Molecular Motion Anisotropy as Reflected by a "Pseudosolid" Nuclear Spin Echo: Observation of Chain Constraints in Molten cis-1, 4-Polybutatiene},
  year     = {1974},
  number   = {16},
  pages    = {940--944},
  volume   = {33},
  abstract = {A nuclear spin echo ("pseudosolid echo") analogous to a "solid echo" is predicted to be observed even within the motional-narrowing approximation, whenever the molecular motion symmetry gives rise to a nonzero average dipolar spin coupling. It is considered as a new characterization of molecular motion anisotropy. New features are discussed. They are well illustrated by "pseudosolid echoes" observed, for the first time, on protons bound to long chains in a molten polymer system. Echoes are shown to reflect chain constraints.},
  file     = {:Cohen-Addad1974 - Molecular Motion Anisotropy As Reflected by a _Pseudosolid_ Nuclear Spin Echo_ Observation of Chain Constraints in Molten Cis 1, 4 Polybutatiene.pdf:PDF},
  groups   = {All entries},
  keywords = {pseudo-solid echo, NMR, polymer melt},
  printed  = {printed},
  ranking  = {rank3},
}

@Article{Lutz2005,
  author   = {Jean-Francois Lutz and Krzysztof Matyjaszewski},
  journal  = {Journal of Polymer Science Part A: Polymer Chemistry},
  title    = {Nuclear Magnetic Resonance Monitoring of Chain-End Functionality in the Atom Transfer Radical Polymerization of Styrene},
  year     = {2005},
  pages    = {897--910},
  volume   = {43},
  abstract = {The evolution of the bromine end functionality during the bulk atom transfer radical polymerization (ATRP) of styrene [in the presence of the catalyst CuBr/4,4-di-(5-nonyl)-2,2-bipyridine] was monitored with 600-MHz 1H NMR. A decrease in the functionality versus the conversion was observed. The loss of functionality was especially significant at very high conversions (90%). The experimental data were compared with a kinetic model of styrene ATRP. The latter indicated that the loss of chain-end functionality was partly due to bimolecular terminations but was mainly due to -H elimination reactions induced by the copper(II) deactivator. These elimination reactions, which occurred later in the reaction, did not significantly affect the polymer molecular weights and the polydispersity. Therefore, a linear evolution of the molecular weights and low-polydispersity polymers were still observed, despite a loss of functionality. Understanding these side reactions helped in the selection of the proper conditions for reducing the contribution of the elimination process and for preparing well-defined polystyrene (number-average molecular weight 10,000 g mol1; weight-average molecular weight/number-average molecular weight 1.1) with a high functionality (92%).},
  file     = {:Lutz2005 - Nuclear Magnetic Resonance Monitoring of Chain End Functionality in the Atom Transfer Radical Polymerization of Styrene.pdf:PDF},
  groups   = {All entries},
  keywords = {NMR, polymer synthesis, ATRP},
}

@Article{Li2016,
  author   = {Cheng-Wu Li and Holger Merlitz and Chen-Xu Wu and Jens-Uwe Sommer},
  journal  = {Polymer},
  title    = {The structure of brushes made of dendrimers: Recent advances},
  year     = {2016},
  pages    = {437--477},
  volume   = {98},
  abstract = {In recent publications, a couple of theoretical models, ranging from simple scaling approaches and boxlike mean-field models to self-consistent field techniques, have been proposed to describe the structure of brushes that are composed of dendrimers. In this work, we carry out molecular dynamics simulations in various density regimes, and compare the resulting data with predictions of the latest theoretical models. This study enables us to access the ranges of validity and accuracy of the respective models, as well as their shortcomings. Significant differences in the predicted conformations of the dendrimers are observed and analyzed in the context of their elastic properties in the different models. This work offers guidelines for future research directions, which may lead to further progress regarding the understanding of branched polymer brushes},
  file     = {:Li2016 - The Structure of Brushes Made of Dendrimers_ Recent Advances.pdf:PDF},
  groups   = {All entries},
  keywords = {review, polymer brush, simulation, model},
  printed  = {printed},
  ranking  = {rank3},
}

@Article{Lu2011,
  author   = {Yan Lu and Matthias Ballauff},
  journal  = {Progress in Polymer Science},
  title    = {Thermosensitive core-shell microgels: From colloidal model systems to nanoreactors},
  year     = {2011},
  pages    = {767--792},
  volume   = {36},
  abstract = {We review recent work done on thermosensitive core--shell particles that consist of a solid core onto which a shell of crosslinked polymer as, e.g., poly(N-isopropylacrylamide) (PNIPA) has been grafted. Immersed in cold water the shell of these particles having dimensions of typically 150nm in diameter will swell. At ca. 32^\circC a volume transition takes place in the PNIPA-network and the shell shrinks considerably. In this review we present a survey of recent work done with these particles. The synthesis by a two-step route as well as by photo-emulsion polymerization will be discussed. Recent progress in the characterization of the systems by cryogenic transmission electron microscopy is presented and compared to work employing scattering methods. The phase diagram of the thermosensitive network and its description in terms of the Flory-Rehner-theory is reviewed. Moreover, the internal dynamics of the network could be studied by depolarized dynamic light scattering (DDLS). Since the degree of swelling can be reversibly adjusted by temperature, the effective volume fraction in aqueous solution can be adjusted within a wide range. Thus, the particles act as inflatable spheres and have been used for an in-depth study of the rheology of concentrated suspensions. As a final point, we present an overview of the use of these particles as nanoreactors. Here metal nanoparticles and enzymes are immobilized in the shell of the particles and used for catalysis. All results obtained so far demonstrate that thermosensitive core--shell particles present a class of model colloids with excellent stability and great versatility.},
  file     = {:Lu2011 - Thermosensitive Core Shell Microgels_ from Colloidal Model Systems to Nanoreactors.pdf:PDF},
  groups   = {All entries},
  keywords = {thermoresponsive, review, microgel, spherical brush, DLS, PNIPAM},
}

@Article{Pesek2016,
  author   = {Stacy L. Pesek and Yen-Hao Lin and Hui Zhen Mah and Will Kasper and Bo Chen and Bruan J. Rohde and Megan L. Robertson and Gila E. Stein and Rafael Verduzco},
  journal  = {Polymer},
  title    = {Synthesis of bottlebrush copolymers based on poly(dimethylsiloxane) for surface active additives},
  year     = {2016},
  pages    = {495--504},
  volume   = {98},
  abstract = {Bottlebrush polymers have been used as surface-active additives for chemically-identical linear polymers because they spontaneously accumulate at surfaces through an entropy-mediated process. In this work, we design functional bottlebrush polymer additives with mixed side-chain chemistries that can deliver unique surface properties. Bottlebrush polymers with poly(dimethylsiloxane) (PDMS) side-chains and bottlebrush copolymers with PDMS and poly(lactic acid) (PLA) side-chains are synthesized using ring opening metathesis polymerization. Contact angle goniometry, X-ray photoelectron spectroscopy (XPS), and microscopy demonstrate a spontaneous accumulation of these additives at the film surface without lateral phase segregation. Bottlebrush polymers were found to enrich the film surface more strongly than linear block copolymers of PDMS-b-PLA, and the surface contact angle was tunable by varying the composition and quantity of added bottlebrush copolymer. Significantly, bottlebrush additives segregate rapidly, during film casting. This work demonstrates that low-surface energy bottlebrush copolymer additives can be used to introduce new surface properties in polymer films.},
  file     = {:Pesek2016 - Synthesis of Bottlebrush Copolymers Based on Poly(dimethylsiloxane) for Surface Active Additives.pdf:PDF},
  groups   = {All entries},
  keywords = {polymer brush, bottlebrush, copolymer, PDMS, polymer synthesis},
}

@Article{Ballauff2007,
  author   = {M. Ballauff},
  journal  = {Progress in Polymer Science},
  title    = {Spherical polyelectrolyte brushes},
  year     = {2007},
  pages    = {1135--1151},
  volume   = {32},
  abstract = {We review recent work on colloidal particles bearing a dense layer of linear polyelectrolyte chains on their surface. These systems have been termed {\textquoteleft}{\textquoteleft}spherical polyelectrolyte brush{\textquoteright}{\textquoteright} (SPB) because the polyelectrolyte chains have been grafted densely to the surface of the core particles. The different methods to generate such particles, namely self-assembly to form micelles, adsorption of block copolymers onto spherical colloid particles, and photo-emulsion polymerization are reviewed. The equilibrium structure of the surface layer of the particles in aqueous solution can be determined by scattering methods and electron microscopy. The structure of SPB is governed by the marked osmotic pressure of the counterions that are confined within the brush layer. This is in full accord with recent theoretical deductions discussed in detail herein. The accumulation of counterions can be used to generate metallic nanoparticles within the brush layer. The dynamics of the particles in aqueous suspension as e.g. the flow behavior in dilute solution can directly be derived from static data. Moreover, the interaction of the SPB with solid interfaces is discussed. It is demonstrated that particles bearing positively charged polyelectrolyte chains interact strongly with negatively charged surfaces. A final point discussed here is the interaction of SPB with proteins in aqueous solution. Here it is shown that these systems have a great potential as novel carrier particles for functional biomolecules.},
  file     = {:Ballauff2007 - Spherical Polyelectrolyte Brushes.pdf:PDF},
  groups   = {All entries},
  keywords = {spherical brush, polyelectrolyte, review, polymer synthesis, SAXS, SANS},
}

@Article{Xie2016,
  author   = {Guojun Xie and Hangjun Ding and William F. M. Daniel and Zongyu Wang and Joanna Pietrasik and Sergei S. Sheiko and Krzysztof Matyjaszewski},
  journal  = {Polymer},
  title    = {Preparation of titania nanoparticles with tunable anisotropy and branched structure from core-shell molecular bottlebrushes},
  year     = {2016},
  pages    = {481--486},
  volume   = {98},
  abstract = {Core-shell molecular bottlebrushes with various topologies and with poly (tert-butyl acrylate)-b-polystyrene (PtBA-b-PS) block copolymer side chains were synthesized via atom transfer radical polymerization (ATRP). After hydrolysis of the PtBA segments and their conversion to poly (acrylic acid) (PAA), the materials were used as templates to prepare titania nanoparticles. Transmission electron microscopy (TEM) images showed that the particles retained the characteristic shape of the templates, including branches and cylindrical geometry. The cylindrical dimensions, i.e. diameter and length, were controlled by the number average degrees of polymerization of the PAA side-chain block and the polymethacrylate backbone, respectively. Thermogravimetric analysis (TGA) showed the weight fraction of inorganic content ranged from 17% to 35%, depending on the ratio of the length of PAA and PS blocks.},
  file     = {:PreparationOfTitaniaNanoparticlesWithTunableAnisotropyAndBranchedStructureFromCoreShellMolecularBottlebrushes_XieEtAl_Polymer2016.pdf:PDF},
  groups   = {All entries},
  keywords = {bottlebrush, polystyrene, polymer brush, ATRP, PAA, block copolymer, Thermogravimetric analysis (TGA)},
}

@Article{Ruettiger2016,
  author   = {Chrstian R{\"{u}}ttiger and Sabrina Mehlhase and Steffen Vowinkel and Gennady Cherkashinin and Na Lui and Christian Dietz and Robert W. Stark and Markus Biesalski and Markus Gallei},
  journal  = {Polymer},
  title    = {Redox-mediated flux control in functional paper},
  year     = {2016},
  pages    = {429--436},
  volume   = {98},
  abstract = {It is still a challenge to control the structure and functionality of a porous material in a way that its properties can be changed by external triggers. To this end, the combination of porous paper substrates with redox-responsive ferrocene-containing polymer brushes is a promising approach. Here, surfaceinitiated Atom Transfer Radical Polymerization (SI-ATRP) protocols for a ferrocenyl methacrylate derivative, i.e. (2-(methacryloyloxy)ethyl ferrocenecarboxylate) (FcMA), were applied. The redoxresponsiveness of the polymer-modified paper substrate was shown by chemical means and Kelvin probe force microscopy (KPFM), while X-ray photoelectron spectroscopy (XPS) revealed insights into the oxidation states of the ferrocene moieties. The control over the oxidation state enabled the precise control over the material's wettability as shown by contact angle (CA) measurements and capillary rise tests. Thus, these redox-mediated functional papers open a variety of applications for microfluidic devices.},
  file     = {:Ruettiger2016 - Redox Mediated Flux Control in Functional Paper.pdf:PDF},
  groups   = {All entries},
  keywords = {polymer brush, SI-ATRP, control parameter},
}

@Article{Ballauff2016,
  author   = {Matthias Ballauff and Oleg V. Borisov},
  journal  = {Polymer},
  title    = {Phase transitions in brushes of homopolymers},
  year     = {2016},
  pages    = {402--408},
  volume   = {98},
  comment  = {- uncharged polymer brushes vs. polyelectrolyte brushes
- flory-huggins theory vs. n-cluster model
-lateral uniformity lost if brush height is less than Gaussian expectation {(HSqrt(N))}
-pressure acts antagonistically to temperature
-dense proximal layers and dilute outer layers},
  file     = {:Ballauff2016 - Phase Transitions in Brushes of Homopolymers.pdf:PDF},
  groups   = {All entries},
  keywords = {polymer brush, planar brush, spherical brush, bottlebrush, neutral brush, polyelectrolyte, control parameter, review},
  printed  = {printed},
  ranking  = {rank5},
}

@Article{Ott2016,
  author   = {Marcus W. Ott and Heike Herbert and Michael Graf and Markus Biesalski},
  journal  = {Polymer},
  title    = {Cellulose-graft-polystryrene bottle-brush copolymers by homogeneous RAFT polymerization of soluble cellulose macro-CTAs and "CTA-shuttled" R-group approach},
  year     = {2016},
  pages    = {505--515},
  volume   = {98},
  abstract = {In this work we introduce well-defined cellulose-graft-copolymers prepared from CTA-functionalized cellulose and an CTA-shuttled R-approach in solution. Micro-crystalline cellulose was transferred into a cellulose-CTA in a three-step approach with degrees of substitution for CTA, DS(CTA), of about 0.2e0.6. Additional transfer of residual OH-groups with propionic ester groups resulted in cellulose-CTA molecules that were well-soluble in a large number of organic solvents. Model polymerizations using styrene monomer, AIBN as initiator and added free CTA produced well-defined cellulose-graft-PS copolymers. The molar mass of the macromolecules generated on the cellulose backbone were found to be similar as the molar mass of the polymers obtained from the CTA free in solution, which allowed a simple analysis of the graft copolymers. The molar mass of the cellulose-grafted PS could be well-controlled between less than 5000 g/mol to more than 40,000 g/mol by adjusting the reaction conversion through variation of the polymerization time. Analysis of the initiation efficiency showed that by using the CTA-shuttled approach for the generation of cellulose-graft-copolymers one can obtain very high grafting densities (relative amount of grafted chains on the cellulose backbone) as well as grafting ratios (relative mass gain due to grafting of the polymers onto the cellulose backbone). The presented results thus offer a number of possibilities for future design of functional cellulose-based bottle brush architectures.},
  file     = {:Ott2016 - Cellulose Graft Polystryrene Bottle Brush Copolymers by Homogeneous RAFT Polymerization of Soluble Cellulose Macro CTAs and _CTA Shuttled_ R Group Approach.pdf:PDF},
  groups   = {All entries},
  keywords = {polystyrene, bottlebrush, copolymer, polymer synthesis},
}

@Book{Levitt2000,
  author    = {Malcom H. Levitt},
  publisher = {Wiley},
  title     = {Spin Dynamics - Basics of Nuclear Magnetic Resonance},
  year      = {2000},
  file      = {:Levitt2000 - Spin Dynamics Basics of Nuclear Magnetic Resonance.pdf:PDF},
  groups    = {Books},
  keywords  = {book, NMR},
}

@Book{Duer2002,
  editor    = {Melinda J. Duer},
  publisher = {Blackwell Science},
  title     = {Solid-State NMR Spectroscopy: Principles and Applications},
  year      = {2002},
  file      = {:Duer - Solid State NMR Spectroscopy_ Principles and Applications.pdf:PDF},
  groups    = {Books},
  keywords  = {Book, NMR},
}

@Article{McBrierty1974,
  author   = {Vincent J. McBrierty},
  journal  = {Journal of Chemical Physics},
  title    = {Use of rotation operators in the general description of polymer properties},
  year     = {1974},
  volume   = {61},
  abstract = {In this paper we are concerned with the formulation of a general mathematical scheme which may be used to describe many polymer properties of interest. The responses of polymers to the following experimental techniques h ve been analysed: infrared absorption, x-ray diffraction, nuclear magnetic resonance absorption, fluorescence polarization, and elasticity measurements. A principal feature of the analysis is the use of matrix elements of the three-di ensional rotation operator. This approach greatly facilitates the treatment of the various types of symmetry, both statistical and crystallographic, which are often an inherent feature of polymer structure. It is clearly demonstrated  ow measurements from different experiments can complement each other and lead to a more complete description of the polymer.},
  file     = {:McBrierty1974 - Use of Rotation Operators in the General Description of Polymer Properties.pdf:PDF},
  groups   = {Experimental Methods},
  keywords = {polymer, experimental methods, NMR, infrared, x-ray, elasticity, flourescence},
}

@Article{Hindman1966,
  author   = {J. C. Hindman},
  journal  = {Journal of Chemical Physics},
  title    = {Proton Resonance Shift of Water in the Gas and Liquid States},
  year     = {1966},
  volume   = {44},
  abstract = {Temperature-dependence measurements have been made on the chemical shift of the proton of a water molecule in the liquid state and in the gas state at varying pressure. The problem of relating these experimental data to the intermolecular forces leading to cohesion and to hydrogen-bond formation between water molecules is considered in detail. It is shown that a consistent treatment of the chemical shift, thermal, and dielectric data for water can be given based on a two-state model involving an equilibrium between a hydrogen-bonded "icelike" fraction and a "monomer" fraction whose interaction with the lattice arises entirely from London dispersion forces. Using semiempirically derived values of the chemical shift and energy associated with the condensation of water vapor to "monomer," the magnitude of the shift associated with the transformation to ice is calculated. It is then shown that, on the assumption that the hydrogen bond is electrostatic in character, the "polar" contribution to this shift can be related through the appropriate shielding equations to the dipole moment of the water molecule in ice. The magnitude of the dipole moment derived from these relationships is found to be in excellent agreement with values derived from dielectric data. The possibility that the shielding changes may in part be due to processes other than the breaking of hydrogen bonds is considered. It is shown that the model leads to the conclusion that the chemical shift in the transformation of ice to water at O{$^{\circ}$}C could be entirely accounted for either by a stretching of the hydrogen bonds or a small amount of bending of the bonds. It is noted that if some bond breaking does occur, as required by the fact that water is a liquid, then the amount of stretching and/or bending will be limited.},
  file     = {:Hindman1966 - Proton Resonance Shift of Water in the Gas and Liquid States.pdf:PDF},
  keywords = {NMR, chemical shift, dielectric},
}

@Article{Dickinson1951,
  author   = {W. C. Dickinson},
  journal  = {Physical Review},
  title    = {The Time Average Magnetic Field at the Nucleus in Nuclear Magnetic Resonance Experiments},
  year     = {1951},
  number   = {5},
  pages    = {717--731},
  volume   = {81},
  abstract = {For the high precision measurement of a nuclear gyromagnetic ratio by the Purcell or Bloch resonance methods, accurate knowledge of the time average magnetic field BA{\quotedblbase}at the positions of the nuclei is necessary. The various component fields contributing to BA, are listed. An experimental study is made of two of these Gelds: the magnetic shielding field in molecules and the magnetization field of paramagnetic ions added to a sample. In an earlier paper accurate computed values were given of the magnetic shielding field for free atoms and monatomic ions. The eGect of these fields on the attainable precision. in the measurement of nuclear moments is discussed.},
  file     = {:Dickinson1951 - The Time Average Magnetic Field at the Nucleus in Nuclear Magnetic Resonance Experiments.pdf:PDF},
  keywords = {NMR, chemical shift},
}

@Article{Harris2001,
  author   = {Robin K. Harris and Edwin D. Becker and Sonia M. Cabral de Menezes and Robin Goodfellow and Pierre Granger},
  journal  = {Pure and Applied Chemistry},
  title    = {NMR Nomenclature. Nuclear Spin Properties and Conventions for Chemical Shifts (IUPAC Recommendations 2001)},
  year     = {2001},
  number   = {11},
  pages    = {1795--1818},
  volume   = {73},
  file     = {:Harris2001 - NMR Nomenclature. Nuclear Spin Properties and Conventions for Chemical Shifts (IUPAC Recommendations 2001).pdf:PDF},
  keywords = {NMR, Chemical Shift},
}

@Article{Gottlieb1997,
  author     = {Hugo E. Gottlieb and Vadim Kotlyar and Abraham Nudelman},
  journal    = {Journal of Organic Chemistry},
  title      = {NMR Chemical Shifts of Common Laboratory Solvents as Trace Impurities},
  year       = {1997},
  pages      = {7512--7515},
  volume     = {62},
  abstract   = {In the course of the routine use of NMR as an aid for organic chemistry, a day-to-day problem is the identification of signals deriving from common contaminants (water, solvents, stabilizers, oils) in less-than-analytically-pure samples. This data may be available in the literature, but the time involved in searching for it may be considerable. Another issue is the concentration dependence of chemical shifts (especially 1 H); results obtained two or three decades ago usually refer to much more concentrated samples, and run at lower magnetic fields, than today{\textquoteright}s practice. We therefore decided to collect 1 H and 13 C chemical shifts of what are, in our experience, the most popular {\textquotedblleft}extra peaks{\textquotedblright} in a variety of commonly used NMR solvents, in the hope that this will be of assistance to the practicing chemist.},
  doi        = {https://doi.org/10.1021/jo971176v},
  file       = {:Gottlieb1997 - NMR Chemical Shifts of Common Laboratory Solvents As Trace Impurities.pdf:PDF},
  groups     = {Polymer Usage},
  keywords   = {NMR, Chemical Shift},
  printed    = {printed},
  ranking    = {rank2},
  readstatus = {skimmed},
}

@Article{Wishart1995,
  author   = {David S. Wishart and Colin G. Bigam and Jian Yao and Frits Abildgaard and H. Jane Dyson and Eric Oldfield and John L. Markley and Brian D. Sykes},
  journal  = {Journal of Biomolecular NMR},
  title    = {$^{1}$H, $^{13}$C and $^{15}$N chemical shift referencing in biomolecular NMR},
  year     = {1995},
  pages    = {135--140},
  volume   = {6},
  abstract = {A considerable degree of variability exists in the way that 1H, 13C and 15N chemical shifts are reported and referenced for biomolecules. In this article we explore some of the reasons for this situation and 13 propose guidelines for future chemical shift referencing and for conversion from many common 1H, 13C and 15N chemical shift standards, now used in biomolecular NMR, to those proposed here.},
  comment  = {Published before IUPAC recommendations},
  keywords = {NMR, chemical shift},
  url      = {https://doi.org/10.1007/BF00211777},
}

@Article{Ward2000,
  author   = {K. M. Ward and R. S. Balaban},
  journal  = {Magnetic Resonance in Medicine},
  title    = {Determination of pH Using Water Protons and Chemical Exchange Dependent Saturation Transfer (CEST)},
  year     = {2000},
  pages    = {799--802},
  volume   = {44},
  abstract = {Solution pH was measured using water proton NMR via chemical exchange dependent saturation transfer (CEST) with selected chemical exchange sites. Several useful pH-sensitive proton chemical exchange agents were found: 5,6-dihydrouracil, 5-hydroxytryptophan, and a combination of 5-hydroxytryptophan and 2-imidazolidinethione. A ratiometric approach was developed that permitted pH determinations that were independent of water T 1 or exchange site concentration.},
  file     = {:Ward2000 - Determination of PH Using Water Protons and Chemical Exchange Dependent Saturation Transfer (CEST).pdf:PDF},
  keywords = {NMR, chemical shift, pH},
}

@Article{Pfrommer2000,
  author   = {Bernd G. Pfrommer and Francesco Mauri and Steven G. Louie},
  journal  = {Journal of the American Chemical Society},
  title    = {NMR Chemical Shifts of Ice and Liquid Water: The Effects of Condensation},
  year     = {2000},
  volume   = {122},
  abstract = {We report the results of ab initio density functional theory calculations of the NMR chemical shift of liquid water and hexagonal ice. Depending on the structural model used, the calculated isotropic shift of ice Ih with respect to the gas phase is -8.0 +- 0.2 or -8.1 +- 0.1 ppm for the proton, and -48.6 +- 0.02 or -48.1 +- 0.02 ppm for oxygen. The proton anisotropy is -33.4 +- 0.2 or -33.6 +- 0.2 ppm. Using snapshots from ab initio molecular dynamics simulations, we find a gas-to-liquid shift of -5.8 +- 0.1 ppm for hydrogen, and -36.6 +- 0.5 ppm for oxygen. Molecules beyond the first solvation shell influence the proton chemical shift predominantly via the electric field generated by their permanent electric dipole moment. Finally, we show that it is possible to reproduce the proton chemical shifts in the condensed phases by an empirical function of the local molecular geometry.},
  file     = {:Pfrommer2000 - NMR Chemical Shifts of Ice and Liquid Water_ the Effects of Condensation.pdf:PDF},
  keywords = {NMR, Chemical Shift, Simulation},
}

@Article{Pincus1991,
  author   = {P. Pincus},
  journal  = {Macromolecules},
  title    = {Colloid Stabilization with Grafted Polyelectrolytes},
  year     = {1991},
  pages    = {2912--2919},
  volume   = {24},
  abstract = {We consider the structure of a surface with a fairly dense array of polyelectrolytes end-grafted to it. A simple theory for the scaling properties of the corona thickness, counterion distribution, and disjoining pressure between opposing layers is presented, which makes contact with previous numerical studies. We show that by distributing the charges on a macromolecule the interlayer force is considerably less sensitive to Debye screening by added electrolytes. This provides the physical basis for the importance of polyelectrolytes in colloid control in polar solvents. The flat layer studies are extended to the case of small (spherical) colloidal particles. Finally some speculations are made concerning the role of grafted polyelectrolytes on contributing to the bending energies of flexible membranes.},
  file     = {:Pincus1991 - Colloid Stabilization with Grafted Polyelectrolytes.pdf:PDF},
  keywords = {Spherical Brush, polyelectrolyte, colloid stabilization},
  printed  = {printed},
  ranking  = {rank2},
}

@Article{Witten1986,
  author   = {T. A. Witten and P. A. Pincus},
  journal  = {Macromolecules},
  title    = {Colloid Stabilization by Long Grafted Polymers},
  year     = {1986},
  volume   = {19},
  abstract = {Two colloidal particles, each with f long polymers grafted to it, experience an effective mutual repulsion in a good solvent. The effective interaction potential depends logarithmically on the separation between the particles, with a universal coefficient depending on the functionality f. We deduce this coefficient for f = 1 and 2 using results of des Cloizeaux for interior correlations within a self-avoiding walk. For f {\guillemotright} 1 we deduce that this coefficient varies as f^(3/2), using the semidilute scaling properties of the polymeric {\textquotedblleft}corona{\textquotedblright} around a colloidal particle. We show that the repulsive interaction arising from the polymers can be sufficient to stabilize a dispersion of colloidal particles, despite their inherent tendency to precipitate owing to van der Waals attractions. The repulsions also give rise to a peak in the scattering structure factor S(q) for concentrations near the overlap concentration c*. We show that the height of this peak scales as f^(3/2) and predict a macrocrystalline phase for c near c* and for sufficiently large f.},
  file     = {:Witten1986 - Colloid Stabilization by Long Grafted Polymers.pdf:PDF},
  keywords = {spherical brush, colloid stabilization},
  printed  = {printed},
  ranking  = {rank2},
}

@Article{Milner1988,
  author   = {S. T. Milner and T. A. Witten and M. E. Cates},
  journal  = {Macromolecules},
  title    = {Theory of the Grafted Polymer Brush},
  year     = {1988},
  volume   = {21},
  abstract = {We calculate the free energy of surfaces coated with grafted polymers in a solvent. We use a self-consistent field (SCF) method appropriate for weak excluded-volume interactions and at moderately high surface coverage. We give the exact solution for the {\textquotedblleft}classical limit{\textquotedblright} of our SCF equations which shows that, at high molecular weight, the concentration profile approaches a parabolic form rather than the step-function suggested by Alexander and de Gennes. Accordingly, the energy required to slightly compress the brush varies as the cube of the compression distance. An extension of the method to the good-solvent, semidilute regime is described.},
  file     = {:Milner1988 - Theory of the Grafted Polymer Brush.pdf:PDF},
  keywords = {spherical brush, calculation},
  printed  = {printed},
  ranking  = {rank2},
}

@PhdThesis{Reinhardt2013,
  author   = {Matthias Reinhardt},
  school   = {Humboldt-Universit{\"{a}}t zu Berlin},
  title    = {Functional interfaces Polymer brushes and their response to temperature and hydrostatic pressure},
  year     = {2013},
  type     = {phdthesis},
  abstract = {The functionality of an interface can be modified by polymer brushes. Out of the variety of polymers which can be used to achieve this functional modification, the focus of this work is on brushes of either polyacrylic acid (PAA) or poly(N,N-dimethylaminoethyl methacry- late) (PDMAEMA). PAA brushes provide a soft interface that prevents the denaturation of adsorbed proteins. PDMAEMA is known to respond to external stimuli. The lower critical solution temperature (LCST) of PDMAEMA can be used to tune the hydrophobicity of the interface with temperature. For the first time, the effect of elevated hydrostatic pressure, up to 1000 bar, on the functionality of these systems is investigated. Planar PAA and PDMAEMA brushes are prepared from precursor diblock copolymer Langmuir layers with varied grafting density $\sigma$ utilizing the Langmuir-Sch{\"{a}}fer transfer technique. For the PAA brushes, neutron reflectivity (NR) measurements are conducted in the solvent- swollen state at the solid-liquid interface after incubation in buffered D 2 O and after the adsorption of bovine serum albumin (BSA) from the aqueous liquid phase at 1 bar and 900 bar. From these measurements the detailed volume fraction profiles of the PAA brush $\phi$ PAA (z) and adsorbed BSA proteins $\phi$ BSA (z) are extracted. The amount of adsorbed BSA is found to scale linearly with grafting density. An elevated hydrostatic pressure of 900 bar is found to have no impact on the structure of the PAA brush and its capability to bind BSA proteins. The PDMAEMA brushes are investigated by NR at the solid-liquid interface in a temperature range of 20 to 60^\circC for hydrostatic pressures from 1 to 1000 bar. A novel theoretical model of the brush density profile as a function of $\sigma$ , T and P is used to fit the experimental NR data. Increasing the temperature causes a continuous decrease of the polymer brush thickness. The reason for this response is a hydrophobic coil to globule transition of the polymer chains when crossing the LCST. Hydrostatic pressure is found to act antagonistic to temperature. The hydrophobic collapse of the PDMAEMA brush that is caused by a temperature increase of 10 K is counterbalanced by a pressure increase of 1000 bar. While the value of the LCST of the polymer brush is found to decrease with the grafting density, the antagonistic effect of hydrostatic pressure is not affected.},
  file     = {:Reinhardt2013 - Functional Interfaces Polymer Brushes and Their Response to Temperature and Hydrostatic Pressure.pdf:PDF},
  keywords = {polymer brush, PAA, PDMAEMA, thermoresponsive, pressure, neutron, planar brush, LCST},
}

@Article{Mei2005,
  author   = {Y. Mei and M. Ballauff},
  journal  = {European Physical Journal E: Soft Matter},
  title    = {Effect of counterions on the swelling of spherical polyelectrolyte brushes},
  year     = {2005},
  pages    = {341--349},
  volume   = {16},
  abstract = {We investigate the swelling of colloidal spherical polyelectrolyte brushes in the presence of different counterions. The colloidal particles consist of a solid poly(styrene) core of ca. 100 nm diameter onto which linear polyelectrolyte chains are chemically grafted. Two types of polyelectrolyte chains have been used here: The cationic polyelectrolyte poly(2-(acryloyl)ethyltrimethylammonium chloride)) (PATAC) and the anionic poly(styrenesulfonate) (PSS). Both systems are dispersed in water and the degree of swelling of the surface layer is studied by dynamic light scattering. Adding more and more salt leads to a strong shrinking of the surface layer as expected for polyelectrolyte brushes. It is shown that data obtained at low ionic strength can be collapsed on suitable master curves for monovalent and divalent counterions, respectively. For some ions, however, high salt concentrations may lead to a re-swelling of the brush layer in case of the cationic systems. This points to specific interactions of the counterions with the PATAC chains. This strong specific interaction between the counterions and the attached polyelectrolyte may even lead to flocculation of the particles at intermediate salt concentration. Surprisingly, for iodide and magnesium counterions the solubility increases again if the salt concentration is raised to 1 mol/l. Hence, specific interaction leads to salting-out effects as well as to salting-in effects for these colloidal particles. All specific effects seen at high concentrations of added salt can be explained by the increase of the reduced excluded-volume parameter which is due to the adsorption of salt ions.},
  file     = {:Mei2005 - Effect of Counterions on the Swelling of Spherical Polyelectrolyte Brushes.pdf:PDF},
  keywords = {spherical brush, polyelectrolyte, counterion, polystyrene, PATAC, PSS, DLS, ionic strength, valency, salting-in salting-out},
}

@Article{Hur2010,
  author   = {Jaehyun Hur and Kevin N. Witte and Wei Sun and You-Yeon Won},
  journal  = {Langmuir},
  title    = {On the Origins of the Salt-Concentration-Dependent Instability and Lateral Nanoscale Heterogeneities of Wark Polyelectrolyte Brushes: Gradient Brush Experiment and Flory-Type Theoretical Analysis},
  year     = {2010},
  number   = {3},
  pages    = {2021--2034},
  volume   = {26},
  abstract = {We investigated, by experiment and theory, the lateral structure of a weak polyelectrolyte brush at various added salt concentrations and chain grafting densities. Model poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes with grafting density gradients were developed for this study by using a novel {\textquotedblleft}Langmuir-Blodgett-deposition-under-compression{\textquotedblright} (LB\C) method. Fluid AFM images of these brushes indicate that the lateral structure of the brush system is sensitive to both added salt concentration and grafting density. Under low salt conditions, 0-20 mM NaCl, the brush structure shows strong microscopic lateral heterogeneities at high grafting densities; both the width and height of the heterogeneities increase with increasing grafting density but are independent of the salt concentration. As the bulk salt concentration is increased to an intermediate regime, 60-100 mM NaCl, these heterogeneities become smaller in size and number, coexisting with smooth homogeneous regions. At high enough concentrations, 300-500 mM NaCl, the entire surface becomes homogeneous. A simple free energy-based Flory-type argument is presented which explains the essential features of the thermodynamic behavior of the brush system. In the zero-salt limit, relatively few monomers are charged, and the hydrophobicity of the backbone chain drives the collapse/aggregation of the chains. At high salt concentrations, the brush chains become sufficiently charged to overcome the hydrophobic nature of the monomers and stabilize the homogeneous state. However, at intermediate salt concentrations, it is found that the osmotic pressure of the counterions surrounding the charged polymer moieties can be decreased by collapsing the chain structure while simultaneously decreasing the number of charges along the backbone and releasing small ions into the bulk solution. This effect, which we term {\textquotedblleft}osmotic instability{\textquotedblright}, serves to destabilize the homogeneous brush configuration.},
  doi      = {10.1021/la902549b},
  file     = {:Hur2010 - On the Origins of the Salt Concentration Dependent Instability and Lateral Nanoscale Heterogeneities of Wark Polyelectrolyte Brushes_ Gradient Brush Experiment and Flory Type Theoretical Analysis.pdf:PDF},
  keywords = {weak brush, ionic strength, grafting density, PDMAEMA, AFM},
}

@Article{Hu2007,
  author   = {Kang Hu and James M. Dickson},
  journal  = {Journal of Membrane Science},
  title    = {Development and characterization of poly(vinylidene flouride)-poly(acrylic acid) pore-filled pH-sensitive membranes},
  year     = {2007},
  pages    = {19--28},
  volume   = {301},
  abstract = {Pore-filled pH-sensitive membranes were developed by in situ cross-linking poly(acrylic acid) inside poly(vinylidene fluoride) hydrophobic microporous substrate membranes. The incorporation of the poly(acrylic acid) gel, expressed as membrane mass gain, increased with the monomer concentration in polymerization solution and the amount of cross-linking degree. By the incorporation of the poly(acrylic acid) gel, the membrane performance was substantially altered. These membranes demonstrated a rapid and reversible response of flux to environmental pH as the pH was changed between 2.5 and 7.4. This pH-valve effect was observed at pH between 3.5 and 5.5. The membrane pure water permeability and valve ratio, as a function of environmental pH, were characterized by pressure-driven experiments in terms of the membrane mass gain and the cross-linking degree. The effects of the mass gain and the cross-linking degree were different at pH acidic and neutral. The overall effect was that as the mass gain decreased or the cross-linking degree increased, the pure water permeability increased. A high valve ratio was obtained when the mass gain was low and the cross-linking degree was high.},
  doi      = {10.1016/j.memsci.2007.05.031},
  file     = {:Hu2007 - Development and Characterization of Poly(vinylidene Flouride) Poly(acrylic Acid) Pore Filled PH Sensitive Membranes.pdf:PDF},
  keywords = {PAA, cross-link, membrane, pH control, porous},
}

@PhdThesis{Liang2014,
  author   = {Hua Liang},
  school   = {Humboldt-Universit{\"{a}}t zu Berlin},
  title    = {Structures and Mechanical Properties of Single Macromolecules at surfaces},
  year     = {2014},
  type     = {phdthesis},
  abstract = {In order to investigate correlations between structure, properties and potential applications at the single molecule level, I chose three macromolecular systems: DNA, amphiphilic cylindrical polymer brushes, and amphiphilic core-shell structured hyperbranched polyglycerol (hPG). They form quasi one-, two-, and three dimensional structures on suitable surfaces, exhibit interesting mechanical properties, and also offer potential for applications. First, I report a simple high throughput method to control the conformation of plasmid double-stranded DNA on a graphene surface, pre-coated with a layer of flat lying alkylamines. Depending on the surface concentration, the alkylamines self-assemble into various nanostructures and induce different DNA conformations: (i) supercoiled DNA, (ii) stretched DNA, partially melted into two single strands, (iii) DNA with an overstretched backbone up to 0.42 $\pm$ 0.01 nm per base on the surface as compared to 0.34 $\pm$ 0.01 nm in a physiological solution, (iv) relaxed circles without stretching, and (v) compact coils. This method allows to directly correlate DNA conformations to mechanical properties such as twist-stretch coupling. The plasmid DNA molecules were stretched further, up to 2.1 times their native B-form length and ruptured with a Scanning Force Microscope (SFM), exerting a force parallel to the surface. This force is either large enough to break the molecule immediately, or it is compensated by the elastic restoring force of the DNA backbone, which allows to stabilizes the molecular length of the DNA on the immobilizing surface. However, also the size-stabilized molecules break with time, the longer the molecules the quicker. The breakage of different lengths of stabilized molecules was recorded in order to study the time-dependent mechanical properties of the molecules under constant forces. From these data a rather high rate constant for breakage, k 0 = (2.2 $\pm$ 0.1) $\times$ 10 -7 s -1 , was calculated. Moreover, I found a non-linear stress-strain dependence of DNA on the surface, which I attribute to DNA conformational transitions. Assuming that the structural transition on the surface is similar to that in solution I estimated the forces needed to stretch the molecules and thereby verified the estimated activation energy barrier.

The second system I studied was dual cylindrical polymer brushes, whose self-assembly I investigated at different surfaces. The brush polymers reveal worm-like chain conformations on mica, after being deposited from a chloroform solution. Due to different affinities of the side chains to the surface, parts of the side chains collapsed, while others fully extended on the surface, resulting in a {\textquotedblleft}tadpole like{\textquotedblright} or a back-folding structure. Deposited from an aqueous solution, the dual cylindrical polymer brushes form supramolecular aggregates on the surface. These aggregates form clusters of different size and self-sort according to their size on the surface. The size of the clusters depends on their motilities on the surface. The third system, I report on, is an innovative bi-functional nanocarrier. I investigated its supramolecular structure and its encapsulation and transportation capacities for typical guest molecules, such as nile red and pyrene. The polymer has been obtained by chemically tailoring hyperbranched polyglycerol to form an amphiphilic core-shell structure, which creates a large hydrophobic gradient across the polymer molecule leading to better selective transport capacities and better water solubility. SFM, light scattering, and spectroscopic results show that it encapsulates and transports guest molecules in both, a {\textquotedblleft}unimolecular micelle{\textquotedblright} and polymeric micelle type mechanism. The capacity of co-loading of two drugs and controlled release makes it a promising candidate for simultaneous delivery of two hydrophobic drugs in cancer combination therapy.},
  comment  = {Gutachter Ballauff},
  file     = {:Liang2014 - Structures and Mechanical Properties of Single Macromolecules at Surfaces.pdf:PDF},
  keywords = {DNA, polymer brush, SFM, drug delivery, application focused, application-focused},
}

@Book{Cloitre2010,
  editor    = {M. Cloitre},
  publisher = {Springer},
  title     = {High Solid Dispersions},
  year      = {2010},
  isbn      = {978-3-642-16381-4},
  series    = {Advances in Polymer Science},
  abstract  = {From Polymers to Colloids: Engineering the Dynamic
Properties of Hairy Particles 

Nonlinear Rheological Properties of Dense Colloidal
Dispersions Close to a Glass Transition Under Steady Shear

Micromechanics of Soft Particle Glasses 

Quantitative Imaging of Concentrated Suspensions Under Flow

Soft and Wet Materials: From Hydrogels to Biotissues},
  doi       = {10.1007/978-3-642-16382-1},
  file      = {:Cloitre2010 - High Solid Dispersions.pdf:PDF},
  keywords  = {Rheology, spherical brush, microgel, block copolymer},
}

@Article{Reinhardt2013a,
  author   = {Matthias Reinhardt and Joachim Dzubiella and Marcus Trapp and Philipp Gutfreund and Martin Kreuzer and Andre H. Gr{\"{o}}schel and Axel H. E. M{\"{u}}ller and Matthias Ballauff and Roland Steitz},
  journal  = {Macromolecules},
  title    = {Fine-Tuning the Structure of Stimuli-Responsive Polymer Films by Hydrostatic Pressure and Temperature},
  year     = {2013},
  number   = {16},
  pages    = {6541--6547},
  volume   = {46},
  abstract = {The response of stimuli-responsive polymer brushes to moderately elevated pressure is investigated by neutron reflectivity and a thermodynamically consistent density functional theory where pressure effects are included by a hydrophobic cavity model. Evidence is provided that temperature and pressure effects on the brush spatial structure are entirely antagonistic. A $\sim$100 bar/K cancellation effect is found, which we argue is a general feature for hydrophobically associating homopolymers and serves for experimental guidance and fine-control of polymer film structure. Our results also suggest that polymeric interfaces which do not show a marked temperature dependence are also rather insensitive to pressure effects for applied pressures below 1 kbar.},
  doi      = {10.1021/ma400962p},
  file     = {:Reinhardt2013a - Fine Tuning the Structure of Stimuli Responsive Polymer Films by Hydrostatic Pressure and Temperature.pdf:PDF},
}

@Article{Morse1994,
  author   = {David C. Morse and Glenn H. Fredrickson},
  journal  = {Physical Review Letters},
  title    = {Semiflexible Polymers near Interfaces},
  year     = {1994},
  number   = {24},
  pages    = {3235--3239},
  volume   = {73},
  abstract = {We present a theory of semiflexible polymers in inhomogeneous environments, which we use to analyze a symmetric interface between two immiscible, semiflexible polymers. Our theory reduces in the limit of small chain rigidity to the existing self-consistent-field theory of flexible polymers, but yields qualitatively different behavior in the limit of large rigidity, where we predict strong orientational order, weak interpenetration, and a universal behavior of the orientational profile and interfacial tension similar to that of a single component near an impenetrable wall.},
  file     = {:Morse1994 - Semiflexible Polymers near Interfaces.pdf:PDF},
  keywords = {block copolymer, theory},
}

@Article{Gennes1974,
  author   = {P. G. de Gennes},
  journal  = {Physics Letters A},
  title    = {General Features of Lipid Organization},
  year     = {1974},
  number   = {2},
  volume   = {47A},
  abstract = {In block systems made of long chain molecules (lipids, detergents, copolymers), attached by one end at an interface, the steric interactions impose a non zero chain alignment even if the chains are very flexible. This may explain why, in recent experiments on deuterated lammellar lipids, the quadrupolar order parameter S appears to be the same for most of the CD2 groups},
  file     = {:Gennes1974 - General Features of Lipid Organization.pdf:PDF},
  keywords = {block copolymer},
}

@Article{Xu2009,
  author   = {Youyong Xu and Sreenath Bolisetty and Markus Drechsler and Bing Fang and Jiayin Yuan and Ludger Harnau and Matthias Ballauff and Axel H. E. M{\"{u}}ller},
  journal  = {Soft Matter},
  title    = {Manipulating cylindrical polyelectrolyte brushes on the nanoscale by counterions: collapse transition to helical structures},
  year     = {2009},
  pages    = {379--384},
  volume   = {5},
  doi      = {10.1039/b812179f},
  file     = {:Xu2009 - Manipulating Cylindrical Polyelectrolyte Brushes on the Nanoscale by Counterions_ Collapse Transition to Helical Structures.pdf:PDF},
  keywords = {polyelectrolyte, polymer brush, counterion, valency, DLS, AFM, cryo-TEM, ionic strength, bottlebrush},
  printed  = {printed},
  ranking  = {rank2},
}

@Article{Samokhina2007,
  author   = {Larysa Samokhina and Marc Schrinner and Matthias Ballauff and Markus Drechsler},
  title    = {Binding Oppositely Charged Surfactants to Spheical Polyelectrolyte Brushes: A Study by Cryogenig Transmission Electron Microscopy},
  journal  = {Langmuir},
  year     = {2007},
  volume   = {23},
  pages    = {3615--3619},
  abstract = {The formation of a complex between an anionic spherical polyelectrolyte brush (SPB) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) is investigated. The SPB consists of long chains of the strong polyelectrolyte poly(styrene sulfonate) (PSS), which are bound chemically to a solid poly(styrene) core of 56 nm in radius. The SPB are dispersed in water, and the ionic strength is adjusted by addition of NaBr. The resulting complexes are investigated in dilute solution by dynamic light scattering, by electrophoretic light scattering, and by cryogenic transmission electron microscopy (cryo-TEM). The formation of the complex between the SPB and the surfactant can be monitored by a strong shrinking of the surface layer when adding CTAB to dilute suspensions (0.01 wt %) and by a decrease of the effective charge of the complexes. Complex formation starts at CTAB concentrations lower than the critical micelle concentration of this surfactant. If the ratio r of the charges on the SPB to the charge of the added surfactant is exceeding unity, the particles start to flocculate. Cryo-TEM images of the complexes at r ) 0.6 measured in salt-free solution show that the surface layer composed of the PSS chains and the adsorbed CTAB molecules is partially collapsed: A part of the chains form a dense surface layer while another part of the chains or aggregates thereof are still sticking out. This can be deduced from the cryo-TEM micrographs as well as from the hydrodynamic radius, which is still of appreciable magnitude. The 1:1 complex (r ) 1.0) exhibits a fully collapsed layer formed by the PSS chains and CTAB. If the complex is formed in the presence of 0.05 M NaBr, r ) 0.6 leads to globular structures directly attached to the surface of the core particles. All structures seen in the cryo-TEM images can be explained by a collapse transition of the surface layer brought about by the hydrophobic attraction between the polyelectrolyte chains that became partially hydrophobic through adsorption of CTAB.},
  file     = {:2007 - Binding Oppositely Charged Surfactants to Spheical Polyelectrolyte Brushes_ a Study by Cryogenig Transmission Electron Microscopy.pdf:PDF},
  keywords = {polyelectrolyte, polymer brush, spherical brush, surfactant, PSS, strong brush, cryo-TEM},
}

@Article{Zhulina1991,
  author   = {E. B. Zhulina and O. V. Borisov and V. A. Pryamitsyn and T. M. Birshtein},
  journal  = {Macromolecules},
  title    = {Coil-Globule Type Transitions in Polymers. 1. Collapse of Layers of Grafted Polymer Chains},
  year     = {1991},
  pages    = {140--149},
  volume   = {24},
  abstract = {The mean-field analytical theory describing the conformational transition related to the collapse of the layers of polymer chains grafted onto the impermeable surfaces of different morphologies (a planar surface, a sphere, and a cylinder) has been developed. The dependence of the character of this transition on the type of the surface morphology is analyzed. It is shown that in the case of a planar surface this transition is not a true thermodynamic phase transition. The structural rearrangement of the layers accompanying their collapse is investigated. The most precise analysis was carried out for the case of a planar layer. It is shown that in contrast to the blob picture the planar layer is inhomogeneous as a whole at any solvent strength. Analytical expressions describing the distribution of monomer units density and chain ends along the layer height at arbitrary solvent strength are obtained.},
  file     = {:Zhulina1991 - Coil Globule Type Transitions in Polymers. 1. Collapse of Layers of Grafted Polymer Chains.pdf:PDF},
  keywords = {theory, polymer brush, spharical brush, planar brush, bottlebrush, collapse, solvent quality},
  printed  = {printed},
  ranking  = {rank4},
}

@Article{Farina2015,
  author   = {Robert Farina and Nicolas Laugel and Jing Yu and Matthew Tirrell},
  journal  = {Journal of Physical Chemistry C},
  title    = {Reversible Adhesion with Polyelectrolyte Brushes Tailored via the Uptake and Release of Trivalent Lanthanum Ions},
  year     = {2015},
  pages    = {14805--14814},
  volume   = {119},
  abstract = {Applications of end-tethered polyelectrolyte {\textquotedblleft}brushes{\textquotedblright} to modify solid surfaces have been developed and studied for their colloidal stabilization and high lubrication properties. Current efforts have expanded into biological realms and stimuli-responsive materials. Our work explores responsive and reversible aspects of polyelectrolyte brush behavior when polyelectrolyte chains interact with oppositely charged multivalent ions and complexes, which act as counterions. There is a significant void in the polyelectrolyte literature regarding interactions with multivalent species. This paper demonstrates that interactions between solid surfaces bearing negatively charged polyelectrolyte brushes are highly sensitive to the presence of trivalent lanthanum, La 3+ . Lanthanum cations have unique interactions with polyelectrolyte chains, in part due to their small size and hydration radius which results in a high local charge density. Using La 3+ in conjunction with the surface forces apparatus (SFA), adhesion has been observed to reversibly appear and disappear upon the uptake and release, respectively, of these multivalent cations acting as counterions. In media of fixed ionic strength set by monovalent sodium salt, at I 0 = 0.003 M and I 0 = 0.3 M, the sign of the interaction forces between overlapping brushes changes from repulsive to attractive when La 3+ concentrations reach 0.1 mol % of the total ion concentration. These results are also shown to be generally consistent with, but subtlety different from, previous polyelectrolyte brush experiments using trivalent ruthenium hexamine in the role of the multivalent counterion.},
  doi      = {10.1021/acs.jpcc.5b02121},
  file     = {:Farina2015 - Reversible Adhesion with Polyelectrolyte Brushes Tailored Via the Uptake and Release of Trivalent Lanthanum Ions.pdf:PDF},
  printed  = {printed},
  ranking  = {rank3},
}

@Article{Schorr2003,
  author   = {Phillip A. Schorr and Thomas C. B. Kwan and S. Michael {Kilbey II} and Eric S. G. Shaqfeh and Matthew Tirrell},
  journal  = {Macromolecules},
  title    = {Shear Forces between Tethered Polymer Chains as a Function of Compression, Sliding Velocity and Solvent Quality},
  year     = {2003},
  number   = {2},
  volume   = {36},
  abstract = {The shear forces between polystyrene chains end-tethered to opposing surfaces have been measured with the surface forces apparatus (SFA) in both good and near-{{$\Theta$}} solvents. When the shearing velocity was varied, the complex polymer/solvent system responded in a Newtonian-like fashion with the shear force increasing linearly with the shear velocity. The effective viscosity of the end-tethered systems in this Newtonian-like regime was found to be an order of magnitude greater than the viscosity of semidilute solutions of equivalent molecular weight free chains. At larger shear velocities or higher extents of compression, Brownian dynamics simulations suggest the interfacial width will thin, leading to a sublinear increase in the shear force with sliding velocity. Experimental limitations prevented exploration of the higher shear velocities simulated with the Brownian dynamics approach, but increasing confinement eventually did lead to sublinear behavior, in agreement with the simulation prediction.},
  doi      = {10.1021/ma011207v},
  file     = {:Schorr2003 - Shear Forces between Tethered Polymer Chains As a Function of Compression, Sliding Velocity and Solvent Quality.pdf:PDF},
}

@Article{Tamashiro2001,
  author   = {Tamashiro, M. N. and Hern{\'{a}}ndez-Zapata, E. and Schorr, P. A. and Balastre, M. and Tirrell, M. and Pincus, P.},
  journal  = {Journal of Chemical Physics},
  title    = {Salt dependence of compression normal forces of quenched polyelectrolyte brushes},
  year     = {2001},
  number   = {4},
  pages    = {1960--1969},
  volume   = {115},
  abstract = {We obtained mean-field expressions for the compression normal forces between two identical opposing quenched polyelectrolyte brushes in the presence of monovalent salt. The brush elasticity is modeled using the entropy of ideal Gaussian chains, while the entropy of the microions and the electrostatic contribution to the grand potential is obtained by solving the nonlinear Poisson--Boltzmann equation for the system in contact with a salt reservoir. The interplay between these distinct contributions upon variations of the ionic strength determines the brush thickness. For the polyelectrolyte brush we considered both an isotropic charged slab as well as a longitudinally heterogeneous charge profile obtained using a self-consistent field theory. Using the Derjaguin approximation, we related the planar-geometry results to the realistic two-crossed cylinders experimental setup. Theoretical predictions are compared to experimental measurements of the salt dependence of the compression normal forces between two quenched polyelectrolyte brushes formed by the adsorption of diblock copolymers poly(tert-butyl styrene)-sodium poly(styrene sulfonate) onto an octadecyltriethoxysilane hydrophobically modified mica surface.},
  doi      = {10.1063/1.1381579},
  eprint   = {https://doi.org/10.1063/1.1381579},
  file     = {:Tamashiro2001 - Salt Dependence of Compression Normal Forces of Quenched Polyelectrolyte Brushes.pdf:PDF},
  keywords = {polyelectrolyte, ionic strength, polymer brush, block copolymer, poly(tert-butyl styrene)-sodium, PSS, theory},
  url      = {https://doi.org/10.1063/1.1381579},
}

@Article{Balastre2002,
  author   = {Marc Balastre and Feng Li and Phillip Schorr and Jinchuan Yang and Jimmy W. Mays and Matthew V. Tirrell},
  journal  = {Macromolecules},
  title    = {A Study of Polyelectrolyte Brushes Formed from Adsorption of Amphiphilic Diblock Copolymers Using the Surface Forces Apparatus},
  year     = {2002},
  number   = {25},
  pages    = {9480--9486},
  volume   = {35},
  abstract = {Polyelectrolyte brushes were formed at the interface between hydrophobized mica and water by adsorbing amphiphilic diblock copolymers consisting of a hydrophobic and a charged block. We measured force-distance profiles with the surface force apparatus (SFA) for several polyelectrolyte brushes of different lengths as a function of aqueous 1:1 electrolyte concentration. Long-ranged electrostatic double-layer forces were not observed in the force curves, and our results suggest that more counterions than predicted by the Manning theory are condensed onto the polymer backbones inside the brush. The brush height observed with the SFA follows the predictions of the mean field theory: at low ionic strength the height is independent of the external salt concentration c_s , whereas at high external ionic strength the height shrinks with a weak power law L_0 $\propto$ c_s^{-1/3} . All force vs separation data for three different brushes, with various salt concentrations, collapse with reasonable accuracy into two reduced plots of data in the osmotic and salted brush regimes, respectively, the variables of which are developed in the scope of the mean-field brush theory.},
  doi      = {10.1021/ma011875g},
  file     = {:Balastre2002 - A Study of Polyelectrolyte Brushes Formed from Adsorption of Amphiphilic Diblock Copolymers Using the Surface Forces Apparatus.pdf:PDF},
  keywords = {polyelectrolyte, polymer brush, block copolymer, SFA, counterion, ionic strength},
}

@Article{Toomey2008,
  author     = {Ryan Toomey and Matthew Tirrell},
  journal    = {Annual Review of Physical Chemistry},
  title      = {Functional Polymer Brushes in Aqueous Media from Self-Assembled and Surface-Initiated Polymers},
  year       = {2008},
  volume     = {59},
  abstract   = {This review focuses on the behavior of single-component, water-soluble neutral and charged brushes. Selected examples illustrate how solvation effects, hydrophobic interactions, and electrostatic interactions create complex behaviors not easily captured in mean-field treatments. In particular, we distinguish between two classes of polymer brushes: those that can be described classically within the context of generalized van der Waals potentials and those that can be described by model-dependent potentials arising from specific interactions. In classical systems, only a few global parameters are needed to predict behavior. Nonclassical systems, in contrast, necessitate several local details, which do not necessarily lead to universal scaling laws. Although these nonclassical interactions present unique opportunities for engineering functional surfaces, they also present new challenges for designing well-defined systems with precise control over distributions in the degree of polymerization and tethering density.},
  doi        = {10.1146/annurev.physchem.59.032607.093623},
  file       = {:Toomey2008 - Functional Polymer Brushes in Aqueous Media from Self Assembled and Surface Initiated Polymers.pdf:PDF},
  keywords   = {neutral brush, polyelectrolyte brush, polymer brush, review},
  printed    = {printed},
  ranking    = {rank3},
  readstatus = {skimmed},
}

@Article{Farina2013,
  author   = {Robert Farina and Nicolas Laugel and Philip Pincus and Matthew Tirrell},
  journal  = {Soft Matter},
  title    = {Brushes of strong polyelectrolytes in mixed mono- and tri-valent ionic media at fixed total ionic strengths},
  year     = {2013},
  pages    = {10458--10472},
  volume   = {9},
  abstract = {This paper describes the structure and properties of end-tethered anionic polyelectrolyte brushes containing counterions of tri-valent ruthenium hexamine (Ru(NH_3)_6^{3+}) and mono-valent sodium (Na+). Detailed studies of these planar brushes composed of the strong polyelectrolyte, poly(sodium styrenesulfonate), were performed via electrochemical experiments using cyclic voltametry (CV) and surface force experiments using the Surface Forces Apparatus (SFA). A comparison between electrochemical and force measurements provided physical information regarding polyelectrolyte brush height and the population of tri-valent Ru(NH_3)_6^{3+} counterions inside a brush. Polyelectrolyte brushes were observed to transform from extended brushes dominated by the presence of mono-valent counterions, to collapsed brushes saturated with tri-valent counterions. This transformation occurred as a  result of Ru(NH_3)_6^{3+} replacement of Na^+ counterions in the polyelectrolyte brushes. This Ru(NH_3)_6^{3+} uptake was seen to be limited by either the diffusion of tri-valent ions in low ionic strength solutions or the equilibrium between mono and tri-valent ions at higher fixed ionic strengths. The collapsed state, seen only with brushes dominated by multi-valent counterions, also corresponded to an observed adhesive state between brushes. Adhesion was never seen with exclusively mono-valent ions present in solution. Ru(NH_3)_6^{3+} was observed to be released from saturated brushes when placed in a purely mono-valent salt solution of sufficiently high ionic strength. All SFA and CV experiments were performed in solutions of three separate fixed ionic strengths, with brush collapse/saturation occurring more sudden and producing higher adhesion at lower total ionic strength.},
  doi      = {10.1039/c3sm51450a},
  file     = {:Farina2013 - Brushes of Strong Polyelectrolytes in Mixed Mono and Tri Valent Ionic Media at Fixed Total Ionic Strengths.pdf:PDF},
  keywords = {polymer brush, strong brush, polyelectrolyte brush, valency, ionic strength, planar brush, poly(sodium styrenesulfonate), PSS, SFA, cyclic voltametry, counterion,},
}

@Article{Brettmann2016,
  author   = {Blair Kathryn Brettmann and Nicolas Laugel and Norman Hoffmann and Philip Pincus and Matthew Tirrell},
  journal  = {Journal of Polymer Science Part A: Polymer Chemistry},
  title    = {Bridging Contributions to Polyelextrolyte Brush Collapse in Multivalent Salt Solutions},
  year     = {2016},
  pages    = {284--291},
  volume   = {54},
  abstract = {Polyelectrolyte brushes are essential in many aspects of surface functionality, particularly for colloidal stabilization and lubrication in biological and materials science applications. It has been shown experimentally that the brushes undergo an abrupt shrinkage in the presence of multivalent counter-ions. This transition is studied here using a phenomenological mean-field approach with a model that specifically includes bridging of the polyelectrolyte chains by the multiple charges on the multivalent counter-ions. Using an energy balance represented by the sum of electrostatic, polymeric and entropic mean-field terms, additional parameterized phenomenological terms are introduced for counter-ion condensation and for the attractive interaction between adjacent polyelectrolyte chains to account for the bridging effect. The free energy is minimized with respect to the counter-ion populations and the brush height. In agreement with experimental observations, increasing the concentration of multivalent ions leads to a sharp collapse of the polyelectrolyte brush height.},
  doi      = {10.1002/pola.27959},
  file     = {:Brettmann2016 - Bridging Contributions to Polyelextrolyte Brush Collapse in Multivalent Salt Solutions.pdf:PDF},
  keywords = {polyelectrolyte brush, valency, ionic strength, counterion},
}

@Book{Binnewies2016,
  author    = {Michael Binnewies and Maik Finze and Manfred J{\"{a}}ckel and Peer Schmidt and Helge Willner and Geoff Rayner-Canham},
  publisher = {Springer Berlin Heidelberg},
  title     = {Allgemeine und Anorganische Chemie},
  year      = {2016},
  edition   = {Third},
  isbn      = {9783662450673},
  doi       = {10.1007/978-3-662-45067-3},
  file      = {:Binnewies2016 - Allgemeine Und Anorganische Chemie.pdf:PDF},
  keywords  = {Chemistry Basics},
}

@Book{FallertMueller2019,
  author    = {Angelika Fallert-M{\"{u}}ller and Birgit Jarosch and Angela Simeon},
  publisher = {Springer Berlin Heidelberg},
  title     = {Pocket Guide Chemie},
  year      = {2019},
  edition   = {1},
  isbn      = {978-3-662-58747-8},
  file      = {:FallertMueller2019 - Pocket Guide Chemie.pdf:PDF},
  keywords  = {Chemistry Basics},
}

@Book{Felixberger2017,
  author    = {Josef K. Felixberger},
  publisher = {Springer Berlin Heidelberg},
  title     = {Chemie f{\"{u}}r Einsteiger},
  year      = {2017},
  edition   = {1},
  isbn      = {978-3-662-52821-1},
  keywords  = {Chemistry Basics},
}

@Article{Reznik2008,
  author   = {Carmen Reznik and Qusai Darugar and Andrea Wheat and Tim Fulghum and Rigoberto C. Advincula and Christy F. Landes},
  journal  = {The Journal of Physical Chemistry B},
  title    = {Single Ion Diffusive Transport within a Poly(styrene sulfonate) Polymer Brush Matrix Probed by Flourescence Correlation Spectroscopy},
  year     = {2008},
  number   = {35},
  pages    = {10890--10897},
  volume   = {112},
  abstract = {Diffusive transport within complex environments is a critical piece of the chemistry occurring in such diverse membrane systems as proton exchange and bilayer lipid membranes. In the present study, fluorescence correlation spectroscopy was used to evaluate diffusive charge transport within a strong polyelectrolyte polymer brush. The fluorescent cation rhodamine-6G was used as a counterion probe molecule, and the strong polyelectrolyte poly(styrene sulfonate) was the polymer brush. Such strong polyelectrolyte brushes show promise for charge storage applications, and thus it is important to understand and tune their transport efficiencies. The polymer brush demonstrated preferential solvation of the probe counterion as compared to solvation by the aqueous solvent phase. Additionally, diffusion within the polymer brush was strongly inhibited, as evidenced by a decrease in diffusion constant of 4 orders of magnitude. It also proved possible to tune the transport characteristics by controlling the solvent pH, and thus the ionic strength of the solvent. The diffusion characteristics within the charged brush system depend on the brush density as well as the effective interaction potential between the probe ions and the brush. In response to changes in ionic strength of the solution, it was found that these two properties act in opposition to each other within this strong polyelectrolyte polymer brush environment. A stochastic random walk model was developed to simulate interaction of a diffusing charged particle with a periodic potential, to show the response of characteristic diffusion times to electrostatic field strengths. The combined results of the experiments and simulations demonstrate that responsive diffusion characteristics in this brush system are dominated by changes in Coulombic interactions rather than changes in brush density. More generally, these results support the use of FCS to evaluate local charge transport properties within polyelectrolyte brush systems, and demonstrate that the technique shows promise in the development of novel polyelectrolyte films for charge storage/transport materials.},
  doi      = {10.1021/jp803718p},
  file     = {:Reznik2008 - Single Ion Diffusive Transport within a Poly(styrene Sulfonate) Polymer Brush Matrix Probed by Flourescence Correlation Spectroscopy.pdf:PDF},
  keywords = {Diffusion, PSS, Polymer Brush, Flourescence, Polyelectrolyte, Strong Brush, counterion, charge transport, charge strorage, control parameter, pH control, ionic strength, simulation,},
}

@Article{Kawasaki2019,
  author   = {Takeshi Kawasaki and Kang Kim},
  journal  = {Scientific Reports},
  title    = {Spurious violation of the Stokes--Einstein--Debye relation in supercooled water},
  year     = {2019},
  volume   = {9},
  abstract = {The theories of Brownian motion, the Debye rotational diffusion model, and hydrodynamics together provide us with the Stokes--Einstein--Debye (SED) relation between the rotational relaxation time of the {\boldsymbol{\ell }}{$\ell$}-th degree Legendre polynomials {{\boldsymbol{\tau }}}_{{\boldsymbol{\ell }}}$\tau${$\ell$}, and viscosity divided by temperature, $\eta$/T. Experiments on supercooled liquids are frequently performed to measure the SED relations, {{\boldsymbol{\tau }}}_{{\boldsymbol{\ell }}}$\tau${$\ell$}kBT/$\eta$ and Dt{{\boldsymbol{\tau }}}_{{\boldsymbol{\ell }}}$\tau${$\ell$}, where Dt is the translational diffusion constant. However, the SED relations break down, and its molecular origin remains elusive. Here, we assess the validity of the SED relations in TIP4P/2005 supercooled water using molecular dynamics simulations. Specifically, we demonstrate that the higher-order {{\boldsymbol{\tau }}}_{{\boldsymbol{\ell }}}$\tau${$\ell$}values exhibit a temperature dependence similar to that of $\eta$/T, whereas the lowest-order {{\boldsymbol{\tau }}}_{{\boldsymbol{\ell }}}$\tau${$\ell$}values are decoupled with $\eta$/T, but are coupled with the translational diffusion constant{~}Dt. We reveal that the SED relations are so spurious that they significantly depend on the degree of Legendre polynomials.},
  doi      = {10.1038/s41598-019-44517-4},
  keywords = {Diffusion, SED, simulation},
}

@Article{Seghrouchni1998,
  author   = {R. Seghrouchni and G. Petekidis and D. Vlassopoulos and G. Fytas and A. N. Semenov and J. Roovers and G. Fleischer},
  journal  = {Europhysics Letters},
  title    = {Controlling the dynamics of soft spheres: From polymeric to colloidal behaviour},
  year     = {1998},
  number   = {3},
  pages    = {271--276},
  volume   = {42},
  file     = {:Seghrouchni1998 - Controlling the Dynamics of Soft Spheres_ from Polymeric to Colloidal Behaviour.pdf:PDF},
  keywords = {NMR, PCS, Diffusion, spherical brush, multiarm},
}

@Article{Semenov1999,
  author   = {A. N. Semenov and D. Vlassopoulos and G. Fytas and G. Vlachos and G. Fleischer and J. Roovers},
  journal  = {Langmuir},
  title    = {Dynamic Structure of Interacting Spherical Polymer Brushes},
  year     = {1999},
  number   = {2},
  pages    = {358--368},
  volume   = {15},
  abstract = {Multiarm star polymers represent a valuable model system for investigating the dynamics of tethered chains, spherical brushes, or grafted colloidal spheres. Because of their topology, the multiarm stars exhibit a nonuniform monomer density distribution leading to a core-shell morphology, which is responsible for their rich dynamic structure. When the stars interpenetrate, they exhibit liquidlike (macrocrystalline) order due to the enhanced osmotic pressure which balances the entropic stretching of the near-core segments and the excluded volume effects. Using dynamic light scattering, we probe three relaxation modes in the semidilute regime: (i) the fast cooperative diffusion, which is characteristic of their polymeric nature (entangled shell arms); (ii) the self-diffusion of the stars (essentially cores), probed because of finite functionality polydispersity, as confirmed by independent pulsed-field gradient NMR measurements; and (iii) the structural mode, which corresponds to rearrangements of the ordered stars. We develop a mean-field scaling theory, which captures all features observed experimentally with good quantitative agreement. The two slow modes, ii and iii, are reminiscent of the behavior of interacting hard colloidal spheres and are governed essentially by the same physics. We propose these model soft spheres as appropriate vehicles for unifying the descriptions of the dynamics of polymers and soft colloidal dispersions.},
  comment  = {NMR advantages over DLS},
  doi      = {10.1021/la980794j},
  file     = {:Semenov1999 - Dynamic Structure of Interacting Spherical Polymer Brushes.pdf:PDF},
  keywords = {spherical brush, multiarm, DLS, diffusion, NMR, PFG diffusion},
}

@Article{Koenderink2000,
  author   = {Gijsberta H. Koenderink and Albert P. Philipse},
  journal  = {Langmuir},
  title    = {Rotational and Translational Self-Diffusion in Colloidal Sphere Suspensions and the Applicability of Generalized Stokes-Einstein Relataions},
  year     = {2000},
  number   = {13},
  pages    = {5631--5638},
  volume   = {16},
  abstract = {We investigate long-time translational and rotational self-diffusion of fluorocarbon tracer spheres (100 nm radius) in aqueous dispersions of silica host spheres (10 nm radius). Diffusion is measured as a function of ionic strength (0-10 mM NaCl) and for host-sphere volume fractions up to 37% using depolarized dynamic light scattering. Both translational and rotational self-diffusion are strongly hindered and have a similar concentration dependence as the low-shear viscosity, except at the lowest ionic strength. Our results show that the Stokes-Einstein (SE) relations, linking viscosity and diffusion at infinite dilution, can be extended to dense colloidal systems whenever the dynamics of the host spheres is fast compared to the experimental time scale. However, when the host-sphere dynamics is relatively slow, such as in the case of very large host particles or charged particles at low ionic strength, tracer-sphere diffusion (in particular rotation) generally is faster than the SE relations.},
  doi      = {10.1021/la000099n},
  file     = {:Koenderink2000 - Rotational and Translational Self Diffusion in Colloidal Sphere Suspensions and Teh Applicability of Generalized Stokes Einstein Relataions.pdf:PDF},
  keywords = {diffusion, stokes-einstein, ionic strength, DLS, rheology},
  printed  = {printed},
  ranking  = {rank4},
}

@Book{Hinrichs2018,
  editor    = {Karsten Hinrichs and Klaus-Jochen Eichhorn},
  publisher = {Springer International Publishing},
  title     = {Ellipsometry of Functional Organic Surfaces and Films},
  year      = {2018},
  edition   = {Second},
  isbn      = {978-3-319-75895-4},
  series    = {Springer Series in Surface Science},
  volume    = {52},
  doi       = {10.1007/978-3-319-75895-4},
  file      = {:Hinrichs2018 - Ellipsometry of Functional Organic Surfaces and Films.pdf:PDF},
  keywords  = {ellipsometry, book},
  printed   = {printed},
}

@Article{Gunes2013,
  author   = {Deniz Gunes and Omer Batu Kurtarel and Niyazi Bicak},
  journal  = {Journal of Applied Polymer Science},
  title    = {Poly(N-hydroxyethyl acrylamide)-b-Polystyrene by Combination of ATRP and Aminolysis Processes},
  year     = {2013},
  pages    = {2684--2689},
  abstract = {Block copolymers of very hydrophilic poly(N-hydroxyethyl acrylamide) (PHEAA) with polystyrene (PS) were successfully synthesized by sequential atom transfer radical polymerization of ethyl acrylate (EA) and styrene monomers and subsequent aminolysis of the acrylic block with ethanolamine. Quantitative aminolysis of poly(ethyl acrylate) (PEA) block yielded poly(N-hydroxyethyl acrylamide)-b-polystyrene in well-defined structures, as evidenced by Fourier transform infrared spectroscopy (FTIR) and 1 H-NMR spectros- copy techniques. Three copolymers with constant chain length of PHEAA (degree of polymerization: 80) and PS blocks with 21, 74, and 121 repeating units were prepared by this method. Among those, the block copolymer with 21 styrene repeating units showed excellent micellation behavior in water without phase inversion below 100  C, as inferred from dynamical light scattering, environmental scanning electron microscopy, and fluorescence measurements.},
  doi      = {10.1002/APP.37604},
  file     = {:Gunes2013 - Poly(N Hydroxyethyl Acrylamide) B Polystyrene by Combination of ATRP and Aminolysis Processes.pdf:PDF},
  keywords = {ATRP, polystyrene, block copolymer, PHEAA, infrared, NMR, DLS, flourescence, Environmental Scanning Electron Microscopy},
}

@Article{Zhao2011,
  author   = {Chao Zhao and Jie Zheng},
  journal  = {Biomacromolecules},
  title    = {Synthesis and Characterization of Poly(N-hdydroxyethylacrylamide) for Long-Term Antifouling Ability},
  year     = {2011},
  pages    = {4071--4079},
  volume   = {12},
  abstract = {Development of biomaterials with long-term biocompatibility, durability, and stability remains a critical challenge for biomedical devices. Here, we synthesize, characterize, and graft poly(N-(2-hydroxyethyl)acrylamide) (polyHEAA) onto both gold surfaces and gold nanoparticles (AuNPs) via surface-initiated atom transfer radical polymerization (SI-ATRP) to form a stable antifouling coating to resist nonspecific protein adsorption and bacterial attachment. Surface plasmon resonance (SPR) results demonstrate that all of polyHEAA brushes coated on the gold substrate at a wide range of film thickness of $\sim$10$-$40 nm can achieve almost zero protein adsorption from undiluted blood plasma and serum for 1 h, while static bacteria assay results show that polyHEAA brushes prohibit long-term bacterial colonization by Staphylococcus epidermidis and Escherichia coli RP437 up to 3 days. Moreover, the polyHEAA-coated AuNPs with different diameters remain their hydrodynamic sizes unchanged in human blood plasma and serum for up to 7 days. All these data indicate that polyHEAA can serve as promising biomaterials with long-term biocompatibility and durability suitable for applications in complex biological media.},
  doi      = {10.1021/bm2011455},
  file     = {:Zhao2011 - Synthesis and Characterization of Poly(N Hdydroxyethylacrylamide) for Long Term Antifouling Ability.pdf:PDF},
  keywords = {PHEAA, polymer synthesis, SI-ATRP, application focused, surface plasmon resonance, biophysics, application-focused},
}

@Article{Zhao2013,
  author   = {Chao Zhao and Kunal Patel and Lindsay Marie Aichinger and Zhaoqian Liu and Rundong Hu and Hong Chen and Xiaosi Li and Lingyan Li and Ge Zhang and Yung Chang and Jie Zheng},
  journal  = {RCS Advances},
  title    = {Antifouling and biodegradable poly(N-hydroxyethyl acrylamide) (polyHEAA)-based nanogels},
  year     = {2013},
  pages    = {19991--20000},
  volume   = {3},
  abstract = {We synthesize and characterize two types of poly(N-hydroxyethyl acrylamide) (polyHEAA)-based nanogels: antifouling poly(2-(methacryloyloxy) ethyl trimethyl ammonium-g-N-hydroxyethyl acrylamide) (polyTM-g-HEAA) by a new two-step polymerization method of inverse microemulsion ATRP and surface-initiated atom transfer radical polymerization (SI-ATRP), and pH-responsive biodegradable polyHEAA nanogels by the inverse microemulsion free radical polymerization method. PolyTM-g-HEAA nanogels with a core--shell structure by grafting antifouling polyHEAA onto the cationic polyTM core are tested for their antifouling property and stability in fetal bovine serum (FBS) and nanogels-induced cell toxicity. Results show that with the antifouling protection of polyHEAA, polyTM-g-HEAA nanogels significantly improve their long-term stability in FBS up to 7 days by preventing nonspecific protein adsorption, and they also improve cell viability to 94% and exhibit almost neglectable cell toxicity. Further, polyHEAA nanogels cross-linked with acid-liable ethylidenebis(oxy-2,1-ethanediyl) ester (EOE) are synthesized, which exhibit both biodegradation and control-release of encapsulated rhodamine 6G (R6G) at acid conditions. Conjugation of transferrin ligands onto R6G-loaded polyHEAA nanogels further enhances cellular uptake efficiency and intracellular drug release for targeting drug delivery. This work demonstrates that polyHEAA-based nanogels with easy synthesis, excellent antifouling property and stability, biodegradability, low toxicity, and pH-responsive intracellular drug release are highly promising for targeted drug delivery systems for biomedical applications.},
  doi      = {10.1039/c3ra42323a},
  file     = {:Zhao2013 - Antifouling and Buidegradable Poly(N Hydroxyethyl Acrylamide) (polyHEAA) Based Nanogels.pdf:PDF},
  keywords = {PHEAA, microgel, ATRP, SI-ATRP, pH control, biophysics, drug delivery},
}

@Book{Mezei2003,
  editor    = {Ferenc Mezei and Catherine Pappas and Thomas Gutberlet},
  publisher = {Springer-Verlag Berlin Heidelberg},
  title     = {Neutron Spin Echo Spectroscopy: Basics, Trends and Applications},
  year      = {2003},
  isbn      = {3-540-44293-6},
  series    = {Lecture Notes in Physics},
  file      = {:Mezei2003 - Neutron Spin Echo Spectroscopy_ Basics, Trends and Applications.pdf:PDF},
  keywords  = {neutron, book},
}

@Book{Arbe2005,
  editor    = {Arantxa Arbe and Juan Colmenero and M. Monkenbusch and Dieter Richter},
  publisher = {Springer-Verlag GmbH},
  title     = {Neutron Spin Echo in Polymer Systems},
  year      = {2005},
  isbn      = {978-3-540-22862-2},
  series    = {Advances in Polymer Science},
  doi       = {10.1007/b99835},
  file      = {:Arbe2005 - Neutron Spin Echo in Polymer Systems.pdf:PDF},
  keywords  = {neutron, book},
}

@Book{Braun2005,
  author    = {Dietrich Braun and Harald Cherdron and Matthias Rehahn and Helmut Ritter and Brigitte Voit},
  publisher = {Springer Berlin Heidelberg},
  title     = {Polymer Synthesis: Theory and Practice: Fundamentals, Methods, Experiments},
  year      = {2005},
  edition   = {Fourth},
  isbn      = {3-540-20770-8},
  file      = {:Braun2005 - Polymer Synthesis_ Theory and Practice_ Fundamentals, Methods, Experiments.pdf:PDF},
  keywords  = {book, polymer synthesis, chemistry Basics, experimental methods},
}

@MastersThesis{Lilge2017,
  author    = {Inga Lilge},
  school    = {Universit{\"{a}}t Siegen},
  title     = {Polymer Brush Films with Varied Grafting and Cross-Linking Density via SI-ATRP: Analysis of the Mechanical Properties by AFM},
  year      = {2017},
  abstract  = {This thesis focuses on a systematic study of poly(acryl amide) (PAAm) brushes prepared by surface-initiated atom transfer radical polymerization (SI-ATRP). In addition to the analysis of the time dependence of the polymer brush growth, the conformation of the polymer brushes will be varied by grafting or cross-linking density. The grafting density is varied by the use of mixed self-assembled monolayers (SAMs) comprising of 16-mercaptohexadecanoic acid (MHDA) and LJ-mercaptoundecyl bromoisobutyrate (MUBiB) to initiate the controlled radical polymerization from gold substrates. The cross-linking density is varied by an additional feed of a cross-linker, N,N{\textquoteright}-methylenebis(acrylamide) (bisAAm), in the polymerization solution. The film thicknesses of polymer brushes in the dry state were obtained by ellipsometry and the surfaces were characterized by water contact angle measurements and FTIR spectroscopy. It was found that mixed SAMs have a preferential adsorption of the thiol with the dummy functionalized head group (MHDA). SAMs composed of 45% initiator (MUBiB) on the surface have an initiator density, beyond which the polymer brush thickness no further increases. For lower values, the film thickness decreases to a minimum of 10 nm. Finally, the density of polymer brushes depends on the initiator density at the beginning of the polymerization. The polymer brush film thickness is also strongly influenced by the cross-linking density in an exponential manner, whereas the fraction of cross-linker in the polymerization solution reduces the resulting thickness of the polymer brushes. Force curve measurements with atomic force microscopy (AFM) revealed that the variation of cross-linking density of polymer brushes influences the mechanical properties and swelling characteristics. In this case, the stiffness of the polymer brushes increases with increasing fraction of cross-linker and the swelling ratio decreases. These facts provide an interesting feature to control and tune the mechanical properties of surface grafted polymer brushes. All in all, the tunable mechanical properties and reduced amounts of reactant molecules on the surface open a new way of varying surface interactions with cells, which are unknown to date and an interesting feature to investigate.},
  doi       = {10.1007/978-3-658-19595-3},
  file      = {:Lilge2017 - Polymer Brush Films with Varied Grafting and Cross Linking Density Via SI ATRP_ Analysis of the Mechanical Properties by AFM.pdf:PDF},
  isbn      = {978-3-658-19595-3},
  keywords  = {AFM, SI-ATRP, Contact Angle, Ellipsometry, Infrared, polymer brush,},
  publisher = {Springer Fachmedien Wiesbaden},
  series    = {BestMasters},
}

@Article{Feng2018,
  author   = {Chung Feng and Xiaoyu Huang},
  journal  = {Accounts of Chemical Research},
  title    = {Polymer Brushes: Efficient Synthesis and Applications},
  year     = {2018},
  pages    = {2314--2323},
  volume   = {51},
  abstract = {Polymer brushes are special macromolecular structures with polymer chains densely tethered to another polymer chain (one-dimensional, 1D) or the surface of a planar (two-dimensional, 2D), spherical or cylindrical (three-dimensional, 3D) solid via a stable covalent or noncovalent bond linkage. In comparison with the corresponding linear counterpart with similar molecular composition, one-dimension polymer brushes have some fascinating properties including wormlike conformation, compact molecular dimension, and notable chain end effects due to their compact and confined densely grafted structure. The introduction of polymer chains onto the surface of planar and spherical or cylindrical matrix will not only significantly change the surface-related properties of the matrix but also endows the obtained hybrid polymer brushes with new functionalities. Thus, polymer brushes are of great interest in the fields of polymer and material science due to their broad applications, such as catalysis, nanolithography, biomineralization, drug delivery, medical diagnosis, optoelectronics, and so on. Although a variety of 1D, 2D, and 3D polymer brushes have been prepared with the advent of living/controlled polymerization, the development of more efficient and facile synthetic protocols that permit access to polymer brushes with precisely controlled composition, structure, and functionality still represents a key contemporary challenge. In this Account, we summarize our recent efforts on the development of efficient methods to prepare 1D, 2D, and 3D polymer brushes and exploration of their potential applications in drug delivery, antifouling coating, catalysis, and lithium-ion batteries and also highlight related achievements by other groups. First, we briefly introduce the precedent examples of efficient synthesis of polymer brushes with different structures and functionalities by the combination of monomer design with living/controlled polymerization. Given the excellent tolerance and use of the same catalytic system without any mutual interference of ATRP and Cu-catalyzed alkyne$-$azide cyclization (CuAAC) click reaction, a versatile and efficient platform for precise synthesis of complex asymmetric (Janus-type) 1D polymer brushes was developed on the basis of the {\textquotedblleft}trifunctional monomer{\textquotedblright} strategy without polymeric functionality transformation. Subsequently, a noncovalent strategy based on crystallization-driven self assembly to prepare well-defined polymer brushes with precise control over their composition and dimensions is described. Notably, the crystallization-driven self assembly can be treated as a living/controlled polymerization of {\textquotedblleft}polymeric monomer{\textquotedblright} with a special building segment for crystallization, which allows for preparing linear polymer brushes with length as high as tens of micrometers. Moreover, the properties and related applications of polymer brushes as interesting building blocks for constructing hierarchical nanostructures, efficient drug deliver carriers, antifouling films, and lithium-ion batteries are addressed by some typical examples. These advancements in this field will provide a new avenue for obtaining fascinating polymer-brush-based functional materials.},
  doi      = {10.1021/acs.accounts.8b00307},
  file     = {:Feng2018 - Polymer Brushes_ Efficient Synthesis and Applications.pdf:PDF},
  keywords = {polymer brush, polymer synthesis},
  printed  = {printed},
  ranking  = {rank1},
}

@Book{Perchyonok2009,
  author    = {Tamara Perchyonok},
  editor    = {James H. Clark and George A. Kraus},
  publisher = {Royal Society of Chemistry},
  title     = {Radical Reactions in aqueous media},
  year      = {2009},
  series    = {RSC Green chemistry},
  doi       = {10.1039/9781849730761-00001},
  file      = {:Perchyonok2009 - Radical Reactions in Aqueous Media.pdf:PDF;:Perchyonok2009_Chapter2.pdf:PDF;:Perchyonok2009_Chapter3.pdf:PDF;:Perchyonok2009_Chapter4.pdf:PDF;:Perchyonok2009_Chapter5.pdf:PDF;:Perchyonok2009_Chapter6.pdf:PDF;:Perchyonok2009_Chapter7.pdf:PDF;:Perchyonok2009_Chapter8.pdf:PDF;:Perchyonok2009_Chapter9.pdf:PDF;:Perchyonok2009_Chapter10.pdf:PDF;:Perchyonok2009_Index.pdf:PDF},
  keywords  = {polymer synthesis, book},
}

@Article{Zhou2006,
  author   = {Feng Zhou and Wilhelm T. S. Huck},
  journal  = {Physical Chemistry Chemical Physics},
  title    = {Surface grafted polymer brushes as ideal building blocks for "smart" surfaces},
  year     = {2006},
  pages    = {3815--3823},
  volume   = {8},
  abstract = {Polymer brushes are assemblies of macromolecules chemically tethered at one end to a substrate. They provide an alternative to self-assembled monolayers because of the intrinsically large size of the building blocks and the ensuing entropic contribution to the film morphology. In this article, an overview of a number of representative polymer brush systems will be presented and their potential application for surfaces with controlled wettability, smart surfaces and nanoactuators will be explored in some detail.},
  doi      = {10.1039/b606415a},
  file     = {:Zhou2006 - Surface Grafted Polymer Brushes As Ideal Building Blocks for _smart_ Surfaces.pdf:PDF},
  keywords = {review, polymer brushes, application focused, application-focused},
}

@Article{Rumens2015,
  author   = {C. V. Rumens and M. A. Ziai and K. E. Belsey and J. C. Batchelor and S. J. Holder},
  journal  = {Journal of Materials Chemistry C},
  title    = {Swelling of PDMS networks in solvent vapours; applications for passive RFID wireless sensors},
  year     = {2015},
  issn     = {2050-7526},
  month    = oct,
  number   = {39},
  pages    = {10091--10098},
  volume   = {3},
  abstract = {The relative degree of swelling of a poly(dimethylsiloxane) (PDMS) network in organic vapours is demonstrated to be related to the chemical and physical properties of the organic compounds. The swelling ratio, based on volume change, Q V , is directly correlated with the Hansen solubility parameters, delta_d , delta_p and delta_h and the vapour pressures of the organic vapours employed. A practical use for such PDMS networks in combination with an understanding of the relationship is demonstrated by the use of PDMS as a mechanical actuator in a prototype wireless RFID passive sensor. The swelling of the PDMS displaces a feed loop resulting in an increase in transmitted power, at a fixed distance.},
  comment  = {Electronic Supplementary Material available},
  doi      = {10.1039/c5tc01927c},
  file     = {:- Swelling of PDMS Networks in Solvent Vapours\; Applications for Passive RFID Wireless Sensors.pdf:PDF;:SwellingOfPDMSNetworksInSolventVapours-ApplicationsForPassiveRFIDWirelessSensors_RumensEtAl_JMaterChemC2015_SupplementaryInformation.pdf:PDF},
  keywords = {PDMS, polymer network, application focused, application-focused},
}

@Article{Baysal1994,
  author   = {Bahattin Baysal and Elif Hamurcu},
  journal  = {Journal of Polymer Science, Part B: Polymer Physics},
  title    = {Solubility parameter of a poly(dimethylsiloxane) network},
  year     = {1994},
  pages    = {591--594},
  volume   = {32},
  file     = {:Baysal1994 - Solubility Parameter of a Poly(dimethylsiloxane) Network.pdf:PDF},
  keywords = {PDMS, polymer network, solubility parameter},
}

@Article{MojsiewiczPienkowska2003,
  author   = {K. Mojsiewicz-Pienkowska and Z. Jamrogiewicz and J. Bukasiak},
  journal  = {Food Additives and Contaminants},
  title    = {Determination of polymethylsiloxanes by 1H-NMR in wine and edible oils},
  year     = {2003},
  issn     = {1464-5122},
  number   = {5},
  pages    = {438--444},
  volume   = {20},
  abstract = {Fourier transform 1 H-nuclear magnetic resonance (NMR) spectroscopy was suitable for the quantitative determination of polydimethylsiloxanes (PDMS) in wine and edible oil samples. This approach offers highly specific qualitative and quantitative analysis due to silicone-specific location of proton signals linked to carbon atoms located directly next to silicon atoms (0--0.5 ppm), as well as a different location of signals in the range for different organosilicon structures. The method can be used for the control of PDMS at regulatory limits in foodstuffs (10 mg kg-1 ) using hexamethyldisiloxane (HDMS) as an internal standard. Samples were prepared by extraction under suitable conditions to separate the analyte, and with analyte enrichment before 1 H-NMR analysis. Analytical procedures were developed to permit the determination of PDMS at 0.06 mg kg--1 in wine and at 6 mg kg--1 in edible oils samples using readily available NMR instrumentation. It was, however, possible to lower the limit of detection to 6 ug kg-1 for wine and to 60 ug kg-1 for edible oils using a higher field instrument (500 MHz). Relative standard deviations (S r ) were obtained for wine (0.028) and for oil samples (0.043), which when compared with values obtained for samples spiked with PDMS (0.021) indicated that the sample preparation was the main factor determining the precision of the method. The average recovery rates for PDMS were 97 and 95% for wine and edible oils, respectively. PDMS was detected in four brands of Italian wine, with Chianti-Rafaello containing the highest concentration (0.35 mg kg-1 ), and in four types of edible oils, highest concentration (11.9 mg kg-1 ) being found in Italian corn oil. None of the levels of PDMS found in the food samples exceeded the permis- sible standards laid down by the Codex Alimentarius Commission (10 mg kg-1 ), with the exception of the one corn oil sample.},
  doi      = {10.1080/0265203031000136288},
  keywords = {PDMS, NMR, Chemical Shift},
}

@Article{Wang2011,
  author   = {Yuli Wang and Josepf Balowski and Colleen Phillips and Ryan Phillips and Christopher E. Sims and Nancy L. Allbritton},
  journal  = {Lab on a Chip},
  title    = {Benchtop micromolding of polystyrene by soft lithography},
  year     = {2011},
  pages    = {3089--3097},
  volume   = {11},
  abstract = {Polystyrene (PS), a standard material for cell culture consumable labware, was molded into microstructures with high fidelity of replication by an elastomeric polydimethylsiloxane (PDMS) mold. The process was a simple, benchtop method based on soft lithography using readily available materials. The key to successful replica molding by this simple procedure relies on the use of a solvent, for example, gamma-butyrolactone, which dissolves PS without swelling the PDMS mold. PS solution was added to the PDMS mold, and evaporation of the solvent was accomplished by baking the mold on a hotplate. Microstructures with feature sizes as small as 3 mm and aspect ratios as large as 7 were readily molded. Prototypes of microfluidic chips made from PS were prepared by thermal bonding of a microchannel molded in PS with a flat PS substrate. The PS microfluidic chip displayed much lower adsorption and absorption of hydrophobic molecules (e.g. rhodamine B) compared to a comparable chip created from PDMS. The molded PS surface exhibited stable surface properties after plasma oxidation as assessed by contact angle measurement. The molded, oxidized PS surface remained an excellent surface for cell culture based on cell adhesion and proliferation. To demonstrate the application of this process for cell biology research, PS was micromolded into two different microarray formats, microwells and microposts, for segregation and tracking of non-adherent and adherent cells, respectively. The micromolded PS possessed properties that were ideal for biological and bioanalytical needs, thus making it an alternative material to PDMS and suitable for building lab-on-a-chip devices by soft lithography methods.},
  comment  = {Electronic Supplementary Material available},
  doi      = {10.1039/c1lc20281b},
  file     = {:Wang2011 - Benchtop Micromolding of Polystyrene by Soft Lithography.pdf:PDF;:BenchtopMicromoldingOfPolystyreneBySoftLithography_WangEtAl_LabChip2011_SupplementaryInformation.pdf:PDF},
  keywords = {PDMS, polystyrene, lithography, application focused, application-focused},
}

@Article{Pauw2013,
  author    = {Brian Richard Pauw},
  journal   = {Journal of Physics: Condensed Matter},
  title     = {Everything {SAXS}: small-angle scattering pattern collection and correction},
  year      = {2013},
  month     = aug,
  number    = {38},
  pages     = {383201},
  volume    = {25},
  abstract  = {For obtaining reliable nanostructural details of large amounts of sample---and if it is applicable---small-angle scattering (SAS) is a prime technique to use. It promises to obtain bulk-scale, statistically sound information on the morphological details of the nanostructure, and has thus led to many a researcher investing their time in it over the last eight decades of development. Due to pressure  from scientists requesting more details on increasingly complex nanostructures, as well as the ever improving instrumentation leaving less margin for ambiguity, small-angle scattering methodologies have been evolving at a high pace over the past few decades.As the quality of any results can only be as good as the data that go into these methodologies, the improvements in data collection and all imaginable data correction steps are reviewed here. This work is intended to provide a comprehensive overview of all data corrections, to aid the small-angle scatterer to decide which are relevant for their measurement and how these corrections are performed. Clear mathematical descriptions of the corrections are provided where feasible. Furthermore, as no quality data exist without a decent estimate of their precision, the error estimation and propagation through all these steps are provided alongside the corrections. With these data corrections, the collected small-angle scattering pattern can be made of the highest standard, allowing for authoritative nanostructural characterization through its analysis. A brief background of small-angle scattering, the instrumentation developments over the years, and pitfalls that may be encountered upon data interpretation are provided as well.},
  doi       = {10.1088/0953-8984/25/38/383201},
  file      = {:Pauw2013 - Everything SAXS_ Small Angle Scattering Pattern Collection and Correction.pdf:PDF;:SAXS-PatternCollectionAndCorrection_Corrigendum_Pauw2014_JPhysCondensMatter.pdf:PDF},
  keywords  = {SAXS, review},
  printed   = {printed},
  publisher = {{IOP} Publishing},
  url       = {https://doi.org/10.1088%2F0953-8984%2F25%2F38%2F383201},
}

@Booklet{Jackson2008,
  title        = {Introduction to Small-Angle Neutron Scattering and Neutron Reflectometry},
  author       = {Andrew J. Jackson},
  howpublished = {NIST Center for Neutron Research},
  month        = may,
  year         = {2008},
  file         = {:Jackson2008 - Introduction to Small Angle Neutron Scattering and Neutron Reflectometry.pdf:PDF},
  keywords     = {neutron, SANS, uncitable},
}

@Book{Hunklinger2017,
  author    = {Siegfried Hunklinger},
  publisher = {De Gruyter},
  title     = {Festk{\"{o}}rperphysik},
  year      = {2017},
  edition   = {Fifth},
  isbn      = {978-3-11-056775-5},
  month     = dec,
  series    = {De Gruyter Studium},
  keywords  = {book, experimental methods},
}

@Book{Gross2018,
  author    = {Rudolf Gross and Achim Marx},
  publisher = {De Gruyter},
  title     = {Festk{\"{o}}rperphysik},
  year      = {2018},
  edition   = {Third},
  isbn      = {978-3-11-055918-7},
  series    = {De Gruyter Studium},
  keywords  = {book, experimental methods},
}

@Book{Kuzmany2009,
  author    = {Hans Kuzmany},
  publisher = {Springer Berlin Heidelberg},
  title     = {Solid-State Spectroscopy An Introduction},
  year      = {2009},
  edition   = {Second},
  isbn      = {978-3-642-01479-6},
  doi       = {10.1007/978-3-642-01479-6},
  file      = {:Kuzmany2009 - Solid State Spectroscopy an Introduction.pdf:PDF},
  keywords  = {book, experimental methods},
}

@Article{Divandari2016,
  author   = {Mohammad Divandari and Ella S. Dehghani and Nicholas D. Spencer and Shivaprakash N. Ramakrishna and Edmondo M. Benetti},
  journal  = {Polymer},
  title    = {Understanding the effect of hydrophobic protecting blocks on the stability and biopassivity of polymer brushes in aqueous environments: A Tiramisu for cell-culture applications},
  year     = {2016},
  pages    = {470--480},
  volume   = {98},
  abstract = {Despite the wide range and versatility of polymer-grafting methods to produce biopassive interfaces, commonly applied polymer brushes suffer from an intrinsic lack of long-term stability when incubated in aqueous media under physiological conditions. The robustness of brush films in such environments can be greatly improved by applying a hydrophobic, {\textquotedblleft}protecting{\textquotedblright} layer between the supporting substrate and the interfacial, biopassive brush. Block-copolymer brushes synthesized by sequential surface-initiated atom transfer radical polymerization (SI-ATRP) forming well-defined bilayered architectures can produce coatings with tunable interfacial properties and improved stability when subjected to cell-culture conditions. Three poly(n-alkyl methacrylates) (PAMA), exhibiting different mechanical properties, have been tested as protecting layers. A biopassive, hydrophilic brush is chosen to constitute the interfacial layer in all three cases. On the one hand, the structure of the interfacial layer clearly regulates film biopassivity, as well as its nanomechanical and nanotribological properties, as determined by atomic force microscopy (AFM) techniques. On the other hand, the composition and the mechanical properties of the polymer constituting the substrate-bound layer govern the stability of the entire bilayered film in the aqueous cell-culture environment. Precise control of bilayered brush architecture thus determines the film{\textquoteright}s applicability for cell manipulation or biomaterials surface engineering.},
  doi      = {10.1016/j.polymer.2016.04.042},
  file     = {:Divandari2016 - Understanding the Effect of Hydrophobic Protecting Blocks on the Stability and Biopassivity of Polymer Brushes in Aqueous Environments_ a Tiramisu for Cell Culture Applications.pdf:PDF},
  keywords = {polymer brush, biophysics, block copolymer, SI-ATRP, AFM},
}

@Article{Yu2016,
  author   = {Jing Yu and Jun Mao and Guangcui Yuan and Sushil Satija and Wei Chen and Matthew Tirrell},
  journal  = {Polymer},
  title    = {The effect of multivalent counterions to the structure of highly dense polystyrene sulfonate brushes},
  year     = {2016},
  pages    = {448--453},
  volume   = {98},
  abstract = {Surface tethered polyelectrolyte brushes are scientifically interesting and technologically relevant to many applications, ranging from colloidal stabilization to responsive and tunable materials to lubrication. Many applications operate in environments containing multi-valent ions, media in which our scientific understanding is not yet well-developed. We synthesized high-density polystyrene sulfonate (PSS) brushes via surface initiated atom-transfer radical polymerization, and performed neutron reflectivity (NR) measurements to investigate and compare the effects of mono-valent Rb {\th} and tri-valent Y 3{\th} counterions to the structure of the densely tethered PSS brushes. Our NR results show that in mono- valent RbNO 3 solution, the dense PSS brush retained its full thickness up to a salt concentration of 1 M, whereas it immediately collapsed upon adding 1.67 mM of tri-valent Y 3{\th} . Increasing the concen- tration of Y 3{\th} beyond this level did not lead to any significant further structure change of the PSS brush. Our findings demonstrate that the presence of multi-valent counterions can significantly alter the structure of polyelectrolyte brushes, in a manner different from mono-valent ions, which has implications for the functionality of the brushes.},
  doi      = {10.1016/j.polymer.2016.02.053},
  file     = {:Yu2016 - The Effect of Multivalent Counterions to the Structure of Highly Dense Polystyrene Sulfonate Brushes.pdf:PDF},
  keywords = {polyelectrolyte, PSS, valency, counterion, polymer brush, SI-ATRP, neutron reflectivity},
}

@Article{Wu2008,
  author   = {Tao Wu and Yanfeng Zhang and Xiaofeng Wang and Shiyong Liu},
  journal  = {Chemistry of Materials},
  title    = {Fabrication of Hybrid Silica Nanoparticles Densely Grafted with Thermoresponsive Poly(N-isopropylacrylamide) Brushes of Controlled Thickness via Surface-Initiated Atom Transfer Radical Polymerization},
  year     = {2008},
  pages    = {101--109},
  volume   = {20},
  abstract = {This article reports on the fabrication of hybrid silica nanoparticles densely grafted with thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) brushes and their thermal phase transition behavior. Surface-initiated atom transfer radical polymerization (ATRP) of N-isopropylacrylamide (NIPAM) was conducted in 2-propanol at ambient temperature using CuCl/CuCl2/tris(2-(dimethylamino)ethyl)amine (Me6TREN) as the catalytic system, starting from the surface of silica nanoparticles derivatized with ATRP initiators (0.35 nm2/initiator). The surface-initiated ATRP can be conducted in a well-controlled manner, as revealed by the linear kinetic plot, linear evolution of number-average molecular weights (Mn) versus monomer conversions, and the relatively narrow molecular weight distributions (Mw/Mn  1.25) of the grafted PNIPAM chains. The grafting density of PNIPAM chains at the surface of silica nanoparticls was estimated to be 2.2 nm$^{2}$/chain based on transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) characterization results. Laser light scattering (LLS) and optical transmittance were then employed to study the thermal phase transitions of PNIPAM brushes at the surface of silica nanoparticles. Both the intensity-average hydrodynamic radius, \textlangle Rh \textrangle, and average radius of gyration, \textlangle Rg \textrangle, exhibit a two-stage decrease upon heating over the broad temperature range of 20-37 {$^{\circ}$}C, which is in contrast to the fact that free PNIPAM homopolymer in aqueous solution exhibits a phase transition at ca. 32 {$^{\circ}$}C within a narrow temperature range. The first phase transition takes place in the temperature range of 20-30 {$^{\circ}$}C, which can be tentatively ascribed to the n-cluster-induced collapse of the inner region of PNIPAM brushes close to the silica core; the second phase transition occurs above 30 {$^{\circ}$}C, which can be ascribed to the outer region of PNIPAM brushes, possessing much lower chain density compared to that of the inner part. We tentatively expect that the observed unique double phase transition behavior of polymer brushes coated at the surface of inorganic nanoparticle cores can be further utilized to fabricate novel nanostructured devices with more complex functions.},
  doi      = {10.1021/cm702073f},
  file     = {:Wu2008 - Fabrication of Hybrid Silica Nanoparticles Densely Grafted with Thermoresponsive Poly(N Isopropylacrylamide) Brushes of Controlled Thickness Via Surface Initiated Atom Transfer Radical Polymerization.pdf:PDF},
  keywords = {polymer synthesis, PNIPAM, thermoresponsive, SI-ATRP, TEM, light scattering, key article, review, NMR, thermogravimetric analysis, gel permeation chomotography},
}

@Article{Altay2016,
  author   = {Esra Altay and Javid Rzayev},
  journal  = {Polymer},
  title    = {Synthesis of star-brush polymer architectures from end-reactive molecular bottlebrushes},
  year     = {2016},
  pages    = {487--494},
  volume   = {98},
  abstract = {Reactive bottlebrush-linear block copolymers with poly(methyl methacrylate) side chains and linear poly(glycidyl methacrylate) (PGMA) end blocks were utilized for the fabrication of brush-star architectures. Well-defined bottlebrush copolymers with reactive end blocks were prepared by a grafting-from method, where a block copolymer backbone was synthesized by sequential reversible addition efragmentation chain transfer (RAFT) polymerization of functionalized monomers, while side chains were installed by atom transfer radical polymerization (ATRP) of methyl methacrylate initiated from the bromide groups of the backbone. LiBr-catalyzed ring-opening of epoxides in the presence of ethyl-enediamine at room temperature was utilized for efficient cross-linking of PGMA blocks leading to star-brush architectures. Various structural parameters, such as side chain length and reactive end block length, were found to impact the efficacy of the cross-linking step. The developed method provided means to connect giant bottlebrush copolymer arms (M n > 300 kg/mol) into a star architecture in an effective and tunable manner.},
  doi      = {10.1016/j.polymer.2016.02.022},
  file     = {:Altay2016 - Synthesis of Star Brush Polymer Architectures from End Reactive Molecular Bottlebrushes.pdf:PDF},
  keywords = {polymer synthesis, polymer brush, bottlebrush, block copolymer, PMMA, PGMA, grafting-from, RAFT, ATRP, PMMA, Polymethylmethacrylat},
}

@Article{Lilge2016,
  author   = {Inga Lilge and Holger Sch{\"{o}}nherr},
  journal  = {Polymer},
  title    = {Synthesis and characterization of well-defined ligand-terminated block copolymer brushes for multifunctional biointerfaces},
  year     = {2016},
  pages    = {409--420},
  volume   = {98},
  abstract = {Polymer brush-functionalized surfaces promise to provide access to absolute control over the bio-interface functionality. To enable in this context systematic studies of cell attachment and proliferation, we investigated the synthesis of well-defined block copolymer brushes of poly(acrylamide) (PAAm), poly(oligo(ethylene glycol)methylether methacrylate) (POEGMA) and poly(acrylic acid) (PAA) by surface-initiated atom transfer radical polymerization (SI-ATRP) and subsequently the introduction of exposed ligands for cell adhesion. Detailed X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, time of flight secondary ion mass spectrometry (ToF-SIMS) and ellipsometry measurements unraveled the progress and the livingness of the homo- and copolymerization of the three monomers. In particular, the correlation of the temporal evolution of the ellipsometric thickness with the decrease in bromine content pointed to a progressive loss of active chain ends, which limits the attainable maximum brush thickness. Non-fouling brushes of POEGMA and PAAm exhibited long term stability and full functionality in cell medium for more than 1 month. Block copolymer brushes with defined thickness comprising a non-fouling POEGMA or PAAm block and a short terminal PAA block were functionalized with a peptide containing the arginine-glycine-aspartic acid (RGD) sequence. Cell attachment assays with fibroblasts revealed facilitated cell adhesion on RGD modified block copolymer brushes. The specific signaling was further confirmed with inhibited cell adhesion on arginine-alanine-aspartic acid (RAD) functionalized brushes (negative control). Hence on the basis of the unraveled synthesis behavior of block copolymer brushes and side chain modification a versatile strategy to fabricate biologically inert surfaces that facilitate integrin-specific cell adhesion has been developed.},
  doi      = {10.1016/j.polymer.2016.03.031},
  file     = {:Lilge2016 - Synthesis and Characterization of Well Defined Ligand Terminated Block Copolymer Brushes for Multifunctional Biointerfaces.pdf:PDF},
  keywords = {polymer synthesis, block copolymer, polymer brush, PAA, PAAm, SI-ATRP, X-ray, infrared, mass spectrometry, ellipsometry,},
}

@Article{Murakami2016,
  author   = {Daiki Murakami and Motoyasu Kobayashi and Yuji Higaki and Hiroshi Jinnai and Atsushi Takahara},
  journal  = {Polymer},
  title    = {Swollen structure and electrostatic interactions of polyelectrolyte brush in aqueous solution},
  year     = {2016},
  pages    = {464--469},
  volume   = {98},
  abstract = {Surface grafting of polyelectrolytes on materials brings about various significant changes in surface properties such as wettability, adhesion, and friction, because of their excellent hydrophilicity and unique intermolecular interactions that depend on the ionic strength of the solution. This review paper describes the characterization of the swollen structure and electrostatic interaction of polyelectrolyte brushes in aqueous solution by use of optical tweezers and neutron reflectivity, in order to discuss the dissociation of ionic groups and charge distribution in the polyelectrolyte brush. In addition, the spreading and structure of water on the polyelectrolyte brush surface were characterized by high spatial resolution IR spectroscopy.},
  doi      = {10.1016/j.polymer.2016.04.041},
  file     = {:Murakami2016 - Swollen Structure and Electrostatic Interactions of Polyelectrolyte Brush in Aqueous Solution.pdf:PDF},
  keywords = {polymer brush, polyelectrolyte, review, neutron reflectivity, optical tweezer, ionic strength, infrared, wetting},
}

@Article{Ma2016,
  author   = {Shuanhong Ma and Bo Yu and Xiaowei Pei and Feng Zhou},
  title    = {Structural hydrogels},
  journal  = {Polymer},
  year     = {2016},
  volume   = {98},
  pages    = {516--535},
  abstract = {Research on hydrogel systems with structural features has aroused great interests due to its wide range of applications, including actuators, microfluidic units, synthetic adhesives, transplantable tissue organs, and cell scaffolds. This review article describes, with special emphasis, the design and fabrication of structural hydrogels with diversified geometric shapes and dimensions. These hydrogel structures include gradient gel, anisotropic gel, gel patterns, gel wrinkle, gel arrays and gel tubes. Several typical applications of such structural hydrogels are introduced, such as for controlling cell behavior, developing responsive actuators, and designing nature inspired bio-lubrication surface. Some perspectives on future development of structural hydrogel systems are provided.},
  doi      = {10.1016/j.polymer.2016.06.053},
  file     = {:Ma2016 - Structural hydrogels.pdf:PDF},
  keywords = {microgel, review},
}

@Article{Liu2010,
  author   = {Fang Liu and Marek W. Urban},
  journal  = {Progress in Polymer Science},
  title    = {Recent advances and challenges in designing stimuli-responsive polymers},
  year     = {2010},
  pages    = {3--23},
  volume   = {35},
  abstract = {Synthetic materials capable of responses to external or internal stimuli represent one of the most exciting and emerging areas of scientific interest and unexplored commercial applications. While there are many exciting challenges facing this field, there are a number of opportunities in design, synthesis, and engineering of stimuli-responsive polymeric systems and Mother Nature serves as a supplier of endless inspirations. This review examines physico-chemical requirements necessary to achieve stimuli-responsiveness in heterogeneous polymer networks as well as discusses recent developments and future trends. While individual structural components of polymeric networks are responsible for localized chain-responsiveness, desirable spatial and energetic network properties are necessary for collective and orchestrated responsiveness to external or internal stimuli. These attributes significantly vary for stimuli-responsive polymeric solutions, surfaces and interfaces, polymeric gels, and solid networks.},
  doi      = {10.1016/j.progpolymsci.2009.10.002},
  file     = {:Liu2010 - Recent Advances and Challenges in Designing Stimuli Responsive Polymers.pdf:PDF},
  keywords = {control parameter, review, polymer network. microgel},
}

@Article{Kopyshev2016,
  author   = {Alexey Kopyshev and Casey J. Galvin and Jan Genzer and Nino Lomadze and Svetlana Santer},
  journal  = {Polymer},
  title    = {Polymer brushes modified by photosensitive azobenzene containing polyamines},
  year     = {2016},
  pages    = {421--428},
  volume   = {98},
  abstract = {This paper describes a strategy for preparing photosensitive polymeric grafts on flat solid surfaces by loading diblock-copolymer or homopolymer brushes with cationic azobenzene-containing surfactants. In contrast to previous work, we utilize photosensitive surfactants that bear positively-charged polyamine head groups whose charge varies between 1{\th} and 3{\th}. Poly(methylmethacrylate-b-methacrylic acid) (PMMA-b-PMAA) brushes were prepared by employing atom transfer radical polymerization, where the bottom poly(methyl methacrylate) block was grown first followed by the synthesis of t-butyl methacrylate block that after de-protection yielded poly(methacrylic acid). We used PMMA-b-PMAA brushes with constant grafting density and length of the PMMA block, and three different lengths of the PMAA block. The azobenzene-based surfactants attached only to the PMAA block. The degree of binding (i.e., the number of surfactant molecules per binding site on the brush backbone) of the surfactants to the brush depends strongly on the valence of the surfactant head-group; within the brushes the concentration of the surfactant carrying unit charge is larger than that of multivalent surfactants. We detect pronounced response of the brush topography on irradiation with UV interference pattern even at very low degree of binding (as small as 0.08) of multi-valence surfactant. Areas on the sample that receive the highest UV dose exhibit chain scission. By removing the ruptured chains from the substrate via good solvent, one uncovers a surface topographical relief grating, whose spatial arrangement follows the intensity distribution of the UV light on the sample during irradiation. Due to strong coupling of the multi-valence surfactants to the polymer brush, it was possible in some cases to completely remove the polyelectrolyte block from the PMMA layer. The application of multi-valence azobenzene surfactants for triggering brush photosensitive has important advantage over usage of surfactant with unit charge because relative to single-valence surfactants much lower concentrations of the multivalent surfactant are needed to achieve comparable response upon UV irradiation.},
  doi      = {10.1016/j.polymer.2016.03.050},
  file     = {:Kopyshev2016 - Polymer Brushes Modified by Photosensitive Azobenzene Containing Polyamines.pdf:PDF},
  keywords = {polymer brush, polymer synthesis, PMMA, PMAA, ATRP, valency, polyelectrolyte, photosensitive, PMMA, Polymethylmethacrylat},
}

@Article{Ballauff2016a,
  author     = {Matthias Ballauff and Markus Biesalsi and Axel H. E. M{\"{u}}ller},
  journal    = {Polymer},
  title      = {Polymer brushes},
  year       = {2016},
  pages      = {387--388},
  volume     = {98},
  comment    = {editorial},
  doi        = {10.1016/j.polymer.2016.06.027},
  file       = {:Ballauff2016 - Polymer Brushes.pdf:PDF},
  keywords   = {review, editorial},
  printed    = {printed},
  ranking    = {rank3},
  readstatus = {skimmed},
}

@Article{Ballauff2006,
  author   = {Matthias Ballauff and Oleg Borisov},
  journal  = {Current Opinion in Colloid and Interface Science},
  title    = {Polyelectrolyte brushes},
  year     = {2006},
  pages    = {316--232},
  volume   = {11},
  abstract = {We survey recent progress made in the field of polyelectrolyte brushes. These systems consist of long polyelectrolyte chains that are grafted densely to planar or curved surfaces. The main feature of all polyelectrolyte brushes is the strong confinement of the counterions within the brush layer. The high osmotic pressure which is thus built up explains the unusual features of these systems. Here we focus on the most recent experimental developments which are rationalized on the basis of existing theoretical predictions and opens new challenging problems. In particular, we shall discuss briefly the experimental systems used for comparing theory and experiment lately. Moreover, we review various aspects related to the experimental analysis of polyelectrolyte brushes. As a final point, we survey trends in recent applications which demonstrate that polyelectrolyte brushes have an excellent prospect for future nanotechnology.},
  doi      = {10.1016/j.cocis.2006.12.002},
  file     = {:Ballauff2006 - Polyelectrolyte Brushes.pdf:PDF},
  keywords = {polyelectrolyte, polymer brush, review, counterion},
}

@Article{Krause2016,
  author   = {Beate Krause and Petra P{\"{a}}tschke and Evgeny Ilin and Mikhail Predtechenskiy},
  journal  = {Polymer},
  title    = {Melt mixed SWCNT-polypropylene composites with very low electrical percolation},
  year     = {2016},
  pages    = {45--50},
  volume   = {98},
  abstract = {Singlewalled carbon nanotube material of the type TUBALLTM (OCSiAl) was used to prepare composites with polypropylene by melt mixing using a conical twin screw micro-compounder. The compression moulded composites showed electrical percolation between 0.075 and 0.1 wt % and achieved volume resistivity values lower than 1 kOhm-cm already at 0.8 wt % loading. Light microscopy and scanning electron microscopy revealed good distribution and dispersion into small diameter bundles as well as retained high nanotube length. In connection with the very low percolation threshold this indicates that the SWCNT material shows an exceptionally good dispersibility which may be due to relatively high nanotube diameters with a mean value of 1.6 nm. In tensile tests already 0.1 wt % nanotube additions resulted in slight increase in Young{\textquoteright}s modulus and maximum stress. TuballTM SWCNT material seems to be very promising for conductivity enhancement.},
  doi      = {10.1016/j.polymer.2016.06.004},
  file     = {:Krause2016 - Melt Mixed SWCNT Polypropylene Composites with Very Low Electrical Percolation.pdf:PDF},
  keywords = {polypropylene, electrical percolation, scanning electron microscopy, conductivity},
}

@Article{Wilkinson2016,
  author   = {Arthur N. Wilkinson and Ian A. Kinloch and Raja N. Othman},
  journal  = {Polymer},
  title    = {Low viscosity processing using hybrid CNT-coated silica particles to form electrically conductive epoxy resin composites},
  year     = {2016},
  pages    = {32--38},
  volume   = {98},
  abstract = {Hybrid particles of multiwall carbon nanotubes (CNTs) grafted onto silica gel were shown to provide a low viscosity processing route to forming electrically-conductive epoxy resin composites. Rheological studies showed the viscoelastic shear moduli of epoxy resin suspensions containing these particles (named SG6_3) remained within the same order of magnitude as that of the neat resin at 5 wt% loading (containing up to 1.65 wt% of grafted CNTs). Whereas, the addition of 1.65 wt% of discrete (non-grafted) CNTs into the same resin increased shear moduli by up to seven orders of magnitude. The complex viscosities of suspensions containing 5 wt% of SG6_3 remained essentially unchanged, whereas an increase of up to five orders of magnitude resulted upon the addition of 1.65 wt% of nonegrafted CNTs. Whilst rheological studies showed SG6_3 did not form a percolated network at levels 5 wt%, addition of only 2 wt% (containing 0.66 wt% CNT) was found to form an electricallyeconductive percolated network in an epoxy resin composite with conductivity ~ 10 4 S/m.},
  doi      = {10.1016/j.polymer.2016.06.009},
  file     = {:Wilkinson2016 - Low Viscosity Processing Using Hybrid CNT Coated Silica Particles to Form Electrically Conductive Epoxy Resin Composites.pdf:PDF},
  keywords = {conductivity, rheology, electrical percolation},
}

@Article{Muenstedt2016,
  author   = {Helmut M{\"{u}}nstedt and Zdenek Stary},
  journal  = {Polymer},
  title    = {Is electrical percolation in carbon-filled polymers reflected by rheological properties?},
  year     = {2016},
  pages    = {51--60},
  volume   = {98},
  abstract = {It is well known that the electrical conductivity of particle filled polymers exhibits a distinct percolation behavior. In the literature it is stated that this percolation is accompanied by a comparable change of rheological properties designated {\textquotedblleft}rheological percolation{\textquotedblright}. Evaluating dynamic-mechanical measurements from the literature and using own results from creep experiments on polymethylmethacrylate melts filled with graphite it is demonstrated that rheological properties change continuously as a function of particle concentration in the range of the threshold of electrical conductivity. A model is proposed and discussed, which describes the electrical and rheological properties. For rendering a polymer conductive, continuous pathways of conducting fillers are necessary. The rheological behavior in the percolation regime is determined by matrix molecules that become hindered in their mobility by an attachment to the particles.},
  doi      = {10.1016/j.polymer.2016.05.042},
  file     = {:IsElectricalPercolationInCarbonFilledPolymersReflectedByRheologicalProperties_MuenstedtEtAl_Polymer2016.pdf:PDF},
  keywords = {electrical percolation, rheology, conductivity, PMMA, PMMA, Polymethylmethacrylat},
}

@Article{Min2016,
  author   = {Kyoungmin Min and Yaeji Kim and Sushmit Goyal and Sung Hoon Lee and Matt McKenzie and Hyunhang Park and Elizabeth S. Savoy and Aravind R. Rammohan and John C. Mauro and Hyunbin Kim and Kyungchan Chae and Hyo Sug Lee and Jaikwang Shin and Eunseog Cho},
  journal  = {Polymer},
  title    = {Interfacial adhesion behavior of polyimides on silica glass: A molecular dynamics study},
  year     = {2016},
  pages    = {1--10},
  volume   = {98},
  abstract = {We investigate the adhesion behavior between polyimide and silica glass using molecular dynamics simulations, which is important for improving the manufacturing process of flexible displays. Various polyimides are simulated to understand the complex adhesion mechanisms that occur at the interface with inorganic glass. Through the pulling process implemented within the framework of steered molecular dynamics using reactive force-field, we calculate properties such as potential of mean force, pulling distance, and pulling force, which govern the adhesion behavior at the polymer-glass interface. It is found that a polyimide with a lower coefficient of thermal expansion requires a greater force but a shorter pulling distance to completely detach it from the silica surface. The change in the chain conformation during the pulling process reveals that polyimide chains near the interface dominate the molecular response due to their stronger adhesion to the glass surface. The decomposed energy terms from the interatomic potential indicate that the contribution from bonds and coulombic energy play the most significant role in the deformation of the system. Finally, failure mode analysis demonstrates that adhesive failure is the dominant mechanism regardless of the type of polyimide.},
  doi      = {10.1016/j.polymer.2016.06.017},
  file     = {:Min2016 - Interfacial Adhesion Behavior of Polyimides on Silica Glass_ a Molecular Dynamics Study.pdf:PDF},
  keywords = {simulation},
}

@Article{Singha2016,
  author   = {Shuvra Singha and Tushar Jana},
  journal  = {Polymer},
  title    = {Influence of interfactial interactions on the properties of polybenzimidazole/clay nanocomposite electrolyte membrane},
  year     = {2016},
  pages    = {20--31},
  volume   = {98},
  abstract = {Despite the wide range of studies illustrating the influence of type and quantity of nanoclay on the macro properties of polymer nanocomposites, it has always remained a biggest challenge to study the chemistry of organic/inorganic interface on the final properties of polymer nanocomposites, a study that can indeed aid us in designing tailor-made materials e.g. proton exchange membranes (PEM). Hence in this study, we aimed to explore the influence of interface chemistry of nano-clay on the properties of poly(4,4 0 -diphenylether-5,5 0 -bibenzimidazole) (OPBI)/clay nanocomposite PEM for fuel cell. Cloisite clay modified organically with three surfactant molecules differing structurally in their cationic head group - cetyltrimethyl ammonium bromide (CTAB), cetylpyridinium bromide (CPyB) and cetylimidazolium bromide (CImiB) was utilized for making OPBI nanocomposite membranes by a simple solution blending route. 13 C CP MAS solid state NMR confirmed the hydrogen bonding interactions between the OPBI chains and clay particles. Formation of intercalated clay nanostructures in the OPBI matrix was revealed by WAXD and TEM analyses and this morphology was found to influence different properties in a favorable manner. TGA and DMA studies highlighted the influence of the different surfactants on the interfacial interactions in elevating/decreasing the thermal and glass transition temperatures of the nanocomposite membranes. The use of different surfactant modified clays induced sufficient hydrophobicity in the membranes that led to higher phosphoric acid (PA) loading and controlled dimensional swelling in both water and PA. The proton conductivity data particularly underscored the different degrees of interfacial interactions each of the three differently modified clays had in creating efficient proton transport pathways giving rise to higher proton conductivity while decreasing the activation energy barrier for the proton hopping. The results also revealed the critical role played by the clay particles especially by the organic modifier in preventing the leaching away of the doped acid from the nanocomposites membranes.},
  doi      = {10.1016/j.polymer.2016.06.007},
  file     = {:Singha2016 - Influence of Interfactial Interactions on the Properties of Polybenzimidazole_clay Nanocomposite Electrolyte Membrane.pdf:PDF},
  keywords = {membrane, NMR, TEM},
}

@Article{Zhang2016,
  author   = {Dandan Zhang and Dongquing Liu and Qingjuan Ren and Yingbo Chen and Cuiyu Yin},
  journal  = {Polymer},
  title    = {Fabrication of polyamide-6 fiber of high SO3H content surface through electrospinning},
  year     = {2016},
  pages    = {11--19},
  volume   = {98},
  abstract = {Benzenesulfonic group containing polyamide-6 (PA6) were fabricated through melting polymerized using $\epsilon$-caprolactam and different proportions of 5-sulphosalicylic acid (5SA). The physicochemical properties of SO 3 H containing PA6s (SPA6) were determined through FT-IR spectroscopy, TGA and DSC. The morphology of electrospinning fibers of SPA6s were investigated by FE-SEM. Fiber diameters increased with 5SA, and the polymer became un-electrospinnable as 5SA up to 5 wt%. Solution conductivity was a crucial factor for the spinnability of polyelectrolyte. Direction of electric field and material quality of collector could also influence the electrospinning of polyelectrolyte. Sulfonic groups preferred to distribute over the surface of fibers during electrospinnning process comparing to melting spinning, which could render fiber surface more hydrophilic.},
  doi      = {10.1016/j.polymer.2016.05.072},
  file     = {:Zhang2016 - Fabrication of Polyamide 6 Fiber of High SO3H Content Surface through Electrospinning.pdf:PDF},
  keywords = {polymer synthesis, infrared, thermogravimetric analysis, DSC, polyelectrolyte},
}

@Article{Christau2016,
  author   = {Stephanie Christau and Tim M{\"{o}}ller and Felix Brose and Jan Genzer and Olaf Soltwedel and Regina von Klitzing},
  journal  = {Polymer},
  title    = {Effect of gold nanoparticle hydrophobicity on thermally induced color change of PNIPAM brush/gold nanoparticle hybrids},
  year     = {2016},
  pages    = {454--463},
  volume   = {98},
  abstract = {This paper addresses the relation between gold nanoparticle (AuNP) distribution in thermoresponsive polymer brushes and the thermally induced color change of the polymer brush/AuNP hybrids. Therefore, we report on the effect of AuNP surface functionalization on the structure and optical response of the nanoparticles in thermoresponsive poly(N- isopropylacrylamide) (PNIPAM) brushes. Two different types of gold nanoparticles are attached to the PNIPAM brushes: (1) AuNPs that are coated with citrate anions (AuNP-citrate), and (2) AuNPs stabilized with 12-mercaptododecanoic acid ligands (AuNP-MDA). Neutron reflectivity (NR) measurements indicate that the spatial structure of the hybrid depends on the particle type. A strong increase in thickness is observed after attachment of AuNP-citrate; this is not the case for AuNP-MDA. The thermoinduced color change of the PNIPAM/AuNP hybrids depends strongly on the particle type. While a red-shift of the surface plasmon band occurs in case of AuNP-citrate, a blue-shift is found for AuNP-MDA when the temperature is increased above the PNIPAM's volume phase transition temperature. This blue-shift vanishes after a certain number of heating/cooling cycles, indicating a rearrangement of the AuNPs in the brush. The different behavior of AuNP-citrate as compared to AuNP-MDA can be explained by the hydrophobic nature of the 12-mercaptododecanoic acid ligands.},
  doi      = {10.1016/j.polymer.2016.03.088},
  file     = {:Christau2016 - Effect of Gold Nanoparticle Hydrophobicity on Thermally Induced Color Change of PNIPAM Brush_gold Nanoparticle Hybrids.pdf:PDF},
  keywords = {polymer brush, PNIPAM, control parameter, thermoresponsive, neutron reflectivity},
  printed  = {printed},
}

@Article{Muellner2016,
  author   = {Markus M{\"{u}}llner and Axel H. E. M{\"{u}}ller},
  journal  = {Polymer},
  title    = {Cylindrical polymer brushes - Anisotropic building blocks, unimolecular templates and particulate nanocarriers},
  year     = {2016},
  pages    = {389--401},
  volume   = {98},
  abstract = {This article presents an overview of the latest key developments and research activities in the area of cylindrical polymer brushes (CPBs), also known as {\textquoteleft}molecular bottlebrushes{\textquoteright}. CPBs consist of a polymer backbone containing polymer side chains that cause the backbone to extend and adopt a worm-like conformation. The extent of backbone stretching and the aspect ratio of CPBs is determined by the length and grafting density of the side chains. The latest developments in controlled/living polymerisation techniques led to novel and more efficient ways of producing delicate polymer architectures, such as block copolymer CPBs, and resulted in a considerable expansion of the field of application for these soft anisotropic materials. In this feature article, we focus on important recent findings and applications in the areas concerning solution and bulk self-assembly of block copolymer CPBs, unimolecular templating and brush-based drug delivery systems in nanomedicine.},
  doi      = {10.1016/j.polymer.2016.03.076},
  file     = {:Muellner2016 - Cylindrical Polymer Brushes Anisotropic Building Blocks, Unimolecular Templates and Particulate Nanocarriers.pdf:PDF},
  keywords = {polymer brush, review, bottlebrush, block copolymer, drug delivery},
}

@Article{Tapa2016,
  author   = {Marcel Ockhoma Tapa and Soo Hyung Choi},
  journal  = {Polymer},
  title    = {Concentration dependent structure of poly(styrene-b-ethylene-alt-propylene) in 1-phenyldodecane},
  year     = {2016},
  pages    = {39--44},
  volume   = {98},
  abstract = {The concentration and temperature dependence of the structure formed by poly(styrene-b-ethylene-alt-propylene) (PS-PEP) diblock copolymer in 1-phenyldodecane, a nearly neutral solvent, was studied using small-angle X-ray scattering (SAXS). As the polymer concentration decreases from 100 wt% to 10 wt%, PS-PEP (M n , PS 1/4 42,000 g/mol, M n , PEP 1/4 62,000 g/mol, M w /M n 1/4 1.04) solutions form lamellae, hexagonally packed cylinders, and disordered structure. The results show that the neutral solvent mainly attenuates the unfavorable interaction between PS and PEP blocks, and thus reduces the domain spacing. The slight selective nature of the solvent, however, leads to uneven solvent distribution on the two domains. In particular, SAXS analysis equipped with the form factor fitting results in quantitative estimate of averaged solvent composition in micro-phase separated domains.},
  doi      = {10.1016/j.polymer.2016.06.008},
  file     = {:Tapa2016 - Concentration Dependent Structure of Poly(styrene B Ethylene Alt Propylene) in 1 Phenyldodecane.pdf:PDF},
  keywords = {polystyrene, block copolymer, SAXS},
}

@Book{Sequeira2010,
  editor    = {Cesar Sequeira and Diogo Santos},
  publisher = {Woodhead Publishing},
  title     = {Polymer Electrolytes: Fundamentals and Applications},
  year      = {2010},
  isbn      = {978-1-84569-772-3},
  comment   = {note chapter 3.5: Magnetic resonance spectroscopy of polymer electrolytes obtained from natural polymers},
  file      = {:Sequeira2010 - Polymer Electrolytes_ Fundamentals and Applications.pdf:PDF;:2---Ceramic-polymer-electrolytes_2010_Polymer-Electrolytes.pdf:PDF;:3---Polymer-electrolytes-based-on-natural-polymers_2010_Polymer-Electrolytes.pdf:PDF;:4---Composite-polymer-electrolytes-for-electrochemica_2010_Polymer-Electroly.pdf:PDF;:5---Lithium-doped-hybrid-polymer-electrolytes_2010_Polymer-Electrolytes.pdf:PDF;:6---Hybrid-inorganic-organic-polymer-electrolytes_2010_Polymer-Electrolytes.pdf:PDF;:7---Using-nuclear-magnetic-resonance-spectroscopy-in-poly_2010_Polymer-Elect.pdf:PDF;:8---Molecular-dynamics-simulations-of-Li-ion-and-H-conduc_2010_Polymer-Elect.pdf:PDF;:9---Characterisation-and-modelling-of-multivalent-polym_2010_Polymer-Electro.pdf:PDF;:10---Polymer-electrolytes-for-dye-sensitized-solar-c_2010_Polymer-Electrolyt.pdf:PDF;:11---Solid-polymer-electrolytes-for-supercapacitors_2010_Polymer-Electrolyte.pdf:PDF;:12---Polymer-electrolytes-for-electrochromic-device_2010_Polymer-Electrolyte.pdf:PDF;:13---Hyperbranched-polymer-electrolytes-for-high-temper_2010_Polymer-Electro.pdf:PDF;:14---Polymer-electrolytes-as-solid-solvents-and-their-_2010_Polymer-Electrol.pdf:PDF;:15---Hybrid-polymer-electrolytes-for-electrochemical-_2010_Polymer-Electroly.pdf:PDF;:Contributor-contact-details_2010_Polymer-Electrolytes.pdf:PDF;:Copyright_2010_Polymer-Electrolytes.pdf:PDF;:Front-matter_2010_Polymer-Electrolytes.pdf:PDF;:Index_2010_Polymer-Electrolytes.pdf:PDF;:Preface_2010_Polymer-Electrolytes.pdf:PDF},
  keywords  = {polyelectrolyte, book, NMR},
}

@Article{Dempsey2001,
  author   = {Christopher E. Dempsey},
  journal  = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title    = {Hydrogen exchange in peptides and proteins using NMR spectroscopy},
  year     = {2001},
  issn     = {0079-6565},
  number   = {2},
  pages    = {135--170},
  volume   = {39},
  doi      = {10.1016/S0079-6565(01)00032-2},
  file     = {:Dempsey2001 - Hydrogen Exchange in Peptides and Proteins Using NMR Spectroscopy.pdf:PDF},
  keywords = {Hydrogen exchange, NMR, simulation, Membrane},
  printed  = {printed},
  url      = {http://www.sciencedirect.com/science/article/pii/S0079656501000322},
}

@Article{Englander1972,
  author  = {Englander, S. W. and Downer, N. W. and Teitelbaum, H.},
  journal = {Annual Review of Biochemistry},
  title   = {Hydrogen Exchange},
  year    = {1972},
  note    = {PMID: 4563445},
  number  = {1},
  pages   = {903--924},
  volume  = {41},
  doi     = {10.1146/annurev.bi.41.070172.004351},
  eprint  = {https://doi.org/10.1146/annurev.bi.41.070172.004351},
  file    = {:Englander1972 - Hydrogen Exchange.pdf:PDF},
  printed = {printed},
  url     = {https://doi.org/10.1146/annurev.bi.41.070172.004351},
}

@Article{Ohno2007,
  author   = {Kohji Ohno and Takashi Morinaga and Satoshi Takeno and Yoshinobu Tsujii and Takeshi Fukuda},
  journal  = {Macromolecules},
  title    = {Suspensions of Silica Particles Grafted with Concentrated Polymer Bruh: Effects of Graft Chain Length on Brush Layer Thickness and Colloidal Crystallization},
  year     = {2007},
  number   = {25},
  pages    = {9143--9150},
  volume   = {40},
  abstract = {We previously reported that monodisperse silica particles (SiPs) afforded with a high-density brush of poly(methyl methacrylate) (PMMA) and suspended in a good solvent for PMMA formed a colloidal crystal in a certain concentration range (Macromolecules2006, 39, 1245). Here we investigated similar hybrid particles with respect to the influence of graft chain length Lc on their hydrodynamic diameter Dh in dilute suspension and on colloidal crystallization in more concentrated suspension. The average radius r0 of SiPs was 65 nm, and the surface density $\sigma$0 of PMMA grafts at the SiP surface was about 0.7 chains/nm2 (about 36\hspace{0.167em}000 chains per particle). The hydrodynamic thickness of the swollen brush layer h (=Dh/2 $-$ r0) was qualitatively interpretable by a modified Daoud$-$Cotton-type scaling model. Namely, for short graft chains, h obeyed the universal relation, h[1 + (h/2r0)] $\sim$ Lc$\sigma$01/2, applicable to concentrated polymer brushes on flat as well as spherical surfaces, and for chains longer than a critical length, h showed positive deviations from this linear relation, indicating the brush layer getting into the semidilute polymer brush regime. Suspensions of the hybrid particles showed a phase transition from a (disordered) fluid to a fully crystallized system with a narrow fluid/crystal coexisting regime. The critical concentration of crystallization (melting point) decreased with increasing graft chain length, and the nearest-neighbor interparticle distance Ddis in the crystal approached to a micrometer scale as the graft molecular weight reached 500\hspace{0.167em}000. Good correlation was observed between Dh and Ddis such that Ddis = (1.15 $\pm$ 0.05)Dh. Confocal laser scanning microscopic observation suggested that the colloidal crystal generally include both hexagonal close-packed (hcp) and face-centered cubic (fcc) lattice arrangements with the fcc arrangement likely to increase with increasing chain length.},
  doi      = {10.1021/ma071770z},
  file     = {:Ohno2007 - Suspensions of Silica Particles Grafted with Concentrated Polymer Bruh_ Effects of Graft Chain Length on Brush Layer Thickness and Colloidal Crystallization.pdf:PDF},
  keywords = {PMMA, spherical brush, polymer brush, Polymethylmethacrylat},
  printed  = {printed},
  ranking  = {rank4},
}

@Book{Borsali2008,
  editor    = {Redouane Borsali and Robert Pecora},
  publisher = {Springer Netherlands},
  title     = {Soft-Matter Characterization},
  year      = {2008},
  edition   = {1},
  isbn      = {978-1-4020-4465-6},
  file      = {:Borsali2008 - Soft Matter Characterization.pdf:PDF},
  keywords  = {book, experimental methods},
}

@Misc{Starkey,
  author       = {Dr. Laurie S. Starkey},
  title        = {1H NMR chemical shift ppm table},
  howpublished = {California State Polytechnic University, Pomona},
  file         = {:Starkey - 1H NMR chemical shift ppm table.pdf:PDF},
  keywords     = {NMR, chemical shift, uncitable},
}

@Article{Lei2017,
  author   = {Yufeng Lei and Yaling Lin and Anqiang Zhang},
  journal  = {Applied Surface Science},
  title    = {The synthesis and protein resistance of amphiphilic PDMS-b-(PDMS-g-cysteine) copolymers},
  year     = {2017},
  issn     = {0169-4332},
  pages    = {393--398},
  volume   = {419},
  abstract = {Zwitterionic polymers have been used to cope with nonspecific protein adsorption and bio-fouling problems for a wide range of materials, including biomedical devices, marine coatings and membrane separation. However, direct surface modification with highly water-soluble zwitterionic polymers is rather difficult due to their poor attachment to hydrophobic solid surfaces. In this work, we utilize the hydrophobic interaction to anchor zwitterionic polysiloxanes grafted with cysteine onto surfaces by adding an hydrophobic block of polydimethylsiloxanes, referred as PDMS-b-(PDMS-g-Cys)s. The synthesis involves only three steps of reactions, and the structures of each product were characterized using GPC, FT-IR and 1H NMR. The adsorption and protein resistance of PDMS-b-(PDMS-g-Cys)s on a gold surface are investigated with QCM-D. The results show that the hydrophobic interaction moieties of the additional PDMS blocks help the hydrophilic cysteine-grafted blocks stably attach and then function on the sensor. These findings suggest that the addition of hydrophobic moieties provides an effective approach to construct anti-fouling interfaces with zwitterionic polymers in aqueous solution.},
  doi      = {https://doi.org/10.1016/j.apsusc.2017.05.063},
  file     = {:Lei2017 - The Synthesis and Protein Resistance of Amphiphilic PDMS B (PDMS G Cysteine) Copolymers.pdf:PDF},
  keywords = {block copolymer, PDMS, NMR, chemical shift, polymer synthesis, infrared},
  url      = {http://www.sciencedirect.com/science/article/pii/S0169433217313752},
}

@Article{Protsak2019,
  author   = {Iryna S. Protsak and Yevehnii M. Morozov and Wen Dong and Zichun Le and Dong Zhang and Ian M. Henderson},
  journal  = {Nanoscale Research Letters},
  title    = {A 29Si, 1H, and 13C Solid-State NMR Study on the Surface Species of Various Depolymerized Organosiloxanes at Silica Surface},
  year     = {2019},
  pages    = {160--174},
  volume   = {14},
  abstract = {Three poly(organosiloxanes) (hydromethyl-, dimethyl-, and epoxymethylsiloxane) of different chain lengths and pendant groups and their mixtures of dimethyl (DMC) or diethyl carbonates (DEC) were applied in the modification of fumed silica nanoparticles (FSNs). The resulting modified silicas were studied in depth using 29 Si, 1 H, and 13 C solid-state NMR spectroscopy, elemental analysis, and nitrogen adsorption-desorption (BET) analysis. The obtained results reveal that the type of grafting, grafting density, and structure of the grafted species at the silica surface depend strongly on the length of organosiloxane polymer and on the nature of the {\textquotedblleft}green{\textquotedblright} additive, DMC or DEC. The spectral changes observed by solid-state NMR spectroscopy suggest that the major products of the reaction of various organosiloxanes and their DMC or DEC mixtures with the surface are D (RR{\textquoteright}Si(O 0.5 ) 2 ) and T (RSi(O 0.5 ) 3 ) organosiloxane units. It was found that shorter methylhydro (PMHS) and dimethylsiloxane (PDMS) and their mixtures with DMC or DEC form a denser coverage at the silica surface since S BET diminution is larger and grafting density is higher than the longest epoxymethylsiloxane (CPDMS) used for FSNs modification. Additionally, for FSNs modified with short organosiloxane PMHS/DEC and also medium organosiloxane PDMS/DMC, the dense coverage formation is accompanied by a greater reduction of isolated silanols, as shown by solid-state 29 Si NMR spectroscopy, in contrast to reactions with neat organosiloxanes. The surface coverage at FSNs with the longest siloxane (CPDMS) greatly improves with the addition of DMC or DEC. The data on grafting density suggest that molecules in the attached layers of FSNs modified with short PMHS and its mixture of DMC or DEC and medium PDMS and its mixture of DMC form a {\textquotedblleft}vertical{\textquotedblright} orientation of the grafted methylhydrosiloxane and dimethylsiloxane chains, in contrast to the reaction with PDMS/DEC and epoxide methylsiloxane in the presence of DMC or DEC, which indicates a {\textquotedblleft}horizontal{\textquotedblright} chain orientation of the grafted methyl and epoxysiloxane molecules. This study highlights the major role of solid-state NMR spectroscopy for comprehensive characterization of solid surfaces.},
  doi      = {10.1186/s11671-019-2982-2},
  file     = {:Protsak2019 - A 29Si, 1H, and 13C Solid State NMR Study on the Surface Species of Various Depolymerized Organosiloxanes at Silica Surface.pdf:PDF},
  keywords = {NMR, chemical shift, PDMS},
}

@InProceedings{Cosgrove2016,
  author   = {Terence Cosgrove and Steven Swier and Randall Gene Schmidt and Stewart Prescott and Sairoong Muangpil and Peter J. F. Griffiths and Youssef Espidel},
  title    = {Study of Poly ( dimethylsiloxane ) and End-Tethered Polyhedral Resin Nanoparticles},
  year     = {2016},
  abstract = {A series of the dumbbell shape nanocomposite materials of polydimethylsiloxanes (PDMS) and polyhedral oligomeric silsesquioxanes (POSS) was synthesised through hydrosilylation reactions of allyl- and vinyl-POSS and hydride-terminated PDMS. The chemical structures of the dumbbell shaped materials, so called POSS-PDMS-POSS triblocks, were characterised by 1H NMR and FT-IR spectroscopy. The molecular weights of the triblock polymers were de- termined by gel permeation chromatography (GPC). Their size was analysed by small-angle neutron scattering (SANS) and pulsed-field gradient stimulated echo (PFG STE) NMR ex- periments. The impact of POSS on the molecular mobility of the PDMS middle chain was observed by using 1 H spin-spin (T 2 ) relaxation NMR. In contrast to the linear melts, the tri- blocks showed an increase in mobility with increasing molecular weight over the range studied due to the constraints imposed by the tethered nanoparticles. The triblocks were also utilized to compare the impact of tethered nanoparticles on the mobility of the linear component com- pared to the mobility of the polymer in conventional blended nanocomposites. It appears that up to a critical concentration the tethered chains provide more reinforcement than physically dispersed particles},
  file     = {:Cosgrove2016StudyOP - Study of Poly ( Dimethylsiloxane ) and End Tethered Polyhedral Resin Nanoparticles.pdf:PDF},
  keywords = {NMR, PFG, SANS, infrared, gel permeation chromotography, PDMS, block copolymer},
}

@Article{Goff2012,
  author   = {Jonathan Goff and Barry Arkles and Laura Olenick and Ed Kimble},
  journal  = {Polymer Preprints},
  title    = {Silicone Elastomers by Step-Growth Polymerization of Monodisperse Dual Functional Silicones},
  year     = {2012},
  number   = {1},
  pages    = {486},
  volume   = {53},
  abstract = {Silicones formed via the living anionic ring-opening polymerization of a cyclic trisiloxane historically contain a single functional group. These asymmetric silicones afford the advantages of precise molecular weight control, narrow molecular weight distribution, and absence of low molecular weight impurities when compared to dual functional silicones synthesized by chain-growth equilibration methods. A new class of dual functional silicones synthesized from a living polymerization approach has been developed. These materials allow for post-polymerization reactions previously limited to their chain-growth silicone analogues. With appropriate functionality, they can undergo radical, vinyl-addition or ROMP polymerization and cure. Functionality of the polymer endgroups can be tuned to produce symmetric and asymmetric dual functional silicones. This paper focuses on the synthesis of monovinyl, monohydride terminated polydimethylsiloxanes. These monodisperse asymmetric dual functional silicones conform to the general structure of an A-B step-growth monomer. A low temperature platinumcatalyzed intermolecular hydrosilylation step-growth process of these materials leads to high molecular weight silicones with elastomeric properties},
  file     = {:Goff2012 - Silicone Elastomers by Step Growth Polymerization of Monodisperse Dual Functional Silicones.pdf:PDF},
  keywords = {NMR, chemical shift, polymer synthesis},
}

@Article{Saxena2007,
  author   = {Saxena, Anubhav and Rajaraman, Suresh and Leatherman, Mark},
  journal  = {Macromolecules},
  title    = {Synthesis of Narrowly Dispersed Bis-Hydride-Capped Polydimethylsiloxane Using Difunctional Anionic Initiator Based on 1,3-Diisopropenylbenzene},
  year     = {2007},
  number   = {3},
  pages    = {752--755},
  volume   = {40},
  abstract = {[...] This paper reports the method for the preparation of narrowly dispersed difunctional terminated polydimethylsiloxane. The bis-hydride-capped polydimethylsiloxane was synthesized using a difunctional anionic initiator, which is generated in situ by reacting 1,3-diisopropenylbenzene (DIB) with tert-butyllithium (t-BuLi). The polysiloxane with functional groups at both ends was well characterized by FTIR spectroscopy, NMR ( 1 H and 29 Si) spectroscopy, gas chromatography (GC), and gel permeation chromatography (GPC).},
  doi      = {10.1021/ma062337c},
  eprint   = {https://doi.org/10.1021/ma062337c},
  file     = {:Saxena2007 - Synthesis of Narrowly Dispersed Bis Hydride Capped Polydimethylsiloxane Using Difunctional Anionic Initiator Based on 1,3 Diisopropenylbenzene.pdf:PDF},
  keywords = {PDMS, NNR, chemical shift, polymer synthesis, infrared, gel permeation chromotography},
  url      = {https://doi.org/10.1021/ma062337c},
}

@Article{Saxena2004,
  author   = {Saxena, Anubhav and Okoshi, Kento and Fujiki, Michiya and Naito, Masanobu and Guo, Guangqing and Hagihara, Takahiro and Ishikawa, Masaaki},
  journal  = {Macromolecules},
  title    = {Spectroscopic Evidence of Si$-$H End Groups in Dialkylpolysilanes Synthesized via Wurtz Coupling},
  year     = {2004},
  number   = {2},
  pages    = {367--370},
  volume   = {37},
  abstract = {We demonstrate unambiguously the presence of Si$-$H end groups in $\sigma$-conjugated polysilanes 1$-$5, with alkyl groups as side chains synthesized via Wurtz coupling by means of IR, 1H, 29Si, and {1H$-$29Si} heteronuclear correlation NMR spectroscopy. However, there were no detectable Si$-$Cl, Si$-$OH, and Si$-$OR groups that would be associated with end groups of polysilanes. This implies that either such groups are not present or are too small to be detectable by IR and NMR spectra. The presence of Si$-$H end groups in low as well as high molecular weight polysilanes suggests the sequential existence of silyl radicals and anions in Wurtz coupling reactions and termination reaction involving a radical coupling in the solvent phase as previously described.},
  doi      = {10.1021/ma034854q},
  eprint   = {https://doi.org/10.1021/ma034854q},
  file     = {:SpectroscopicEvidenceOfSiHEndGroupsInDialkylpolysilanesSynthesizedViaWurtzCoupling_SaxenaEtAl_Macromolecules2004_SupportingInformation.pdf:PDF},
  keywords = {infrared, NMR, polymer synthesis, chemical shift},
  url      = {https://doi.org/10.1021/ma034854q},
}

@Article{Shankar2001,
  author   = {Ravi Shankar and Anubhav Saxena and Ajaib S. Brar},
  journal  = {Journal of Organometallic Chemistry},
  title    = {Synthesis and reactivity of novel oligosilanes bearing functional carbosilane side chains},
  year     = {2001},
  issn     = {0022-328X},
  number   = {2},
  pages    = {262--270},
  volume   = {628},
  abstract = {New carbosilane monomers R1R2R3SiXSiH3 (X=CH2CH2 and CH(CH3); R1=H, R2=Me, R3=Ph (1a); R1=H, R2, R3=Ph (2a); R1, R2, R3=Et (3a) bearing primary and/or tertiary SiH groups undergo Cp2TiCl2/n-BuLi catalyzed dehydropolymerization selectively at the primary SiH site to afford the corresponding oligosilanes 1--3, [R1R2R3SiXSiH]n (n=12--15). Treatment of the oligosilanes 1 and 2 with methanol in the presence of a catalytic amount of biguanide base results in the chemoselective transformation of the pendant carbosilyl SiH to SiOMe groups, yielding the methoxy- substituted oligosilanes 4 and 5 (R1=OMe), respectively. The reaction of 3 with methanol under a similar base catalyzed conditions reveals only 5\% conversion of the skeletal SiH to SiOMe groups. The oligosilanes 1--5 are characterized by IR, UV, 1H, 13C, 29Si, (1H--29Si) HSQC-NMR spectroscopy, GPC and TGA.},
  doi      = {https://doi.org/10.1016/S0022-328X(01)00784-7},
  file     = {:Shankar2001 - Synthesis and Reactivity of Novel Oligosilanes Bearing Functional Carbosilane Side Chains.pdf:PDF},
  keywords = {polymer synthesis, NMR, gel permeation chromotography, thermogravimetric analysis, chemical shift},
  url      = {http://www.sciencedirect.com/science/article/pii/S0022328X01007847},
}

@Article{Ohta1991,
  author   = {Ohta, Hideo and Ando, Isao and Fujishige, Shoei and Kubota, Kenji},
  journal  = {Journal of Polymer Science, Part B: Polymer Physics},
  title    = {Molecular motion and 1H NMR relaxation of aqueous poly(N-isopropylacrylamide) solution under high pressure},
  year     = {1991},
  number   = {8},
  pages    = {963--968},
  volume   = {29},
  abstract = {In order to obtain useful information about the molecular motion and structure of poly(N-isopropylacrylamide) (PNiPAM) in aqueous solution, proton spin-lattice relaxation times, proton spin-spin relaxation times, and volume changes were measured at pressures from 1 to 400 kg/cm2 as a function of temperature. We found that the molecular motion and the structure of water and PNiPAM in PNiPAM/water solution transitionally change at gelation temperature (31{$^{\circ}$}C). The effect of pressure on such transitional changes is studied. It is suggested that application of pressure to the system prevents the gelation.},
  doi      = {10.1002/polb.1991.090290806},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.1991.090290806},
  file     = {:Ohta1991 - Molecular Motion and 1H NMR Relaxation of Aqueous Poly(N Isopropylacrylamide) Solution under High Pressure.pdf:PDF},
  keywords = {PNIPAM, NMR review},
  printed  = {printed},
  ranking  = {rank5},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.1991.090290806},
}

@Article{SierraMartin2014,
  author   = {Benjamin Sierra-Martin and Jorge Rubio Retama and Marco Laurenti and Antonio Fern{\'{a}}ndez Barbero and Enrique L{\'{o}}pez Cabarcos},
  journal  = {Advances in Colloid and Interface Science},
  title    = {Structure and polymer dynamics within PNIPAM-based microgel particles},
  year     = {2014},
  issn     = {0001-8686},
  note     = {Special Issue in honor of Bjorn Lindman},
  pages    = {113--123},
  volume   = {205},
  abstract = {The synthesis of temperature-responsive microgels of poly(N-isopropylacrylamide) (PNIPAM) was first reported in 1986 and, since then, there have been hundreds of publications describing the preparation, characterization and applications of these systems. This paper reviews the developments concerning the study of the structure of PNIPAM-based microgels performed over the last years using small angle neutron scattering (SANS) and also the investigations of the polymer-chain dynamics within the microgels carried out with incoherent elastic and quasielastic neutron scattering, and pulse field gradient nuclear magnetic resonance (PFG-NMR) techniques. Furthermore, the self-diffusion coefficient of the water molecules within the microgel, determined by means of solvent relaxation NMR, is also discussed as a function of the polymer volume fraction of the microgels.},
  doi      = {https://doi.org/10.1016/j.cis.2013.11.001},
  file     = {:SierraMartin2014 - Structure and Polymer Dynamics within PNIPAM Based Microgel Particles.pdf:PDF},
  keywords = {Microgel, PNIPAM, SANS, PFG, NMR, review, neutron},
  url      = {http://www.sciencedirect.com/science/article/pii/S0001868613001462},
}

@Article{Pelton2010,
  author   = {Robert Pelton},
  journal  = {Journal of Colloid and Interface Science},
  title    = {Poly(N-isopropylacrylamide) (PNIPAM) is never hydrophobic},
  year     = {2010},
  issn     = {0021-9797},
  number   = {2},
  pages    = {673--674},
  volume   = {348},
  abstract = {PNIPAM chains have hydrophobic and hydrophilic domains below and above the LCST. Temperature dependent interactions between PNIPAM and solutes arise because of changes in the local environment around the hydrophobic isopropyl domains. Below the LCST the isopropyl groups are surrounded by water, whereas above the LCST the hydrophobic groups are in contact with both water and polymer segments. Contrary to numerous claims in the literature, PNIPAM is not a hydrophobic material at temperatures above the LCST.},
  doi      = {https://doi.org/10.1016/j.jcis.2010.05.034},
  file     = {:Pelton2010 - Poly(N Isopropylacrylamide) (PNIPAM) Is Never Hydrophobic.pdf:PDF},
  keywords = {PNIPAM},
  url      = {http://www.sciencedirect.com/science/article/pii/S0021979710005618},
}

@Article{SierraMartin2005,
  author   = {B. Sierra-Martin and M. S. Romero-Cano and Terence Cosgrove and B. Vincent and A. Fernandez-Barbero},
  journal  = {Colloids and Surfaces A: Physicochemical and Engineering Aspects},
  title    = {Solvent relaxation of swelling PNIPAM microgels by NMR},
  year     = {2005},
  issn     = {0927-7757},
  note     = {Liquids and MesoScience},
  pages    = {296--300},
  volume   = {270-271},
  abstract = {The dynamics of solvent inside swelling microgel particles is studied using 1H NMR. Solvent relaxation is sensitive to the microgel volume transition after temperature changes, showing the effect of the local environmental conditions on solvent confinement. A microscopic view of the volume phase transition of microgel particles is then shown. NMR measurements indicate that solvent dynamics is controlled only by the swelling degree of the microgel particles. Along the volume phase transition, the collapse of the polymer network restricts the mobility of bound water defining the confinement state. The effect of the amount of microgel polymer on the solvent molecules mobility is also investigated. In the collapsed state, water molecules still exist inside the microgel particles, being strongly confined within the polymer network. Despite that there are not many bound molecules under this circumstance, they contribute so strongly to the total averaged relaxation time that the behaviour is controlled by the presence of those. On the other hand, the solvent molecules were found to be weakly constrained for swollen microgels.},
  doi      = {https://doi.org/10.1016/j.colsurfa.2005.06.044},
  file     = {:SierraMartin2005 - Solvent Relaxation of Swelling PNIPAM Microgels by NMR.pdf:PDF},
  keywords = {PNIPAM, Microgel, NMR},
  url      = {http://www.sciencedirect.com/science/article/pii/S0927775705004656},
}

@Article{Wu2009,
  author   = {Wu, Tao and Zou, Gang and Hu, Jinming and Liu, Shiyong},
  journal  = {Chemistry of Materials},
  title    = {Fabrication of Photoswitchable and Thermotunable Multicolor Fluorescent Hybrid Silica Nanoparticles Coated with Dye-Labeled Poly(N-isopropylacrylamide) Brushes},
  year     = {2009},
  number   = {16},
  pages    = {3788--3798},
  volume   = {21},
  abstract = {We report on the fabrication of hybrid silica nanoparticles densely grafted with thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) brushes with inner and outer layers selectively labeled with fluorescence resonance energy transfer (FRET) donors, 4-(2-acryloyloxyethylamino)-7-nitro-2,1,3-benzoxadiazole (NBDAE), and photoswitchable acceptors, 1$\prime$-(2-methacryloxyethyl)-3$\prime$,3$\prime$-dimethyl-6-nitro-spiro(2H-1-benzo-pyran-2,2$\prime$-indoline) (SPMA), respectively, via surface-initiated sequential atom transfer radical polymerization (ATRP). P(NIPAM-co-NBDAE)-b-P(NIPAM-co-SPMA) brushes at the surface of silica core exhibit collapse in the broad temperature range of 20$-$37 {$^{\circ}$}C. UV irradiation of the aqueous dispersion of hybrid silica nanoparticles induces the transformation of SPMA moieties in the outer layer of polymer brushes from nonfluorescent spiropyran (SP) form to fluorescent merocyanine (MC) form, leading to occurrence of the FRET process between NBDAE and SPMA residues. Most importantly, the FRET efficiency can be facilely tuned via thermo-induced collapse/swelling of P(NIPAM-co-NBDAE)-b-P(NIPAM-co-SPMA) brushes by changing the relative distance between donor and acceptor species located within the inner and outer layers of polymer brushes, respectively. Thus, hybrid silica nanoparticles coated with P(NIPAM-co-NBDAE)-b-P(NIPAM-co-SPMA) brushes can serve as a sensitive ratiometric fluorescent thermometer. On the other hand, when the hybrid nanoparticle dispersion was irradiated with visible light again after UV irradiation, the MC form of SPMA moieties reverts back to the nonfluorescent SP form, leading to the turn-off of FRET process. Overall, aqueous dispersion of this novel type of hybrid silica nanoparticle is capable of emitting multicolor fluorescence, which can be facilely tuned by UV irradiation, visible light, and temperatures or a proper combination of these factors.},
  doi      = {10.1021/cm901072g},
  eprint   = {https://doi.org/10.1021/cm901072g},
  file     = {:Wu2009 - Fabrication of Photoswitchable and Thermotunable Multicolor Fluorescent Hybrid Silica Nanoparticles Coated with Dye Labeled Poly(N Isopropylacrylamide) Brushes.pdf:PDF},
  keywords = {PNIPAM, polymer synthesis},
  url      = {https://doi.org/10.1021/cm901072g},
}

@Article{Saunders1999,
  author   = {Brian R. Saunders and Brian Vincent},
  journal  = {Advances in Colloid and Interface Science},
  title    = {Microgel particles as model colloids: theory, properties and applications},
  year     = {1999},
  issn     = {0001-8686},
  number   = {1},
  pages    = {1--25},
  volume   = {80},
  abstract = {This review presents an overview of the literature concerning microgel particles with emphasis on work performed during the past 5 years. Microgel particles are cross-linked latex particles that are swollen in a good solvent. The particles are conveniently prepared by surfactant-free emulsion polymerisation (SFEP) and may be viewed as sterically stabilised particles without a core. The narrow particle size distribution combined with the inherent steric stabilisation of particles prepared by SFEP makes them ideal model systems for the study of solution-dependent phenomena (e.g. osmotic de-swelling). The poly(NIPAM) (NIPAM=N-isopropylacrylamide) microgel system is considered in detail in terms of swelling, rheological, small-angle neutron scattering (SANS) and kinetic data. The review concludes with a discussion of the internal structure for microgel particles and consideration of areas for further research.},
  comment  = {Surfactant-free emulsion polymerization (SFEP) is ideally suited to the preparation of poly(NIPAM). Typically, NIPAM is polymerised in the presence of persulfate and cross-linking monomer at a temperature of ~70°C. The particles gradually swell when the temperature is decreased with the maximum degree of swelling occurring around 32°C; this avoids the need to transfer the particles from a good to poor solvent after preparation. Fig. 3 shows the salient features of SFEP. Thermal decomposition of the ionic initiator (S_2O_8^{2-}) initiates free-radical polymerisation. The oligomers produced are surface active and form nuclei when the length of the oligomers exceeds the solubility limit of the solvent. The nuclei then undergo limited aggregation, thereby increasing the surface charge until electrostatic stabilisation is achieved [14]. Further particle growth occurs through absorption of monomer and/or oligomeric chains. This process results in a decrease in the concentration of oligomers to below the critical value required for particle formation. Polymerisation continues within the particles until another radical species enters the growing particle and termination occurs. The key feature of SFEP is that the particle nucleation period is very short (of the order of minutes) which ensures a narrow particle size distribution. The final particle size achieved by SFEP increases with electrolyte concentration and decreasing initiator concentration [14].},
  doi      = {https://doi.org/10.1016/S0001-8686(98)00071-2},
  file     = {:Saunders1999 - Microgel Particles As Model Colloids_ Theory, Properties and Applications.pdf:PDF},
  keywords = {Microgel, review, PNIPAM, polymer synthesis, rheology, SANS},
  url      = {http://www.sciencedirect.com/science/article/pii/S0001868698000712},
}

@Article{Conley2016,
  author   = {Gaurasundar M. Conley and Sofi N{\"{o}}jd and Marco Braibanti and Peter Schurtenberger and Frank Scheffold},
  journal  = {Colloids and Surfaces A: Physicochemical and Engineering Aspects},
  title    = {Superresolution microscopy of the volume phase transition of pNIPAM microgels},
  year     = {2016},
  issn     = {0927-7757},
  pages    = {18--23},
  volume   = {499},
  abstract = {Hierarchical polymer structures such as pNIPAM microgels have been extensively studied for their ability to undergo structural and physical transformations that can be controlled by external stimuli such as temperature, pH or solvent composition. However, a direct three-dimensional visualization of individual particles in-situ has so far been hindered by insufficient resolution, with optical microscopy, or contrast, with electron microscopy. In recent years superresolution microscopy techniques have emerged that can provide nanoscopic optical resolution. Here we report on the in-situ superresolution microscopy of dye-labelled submicron sized pNIPAM microgels revealing the internal density profile during swelling and collapse of individual particles. Using direct STochastic Optical Reconstruction Microscopy (dSTORM) we demonstrate a lateral optical resolution of 30nm and an axial resolution of 60nm.},
  doi      = {https://doi.org/10.1016/j.colsurfa.2016.03.010},
  file     = {:Conley2016 - Superresolution Microscopy of the Volume Phase Transition of PNIPAM Microgels.pdf:PDF},
  keywords = {Microgel, PNIPAM},
  url      = {http://www.sciencedirect.com/science/article/pii/S0927775716301388},
}

@Article{SierraMartin2005a,
  author     = {Sierra-Martin, B. and Choi, Y. and Romero-Cano, M. S. and Cosgrove, T. and Vincent, B. and Fern{\'{a}}ndez-Barbero, A.},
  journal    = {Macromolecules},
  title      = {Microscopic Signature of a Microgel Volume Phase Transition},
  year       = {2005},
  number     = {26},
  pages      = {10782--10787},
  volume     = {38},
  abstract   = {This paper discusses the dynamics of water molecules in poly(NIPAM) microgel dispersions. 1H NMR spectroscopy is used to determine the self-diffusion coefficient of the water molecules. The capability of the microgel particles to restrict the motion of water molecules depends on the degree of swelling, as determined by dynamic light scattering. The dependence of molecular diffusion on the network density is established. This is tested against Yasuda's free volume model and Ogston's obstruction model, which have been modified to account for the dependence of the network pore size on the extent of swelling.},
  comment    = {Calculate diffusion coeffictients from T2 relaxation. (Need to validate SED relation first?)},
  doi        = {10.1021/ma0510284},
  eprint     = {https://doi.org/10.1021/ma0510284},
  file       = {:SierraMartin2005a - Microscopic Signature of a Microgel Volume Phase Transition.pdf:PDF},
  keywords   = {PNIPAM, NMR, diffusion, microgel, DLS, TEM, T2 relaxation, CPMG},
  printed    = {printed},
  ranking    = {rank4},
  readstatus = {read},
  url        = {https://doi.org/10.1021/ma0510284},
}

@Article{Morgan2002,
  author   = {Morgan, Andre M. and Pollack, Steven K. and Beshah, Kebede},
  journal  = {Macromolecules},
  title    = {Synthesis and Multidimensional NMR Characterization of PDMS-b-PS Prepared by Combined Anionic Ring-Opening and Nitroxide-Mediated Radical Polymerization},
  year     = {2002},
  number   = {11},
  pages    = {4238--4246},
  volume   = {35},
  abstract = {The synthesis of PDMS-b-PS copolymers by anionic and nitroxide-mediated radical polymerization (NMRP) is discussed. Hydride end-capped PDMS is hydrosilylated with an allylic alkoxyamine to form a TEMPO functional macroinitiator. The macroinitiator is reacted with styrene to form diblock copolymer. NMRP of styrene initiated by the PDMS macroinitiator (Mw/Mn = 1.22) gave diblocks with Mw/Mn between 1.28 and 1.35. Microstructure characterization by one (1D) and two (2D) dimensional solution NMR verified the composition of the copolymer end groups and block junction. LC-NMR analysis shows that nearly homopolymer free diblocks were obtained by this method. Solid-state NMR analysis verified a phase-separated morphology.},
  doi      = {10.1021/ma0114178},
  eprint   = {https://doi.org/10.1021/ma0114178},
  file     = {:Morgan2002 - Synthesis and Multidimensional NMR Characterization of PDMS B PS Prepared by Combined Anionic Ring Opening and Nitroxide Mediated Radical Polymerization.pdf:PDF},
  keywords = {PDMS, polystyrene, NMR, chemical shift, polymer synthesis, block copolyer},
  url      = {https://doi.org/10.1021/ma0114178},
}

@Article{VanderBeek1991,
  author   = {Van der Beek, G. P. and Stuart, M. A. Cohen. and Cosgrove, T.},
  journal  = {Langmuir},
  title    = {Polymer adsorption and desorption studies via proton NMR relaxation of the solvent},
  year     = {1991},
  number   = {2},
  pages    = {327--334},
  volume   = {7},
  abstract = {Proton NMR relaxation measurements of the sovlent in silica dispersions have been carried out as a function of polymer coverage, solution pH, and added displacer. We find that the solvent spin-lattice relaxation rate is enhanced as a result of polymer adsorption and that, with proper calibration, this enhancement can be used to obtain the adsorbed amount in trains. The results are consistent with bound fraction estimates obtained from the Scheutjens-Fleer theory of polymer adsorption and also with recent results on the hydrodynamic thickness of adsorbed polymer layers. Besides information about the conformation of adsorbed polymers, the effective polymer adsorption energy can also be determined by this NMR technique.},
  doi      = {10.1021/la00050a022},
  eprint   = {https://doi.org/10.1021/la00050a022},
  file     = {:VanderBeek1991 - Polymer Adsorption and Desorption Studies Via Proton NMR Relaxation of the Solvent.pdf:PDF},
  keywords = {NMR, T1 relaxation, solvent dynamics},
  url      = {https://doi.org/10.1021/la00050a022},
}

@Article{Groves2017,
  author    = {Groves, Patrick},
  journal   = {Polymer Chemistry},
  title     = {Diffusion ordered spectroscopy (DOSY) as applied to polymers},
  year      = {2017},
  pages     = {6700--6708},
  volume    = {8},
  abstract  = {Diffusion ordered spectroscopy (DOSY) is a well established NMR method that reports diffusion coefficients for individual resonances in NMR spectra. DOSY is primarily used to analyse mixtures of small molecules and the oligomeric state of biomolecules. DOSY has also been used to analyse polymers and investigate micellization properties but different acquisition and processing parameters are recommended for polymers. In particular{,} the molecular weight dispersion of polymers and micelles are at odds with the physical limits of DOSY. Confidence in the quality of published DOSY data is lowered when critical parameters are poorly optimized or not reported. This tutorial provides a {\textquoteleft}top ten{\textquoteright} of DOSY parameters{,} an explanation of their source and importance{,} as well as suggested starting parameters and optimization for polymer/micelle samples. By following these guidelines{,} DOSY can emerge from being an occasional method to confirm data obtained from other experimental techniques{,} to one that provides strong physical evidence in its own right as the originators of DOSY intended.},
  doi       = {10.1039/C7PY01577A},
  file      = {:Groves2017 - Diffusion Ordered Spectroscopy (DOSY) As Applied to Polymers.pdf:PDF},
  issue     = {44},
  keywords  = {NMR, DOSY},
  publisher = {The Royal Society of Chemistry},
  url       = {http://dx.doi.org/10.1039/C7PY01577A},
}

@Article{Mears1998,
  author   = {Mears, S. J. and Cosgrove, T. and Thompson, L. and Howell, I.},
  journal  = {Langmuir},
  title    = {Solvent Relaxation NMR Measurements on Polymer, Particle, Surfactant Systems},
  year     = {1998},
  number   = {5},
  pages    = {997--1001},
  volume   = {14},
  abstract = {1H NMR solvent relaxation has been used to probe the effect of SDS on the adsorption of poly(ethylene oxide) at the silica$-$water interface. In the absence of SDS an enhancement in the water relaxation rate resulting from the adsorption of PEO was observed while for PEO in the absence of particles only a negligible enhancement was observed. However, upon addition of SDS to the PEO/silica system a sequential reduction in the relaxation rate with increasing SDS was found. The results are discussed in terms of the levels of adsorbed polymer and its conformation at the interface.},
  comment  = {Time scale of polymer proton relaxation vs. solvent proton relaxation},
  doi      = {10.1021/la970744z},
  eprint   = {https://doi.org/10.1021/la970744z},
  file     = {:Mears1998 - Solvent Relaxation NMR Measurements on Polymer, Particle, Surfactant Systems.pdf:PDF},
  keywords = {NMR, solvent relaxation},
  url      = {https://doi.org/10.1021/la970744z},
}

@Article{Hubbard1963,
  author    = {Hubbard, Paul S.},
  journal   = {Physical Review},
  title     = {Nuclear Magnetic Relaxation by Intermolecular Dipole-Dipole Interactions},
  year      = {1963},
  month     = jul,
  pages     = {275--282},
  volume    = {131},
  abstract  = {The contribution of intermolecular dipole-dipole interactions to the nuclear magnetic relaxation of identical spin-$\sfrac{1}{2}$ nuclei at equivalent positions in spherical molecules in a liquid is calculated. The assumptions made are that: (1), the effect of cross correlations of different dipole-dipole interactions is negligible, so that the relaxations of the longitudinal and transverse components of the nuclear magnetization are simple exponential decays with relaxation times T1 and T2, respectively; (2), the motions of the molecules can be considered to be translational and rotational diffusion; and (3), the correlation time $\tau$0 $\equiv$ (2a^2/D), where  a  is the radius of a molecule and  D  is the translational diffusion coefficient, is sufficiently short that  ($\omega$0$\tau$0)^2$\ll$1, where $\omega$0 is the Larmor frequency of the nuclei. As a result of the short correlation time assumption (3), the contributions of the intermolecular interactions to (1/T1) and (1/T2) are found to be the same and are given by an infinite series, the first three terms of which are (1/T1)''=(1/T2)''=n$\phi\gamma$^4ℏ^2/(5aD)[1+0.233(b/a)^2+0.15(b/a)^4+$\cdots$], where n is the number of spins per unit volume, $\gamma$ is the gyromagnetic ratio of each nucleus, and b is the distance of each nucleus from the center of the molecule in which it is contained. The first term in the series is the result obtained in previous calculations in which the effect of the rotations of the molecules was neglected. In a typical case in which  (b/a)$\approx$1/2, the second and third terms are 6.8% of the first term.},
  doi       = {10.1103/PhysRev.131.275},
  file      = {:Hubbard1963 - Nuclear Magnetic Relaxation by Intermolecular Dipole Dipole Interactions.pdf:PDF},
  issue     = {1},
  keywords  = {NMR, relaxation},
  numpages  = {0},
  publisher = {American Physical Society},
  url       = {https://link.aps.org/doi/10.1103/PhysRev.131.275},
}

@Article{Price1989,
  author   = {William S. Price and Philip W. Kuchel and Bruce A. Cornell},
  journal  = {Biophysical Chemistry},
  title    = {Microviscosity of human erythrocytes studied with hypophosphite and 31P-NMR},
  year     = {1989},
  issn     = {0301-4622},
  number   = {3},
  pages    = {205--215},
  volume   = {33},
  abstract = {A 31P-NMR method, which complements earlier 13C-NMR procedures for probing the intra-erythrocyte microenvironment, is described. Hypophosphite is an almost unique probe of the erythrocyte microenvironment, since it is rapidly transported into the cell via the band 3 protein, and intra- and extracellular populations give rise to distinct resonances in the 31P-NMR spectrum. Relaxation mechanisms of the 31P nucleus in the hypophosphite ion were shown to be spin-rotation and dipole-dipole. Analysis of longitudinal relaxation rates in human erythrocytes, haemolysates and concentrated glycerol solutions allowed the determination of microviscosity using the Debye equation. Bulk viscosities of lysates and glycerol solutions were measured using Ostwald capillary viscometry. Translational diffusion coefficients were then calculated from the viscosity estimates using the Stokes-Einstein equation. The results with a range of solvent systems showed that {\textquoteleft}viscosity{\textquoteright} is a relative phenomenon and that bulk (i.e., macro-) viscosity is therefore not necessarily related to the NMR-determined viscosity. The intracellular NMR-determined viscosities from red cells, ranging in volume from 65.5 to 100.1 fl, varied from 2.10 to 2.67 mPa s. This is consistent with the translational diffusion coefficients of the hypophosphite ion altering by only 20%, whereas the values determined from bulk viscosity measurements conducted on lysates of these cells are consistent with a 230% change.},
  doi      = {https://doi.org/10.1016/0301-4622(89)80022-5},
  file     = {:PRICE1989205 - Microviscosity of Human Erythrocytes Studied with Hypophosphite and 31P NMR.pdf:PDF},
  keywords = {NMR, P-, Erythrocyte, Microviscosity, Hypophosphite ion, T1 relaxation, Spin-rotation relaxation, (Human)},
  url      = {http://www.sciencedirect.com/science/article/pii/0301462289800225},
}

@Article{Heskins1968,
  author    = {M. Heskins and J. E. Guillet},
  journal   = {Journal of Macromolecular Science, Part A: Pure and Applied Chemistry},
  title     = {Solution Properties of Poly(N-isopropylacrylamide)},
  year      = {1968},
  number    = {8},
  pages     = {1441--1455},
  volume    = {2},
  abstract  = {Aqueous solutions of poly(N-isopropyl acrylamide) show a lower critical solution temperature. The thermodynamic properties of the system have been evaluated from the phase diagram and the heat absorbed during phase separation and the phenomenon is ascribed to be primarily due to an entropy effect. From viscosity, sedimentation, and light-scattering studies of solutions close to conditions of phase separation, it appears that aggregation due to formation of nonpolar and intermolecular hydrogen bonds is important. In addition, a weakening of the ordering effect of the water-amide hydrogen bonds as the temperature is raised contributes to the stability of the two-phase system.},
  comment   = {PNIPAM LCST observed for the (first?) time},
  doi       = {10.1080/10601326808051910},
  eprint    = {https://doi.org/10.1080/10601326808051910},
  file      = {:Heskins1968 - Solution Properties of Poly(N Isopropylacrylamide).pdf:PDF},
  keywords  = {PNIPAM},
  publisher = {Taylor and Francis},
  url       = {https://doi.org/10.1080/10601326808051910},
}

@Article{Zhang1995,
  author   = {Zhang, Ju and Pelton, Robert and Deng, Yulin},
  journal  = {Langmuir},
  title    = {Temperature-Dependent Contact Angles of Water on Poly(N-isopropylacrylamide) Gels},
  year     = {1995},
  number   = {6},
  pages    = {2301--2302},
  volume   = {11},
  doi      = {10.1021/la00006a071},
  eprint   = {https://doi.org/10.1021/la00006a071},
  file     = {:Zhang1995 - Temperature Dependent Contact Angles of Water on Poly(N Isopropylacrylamide) Gels.pdf:PDF},
  keywords = {PNIPAM, contact angle, microgel},
  url      = {https://doi.org/10.1021/la00006a071},
}

@InBook{Orski,
  author    = {Orski, Sara V. and Page, Kirt A. and Chan, Edwin P. and Beers, Kathryn L.},
  chapter   = {6},
  pages     = {91--115},
  title     = {Model Polymer Thin Films To Measure Structure and Dynamics of Confined, Swollen Networks},
  abstract  = {In this chapter, we discuss applying X-ray reflectivity to study the structure and dynamics of dense and ultrathin polymer films upon exposure to solvent vapors. These vapor swelling studies permit the measurement of thermodynamic parameters using established mean-field models such as Flory-Huggins, Flory-Rehner, and Painter-Shenoy to understand the elastic contributions to swelling, as well as the polymer solvent interaction parameter of these confined films. This chapter describes the various experimental approaches to leverage mean-field theories towards describing and understanding swelling behavior of thin film networks and brushes, the applications, and their limitations.},
  booktitle = {Gels and Other Soft Amorphous Solids},
  doi       = {10.1021/bk-2018-1296.ch006},
  eprint    = {https://pubs.acs.org/doi/pdf/10.1021/bk-2018-1296.ch006},
  keywords  = {X-ray, polymer film, swelling},
  url       = {https://pubs.acs.org/doi/abs/10.1021/bk-2018-1296.ch006},
}

@Article{Duinen2019,
  author   = {van Duinen, David and Butt, Hans-J{\"{u}}rgen and Berger, R{\"{u}}diger},
  journal  = {Langmuir},
  title    = {Two-Stage Collapse of PNIPAM Brushes: Viscoelastic Changes Revealed by an Interferometric Laser Technique},
  year     = {2019},
  note     = {PMID: 31633361},
  number   = {48},
  pages    = {15776--15783},
  volume   = {35},
  abstract = {Many temperature-responsive polymers exhibit a single-phase transition at the lower critical solution temperature (LCST). One exception is poly(N-isopropylacryamide) (PNIPAM). PNIPAM brush layers (51 $\pm$ 3 nm thick) that are end-grafted onto glass beads collapse in two stages. The viscoelastic changes of a PNIPAM brush layers were investigated with an interferometric laser method at different temperatures. This method is able to measure the two-stage collapse of beads coated with a polymer brush layer. When these beads are situated close to a hydrophilic glass surface, they exhibit Brownian motion. As this Brownian motion changes with temperature, the collapse of the polymer layer is revealed. The characteristic spectrum of the Brownian motion of beads is modeled by a damped harmonic oscillator, where the polymer layer acts as both spring and damping elements. The change of the Brownian motion spectrum with temperature indicates two transitions of the PNIPAM brush layer, one at 36 {$^{\circ}$}C and one at 46 {$^{\circ}$}C. We attribute the first transition to the LCST volume collapse of PNIPAM. Here, changes of the density and viscosity of the brush dominate. The second transition is dominated by a stiffening of the brush layer.},
  doi      = {10.1021/acs.langmuir.9b03205},
  eprint   = {https://doi.org/10.1021/acs.langmuir.9b03205},
  file     = {:Duinen2019 - Two Stage Collapse of PNIPAM Brushes_ Viscoelastic Changes Revealed by an Interferometric Laser Technique.pdf:PDF},
  keywords = {PNIPAM, polymer brush, interferometer},
  url      = {https://doi.org/10.1021/acs.langmuir.9b03205},
}

@Article{Yim2005,
  author    = {Yim, H. and Kent, M. S. and Satija, S. and Mendez, S. and Balamurugan, S. S. and Balamurugan, S. and Lopez, G. P.},
  journal   = {Physical Review E},
  title     = {Evidence for vertical phase separation in densely grafted, high-molecular-weight poly($N$-isopropylacrylamide) brushes in water},
  year      = {2005},
  month     = nov,
  pages     = {051801},
  volume    = {72},
  abstract  = {The detailed conformational change of poly(N-isopropylacrylamide) (PNIPAM) brushes at high grafting density in D2O was investigated as a function of temperature using neutron reflection. PNIPAM chains were grafted at high surface density from gold and silicon oxide surfaces by atom transfer radical polymerization. Whereas single layer profiles were observed for temperatures below and above the transition region, bilayer profiles were observed for a narrow range of temperatures near the transition. This nonmonotonic change in the concentration profile with temperature is discussed in the context of theoretical models of vertical phase separation within a brush.},
  doi       = {10.1103/PhysRevE.72.051801},
  file      = {:Yim2005 - Evidence for Vertical Phase Separation in Densely Grafted, High Molecular Weight Poly($N$ Isopropylacrylamide) Brushes in Water.pdf:PDF},
  issue     = {5},
  keywords  = {PNIPAM, neutron, ATRP, vertical phase separation},
  numpages  = {7},
  publisher = {American Physical Society},
  url       = {https://link.aps.org/doi/10.1103/PhysRevE.72.051801},
}

@Article{Humphreys2019,
  author    = {Humphreys, Ben A. and Prescott, Stuart W. and Murdoch, Timothy J. and Nelson, Andrew and Gilbert, Elliot P. and Webber, Grant B. and Wanless, Erica J.},
  journal   = {Soft Matter},
  title     = {Influence of molecular weight on PNIPAM brush modified colloidal silica particles},
  year      = {2019},
  pages     = {55--64},
  volume    = {15},
  abstract  = {The effect of molecular weight and temperature on the phase transition and internal structure of poly(N-isopropylacrylamide) brush modified colloidal silica particles was investigated using dynamic light scattering (DLS) and small angle neutron scattering (SANS) between 15 and 45 {$^{\circ}$}C. Dry particle analysis utilising transmission electron microscopy (TEM){,} Fourier-transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) all confirmed the thickness of the polymer brush shell increased as a function of polymerisation time. Hydrodynamic diameter and electrophoretic mobility results revealed that the brush modified particles transitioned from swollen shells to a collapsed conformation between 15 and 35 {$^{\circ}$}C. The dispersions were electrosterically stabilised over the entire temperature range investigated{,} with minimal thermal hysteresis recorded. Modelling of the hydrodynamic diameter enabled the calculation of a lower critical solution temperature (LCST) which increased as a function of brush thickness. The internal structure determined via SANS showed a swollen brush at low temperatures (18 and 25 {$^{\circ}$}C) which decayed radially away from the substrate{,} while a collapsed block-like conformation with 60% polymer volume fraction was present at 40 {$^{\circ}$}C. Radial phase separation was evident at intermediate temperatures (30 and 32.5 {$^{\circ}$}C) with the lower molecular weight sample having a greater volume fraction of polymer in the dense inner region at these temperatures.},
  doi       = {10.1039/C8SM01824C},
  file      = {:Humphreys2019 - Influence of Molecular Weight on PNIPAM Brush Modified Colloidal Silica Particles.pdf:PDF},
  issue     = {1},
  keywords  = {PNIPAM, polymer bruh, spherical brush, molecular weight, DLS, SANS, TEM, infrared, thermogravimetric analysis, LCST, radial phase separation},
  publisher = {The Royal Society of Chemistry},
  url       = {http://dx.doi.org/10.1039/C8SM01824C},
}

@Article{Humphreys2019a,
  author   = {Humphreys, Ben A. and Johnson, Edwin C. and Wanless, Erica J. and Webber, Grant B.},
  journal  = {Langmuir},
  title    = {Poly(N-isopropylacrylamide) Response to Salt Concentration and Anion Identity: A Brush-on-Brush Study},
  year     = {2019},
  note     = {PMID: 31339320},
  number   = {33},
  pages    = {10818--10830},
  volume   = {35},
  abstract = {The stability of poly(N-isopropylacrylamide) (PNIPAM) brush-modified colloidal silica particles was compared to asymmetric and symmetric PNIPAM brush direct force measurements in the presence of 1, 10, and 500 mM aqueous salt solution of KCl, KNO3, and KSCN between 10 and 45 {$^{\circ}$}C. Dynamic light scattering measurements highlighted subtle variations in the salt-mediated thermoresponse, while atomic force microscopy (AFM) force curves between a bare silica or PNIPAM brush-modified colloid probe and a planar PNIPAM brush elucidated differences in brush interactions. The AFM force curves in the presence of KCl primarily revealed steric interactions between the surfaces, while KNO3 and KSCN solutions exhibited electrosteric interactions on approach as a function of the chaotropic nature of the ion and the solution concentration. The symmetric PNIPAM brush interaction highlighted significant variations between KCl and KSCN at 1 and 500 mM concentrations, while the approach and retraction force curves were relatively similar at 10 mM concentration. The combination of these techniques enabled the stability of PNIPAM brush-modified colloidal dispersions in the presence of electrolyte to be better understood with specific ion binding and the solution Debye length playing a significant role.},
  doi      = {10.1021/acs.langmuir.9b00695},
  eprint   = {https://doi.org/10.1021/acs.langmuir.9b00695},
  file     = {:Humphreys2019a - Poly(N Isopropylacrylamide) Response to Salt Concentration and Anion Identity_ a Brush on Brush Study.pdf:PDF},
  keywords = {PNIPAM, polymer brush, spherical brush, ionic strength, DLS, thermoresponsive, AFM, colloid stabilization},
  url      = {https://doi.org/10.1021/acs.langmuir.9b00695},
}

@Article{Humphreys2016,
  author    = {Humphreys, Ben A. and Willott, Joshua D. and Murdoch, Timothy J. and Webber, Grant B. and Wanless, Erica J.},
  journal   = {Physical Chemistry Chemical Physics},
  title     = {Specific ion modulated thermoresponse of poly(N-isopropylacrylamide) brushes},
  year      = {2016},
  pages     = {6037--6046},
  volume    = {18},
  abstract  = {The influence of specific anions on the equilibrium thermoresponse of poly(N-isopropylacrylamide) (pNIPAM) brushes has been studied using in situ ellipsometry{,} quartz crystal microbalance with dissipation (QCM-D) and static contact angle measurements between 20 and 45 {$^{\circ}$}C in the presence of up to 250 mM acetate and thiocyanate anions in water. The thickness and changes in dissipation exhibited a broad swelling transition spanning approximately 15 {$^{\circ}$}C from collapsed (high temperatures) to swollen conformation (low temperatures) while the brush surface wettability changed over approximately 2 {$^{\circ}$}C. In the presence of the kosmotropic acetate anions{,} the measured lower critical solution temperature (LCST) by the three techniques was very similar and decreased linearly as a function of ionic strength. Conversely{,} increasing the concentration of the chaotropic thiocyanate anions raised the LCST of the pNIPAM brushes with variation in the measured LCST between the three techniques increasing with ionic strength. The thickness of the pNIPAM brush was seen to progressively increase with increasing thiocyanate concentration at all temperatures. It is proposed that specific ion binding of the chaotropic thiocyanate anion with pNIPAM amide moieties increases the electrostatic intra- and intermolecular repulsion within and between pNIPAM chains. This allows the brush to begin to swell at higher temperatures and to an overall greater extent.},
  doi       = {10.1039/C5CP07468A},
  file      = {:Humphreys2016 - Specific Ion Modulated Thermoresponse of Poly(N Isopropylacrylamide) Brushes.pdf:PDF},
  issue     = {8},
  keywords  = {PNIPAM, ellipsometry, quartz crystal microbalance, contact angle, thermoresponsive, ionic strength, LCST},
  publisher = {The Royal Society of Chemistry},
  url       = {http://dx.doi.org/10.1039/C5CP07468A},
}

@Article{Zhu2007,
  author   = {Zhu, X. and Yan, C. and Winnik, F. M. and Leckband, D.},
  journal  = {Langmuir},
  title    = {End-Grafted Low-Molecular-Weight PNIPAM Does Not Collapse above the LCST},
  year     = {2007},
  note     = {PMID: 17190499},
  number   = {1},
  pages    = {162--169},
  volume   = {23},
  abstract = {The interfacial properties of end-grafted temperature-responsive poly(N-isopropylacryamide) (PNIPAM) were quantified by direct force measurements both above and below the lower critical solution temperature (LCST) of 32 {$^{\circ}$}C. The forces were measured between identical, opposing PNIPAM films and between a PNIPAM film and a lipid membrane. At the grafting densities and molecular weights investigated, the polymer extension did not change significantly above the LCST, and the polymers did not adhere. Below the LCST, the force$-$distance profiles suggest a vertical phase separation, which results in a diluter outer layer and a dense surface proximal layer. At large separations, the force profiles agree qualitatively with simple polymer theory but deviate at small separations. Importantly, at these low grafting densities and molecular weights, the end-grafted PNIPAM does not collapse above the LCST. This finding has direct implications for triggering liposomal drug release with end-grafted PNIPAM, but it increases the temperature range where these short PNIPAM chains function as steric stabilizers.},
  doi      = {10.1021/la061577i},
  eprint   = {https://doi.org/10.1021/la061577i},
  file     = {:Zhu2007 - End Grafted Low Molecular Weight PNIPAM Does Not Collapse above the LCST.pdf:PDF},
  keywords = {PNIPAM, thermoresponsive, molecular weigth, LCST, direct force, vertical phase separation, colloid stabilization, drug delivery, lipid bilayer},
  printed  = {printed},
  ranking  = {rank4},
  url      = {https://doi.org/10.1021/la061577i},
}

@Article{Mahalik2017,
  author   = {Mahalik, J. P. and Sumpter, Bobby G. and Kumar, Rajeev},
  journal  = {Langmuir},
  title    = {Attraction between Opposing Planar Dipolar Polymer Brushes},
  year     = {2017},
  note     = {PMID: 28763222},
  number   = {36},
  pages    = {9231--9240},
  volume   = {33},
  abstract = {We use a field theory approach to study the effects of permanent dipoles on interpenetration and free energy changes as a function of distance between two identical planar polymer brushes. Melts (i.e., solvent-free) and solvated brushes made up of polymers grafted on nonadsorbing substrates are studied. In particular, the weak coupling limit of the dipolar interactions is considered, which leads to concentration-dependent pairwise interactions, and the effects of orientational order are neglected. It is predicted that a gradual increase in the dipole moment of the polymer segments can lead to attractive interactions between the brushes at intermediate separation distances. Because classical theory of polymer brushes based on the strong stretching limit (SSL) and the standard self-consistent field theory (SCFT) simulations using the Flory{\textquoteright}s $\chi$ parameter always predicts repulsive interactions at all separations, our work highlights the importance of dipolar interactions in tailoring and accurately predicting forces between polar polymeric interfaces in contact with each other.},
  doi      = {10.1021/acs.langmuir.7b01566},
  eprint   = {https://doi.org/10.1021/acs.langmuir.7b01566},
  file     = {:Mahalik2017 - Attraction between Opposing Planar Dipolar Polymer Brushes.pdf:PDF},
  keywords = {polymer brush, planar brush, polymer melt},
  url      = {https://doi.org/10.1021/acs.langmuir.7b01566},
}

@Article{Zhang2007,
  author   = {Zhang, Yanjie and Furyk, Steven and Sagle, Laura B. and Cho, Younhee and Bergbreiter, David E. and Cremer, Paul S.},
  journal  = {Journal of Physical Chemistry C},
  title    = {Effects of Hofmeister Anions on the LCST of PNIPAM as a Function of Molecular Weight},
  year     = {2007},
  note     = {PMID: 18820735},
  number   = {25},
  pages    = {8916--8924},
  volume   = {111},
  abstract = {The effect of a series of sodium salts on the lower critical solution temperature (LCST) of poly(N-isopropylacrylamide), PNIPAM, was investigated as a function of molecular weight and polymer concentration with a temperature gradient microfluidic device under a dark-field microscope. In solutions containing sufficient concentrations of kosmotropic anions, the phase transition of PNIPAM was resolved into two separate steps for higher molecular weight samples. The first step of this two-step transition was found to be sensitive to the polymer's molecular weight and solution concentration, while the second step was not. Moreover, the binding of chaotropic anions to the polymer was also influenced by molecular weight. Both sets of results could be explained by the formation of intramolecular and intermolecular hydrogen-bonding between polymer chains. By contrast, the hydrophobic hydration of the isopropyl moieties and polymer backbone was found to be unaffected by either the polymer's molecular weight or solution concentration.},
  doi      = {10.1021/jp0690603},
  eprint   = {https://doi.org/10.1021/jp0690603},
  file     = {:Zhang2007 - Effects of Hofmeister Anions on the LCST of PNIPAM As a Function of Molecular Weight.pdf:PDF;:EffectsOfHofmeisterAnionsOnTheLCSTOFPNIPAMAsAFUnctionOfMolecularWeight_ZhangEtAl_JPC2007_SI.pdf:PDF},
  keywords = {PNIPAM, LCST, ionic strength, dark field, molecular weight},
  url      = {https://doi.org/10.1021/jp0690603},
}

@Article{Koenig2018,
  author   = {Koenig, Meike and Rodenhausen, Keith Brian and Rauch, Sebastian and Bittrich, Eva and Eichhorn, Klaus-Jochen and Schubert, Mathias and Stamm, Manfred and Uhlmann, Petra},
  journal  = {Langmuir},
  title    = {Salt Sensitivity of the Thermoresponsive Behavior of PNIPAAm Brushes},
  year     = {2018},
  note     = {PMID: 29356537},
  number   = {7},
  pages    = {2448--2454},
  volume   = {34},
  abstract = {We report investigations on the salt sensitivity of the thermoresponsive behavior of PNIPAAm brushes applying the quartz crystal microbalance coupled with spectroscopic ellipsometry technique. This approach enables a detailed study of the optical and mechanical behavior of the polymer coatings. Additional conclusions can be drawn from the difference between both techniques due to a difference in the contrast mechanism of both methods. A linear shift of the phase-transition temperature to lower temperatures with the addition of sodium chloride was found, similar to the behavior of free polymer chains in solution. The thermal hysteresis was found to be decreased by the addition of sodium chloride to the solution, hinting to the interaction of the ions with the amide groups of the polymer, whereby the formation of hydrogen bonds is hindered. The results of this study are of relevance to the application of PNIPAAm brushes in biological fluids and demonstrate the additional potential of the ion sensitivity besides the better known thermosensitivity.},
  doi      = {10.1021/acs.langmuir.7b03919},
  eprint   = {https://doi.org/10.1021/acs.langmuir.7b03919},
  file     = {:Koenig2018 - Salt Sensitivity of the Thermoresponsive Behavior of PNIPAAm Brushes.pdf:PDF},
  keywords = {PNIPAM, ionic strength, quartz crystal microbalance, ellipsometry, polymer brush},
  url      = {https://doi.org/10.1021/acs.langmuir.7b03919},
}

@Article{Plunkett2006,
  author   = {Plunkett, Kyle N. and Zhu, Xi and Moore, Jeffrey S. and Leckband, Deborah E.},
  journal  = {Langmuir},
  title    = {PNIPAM Chain Collapse Depends on the Molecular Weight and Grafting Density},
  year     = {2006},
  note     = {PMID: 16618173},
  number   = {9},
  pages    = {4259--4266},
  volume   = {22},
  abstract = {This study demonstrates that the thermally induced collapse of end-grafted poly(N-isopropylacrylamide) (PNIPAM) above the lower critical solution temperature (LCST) of 32{$^{\circ}$}C depends on the chain grafting density and molecular weight. The polymer was grafted from the surface of a self-assembled monolayer containing the initiator (BrC(CH3)2COO(CH2)11S)2, using surface-initiated atom transfer radical polymerization. Varying the reaction time and monomer concentration controlled the molecular weight, and diluting the initiator in the monolayer altered the grafting density. Surface force measurements of the polymer films showed that the chain collapse above the LCST decreases with decreasing grafting density and molecular weight. At T > LCST, the advancing water contact angle increases sharply on PNIPAM films of high molecular weight and grafting density, but the change is less pronounced with films of low-molecular-weight chains at lower densities. Below the LCST, the force$-$distance profiles exhibit nonideal polymer behavior and suggest that the brush architecture comprises dilute outer chains and much denser chains adjacent to the surface.},
  doi      = {10.1021/la0531502},
  eprint   = {https://doi.org/10.1021/la0531502},
  file     = {:Plunkett2006 - PNIPAM Chain Collapse Depends on the Molecular Weight and Grafting Density.pdf:PDF},
  keywords = {PNIPAM, molecular weight, SI-ATRP, contact angle},
  ranking  = {rank4},
  url      = {https://doi.org/10.1021/la0531502},
}

@Article{Korde2019,
  author   = {Korde, Jay M. and Kandasubramanian, Balasubramanian},
  journal  = {Industrial and Engineering Chemistry Research},
  title    = {Fundamentals and Effects of Biomimicking Stimuli-Responsive Polymers for Engineering Functions},
  year     = {2019},
  number   = {23},
  pages    = {9709--9757},
  volume   = {58},
  abstract = {Over the past few decades, reversible responsive polymer materials have received interest conjointly from academia as well as industry owing to their ability to adapt to the surrounding environment, change adhesion and wettability of copious species upon extraneous stimulus, and regulate transportation of molecules and ions. Stimuli-responsive polymers or macromolecules also exhibit the ability to convert biochemical and chemical signals into mechanical, thermal, optical, and electrical signals, and vice versa, for which they are utilized in an array of applications like {\textquotedblleft}smart{\textquotedblright} optical systems, drug delivery, diagnostics, and tissue engineering, in conjunction with coatings, textiles, biosensors, and microelectromechanical systems. Extensive exploration on reversible responsive polymeric systems for a variety of engineering functionalities has been done; however, no collection of all the information is available as such. This Review consolidates profuse studies of reversible responsive polymers utilized in an assorted array of functions, inclusive of sensors, drug delivery, smart and self-healing coatings, etc.},
  doi      = {10.1021/acs.iecr.9b00683},
  eprint   = {https://doi.org/10.1021/acs.iecr.9b00683},
  file     = {:Korde2019 - Fundamentals and Effects of Biomimicking Stimuli Responsive Polymers for Engineering Functions.pdf:PDF;:FundamentalsAndEffectsOfBiomimickingStimuliResponsivePolymersForEngineeringFunctions-Correction_KordeEtAl_IndustrEngineerChemistryResearch2020.pdf:PDF},
  keywords = {review, application focused, drug delivery, smart interfaces, application-focused},
  printed  = {printed},
  url      = {https://doi.org/10.1021/acs.iecr.9b00683},
}

@Article{Korde2020,
  author   = {Korde, Jay M. and Kandasubramanian, Balasubramanian},
  journal  = {Industrial and Engineering Chemistry Research},
  title    = {Correction to {\textquotedblleft}Fundamentals and Effects of Biomimicking Stimuli-Responsive Polymers for Engineering Functions{\textquotedblright}},
  year     = {2020},
  number   = {10},
  pages    = {4838--4841},
  volume   = {59},
  doi      = {10.1021/acs.iecr.0c00720},
  eprint   = {https://doi.org/10.1021/acs.iecr.0c00720},
  file     = {:FundamentalsAndEffectsOfBiomimickingStimuliResponsivePolymersForEngineeringFunctions_KordeEtAl_IndustrEngineerChemistryResearch2019.pdf:PDF},
  keywords = {review, application focused, drug delivery, smart interfaces, correction, application-focused},
  printed  = {printed},
  url      = {https://doi.org/10.1021/acs.iecr.0c00720},
}

@Article{RubioRetama2008,
  author   = {Rubio-Retama, J. and Frick, B. and Seydel, T. and Stamm, M. and Fernandez-Barbero, A. and L{\'{o}}pez-Cabarcos, E.},
  journal  = {Macromolecules},
  title    = {Polymer Chain Dynamics of Core$-$Shell Thermosensitive Microgels},
  year     = {2008},
  number   = {13},
  pages    = {4739--4745},
  volume   = {41},
  abstract = {Microgels of poly(N-isopropylacrylamide) (PNIPAM) have the ability to change size in response to temperature. PNIPAM microgels with 0.25 wt \% cross-linker content were used to investigate the molecular dynamics of the polymer chains in the swollen and collapsed states. The study was performed using incoherent elastic (IES) and quasielastic neutron scattering (IQNS), and pulsed field gradient NMR spectroscopy (PFG$-$NMR). From IES the volume transition is characterized by a sharp increase of the elastic intensity at the transition temperature. Using IQNS, a diffusive motion of the polymer chains was identified with self-diffusion coefficient D = 1.1 $\pm$ 0.2 $\times$ 10$-$11 m2/s at 290 K which decreases down to D = 8.6 $\pm$ 0.1 $\times$ 10$-$13 m2/s when the microgel deswells at 327 K. With PFG$-$NMR spectroscopy we measured two diffusion coefficients in the swollen state that are associated with regions of high and low cross-linking content in the microgel. IQNS and PFG$-$NMR spectroscopy measurements demonstrate that in the swollen state the polymer is behaving as if it is in solution whereas in the collapsed state it resembles as a solid material.},
  doi      = {10.1021/ma800668t},
  eprint   = {https://doi.org/10.1021/ma800668t},
  keywords = {PFG, DOSY, NMR, chemical shift, PNIPAM, microgel, thermosensitive, control parameter, neutron},
  url      = {https://doi.org/10.1021/ma800668t},
}

@Article{Tokuhiro1991,
  author   = {Tokuhiro, Tadashi and Amiya, Takayuki and Mamada, Akira and Tanaka, Toyoichi},
  journal  = {Macromolecules},
  title    = {NMR study of poly(N-isopropylacrylamide) gels near phase transition},
  year     = {1991},
  number   = {10},
  pages    = {2936--2943},
  volume   = {24},
  abstract = {NMR studies have been made on the nonionic and ionic poly(N-isopropylacrylamide) gels near their phase transition. The gels undergo continuous second-order volume phase transition or discontinuous first-order transitions in water in response to temperature changes. The results are compared with the NMR data on the nonionic and ionic poly(N-isopropylacrylamide) polymers, which undergo a phase separation in water. From the analysis of the proton NMR line shapes and relaxation times, we have characterized the environments and motions of the side groups and the backbone polymer chains in terms of molecular dynamic parameters and structures. Some of the results are as follows: (1) The phase transition was characterized by the emergence of a new broad peak in the collapsed state and the disappearance of high-resolution spectra observed in the swollen state. The relaxation behavior of the broad peak characterizes the collapsed state as a solidlike aggregate. (2) The ionic gels consist of two portions, stiff and rather mobile portions. The nonionic gel has a homogeneous structure. (3) There is no appreciable change in the motions of the methylene and methyne protons in the backbone chains throughout the discontinuous phase transition. They remain mobile. (4) The methyl proton in the N-isopropyl group has a large mobility in the swollen state, however, the mobility decreases substantially upon collapse of the gel. It continues to decrease with rising temperature in the collapsed state, and eventually the immobilized portion becomes a significant part of the broad peak.},
  doi      = {10.1021/ma00010a046},
  eprint   = {https://doi.org/10.1021/ma00010a046},
  file     = {:Tokuhiro1991 - NMR Study of Poly(N Isopropylacrylamide) Gels near Phase Transition.pdf:PDF},
  keywords = {NRM, chemical shift, PNIPAM, gel, microgel, thermoresponsive,},
  ranking  = {rank4},
  url      = {https://doi.org/10.1021/ma00010a046},
}

@Article{Larsson2001,
  author   = {Anders Larsson and Dirk Kuckling and Monika Sch{\"{o}}nhoff},
  journal  = {Colloids and Surfaces A: Physicochemical and Engineering Aspects},
  title    = {1H NMR of thermoreversible polymers in solution and at interfaces: the influence of charged groups on the phase transition},
  year     = {2001},
  issn     = {0927-7757},
  number   = {1},
  pages    = {185--192},
  volume   = {190},
  abstract = {The phase transition of thermoreversible polymers occurring at the lower critical solution temperature (LCST) is investigated by 1H NMR. Poly-N-isopropylacrylamide (PNIPAM) shows such a coil to globule transition at 32{$^{\circ}$}C in aqueous solution. To study the effect of charged polymer segments on the phase transition, the temperature dependent properties of PNIPAM and of a charged PNIPAM-copolymer, containing 10% carboxylic groups, are investigated in solution. Experiments are performed by 1H spectra and PFG-NMR diffusion measurements at different polymer concentrations. The 1H liquid signal is sharply decreasing at the phase transition temperature. The transition is found to be equally sharp for the copolymer as for the homopolymer at concentrations below and around the overlap concentration, whereas the transition is broadened at higher concentrations. Diffusion measurements prove that the conformation of the polymer coils is maintained with increasing temperature until close to the phase transition, apart from a minor decrease of the hydrodynamic radius at about 2{$^{\circ}$}C below the LCST. All data indicate identical phase transition properties of the copolymer as compared with the homopolymer. The introduction of charged groups (3% of monomers dissociated) has thus not altered the transition. Therefore, the copolymer is a suitable candidate for exhibiting a phase transition under electrostatic coupling conditions in layers. Both polymers are adsorbed to colloidal silica (Cab-O-Sil) and investigated by 1H NMR in order to monitor the phase transition in the restricted geometry of an adsorption layer. The liquid 1H intensities of both polymers are decreasing with temperature, this is interpreted as a phase transition of the loops and tails. The transition is substantially broader than in solution, especially at low surface coverage. Significant differences between the copolymer and the homopolymer are observed, since above the transition temperature a liquid signal from loops and tails of the copolymer is still observed. This is interpreted as a comparatively mobile arrangement of the copolymer layer, arising from electrostatic repulsion from the surface and between polymer segments, which is partly hindering globule formation.},
  cites    = {Larsson2001-1,Larsson2001-2,Larsson2001-3,Larsson2001-4,Larsson2001-5,Larsson2001-6,Larsson2001-7,Larsson2001-8,Larsson2001-9,Larsson2001-10,Larsson2001-11,Larsson2001-12,Larsson2001-13,Larsson2001-14,Larsson2001-15,Larsson2001-16,Larsson2001-17,Larsson2001-18,Larsson2001-19,Larsson2001-20},
  comment  = {In [^1H NMR] T_2 experiments performed with a solid echo, indeed a biexponential decay with a fast component of T_2 ~ 40 -- 50 ms is found, which is decaying too fast to be detected in a liquid type experiment.},
  doi      = {https://doi.org/10.1016/S0927-7757(01)00678-1},
  file     = {:Larsson2001 - 1H NMR of Thermoreversible Polymers in Solution and at Interfaces_ the Influence of Charged Groups on the Phase Transition.pdf:PDF},
  keywords = {LCST, NMR, PFG Diffusion, thermoresponsive, PNIPAM, chemical shift},
  url      = {http://www.sciencedirect.com/science/article/pii/S0927775701006781},
}

@Article{Deloche1982,
  author   = {B. Deloche and M. Beltzung and J. Herz},
  journal  = {Journal de Physique Lettres},
  title    = {Segmental order in a uniaxially constrained polydimethylsiloxane network: a deuterium magnetic resonance study},
  year     = {1982},
  number   = {22},
  pages    = {763--769},
  volume   = {43},
  doi      = {10.1051/jphyslet:019820043022076300},
  file     = {:Deloche1982 - Segmental Order in a Uniaxially Constrained Polydimethylsiloxane Network_ a Deuterium Magnetic Resonance Study.pdf:PDF},
  keywords = {PDMS, NMR, polymer network},
}

@Article{Pietrasik2007,
  author   = {Joanna Pietrasik and Brent S. Sumerlin and Hyung-il Lee and Roberto R. Gil and Krzysztof Matyjaszewski},
  journal  = {Polymer},
  title    = {Structural mobility of molecular bottle-brushes investigated by NMR relaxation dynamics},
  year     = {2007},
  issn     = {0032-3861},
  number   = {2},
  pages    = {496--501},
  volume   = {48},
  abstract = {The structural mobility of monomeric units of molecular bottle-brushes was studied by a systematic evaluation of NMR relaxation dynamics. The spin--spin relaxation time (T2) was determined by Carr--Purcell--Meiboom--Gill (CPMG) NMR spectroscopic measurements. T2 for protons that reside on the exterior and interior of the bottle-brush macromolecules varied with the grafting density and side chain length in bottle-brush copolymers. Poly((2-(2-bromopropionyloxy)ethyl methacrylate-stat-methyl methacrylate)-graft-butyl acrylate) (poly((BPEM-stat-MMA)-graft-PBA) was studied as a model brush copolymer. The T2 values for protons of MMA units in the brush backbone significantly decreased with increasing side chain length and grafting density of PBA. The mobility and relaxation times T2 for the side chain PBA protons decreased with grafting density. However, after initial increase, the relaxation times eventually decreased with PBA side chain length.},
  doi      = {https://doi.org/10.1016/j.polymer.2006.11.057},
  file     = {:Pietrasik2007 - Structural Mobility of Molecular Bottle Brushes Investigated by NMR Relaxation Dynamics.pdf:PDF},
  keywords = {brush copolymer, ATRP, bottlebrush, NMR, CPMG, T2 relaxation},
  printed  = {printed},
  ranking  = {rank4},
  url      = {http://www.sciencedirect.com/science/article/pii/S0032386106013140},
}

@Article{Carr1954,
  author    = {Carr, H. Y. and Purcell, E. M.},
  journal   = {Physical Review},
  title     = {Effects of Diffusion on Free Precession in Nuclear Magnetic Resonance Experiments},
  year      = {1954},
  month     = may,
  pages     = {630--638},
  volume    = {94},
  doi       = {10.1103/PhysRev.94.630},
  file      = {:Carr1954 - Effects of Diffusion on Free Precession in Nuclear Magnetic Resonance Experiments.pdf:PDF},
  issue     = {3},
  keywords  = {NMR, CPMG, Spin Echoes},
  numpages  = {0},
  publisher = {American Physical Society},
  url       = {https://link.aps.org/doi/10.1103/PhysRev.94.630},
}

@Article{Meiboom1958,
  author   = {Meiboom, S. and Gill, D.},
  journal  = {Review of Scientific Instruments},
  title    = {Modified Spin-Echo Method for Measuring Nuclear Relaxation Times},
  year     = {1958},
  number   = {8},
  pages    = {688--691},
  volume   = {29},
  doi      = {10.1063/1.1716296},
  eprint   = {https://doi.org/10.1063/1.1716296},
  keywords = {NMR, CPMG, Spin Echoes},
  url      = {https://doi.org/10.1063/1.1716296},
}

@Article{Huerlimann2001,
  author   = {M. D. H{\"{u}}rlimann},
  journal  = {Journal of Magnetic Resonance},
  title    = {Carr--Purcell Sequences with Composite Pulses},
  year     = {2001},
  issn     = {1090-7807},
  number   = {1},
  pages    = {109--123},
  volume   = {152},
  abstract = {We present novel Carr--Purcell-like sequences using composite pulses that exhibit improved performance in strongly inhomogeneous fields. The sequences are designed to retain the intrinsic error correction of the standard Carr--Purcell--Meiboom--Gill (CPMG) sequence. This is achieved by matching the excitation pulse with the refocusing cycle such that the initial transverse magnetization lies along the axis {\^{n}}B characterizing the overall rotation of the refocusing cycle. Such sequences are suitable for relaxation measurements. It is shown that in sufficiently inhomogeneous fields, the echo amplitudes have an initial transient modulation that is limited to the first few echoes and then decay with the intrinsic relaxation time of the sample. We show different examples of such sequences that are constructed from simple composite pulses. Sequences of the form 90{$^{\circ}$}0--(90{$^{\circ}$}90$-\theta$/2--$\theta$180$-\theta$/2--90{$^{\circ}$}90$-\theta$/2)n with $\theta\approx$90{$^{\circ}$} and 270{$^{\circ}$} generate signal over a bandwidth larger than that of the conventional CPMG sequence, resulting in an improved signal-to-noise ratio in inhomogeneous fields. The new sequence 127{$^{\circ}$}x,y--(127{$^{\circ}$}x--127{$^{\circ}$}$-$x)n only excites signal off-resonance with a spectrum that is bimodal, peaking at {{$\Delta$}}$\omega$0=$\pm\omega$1. Depending on the phase and exact timing of the first pulse, symmetric or antisymmetric excitation is obtained. We also demonstrate several new sequences with improved dependence on the RF field strength. The sequence (22.5{$^{\circ}$}67.5--90{$^{\circ}$}$-$22.5)--(90{$^{\circ}$}67.5--45{$^{\circ}$}157.5--90{$^{\circ}$}67.5)n has the property that the phase of the signal depends on B1, allowing coarse B1 imaging in a one-dimensional experiment.},
  doi      = {https://doi.org/10.1006/jmre.2001.2370},
  keywords = {NMR, CPMG, Spin Echoes, composite pulse},
  url      = {http://www.sciencedirect.com/science/article/pii/S1090780701923705},
}

@Article{Tu2017,
  author   = {Xiaoyan Tu and Chao Meng and Zhe Liu and Lu Sun and Xianshuo Zhang and Mingkui Zhang and Mingrui Sun and Liweis Ma and Mingzhu Lui and Hua Wei},
  journal  = {Polymers},
  title    = {Synthesis and Phase Transition of Poly(N-isopropylacrylamide)-Based Thermo-Sensitive Cyclic Brush Polymer},
  year     = {2017},
  number   = {301},
  volume   = {9},
  abstract = {Polymers with advanced topological architectures are promising materials for wide applications due to their structure-generated unique properties different from that of the linear analogues. The elegant integration of stimuli-responsive polymers with such advanced architectures can create novel materials with virtues from both moieties, are thus a hot subject of research for both fundamental and practical investigations. To fabricate cyclic brush polymer-based intelligent materials for biomedical applications, herein, we designed and synthesized thermo-sensitive cyclic brush polymers with poly(N-isopropylacrylamide) (PNIPAAm) brushes by controlled living radical polymerization using cyclic multimacroinitiator. The thermo-induced phase transition behaviors of the resultant cyclic brush polymers with different compositions were investigated in detail by temperature-dependent optical transmittance measurements, and compared with the properties of bottlebrush and linear counterparts. Interestingly, the cloud point transition temperature (T_{cp}) of cyclic brush PNIPAAm could be regulated by the chain length of PNIPAAm brush. Although the bottlebrush polymers with the same composition exhibited similarly structurally dependent T_{cp}s behaviors to the cyclic brush polymers, the cyclic brush PNIPAAm did show higher critical aggregation concentration (CAC) and enhanced stability against dilution than the bottlebrush counterpart. The readily tailorable T_{cp}s together with the ability to form highly stable nanoparticles makes thermo-sensitive cyclic brush PNIPAAm a promising candidate for controlled drug delivery.},
  file     = {:Tu2017 - Synthesis and Phase Transition of Poly(N Isopropylacrylamide) Based Thermo Sensitive Cyclic Brush Polymer.pdf:PDF},
  keywords = {PNIPAM, polymer brush, cyclic brush, polymer synthesis, controlled living radical polymerization, colloid stabilization, thermoresponsive, drug delivery},
}

@Article{Alsten1991,
  author   = {John Van Alsten},
  journal  = {Macromolecules},
  title    = {Experimental Measurements of Local Mobility in Adsorbed Poly(dimethylsiloxane) Layers},
  year     = {1991},
  number   = {19},
  pages    = {5320--5323},
  volume   = {24},
  abstract = {13C NMR relaxation measurements have been used to investigate the changes in Brownian dynamics caused by polymer adsorption within a boundary region 5-15 {{\'{A}}} from the adsorbate surface. Brownian dynamics within the boundary region have been found to be sensitive to  he surface coverage (mass of polymer per unit area of surface). Dynamics measured approximately 7 {{\'{A}}} from the surface are found to slow and then increase as chain surface density increases. This is believed to reflect the conformational state of the adsorbed chains, with chain segments lying relatively flat at low coverages and forming small, lowmobility loops and tails at intermediate coverages.},
  keywords = {NMR, PDMS, relaxation, 13C},
}

@Article{Gangoda1987,
  author   = {M. Gangoda and R. K. Gilpin and B. M. F. Ung},
  journal  = {Journal of Magnetic Resonance},
  title    = {Effect of temperature on reversed-phase chromatographic surfaces studied by 13C NMR},
  year     = {1987},
  issn     = {0022-2364},
  number   = {1},
  pages    = {134--138},
  volume   = {74},
  abstract = {Reversed-phase chromatographic surfaces were prepared by reacting 1-13C-nonyltrichlorosilane, 12-13C-dodecyltrichlorosilane, 12-13C-dodecyldimethylchlorosilane, 12-13C-tridecyltrichlorosdane, and 12-13C-tridecyldimethylchlorosilane with porous silica. For each of these labeled materials 13C spin-lattice relaxation times were measured as a function of temperature under both dry and solvated conditions. Activation energies are nearly constant irrespective of the position of the carbon atom in the chain for the dry state materials. However, in the presence of solvent, activation energy depends on the position of carbon in the chain and the contact solvent. These results reflect difference in structuring of the bonded chains under dry and solvated conditions.},
  comment  = {Van Alsten references this paper with regards to the dependence of the spin-lattice relaxation time on local viscosity},
  doi      = {https://doi.org/10.1016/0022-2364(87)90086-2},
  keywords = {NMR, relaxation, 13C},
  url      = {http://www.sciencedirect.com/science/article/pii/0022236487900862},
}

@Article{Gilpin1984,
  author   = {Gilpin, R. K. and Gangoda, M. E.},
  journal  = {Analytical Chemistry},
  title    = {Nuclear magnetic resonance spectrometry of alkyl ligands immobilized on reversed-phase liquid chromatographic surfaces},
  year     = {1984},
  number   = {8},
  pages    = {1470--1473},
  volume   = {56},
  abstract = {Reversed-phase chromatographic surfaces were prepared with 13C enrichment at the terminal and adjacent carbon positions as well as the fourth carbon position by using labeled n-alkylchlorosilanes. In all cases single resonances were observed arising from the site of the enrichment. Similar values for chemical shift were noted before and after bonding for the terminal methyl and adjacent methylene carbons. For a given surface coverage measured 13C spin-lattice relaxation times were relatively constant for the terminal methyl carbon for the various midrange chain lengths studied. However, a decrease In spin-lattice relaxation time was noted with Increasing alkyl surface density. These as well as other observed results support the Idea of significant chain interaction at higher surface coverage. Finally, rotation about the terminal C-C bond seems to be a major factor to spin-lattice relaxation for the terminal carbon.},
  comment  = {Van Alsten references this paper with regards to the dependence of the spin-lattice relaxation time on bound chain length},
  doi      = {10.1021/ac00272a060},
  eprint   = {https://doi.org/10.1021/ac00272a060},
  keywords = {NMR, relaxation, 13C},
  url      = {https://doi.org/10.1021/ac00272a060},
}

@Article{Bischofberger2015,
  author   = {Irmgard Bischofberger and Veronique Trappe},
  journal  = {Scientific Reports},
  title    = {New aspects in the phase behaviour of poly-N-isopropyl acrylamide: systematic temperature dependent shrinking of PNiPAM assemblies well beyond the LCST},
  year     = {2015},
  volume   = {5},
  comment  = {nature paper, shape-retaining shrinkage},
  doi      = {10.1038/srep15520},
  file     = {:Bischofberger2015 - New Aspects in the Phase Behaviour of Poly N Isopropyl Acrylamide_ Systematic Temperature Dependent Shrinking of PNiPAM Assemblies Well beyond the LCST.pdf:PDF},
  keywords = {PNIPAM,LCST,microgel,ageing,kinetics,reversibility,concentration dependence},
  printed  = {printed},
}

@Article{Bischofberger2015a,
  author   = {I. Bischofberger and D. C. E. Calzolari and P. De Los Rios and I. Jelzarov and V. Trappe},
  journal  = {Scientific Reports},
  title    = {Hydrophobic hydration of poly-N-isopropyl acrylamide: a matter of the mean energetic state of water},
  year     = {2015},
  pages    = {4377},
  volume   = {4},
  abstract = {The enthalpically favoured hydration of hydrophobic entities, termed hydrophobic hydration, impacts the phase behaviour of numerous amphiphiles in water. Here, we show experimental evidence that hydrophobic hydration is strongly determined by the mean energetics of the aqueous medium. We investigate the aggregation and collapse of an amphiphilic polymer, poly-N-isopropyl acrylamide (PNiPAM), in aqueous solutions containing small amounts of alcohol and find that the thermodynamic characteristics defining the phase transitions of PNiPAM evolve relative to the solvent composition at which the excess mixing enthalpy of the water/alcohol mixtures becomes minimal. Such correlation between solvent energetics and solution thermodynamics extends to other mixtures containing neutral organic solutes that are considered as kosmotropes to induce a strengthening of the hydrogen bonded water network. This denotes the energetics of water as a key parameter controlling the phase behaviour of PNiPAM and identifies the excess mixing enthalpy of water/kosmotrope mixtures as a gauge of the kosmotropic effect on hydrophobic assemblies.},
  comment  = {At 32{$^{\circ}$}C, PNIPAM undergoes a LCST collapse. The temperature of 32{$^{\circ}$}C is essentially independent of PNIPAM molecular weight and architecture and over a wide range also independent of PNIPAM concentration. The PNIPAM concentration in the globules increases from 32{$^{\circ}$}C to 36{$^{\circ}$}C, reaching 0.4g/mL, but the concentration does not increase further as temperature is raised beyond 36{$^{\circ}$}C. The classical scenario for arrested phase separation (glassy arrest) does not account for the arrest of phase separation in PNiPAM systems. A complex balance of water-PNIPAM interactions appears to set a limit for the maximal release of water from a PNIPAM-rich phase. Arrest is here determined by temperature rather than concentration.},
  doi      = {10.1038/srep04377},
  file     = {:Bischofberger2015a - Hydrophobic Hydration of Poly N Isopropyl Acrylamide_ a Matter of the Mean Energetic State of Water.pdf:PDF},
  keywords = {PNIPAM,phase behaviour,phase behavior,cononsolvency,aqueous alcohols},
}

@Article{Sbeih2019,
  author   = {Suhad Sbeih and Priti S. Mohanty and Michael R. Morrow and Anand Yethiraj},
  journal  = {Journal of Colloid and Interface Science},
  title    = {Structural parameters of soft PNIPAM microgel particles as a function of crosslink density},
  year     = {2019},
  issn     = {0021-9797},
  pages    = {781--793},
  volume   = {552},
  abstract = {Hypothesis
The temperature dependences of hydrodynamic radii in thermo-sensitive microgel suspensions, known as collapse curves, are commonly fitted to the benchmark Flory-Rehner theory but parameters obtained often yield little physical insights. Our study of poly(N-isopropylacrylamide) (PNIPAM) microgel suspensions in water is driven by the hypothesis that fitting to Flory-Rehner theory can yield meaningful parameters that separate into ones that are insensitive to crosslink density or deuteration and ones that are not.
Experiments
Dynamic light scattering (DLS) and rheology experiments were done on 8 microgel variants, protonated and deuterated PNIPAM for four crosslink densities, synthesized under otherwise identical conditions.
Findings
Remarkably, polymer volume fractions in the microgel particle at collapse, ϕcollapse, obtained via rheology, are independent of crosslink density. Along with collapse curves from DLS, this determines the temperature dependence of microgel water and polymer volume fractions. Fitting collapse curves to Flory-Rehner theory yields reference polymer volume fractions, ϕ0, associated with microgel particle elasticity. ϕ0 is much lower than ϕcollapse, and increases with crosslink density. For all microgel sample variants, a crossover temperature, where the elastic contribution to osmotic pressure changes sign, is found to approximate the final temperature after microgel synthesis and also to the free polymer $\theta$ temperature.},
  doi      = {https://doi.org/10.1016/j.jcis.2019.05.047},
  keywords = {Microgel, Rheology, PNIPAM, DLS},
  url      = {http://www.sciencedirect.com/science/article/pii/S0021979719306034},
}

@Article{CaoLuu2019,
  author     = {Ngoc-Hanh Cao-Luu and Quoc-Thai Pham and Zong-Han Yeo and Fu-Ming Wang and Chorng-Shyan Chern},
  journal    = {Journal of Materials Science},
  title      = {Synthesis and characterization of PNIPAM microgel core--silica shell particles},
  year       = {2019},
  pages      = {7503--7516},
  volume     = {54},
  abstract   = {We developed a simple effective approach to prepare poly(N-isopropylacrylamide-co-acrylamide-co-N,N$\prime$-methylenebisacrylamide) (PNIPAM/AM/MBA) microgel core--silica shell particles with narrow particle size distribution via the sol--gel reaction of silica precursor deposited directly on the microgel particle surface in the presence of 3-glycidyloxypropyltrimethoxysilane (GLYMO). MBA was used as the cross-linking agent for the formation of microgel with the cross-linked network structure and GLYMO used as a coupling agent. The morphology of hybrid core--shell particles including the shape, core size, shell thickness and surface roughness was governed by the key components of AM and GLYMO. PNIPAM/AM/MBA microgel core--silica shell particles show desirable spherical shape, distinct core--shell structure and raspberry-like particle morphology. In contrast, PNIPAM/MBA microgel core--silica shell particles formed without resort to AM and GLYMO result in very poor silica encapsulation, thereby leading to undesired particle morphology. Incorporation of AM units into PNIPAM/MBA microgel particles increases the lower critical solution temperature (LCST). Furthermore, encapsulation of PNIPAM/AM/MBA microgel particles by silica does not affect the LCST to an appreciable extent, but it greatly reduces the thermo-sensitivity of the hybrid core--shell particles. Finally, the feasibility of using these PNIPAM-based core--silica shell particles as drug carriers was demonstrated.},
  comment    = {PNIPAM microgel core with silica shell},
  doi        = {10.1007/s10853-019-03317-x},
  keywords   = {PNIPAM, microgel, synthesis, drug delivery},
  readstatus = {skimmed},
}

@Article{Rusu2006,
  author   = {Rusu, Mihaela and Wohlrab, Sebastian and Kuckling, Dirk and M{\"{o}}hwald, Helmuth and Sch{\"{o}}nhoff, Monika},
  journal  = {Macromolecules},
  title    = {Coil-to-Globule Transition of PNIPAM Graft Copolymers with Charged Side Chains:\hspace{0.167em} A 1H and 2H NMR and Spin Relaxation Study},
  year     = {2006},
  number   = {21},
  pages    = {7358--7363},
  volume   = {39},
  abstract = {Graft copolymers of poly(2-vinylpyridine), P2VP, grafted to a backbone of poly(N-isopropyl acrylamide), PNIPAM, are investigated concerning their thermosensitive behavior in aqueous solution. 1H NMR monitors the coil-to-globule transition by quantifying the fraction of mobile segments in the liquid state. Field gradient NMR diffusion studies reveal a decrease of the hydrodynamic radius with temperature as the lower critical solution temperature (LCST) is approached. The LCST and the width of the transition of PNIPAM are increasing with grafting density and decreasing upon salt addition, which is attributed to electrostatic forces. The grafted segments become partially immobilized only for low grafting density. For high grafting density a fraction of the backbone segments remains mobile even above the LCST. 2H spin relaxation rates of the hydration water indicate the presence of water molecules with very slow dynamics in the transition regime, whereas above and below the transition only fast water dynamics is found.},
  doi      = {10.1021/ma060831a},
  eprint   = {https://doi.org/10.1021/ma060831a},
  file     = {:Rusu2006 - Coil to Globule Transition of PNIPAM Graft Copolymers with Charged Side Chains_ a 1H and 2H NMR and Spin Relaxation Study.pdf:PDF},
  keywords = {NMR, PNIPAM, LCST, concentration, grafting density, ionic strength, thermoresponsive, polyelectrolyte, key article},
  ranking  = {rank5},
  url      = {https://doi.org/10.1021/ma060831a},
}

@Article{Tanaka1998,
  author   = {Noriyuki Tanaka and Shingo Matsukawa and Hiromichi Kurosu and Isao Ando},
  journal  = {Polymer},
  title    = {A study on dynamics of water in crosslinked poly (N-isopropylacrylamide) gel by n.m.r. spectroscopy},
  year     = {1998},
  issn     = {0032-3861},
  number   = {20},
  pages    = {4703--4706},
  volume   = {39},
  abstract = {The dynamics of crosslinked poly (N-isopropylacrylamide) gel have been studied by means of pulsed-gradient spin-echo (PGSE) 1H nuclear magnetic resonance (n.m.r.), pulse 1H n.m.r. and 1H n.m.r. imaging. The self-diffusion coefficients of HDO (DHDO) in D2O (containing a small amount of HDO) in the gels with various degree of swellings were determined by the PGSE 1H n.m.r. method. From these experimental results, it was found that the DHDO is decreased as the degree of swelling is decreased, and DHDO in the gels with a constant degree of swelling in going from 20 to 45{$^{\circ}$}C is transitionally decreased at about 32{$^{\circ}$}C, which corresponds to the phase transition temperature. From the detailed analysis of proton spin-spin relaxation time T2 determined by the pulse 1H n.m.r. method, the process of the volume phase transition of the gel has been elucidated. Furthermore, spatial information about the molecular motion of water in the gel sample was obtained by T2 enhanced 1H n.m.r. imaging.},
  doi      = {https://doi.org/10.1016/S0032-3861(97)10210-5},
  file     = {:Tanaka1998 - A Study on Dynamics of Water in Crosslinked Poly (N Isopropylacrylamide) Gel by N.m.r. Spectroscopy.pdf:PDF},
  keywords = {PNIPAM, NMR, microgel, PFG, diffusion},
  url      = {http://www.sciencedirect.com/science/article/pii/S0032386197102105},
}

@Article{Gao1997,
  author    = {Yibing Gao and Steve C. F. Au-Yeung and Shuiqin Zhou and Chi Wu},
  journal   = {Journal of Macromolecular Science, Part B: Physics},
  title     = {NMR evidence of the formation of surfactant micelles inside spherical poly(N-isopropylacrylamide) microgels},
  year      = {1997},
  number    = {3},
  pages     = {417--422},
  volume    = {36},
  abstract  = {In recent years, water-soluble polymers, or hydrogels, with a lower critical solution temperature (LCST) have been intensively studied. One typical example is poly(N-Isopropylacrylamide) (PNIPAM) and its gel. The influence of both the surfactant type and concentration on the volume phase transition of the PNIPAM/water system has been investigated by various methods, such as static and dynamic laser light scattering [1-3] swelling equilibrium [4-6], UV [a], cloud point [6], conductivity [5] and electrophoretic mobility [2], to name but a few. These studies show that the PNIPAM chain or gel network can swell more in the presence of anionic surfactants, and that its volume phase transition temperature increases. The binding of the hydrophobic tail to the PNIPAM chain or gel is believed to be responsible for the additional swelling, but this cannot satisfactorily explain why cationic surfactants with a similar hydrophobic tail have much less effect on swelling whereas nonionic surfactants cause no observable additional swelling over a very wide range of surfactant concentrations. Thus, the detailed structure of the PNIPAM/surfactant complex remains unknown and the insight into this problem is important, as noted by Khokhlov [7], who recently stated: {\textquotedblleft}The theoretical explanation of this pronounced capacity to form self-assemblies in such a complex system is at present lacking; however, it is clear that this fact can have far-reaching technological and biological importance.{\textquotedblright}},
  doi       = {10.1080/00222349708212394},
  eprint    = {https://doi.org/10.1080/00222349708212394},
  file      = {:Gao1997 - NMR Evidence of the Formation of Surfactant Micelles inside Spherical Poly(N Isopropylacrylamide) Microgels.pdf:PDF},
  keywords  = {NMR, PNIPAM, micelle, microgel},
  publisher = {Taylor and Francis},
  url       = {https://doi.org/10.1080/00222349708212394},
}

@Article{Spevacek2012,
  author   = {Jir{\i} Spevacek and Jir{\i} Dybal and Larisa Starovoytova and Alexander Zhignov and Zdenka Sedlakova},
  journal  = {Soft Matter},
  title    = {Temperature-induced phase separation and hydration in poly(N-vinylcaprolactam) aqueous solutions: a study by NMR and IR spectroscopy, SAXS, and quantum-chemical calculations},
  year     = {2012},
  pages    = {6110},
  volume   = {8},
  abstract = {Temperature-induced phase separation and hydration in poly(N-vinylcaprolactam) (PVCL)--D2O solutions were investigated by a combination of NMR and ATR FTIR spectroscopy, SAXS and model quantum-chemical calculations. The existence and character of water bound in PVCL globular-like structures were shown by NMR spin--spin relaxation times of HDO molecules and by FTIR spectroscopy. From FTIR spectra combined with DFT calculations it follows that the amount of fully dehydrated carbonyl groups in PVCL globular structures is rather small. Dehydration at temperatures above the LCST transition mainly consists of transformation of structures where a PVCL carbonyl is directly hydrogen bonded to two water molecules to structures with a single hydrogen bonded water molecule and breaking away indirectly bound water. In the transition region the changes of hydrophilic and hydrophobic interactions proceed simultaneously. The strong dependence of transition temperatures on polymer concentration was revealed by NMR and SAXS. NMR spectroscopy also enabled us to determine thermodynamic parameters DH and DS characterizing the phase transition. SAXS results have shown that above the transition temperature {\textquoteleft}{\textquoteleft}primary{\textquoteright}{\textquoteright} mesoglobules of 50 nm in size are formed which aggregate into large agglomerates.},
  comment  = {PNIPAM alternative},
  doi      = {10.1039/c2sm25432h},
  file     = {:Spevacek2012 - Temperature Induced Phase Separation and Hydration in Poly(N Vinylcaprolactam) Aqueous Solutions_ a Study by NMR and IR Spectroscopy, SAXS, and Quantum Chemical Calculations.pdf:PDF},
  keywords = {NMR, infrared, SAXS, calculation, thermioresponsive, PVCL},
}

@Article{Cooper2013,
  author     = {Cooper, Catherine L. and Cosgrove, Terence and van Duijneveldt, Jeroen S. and Murray, Martin and Prescott, Stuart W.},
  journal    = {Soft Matter},
  title      = {The use of solvent relaxation NMR to study colloidal suspensions},
  year       = {2013},
  pages      = {7211--7228},
  volume     = {9},
  abstract   = {Solvent relaxation nuclear magnetic resonance has been widely used to study the interactions of polymers and surfactants with nanoparticles{,} an important area of research for use in a range of industrial formulations{,} especially with regards to competition effects between components. The ability of the solvent relaxation technique to distinguish between solvent molecules at the surface and those in the bulk solution has been used to obtain valuable information on the interfacial interactions and structure. We focus on systems containing combinations of polymer{,} surfactant and colloidal particles and illustrate how solvent relaxation measurements have addressed problems of stabilisation{,} flocculation and depletion in both academically and industrially relevant systems.},
  doi        = {10.1039/C3SM51067K},
  file       = {:Cooper2013 - The Use of Solvent Relaxation NMR to Study Colloidal Suspensions.pdf:PDF},
  issue      = {30},
  keywords   = {NMR,solvent relaxation,review,pH value,spin-lattice relaxation,T1,spin-spin relaxation,T2,concentration-dependence},
  printed    = {printed},
  publisher  = {The Royal Society of Chemistry},
  ranking    = {rank3},
  readstatus = {read},
  url        = {http://dx.doi.org/10.1039/C3SM51067K},
}

@Article{Shirota1999,
  author   = {Shirota, Hideaki and Kuwabara, Nozomi and Ohkawa, Kazuya and Horie, Kazuyuki},
  journal  = {The Journal of Physical Chemistry B},
  title    = {Deuterium Isotope Effect on Volume Phase Transition of Polymer Gel:\hspace{0.167em} Temperature Dependence},
  year     = {1999},
  number   = {47},
  pages    = {10400--10408},
  volume   = {103},
  abstract = {The deuterium isotope effects on the volume phase transition of a typical temperature-sensitive polymer gel (poly(N-isopropylacrylamide) (PNIPAM) gel) and the phase separation of the linear polymer (PNIPAM) have been investigated. For the comparison between the bulk change and the microenvironment change, the deuterium isotope effects of PNIPAM gel and linear PNIPAM solution have also been investigated by using a fluorescence probe. Both the transition temperature of the polymer gel and the phase separation temperature of the linear polymer in heavy water are about 0.7 {$^{\circ}$}C higher than those in water. However, the deuterium isotope effects on the difference of the transition temperatures in the heating process and the cooling process in the microenvironments of PNIPAM gel and linear PNIPAM solution are not observed.},
  doi      = {10.1021/jp992401a},
  eprint   = {https://doi.org/10.1021/jp992401a},
  file     = {:Shirota1999 - Deuterium Isotope Effect on Volume Phase Transition of Polymer Gel_ Temperature Dependence.pdf:PDF},
  keywords = {PNIPAM, isotope effect, cloud point, linear, microgel, thermoresponsive},
  url      = {https://doi.org/10.1021/jp992401a},
}

@Article{Chakraborty2018,
  author   = {Chakraborty, Ipsita and Mukherjee, Kaustuv and De, Priyadarsi and Bhattacharyya, Rangeet},
  journal  = {The Journal of Physical Chemistry B},
  title    = {Monitoring Coil--Globule Transitions of Thermoresponsive Polymers by Using NMR Solvent Relaxation},
  year     = {2018},
  note     = {PMID: 29750525},
  number   = {22},
  pages    = {6094--6100},
  volume   = {122},
  abstract = {Thermoresponsive polymers exhibit coil--globule transition in aqueous solution where the polymer undergoes transition from the coil-like morphology to a globular form with the change of temperature. Such transitions also reflect changes in the solvent dynamics captured by various spectroscopic methods. In this work, we construct a phenomenological model to capture the dynamics of the NMR relaxation of water molecules of an aqueous solution of thermoresponsive polymers that are known to form hydrogen bonds with the solvent water molecules. The model relies on the behavior of the polymer--solvent hydrogen bonds and the sharing of rotational kinetic energy of water molecules in the vicinity of the polymer chain and the bulk. This is shown to provide a direct estimate of the fractional change of the polymer--water hydrogen bonds across lower critical solution temperature from NMR relaxation data of solvent water along with a reliable estimate of the transition temperature. In addition, it also provides a measure of the dispersion of the strengths of these hydrogen bonds. We exemplify the validity of this model by successfully fitting the experimental data to show that the extracted parameters provide significant insights into the role played by the hydrogen bonds in the process. The possible extension of this model to solvents that form no hydrogen bonds with the polymers is also discussed.},
  comment  = {improved(?) method to calculate mean T2},
  doi      = {10.1021/acs.jpcb.8b02179},
  eprint   = {https://doi.org/10.1021/acs.jpcb.8b02179},
  keywords = {thermoresponsive, coil globule transition, aqueous, NMR, relaxation, LCST, hydrogen bonds, PNIPAM, copolymer, solvent relaxation, T2, transverse relaxation},
  url      = {https://doi.org/10.1021/acs.jpcb.8b02179},
}

@Article{Kametani2017,
  author     = {Shunsuke Kametani and Sokei Sekine and Takahiro Ohkubo and Tomohiro Hirano and Koichi Ute and H. N. Cheng and Tetsuo Asakura},
  journal    = {Polymer},
  title      = {NMR studies of water dynamics during sol-to-gel transition of poly (N-isopropylacrylamide) in concentrated aqueous solution},
  year       = {2017},
  issn       = {0032-3861},
  pages      = {287--296},
  volume     = {109},
  abstract   = {The focus of this work was on the significant changes in the water dynamics of aqueous poly (N-isopropylacrylamide) (PNIPAM) solution during sol-to-gel transition. Through the use of NMR (particularly two-dimensional 2H NMR T1-T2 relaxation) and rheology, we were able to show that below 34{$^{\circ}$}{~}C fast exchange occurs among free water and water molecules adsorbed on the surface of PNIPAM molecules. At 34{$^{\circ}$}{~}C, PNIPAM becomes aggregated; most of the water molecules are trapped in the PNIPAM aggregates, where water molecules with different dynamics are found. Above 34{$^{\circ}$}{~}C, PNIPAM molecules aggregate further to form a gel network; the free bulk water then becomes dominant at this stage. On the basis of these observations, a model where water molecules interact with PNIPAM in different ways during the transition was proposed. We believe that our experimental approach provides new information and fresh perspectives on the sol-to-gel transition of PNIPAM.},
  doi        = {10.1016/j.polymer.2016.12.063},
  file       = {:Kametani2017 - NMR Studies of Water Dynamics during Sol to Gel Transition of Poly (N Isopropylacrylamide) in Concentrated Aqueous Solution.pdf:PDF;:NMRStudiesOfWaterDynamicsDuringSolToGelTransitionOfPolyNIsopropylacrylamideInConcentratedAqueousSolution-SupportingInformation_KametaniEtAl_Polymer2017.pdf:PDF;:NMRStudiesOfWaterDynamicsDuringSolToGelTransitionOfPolyNIsopropylacrylamideInConcentratedAqueousSolution-SupportingInformation_KametaniEtAl_Polymer2017.docx:Word 2007+},
  keywords   = {T1-T2 correlation, spin-lattice relaxation, T1, T2, spin-spin relaxation, 13C NMR, NMR, secondary sources, PNIPAM, Poly(N-isopropylacrylamide), Sol-to-gel transition, Water dynamics, viscosity, hydrodynamic radius},
  ranking    = {rank5},
  readstatus = {read},
  url        = {http://www.sciencedirect.com/science/article/pii/S0032386116311624},
}

@Article{Zhang1999,
  author   = {Zhang, Ju and Pelton, Robert},
  journal  = {Langmuir},
  title    = {Poly(N-isopropylacrylamide) Microgels at the Air$-$Water Interface},
  year     = {1999},
  number   = {23},
  pages    = {8032--8036},
  volume   = {15},
  abstract = {The surface tension of colloidal poly(N-isopropylacrylamide) (PNIPAM) dispersions was measured as functions of surface age, temperature, and the morphology of the PNIPAM microgels. The microgels lowered the surface tension of water to about 43 mJ/m2 at 25 {$^{\circ}$}C and a little less at 40 {$^{\circ}$}C. The steady-state surface tension values were not very sensitive to temperature or to the degree of microgel cross-linking. On the other hand, the time required to reach a steady state was dependent upon microgel morphology. The lower the cross-linking or the lower the particle uniformity, the more rapid was the surface tension decline. Microgels were observed to form an ordered array at the air/water interface when viewed by an environmental scanning electron microscope. It was proposed that the rate of surface tension lowering was in part influenced by the rate of particle spreading after adsorption onto the interface.},
  doi      = {10.1021/la990316o},
  eprint   = {https://doi.org/10.1021/la990316o},
  keywords = {PNIPAM, microgel, interface, morphology},
  url      = {https://doi.org/10.1021/la990316o},
}

@Article{Woessner1961,
  author   = {Woessner, D. E.},
  journal  = {Journal of Chemical Physics},
  title    = {Nuclear Transfer Effects in Nuclear Magnetic Resonance Pulse Experiments},
  year     = {1961},
  number   = {1},
  pages    = {41--48},
  volume   = {35},
  abstract = {The Bloch equations for the nuclear magnetic resonance of a single nuclear species which is transferred between state environments having different relaxation times (T1 or T2 ) and different resonance frequencies have been solved for rf pulse experiments. Expressions have been obtained for the free precession signals in two-pulse experiments. A theoretical study of the signal envelopes has been made for several specific instances. In particular, the effect of the frequency difference between the two states on transverse (T1)
relaxation has been investlgated; the predicted effect is large in some cases. The longitudinal (T1) relaxation is independent of the frequency separation. A reduction of phase dispersion by the second pulse which is Similar to that in molecular diffusion is also predicted.},
  comment  = {recommended by Michael},
  doi      = {10.1063/1.1731931},
  eprint   = {https://doi.org/10.1063/1.1731931},
  file     = {:Woessner1961 - Nuclear Transfer Effects in Nuclear Magnetic Resonance Pulse Experiments.pdf:PDF},
  keywords = {NMR, theory, exchange},
  url      = {https://doi.org/10.1063/1.1731931},
}

@Article{Stannarius1995,
  author    = {Stannarius, R. and Kremer, F. and Arndt, M.},
  journal   = {Physical Review Letters},
  title     = {Dynamic Exchange Effects in Broadband Dielectric Spectroscopy},
  year      = {1995},
  month     = dec,
  pages     = {4698--4701},
  volume    = {75},
  abstract  = {We calculate the consequences of molecular exchange between two states with different relaxation rates in dielectric spectra. In a critical range where exchange rates are of the order of the relaxation rates, both individual processes show apparently increased relaxation frequencies, and the slower process gains intensity from the faster. In the fast exchange limit, only one process with averaged relaxation rate remains. The model is well suited to describe the effects in the dielectric spectra of a microconfined glass-forming liquid (salol) in porous glasses.},
  comment   = {recommended by Michael},
  doi       = {10.1103/PhysRevLett.75.4698},
  file      = {:Stannarius1995 - Dynamic Exchange Effects in Broadband Dielectric Spectroscopy.pdf:PDF},
  issue     = {25},
  keywords  = {exchange, dielectric spectroscopy, theory},
  numpages  = {0},
  printed   = {printed},
  publisher = {American Physical Society},
  url       = {https://link.aps.org/doi/10.1103/PhysRevLett.75.4698},
}

@Article{Chan1999,
  author   = {Chan, Karinne and Pelton, Robert and Zhang, Ju},
  journal  = {Langmuir},
  title    = {On the Formation of Colloidally Dispersed Phase-Separated Poly(N-isopropylacrylamide)},
  year     = {1999},
  number   = {11},
  pages    = {4018--4020},
  volume   = {15},
  abstract = {Poly(N-isopropylacrylamide) (polyNIPAM) is a watersoluble polymer with a lower critical solution temperature of 32 {$^{\circ}$}C.1,2 Homopolymers, copolymers, macrogels, and microgels based on N-isopropylacrylamide have been the subject of many publications because of the fascinating temperature-sensitive properties and potential applications of polyNIPAM materials. Heating concentrated aqueous polyNIPAM results in rapid phase separation at the cloud point temperature, giving a macroscopic coacervate phase containing about two bound water molecules per isopropyl group.3 By contrast, with very dilute polyNIPAM solutions it is possible to use light scattering to follow the collapse of individual chains during heating, thus yielding valuable information about the coil-to-globule transition.4-7 These extremely dilute (1 ppm) dispersions did not aggregate in the time scale of the experimentssan explanation given was that very dilute suspensions have a low probability of brownian contacts.6 The phase separation of intermediate polyNIPAM concentrations (e.g., 10-1000 ppm) yields colloidally stable dispersions as long as the temperature is maintained above the cloud point temperature.8 Reported in this work are the results of a systematic investigation of the factors controlling the particle size of phase-separated polyNIPAM suspensions. This work not only is relevant to properties of polyNIPAM but also shows that this system serves as a possible model for homogeneous nucleation of colloids such as that which occurs in the formation of monodisperse latex.9,10},
  doi      = {10.1021/la9812673},
  eprint   = {https://doi.org/10.1021/la9812673},
  file     = {:Chan1999 - On the Formation of Colloidally Dispersed Phase Separated Poly(N Isopropylacrylamide).pdf:PDF},
  keywords = {pNIPAM, aggregation, kinetics, LCST, light scattering, dilute},
  url      = {https://doi.org/10.1021/la9812673},
}

@Article{Kuo2012,
  author   = {Shiao-Wei Kuo and Jing-Long Hong and Yu-Chan Huang and Jem-Kun Chen and Shih-Kang Fan and Fu-Hsiang Ko and Chih-Wei Chu and Feng-Chih Chang},
  journal  = {Journal of Nanomaterials},
  title    = {Star Poly(N-isopropylacrylamide) Tethered to Polyhedral Oligomeric Silsesquioxane (POSS) Nanoparticles by a Combination of ATRP and Click Chemistry},
  year     = {2012},
  volume   = {2012},
  abstract = {New star poly(N-isopropylacrylamide)-b-polyhedral oligomeric silsesquioxane (PNIPAm-b-POSS) copolymers were synthesized
from octa-azido functionalized POSS (N3 -POSS) and alkyne-PNIPAm, which was prepared using an alkyne-functionalized atom
transfer radical polymerization (ATRP) initiator (propargyl 2-bromo-2-methylpropionamide), via click chemistry. These star
PNIPAm-b-POSS copolymers undergo a sharp coil-globule transition in water at above 32^\circC changing from a hydrophilic state
below this temperature to a hydrophobic state above it, which is similar to linear PNIPAm homopolymers. More interestingly,
we found that these star polymers exhibited strong blue photoluminescence in water above a lower critical solution temperature
(LCST). This photoluminescence was likely due to the constrained geometric freedom and relatively rigid structure caused by
intramolecular hydrogen bonding within the star PNIPAm polymers, which exhibit an intrinsic fluorescent behavior.},
  doi      = {10.1155/2012/749732},
  file     = {:Kuo2012 - Star Poly(N Isopropylacrylamide) Tethered to Polyhedral Oligomeric Silsesquioxane (POSS) Nanoparticles by a Combination of ATRP and Click Chemistry.pdf:PDF},
  keywords = {PNIPAM, NIPAM, NMR, Chemical Shift, copolymer, star-shaped, ATRP, click chemistry, synthesis, thermoresponsive},
}

@Article{Aguilar2016,
  author    = {Aguilar, Juan A. and Kenwright, Simon. J.},
  journal   = {Analyst},
  title     = {Robust NMR water signal suppression for demanding analytical applications},
  year      = {2016},
  pages     = {236--242},
  volume    = {141},
  abstract  = {We describe the design and application of robust{,} general-purpose water signal suppression pulse sequences well suited to chemometric work. Such pulse sequences need to deal well with pulse mis-calibrations{,} radiation damping{,} chemical exchange{,} and the presence of sample inhomogeneities{,} as well as with significant variations in sample characteristics such as pH{,} ionic strength{,} relaxation characteristics and molecular weight. Of course{,} such pulse sequences should produce un-distorted lineshapes and baselines and work well both under automation and in the hands of non-experts. As an example{,} one such pulse sequences{,} Robust-5{,} will be presented. This new pulse sequence meets those criteria and is able to reduce a 50 M proteo water signal down to a 0.9 mM level{,} without fine tuning{,} and under automation{,} and it is therefore well suited to the most demanding of analytical applications.},
  doi       = {10.1039/C5AN02121A},
  file      = {:Aguilar2016 - Robust NMR Water Signal Suppression for Demanding Analytical Applications.pdf:PDF;:RobustNMRWaterSignalSuppressionForDemandingAnalyticalApplications-SupportingInformation_AguilarEtAl_Analyst2016.pdf:PDF},
  issue     = {1},
  keywords  = {NMR, water signal suppression, pulse sequence},
  publisher = {The Royal Society of Chemistry},
  url       = {http://dx.doi.org/10.1039/C5AN02121A},
}

@Article{Wu1998,
  author    = {Wu, Chi and Wang, Xiaohui},
  journal   = {Physical Review Letters},
  title     = {Globule-to-Coil Transition of a Single Homopolymer Chain in Solution},
  year      = {1998},
  month     = may,
  pages     = {4092--4094},
  volume    = {80},
  doi       = {10.1103/PhysRevLett.80.4092},
  file      = {:Wu1998 - Globule to Coil Transition of a Single Homopolymer Chain in Solution.pdf:PDF},
  issue     = {18},
  keywords  = {PNIPAM, hysteresis, thermoresponsive, light scattering},
  numpages  = {0},
  publisher = {American Physical Society},
  url       = {https://link.aps.org/doi/10.1103/PhysRevLett.80.4092},
}

@Article{Schwarz2002,
  author   = {Schwarz, Bernd and Sch{\"{o}}nhoff, Monika},
  journal  = {Langmuir},
  title    = {Surface Potential Driven Swelling of Polyelectrolyte Multilayers},
  year     = {2002},
  number   = {8},
  pages    = {2964--2966},
  volume   = {18},
  abstract = {The adsorption of polyelectrolytes to charged surfaces can be applied to build up multilayers of polyelectrolytes of alternating charge by layer-by-layer assembly. The hydration of such multilayers adsorbed to colloidal particles in dilute aqueous dispersions is investigated by NMR, namely, water 1H spin relaxation rates R2. For the system of alternating layers of poly(diallyl dimethylammonium chloride) (PDADMAC) and poly(sodium 4-styrenesulfate) (PSS) adsorbed to silica particles (PDADMAC/PSS), a linear increase of multilayer thickness and R2 with the number of layers is found, reflecting an increasing amount of hydration water. For the system (PAH)/PSS, involving the weak polyelectrolyte poly(allylamine hydrochloride) (PAH), it is found that while adsorption of a positive layer leads to an increase of R2, a decrease of R2 is observed after the adsorption of a negative layer. This reveals an increase of the net water mobility involving dehydration. Evidence is given that the reversible swelling behavior is a property of the internal layers, not the outer layer. Furthermore, it is driven by changes of the electric potential of the outer layer:\hspace{0.167em} A positive surface charge leads to a swelling of the multilayers, while due to a negative surface charge deswelling occurs. These effects can be due to uncompensated charges within the multilayer assembly, possibly involving changes of the dissociation equilibrium.},
  doi      = {10.1021/la015636y},
  eprint   = {https://doi.org/10.1021/la015636y},
  file     = {:Schwarz2002 - Surface Potential Driven Swelling of Polyelectrolyte Multilayers.pdf:PDF},
  keywords = {NMR, relaxation, polyelectrolyte, surface potential, multilayers, colloid, Poly(diallyl dimethylammonium chloride), PDADMAC, Poly(sodium 4-styrenesulfate), PSS, Poly(allylamine hydrochloride), PAH},
  url      = {https://doi.org/10.1021/la015636y},
}

@Misc{Holmes2004,
  author   = {Daniel Holmes},
  month    = feb,
  title    = {Basic Practical NMR Concepts: A Guide for the Modern Laboratory},
  year     = {2004},
  abstract = {This handout is designed to furnish you with a basic understanding of Nuclear Magnetic Resonance (NMR) Spectroscopy as it pertains to running the instrument. The concepts implicit and fundamental to the operation of a modern NMR spectrometer, with generic illustrations where appropriate, will be described. It can be read without having to be in front of the spectrometer itself. Some basic understanding of NMR spectroscopy is assumed. An excellent introduction to NMR can be found on the web at http://www.cis.rit.edu/htbooks/nmr/inside.htm.},
  file     = {:Holmes2004 - Basic Practical NMR Concepts_ a Guide for the Modern Laboratory.pdf:PDF},
  keywords = {NMR, uncitable, handout, spectrometer operation},
}

@Article{Schwarz2002a,
  author   = {Bernd Schwarz and Monika Sch{\"{o}}nhoff},
  journal  = {Colloids and Surfaces A: Physicochemical and Engineering Aspects},
  title    = {A 1H NMR relaxation study of hydration water in polyelectrolyte mono and multilayers adsorbed to colloidal particles},
  year     = {2002},
  issn     = {0927-7757},
  pages    = {293--304},
  volume   = {198-200},
  abstract = {The adsorption of polyelectrolytes to charged surfaces can be applied to build up multilayers of polyelectrolytes of alternating charge by layer-by-layer assembly. Here, poly-(allylamine hydrochloride) (PAH) is adsorbed to colloidal latex particles in aqueous solution, and to particles precoated with four layers of polyelectrolytes. The method of 1H NMR transverse relaxation is applied to monitor the hydration water in such layers, where relaxation rates R2 serve as a parameter describing the average immobilisation of water molecules. Electrophoretic and relaxation measurements are performed as a function of polymer coverage, surface precoating and salt content in the solution. While the zeta-potential increases monotonously with initial polymer concentration due to a charge reversal from a negatively to a positively charged surface, pronounced structures occur in the R2 curve for monolayers, which are attributed to the contributions arising from different water populations. For adsorption to multilayers, the electrophoretic curves are shifted to higher concentrations, and relaxation rates show an unexpectedly high water immobilisation. The electrophoretic and relaxation data are consistent with a molecular picture of rodlike chains in the absence of salt, and a coil shaped structure for adsorption from salt solution. In both cases, the properties of the fifth layer differ significantly from the first one, this is attributed to the entanglement of adsorbing chains in the precoated layers, leading to larger adsorbed amounts.},
  doi      = {https://doi.org/10.1016/S0927-7757(01)00945-1},
  file     = {:Schwarz2002a - A 1H NMR Relaxation Study of Hydration Water in Polyelectrolyte Mono and Multilayers Adsorbed to Colloidal Particles.pdf:PDF},
  keywords = {Polyelectrolyte, NMR, Spin relaxation, Hydration, Adsorption, Multilayers, Colloid, PAH, electrophoresis, ionic strength, surface potential},
  url      = {http://www.sciencedirect.com/science/article/pii/S0927775701009451},
}

@Book{Vyazovkin2020,
  editor       = {Sergey Vyazovkin},
  publisher    = {MDPI - Multidisciplinary Digital Publishing Institute},
  title        = {Thermal Analysis Kinetics for Understanding Materials Behavior},
  year         = {2020},
  isbn         = {978-3-03936-560-9},
  abstract     = {Changing the temperature of a substance can stimulate dramatic changes of its state. These changes can be intermolecular (physical) and intramolecular (chemical) in nature. Physical changes occur without breaking intramolecular bonds, and lead to transitions between the four major phases: gas, liquid, crystal, and glass. Chemical changes are associated with chemical reactions that originate from breaking intramolecular bonds. Phase transitions as well as chemical reactions occur at finite rates. Measuring the rates of processes is the realm of kinetics. The kinetics of thermally stimulated processes is routinely measured using thermal analysis techniques such as differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Knowing the process rates and their dependence on temperature is of vital importance for understanding the behavior of materials exposed to variations in temperature. In recent years, thermal analysis kinetics has made significant progress by developing computational tools for reliable kinetic analysis. It has also expanded its traditional application area to newly developed nano- and biomaterials. This Special Issue is a series of papers that reflect recent developments in the field and highlight the essential role of thermal analysis kinetics in understanding the processes responsible for the thermal behavior of various materials.},
  comment      = {collection of papers},
  creationdate = {2024-04-22T16:30:22},
  doi          = {https://doi.org/10.3390/books978-3-03936-560-9},
  file         = {:Vyazovkin2020 - Thermal Analysis Kinetics for Understanding Materials Behavior.pdf:PDF},
  keywords     = {book, isoconversional kinetics, theory},
  url          = {https://doi.org/10.3390/books978-3-03936-560-9},
}

@Article{Yoo2000,
  author   = {M. K. Yoo and Y. K. Sung and Y. M. Lee and C. S. Cho},
  journal  = {Polymer},
  title    = {Effect of polyelectrolyte on the lower critical solution temperature of poly(N-isopropyl acrylamide) in the poly(NIPAAm-co-acrylic acid) hydrogel},
  year     = {2000},
  issn     = {0032-3861},
  number   = {15},
  pages    = {5713--5719},
  volume   = {41},
  abstract = {Temperature/pH sensitive hydrogels were prepared by copolymerizing N-isopropyl acrylamide (NIPAAm) and acrylic acid (AAc). The influence of polyelectrolyte on the lower critical solution temperature (LCST) of temperature/pH sensitive hydrogels was investigated in the pH range of 2$\sim$12. Swelling ratio of hydrogels as a function of pH at various temperatures was obtained by measuring the weight of the hydrogels in buffer solutions. Swelling ratio of the hydrogels in the presence of poly(allyl amine) (PAA) as a polyelectrolyte was also measured at the same conditions. The LCSTs of the poly(N-isopropyl acrylamide-co-acrylic acid) [P(NIPAAm--co--AAc)] hydrogels increased with pH value and disappeared above the pKa value of poly(acrylic acid) (PAAc) except hydrogel containing 10mol% of AAc. The LCSTs of the P(NIPAAm-co-AAc) hydrogels in the presence of PAA could be observed even above the pKa value of PAAc. At same pH, the LCSTs of the P(NIPAAm-co-AAc) hydrogels in the presence of PAA were lower than those of the P(NIPAAm-co-AAc) hydrogels due to the polyelectrolyte complex formation between PAAc and PAA. The swelling ratio of P(NIPAAm-co-AAc) gel was the largest at 20mol% of AAc content and decreased by polyelectrolyte complex formation with PAA. The swelling kinetics of P(NIPAAm-co-AAc) hydrogel was strongly dependent on pH value, temperature and polyelectrolyte solute.},
  doi      = {https://doi.org/10.1016/S0032-3861(99)00779-X},
  file     = {:Yoo2000 - Effect of Polyelectrolyte on the Lower Critical Solution Temperature of Poly(N Isopropyl Acrylamide) in the Poly(NIPAAm Co Acrylic Acid) Hydrogel.pdf:PDF},
  keywords = {Polyelectrolyte, Lower critical solution temperature, Temperature/pH sensitive hydrogel, PNIPAM, pH-sensitive, thermoresponsive, copolymer},
  url      = {http://www.sciencedirect.com/science/article/pii/S003238619900779X},
}

@Article{Schoenhoff2003,
  author    = {Monika Sch{\"{o}}nhoff},
  journal   = {Journal of Physics: Condensed Matter},
  title     = {Layered polyelectrolyte complexes: physics of formation and molecular properties},
  year      = {2003},
  month     = nov,
  number    = {49},
  pages     = {R1781--R1808},
  volume    = {15},
  abstract  = {Multilayers of charged polymers can be formed by the alternating adsorption of polyanions and polycations. By this so-called layer-by-layer self-assembly method, planar surfaces or colloidal templates can be coated. This method is reviewed here with respect to the basic physical principles governing multilayer formation. Particular emphasis is put on the adsorption process of a single polyelectrolyte layer to a multilayer surface as the process controlling the charge complexation and the local molecular structure. Then, the implications for the properties of the multilayer assembly are discussed. In particular, molecular properties such as the internal stoichiometry, the local interactions, and the conformation on a molecular scale are reviewed.},
  doi       = {10.1088/0953-8984/15/49/r01},
  file      = {:Schoenhoff2003 - Layered Polyelectrolyte Complexes_ Physics of Formation and Molecular Properties.pdf:PDF},
  keywords  = {colloid, multilayer, review, theory},
  publisher = {{IOP} Publishing},
  url       = {https://doi.org/10.1088%2F0953-8984%2F15%2F49%2Fr01},
}

@Article{Tiktopulo1994,
  author   = {Tiktopulo, E. I. and Bychkova, V. E. and Ricka, J. and Ptitsyn, O. B.},
  journal  = {Macromolecules},
  title    = {Cooperativity of the Coil-Globule Transition in a Homopolymer: Microcalorimetric Study of Poly(N-isopropylacrylamide)},
  year     = {1994},
  number   = {10},
  pages    = {2879--2882},
  volume   = {27},
  doi      = {10.1021/ma00088a031},
  eprint   = {https://doi.org/10.1021/ma00088a031},
  keywords = {cooperativity, coil globule, PNIPAM, microcalorimetry},
  url      = {https://doi.org/10.1021/ma00088a031},
}

@Article{Kunugi1999,
  author   = {Kunugi, S. and Yamazaki, Y. and Takano, K. and Tanaka, N. and Akashi, M.},
  journal  = {Langmuir},
  title    = {Effects of Ionic Additives and Ionic Comonomers on the Temperature and Pressure Responsive Behavior of Thermoresponsive Polymers in Aqueous Solutions},
  year     = {1999},
  number   = {12},
  pages    = {4056--4061},
  volume   = {15},
  abstract = {The cloud points of the aqueous solutions of poly(N-vinylisobutyramide) (PNVIBA) and poly(N-isopropylacrylamide) (PNIPAM) were measured down to a subzero temperature under elevated pressures, and the effects of ionic additives and the ionic comonomer were studied. The polymers with higher molecular weight showed lower transition pressure (Pt) and smaller ellipsoids, due to larger absolute values of {{$\Delta$}}Cp and {{$\Delta$}}$\beta$. Addition of 0.02\% sodium dodecyl sulfate (SDS) into aqueous solutions of these polymers apparently extinguished the clouding phenomenon, but even under these conditions the dynamic light scattering measurement showed the chain collapse of the random coil preceding the interchain aggregations. Pt and transition temperature (Tt) were highly dependent on the addition of inert anions. Less lyotropic ions showed lower Pt and Tt, producing smaller ellipses as a result, while additions of SCN- and I- caused a slight increase in both Pt and Tt and therefore larger ellipses. Introduction of ionic comonomer (4-pentenoic acid) into PNIPAM (less than 20\%) made the transition P$-$T curves pH dependent and Pt was much more influenced by the charged comonomer than Tt. Anionic residues less than 5\% were sufficient to screen the cloud point (20 {$^{\circ}$}C and 400 MPa).},
  doi      = {10.1021/la981184m},
  eprint   = {https://doi.org/10.1021/la981184m},
  file     = {:Kunugi1999 - Effects of Ionic Additives and Ionic Comonomers on the Temperature and Pressure Responsive Behavior of Thermoresponsive Polymers in Aqueous Solutions.pdf:PDF},
  keywords = {PNIPAM, light scattering, Poly(N-vinylisobutyramide), PNVIBA, pressure, ionic strength, sodium dodecyl sulfate, SDS, pH-sensitive},
  url      = {https://doi.org/10.1021/la981184m},
}

@Article{Richter2004,
  author   = {Richter, Andreas and Howitz, Steffen and Kuckling, Dirk and Kretschmer, Katja and Arndt, Karl-Friedrich},
  journal  = {Macromolecular Symposia},
  title    = {Automatically and electronically controllable hydrogel based valves and microvalves -- design and operating performance},
  year     = {2004},
  number   = {1},
  pages    = {447--456},
  volume   = {210},
  abstract = {This paper describes automatically and electronically controlled valves and microvalves based on smart hydrogels. The operating performance of such devices will be discussed in dependence on various design parameters. Furthermore, it will be shown that hydrogel based valves are showing an outstanding possibility of miniaturization, a leakage free switching behavior up to a pressure drop of 8.4 bar, and a pronounced particle tolerance.},
  doi      = {10.1002/masy.200450650},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/masy.200450650},
  keywords = {automatic control, electronic control, hydrogel, microvalve, operating performance, valve, PNIPAM, application focused, application-focused},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/masy.200450650},
}

@Article{Schild1992,
  author   = {H. G. Schild},
  journal  = {Progress in Polymer Science},
  title    = {Poly(N-isopropylacrylamide): experiment, theory and application},
  year     = {1992},
  issn     = {0079-6700},
  number   = {2},
  pages    = {163--249},
  volume   = {17},
  abstract = {The effect of cross-linker (methylene-bis-acrylamide) (MBA) on the volume phase transition, mechanical properties and de-swelling of Poly(N-isopropyl acrylamide-co-methylene-bis-acrylamide) hydrogel (PNIPAAm/MBA hydrogel) was investigated. A new method, namely isothermal thermo-gravimetry was developed for monitoring de-swelling of PNIPAAm/MBA hydrogel. Monomer/ Cross-linker ratio of the initial monomer composition R = moleNIPAAm/moleMBA was introduced. It has been proven earlier that initial monomer composition is close to the copolymer composition; hence R values may be used to express cross-link density. Hydrogels from R10 to R150 were investigated. The results of DSC analysis revealed that the less the cross-linker ratio in the gel (from R10 to R150) the more sharp the temperature range of volume phase transition and the higher its enthalpy. Cross-link density, namely increasing cross-linker content in the copolymer (R from 150 to 10) does not significantly affect the temperature range of volume phase transition. It sets on at 33{$^{\circ}$}C - 34{$^{\circ}$}C, and ends between 35?C and 38?C. Cross-link density has significant effect on compression modulus. By decreasing the ratio of cross-linker (by increasing R from 10 to 150), the compression modulus increases, goes through a maximum, and then decreases. The highest compression modulus was measured for PNIPAAm/MBA hydrogel R20. Hydrogels with cross-linker content between R100 and 30 are strong enough and have their thermoresponsivity. Isothermal thermograms of de-swelling are of similar character for all the gels with different cross-linker content. During the initial stage of de-swelling for gels with higher cross-linker content (R10 - R15) the solute release is quicker than for gels R20 - 150 and the thermograms are drawn out. In the initial stage of de-swelling, i.e. during the first 40 minutes the rate of solute release is the highest for gels R70 - 150. The cross-linker content effects solute release, especially for gels with high cross-linker content. It is noteworthy that gels R10 - 15 release solute quicker than gels R30 - 50 and their rate of de-swelling is comparable to that of gels R100 - 150. The novel thermogravimetric method enables the selection of gels based on the rate of solute release and it can also be applied for other  cross-linked gels.},
  comment  = {Elsevier},
  doi      = {https://doi.org/10.1016/0079-6700(92)90023-R},
  file     = {:Schild1992 - Poly(N Isopropylacrylamide)_ Experiment, Theory and Application.pdf:PDF},
  keywords = {review, PNIPAM},
  url      = {http://www.sciencedirect.com/science/article/pii/007967009290023R},
}

@Article{Zhu1996,
  author   = {Peng Wei Zhu and Donald H. Napper},
  journal  = {Colloids and Surfaces A: Physicochemical and Engineering Aspects},
  title    = {Interfacial coil-to-globule transitions: the effects of molecular weight},
  year     = {1996},
  issn     = {0927-7757},
  number   = {1},
  pages    = {145--153},
  volume   = {113},
  abstract = {The coil-to-globule transitions of fractionated poly(N-isopropylacrylamide) chains attached to electrosterically stabilized polystyrene latex particles were studied for molecular weights ranging from 3 $\times$ 105 to 2 $\times$ 106. The shapes of the transitions proved to be a sensitive function of the polymer molecular weight: the component of the transition that occurred under better than $\theta$-solvency conditions increased significantly (from 30 to 80%) as the molecular weight was decreased by an order of magnitude; concomitantly, the component that occurred under worse than $\theta$-solvency conditions was substantially decreased. Studies carried out with 13C NMR supported the hypothesis that these two types of transitions were phenomenologically different. The transitions in worse than $\theta$-solvents can be attibuted to the strong attractive binary interactions that characterize worse than $\theta$-solvents, whereas the transitions in better than $\theta$-solvents arose from the weaker attractive many-body interactions, i.e. n-clustering. Simple scaling law considerations imply that the component of the coil-to-globule transitions arising from n-clusters should decrease with increasing molecular weight of the interfacial polymer, in conformity with the experimental data.},
  doi      = {https://doi.org/10.1016/0927-7757(96)03520-0},
  file     = {:Zhu1996 - Interfacial Coil to Globule Transitions_ the Effects of Molecular Weight.pdf:PDF},
  keywords = {Coil-to-globule transitions, n-Cluster effects, Interfacial chains, Molecular weight, PNIPAM, Polystyrene latex},
  url      = {http://www.sciencedirect.com/science/article/pii/0927775796035200},
}

@Article{Zhu1996a,
  author   = {Peng Wei Zhu and Donald H. Napper},
  journal  = {Journal of Colloid and Interface Science},
  title    = {Coil-to-Globule Type Transitions and Swelling of Poly(N-isopropylacrylamide) and Poly(acrylamide) at Latex Interfaces in Alcohol--Water Mixtures},
  year     = {1996},
  issn     = {0021-9797},
  number   = {2},
  pages    = {343--352},
  volume   = {177},
  abstract = {The coil-to-globule type transition and swelling of poly(N-isopropylacrylamide) chains at latex interfaces in mixed dispersion media were studied. A combined collapse--swelling behavior was observed on the addition of lower alcohols (methanol, ethanol, or 2-propanol) to an aqueous dispersion medium. The PNIPAM chains collapsed to a minimum size in the water-rich region and then reswelled on further addition of the alcohol. Both collapse and reswelling were reversible. The collapse of the higher molecular weight PNIPAM chains with narrower polydispersity was found to proceed almost to completion and to be relatively sharp prior to the attainment of $\theta$ conditions. It was found that the minimum size of the collapsed chains was dependent upon both the number of carbon atoms in the alcohol and the temperature studied. The volume fraction of alcohol corresponding to this minimum size was also dependent upon the number of carbon atoms in the alcohol but was essentially independent of the temperature of the dispersion medium. The experimental observations have been explained by the variations in the hydrophobic interactions and the hydration of the polymer chains. The results suggest that the collapse of interfacial PNIPAM chains in the alcohol--water mixed media occurs as a consequence of the effects of alcohols on the environment of the PNIPAM chains, whereas the chain swelling results from the direct interaction of the alcohol molecules with the hydrophobic groups in the PNIPAM macromolecules. The attractive hydrophobic interactions in PNIPAM layers are believed to play an important role in promoting the chain collapse after the interactions between the PNIPAM chains and the alcohols are diminished. The validity of this interpretation was supported by similar studies on poly(acrylamide).},
  doi      = {https://doi.org/10.1006/jcis.1996.0042},
  file     = {:Zhu1996a - Coil to Globule Type Transitions and Swelling of Poly(N Isopropylacrylamide) and Poly(acrylamide) at Latex Interfaces in Alcohol Water Mixtures.pdf:PDF},
  keywords = {PNIPAM, Latex, coil to globule, light scattering, binary mixtures, alcohol, aqueous},
  url      = {http://www.sciencedirect.com/science/article/pii/S0021979796900429},
}

@Article{Barnett1981,
  author   = {Barnett, K. G. and Cosgrove, T. and Vincent, B. and Cohen-Stuart, M. and Sissons, D. S.},
  journal  = {Macromolecules},
  title    = {The measurement of the polymer-bound fraction at the solid-liquid interface by pulsed nuclear magnetic resonance},
  year     = {1981},
  number   = {4},
  pages    = {1018--1020},
  volume   = {14},
  abstract = {Pulsed nuclear magnetic resonance (NMR) techniques have been used to estimate the polymer-bound fraction, (p), at solid surfaces in both aqueous and nonaqueous dispersions. The measured values are consistent with estimates of the strength of the polymer / substrate interaction energy. Spectra have also been obtained for a terminally anchored polymer.},
  doi      = {10.1021/ma50005a023},
  eprint   = {https://doi.org/10.1021/ma50005a023},
  file     = {:doi_10.1021_ma50005a023 - The Measurement of the Polymer Bound Fraction at the Solid Liquid Interface by Pulsed Nuclear Magnetic Resonance.pdf:PDF},
  keywords = {pulse sequence, NMR, infrared, equivalent series resistance, ESR, adsorption},
  url      = {https://doi.org/10.1021/ma50005a023},
}

@Article{Zhu1998,
  author    = {Zhu, Peng Wei and Napper, Donald H.},
  journal   = {Physical Review E},
  title     = {Effects of thermal history on the dynamics of relaxation of poly($N$-isopropylacrylamide) adsorbed at latex interfaces in water},
  year      = {1998},
  month     = mar,
  pages     = {3101--3106},
  volume    = {57},
  abstract  = {The dynamics of the relaxation of poly(N-isopropylacrylamide) (PNIPAM) chains absorbed from water onto the surfaces of poly(N-tert-butylacrylamide) latex particles has been studied. The dynamic behavior studied was induced by heating samples to 60 {$^{\circ}$}C and then cooling to 6 {$^{\circ}$}C. We report measurements of the effects of the thermal history on relaxation dynamics of interfacially adsorbed PNIPAM under better than \tehta-solvency conditions. The dynamic relaxation of the adsorbed PNIPAM chains proved to be very sluggish, displaying some features analogous to bulk glassy relaxations, especially at longer aging times. The average relaxation time, calculated from a stretched exponential function, significantly increased with increasing aging time. The extended PNIPAM layers formed under the experimental protocol adopted were found to become kinetically locked into nonequilibrium states for unexpectedly long times. The time at which the dynamic evolution of the adsorbed chains commenced depended upon the thermal history.},
  doi       = {10.1103/PhysRevE.57.3101},
  file      = {:Zhu1998 - Effects of Thermal History on the Dynamics of Relaxation of Poly($N$ Isopropylacrylamide) Adsorbed at Latex Interfaces in Water.pdf:PDF},
  issue     = {3},
  keywords  = {PNIPAM, Latex, DLS, light scattering, hysteresis},
  numpages  = {0},
  publisher = {American Physical Society},
  url       = {https://link.aps.org/doi/10.1103/PhysRevE.57.3101},
}

@Book{Watarai2005,
  editor    = {Hitoshi Watarai and Norio Teramae and Tsuguo Sawada},
  publisher = {Springer, Boston, MA},
  title     = {Interfacial Nanochemistry - Molecular Science and Engineering at Liquid-Liquid Interfaces},
  year      = {2005},
  edition   = {1},
  isbn      = {978-0-387-27541-3},
  doi       = {10.1007/0-387-27541-X},
  file      = {:Watarai2005 - Interfacial Nanochemistry Molecular Science and Engineering at Liquid Liquid Interfaces.pdf:PDF},
  keywords  = {book},
}

@Book{Noy2008,
  editor    = {Aleksandr Noy},
  publisher = {Springer, Boston, MA},
  title     = {Handbook of Molecular Force Spectroscopy},
  year      = {2008},
  edition   = {1},
  isbn      = {978-0-387-49989-5},
  doi       = {10.1007/978-0-387-49989-5},
  file      = {:Noy2008 - Handbook of Molecular Force Spectroscopy.pdf:PDF},
  keywords  = {book},
}

@Article{Spevacek2009,
  author     = {Ji{{\v{r}}}{\'{i}} Sp{\v{e}}v{\'{a}}{\v{c}}ek},
  journal    = {Current Opinion in Colloid and Interface Science},
  title      = {NMR investigations of phase transition in aqueous polymer solutions and gels},
  year       = {2009},
  issn       = {1359-0294},
  number     = {3},
  pages      = {184--191},
  volume     = {14},
  abstract   = {The use of NMR spectroscopy in investigations of phase transitions in aqueous polymer solutions and gels is reviewed. Results on this subject as obtained mostly for thermoresponsive polymers (e.g., poly(N-isopropylacrylamide) and its copolymers, poly(N-isopropylmethacrylamide) and its copolymers, poly(vinyl methyl ether)) from temperature dependences of 1H and 13C NMR spectra, spin--lattice and spin--spin relaxation times, diffusion coefficients and NMR images are discussed.},
  doi        = {https://doi.org/10.1016/j.cocis.2008.10.003},
  file       = {:Spevacek2009 - NMR Investigations of Phase Transition in Aqueous Polymer Solutions and Gels.pdf:PDF},
  keywords   = {Phase transition, Aqueous polymer solution, Hydrogel, NMR, review},
  printed    = {printed},
  ranking    = {rank5},
  readstatus = {read},
  url        = {http://www.sciencedirect.com/science/article/pii/S1359029408000915},
}

@Article{Blum2009,
  author   = {Frank D. Blum and Piyawan Krisanangkura},
  journal  = {Thermochimica Acta},
  title    = {Comparison of differential scanning calorimetry, FTIR, and NMR to measurements of adsorbed polymers},
  year     = {2009},
  issn     = {0040-6031},
  note     = {Calorimetry on a Nano-scale},
  number   = {1},
  pages    = {55--60},
  volume   = {492},
  abstract = {Temperature modulated differential scanning calorimetry (TMDSC) measurements on samples with very small amounts of polymers adsorbed on silica particles have been contrasted with spectroscopic techniques (FTIR and NMR) on the same or similar systems. The results are consistent in that the hydrogen bonding of the polymers to surface silanols reduces the mobility of some of the adsorbed polymer segments and results in higher glass transition temperatures for those polymer segments. These experiments reinforce the notion of an interface that is graded in terms of mobility. In contrast to bulk polymers, where the glass transition process can be considered spatially homogeneous, interfacial polymers can be considered heterogeneous on the scale of the interface. The results also suggest that the heterogeneous nature of the interfacial polymers and various sensitivities of the different techniques may result in apparently different conclusions about the surface effect and its reach.},
  doi      = {https://doi.org/10.1016/j.tca.2009.03.011},
  file     = {:Blum2009 - Comparison of Differential Scanning Calorimetry, FTIR, and NMR to Measurements of Adsorbed Polymers.pdf:PDF},
  keywords = {Adsorbed polymers, Glass transition, Composites, Interface, Temperature modulated differential scanning calorimetry, Fourier transform infrared spectroscopy, Nuclear magnetic resonance, review, NMR, infrared, DSC, methodology},
  url      = {http://www.sciencedirect.com/science/article/pii/S0040603109001658},
}

@Article{Schoenhoff2013,
  author   = {Monika Sch{\"{o}}nhoff},
  journal  = {Current Opinion in Colloid and Interface Science},
  title    = {NMR studies of sorption and adsorption phenomena in colloidal systems},
  year     = {2013},
  issn     = {1359-0294},
  number   = {3},
  pages    = {201--213},
  volume   = {18},
  abstract = {NMR methods provide chemically selective tools, particularly suitable to detect the molecular environment of molecular species in micro-heterogeneous materials. They are consequently applied to solve many questions in colloid science. The present review covers NMR studies of molecular adsorption onto particle surfaces as well as sorption into colloidal particles. Various methods ranging from liquid or solid state spectral analysis over spin relaxation to pulsed field gradient diffusion NMR have been employed in this field, monitoring either the chemical environment or the restricted dynamics of adsorbed or encapsulated guest molecules. Adsorption systems include surfactant layers, stabilizing ligands, small molecules, polymer layers or polyelectrolyte multilayers at the surface of various types of particles. Sorption into colloidal particles and detection of their position in specific compartments of the colloid are particularly relevant in systems employed as colloidal carriers, such as micelles, vesicles, or hollow polymeric capsules. With guest molecules considered as model compounds for drugs these studies have large relevance for the development of nanoparticle drug delivery systems.},
  doi      = {https://doi.org/10.1016/j.cocis.2013.03.004},
  file     = {:Schoenhoff2013 - NMR Studies of Sorption and Adsorption Phenomena in Colloidal Systems.pdf:PDF},
  keywords = {Adsorption, NMR, Colloid, Sorption, Encapsulation, Diffusion, Guest molecule, Drug delivery, review, relaxation, PFG,},
  printed  = {printed},
  url      = {http://www.sciencedirect.com/science/article/pii/S1359029413000435},
}

@Article{Nolan2006,
  author   = {Nolan, Christine M. and Gelbaum, Leslie T. and Lyon, L. Andrew},
  journal  = {Biomacromolecules},
  title    = {1H NMR Investigation of Thermally Triggered Insulin Release from Poly(N-isopropylacrylamide) Microgels},
  year     = {2006},
  note     = {PMID: 17025370},
  number   = {10},
  pages    = {2918--2922},
  volume   = {7},
  abstract = {We describe investigations of insulin release from thermoresponsive microgels using variable temperature 1H NMR. Microgel particles composed of poly(N-isopropylacrylamide) were loaded with the peptide via a swelling technique, and this method was compared to simple equilibrium partitioning. Variable temperature 1H NMR studies suggest that the swelling loading method results in enhanced entrapment of the peptide versus equilibrium partitioning. A centrifugation-loading assay supports this finding. Pseudo-temperature jump 1H NMR measurements suggest that the insulin release rate is partially decoupled from microgel collapse. These types of direct release investigations could prove to be useful methods in the future design of controlled macromolecule drug delivery devices.},
  doi      = {10.1021/bm060718s},
  eprint   = {https://doi.org/10.1021/bm060718s},
  file     = {:Nolan2006 - H NMR Investigation of Thermally Triggered Insulin Release from Poly(N Isopropylacrylamide) Microgels.pdf:PDF},
  keywords = {application focused, PNIPAM, NMR, microgel, application-focused},
  url      = {https://doi.org/10.1021/bm060718s},
}

@Article{Griffiths2008,
  author   = {Griffiths, Peter C. and Alexander, Cameron and Nilmini, Renuka and Pennadam, Sivanand S. and King, Stephen M. and Heenan, Richard K.},
  journal  = {Biomacromolecules},
  title    = {Physicochemical Characterization of Thermoresponsive Poly(N-isopropylacrylamide)$-$poly(ethylene imine) Graft Copolymers},
  year     = {2008},
  note     = {PMID: 18348532},
  number   = {4},
  pages    = {1170--1178},
  volume   = {9},
  abstract = {Synthetic polycations have shown promise as gene delivery vehicles but suffer from an unacceptable toxicity and low transfection efficiency. Novel architectures are being explored to increase transfection efficiency, including copolymers with a thermoresponsive character. The physicochemical characterization of a family of copolymers comprising a core of the cationic polymer poly(ethylene imine) (PEI) with differing thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) grafts has been carried out using pulsed-gradient spin--echo NMR (PGSE-NMR) and small-angle neutron scattering (SANS). For the copolymers that have longer chain PNIPAM grafts, there is clear evidence of the collapse of the grafts with increasing temperature and the associated emergence of an attractive interpolymer interaction. These facets depend on the number of PNIPAM grafts attached to the PEI core. While a collapse in the smaller PNIPAM grafts is observed for the third polymer, there is no appearance of the interpolymer attractive interaction. These observations provide further insight into the association behavior of these copolymers, which is fundamental to developing a full understanding of how they interact with nucleic acids. Furthermore, the differing behaviors of the three copolymers over temperatures in which the PNIPAM blocks undergo coil-to-globule transitions is indicative of changes in the presentation of charged-core and hydrophobic chain components, which are key factors affecting nucleic acid binding and, ultimately, cell transfection ability.},
  doi      = {10.1021/bm701096p},
  eprint   = {https://doi.org/10.1021/bm701096p},
  file     = {:PhysicochemicalCharacterizationOfThermoresponsivePolyNIsopropylacrylamidePolyEthyleneImineGraftCopolymers_GriffithsEtAl_Biomacromolecules2008_SupportingInformation.pdf:PDF},
  keywords = {NMR, SANS, PFG, PNIPAM, poly(ethylene imine), PEI, copolymer},
  url      = {https://doi.org/10.1021/bm701096p},
}

@Article{Flood2008,
  author   = {Flood, Charlie and Cosgrove, Terence and Espidel, Youssef and Welfare, Eloise and Howell, Ian and Revell, Patricia},
  journal  = {Langmuir},
  title    = {Fourier-Transform Carr$-$Purcell$-$Meiboom$-$Gill NMR Experiments on Polymers in Colloidal Dispersions: How Many Polymer Molecules per Particle?},
  year     = {2008},
  note     = {PMID: 18588323},
  number   = {15},
  pages    = {7875--7880},
  volume   = {24},
  abstract = {Fourier transform relaxation NMR has been used to study how the mobility of poly(ethylene oxide) is affected by its adsorption onto colloidal silica particles of various sizes. Novel results have been obtained which illustrate the unexploited potential of this method for the study of interfacial species in complex systems. The results quantify how polymer mobility varies along an adsorption isotherm. When the particles are in excess, the polymer is strongly adsorbed and hence has a large spin$-$spin magnetic relaxation rate constant, R2. The value of R2 in this region increases with particle size, because the associated reduction in particle surface curvature results in a reduction in the mobility of the adsorbed polymer. This is accompanied by a reduction in the signal intensity, as a higher fraction of the polymer is adsorbed in the form of train segments too immobile to detect using the Carr$-$Purcell$-$Meiboom$-$Gill pulse sequence. When the polymer concentration reaches $\sim$0.5 mg m$-$2, the initial region of high affinity adsorption ends and so the polymer solution concentration increases. This is accompanied by a reduction in R2, which then approaches the value for a simple polymer solution in the absence of particles. The results are corroborated by comparison with rheological measurements and molecular dynamics simulations of an analogous particle$-$polymer system.},
  doi      = {10.1021/la800144c},
  eprint   = {https://doi.org/10.1021/la800144c},
  keywords = {NMR, CPMG, experimental, rheology, simulation},
  ranking  = {rank4},
  url      = {https://doi.org/10.1021/la800144c},
}

@Article{Shan2004,
  author   = {Shan, Jun and Chen, Jie and Nuopponen, Markus and Tenhu, Heikki},
  journal  = {Langmuir},
  title    = {Two Phase Transitions of Poly(N-isopropylacrylamide) Brushes Bound to Gold Nanoparticles},
  year     = {2004},
  note     = {PMID: 15969180},
  number   = {11},
  pages    = {4671--4676},
  volume   = {20},
  abstract = {The thermally induced phase transition of the poly(N-isopropylacrylamide) (PNIPAM) brush covalently bound to the surface of the gold nanoparticles was studied using high-sensitivity microcalorimetry. Two types of PNIPAM monolayer protected clusters (MPCs) of gold nanoparticles were employed, denoted as the cumyl- and the cpa-PNIPAM MPCs, bearing either a phenylpropyl end group or a carboxyl end group on each PNIPAM chain, respectively. The PNIPAM chains of both MPCs exhibit two separate transition endotherms; i.e., the first transition with a sharp and narrow endothermic peak occurs at lower temperature, while the second one with a broader peak occurs at higher temperature. With increase of the MPC concentration, the transition temperature corresponding to the first peak only slightly changes but the second transition temperature strongly shifts to lower temperature. The calorimetric enthalpy change in the first transition is much smaller than that in the second transition. The ratio of the calorimetric enthalpy change to the van't Hoff enthalpy change indicates that in the first transition PNIPAM segments show much higher cooperativity than in the second one. The investigation of pH dependence of two-phase transitions further indicates the PNIPAM brush reveals two separate transitions even with a change in interchain/interparticle association. The observations are tentatively rationalized by assuming that the PNIPAM brush can be subdivided into two zones, the inner zone and the outer zone. In the inner zone, the PNIPAM segments are close to the gold surface, densely packed, less hydrated, and undergo the first transition. In the outer zone, on the other hand, the PNIPAM segments are looser and more hydrated, adopt a restricted random coil conformation, and show a phase transition, which is dependent on both concentration of MPC and the chemical nature of the end groups of the PNIPAM chains. Aggregation of the particles, which may also affect the phase transition, is briefly discussed.},
  doi      = {10.1021/la0363938},
  eprint   = {https://doi.org/10.1021/la0363938},
  file     = {:Shan2004 - Two Phase Transitions of Poly(N Isopropylacrylamide) Brushes Bound to Gold Nanoparticles.pdf:PDF},
  keywords = {PNIPAM, gold particle, calorimetry, microcalorimetry, pH dependence},
  printed  = {printed},
  ranking  = {rank4},
  url      = {https://doi.org/10.1021/la0363938},
}

@Article{Yim2004,
  author   = {Yim, H. and Kent, M. S. and Mendez, S. and Balamurugan, S. S. and Balamurugan, S. and Lopez, G. P. and Satija, S.},
  journal  = {Macromolecules},
  title    = {Temperature-Dependent Conformational Change of PNIPAM Grafted Chains at High Surface Density in Water},
  year     = {2004},
  number   = {5},
  pages    = {1994--1997},
  volume   = {37},
  doi      = {10.1021/ma0354290},
  eprint   = {https://doi.org/10.1021/ma0354290},
  file     = {:Yim2004 - Temperature Dependent Conformational Change of PNIPAM Grafted Chains at High Surface Density in Water.pdf:PDF},
  keywords = {PNIPAM,},
  url      = {https://doi.org/10.1021/ma0354290},
}

@Article{Yim2006,
  author   = {Yim, H. and Kent, M. S. and Mendez, S. and Lopez, G. P. and Satija, S. and Seo, Y.},
  journal  = {Macromolecules},
  title    = {Effects of Grafting Density and Molecular Weight on the Temperature-Dependent Conformational Change of Poly(N-isopropylacrylamide) Grafted Chains in Water},
  year     = {2006},
  number   = {9},
  pages    = {3420--3426},
  volume   = {39},
  abstract = {Poly(N-isopropylacrylamide) (PNIPAM) is perhaps the most well-known member of the class of responsive polymers. Free PNIPAM chains have a lower critical solution temperature (LCST) in water at about 30 {$^{\circ}$}C. This very sharp transition (about 5 {$^{\circ}$}C) is attributed to alterations in the hydrogen-bonding interactions of the amide groups. Grafted chains of PNIPAM have shown promise for creating responsive surfaces. Conformational changes of the polymer are likely to play a role in some of these applications, in addition to changes in local interactions. In this work we investigated the temperature-dependent conformational changes of grafted PNIPAM chains in D2O over a range of surface density and molecular weight using neutron reflection. The surface density was controlled using mixed self-assembled monolayers. The molecular weight was controlled using atom transfer radical polymerization (ATRP). Grafted layers were synthesized on gold and also on silicon oxide. The largest conformational changes were observed for intermediate grafting densities and high molecular weights. This is explained by a competition between the well-known chain stretching effect of laterally interacting tethered chains and the phenomenological $\chi$($\phi$) determined empirically for PNIPAM free chains in water. Comparison is made with the recent numerical SCF calculations of Mendez et al.},
  doi      = {10.1021/ma0520949},
  eprint   = {https://doi.org/10.1021/ma0520949},
  file     = {:Yim2006 - Effects of Grafting Density and Molecular Weight on the Temperature Dependent Conformational Change of Poly(N Isopropylacrylamide) Grafted Chains in Water.pdf:PDF},
  keywords = {PNIPAM, grafting density},
  url      = {https://doi.org/10.1021/ma0520949},
}

@Article{Anoardo2001,
  author   = {E. Anoardo and G. Gali and G. Ferrante},
  journal  = {Applied Magnetic Resonance},
  title    = {Fast-field-cycling NMR: Applications and Instrumentation},
  year     = {2001},
  pages    = {365--404},
  volume   = {20},
  abstract = {Magnetic field cycling in nuclear magnetic resonance (NMR) experiments has been used since the early days of NMR. Originally such time-dependent magnetic field experiments were motivated to study cross relaxation, spin system thermodynamics and indirect detection of quadrupolar resonance. The first apparatus used mechanical or pneumatic systems to shoot the sample between two magnets, the typical {\textquotedblleft}flying time{\textquotedblright} being a few hundreds of milliseconds. As a natural evolution of the experimental technique and the need to extend its application to samples with higher relaxation rates, faster magnetic field switching devices were developed during the last years. Special electric networks combined with sophisticated air core magnets allowed one to switch magnetic fields between zero and fields of the order of 0.5 T in a few milliseconds. Today we refer to this new generation of instruments as {\textquotedblleft}fast-field-cycling{\textquotedblright} devices. The technique has been successfully used during the last years to obtain information on the molecular dynamics and order in different materials, ranging from organic solids, metals, polymers, liquid crystals, porous media to biological systems. At present it is also turning to be an important tool for the design of contrast agents for magnetic resonance imaging. Fast field cycling was mainly oriented toT1 relaxometry as a unique technique offering a dynamic window of several decades, ranging from few kilohertz to several megahertz. However, there exist less conventional applications of the technique that can also provide relevant information concerning molecular dynamics, structure and molecular order. In this article we will briefly deal with basic aspects of the technique, its evolution, present-day relevant applications and the last improvements concerning specialized instrumentation.},
  doi      = {https://doi.org/10.1007/BF03162287},
  file     = {:Anoardo2001 - Fast Field Cycling NMR_ Applications and Instrumentation.pdf:PDF},
  keywords = {NMR, field cycling, T1 relaxation},
}

@Article{Fischer1998,
  author   = {Fischer, Elmar and Grinberg, Farida and Kimmich, Rainer and Hafner, Siegfried},
  journal  = {Journal of Chemical Physics},
  title    = {Characterization of Polymer Networks Using the Dipolar Correlation Effect on the Stimulated Echo and Field-cycling Nuclear-magnetic Resonance Relaxometry},
  year     = {1998},
  month    = jul,
  pages    = {846--854},
  volume   = {109},
  abstract = {Chain dynamics in a series of styrene-butadiene rubbers (SBR) was studied with the aid of the dipolar correlation effect (DCE) and field-cycling NMR relaxometry (FCR). The typical time scales of the two techniques are t>10^-4 s and t10^-3 s, respectively, and therefore complementary. The crosslink density of the polymer networks was varied in a wide range. In order to prevent sinusoidal undulations of the stimulated-echo attenuation curves due to spin exchange between groups with different chemical-shift offsets, the DCE of the samples was examined using a modified radio frequency pulse sequence with additional pi pulses inserted in the free-evolution intervals. Residual dipolar couplings can thus be probed in samples where chemical-shift and dipolar interactions are of the same order. The dipolar correlations probed with the DCE in SBR networks turned out to exist on a time scale exceeding 300 ms. The short-time fluctuations (probed by FCR) and the long-time dynamics (probed by DCE) can be approached by power-law dipolar correlation functions with exponents -0.78+-0.02 and -1.5+-0.1, respectively. The crossover time is in the order of 1 ms. In contrast to FCR, the DCE data strongly depend on the crosslink density but not on the temperature in a range from 30 to 80 {$^{\circ}$}C. On this basis determinations of the crosslink density may be possible as an alternative to the usual mechanical torsion modulus measurements.},
  doi      = {10.1063/1.476624},
  file     = {:Fischer1998 - Characterization of Polymer Networks Using the Dipolar Correlation Effect on the Stimulated Echo and Field Cycling Nuclear Magnetic Resonance Relaxometry.pdf:PDF},
  keywords = {NMR, polymer, rubber, dipolar correlation effect, DCE, field-cycling relaxometry, FCR, chemical shift, crosslink density},
}

@Article{Halperin2015,
  author   = {Halperin, Avraham and Kr{\"{o}}ger, Martin and Winnik, Fran{\c{c}}oise M.},
  journal  = {Angewandte Chemie - International Edition},
  title    = {Poly(N-isopropyl\-acrylamide) Phase Diagrams: Fifty Years of Research},
  year     = {2015},
  number   = {51},
  pages    = {15342--15367},
  volume   = {54},
  abstract = {In 1968, Heskins and Guillet published the first systematic study of the phase diagram of poly(N-isopropylacrylamide) (PNIPAM), at the time a {\textquotedblleft}young polymer{\textquotedblright} first synthesized in 1956. Since then, PNIPAM became the leading member of the growing families of thermoresponsive polymers and of stimuli-responsive, {\textquotedblleft}smart{\textquotedblright} polymers in general. Its thermal response is unanimously attributed to its phase behavior. Yet, in spite of 50\hspace{0.25em}years of research, a coherent quantitative picture remains elusive. In this Review we survey the reported phase diagrams, discuss the differences and comment on theoretical ideas regarding their possible origins. We aim to alert the PNIPAM community to open questions in this reputably mature domain.},
  comment  = {Bulk PNIPAM phase diagram review. Attempt to explain differences and significance.},
  doi      = {10.1002/anie.201506663},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201506663},
  file     = {:Halperin2015 - Poly(N Isopropylacrylamide) Phase Diagrams_ Fifty Years of Research.pdf:PDF},
  keywords = {lower critical solution temperature, mesoglobules, metastability, tacticity, type II phase behavior, PNIPAM, review},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201506663},
}

@Article{Raiford1979,
  author   = {Raiford, David S. and Fisk, Cherie L. and Becker, Edwin D.},
  journal  = {Analytical Chemistry},
  title    = {Calibration of methanol and ethylene glycol nuclear magnetic resonance thermometers},
  year     = {1979},
  number   = {12},
  pages    = {2050--2051},
  volume   = {51},
  comment  = {R2D2 temperature calibration},
  doi      = {10.1021/ac50048a040},
  eprint   = {https://doi.org/10.1021/ac50048a040},
  file     = {:Raiford1979 - Calibration of Methanol and Ethylene Glycol Nuclear Magnetic Resonance Thermometers.pdf:PDF},
  keywords = {NMR, chemical shift, calibration, ethylene glycol},
  url      = {https://doi.org/10.1021/ac50048a040},
}

@Article{Schnauss1992,
  author   = {Schnauss, W. and Fujara, F. and Sillescu, H.},
  journal  = {Journal of Chemical Physics},
  title    = {The molecular dynamics around the glass transition and in the glassy state of molecular organic systems: A 2H$-$nuclear magnetic resonance study},
  year     = {1992},
  number   = {2},
  pages    = {1378--1389},
  volume   = {97},
  abstract = {2H-nuclear magnetic resonance (NMR)-spin-lattice relaxation experiments have been
performed for studying the crossover from viscous (a process) to secondary (fJ processes)
dynamics in the van der Waals liquid orthoterphenyl and the H-bridged network glycerol. The
essential and general features, observed in both systems, are the following: (a) a dominating a
process in the liquid and viscous regime; (b) a change from exponential to nonexponential
spin-lattice relaxation as the temperature is lowered below a characteristic temperature above
Tg; (c) the existence of a slow ( > 10 - 9 s) secondary reorientational process in the highly
viscous regime; and (d) the existence of a fast ( ~ 10 - 12 s) local process in the glassy state.
Whereas the slower process is shown to be the one known from dielectric studies, we attribute
the fast mode to a fJ process found in quasielastic neutron scattering.},
  doi      = {10.1063/1.463264},
  eprint   = {https://doi.org/10.1063/1.463264},
  keywords = {NMR, glycerol, glycerin,, spin-spin relaxation, t2, t1, relaxation},
  url      = {https://doi.org/10.1063/1.463264},
}

@Article{Hung2010,
  author   = {Ivan Hung and Zhehong Gan},
  journal  = {Journal of Magnetic Resonance},
  title    = {On the practical aspects of recording wideline QCPMG NMR spectra},
  year     = {2010},
  issn     = {1090-7807},
  number   = {2},
  pages    = {256--265},
  volume   = {204},
  abstract = {The practical aspects of applying CPMG for acquisition of wideline powder patterns are examined. It is shown that most distortions/modulations of spikelet spectra can be traced to the incoherent signal averaging from multiple coherence transfer pathways. A strategy for minimizing these distortions/modulations is described. Also, a few interesting observations regarding the implementation of the wideline WURST-QCPMG experiment are presented, namely the accumulation of second-order signal phase and the effects of varying the sweep rate and rf field of chirp pulses.},
  doi      = {https://doi.org/10.1016/j.jmr.2010.03.001},
  file     = {:HUNG2010 - On the practical aspects of recording wideline QCPMG NMR spectra.pdf:PDF},
  keywords = {NMR, CPMG, QCPMG, WURST, Second-order phase, Cl, Solid-state, NHMFL, Zirconocene dichloride},
  url      = {http://www.sciencedirect.com/science/article/pii/S1090780710000571},
}

@Article{Larsen1997,
  author   = {Larsen, Flemming H. and Jakobsen, Hans J. and Ellis, Paul D. and Nielsen, Niels Chr.},
  journal  = {The Journal of Physical Chemistry A},
  title    = {Sensitivity-Enhanced Quadrupolar-Echo NMR of Half-Integer Quadrupolar Nuclei. Magnitudes and Relative Orientation of Chemical Shielding and Quadrupolar Coupling Tensors},
  year     = {1997},
  number   = {46},
  pages    = {8597--8606},
  volume   = {101},
  abstract = {A novel approach to quadrupolar-echo (QE) NMR of half-integer quadrupolar nuclei in static powders is analyzed. By acquisition of the QE spectrum during a Carr$-$Purcell$-$Meiboom$-$Gill (CPMG) train of selective $\phi$ pulses, the second-order quadrupolar line shape for the central transition is split into a comb of sidebands leading to a considerable increase in the sensitivity compared to a conventional QE spectrum. The applicability of the method for determination of magnitudes and relative orientation of chemical shielding and quadrupolar coupling tensors is examined. Through numerical simulation and iterative fitting of experimental 87Rb (RbClO4 and RbVO3) and 59Co spectra (Co(NH3)5 Cl3), it is demonstrated that the quadrupolar CPMG experiment represents a useful method for studying half-integer quadrupolar nuclei exhibiting large quadrupolar coupling combined with anisotropic chemical shielding interactions. Sensitivity enhancements by a factor of up to about 30 are observed for the samples studied.},
  doi      = {10.1021/jp971547b},
  eprint   = {https://doi.org/10.1021/jp971547b},
  file     = {:Larsen1997 - Sensitivity-Enhanced Quadrupolar-Echo NMR of Half-Integer Quadrupolar Nuclei. Magnitudes and Relative Orientation of Chemical Shielding and Quadrupolar Coupling Tensors.pdf:PDF},
  keywords = {NMR, CPMG, Phase Cycle, quadrupole, quadrupolar interaction, t2, spin-spin, relaxation, QCPMG},
  url      = {https://doi.org/10.1021/jp971547b},
}

@Article{Larsen1998,
  author   = {Flemming H. Larsen and Hans J. Jakobsen and Paul D. Ellis and Niels Chr. Nielsen},
  journal  = {Chemical Physics Letters},
  title    = {Molecular dynamics from 2H Quadrupolar Carr--Purcell--Meiboom--Gill solid-state NMR spectroscopy},
  year     = {1998},
  issn     = {0009-2614},
  number   = {4},
  pages    = {467--473},
  volume   = {292},
  abstract = {The 2H quadrupolar Carr--Purcell--Meiboom--Gill (QCPMG) NMR experiment is proposed as a convenient method to obtain detailed information about molecular dynamics in solids. Compared to the quadrupolar-echo (QE) experiment QCPMG offers two advantages. First, a sensitivity enhancement by about an order of magnitude is achieved by splitting the QE spectrum into spin-echo sidebands. Second, the lineshape of the individual sidebands provides detailed information about the molecular dynamics and increases the dynamic range by two orders of magnitude. The 2H QCPMG method is demonstrated experimentally and numerically using the two-fold flip process in dimethyl sulfone.},
  doi      = {https://doi.org/10.1016/S0009-2614(98)00777-5},
  keywords = {NMR, CPMG, QCPMG, 2H, deuteron, spin-spin, t2, relaxation},
  url      = {http://www.sciencedirect.com/science/article/pii/S0009261498007775},
}

@Article{Bloom1987,
  author   = {Bloom, Myer and Sternin, Edward},
  journal  = {Biochemistry},
  title    = {Transverse nuclear spin relaxation in phospholipid bilayer membranes},
  year     = {1987},
  number   = {8},
  pages    = {2101--2105},
  volume   = {26},
  abstract = {Experimental proof is presented that some of the motions responsible for transverse relaxation (T2) in deuterium magnetic resonance (2H NMR) experiments on acyl chains of a model membrane in the liquid-crystalline phase are extremely slow on the 2H NMR time scale being characterized by a correlation time \tau_2>>10$\prime$-5s. The experiments used to investigate these slow motions involve a form of the Carr-Purcell-Meiboom-Gill pulse sequence modified so as to be suitable for 2H NMR. The most plausible mechanism responsible for T2 relaxation is the gradual change in the average molecular orientation due to lateral diffusion of the phospholipid molecules along curved membrane surfaces. A procedure for separating contributions to T2 relaxation due to slow and fast motions is described.},
  doi      = {10.1021/bi00382a007},
  eprint   = {https://doi.org/10.1021/bi00382a007},
  file     = {:Bloom1987 - Transverse nuclear spin relaxation in phospholipid bilayer membranes.pdf:PDF},
  keywords = {NMR, CPMG, QCPMG, 2H, T2, transverse relaxation, spin-spin, deuteron},
  url      = {https://doi.org/10.1021/bi00382a007},
}

@Article{Vega1989,
  author   = {A. J. Vega and R. Poupko and Z. Luz},
  journal  = {Journal of Magnetic Resonance},
  title    = {Dynamic 2H NMR by quadrupole echo train in the fast-exchange limit. Ring inversion of cyclohexane-d12 in liquid crystalline solvents},
  year     = {1989},
  issn     = {0022-2364},
  number   = {1},
  pages    = {111--127},
  volume   = {83},
  abstract = {A NMR method is proposed to determine the kinetic and magnetic parameters for spin I = 1 nuclei with quadrupole interactions, undergoing exchange in the fast dynamic limit. The method consists of measuring the quadrupole echo decay rate under the effect of a sequence of $\phi$2 pulses and is the quadrupole echo analog of the Can-Purcell-Meiboom-Gill experiment on spin I = 12 systems. The echo decay is exponential, and by use of the average Hamiltonian formalism, a general expression is derived for its relaxation rate as function of the pulse repetition rate and the $\phi$2 pulse width. Expressions are also given for the limiting cases of infinitely narrow pulses at one end and spin-lock conditions which correspond to T1$_\rho$, on the other. The method is applied to a liquid crystalline solution of cyclohexane-d12 undergoing rapid ring inversion. The kinetic and magnetic parameters derived by the present method are in perfect agreement with those obtained earlier by complete lineshape analysis of the deuteron NMR spectrum of this system.},
  doi      = {https://doi.org/10.1016/0022-2364(89)90295-3},
  file     = {:Vega1989 - Dynamic 2H NMR by quadrupole echo train in the fast-exchange limit. Ring inversion of cyclohexane-d12 in liquid crystalline solvents.pdf:PDF},
  keywords = {NMR, CPMG, QCPMG, quadrupole, exchange, 2H, deuteron},
  url      = {http://www.sciencedirect.com/science/article/pii/0022236489902953},
}

@Article{Mueller1991,
  author   = {K. M{\"{u}}ller and R. Poupko and Z. Luz},
  journal  = {Journal of Magnetic Resonance},
  title    = {2D Presentation of the quadrupole-echo modulation in chemically exchanging systems of spins I = 1},
  year     = {1991},
  issn     = {0022-2364},
  number   = {2},
  pages    = {291--298},
  volume   = {93},
  abstract = {The intensity of the NMR echo signal in a system undergoing slow exchange exhibits modulation effects when recorded as function of the time interval, $\tau$, between the excitation and refocusing pulses. In the present work this phenomenon is investigated in terms of 2D Fourier transform spectra of quadrupole-echo experiments performed on pairs of interchanging nuclei of spin I = 1. It is shown that the dynamic process in the extreme slow-exchange limit gives rise to characteristic sidebands and ridges whose relative phases and shapes depend on the exchange rate and on the relative signs of the quadrupole interactions of the interchanging nuclei. The theoretical predictions are compared with deuterium NMR measurements performed on cyclohexane-d12 dissolved in a nematic solvent as well as on a number of other dynamic systems in liquid crystalline solutions. Potential applications of the method for determining reaction mechanisms and relative signs of quadrupole-interaction constants are discussed.},
  doi      = {https://doi.org/10.1016/0022-2364(91)90006-F},
  file     = {:MULLER1991 - 2D Presentation of the quadrupole-echo modulation in chemically exchanging systems of spins I = 1.pdf:PDF},
  keywords = {NMR, CPMG, QCPMG, spin-1, 2H, deuteron},
  url      = {http://www.sciencedirect.com/science/article/pii/002223649190006F},
}

@Article{Mueller1990,
  author   = {K. M{\"{u}}ller and R. Poupko and Z. Luz},
  journal  = {Journal of Magnetic Resonance},
  title    = {Deuterium quadrupole and carr-purcell echo relaxation in chemically exchanging systems. theory and experiments for the two-site case},
  year     = {1990},
  issn     = {0022-2364},
  number   = {1},
  pages    = {19--39},
  volume   = {90},
  abstract = {A theoretical analysis of the quadrupole echo and Carr-Purcell echo experiments for pairs of I = 1 quadrupole nuclei undergoing mutual exchange is given. Exact numerical calculations of the echo intensities as a function of the time interval between the pulses and the kinetic and magnetic parameters are presented. The results are compared with deuterium NMR measurements performed on two systems involving cyclohexane-d12 under conditions at which the molecules undergo ring inversion. These include a liquid crystalline solution of C6D12 aligned in a magnetic field and a powder sample of the thiourea-C6 D12 inclusion compound. Three experimental methods were applied to study these systems: (i) complete analysis of the ID spectrum lineshape, (ii) quadrupole echo intensity measurements as a function of the time interval between pulses, and (iii) Carr-Purcell echo relaxation measurements as a function of the pulse repetition rates. Within the experimental accuracy all three methods gave identical results. It is argued that under certain conditions pulse experiments may be advantageous or even necessary for a complete quantitative analysis of dynamic effects in deuterium NMR of solids.},
  doi      = {https://doi.org/10.1016/0022-2364(90)90363-E},
  file     = {:Mueller1990 - Deuterium quadrupole and carr-purcell echo relaxation in chemically exchanging systems. theory and experiments for the two-site case.pdf:PDF},
  keywords = {NMR, 2H, CPMG, QCPMG, quadrupole, relaxation, chemical exchange},
  url      = {http://www.sciencedirect.com/science/article/pii/002223649090363E},
}

@Article{Brittain2007,
  author   = {William J. Brittain and Sergiy Minko},
  journal  = {Journal of Polymer Science Part A: Polymer Chemistry},
  title    = {A Structural Definition of Polymer Brushes},
  year     = {2007},
  abstract = {In this article, we consolidate several literature re- ports in an attempt to provide a structural definition of a polymer brush as a tethered polymer layer with a high grafting density of polymer chains. We will try to distinguish a brush from grafted polymer layers and coated layers and provide a reasonable approach to the description of the brush regime with a single parameter S---reduced grafting density. Furthermore, we will attempt to describe the relevance of this description to applications. This article is timely given the continuing interest relating to brushes on flat substrates, nanoparticles, and the walls of micro-channels.},
  doi      = {10.1002/pola.22180},
  file     = {:Brittain2007 - A Structural Definition of Polymer Brushes.pdf:PDF},
  keywords = {films, monolayers, nanoparticles, polymer, brush},
}

@Article{Zhang2018,
  author   = {Zhang, Li and Bei, Ho Pan and Piao, Yun and Wang, Yufeng and Yang, Mo and Zhao, Xin},
  journal  = {ChemPhysChem},
  title    = {Polymer-Brush-Grafted Mesoporous Silica Nanoparticles for Triggered Drug Delivery},
  year     = {2018},
  number   = {16},
  pages    = {1956--1964},
  volume   = {19},
  abstract = {Mesoporous silica nanoparticles (MSNs) have been demonstrated to be one of the most promising drug-delivery systems (DDSs) to transport a variety of drugs/biomolecules. Functionalization of MSN surfaces with responsive polymer brushes leads to intelligent and controllable drug-delivery properties, that is, the encapsulated drugs/biomolecules will only be released upon certain stimuli including pH, temperature, light, enzyme, ultrasound, or redox, thus maximizing their therapeutic efficiency and minimizing side effects. These polymer brushes can also increase the stability and extend the release period of the loaded cargoes. This Minireview presents an overview of recent research progress on stimuli-responsive controlled DDSs based on polymer-brush-grafted MSNs. Utilizing the switching abilities of the grafted responsive polymer brushes, the smart DDSs show great potential for biomedical applications, especially for cancer therapy.},
  doi      = {10.1002/cphc.201800018},
  eprint   = {https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/cphc.201800018},
  file     = {:Zhang2018 - Polymer-Brush-Grafted Mesoporous Silica Nanoparticles for Triggered Drug Delivery.pdf:PDF},
  keywords = {MSNs, polymer brushes, smart drug delivery, application focused, bilder, application-focused},
  url      = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/cphc.201800018},
}

@Article{Ayres2010,
  author     = {Ayres, Neil},
  journal    = {Polymer Chemistry},
  title      = {Polymer brushes: Applications in biomaterials and nanotechnology},
  year       = {2010},
  pages      = {769--777},
  volume     = {1},
  abstract   = {Surface-confined macromolecules known as polymer brushes are being increasing applied to a variety of areas. As more information is gained on the molecular structure of polymer brushes and how they respond to environmental stimuli{,} these applications are becoming wider ranging and better defined. This review seeks to highlight recent contributions in two broad areas: biotechnology and nanotechnology. These are positions in which polymer brushes are well-suited to offer performance gains. Examples are given that describe the benefits of using a well defined{,} covalently bound{,} and densely grafted polymer including in areas such as prevention of bacterial adherence{,} cell attachment{,} electrochemistry{,} and formation of colloidal crystals.},
  doi        = {10.1039/B9PY00246D},
  file       = {:Ayres2010 - Polymer brushes_ Applications in biomaterials and nanotechnology.pdf:PDF},
  issue      = {6},
  keywords   = {polymer brush, application focused, review, application-focused},
  publisher  = {The Royal Society of Chemistry},
  ranking    = {rank4},
  readstatus = {read},
  url        = {http://dx.doi.org/10.1039/B9PY00246D},
}

@Book{Advincula2005,
  editor    = {Rigoberto C. Advincula and William J. Brittain and Kenneth C. Caster and J{\"{u}}rgen R{\"{u}}he},
  publisher = {John Wiley \& Sons, Ltd},
  title     = {Polymer Brushes: Synthesis, Characterization, Applications},
  year      = {2005},
  isbn      = {3-527-31033-9},
  abstract  = {In recent years, the synthesis of polymer brushes through surface-initiated polymerization reactions has received significant attention. In this overview, several different synthetic strategies for the generation of polymer brushes are reviewed. The unique physical properties of polymer brushes that arise from the covalent anchoring of the polymer chains to the solid substrate are discussed and compared to the properties of polymer layers deposited by other techniques of thin film generation. Finally, examples are provided that highlight some recent developments aimed at strategies for the functionalization of surfaces with polymer brushes, at ways of realizing smart surfaces with switchable properties, and at the generation of micro- and nanostructured polymer monolayers.},
  doi       = {10.1002/3527603824.fmatter},
  eprint    = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/3527603824.fmatter},
  file      = {:Advincula2005 - Polymer Brushes_ Synthesis, Characterization, Applications.pdf:PDF},
  keywords  = {polymer brushes, book, application focused, application-focused},
  url       = {https://onlinelibrary.wiley.com/doi/book/10.1002/3527603824},
}

@Article{Gurumoorthy2011,
  author   = {Anand V. P. Gurumoorthy and K. H. Khan},
  journal  = {Recent Research in Science and Technology},
  title    = {Polymers at Interfaces: Biological and Non-biological Applications},
  year     = {2011},
  month    = feb,
  number   = {2},
  volume   = {3},
  file     = {:Gurmoorthy2011 - Polymers at Interfaces_ Biological and Non-biological Applications.pdf:PDF},
  keywords = {bilder, trian loop tail},
  url      = {http://updatepublishing.com/journal/index.php/rrst/article/view/611},
}

@Article{Antonijevic2003,
  author   = {Sasa Antonijevic and Stephen Wimperis},
  journal  = {Journal of Magnetic Resonance},
  title    = {Refocussing of Chemical and Paramagnetic shift anisotropies in 2H NMR using the quadrupolar-echo experiment},
  year     = {2003},
  issn     = {1090-7807},
  number   = {2},
  pages    = {343--350},
  volume   = {164},
  abstract = {A simple two-pulse spin-echo experiment is shown to refocus inhomogeneous broadening arising from both chemical and/or paramagnetic shift anisotropy and a first-order I=1 quadrupolar interaction. The method is shown to yield 2H NMR spectra of a paramagnetic solid (CuCl2$\cdot$2D2O) and of a non-paramagnetic solid (D2C2O4$\cdot$2D2O) that are significantly less distorted than those provided by the conventional quadrupolar-echo method. The technique will thus prove useful in studies of motion and dynamics where detailed analysis of the 2H lineshape is performed.},
  doi      = {https://doi.org/10.1016/S1090-7807(03)00272-6},
  file     = {:Antonijevic2003 - Refocussing of Chemical and Paramagnetic shift anisotropies in 2H NMR using the quadrupolar-echo experiment.pdf:PDF},
  keywords = {NMR, 2H NMR, solid echo, chemical shift, pulse sequence, phase cycle},
  printed  = {printed},
  url      = {http://www.sciencedirect.com/science/article/pii/S1090780703002726},
}

@Book{Kimmich1997,
  author    = {Rainer Kimmich},
  publisher = {Springer-Verlag Berlin Heidelberg},
  title     = {NMR: tomography, diffusometry, relaxometry},
  year      = {1997},
  isbn      = {3540618228},
  file      = {:Kimmich1997 - NMR_ Tomography, Diffusometry, Relaxometry.pdf:PDF;:Chapter01.pdf:PDF;:Chapter02.pdf:PDF;:Chapter03.pdf:PDF;:Chapter04.pdf:PDF;:Chapter05.pdf:PDF;:Chapter06.pdf:PDF;:Chapter07.pdf:PDF;:Chapter08.pdf:PDF;:Chapter09.pdf:PDF;:Chapter10.pdf:PDF;:Chapter11.pdf:PDF;:Chapter12.pdf:PDF;:Chapter13.pdf:PDF;:Chapter14.pdf:PDF;:Chapter15.pdf:PDF;:Chapter16.pdf:PDF;:Chapter17.pdf:PDF;:Chapter18.pdf:PDF;:Chapter19.pdf:PDF;:Chapter20.pdf:PDF;:Chapter21.pdf:PDF;:Chapter22.pdf:PDF;:Chapter23.pdf:PDF;:Chapter24.pdf:PDF;:Chapter25.pdf:PDF;:Chapter26.pdf:PDF;:Chapter27.pdf:PDF;:Chapter28.pdf:PDF;:Chapter29.pdf:PDF;:Chapter30.pdf:PDF;:Chapter31.pdf:PDF;:Chapter32.pdf:PDF;:Chapter33.pdf:PDF;:Chapter34.pdf:PDF;:Chapter35.pdf:PDF;:Chapter36.pdf:PDF;:Chapter37.pdf:PDF;:Chapter38.pdf:PDF;:Chapter39.pdf:PDF;:Chapter40.pdf:PDF;:Chapter41.pdf:PDF;:Chapter42.pdf:PDF;:Chapter43.pdf:PDF;:Chapter44.pdf:PDF;:Chapter45.pdf:PDF;:Chapter46.pdf:PDF;:Chapter47.pdf:PDF;:Chapter48.pdf:PDF;:Chapter49.pdf:PDF;:Chapter50.pdf:PDF;:Chapter51.pdf:PDF;:Chapter52.pdf:PDF;:References.pdf:PDF;:SubjectIndex.pdf:PDF;:SymbolsAbbreviations.pdf:PDF;:TitlePreface.pdf:PDF},
  keywords  = {NMR, book, irreducible tensor operators},
}

@Article{Li2020,
  author   = {Li, Danyang and Xu, Lizhou and Wang, Jing and Gautrot, Julien E.},
  journal  = {Advanced Healthcare Materials},
  title    = {Responsive Polymer Brush Design and Emerging Applications for Nanotheranostics},
  year     = {2020},
  pages    = {2000953},
  abstract = {Responsive polymer brushes are a category of polymer brushes that are capable of conformational and chemical changes in response to external stimuli. They offer unique opportunities for the control of bio$-$nano interactions due to the precise control of chemical and structural parameters such as the brush thickness, density, chemistry, and architecture. The design of responsive brushes at the surface of nanomaterials for theranostic applications has developed rapidly. These coatings can be generated from a very broad range of nanomaterials, without compromising their physical, photophysical, and imaging properties. Although the use of responsive brushes for nanotheranostic remains in its early stages, in this review, the aim is to present how the systems developed to date can be combined to control sensing, imaging, and controlled delivery of therapeutics. The recent developments for such design and associated methods for the synthesis of responsive brushes are discussed. The responsive behaviors of homo polymer brushes and brushes with more complex architectures are briefly reviewed, before the applications of responsive brushes as smart delivery systems are discussed. Finally, the recent work is summarized on the use of responsive polymer brushes as novel biosensors and diagnostic tools for the detection of analytes and biomarkers.},
  doi      = {10.1002/adhm.202000953},
  eprint   = {https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/adhm.202000953},
  keywords = {biosensing, diagnosis, drug delivery, nanomaterials, nanotheranostics, polymer brushes, application focused, medical, review, application-focused},
  url      = {https://www.onlinelibrary.wiley.com/doi/abs/10.1002/adhm.202000953},
}

@Article{Ren2020,
  author   = {Ren, Hao and Qiu, Xing-Ping and Shi, Yan and Yang, Peng and Winnik, Fran{\c{c}}oise M.},
  journal  = {Macromolecules},
  title    = {The Two Phase Transitions of Hydrophobically End-Capped Poly(N-isopropylacrylamide)s in Water},
  year     = {2020},
  number   = {13},
  pages    = {5105--5115},
  volume   = {53},
  abstract = {High-sensitivity differential scanning calorimetry (HS-DSC) thermograms of aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions present a sharp unimodal endotherm that signals the heat-induced dehydration/collapse of the PNIPAM chain. Similarly, $\alpha$,$\omega$-di-n-octadecyl-PNIPAM (C18-PN-C18) aqueous solutions exhibit a unimodal endotherm. In contrast, aqueous solutions of $\alpha$,$\omega$-hydrophobically modified PNIPAMs with polycyclic terminal groups, such as pyrenylbutyl (Py-PN-Py), adamantylethyl (Ad-PN-Ad), and azopyridine- (C12-PN-AzPy) moieties, exhibit bimodal thermograms. The origin of the two transitions was probed using microcalorimetry measurements, turbidity tests, variable temperature 1H NMR (VT-NMR) spectroscopy, and 2-dimensional NOESY experiments with solutions of polymers of molar mass (Mn) from 5 to 20 kDa and polymer concentrations of 0.1 to 3.0 mg/mL. The analysis outcome led us to conclude that the difference of the thermograms reflects the distinct self-assembly structures of the polymers. C18-PN-C18 assembles in water in the form of flower micelles held together by a core of tightly packed n-C18 chains. In contrast, polymers end-tagged with azopyridine, pyrenylbutyl, or adamantylethyl form a loose core that allows chain ends to escape from the micelles, to reinsert in them, or to dangle in surrounding water. The predominant low temperature (T1) endotherm, which is insensitive to polymer concentration, corresponds to the dehydration/collapse of PNIPAM chains within the micelles, while the higher temperature (T2) endotherm is attributed to the dehydration of dangling chains and intermicellar bridges. This study of the two phase transitions of telechelic PNIPAM homopolymer highlights the rich variety of morphologies attainable via responsive hydrophobically modified aqueous polymers and may open the way to a variety of practical applications.},
  doi      = {10.1021/acs.macromol.0c00487},
  eprint   = {https://doi.org/10.1021/acs.macromol.0c00487},
  keywords = {PNIPAM, DSC, microcalorimetry, NMR, turbidity,},
  url      = {https://doi.org/10.1021/acs.macromol.0c00487},
}

@Article{Mishra2020,
  author   = {Smrutirekha Mishra and Arti Kataria and Bishwajit Kundu and Leena Nebhani},
  journal  = {Applied Nanoscience},
  title    = {Hybrid mesoporous silica-based nanocarriers for responsive drug release in cancerous cell line},
  year     = {2020},
  abstract = {In this work, the synthesis of organic--inorganic hybrids based on pH-responsive, poly(acrylic acid) (PAA) and thermoresponsive, poly(N-isopropyl acrylamide) (PNIPAM), grafted from RAFT agent-primed mesoporous silica nanoparticles (MSNs), has been studied. The confirmation of polymer grafting was obtained through several techniques, for example, FTIR spectroscopy, NMR spectroscopy, etc. The presence of C--H stretching vibrations from FTIR confirmed the presence of organic network in the inorganic MSNs. Further support appeared as notable resonances in 13C solid-state NMR. The resonance at 175{~}ppm from C=O group for PAA-grafted MSNs, and at 170--172{~}ppm from C=O group for PNIPAM-grafted MSNs confirmed the grafting of polymer from the RAFT agent-primed MSNs. Morphological analysis for PAA- and PNIPAM-grafted MSNs was performed using FESEM and TEM. The images manifested spherical shape for isobutyric acid group, and short rod shape for phenyl ethyl group-containing RAFT agent-primed MSNs. Subsequently, for assessing their effectiveness as drug delivery vehicle, the anti-cancerous drug doxorubicin hydrochloride (Dox) was loaded into the MSNs. An effective loading in the range of 50--55% in case of PAA-grafted and 49--61% in case of PNIPAM-grafted MSNs (at pH 7.4, 25{~}{$^{\circ}$}C) was observed. Subsequently release efficiencies for these Dox-encapsulated MSNs were studied at varying pH, temperature and time. The treatment of cultured MCF-7 cell lines by the control MSNs and polymer-grafted MSNs revealed that they are non-toxic. However, when the MSNs were Dox-loaded, the PAA-grafted ones demonstrated higher cytotoxicity than the PNIPAM-grafted MSNs at equivalent dose at pH 7.4 and 37{$^{\circ}$}C. Together with other established features, we show that the polymer-grafted MSNs studied in this work can be utilized as an efficient drug delivery system for different therapeutic applications.},
  doi      = {https://doi.org/10.1007/s13204-020-01564-y},
  keywords = {PAA, PNIPAM, NMR, drug delivery, application focused, mesoporous silica nanoparticles, FTIR, RAFT, TEM, application-focused},
}

@Article{Zhang2008,
  author    = {Zhang, Jianming and Nylander, Tommy and Campbell, Richard A. and Rennie, Adrian R. and Zauscher, Stefan and Linse, Per},
  journal   = {Soft Matter},
  title     = {Novel evaluation method of neutron reflectivity data applied to stimulus-responsive polymer brushes},
  year      = {2008},
  pages     = {500--509},
  volume    = {4},
  abstract  = {Neutron reflectivity (NR) measurements have been performed on stimulus-responsive polymer brushes containing N-isopropylacrylamide (NIPAAM) at different temperatures and contrasts using two different brush samples of roughly the same grafting density and layer thickness. The NR data were analyzed using a novel method employing polymer density profiles predicted from lattice mean-field theory augmented with a polymer model to describe polymer solubility that decreases with increasing temperature. The predicted density profiles at the different temperatures were self-consistent with the experimentally observed profiles; hence the experimental data lend credibility to the theory. We found that the brush thickness decreased from 220 to 160 nm and the polymer volume fraction increased from 55 to 75% when increasing temperature from 293 to 328 K. The new evaluation approach involved significantly fewer independent fitting parameters than methods involving layers of uniform densities. Furthermore{,} the approach can straightforwardly be extended to analyze neutron reflectivity data of grafted{,} weakly charged polymers that display pH-sensitive behaviour and also to block copolymers and to surfaces with adsorbed polymers. We propose that such accurate model calculations provide a tool to interpret results from NR experiments more effectively and design neutron reflectivity experiments for optimal outcome.},
  doi       = {10.1039/B714911E},
  file      = {:Zhang2008 - Novel Evaluation Method of Neutron Reflectivity Data Applied to Stimulus Responsive Polymer Brushes.pdf:PDF},
  issue     = {3},
  keywords  = {polymer brush, neutron reflectivity, stimuli responsive},
  publisher = {The Royal Society of Chemistry},
  url       = {http://dx.doi.org/10.1039/B714911E},
}

@Article{Akgun2005,
  author   = {Akgun, Bulent and Brittain, William J. and Li, Xuefa and Wang, Jin and Foster, Mark D.},
  journal  = {Macromolecules},
  title    = {Interface Roughness Correlation in Diblock Copolymer Brushes Synthesized by Atom Transfer Radical Polymerization},
  year     = {2005},
  number   = {21},
  pages    = {8614--8616},
  volume   = {38},
  comment  = {Here we show for the first time that,indeed, the interfaces of diblock copolymer brushes canbe correlated over a wide range of thicknesses, that theexistence of the correlation is not an artifact of deposi-tion history, and that weakening the segregation at theinternal interface by swelling with a nonselective goodsolvent weakens the interface correlation.},
  doi      = {10.1021/ma051277s},
  eprint   = {https://doi.org/10.1021/ma051277s},
  file     = {:Akgun2005 - Interface Roughness Correlation in Diblock Copolymer Brushes Synthesized by Atom Transfer Radical Polymerization.pdf:PDF},
  keywords = {polymer brush, x-ray reflectometry},
  url      = {https://doi.org/10.1021/ma051277s},
}

@Article{Ishida2007,
  author   = {Ishida, Naoyuki and Biggs, Simon},
  journal  = {Langmuir},
  title    = {Direct Observation of the Phase Transition for a Poly(N-isopropylacryamide) Layer Grafted onto a Solid Surface by AFM and QCM-D},
  year     = {2007},
  note     = {PMID: 17902714},
  number   = {22},
  pages    = {11083--11088},
  volume   = {23},
  abstract = {The temperature-induced structural changes of a thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) layer grafted onto a silica substrate were investigated in aqueous solution using an atomic force microscope (AFM) and a quartz crystal microbalance with dissipation (QCM-D). A PNIPAM layer was grafted onto the silicon wafer surface by free radical polymerization of NIPAM to obtain a high molecular weight polymer layer with low-grafting density overall. By AFM imaging, the transition of the grafted PNIPAM chains from a brush-like to a mushroom-like state was clearly visualized:\hspace{0.167em} The surface images of the plate were featureless at temperatures below the LCST commensurate with a brush-like layer, whereas above the LCST, a large number of domain structures with a characteristic size of $\sim$100 nm were seen on the surface. Both frequency and dissipation data obtained using QCM-D showed a significant change at the LCST. Analysis of these data confirmed that the observed PNIPAM structural transition was caused by a collapse of the brush-like structure as a result of dehydration of the polymer chains.},
  doi      = {10.1021/la701461b},
  eprint   = {https://doi.org/10.1021/la701461b},
  file     = {:Ishida2007 - Direct Observation of the Phase Transition for a Poly(N Isopropylacryamide) Layer Grafted onto a Solid Surface by AFM and QCM D.pdf:PDF},
  keywords = {PNIPAM, AFM, QCM, polymer brush},
  ranking  = {rank3},
  url      = {https://doi.org/10.1021/la701461b},
}

@Book{Jordan2006,
  editor    = {Rainer Jordan},
  publisher = {Springer Berlin Heidelberg},
  title     = {Surface-Initiated Polymerization 1},
  year      = {2006},
  isbn      = {9783540302476},
  series    = {Advances in Polymer Science},
  file      = {:Jordan2006 - Surface Initiated Polymerization 1.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Polymerbrush_Synthesis/SurfaceInitiatedPolymerization/SurfaceInitiatedPolymerization_1/Tsujii2006_Chapter_StructureAndPropertiesOfHigh-D.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Polymerbrush_Synthesis/SurfaceInitiatedPolymerization/SurfaceInitiatedPolymerization_1/2006_Bookmatter_Surface-InitiatedPolymerizatio_Backmatter.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Polymerbrush_Synthesis/SurfaceInitiatedPolymerization/SurfaceInitiatedPolymerization_1/Advincula2006_Chapter_PolymerBrushesByAnionicAndCati.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Polymerbrush_Synthesis/SurfaceInitiatedPolymerization/SurfaceInitiatedPolymerization_1/Buchmeiser2006_Chapter_MetathesisPolymerizationToAndF.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Polymerbrush_Synthesis/SurfaceInitiatedPolymerization/SurfaceInitiatedPolymerization_1/Dyer2006_Chapter_PhotoinitiatedSynthesisOfGraft.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Polymerbrush_Synthesis/SurfaceInitiatedPolymerization/SurfaceInitiatedPolymerization_1/Matsuda2006_Chapter_Photoiniferter-DrivenPrecision.pdf:PDF},
  keywords  = {book, polymer brush synthesis},
}

@Book{Jordan2006a,
  editor    = {Rainer Jordan},
  publisher = {Springer Berlin Heidelberg},
  title     = {Surface-Initiated Polymerization 2},
  year      = {2006},
  isbn      = {9783540302513},
  series    = {Advances in Polymer Science},
  file      = {:/autohome/saeckech/Promotion/Literatur/Polymerbrush_Synthesis/SurfaceInitiatedPolymerization/SurfaceInitiatedPolymerization_2/2006_Bookmatter_Surface-InitiatedPolymerizatio_Frontmatter.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Polymerbrush_Synthesis/SurfaceInitiatedPolymerization/SurfaceInitiatedPolymerization_2/2006_Bookmatter_Surface-InitiatedPolymerizatio_Backmatter.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Polymerbrush_Synthesis/SurfaceInitiatedPolymerization/SurfaceInitiatedPolymerization_2/Bergbreiter-Kippenberger2006_Chapter_HyperbranchedSurfaceGraftPolym.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Polymerbrush_Synthesis/SurfaceInitiatedPolymerization/SurfaceInitiatedPolymerization_2/Bhat2006_Chapter_Surface-GraftedPolymerGradient.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Polymerbrush_Synthesis/SurfaceInitiatedPolymerization/SurfaceInitiatedPolymerization_2/Brittain2006_Chapter_SurfaceRearrangementOfDiblockC.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Polymerbrush_Synthesis/SurfaceInitiatedPolymerization/SurfaceInitiatedPolymerization_2/Naji2006_Chapter_TheoreticalApproachesToNeutral.pdf:PDF},
  keywords  = {book, polymer brush synthesis},
}

@Article{Mizutani2008,
  author   = {Aya Mizutani and Akihiko Kikuchi and Masayuki Yamato and Hideko Kanazawa and Teruo Okano},
  journal  = {Biomaterials},
  title    = {Preparation of thermoresponsive polymer brush surfaces and their interaction with cells},
  year     = {2008},
  issn     = {0142-9612},
  number   = {13},
  pages    = {2073--2081},
  volume   = {29},
  abstract = {Poly(N-isopropylacrylamide) (PIPAAm) brush surfaces with different layer thickness on polystyrene substrates were prepared by surface-initiated atom transfer radical polymerization (ATRP). Surface characteristics of PIPAAm brushes and their influence on adhesion and detachment of bovine carotid artery endothelial cells (ECs) were controlled by PIPAAm layer thickness. Surface hydrophilicity increased with PIPAAm layer thickness at 37{$^{\circ}$}C because PIPAAm brush surfaces with higher thickness provide more extended chain conformations with relatively high chain mobility, and accompanying polymer chain hydration. These surface property alterations lead to negligible cell adhesion through minimal matrix protein adsorption and also modified surface modulus. By adjusting polymerization reaction conditions and time, polymer layers supporting confluent cultures of ECs were possible. Confluent EC monolayers spontaneously detached as contiguous cell sheets from PIPAAm brush surfaces at reduced temperatures. Thermoresponsive cell adhesion and detachment behavior were analyzed from the standpoint of surface physicochemical characteristics. Thermoresponsive surfaces prepared by surface-initiated ATRP techniques allow surface selection in preparing cell sheets from attachment-dependent cells having relatively strong adhesive property for tissue engineering applications.},
  doi      = {https://doi.org/10.1016/j.biomaterials.2008.01.004},
  file     = {:Mizutani2008 - Preparation of Thermoresponsive Polymer Brush Surfaces and Their Interaction with Cells.pdf:PDF},
  keywords = {Thermoresponsive polymer, Poly(-isopropylacrylamide), PNIPAM, Atom transfer radical polymerization, Cell culture, Polystyrene substrates, brush, application focused, application-focused},
  url      = {http://www.sciencedirect.com/science/article/pii/S0142961208000227},
}

@Article{Matsuda2007,
  author   = {Matsuda, N. and Shimizu, T. and Yamato, M. and Okano, T.},
  journal  = {Advanced Materials},
  title    = {Tissue Engineering Based on Cell Sheet Technology},
  year     = {2007},
  number   = {20},
  pages    = {3089--3099},
  volume   = {19},
  abstract = {Cell sheet technology enables novel approaches to tissue engineering without the use of biodegradable scaffolds. Cell sheet technology consists of a temperature-responsive culture dish, which enables reversible cell adhesion to and detachment from the dish surface by controllable hydrophobicity of the surface. This allows for a non-invasive harvest of cultured cells as an intact monolayer cell sheet including deposited extra cellular matrices. The monolayer cell sheet can be transplanted to host tissues without using biodegradable scaffolds and sutures. Thick tissue constructs and patterned cell sheets using two or more kinds of cell source are also developed by means of layered cell sheets in vitro. This Progress Report summarizes temperature-controlled cell adhesion-detachment behavior and applications of the cell sheet technology to regeneration of cornea, periodontal ligament, bladder epithelia, oesophageal epithelia, myocardium, and liver.},
  doi      = {https://doi.org/10.1002/adma.200701978},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/adma.200701978},
  file     = {:Matsuda2007 - Tissue Engineering Based on Cell Sheet Technology.pdf:PDF},
  keywords = {Biocompatible materials, Bionanotechnology, Cells, Polymers, Tissue engineering, application focused, pnipam, thermoresponsive, application-focused},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.200701978},
}

@Article{Fries2008,
  author    = {Fries, Kristen and Samanta, Satyabrata and Orski, Sara and Locklin, Jason},
  journal   = {Chemical Communications},
  title     = {Reversible colorimetric ion sensors based on surface initiated polymerization of photochromic polymers},
  year      = {2008},
  pages     = {6288--6290},
  abstract  = {Spiropyran containing polymer brushes were used as reversible{,} photoswitchable optical sensors that show selectivity for different metal ions and drastic changes in surface wettability.},
  doi       = {10.1039/B818042C},
  file      = {:Fries2008 - Reversible Colorimetric Ion Sensors Based on Surface Initiated Polymerization of Photochromic Polymers.pdf:PDF},
  issue     = {47},
  keywords  = {application focused, polymer brush, sensor, application-focused},
  publisher = {The Royal Society of Chemistry},
  url       = {http://dx.doi.org/10.1039/B818042C},
}

@Article{Bilen2007,
  author   = {Bilen, Bukem and Skarlatos, Yani and Aktas, Gulen and Inci, Mehmet Naci and Dispinar, Tugba and Kose, Meliha Merve and Sanyal, Amitav},
  journal  = {Journal of Applied Physics},
  title    = {In situ measurement of humidity induced changes in the refractive index and thickness of polyethylene glycol thin films},
  year     = {2007},
  number   = {7},
  pages    = {073534},
  volume   = {102},
  doi      = {10.1063/1.2794708},
  eprint   = {https://doi.org/10.1063/1.2794708},
  file     = {:Bilen2007 - In Situ Measurement of Humidity Induced Changes in the Refractive Index and Thickness of Polyethylene Glycol Thin Films.pdf:PDF},
  keywords = {application focused, polymer brush, sensor, application-focused},
  url      = {https://doi.org/10.1063/1.2794708},
}

@Article{Jain2009,
  author   = {Jain, Parul and Baker, Gregory L. and Bruening, Merlin L.},
  journal  = {Annual Review of Analytical Chemistry},
  title    = {Applications of Polymer Brushes in Protein Analysis and Purification},
  year     = {2009},
  note     = {PMID: 20636068},
  number   = {1},
  pages    = {387--408},
  volume   = {2},
  abstract = {This review examines the application of polymer brush--modified flat surfaces, membranes, and beads for protein immobilization and isolation. Modification of porous substrates with brushes yields membranes that selectively bind tagged proteins to give 99\% pure protein at capacities as high as 100 mg of protein per cubic centimeter of membrane. Moreover, enrichment of phosphopeptides on brush-modified matrix-assisted laser desorption/ionization (MALDI) plates allows detection and characterization of femtomole levels of phosphopeptides by MALDI mass spectrometry. Because swollen hydrophilic brushes can resist nonspecific protein adsorption while immobilizing a high density of proteins, they are attractive as substrates for protein microarrays. This review highlights the advantages of polymer brush--modified surfaces over self-assembled monolayers and identifies some research needs in this area.},
  doi      = {10.1146/annurev-anchem-060908-155153},
  eprint   = {https://doi.org/10.1146/annurev-anchem-060908-155153},
  file     = {:Jain2009 - Applications of Polymer Brushes in Protein Analysis and Purification.pdf:PDF},
  keywords = {application focused, polymer brush, protein immobilization, phosphopeptide enrichment, protein microarrays, immbilized metal-affinity chromatography, ion exchange, size exclusion, application-focused},
  url      = {https://doi.org/10.1146/annurev-anchem-060908-155153},
}

@Article{Yameen2009,
  author   = {Yameen, Basit and Ali, Mubarak and Neumann, Reinhard and Ensinger, Wolfgang and Knoll, Wolfgang and Azzaroni, Omar},
  journal  = {Nano Letters},
  title    = {Synthetic Proton-Gated Ion Channels via Single Solid-State Nanochannels Modified with Responsive Polymer Brushes},
  year     = {2009},
  note     = {PMID: 19518086},
  number   = {7},
  pages    = {2788--2793},
  volume   = {9},
  abstract = {The creation of switchable and tunable nanodevices displaying transport properties similar to those observed in biological pores poses a major challenge in molecular nanotechnology. Here, we describe the construction of a fully {\textquotedblleft}abiotic{\textquotedblright} nanodevice whose transport properties can be accurately controlled by manipulating the proton concentration in the surrounding environment. The ionic current switching characteristics displayed by the nanochannels resemble the typical behavior observed in many biological channels that fulfill key pH-dependent transport functions in living organisms, that is, the nanochannel can be switched from an {\textquotedblleft}off{\textquotedblright} state to an {\textquotedblleft}on{\textquotedblright} state in response to a pH drop. The construction of such a chemical nanoarchitecture required the integration of stable and ductile macromolecular building blocks constituted of pH-responsive poly(4-vinyl pyridine) brushes into solid state nanopores that could act as gate-keepers managing and constraining the flow of ionic species through the confined environment. In this context, we envision that the integration of environmental stimuli-responsive brushes into solid-state nanochannels would provide a plethora of new chemical alternatives for molecularly design robust signal-responsive {\textquotedblleft}abiotic{\textquotedblright} devices mimicking the function of proton-gated ion channels commonly encountered in biological membranes.},
  doi      = {10.1021/nl901403u},
  eprint   = {https://doi.org/10.1021/nl901403u},
  file     = {:Yameen2009 - Synthetic Proton Gated Ion Channels Via Single Solid State Nanochannels Modified with Responsive Polymer Brushes.pdf:PDF},
  keywords = {application focused, gated channel, polymer brush, stimuli responsive, application-focused},
  url      = {https://doi.org/10.1021/nl901403u},
}

@Article{Jonas2007,
  author   = {Jonas, Alain M. and Glinel, Karine and Oren, Ron and Nysten, Bernard and Huck, Wilhelm T. S.},
  journal  = {Macromolecules},
  title    = {Thermo-Responsive Polymer Brushes with Tunable Collapse Temperatures in the Physiological Range},
  year     = {2007},
  number   = {13},
  pages    = {4403--4405},
  volume   = {40},
  abstract = {Stimuli-responsive polymers 1 have attracted considerable interest for applications such as actuation, 2 drug delivery, 3 affinity control, 4 fabrication of materials of tunable shape and surface properties, 5 or stimuli-gated filtration. 6 Among these systems, hydrogels, 7 brushes, 8 and micro- or nanopatterned brushes 9 of poly(N-isopropylacrylamide) (PNIPAM) and of related copolymers have been studied extensively, because these polymers exhibit a lower critical solution temperature (LCST) in water at about 32 {$^{\circ}$}C, which means that they undertake a reversible change in surface properties and swelling in water at temperatures close to physiological ones. Recently, the pre- dominance of PNIPAM as the paradigmatic example of thermoresponsive polymer was challenged by the discovery that random copolymers of 2-(2-methoxyethoxy)ethyl methacrylate (MEO 2 MA) and oligo(ethylene glycol) methacrylate (OEGMA) exhibit a LCST in water, which can be finely tuned anywhere between 26 and 90 {$^{\circ}$}C depending on OEGMA content, 10 and which is almost independent of molar mass, concentration, and ionic strength, contrarily to PNIPAM. 10c In addition, in contrast with PNIPAM which was recently shown to be moderately cytotoxic at 37 {$^{\circ}$}C, 11 these poly(ethylene glycol)-based copolymers are expected to be nontoxic and non-immunogenic, since the addition of oligo(ethylene oxide) sequences to responsive polymers was also shown to decrease cytotoxicity. 11 Here, we exploit the unique features of these copolymers to prepare novel thermoresponsive surfaces with finely tunable collapse temper- atures located in the physiological range. By measuring the temperature derivative of their equilibrium water contact angles, we succeed in obtaining thermodynamically relevant collapse transition temperatures, in stark contrast with previously reported attempts on thermoresponsive surfaces, which were devoid of thermodynamic meaning as shown below.},
  doi      = {10.1021/ma070897l},
  eprint   = {https://doi.org/10.1021/ma070897l},
  file     = {:Jonas2007 - Thermo Responsive Polymer Brushes with Tunable Collapse Temperatures in the Physiological Range.pdf:PDF;:ThermoResponsivePolymerBrushesWithTunableCollapseTemperaturesInThePhysiologicalRange_SupplInfo_JonasEtAl_Macromolecules2007.pdf:PDF},
  keywords = {PNIPAM alternative, polymer brush, thermo-responsive},
  url      = {https://doi.org/10.1021/ma070897l},
}

@Article{Netz1998,
  author     = {Netz, Roland R. and Schick, M.},
  journal    = {Macromolecules},
  title      = {Polymer Brushes:\hspace{0.167em} From Self-Consistent Field Theory to Classical Theory},
  year       = {1998},
  note       = {PMID: 9680451},
  number     = {15},
  pages      = {5105--5122},
  volume     = {31},
  abstract   = {We consider planar brushes formed by end-grafted polymers with moderate to strong excluded-volume interactions. We first rederive the mean-field theory and solve the resulting self-consistent equations numerically. In the continuum limit, the results depend sensitively on a single parameter, $\beta$, whose square is the ratio of the scaling prediction for the brush height to the unperturbed polymer radius of gyration, and which measures therefore the degree to which the polymers are stretched. For large values of $\beta$, the density profile is close to parabolic, as predicted by the infinite-stretching theory of Zhulina et al. and of Milner et al. As $\beta$ decreases, the profile deviates strongly from a parabolic one. By calculating the most probable paths and comparing their contribution to various properties with those obtained from the full self-consistent theory, we determine the effect of the fluctuations about such paths. At large values of $\beta$, these effects are very small everywhere. As $\beta$ decreases, fluctuation effects on the density profile become increasingly important near the grafting surface, but remain small far from it. For all values of $\beta$, we find that polymer paths which begin far from the grafting surface are strongly, and almost uniformly, stretched throughout their length, including their free end points. Paths which begin close to the grafting surface are also stretched, but they initially move away from the grafting surface before reaching a maximum height and then returning to it. The classical theory is then derived from the self-consistent field equations by retaining, for each end point location, only that single trajectory which minimizes the free energy of the system. This free energy contains an entropy, of relative weight $\beta$-1, which arises from the distribution of end points. Even for brushes which are only moderately stretched, the results of the classical theory for the brush profile and polymer end point distribution agree well with those of the full self-consistent theory except near the grafting surface itself. There the density profile as calculated in the self-consistent theory shows a characteristic decrease which is not captured by the classical theory. However it does capture the fact that the individual polymer paths are stretched in general throughout their length, including the end points, and yields nonmonotonic paths for polymers whose end points are close to the grafting surface. In addition, it reproduces extremely well the form of the density distribution far from the grafting surface, which is essentially Gaussian. This results from the fact that the stretching energy dominates the interaction energy of those polymers which extend far from the grafting surface, so that their behavior is nearly ideal. In the limit of infinite stretching, $\beta$ $\rightarrow$ $\infty$, the theory reduces to that of Zhulina et al. and of Milner et al.},
  doi        = {10.1021/ma9717505},
  eprint     = {https://doi.org/10.1021/ma9717505},
  file       = {:Netz1998 - Polymer Brushes_ from Self Consistent Field Theory to Classical Theory.pdf:PDF},
  keywords   = {theory, scft, polymer brush},
  printed    = {printed},
  ranking    = {rank3},
  readstatus = {skimmed},
  url        = {https://doi.org/10.1021/ma9717505},
}

@Article{Yang2006,
  author   = {Yuliang Yang and Feng Qiu and Ping Tang and Hongdong Zhang},
  journal  = {Science in China: Series B Chemistry},
  title    = {Applications of self-consistent field theory in polymer systems},
  year     = {2006},
  pages    = {21--43},
  volume   = {49},
  doi      = {10.1007/s11426-005-0190-7},
  file     = {:Yang2006 - Applications of Self Consistent Field Theory in Polymer Systems.pdf:PDF},
  keywords = {scft, polymer brush, theory},
  url      = {https://doi.org/10.1007/s11426-005-0190-7},
}

@Article{Baulin2003,
  author   = {Baulin, Vladimir A. and Zhulina, Ekaterina B. and Halperin, Avi},
  journal  = {Journal of Chemical Physics},
  title    = {Self-consistent field theory of brushes of neutral water-soluble polymers},
  year     = {2003},
  number   = {20},
  pages    = {10977--10988},
  volume   = {119},
  doi      = {10.1063/1.1619934},
  eprint   = {https://doi.org/10.1063/1.1619934},
  file     = {:Baulin2003 - Self Consistent Field Theory of Brushes of Neutral Water Soluble Polymers.pdf:PDF},
  keywords = {scft, theory, polymer brush},
  url      = {https://doi.org/10.1063/1.1619934},
}

@Article{CringusFundeanu2007,
  author   = {Cringus-Fundeanu, Irina and Luijten, Jeroen and van der Mei, Henny C. and Busscher, Henk J. and Schouten, Arend J.},
  journal  = {Langmuir},
  title    = {Synthesis and Characterization of Surface-Grafted Polyacrylamide Brushes and Their Inhibition of Microbial Adhesion},
  year     = {2007},
  note     = {PMID: 17388616},
  number   = {9},
  pages    = {5120--5126},
  volume   = {23},
  abstract = {A method is presented to prevent microbial adhesion to solid surfaces exploiting the unique properties of polymer brushes. Polyacrylamide (PAAm) brushes were grown from silicon wafers by atom transfer radical polymerization (ATRP) using a three-step reaction procedure consisting of immobilization of a coupling agent $\gamma$-aminopropyltriethoxysilane, anchoring of an ATRP initiator 4-(chloromethyl)benzoyl chloride, and controlled radical polymerization of acrylamide. The surfaces were characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, ellipsometry, and contact-angle measurements. The calculated grafting density pointed to the presence of a dense and homogeneous polymer brush. Initial deposition rates, adhesion after 4 h, and detachment of two bacterial strains (Staphylococcus aureus ATCC 12600 and Streptococcus salivarius GB 24/9) and one yeast strain (Candida albicans GB 1/2) to both PAAm-coated and untreated silicon surfaces were investigated in a parallel plate flow chamber. A high reduction (70$-$92\%) in microbial adhesion to the surface-grafted PAAm brush was observed, as compared with untreated silicon surfaces. Application of the proposed grafting method to silicone rubbers may offer great potential to prevent biomaterials-centered infection of implants.},
  doi      = {10.1021/la063531v},
  eprint   = {https://doi.org/10.1021/la063531v},
  file     = {:CringusFundeanu2007 - Synthesis and Characterization of Surface Grafted Polyacrylamide Brushes and Their Inhibition of Microbial Adhesion.pdf:PDF},
  keywords = {polymer brush, anit-fouling, application-focused, application focused},
  url      = {https://doi.org/10.1021/la063531v},
}

@Article{Leckband1999,
  author    = {D. Leckband and S. Sheth and A. Halperin},
  journal   = {Journal of Biomaterials Science, Polymer Edition},
  title     = {Grafted poly(ethylene oxide) brushes as nonfouling surface coatings},
  year      = {1999},
  number    = {10},
  pages     = {1125--1147},
  volume    = {10},
  abstract  = {The identification of design criteria for the prevention of surface fouling by protein adsorption has been an elusive research goal. The current ideas in this domain assume two different directions. One focuses on correlating protein adsorption with macroscopic surface properties such as the water wettability. The second approach involves tailoring the molecular interactions between the adsorbing proteins and the surface. In this paper, we focus on the experimental results and theoretical ideas concerned with tuning the interfacial forces by means of terminally grafted PEO chains.},
  doi       = {10.1163/156856299X00720},
  eprint    = {https://doi.org/10.1163/156856299X00720},
  file      = {:Leckband1999 - Grafted Poly(ethylene Oxide) Brushes As Nonfouling Surface Coatings.pdf:PDF},
  keywords  = {application focused, polymer brush, anti-fouling, PEO, Poly(Ethylene Oxide), application-focused, PEG},
  publisher = {Taylor \& Francis},
  url       = {https://doi.org/10.1163/156856299X00720},
}

@Article{Kreer2016,
  author    = {Kreer, T.},
  journal   = {Soft Matter},
  title     = {Polymer-brush lubrication: a review of recent theoretical advances},
  year      = {2016},
  pages     = {3479--3501},
  volume    = {12},
  abstract  = {This review compiles recent theoretical advances to describe compressive and shear forces of polymer-brush bilayers{,} which consist of two opposing brushes in contact. Such model systems for polymer-brush lubrication are frequently used as a benchmark to gain insight into biological problems{,} e.g.{,} synovial joint lubrication. Based on scaling theory{,} I derive conformational and collective properties of polymer-brush bilayers in equilibrium and out-of-equilibrium situations{,} such as shear forces in the linear and nonlinear response regimes of stationary shear and under non-stationary shear. Furthermore{,} I discuss the influence of macromolecular inclusions and electrostatic interactions on polymer-brush lubrication. Comparisons to alternative analytical approaches{,} experiments and numerical results are performed. Special emphasis is given to methods for simulating polymer-brush bilayers using molecular dynamics simulations.},
  doi       = {10.1039/C5SM02919H},
  file      = {:Kreer2016 - Polymer Brush Lubrication_ a Review of Recent Theoretical Advances.pdf:PDF},
  issue     = {15},
  keywords  = {polymer brush, theory, lubrication, review},
  publisher = {The Royal Society of Chemistry},
  url       = {http://dx.doi.org/10.1039/C5SM02919H},
}

@Article{Resing1965,
  author   = {Resing, H. A.},
  journal  = {Journal of Chemical Physics},
  title    = {Apparent Phase---Transition Effect in the NMR Spin---Spin Relaxation Time Caused by a Distribution of Correlation Times},
  year     = {1965},
  number   = {2},
  pages    = {669--678},
  volume   = {43},
  doi      = {10.1063/1.1696791},
  eprint   = {https://doi.org/10.1063/1.1696791},
  keywords = {NMR, relaxation, spin-spin relaxation, theory},
  url      = {https://doi.org/10.1063/1.1696791},
}

@Article{Jen1978,
  author   = {Joseph Jen},
  journal  = {Journal of Magnetic Resonance},
  title    = {Chemical exchange and nmr T2 relaxation---The multisite case},
  year     = {1978},
  issn     = {0022-2364},
  number   = {1},
  pages    = {111--128},
  volume   = {30},
  abstract = {The behavior of a Carr-Purcell echo train in a chemical system with more than two exchanging sites is investigated. This paper extends and supplements previous work examining the theory of the spin-echo experiment. By using the condition of microscopic reversibility of the chemical system, it can be shown that the echo maxima, apart from the first few, decay exponentially. The limiting cases of high and low pulse rates are discussed. At high pulse rates the influence of relative chemical shifts between the various sites is eliminated. In this case the echo train agrees with that expected from the Bloch-McConnell equation when chemical shifts are neglected. Closed expressions for the case of exchange between two sites are given.},
  doi      = {https://doi.org/10.1016/0022-2364(78)90229-9},
  keywords = {CPMG, NMR, T2, chemical exchange},
  printed  = {printed},
  ranking  = {rank4},
  url      = {http://www.sciencedirect.com/science/article/pii/0022236478902299},
}

@Article{Kim2020,
  author   = {Kim, Young-Gon and Wagner, Manfred and Th{\'{e}}rien-Aubin, H{\'{e}}lo{\"{i}}se},
  journal  = {Macromolecules},
  title    = {Dynamics of Soft and Hairy Polymer Nanoparticles in a Suspension by NMR Relaxation},
  year     = {2020},
  number   = {3},
  pages    = {844--851},
  volume   = {53},
  abstract = {The design of surface-modified functional nanoparticles (NPs) is used to control the properties of the NPs and the NP/environment interactions. The efficient control of the final behavior of the NPs demands a comprehensive understanding of the resulting system. This is particularly challenging for systems with an architecture of the type polymer core--polymer canopy. In such systems, one of the key parameters influencing the behavior of the NPs is the local dynamics of the polymer canopy. However, because the grafting points of the canopy are experiencing their own local dynamics, predicting the final behavior of such systems is difficult. To get a deeper understanding of NPs made of a soft and swollen polymer core and a swollen polymer canopy, we prepared a library of hairy NPs made of a polystyrene (PS) core and a canopy of grafted poly(methyl acrylate) (PMA) chains. The softness of the PS core and the thickness of the PMA canopy were controlled, and the behavior and dynamics of the soft and hairy PS--PMA NPs in suspension were measured by 1H NMR relaxation and dynamic light scattering. It was observed that the rigid PS core slowed down the subsegmental dynamics of the PMA chains, while thick PMA canopies accelerated the relaxation of the PS core. The dynamics of the NPs in suspension was the result of the interplay between the PS core and the PMA canopy.},
  doi      = {10.1021/acs.macromol.9b01813},
  eprint   = {https://doi.org/10.1021/acs.macromol.9b01813},
  file     = {:Kim2020 - Dynamics of Soft and Hairy Polymer Nanoparticles in a Suspension by NMR Relaxation.pdf:PDF;:DynamicsOfSoftAndHairyPolymerNanoparticlesInASuspensionByNMRRelaxation_KimEtAl_Macromolecules2020_SI.pdf:PDF},
  keywords = {NMR, spherical polymer brush, SPB, PS, PMA, 1H, DLS, relaxation, correlation time},
  url      = {https://doi.org/10.1021/acs.macromol.9b01813},
}

@InBook{Aseyev2005,
  author    = {Aseyev, Vladimir O. and Tenhu Heikki and Winnik, Fran{\c{c}}oise M.},
  chapter   = {Temperature Dependence of the Colloidal Stability of Neutral Amphiphilic Polymers in Water},
  pages     = {1--85},
  publisher = {Springer, Berlin, Heidelberg},
  title     = {Conformation-Dependent Design of Sequences in Copolymers II},
  year      = {2005},
  abstract  = {Various thermally responsive polymers and their derivatives form colloidally stable nanosized particles upon heating of their aqueous solutions. A compilation of the types of polymers reported to exhibit this behaviour is presented in this review, including poly(N-isopropylacrylamide), poly(N-vinylcaprolactam), and poly(vinyl methyl ether) together with their copolymers with either hydrophobic or hydrophilic monomers. In all cases experimental evidence is presented, together with various theoretical models. Possible mechanisms responsible for the stabilisation of these colloids are discussed.},
  doi       = {10.1007/12_052},
  file      = {:Aseyev2005 - Conformation Dependent Design of Sequences in Copolymers II.pdf:PDF},
  keywords  = {PNIPAM,},
  url       = {https://link.springer.com/chapter/10.1007/12_052},
}

@Article{Starovoytova2006,
  author   = {Larisa Starovoytova and Ji{{\v{r}}}{\'{i}} Sp{\v{e}}v{\'{a}}{\v{c}}ek},
  journal  = {Polymer},
  title    = {Effect of time on the hydration and temperature-induced phase separation in aqueous polymer solutions. 1H NMR study},
  year     = {2006},
  issn     = {0032-3861},
  number   = {21},
  pages    = {7329--7334},
  volume   = {47},
  abstract = {Dehydration during temperature-induced phase separation in D2O solutions of poly(vinyl methyl ether) (PVME), poly(N-isopropylmethacrylamide) (PIPMAm) and poly(N-isopropylacrylamide) (PIPAAm) was followed from time dependences of NMR spin--spin relaxation times T2 of HDO. Both the time characterizing the exclusion of the water from mesoglobules (manifested by the increase in T2 values) and the induction period which precedes the increase in T2 values, increased in the order PVMEPIPMAmPIPAAm. For D2O solutions of PIPMAm/PVME (or PIPMAm/PIPAAm) mixtures a direct connection between the state of the mesoglobules (hydrated or dehydrated) formed by the component with lower LCST (PVME, PIPAAm) and the temperatures of the phase transition of the PIPMAm component was established by NMR spectroscopy.},
  doi      = {https://doi.org/10.1016/j.polymer.2006.08.002},
  file     = {:Starovoytova2006 - Effect of Time on the Hydration and Temperature Induced Phase Separation in Aqueous Polymer Solutions. 1H NMR Study.pdf:PDF},
  keywords = {Thermosensitive polymers, Hydration, 1H, NMR spectroscopy, PNIPAM, T2, relaxation},
  url      = {http://www.sciencedirect.com/science/article/pii/S0032386106009347},
}

@Article{Spevacek2005,
  author   = {Sp{\v{e}}v{\'{a}}{\v{c}}ek, Ji{{\v{r}}}{\'{i}} and Hanykov{\'{a}}, Lenka},
  journal  = {Macromolecules},
  title    = {$^{1}$H NMR Study on the Hydration during Temperature-Induced Phase Separation in Concentrated Poly(vinyl methyl ether)/D2O Solutions},
  year     = {2005},
  number   = {22},
  pages    = {9187--9191},
  volume   = {38},
  abstract = {A certain portion of spatially restricted bound water (HDO) was established for concentrated PVME/D2O solutions at temperature above the LCST transition from the measurements of 1H NMR spectra and 1H spin$-$spin relaxation times T2 of HDO. The fast and slow exchange regime between bound and free water was revealed for polymer concentrations c = 2$-$10 wt \% and c = 20$-$60 wt \%, respectively. For the latter case, the residence time of bound HDO $\tau$ $\gg$ 2.7 ms and relatively weak hydrogen bonding follow from the position of the separate NMR signal of bound HDO. For polymer concentrations c = 20$-$60 wt \%, the spin$-$spin relaxation time T2 of bound HDO and the molar ratio [PVME monomeric unit]/[bound D2O] remain virtually constant and equal to T2 $\cong$ 40 ms and [PVME]/[bound D2O] $\cong$ 2.7 on average, thus indicating a direct connection of the fraction of bound water with the conformational structure of phase-separated PVME.},
  doi      = {10.1021/ma051425e},
  eprint   = {https://doi.org/10.1021/ma051425e},
  file     = {:Spevacek2005 - 1H NMR Study on the Hydration during Temperature Induced Phase Separation in Concentrated Poly(vinyl Methyl Ether)_D2O Solutions.pdf:PDF},
  keywords = {NMR, PVME, relaxation, T2, exchange, LCST},
  url      = {https://doi.org/10.1021/ma051425e},
}

@Article{Spevacek2004,
  author   = {Sp{\v{e}}v{\'{a}}{\v{c}}ek, Ji{{\v{r}}}{\'{i}} and Hanykov{\'{a}}, Lenka and Starovoytova, Larisa},
  journal  = {Macromolecules},
  title    = {1H NMR Relaxation Study of Thermotropic Phase Transition in Poly(vinyl methyl ether)/D2O Solutions},
  year     = {2004},
  number   = {20},
  pages    = {7710--7718},
  volume   = {37},
  abstract = {1H NMR line shapes and spin$-$spin relaxation times T2 have shown that in PVME/D2O solutions the LCST transition results in limited mobility of most PVME units, evidently in connection with formation of compact globular-like structures. The minority mobile component, which does not take part in the phase transition, mostly consists of low-molecular-weight fraction of PVME, as shown by SEC. Measurements of spin$-$spin relaxation times of PVME methylene protons have shown that globular structures are more compact in dilute solutions in comparison with semidilute and concentrated solutions where globules contain a certain amount of water. A certain portion of water molecules bound at elevated temperatures in PVME globular structures in semidilute and concentrated solutions was revealed also from measurements of spin$-$spin and selective and nonselective spin$-$lattice relaxation times of residual HDO molecules. While the phase separation in dilute PVME solutions is associated with rapid dehydration of polymer chains, for semidilute and concentrated solutions T2 measurements evidence that with time the originally bound water is slowly released from globular-like structures, and the character of the globules is changed from the spongelike to a rather compact one. From results obtained on D2O solutions of PVME/poly(N-isopropylmethacrylamide) (PIPMAAm) mixtures it follows that this process is significantly slower for more rigid globular-like structures of PIPMAAm in comparison with globules of the flexible PVME.},
  doi      = {10.1021/ma0486647},
  eprint   = {https://doi.org/10.1021/ma0486647},
  file     = {:Spevacek2004 - H NMR Relaxation Study of Thermotropic Phase Transition in Poly(vinyl Methyl Ether)_D2O Solutions.pdf:PDF},
  keywords = {NMR, PVME, 1H, spin-spin, T2, relaxation, D2O, spin-lattice, T1},
  url      = {https://doi.org/10.1021/ma0486647},
}

@Article{Bloembergen1948,
  author     = {Bloembergen, N. and Purcell, E. M. and Pound, R. V.},
  journal    = {Physical Review},
  title      = {Relaxation Effects in Nuclear Magnetic Resonance Absorption},
  year       = {1948},
  month      = apr,
  pages      = {679--712},
  volume     = {73},
  doi        = {10.1103/PhysRev.73.679},
  file       = {:Bloembergen1948 - Relaxation Effects in Nuclear Magnetic Resonance Absorption.pdf:PDF},
  issue      = {7},
  keywords   = {NMR, theory, BPP},
  numpages   = {0},
  printed    = {printed},
  publisher  = {American Physical Society},
  ranking    = {rank5},
  readstatus = {skimmed},
  url        = {https://link.aps.org/doi/10.1103/PhysRev.73.679},
}

@Article{Mao2000,
  author  = {S.-Z. Mao and X.-D. Zhang and J.-M. Dereppe and Y.-R. Du},
  journal = {Colloid and Polymer Science},
  title   = {Nuclear magnetic resonance relaxation studies of polyacrylamide solution},
  year    = {2000},
  pages   = {264--269},
  volume  = {278},
  doi     = {10.1007/s003960050042},
  file    = {:Mao2000 - Nuclear Magnetic Resonance Relaxation Studies of Polyacrylamide Solution.pdf:PDF},
  ranking = {rank4},
  url     = {https://doi.org/10.1007/s003960050042},
}

@Article{Kingsley1995,
  author   = {Kingsley, Peter B.},
  journal  = {Concepts in Magnetic Resonance},
  title    = {Product operators, coherence pathways, and phase cycling part i: product operators, spin-spin coupling, and coherence pathways},
  year     = {1995},
  number   = {1},
  pages    = {29--47},
  volume   = {7},
  abstract = {The vector model is compared with product operator descriptions of NMR pulse sequences. For coupled spins, the relationship between the counter-rotating vectors of the vector model and antiphase product operators is explained. Coherence pathways for an uncoupled spin I = $\sfrac{1}{2}$ are explained in vector terms. The compact Cartesian coordinate product operator (C3PO) formalism is shown to provide complete coherence pathway information with vector pictures.},
  doi      = {https://doi.org/10.1002/cmr.1820070103},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.1820070103},
  file     = {:Kingsley1995 - Product Operators, Coherence Pathways, and Phase Cycling Part I_ Product Operators, Spin Spin Coupling, and Coherence Pathways.pdf:PDF},
  keywords = {NMR, theory, coherence, coherence pathways, product operator, phase cycling},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.1820070103},
}

@Article{Kingsley1995a,
  author   = {Kingsley, Peter B.},
  journal  = {Concepts in Magnetic Resonance},
  title    = {Product operators, coherence pathways, and phase cycling. Part II. coherence pathways in multipulse sequences: spin echoes, stimulated echoes, and multiple-quantum coherences},
  year     = {1995},
  number   = {2},
  pages    = {115--136},
  volume   = {7},
  abstract = {The Compact Cartesian Coordinate Product-Operator (C3PO) descriptions of an uncoupled spin I = $\sfrac{1}{2}$ in one-pulse, two-pulse, and three-pulse sequences are presented. The properties of free induction decays, spin echoes, double spin echoes, and stimulated echoes are discussed. Vector pictures of a 90{$^{\circ}$}--90{$^{\circ}$} spin echo and a stimulated echo are presented. The C3PO descriptions of IS and I3 S spin systems in multipulse sequences are also discussed, including polarization transfer and multiple-quantum coherences. Suggestions for optimizing one coherence pathway and minimizing others are provided.},
  doi      = {https://doi.org/10.1002/cmr.1820070203},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.1820070203},
  file     = {:Kingsley1995a - Product Operators, Coherence Pathways, and Phase Cycling. Part II. Coherence Pathways in Multipulse Sequences_ Spin Echoes, Stimulated Echoes, and Multiple Quantum Coherences.pdf:PDF},
  keywords = {NMR, theory, coherence, coherence pathways, product operator, phase cycling},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.1820070203},
}

@Article{Kingsley1995b,
  author   = {Kingsley, Peter B.},
  journal  = {Concepts in Magnetic Resonance},
  title    = {Product operators, coherence pathways, and phase cycling. Part III: phase cycling},
  year     = {1995},
  number   = {3},
  pages    = {167--192},
  volume   = {7},
  abstract = {The coherence pathway approach allows the systematic design of phase cycles to eliminate unwanted coherence pathway signals in multipulse NMR sequences. Some quadrature receiver imperfections are shown to be equivalent to detection of magnetization in coherence level p = + 1 in addition to the normally observable p = $-$1. Other receiver artifacts do not correspond to p = +1 but also can be removed by phase cycling. Selection of signals in one-, two-, and three-pulse sequences is described for uncoupled and coupled spins.},
  doi      = {https://doi.org/10.1002/cmr.1820070302},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.1820070302},
  file     = {:Kingsley1995b - Product Operators, Coherence Pathways, and Phase Cycling. Part III_ Phase Cycling.pdf:PDF},
  keywords = {NMR, theory, coherence, coherence pathways, product operator, phase cycling},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.1820070302},
}

@Article{Sorensen1984,
  author   = {O. W. S{\o}rensen and G. W. Eich and M. H. Levitt and G. Bodenhausen and R. R. Ernst},
  journal  = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title    = {Product operator formalism for the description of NMR pulse experiments},
  year     = {1984},
  issn     = {0079-6565},
  pages    = {163--192},
  volume   = {16},
  doi      = {https://doi.org/10.1016/0079-6565(84)80005-9},
  file     = {:Soerensen1984 - Product Operator Formalism for the Description of NMR Pulse Experiments.pdf:PDF},
  keywords = {NMR, theory, product operator},
  url      = {http://www.sciencedirect.com/science/article/pii/0079656584800059},
}

@Article{Salwen1955,
  author   = {Harold Salwen},
  journal  = {Physical Review},
  title    = {Resonance Transitions in Molecular Beam Experiments. I. General Theory of Transitions in a Rotating Magnetic Field},
  year     = {1955},
  month    = aug,
  number   = {4},
  pages    = {1274--1286},
  volume   = {99},
  abstract = {The time-dependent Schrodinger equation is solved formally for an atomic or molecular system which is subjected simultaneously to a rotating magnetic field of constant amplitude and angular velocity and to a constant magnetic field along the axis of rotation. The method yields the transition probabilities in terms of the solutions to an eigenvalue problem. This eigenvalue problem is solved both for (a) a normal Zeeman effect and for (b) the case where a transition from a given level is isolated in frequency from other transitions from the same level. Case (a) is exactly soluble and yields a solution which is shown to be the same as that of Bloch and Rabi, but is in a form which is more convenient for integration over the velocity distribution. Case (b) must be solved by an approximate method which results in a prediction of multiple quantum transitions as observed by Kusch.},
  file     = {:Salwen1955 - Resonance Transitions in Molecular Beam Experiments. I. General Theory of Transitions in a Rotating Magnetic Field.pdf:PDF},
  keywords = {NMR, theory, double quantum transition},
}

@Article{Murday1970,
  author   = {Murday, J. S. and Cotts, R. M.},
  journal  = {Journal of Chemical Physics},
  title    = {Self-Diffusion in Liquids: H2O, D2O, and Na},
  year     = {1970},
  number   = {12},
  pages    = {4724--4725},
  volume   = {53},
  doi      = {10.1063/1.1674011},
  eprint   = {https://doi.org/10.1063/1.1674011},
  keywords = {NMR, diffusion, calibration, gradient, h2o, d2o, 1H, 2H},
  url      = {https://doi.org/10.1063/1.1674011},
}

@Article{Winnik1992,
  author   = {Winnik, Francoise M. and Ottaviani, M. Francesca and Bossmann, Stefan H. and Garcia-Garibay, M. and Turro, Nicholas J.},
  journal  = {Macromolecules},
  title    = {Consolvency of poly(N-isopropylacrylamide) in mixed water-methanol solutions: a look at spin-labeled polymers},
  year     = {1992},
  number   = {22},
  pages    = {6007--6017},
  volume   = {25},
  doi      = {10.1021/ma00048a023},
  eprint   = {https://doi.org/10.1021/ma00048a023},
  file     = {:Winnik1992 - Consolvency of Poly(N Isopropylacrylamide) in Mixed Water Methanol Solutions_ a Look at Spin Labeled Polymers.pdf:PDF},
  keywords = {EPR, PNIPAM, cononsolvency},
  ranking  = {rank4},
  url      = {https://doi.org/10.1021/ma00048a023},
}

@Article{Cao2021,
  author   = {Meiwen Cao and Yang Shen and Zengshuai Yan and Qiang Wei and Tifeng Jiao and Yutan Shen and Yuchun Han and Yilin Wang and Shengjie Wang and Yongqing Xia and Tongtao Yue},
  journal  = {Chemical Engineering Journal},
  title    = {Extraction-like removal of organic dyes from polluted water by the graphene oxide/PNIPAM composite system},
  year     = {2021},
  issn     = {1385-8947},
  pages    = {126647},
  volume   = {405},
  abstract = {Graphene oxide (GO)/poly(N-isopropylacrylamide) (PNIPAM) composite materials have been widely applied in waste water treatment by working as free adsorbents with thermoresponsiveness. In this work we report a novel GO/PNIPAM composite system that has been rationally designed for removal of organic dyes from polluted water in a new mechanism, that is, an extraction-like mechanism. The system gives a phase transition to produce a solution phase and a gel phase at temperatures above the lower critical solution temperature (LCST) of PNIPAM, during which the GO sheets are fully transferred into the gel phase. More interestingly, dyes can be efficiently adsorbed and enriched in the gel phase, which can then be conveniently separated from water in an extraction-like process. Compared to conventional extractive separation systems, the GO/PNIPAM composite system gives two phases triggered by temperature change, which have a clear phase boundary and are much easier for separation. Moreover, the system can protect GO from reduction and flocculation so as to retain high stability. PNIPAM and GO can also work synergistically for dye adsorption to give high adsorption capacity and efficiency. This study will provide a new perspective for design and fabrication of novel, safe and effective systems for dye removal and nanomaterial management.},
  comment  = {Elsevier Paper - no access to full text},
  doi      = {https://doi.org/10.1016/j.cej.2020.126647},
  keywords = {Graphene oxide, Poly(N-isopropylacrylamide), Water purification, Phase separation, Extraction-like, Application focused, application-focused},
  url      = {https://www.sciencedirect.com/science/article/pii/S1385894720327753},
}

@Article{Mansfield2021,
  author   = {Edward D. H. Mansfield and Sergey K. Filippov and Victor R. {de la Rosa} and Michael T. Cook and Isabelle Grillo and Richard Hoogenboom and Adrian C. Williams and Vitaliy V. Khutoryanskiy},
  journal  = {Journal of Colloid and Interface Science},
  title    = {Understanding the temperature induced aggregation of silica nanoparticles decorated with temperature-responsive polymers: Can a small step in the chemical structure make a giant leap for a phase transition?},
  year     = {2021},
  issn     = {0021-9797},
  pages    = {249--259},
  volume   = {590},
  abstract = {Temperature-responsive nanomaterials have gained increasing interest over the past decade due their ability to undergo conformational changes in situ, in response to a change in temperature. One class of temperature-responsive polymers are those with lower critical solution temperature, which phase separate in aqueous solution above a critical temperature. When these temperature-responsive polymers are grafted to a solid nanoparticle, a change in their surface properties occurs above this critical temperature, from hydrophilic to more hydrophobic, giving them a propensity to aggregate. This study explores the temperature induced aggregation of silica nanoparticles functionalised with two isomeric temperature-responsive polymers with lower critical solution temperature (LCST) behavior, namely poly(N-isopropyl acrylamide) (PNIPAM), and poly(2-n-propyl-2-oxazoline) (PNPOZ) with similar molecular weights (5000{~}Da) and grafting density. These nanoparticles exhibited striking differences in the temperature of aggregation, which is consistent with LCST of each polymer. Using a combination of small-angle neutron scattering (SANS) and dynamic light scattering (DLS), we probed subtle differences in the aggregation mechanism for PNIPAM- and PNPOZ-decorated silica nanoparticles. The nanoparticles decorated with PNIPAM and PNPOZ show similar aggregation mechanism that was independent of polymer structure, whereby aggregation starts by the formation of small aggregates. A further increase in temperature leads to interaction between these aggregates and results in full-scale aggregation and subsequent phase separation.},
  comment  = {Elsevier Paper - no online access to full text. Subito delivered},
  doi      = {https://doi.org/10.1016/j.jcis.2021.01.044},
  file     = {:Mansfield2021 - Understanding the Temperature Induced Aggregation of Silica Nanoparticles Decorated with Temperature Responsive Polymers_ Can a Small Step in the Chemical Structure Make a Giant Leap for a Phase Transition_.pdf:PDF},
  keywords = {Silica nanoparticles, Aggregation, SANS, Temperature-responsive polymers, PNIPAM, Poly(2-oxazoline), polymer brush, LCST, DLS, thermoresponsive},
  printed  = {printed},
  url      = {https://www.sciencedirect.com/science/article/pii/S0021979721000485},
}

@Article{Balis2020,
  author         = {Bali{{\'{s}}}, Andrzej and Wolski, Karol and Zapotoczny, Szczepan},
  journal        = {Polymers},
  title          = {Thermoresponsive Polymer Gating System on Mesoporous Shells of Silica Particles Serving as Smart Nanocontainers},
  year           = {2020},
  issn           = {2073-4360},
  number         = {4},
  volume         = {12},
  abstract       = {Spherical silica nanoparticles with solid cores and mesoporous shells (SCMS) were decorated with thermoresponsive polymer brushes that were shown to serve as macromolecular valves to control loading and unloading of a model dye within the mesopores. Thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) brushes were grafted from the surfaces of both solid core (SC) and SCMS particles of similar size using surface-initiated atom transfer radical polymerization. Both systems based on porous (SCMS-PNIPAM) and nonporous (SC-PNIPAM) particles were characterized using cryo-TEM, thermogravimetry and elemental analysis to determine the structure and composition of the decorated nanoparticles. The grafted PNIPAM brushes were found to be responsive to temperature changes enabling temperature-controlled gating of the pores. The processes of loading and unloading in the obtained systems were examined using a model fluorescent dye---rhodamine 6G. Polymer brushes in SCMS-PNIPAM systems were shown to serve as molecular valves enabling significant adsorption (loading) of the dye inside the pores with respect to the SC-PNIPAM (no pores) and SCMS (no valves) systems. The effective unloading of the fluorescent cargo molecules from the decorated nanoparticles was achieved in a water/methanol solution. The obtained SCMS-PNIPAM particles may be used as smart nanocontainers or nanoreactors offering also facile isolation from the suspension due to the presence of dense cores.},
  article-number = {888},
  doi            = {10.3390/polym12040888},
  keywords       = {PNIPAM, drug delivery, silica nanoparticles, mesoporous, cryo TEM, thermogravimetry, elemental analysis, dye, cargo},
  pubmedid       = {32290489},
  url            = {https://www.mdpi.com/2073-4360/12/4/888},
}

@Article{Li2021,
  author         = {Li, Runmei and Cheng, Cong and Wang, Zhuorui and Gu, Xuefan and Zhang, Caixia and Wang, Chen and Liang, Xinyue and Hu, Daodao},
  journal        = {Materials},
  title          = {Conformational Stability of Poly (N-Isopropylacrylamide) Anchored on the Surface of Gold Nanoparticles},
  year           = {2021},
  issn           = {1996-1944},
  number         = {2},
  volume         = {14},
  abstract       = {To verify the temperature sensitive failure of poly (N-isopropylacrylamide) (PNIPAM) anchored on the surface of gold nanoparticles (AuNPs), the UV-Vis spectra with temperature variations of the following aqueous solutions respectively containing AuNPs-PNIPAM, Au-PNIPAM/PNIPAM, PNIPAM, in different media (including salt, ethanol, HCl and cetyltrimethylammoniumbromide (CTAB)), were systematically determined. The results indicated that the UV-Vis spectrum of AuNPs-PNIPAM suspension hardly changed even above the Lower Critical Solution Temperature (LCST) of PNIPAM, but that of Au-PNIPAM/PNIPAM sharply increased only in absorbance intensity. A possible mechanism of the failed temperature sensitivity of PNIPAM anchored on the surface of AuNPs was proposed. Being different from free PNIPAM molecules, a strong interaction exists among PNIPAM molecules anchored on the surface of AuNPs, restraining the change in conformation of PNIPAM. The temperature sensitivity of Au-PNIPAM/PNIPAM originates from the free PNIPAM molecules rather than the anchored PNIPAM one. The changing electrostatic interaction could effectively regulate the aggregation behavior of AuNPs-PNIPAM and enhance its sensitivity to temperature.},
  article-number = {443},
  doi            = {10.3390/ma14020443},
  keywords       = {PNIPAM, failed collapse, stability, gold nanoparticle, AU, NP, UV-vis, thermoresponsive},
  pubmedid       = {33477518},
  url            = {https://www.mdpi.com/1996-1944/14/2/443},
}

@Article{Ji2019,
  author   = {Ji, Yuxing and Lin, Xiankun and Zhang, Hongyue and Wu, Yingjie and Li, Junbai and He, Qiang},
  journal  = {Angewandte Chemie - International Edition},
  title    = {Thermoresponsive Polymer Brush Modulation on the Direction of Motion of Phoretically Driven Janus Micromotors},
  year     = {2019},
  number   = {13},
  pages    = {4184--4188},
  volume   = {58},
  abstract = {We report a thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) brush functionalized Janus Au--Pt bimetallic micromotor capable of modulating the direction of motion with the change of the ambient temperature. The PNIPAM@Au--Pt micromotor moved along the Au--Pt direction with a speed of 8.5\hspace{0.25em}$\mu$m\hspace{0.167em}s$-$1 in 1.5\hspace{0.167em}\% H2O2 at 25\hspace{0.167em}{$^{\circ}$}C (below the lower critical solution temperature (LCST) of PNIPAM), whereas it changed the direction of motion (i.e., along the Pt--Au direction) and the speed decreased to 2.3\hspace{0.25em}$\mu$m\hspace{0.167em}s$-$1 at 35\hspace{0.167em}{$^{\circ}$}C (above LCST). Below LCST, PNIPAM brushes grafted on the Au side were hydrophilic and swelled, which permitted the electron transfer and proton diffusion on the Au side, and thus the motion is regarded as a self-electrophoretic mechanism. However, PNIPAM brushes above LCST became hydrophobic and collapsed, and thus the driving mechanism switched to the self-diffusiophoresis like that of Pt-modified Janus silica motors. These motors could reversibly change the direction of motion with the transition of the hydrophobic and hydrophilic states of the grafted PNIPAM brushes. Such a thermoresponsive polymer brush functionalization method provides a new strategy for engineering the kinematic behavior of phoretically driven micro/nanomotors.},
  doi      = {https://doi.org/10.1002/anie.201812860},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201812860},
  keywords = {kinematic behavior, micromotors, phoretic effects, polymer brushes, thermoresponsive, PNIPAM, Janus},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201812860},
}

@Article{Pei2019,
  author   = {Pei, Xiaopeng and Zhai, Kankan and Wang, Chao and Deng, Yukun and Tan, Ying and Zhang, Baichao and Bai, Yungang and Xu, Kun and Wang, Pixin},
  journal  = {Langmuir},
  title    = {Polymer Brush Graft-Modified Starch-Based Nanoparticles as Pickering Emulsifiers},
  year     = {2019},
  note     = {PMID: 31070380},
  number   = {22},
  pages    = {7222--7230},
  volume   = {35},
  abstract = {We study biosourced core--shell particles with a starch-based core and thermo-responsive polymer brush shell using surface-initiated single-electron transfer living radical polymerization (SI-SET-LRP) as a Pickering stabilizer. The shell endows the Pickering stabilizer with reversible emulsification/demulsification of oil and water properties. The initiator attached to the starch-based nanosphere (Br-SNP) core particle was first fabricated using the precipitation method. Subsequently, dense poly(N-isopropylacrylamide) (PNIPAM) brush graft-modified starch-based nanoparticles (SNP-g-PNIPAM) were obtained via the SI-SET-LRP process. Interfacial properties of the resultant particles were analyzed by interfacial tensiometer measurements, as were the effects of the grafted polymer chain length and temperature on the interfacial activity. Pickering emulsion was obtained using SNP-g-PNIPAM particles as the stabilizer. The effect of the concentration of the Pickering stabilizer on the size of emulsion droplets was analyzed. The emulsification/demulsification process of the Pickering emulsion can be reversed and easily repeated by changing the temperature.},
  doi      = {10.1021/acs.langmuir.9b00413},
  eprint   = {https://doi.org/10.1021/acs.langmuir.9b00413},
  keywords = {PNIPAM, pickering emulsion, stability, interfacial tensiometer},
  url      = {https://doi.org/10.1021/acs.langmuir.9b00413},
}

@Book{Webb2006,
  editor    = {Graham A. Webb},
  publisher = {Springer Netherlands},
  title     = {Modern Magnetic Resonance},
  year      = {2006},
  isbn      = {9781402038945 ; 1402038941 ; 9781402039102 (Sekund{\"{a}}rausgabe) ; 1402039107 (Sekund{\"{a}}rausgabe)},
  comment   = {Note the chapter ``Solid-State Deuterium NMR Spectroscopy of Membranes'' pp. 581--603, DOI 10.1007/978-3-319-28388-3_89},
  doi       = {10.1007/978-3-319-28388-3},
  file      = {:/autohome/saeckech/Promotion/Literatur/NMR/ModernMagneticResonance_Webb_Springer2006.pdf:PDF},
  keywords  = {book,review,NMR,polymer networks,polymer gels,2h},
  url       = {https://link.springer.com/referencework/10.1007/978-3-319-28388-3},
}

@Article{Agbim2020,
  author    = {Kenechi A. Agbim and Laura A. Schaefer},
  journal   = {Polymer Reviews},
  title     = {Investigation of Thermoresponsive Microgel Polymer Swelling Theory},
  year      = {2020},
  number    = {4},
  pages     = {648--670},
  volume    = {60},
  abstract  = {This review details the challenges with the canonical polymer swelling theory in its ability to accurately estimate realistic polymer swelling behavior. It is important to quantify this behavior since the development of new and hybrid materials with dynamic environmental response is expected to drive rapid growth and innovation in markets including biomedicine, electronics, pharmaceuticals, building and infrastructure, and aerospace. As many of these markets require high precision and controlled dynamic response, hydrogels are being investigated to help address some of the heat transfer and fluid flow challenges found in these applications. Stimuli-responsive materials usually respond to one stimulus (e.g., light, temperature, etc.) However, hybrid polymer materials that respond to multiple stimuli can be developed through the mixing of monomer chains with differing behaviors. For these materials, the synthesis conditions influence the polymer behavior in changing environmental conditions, and it is imperative to develop a deeper understanding of how the preparation of the polymer networks impacts the viscoelastic nature of the polymer. The work also discusses the influence that synthesis conditions have on the behavior of thermo-responsive Poly(N-isopropylacrylamide) (PNIPAAm). Lastly, the paper describes an inferential, nested regression model developed to highlight the dependence the swelling has on the synthesis technique used.},
  comment   = {no full access},
  doi       = {10.1080/15583724.2019.1711392},
  eprint    = {https://doi.org/10.1080/15583724.2019.1711392},
  keywords  = {stimuli resposive, microgel, swelling, polymer, theory, review},
  publisher = {Taylor \& Francis},
  url       = {https://doi.org/10.1080/15583724.2019.1711392},
}

@Article{Anakhov2020,
  author   = {Mikhail V. Anakhov and Rustam A. Gumerov and Igor I. Potemkin},
  journal  = {Mendeleev Communications},
  title    = {Stimuli-responsive aqueous microgels: properties and applications},
  year     = {2020},
  issn     = {0959-9436},
  number   = {5},
  pages    = {555--562},
  volume   = {30},
  abstract = {Water-soluble microgels have been known for over than three decades. Initially introduced as thermoresponsive polymer colloids with tunable softness, these macromolecular objects become a versatile platform for a broad range of potential applications due to the bursting growth of the diversity of their chemical architecture through the years. The recent progress in the design of stimuli-responsive microgels together with the notable examples of their applications is discussed in this paper.},
  comment  = {Elsevier paper - no full access},
  doi      = {https://doi.org/10.1016/j.mencom.2020.09.002},
  keywords = {microgels, stimuli-responsiveness, drug delivery, emulsion stabilization, catalysis},
  url      = {https://www.sciencedirect.com/science/article/pii/S0959943620302261},
}

@Article{Minier2021,
  author   = {Samuel Minier and Hyeong Jin Kim and Jonathan Zaugg and Surya K. Mallapragada and David Vaknin and Wenjie Wang},
  journal  = {Journal of Colloid and Interface Science},
  title    = {Poly(N-isopropylacrylamide)-grafted gold nanoparticles at the vapor/water interface},
  year     = {2021},
  issn     = {0021-9797},
  pages    = {312--319},
  volume   = {585},
  abstract = {Hypothesis
Grafting nanoparticles surfaces with water-soluble polymers modify interparticle interactions that are pivotal for assembling them into ordered phases. By manipulating salt concentrations of gold nanoparticles (AuNPs) that are grafted with poly(N-isopropylacrylamide) (PNIPAM-AuNPs), we hypothesize that various aggregated phases form at the suspension/vapor interface or in the bulk that depend on the molecular weight (MW) of PNIPAM and on salt concentrations.
Experiments
AuNPs are grafted with thiolated PNIPAM of molecular weights of 3 or 6{~}kDa, and grafting is confirmed by dynamic light scattering. Liquid-surfaces X-ray reflectivity and grazing incidence small-angle X-ray scattering are used to determine the density profiles of the suspension/vapor interface and their inplane structure as salt is added to the suspensions.
Findings
We find that surface enrichment is induced by adding NaCl to the suspensions, and that at low salt concentrations, the monoparticle layer formed is dispersed, and above a threshold salt concentration, depending on MW of PNIPAM, the PNIPAM-AuNPs order in a hexagonal structure. We show that the lattice constant of the two-dimensional hexagonal structure varies with salt concentration, and more significantly with MW of PNIPAM.},
  comment  = {Elsevier paper - no full access},
  doi      = {https://doi.org/10.1016/j.jcis.2020.11.080},
  keywords = {PNIPAM-grafted nanoparticles, Interfacial superlattice, X-ray reflectivity, Grazing incidence small angle X-ray scattering (GI-SAXS)},
  url      = {https://www.sciencedirect.com/science/article/pii/S002197972031599X},
}

@Article{Rey2020,
  author   = {Rey, Marcel and Fernandez-Rodriguez, Miguel Angel and Karg, Matthias and Isa, Lucio and Vogel, Nicolas},
  journal  = {Accounts of Chemical Research},
  title    = {Poly-N-isopropylacrylamide Nanogels and Microgels at Fluid Interfaces},
  year     = {2020},
  note     = {PMID: 31940173},
  number   = {2},
  pages    = {414--424},
  volume   = {53},
  abstract = {ConspectusThe confinement of colloidal particles at liquid interfaces offers many opportunities for materials design. Adsorption is driven by a reduction of the total free energy as the contact area between the two liquids is partially replaced by the particle. From an application point of view, particle-stabilized interfaces form emulsions and foams with superior stability. Liquid interfaces also effectively confine colloidal particles in two dimensions and therefore provide ideal model systems to fundamentally study particle interactions, dynamics, and self-assembly. With progress in the synthesis of nanomaterials, more and more complex and functional particles are available for such studies.In this Account, we focus on poly(N-isopropylacrylamide) nanogels and microgels. These are cross-linked polymeric particles that swell and soften by uptaking large amounts of water. The incorporated water can be partially expelled, causing a volume phase transition into a collapsed state when the temperature is increased above approximately 32 {$^{\circ}$}C.Soft microgels adsorbed to liquid interfaces significantly deform under the influence of interfacial tension and assume cross sections exceeding their bulk dimensions. In particular, a pronounced corona forms around the microgel core, consisting of dangling chains at the microgel periphery. These polymer chains expand at the interface and strongly affect the interparticle interactions. The particle deformability therefore leads to a significantly more complex interfacial phase behavior that provides a rich playground to explore structure formation processes.We first discuss the characteristic {\textquotedblleft}fried-egg{\textquotedblright} or core--corona morphology of individual microgels adsorbed to a liquid interface and comment on the dependence of this interfacial morphology on their physicochemical properties. We introduce different theoretical models to describe their interfacial morphology. In a second part, we introduce how ensembles of microgels interact and self-assemble at liquid interfaces. The core--corona morphology and the possibility to force these elements into overlap upon compression results in a complex phase behavior with a phase transition between microgels with extended and collapsed coronae. We discuss the influence of the internal particle architecture, also including core--shell microgels with rigid cores, on the phase behavior. Finally, we present new routes for the realization of more complex structures, resulting from multiple deposition protocols and from engineering the interaction potential of the individual particles.},
  doi      = {10.1021/acs.accounts.9b00528},
  eprint   = {https://doi.org/10.1021/acs.accounts.9b00528},
  keywords = {PNIPAM, microgel, nanogel, interface},
}

@Article{Widmann2019,
  author   = {Widmann, Tobias and Kreuzer, Lucas P. and Hohn, Nuri and Bie{\ss}mann, Lorenz and Wang, Kun and Rinner, Stephan and Moulin, Jean-Fran{\c{c}}ois and Schmid, Andreas J. and Hannappel, Yvonne and Wrede, Oliver and K{\"{u}}hnhammer, Matthias and Hellweg, Thomas and von Klitzing, Regine and M{\"{u}}ller-Buschbaum, Peter},
  journal  = {Langmuir},
  title    = {Hydration and Solvent Exchange Induced Swelling and Deswelling of Homogeneous Poly(N-isopropylacrylamide) Microgel Thin Films},
  year     = {2019},
  note     = {PMID: 31714092},
  number   = {49},
  pages    = {16341--16352},
  volume   = {35},
  abstract = {The investigation of the response kinetics of smart colloidal microgel films is crucial for their optimization to enable advanced applications. We study the classical thermoresponsive microgel model system N-isopropylacrylamide cross-linked with N,N$\prime$-methylenebisacrylamide. Without the typically used polyelectrolyte coating of the substrate, thin microgel films are prepared in a single spin-coating step. Atomic force microscopy measurements reveal an extremely dense packing, resulting in a homogeneous compact thin film of microgel particles. The hydration kinetics of these films in H2O and D2O atmospheres as well as the kinetics of the solvent exchange between both water species are investigated with in situ time-of-flight neutron reflectometry (TOF-NR) and in situ Fourier-transform infrared (FTIR) spectroscopy. With accounting for a nonconstant humid atmosphere, the intrinsic diffusion dynamics of water molecules into the thin microgel film are modeled and the specific time constant $\tau$ and the effective Flory--Huggins interaction parameter $\chi$eff are determined. Comparing the results in H2O and D2O atmospheres, TOF-NR and FTIR spectroscopy results show an increased affinity of the microgel films toward H2O as compared to D2O. From the FTIR spectroscopy data, we further identify different kinetics of intermolecular processes and order them according to their temporal evolution.},
  doi      = {10.1021/acs.langmuir.9b03104},
  eprint   = {https://doi.org/10.1021/acs.langmuir.9b03104},
  file     = {:/autohome/saeckech/Downloads/HydrationAndSolventExchangeInducedSwellingAndDeswellingOfHomogeneousPolyNIsopropylAcrylamideMicrogelThinFilms_WidmannEtAl_Langmuir2019.pdf:PDF;:/autohome/saeckech/Downloads/HydrationAndSolventExchangeInducedSwellingAndDeswellingOfHomogeneousPolyNIsopropylAcrylamideMicrogelThinFilms_WidmannEtAl_Langmuir2019_SI.pdf:PDF},
  keywords = {PNIPAM,swelling,deswelling,hydration kinetics,thin film,microgel,solvent exchange,neutron reflectometry,time of flight,FTIR,infrared,diffusion,flory huggins interaction parameter,kinetics,isotope effect,gel},
  url      = {https://doi.org/10.1021/acs.langmuir.9b03104},
}

@Article{Lopez2019,
  author   = {Lopez, Carlos G. and Scotti, Andrea and Brugnoni, Monia and Richtering, Walter},
  journal  = {Macromolecular Chemistry and Physics},
  title    = {The Swelling of Poly(Isopropylacrylamide) Near the $\theta$ Temperature: A Comparison between Linear and Cross-Linked Chains},
  year     = {2019},
  number   = {4},
  pages    = {1800421},
  volume   = {220},
  abstract = {Thermoresponsive polymeric gels are a class of smart materials with the ability to absorb or release large amounts of solvent when changes in their environment occur. Scaling theories of gel swelling (de Gennes' c$\ast$ theorem and Obukhov's model) predict that the swelling of a gel correlates with that of a linear chain with equal degree of polymerization to that of a network strand. Data on linear and cross-linked poly(N-isopropylacrylamide) (PNIPAM) in aqueous solutions of different molar masses under $\theta$ temperature and good solvent conditions are examined. The Kuhn length of PNIPAM is evaluated to be LK {~}={~}4{~}$\pm${~}1{~}nm, in strong disagreement with previous estimates by single molecule force spectroscopy. The excluded volume strength (B) varies with the reduced temperature ($\tau$) as B{~}$\simeq${~}4.7$\tau${~}nm. While the power law exponent for the equilibrium swelling as a function of degree of cross-linking is close to the scaling predictions, the degree of swelling observed in cross-linked networks is two to three orders of magnitude larger than that expected from scaling models. The large differences between theoretical predictions and experimental results probably arise from the highly inhomogeneous nature of PNIPAM gels.},
  doi      = {https://doi.org/10.1002/macp.201800421},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/macp.201800421},
  file     = {:Lopez2019 - The Swelling of Poly(Isopropylacrylamide) near the $$ Temperature_ a Comparison between Linear and Cross Linked Chains.pdf:PDF},
  keywords = {excluded volume, Kuhn Length, microgels, PNIPAM, scaling, theta solvent, theta temperature, thermoresponsive},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/macp.201800421},
}

@Article{Witte2019,
  author     = {Witte, Judith and Kyrey, Tetyana and Lutzki, Jana and Dahl, Anna Margarethe and Houston, Judith and Radulescu, Aurel and Pipich, Vitaliy and Stingaciu, Laura and K{\"{u}}hnhammer, Matthias and Witt, Marcus U. and von Klitzing, Regine and Holderer, Olaf and Wellert, Stefan},
  journal    = {Soft Matter},
  title      = {A comparison of the network structure and inner dynamics of homogeneously and heterogeneously crosslinked PNIPAM microgels with high crosslinker content},
  year       = {2019},
  pages      = {1053--1064},
  volume     = {15},
  abstract   = {Poly(N-isopropylacrylamide) microgel particles were prepared via a {\textquotedblleft}classical{\textquotedblright} surfactant-free precipitation polymerization and a continuous monomer feeding approach. It is anticipated that this yields microgel particles with different internal structures{,} namely a dense core with a fluffy shell for the classical approach and a more even crosslink distribution in the case of the continuous monomer feeding approach. A thorough structural investigation of the resulting microgels with dynamic light scattering{,} atomic force microscopy and small angle neutron scattering was conducted and related to neutron spin echo spectroscopy data. In this way a link between structural and dynamic features of the internal polymer network was made.},
  doi        = {10.1039/C8SM02141D},
  file       = {:Witte2019 - A Comparison of the Network Structure and Inner Dynamics of Homogeneously and Heterogeneously Crosslinked PNIPAM Microgels with High Crosslinker Content.pdf:PDF},
  issue      = {5},
  keywords   = {PNIPAM, microgel, network, SANS, NSE, DLS, LLS, Zimm dynamics, AFM},
  printed    = {printed},
  publisher  = {The Royal Society of Chemistry},
  readstatus = {read},
  url        = {http://dx.doi.org/10.1039/C8SM02141D},
}

@Article{Keidel2018,
  author   = {Rico Keidel and Ali Ghavami and Dersy M. Lugo and Gudrun Lotze and otto Virtanen and Peter Beumers and Jan Skov Pedersen and Andre Bardow and Roland G. Winkler and Walter Richtering},
  journal  = {Science Advances},
  title    = {Time-resolved structural evolution during the collapse of responsive hydrogels: The microgel-to-particle transition},
  year     = {2018},
  month    = apr,
  number   = {4},
  volume   = {4},
  abstract = {Adaptive hydrogels, often termed smart materials, are macromolecules whose structure adjusts to external stimuli. Responsive micro- and nanogels are particularly interesting because the small length scale enables very fast response times. Chemical cross-links provide topological constraints and define the three-dimensional structure of the micro-gels, whereas their porous structure permits fast mass transfer, enabling very rapid structural adaption of the microgel to the environment. The change of microgel structure involves a unique transition from a flexible, swollen finite-size macromolecular network, characterized by a fuzzy surface, to a colloidal particle with homogeneous density and a sharp surface. In this contribution, we determine, for the first time, the structural evolution during the microgel-to-particle transition. Time-resolved small-angle x-ray scattering experiments and computer simulations unambiguously reveal a two-stage process: In a first, very fast process, collapsed clusters form at the periphery, leading to an intermediate, hollowish core-shell structure that slowly transforms to a globule. This structural evolution is independent of the type of stimulus and thus applies to instantaneous transitions as in a temperature jump or to slower stimuli that rely on the uptake of active molecules from and/or exchange with the environment. The fast transitions of size and shape provide unique opportunities for various applications as, for example, in uptake and release, catalysis, or sensin},
  doi      = {10.1126/sciadv.aao7086},
  keywords = {hydrogel,two stage collapse,simulation,x-ray,stimuli-responsive,kinetics,microgel,SAXS,cononsolvency,aqueous alcohol,methanol},
}

@Article{Nothdurft2021,
  author       = {Nothdurft, Katja and M{\"{u}}ller, David H. and M{\"{u}}rtz, Sonja D. and Meyer, Anna A. and Guerzoni, Luis P. B. and Jans, Alexander and K{\"{u}}hne, Alexander J. C. and De Laporte, Laura and Brands, Thorsten and Bardow, Andr{\'{e}} and Richtering, Walter},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Is the Microgel Collapse a Two-Step Process? Exploiting Cononsolvency to Probe the Collapse Dynamics of Poly-N-isopropylacrylamide (pNIPAM)},
  year         = {2021},
  note         = {PMID: 33503378},
  number       = {5},
  pages        = {1503--1512},
  volume       = {125},
  abstract     = {Many applications of responsive microgels rely on the fast adaptation of the polymer network. However, the underlying dynamics of the de-/swelling process of the gels have not been fully understood. In the present work, we focus on the collapse kinetics of poly-N-isopropylacrylamide (pNIPAM) microgels due to cononsolvency. Cononsolvency means that either of the pure solvents, e.g., pure water or pure methanol, act as a so-called good solvent, leading to a swollen state of the polymer network. However, in mixtures of water and methanol, the previously swollen network undergoes a drastic volume loss. To further elucidate the cononsolvency transition, pNIPAM microgels with diameters between 20 and 110 $\mu$m were synthesized by microfluidics. To follow the dynamics, pure water was suddenly exchanged with an unfavorable mixture of 20 mol\% methanol (solvent-jump) within a microfluidic channel. The dynamic response of the microgels was investigated by optical and fluorescence microscopy and Raman microspectroscopy. The experimental data provide unique and detailed insight into the size-dependent kinetics of the volume phase transition due to cononsolvency. The change in the microgel{\textquoteright}s diameter over time points to a two-step process of the microgel collapse with a biexponential behavior. Furthermore, the dependence between the two time constants from this biexponential behavior and the microgel{\textquoteright}s diameter in the collapsed state deviates from the square-power law proposed by Tanaka and Fillmore [ J. Chem. Phys. 1979, 70, 1214$-$1218]. The deviation is discussed considering the adhesion-induced deformation of the gels and the physical processes underlying the collapse.},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1021/acs.jpcb.0c10430},
  eprint       = {https://doi.org/10.1021/acs.jpcb.0c10430},
  file         = {:Nothdurft2021 - Is the Microgel Collapse a Two Step Process_ Exploiting Cononsolvency to Probe the Collapse Dynamics of Poly N Isopropylacrylamide (pNIPAM).pdf:PDF},
  keywords     = {PNIPAM, cononsolvency, microgel, polymer network, transition kinetics, optical microscopy, fluorescence microscopy, Raman spectroscopy, two step collapse},
  priority     = {prio1},
  url          = {https://doi.org/10.1021/acs.jpcb.0c10430},
}

@Article{Nun2017,
  author         = {Nun, Nils and Hinrichs, Stephan and Schroer, Martin A. and Sheyfer, Dina and Gr{\"{u}}bel, Gerhard and Fischer, Birgit},
  journal        = {Gels},
  title          = {Tuning the Size of Thermoresponsive Poly(N-Isopropyl Acrylamide) Grafted Silica Microgels},
  year           = {2017},
  issn           = {2310-2861},
  number         = {3},
  volume         = {3},
  abstract       = {Core-shell microgels were synthesized via a free radical emulsion polymerization of thermoresponsive poly-(N-isopropyl acrylamide), pNipam, on the surface of silica nanoparticles. Pure pNipam microgels have a lower critical solution temperature (LCST) of about 32 {$^{\circ}$}C. The LCST varies slightly with the crosslinker density used to stabilize the gel network. Including a silica core enhances the mechanical robustness. Here we show that by varying the concentration gradient of the crosslinker, the thermoresponsive behaviour of the core-shell microgels can be tuned. Three different temperature scenarios have been detected. First, the usual behaviour with a decrease in microgel size with increasing temperature exhibiting an LCST; second, an increase in microgel size with increasing temperature that resembles an upper critical solution temperature (UCST), and; third, a decrease with a subsequent increase of size reminiscent of the presence of both an LCST, and a UCST. However, since the chemical structure has not been changed, the LCST should only change slightly. Therefore we demonstrate how to tune the particle size independently of the LCST.},
  article-number = {34},
  comment        = {Could their UCST-like increase in radius be an aggregation of particles?},
  creationdate   = {2021-03-08T00:00:00},
  doi            = {10.3390/gels3030034},
  file           = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/TuningTheSizeOfThermoresponsivePolyNIsopropylacrylamideGraftedSilicaMicrogels_NunEtAl_Gels2017.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/TuningTheSizeOfThermoresponsivePolyNIsopropylacrylamideGraftedSilicaMicrogels_NunEtAl_Gels2017_SI.pdf:PDF},
  keywords       = {PNIPAM, microgel, LCST, tuning, thermoresponsive, core-shell, silica nanoparticles, UCST},
  url            = {https://www.mdpi.com/2310-2861/3/3/34},
}

@Article{Byun2016,
  author       = {Hongsik Byun and Jiayun Hu and Phakkhananan Pakawanit and Laongnuan Srisombat and Jun-Hyun Kim},
  journal      = {Nanotechnology},
  title        = {Polymer particles filled with multiple colloidal silica viain situsol-gel process and their thermal property},
  year         = {2016},
  month        = dec,
  number       = {2},
  pages        = {025601},
  volume       = {28},
  abstract     = {The in situ formation of dielectric silica (SiO2) particles was carried out in the presence of temperature-responsive poly(N-isopropylacrylamide) particles. Unlike the typical sol-gel method used to prepare various SiO2 particles, the highly uniform growth of SiO2 particles was achieved within the cross-linked polymer particles (i.e., the polymer particles were filled with the SiO2 particles) simply by utilizing interfacial interactions, including the van der Waals attractive force and hydrogen bonding in nanoscale environments. The structural and morphological features as well as the thermal behaviors of these composites were thoroughly examined by electron microscopes, dynamic light scattering, and thermal analyzers. In particular, the thermal properties of these composites were completely different from the bare polymer, SiO2 particles, and their mixtures, which clearly suggested the successful incorporation of multiple SiO2 particles within the cross-linked polymer particles. Similarly, titanium oxide (TiO2) particles were easily embedded within the polymer particle template which exhibited improved overall properties. As a whole, understanding in situ formation of nanoscale inorganic particles within polymer particle templates can allow for designing novel composite materials possessing enhanced chemical and physical properties.},
  comment      = {No full access},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1088/0957-4484/28/2/025601},
  keywords     = {PNIPAM core silica shell},
  publisher    = {{IOP} Publishing},
  url          = {https://doi.org/10.1088/0957-4484/28/2/025601},
}

@Article{Sala2021,
  author       = {Sala, Renata L. and Ven{\^{a}}ncio, Tiago and Camargo, Emerson R.},
  journal      = {Langmuir},
  title        = {Probing the Structural Dynamics of the Coil--Globule Transition of Thermosensitive Nanocomposite Hydrogels},
  year         = {2021},
  note         = {PMID: 33481601},
  number       = {4},
  pages        = {1531--1541},
  volume       = {37},
  abstract     = {Nanocomposite hydrogels have emerged to exhibit multipurpose properties, boosting especially the biomaterial field. However, the development and characterization of these materials can be a challenge, especially stimuli-sensitive materials with dynamic properties in response to external stimuli. By employing UV--vis spectroscopy and NMR relaxation techniques, we could outline the formation and behavior of thermosensitive nanocomposites obtained by in situ polymerization of poly(N-vinylcaprolactam) (PNVCL) and mesoporous silica nanofibers under temperature stimuli. For instance, inorganic nanoparticles covalently linked to PNVCL changed the pattern of temperature-induced phase transition despite showing similar critical temperatures to neat PNVCL. Thermodynamic parameters indicated the formation of an interconnected system of silica and polymer chains with reduced enthalpic contribution and mobility. The investigation of water molecule and polymer segment motions also revealed that the absorption and release of water happened in a wider temperature range for the nanocomposites, and the polymer segments respond in different ways during the phase transition in the presence of silica. This set of techniques was essential to reveal the polymer motions and structural features in nanocomposite hydrogels under temperature stimuli, demonstrating its potential use as experimental guideline to study multicomponent nanocomposites with diverse functionalities and dynamic properties.},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1021/acs.langmuir.0c03079},
  eprint       = {https://doi.org/10.1021/acs.langmuir.0c03079},
  keywords     = {PNVCL, NMR, UV-vis, stimuli-responsive, mesoporoous silica, hydrogel, PVCL, poly(N-vinylcaprolactam)},
  readstatus   = {read},
  url          = {https://doi.org/10.1021/acs.langmuir.0c03079},
}

@Article{Fucinos2014,
  author       = {Fuci{\~{n}}os, Clara and Fuci{\~{n}}os, Pablo AND M{\'{i}}guez, Mart{\'{i}}n AND Katime, Issa AND Pastrana, Lorenzo M. AND R{\'{u}}a, Mar{\'{i}}a L.},
  journal      = {PLOS ONE},
  title        = {Temperature- and pH-Sensitive Nanohydrogels of Poly(N-Isopropylacrylamide) for Food Packaging Applications: Modelling the Swelling-Collapse Behaviour},
  year         = {2014},
  month        = feb,
  number       = {2},
  pages        = {1--15},
  volume       = {9},
  abstract     = {Temperature-sensitive poly(N-isopropylacrylamide) (PNIPA) nanohydrogels were synthesized by nanoemulsion polymerization in water-in-oil systems. Several cross-linking degrees and the incorporation of acrylic acid as comonomer at different concentrations were tested to produce nanohydrogels with a wide range of properties. The physicochemical properties of PNIPA nanohydrogels, and their relationship with the swelling-collapse behaviour, were studied to evaluate the suitability of PNIPA nanoparticles as smart delivery systems (for active packaging). The swelling-collapse transition was analyzed by the change in the optical properties of PNIPA nanohydrogels using ultraviolet-visible spectroscopy. The thermodynamic parameters associated with the nanohydrogels collapse were calculated using a mathematical approach based on the van't Hoff analysis, assuming a two-state equilibrium (swollen to collapsed). A mathematical model is proposed to predict both the thermally induced collapse, and the collapse induced by the simultaneous action of two factors (temperature and pH, or temperature and organic solvent concentration). Finally, van't Hoff analysis was compared with differential scanning calorimetry. The results obtained allow us to solve the problem of determining the molecular weight of the structural repeating unit in cross-linked NIPA polymers, which, as we show, can be estimated from the ratio of the molar heat capacity (obtained from the van't Hoff analysis) to the specific heat capacity (obtained from calorimetric measurements).},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1371/journal.pone.0087190},
  keywords     = {PNIPAM, theory, application, food, packaging, nanogel, hydrogel, DSC},
  publisher    = {Public Library of Science},
  url          = {https://doi.org/10.1371/journal.pone.0087190},
}

@Article{Alf2011,
  author       = {Alf, Mahriah E. and Hatton, T. Alan and Gleason, Karen K.},
  journal      = {Langmuir},
  title        = {Insights into Thin, Thermally Responsive Polymer Layers Through Quartz Crystal Microbalance with Dissipation},
  year         = {2011},
  note         = {PMID: 21806008},
  number       = {17},
  pages        = {10691--10698},
  volume       = {27},
  abstract     = {The thermodynamics of temperature-responsive polymeric layers was analyzed using a two-state coil to globule model to which the van{\textquoteright}t Hoff relationship was applied. For soluble homopolymer poly(N-isopropylacrylamide (pNIPAAm), enthalpies of transition, {{$\Delta$}}HvH, were calculated using varations in ultraviolet--visible (UV--vis) spectroscopy with temperature to be 8400 $\pm$ 30 and 1652 $\pm$ 4 kJ mol-cooperative unit--1 for standard synthesis and initiated chemical vapor deposition (iCVD), respectively. For the insoluble surface-bound layer of cross-linked iCVD poly(N-isopropylacrylamide-co-di(ethylene glycol) divinyl ether) [p(NIPAAm-co-DEGDVE)], {{$\Delta$}}HvH was determined to be 810 $\pm$ 30 kJ mol-cooperative unit--1 using quartz crystal microbalance with dissipation monitoring (QCM-D). Microcalorimetry measurements showed the enthalpies per mole NIPAAm monomer to be 5.8 $\pm$ 0.2, 3.5 $\pm$ 0.6, and 3.1 $\pm$ 0.3 kJ mol-NIPAAm--1, resulting in cooperative unit sizes of 1460 $\pm$ 60, 470 $\pm$ 80, and 260 $\pm$ 30 monomer units for the standard pNIPAAm, iCVD pNIPAAm, and p(NIPAAm-co-DEGDVE) systems, respectively. These values indicate that both per monomer enthalpic contribution as well as cooperative unit size are primary factors contributing to the variations in van{\textquoteright}t Hoff enthalpies for the three systems studied. Diffusion of bovine serum albumin (BSA) into swollen p(NIPAAm-co-DEGDVE) films below its lower critical solution temperature was elucidated via QCM-D measurements. These data provided a calculated diffusion coefficient of (3.5 $\pm$ 0.1) $\times$ 10--14 cm2 s--1 of BSA into the swollen hydrogel film with a mesh size of 6.0 $\pm$ 0.2 nm (compared to the hydrodynamic radius of BSA, rH = 3.36 nm).},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1021/la201935r},
  eprint       = {https://doi.org/10.1021/la201935r},
  keywords     = {PNIPAM, theory, calculation, UV-vis, QCM, enthalpy, vant Hoff},
  url          = {https://doi.org/10.1021/la201935r},
}

@Article{Chung2008,
  author       = {Chung, Po-Wen and Kumar, Rajeev and Pruski, Marek and Lin, Victor S.-Y.},
  journal      = {Advanced Functional Materials},
  title        = {Temperature Responsive Solution Partition of Organic--Inorganic Hybrid Poly(N-isopropylacrylamide)-Coated Mesoporous Silica Nanospheres},
  year         = {2008},
  number       = {9},
  pages        = {1390--1398},
  volume       = {18},
  abstract     = {A series of poly(N-isopropylacrylamide)-coated mesoporous silica nanoparticle materials (PNiPAm-MSNs) has been synthesized by a surface-initiated living radical polymerization with a reversible addition--fragmentation chain transfer (RAFT) reaction. The structure and the degree of polymerization of the PNiPAm-MSNs has been characterized by a variety of techniques, including nitrogen sorption analysis, 29Si and 13C solid-state NMR spectroscopy, transmission electron microscopy (TEM), and powder X-ray diffraction (XRD). The thermally induced changes of the surface properties of these polymer-coated core--shell nanoparticles have been determined by examining their partition activities in a biphasic solution (water/toluene) at different temperatures.},
  creationdate = {2021-03-08T00:00:00},
  doi          = {https://doi.org/10.1002/adfm.200701116},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/adfm.200701116},
  keywords     = {core/shell nanoparticles, mesoporous silica, surface modifcation, PNIPAM, RAFT, NMR, TEM, X-ray},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.200701116},
}

@Article{Schweizerhof2017,
  author       = {Schweizerhof, Sj{\"{o}}ren and Demco, Dan Eugen and Mourran, Ahmed and Keul, Helmut and Fechete, Radu and M{\"{o}}ller, Martin},
  journal      = {Macromolecular Chemistry and Physics},
  title        = {Temperature-Induced Phase Transition Characterization of Responsive Polymer Brushes Grafted onto Nanoparticles},
  year         = {2017},
  number       = {6},
  pages        = {1600495},
  volume       = {218},
  abstract     = {Temperature-induced phase transition parameters of responsive free polymer and brushes onto nanoparticles are measured using high-resolution magic-angle sample spinning (HRMAS) NMR spectroscopy. To this purpose, a two-state statistical model of temperature dependence of thermodynamic observables is developed and applied to obtain parameters which characterize the process of temperature-induced phase transition of stimuli-sensitive polymers. In this investigation the thermodynamic observable is the integral intensity of the 1H HRMAS NMR spectrum peaks and the derived thermodynamic parameters are transition temperature and transition entropy. This approach is applied to investigate the dependence of temperature-induced coil-to-globule transition of poly(N-isopropylacrylamide), (PNIPAm), asymmetric end functionalized with benzyl and thiol groups (Bn--PNIPAm--SH) on molecular weight in the range 3600--30 000 g mol--1 in aqueous solutions. The characteristics of the phase transition represented by transition temperature, and transition entropy are compared to that of Bn--PNIPAm--SH brushes onto gold nanorods in the same range of molecular weight. The method used for measuring the characteristics of phase transition is based on transverse magnetization relaxation (T2) spin-echo enhance editing of the integral intensities of the 1H HRMAS NMR spectra. This NMR observable reflects changes in transverse relaxation times as an indicative of the polymer chains conformations and dynamics reached in the process of temperature-induced phase transition.},
  comment      = {Macromol. Chem. Phys. 2017, 218, 1600495

When the article was first published, the gold nanorod synthesis was presented incorrectly in chapter 2.9.3. The authors would like to correct the first sentence of the synthesis procedure, which should appear as follows:

Under vigorous stirring, 875 μL of (II) was added to (I) and left at high stirring speed for 5 min.

The authors would like to apologize for any inconvenience this mistake may have caused.},
  creationdate = {2021-03-08T00:00:00},
  doi          = {https://doi.org/10.1002/macp.201600495},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/macp.201600495},
  file         = {:Schweizerhof2017 - Temperature Induced Phase Transition Characterization of Responsive Polymer Brushes Grafted onto Nanoparticles.pdf:PDF},
  keywords     = {DSC, UV-vis, cylinder, thermodynamics, modeling, theory, gold nanorods, 1H NMR spectroscopy, polymer brush, poly(N-isopropylacrylamide), PNIPAM, temperature-induced phase transition, thermoresponsive, NMR, MAS, 1H, T2, spin-spin},
  ranking      = {rank4},
  readstatus   = {skimmed},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/macp.201600495},
}

@Article{Mukherji2016,
  author       = {Mukherji, Debashish and Wagner, Manfred and Watson, Mark D. and Winzen, Svenja and de Oliveira, Tiago E. and Marques, Carlos M. and Kremer, Kurt},
  journal      = {Soft Matter},
  title        = {Relating side chain organization of PNIPAm with its conformation in aqueous methanol},
  year         = {2016},
  pages        = {7995--8003},
  volume       = {12},
  abstract     = {Combining nuclear magnetic resonance (NMR){,} dynamic light scattering (DLS){,} and $\mu$s long all-atom simulations with two million particles{,} we establish a delicate correlation between increased side chain organization of PNIPAm and its collapse in aqueous methanol mixtures. We find that the preferential binding of methanol with PNIPAm side chains{,} bridging distal monomers along the polymer backbone{,} results in increased organization. Furthermore{,} methanol--PNIPAm preferential binding is dominated by hydrogen bonding. Our findings reveal that the collapse of PNIPAm is dominated by enthalpic interactions and that the standard poor solvent (entropic) effects play no major role.},
  comment      = {critizised by van der Vegt, Vegt2017a},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1039/C6SM01789D},
  file         = {:Mukherji2016 - Relating Side Chain Organization of PNIPAm with Its Conformation in Aqueous Methanol.pdf:PDF},
  issue        = {38},
  keywords     = {cononsolvency, NMR, DLS, simulation, PNIPAM, conformation, methanol, enthalpy, T2, spin-spin relaxation, hydrogen bond},
  publisher    = {The Royal Society of Chemistry},
  ranking      = {rank4},
  readstatus   = {read},
  url          = {http://dx.doi.org/10.1039/C6SM01789D},
}

@Article{Starovoytova2007,
  author       = {Larisa Starovoytova and Ji{{\v{r}}}{\'{i}} Sp{\v{e}}v{\'{a}}{\v{c}}ek and Miroslava Trchov{\'{a}}},
  journal      = {European Polymer Journal},
  title        = {1H NMR and IR study of temperature-induced phase transition of negatively charged poly(N-isopropylmethacrylamide-co-sodium methacrylate) copolymers in aqueous solutions},
  year         = {2007},
  issn         = {0014-3057},
  number       = {12},
  pages        = {5001--5009},
  volume       = {43},
  abstract     = {1H NMR and IR spectroscopies were used to investigate the temperature-induced phase transition behaviour of poly(N-isopropylmethacrylamide-co-sodium methacrylate) [P(IPMAAm/MNa)] copolymers, containing in aqueous solutions negatively charged MNa units (i=1--10mol%), and the obtained results were compared with those obtained for poly(N-isopropylmethacrylamide) (PIPMAAm) homopolymer. For PIPMAAm/H2O solution, IR spectra indicate that the transition temperatures for the hydrophilic CO groups are slightly higher (by$\sim$2K) in comparison with hydrophobic CH3 groups. The decreasing values of phase-separated fraction pmax and the decrescent hysteresis during gradual heating and cooling, both with increasing content of MNa units i in the copolymer, show that for copolymers with i$\geqslant$5mol% the globular-like structures formed at temperatures above the respective LCST are rather porous and disordered with relatively low degree of polymer--polymer hydrogen bonding. While for P(IPMAAm/MNa) copolymers with i$\geqslant$5mol% most water molecules are expelled from globular structures, for i5mol% a certain portion of water (HDO) molecules is rather tightly bound in globular structures; at the same time no releasing process was detected for the bound water even for 90h.},
  comment      = {elsevier paper - no full access},
  creationdate = {2021-03-08T00:00:00},
  doi          = {https://doi.org/10.1016/j.eurpolymj.2007.09.002},
  file         = {:Starovoytova2007 - 1H NMR and IR Study of Temperature Induced Phase Transition of Negatively Charged Poly(N Isopropylmethacrylamide Co Sodium Methacrylate) Copolymers in Aqueous Solutions.pdf:PDF},
  keywords     = {Thermosensitive polyelectrolytes, Poly(-isopropylmethacrylamide--sodium methacrylate) copolymers, PNIPMAAm, Aqueous solutions, H NMR, FTIR},
  url          = {https://www.sciencedirect.com/science/article/pii/S0014305707004958},
}

@Article{Rice2006,
  author       = {Rice, Charles V.},
  journal      = {Biomacromolecules},
  title        = {Phase-Transition Thermodynamics of N-Isopropylacrylamide Hydrogels},
  year         = {2006},
  note         = {PMID: 17025371},
  number       = {10},
  pages        = {2923--2925},
  volume       = {7},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1021/bm060607t},
  eprint       = {https://doi.org/10.1021/bm060607t},
  keywords     = {PNIPAM, hydrogel, thermodynamics, theory},
  url          = {https://doi.org/10.1021/bm060607t},
}

@Article{Balaceanu2011,
  author       = {Balaceanu, Andreea and Demco, Dan E. and M{\"{o}}ller, Martin and Pich, Andrij},
  journal      = {Macromolecules},
  title        = {Microgel Heterogeneous Morphology Reflected in Temperature-Induced Volume Transition and 1H High-Resolution Transverse Relaxation NMR. The Case of Poly(N-vinylcaprolactam) Microgel},
  year         = {2011},
  number       = {7},
  pages        = {2161--2169},
  volume       = {44},
  abstract     = {The Flory temperature-induced volume transition theory for homopolymer microgels was generalized for the case of bimodal heterogeneous morphology. The most probable morphological parameters were selected from the microscopic and thermodynamic constraints imposed by 1H transverse relaxation NMR and Flory equation of state in the approximation of a homogeneous morphology. Proton transverse magnetization relaxation NMR proved directly the existence of a bimodal heterogeneous morphology of the PVCL microgel particle. The volume polymer fractions in the deswollen state and the number of subchains for the core and corona were obtained from size$-$temperature data for a series of differently cross-linked microgels made of poly(N-vinylcaprolactam) (PVCL) in water. The cross-link density effect given by the different amounts of cross-linker used was investigated using dynamic light scattering. From the combination of Flory heterogeneous theory and NMR transverse relaxation, the number of polymer subchains in core and corona was shown to increase with the amount of cross-linker. Moreover, the ratio of the cross-link density in core and corona could be evaluated from the transverse relaxation times T2 of each decay components. The quantitative characterization of PVCL microgels by size$-$temperature data and 1H transverse relaxation NMR shows the consistency of the assumptions made in the generalization of Flory theory of microgels for heterogeneous morphology.},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1021/ma200103y},
  eprint       = {https://doi.org/10.1021/ma200103y},
  keywords     = {PVCL, microgel, theory, NMR, spin-spin, T2, 1H, Flory, DLS},
  url          = {https://doi.org/10.1021/ma200103y},
}

@Article{Fujishige1989,
  author       = {Fujishige, Shouei and Kubota, K. and Ando, I.},
  journal      = {Journal of Physical Chemistry},
  title        = {Phase transition of aqueous solutions of poly(N-isopropylacrylamide) and poly(N-isopropylmethacrylamide)},
  year         = {1989},
  number       = {8},
  pages        = {3311--3313},
  volume       = {93},
  abstract     = {When aqueous solutions of well-fractionated poly(N-isopropylacrylamide) samples are heated, the polymer molecular dimensions change abruptly at a critical temperature (~32{$^{\circ}$}C), followed by aggregation of individual polymer chains dispersed in a state of globular particles to give an optically detectable phase transition. The transition occurs independently of either the molecular weight of the polymer (5x10^4 to 840x10^4) or its concentration (0.01 to 1wt%). This behavior is reminiscent of the thermal denaturation of proteins in aqueous medium.},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1021/j100345a085},
  eprint       = {https://doi.org/10.1021/j100345a085},
  file         = {:Fujishige1989 - Phase Transition of Aqueous Solutions of Poly(N Isopropylacrylamide) and Poly(N Isopropylmethacrylamide).pdf:PDF},
  keywords     = {PNIPAM, molecular weight, concentration-dependent, light scattering, DLS, SLS, thermoresponsive},
  ranking      = {rank5},
  readstatus   = {read},
  url          = {https://doi.org/10.1021/j100345a085},
}

@Article{Schild1990,
  author       = {Schild, Howard G. and Tirrell, David A.},
  journal      = {Journal of Physical Chemistry},
  title        = {Microcalorimetric detection of lower critical solution temperatures in aqueous polymer solutions},
  year         = {1990},
  number       = {10},
  pages        = {4352--4356},
  volume       = {94},
  abstract     = {A sensitive solution microcalorimeter was used to study lower critical solution temperatures (LCSTs) of aqueous polymer solutions. Endotherms with enthalpies on the order of the strength of hydrogen bonds were observed at temperatures concurring with LCSTs detected by classical cloud-point measurements for solutions of poly(N-isopropylacrylamide) (PNIPAAM), poly(vinylmethylether) (PVME), polypropyleneglycol) (PPG), and hydroxypropylcellulose (HPC). The LCST of PNIPAAM was found to be dependent on the chain length, generally increasing with decreasing M_n in the range M_n =1.6x10^5 to 5.4x10^3. Treatment of the calorimetric endotherm according to a two-state transiton model afforded cooperative unit sizes of the order of the chain length for PNIPAAM, PVME, andPPG. The apparent cooperative unit for the demixing transition of HPC was found to be larger than a single chain, consistent with previous observations of aggregation of HPC below the LCST. Depression of the LCST by added salts was observed.},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1021/j100373a088},
  eprint       = {https://doi.org/10.1021/j100373a088},
  file         = {:Schild1990 - Microcalorimetric Detection of Lower Critical Solution Temperatures in Aqueous Polymer Solutions.pdf:PDF},
  keywords     = {microcalorimetry, LCST, PNIPAM, PVME, PPG},
  url          = {https://doi.org/10.1021/j100373a088},
}

@Article{Ahn2008,
  author       = {Ahn, Suk-kyun and Kasi, Rajeswari M. and Kim, Seong-Cheol and Sharma, Nitin and Zhou, Yuxiang},
  journal      = {Soft Matter},
  title        = {Stimuli-responsive polymer gels},
  year         = {2008},
  pages        = {1151--1157},
  volume       = {4},
  abstract     = {Stimuli-responsive polymer gels have received considerable attention due to their singular mechanical properties{,} which make them materials of choice for niche applications. Polymer gels comprising either physical or chemical cross-links can undergo controlled and reversible shape changes in response to an applied field. The stimulus or external field applied may include thermal{,} electrical{,} magnetic{,} pH{,} UV/visible light{,} ionic or metallic interactions or combinations thereof. The shape change can manifest itself in two-dimensional actuation{,} bending motion{,} or three-dimensional actuation{,} volume change. This reversible contraction and expansion of polymer gels as well as their mechanical properties are similar to that of biological muscles. This review will describe and critique some of the recent advances in the field of stimuli-responsive polymer gels including the design of new classes of polymeric gels{,} controlled actuation in response to external stimuli{,} and ability to tailor material properties for different applications.},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1039/B714376A},
  issue        = {6},
  keywords     = {review, polymer gel, stimuli responsive},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/B714376A},
}

@Article{Schweizerhof2018,
  author       = {Schweizerhof, Sj{\"{o}}ren and Demco, Dan Eugen and Mourran, Ahmed and Fechete, Radu and M{\"{o}}ller, Martin},
  journal      = {Macromolecular Chemistry and Physics},
  title        = {Polymers Diffusivity Encoded by Stimuli-Induced Phase Transition: Theory and Application to Poly(N-Isopropylacrylamide) with Hydrophilic and Hydrophobic End Groups},
  year         = {2018},
  number       = {10},
  pages        = {1700587},
  volume       = {219},
  abstract     = {The self-diffusion of various nano-objects investigated by high-resolution nuclear magnetic resonance diffusometry proves to be an efficient method for the characterization of dynamics, aggregation kinetic, and matrix morphology. This study investigates how the two-state model and Boltzmann function approach can be used for the evaluation of the thermodynamic parameters of temperature-induced phase transition encoded in polymer diffusivity. The characteristics of the phase transition given by the transition temperature, change of entropy, and width of transition are obtained for poly(N-isopropylacrylamide) (PNIPAm) linear polymers with hydrophilic and hydrophobic end-group functionalization. The effect of end groups upon the polymer diffusivity is investigated as a function of molecular weight (M n), from which fractal dimensions and hydrodynamic drag coefficients are obtained. The PNIPAm diffusivity is affected strongly by the end groups, and it is reflected in the hydrodynamic radius dependence upon molecular weight that obeys different power-law relations. In this study, the synthesis of $\alpha$-$\omega$-heterotelechelic PNIPAm of different molecular weights with a thiol end group and a hydrophilic NIPAm-like as well as a hydrophobic benzyl end group are described by reversible addition--fragmentation chain-transfer polymerization.},
  comment      = {see also: Rubio-Retama et al., Macromolecules, 2008, "Polymer Chain Dynamics of Core-Shell Thermosensitive Microgels"},
  creationdate = {2021-03-08T00:00:00},
  doi          = {https://doi.org/10.1002/macp.201700587},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/macp.201700587},
  file         = {:Schweizerhof2018 - Polymers Diffusivity Encoded by Stimuli Induced Phase Transition_ Theory and Application to Poly(N Isopropylacrylamide) with Hydrophilic and Hydrophobic End Groups.pdf:PDF},
  keywords     = {diffusion, end-group functionalization, NMR, poly(N-isopropylacrylamide), PNIPAM, temperature-induced phase transition, thermoresponsive},
  ranking      = {rank5},
  readstatus   = {read},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/macp.201700587},
}

@Article{Arleth2005,
  author       = {Arleth, Lise and Xia, Xiaohu and Hjelm, Rex P. and Wu, Jianzhong and Hu, Zhibing},
  journal      = {Journal of Polymer Science Part B: Polymer Physics},
  title        = {Volume transition and internal structures of small poly(N-isopropylacrylamide) microgels},
  year         = {2005},
  number       = {7},
  pages        = {849--860},
  volume       = {43},
  abstract     = {Monodispersed poly(N-isopropylacrylamide) (PNIPAM) nanoparticles, with hydrodynamic radius less than 50 nm at room temperature, have been synthesized in the presence of a large amount of emulsifiers. These microgel particles undergo a swollen--collapsed volume transition in an aqueous solution when the temperature is raised to around 34 {$^{\circ}$}C. The volume transition and structure changes of the microgel particles as a function of temperature are probed using laser light scattering and small angle neutron scattering (SANS) with the objective of determining the small particle internal structure and particle--particle interactions. Apart from random fluctuations in the crosslinker density below the transition temperature, we find that, within the resolution of the experiments, these particles have a uniform radial crosslinker density on either side of the transition temperature. This result is in contrast to previous reports on the heterogeneous structures of larger PNIPAM microgel particles, but in good agreement with recent reports based on computer simulations of smaller microgels. The particle interactions change across the transition temperature. At temperatures below the transition, the interactions are described by a repulsive interaction far larger than that expected for a hard sphere contact potential. Above the volume transition temperature, the potential is best described by a small, attractive interaction. Comparison of the osmotic second virial coefficient from static laser light scattering at low concentrations with similar values determined from SANS at 250-time greater concentration suggests a strong concentration dependence of the interaction potential. {\copyright} 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 849--860, 2005},
  creationdate = {2021-03-08T00:00:00},
  doi          = {https://doi.org/10.1002/polb.20375},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.20375},
  file         = {:Arleth2005 - Volume Transition and Internal Structures of Small Poly(N Isopropylacrylamide) Microgels.pdf:PDF},
  keywords     = {N-isopropylacrylamide, PNIPAM, nanoparticles, neutron scattering, light scattering, microgel, synthesis},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.20375},
}

@Article{Miura1994,
  author       = {M. Miura and C.-A. Cole and N. Monji and A. S. Hoffman},
  journal      = {Journal of Biomaterials Science, Polymer Edition},
  title        = {Temperature-dependent adsorption/desorption behavior of lower critical solution temperature (LCST) polymers on various substrates},
  year         = {1994},
  note         = {PMID: 8086383},
  number       = {6},
  pages        = {555--568},
  volume       = {5},
  abstract     = {We have been studying adsorption and retention (resistance to desorption) behavior of temperature sensitive LCST polymers on different substrates as a function of temperature. According to our studies with Poly 64 (a copolymer of 60\% (mol) NIPAAm and 40\% (mol) NnBAAm, LCST = 8.5{$^{\circ}$}C in water), the copolymer retention depends on the rinse temperature. When the rinse temperature is above the LCST, the polymer adheres well to most surfaces. On the contrary, at rinse temperatures below the LCST, most of the adsorbed polymer is easily rinsed off. These studies are relevant to our work on the thermally reversible adsorption of LCST polymers conjugated to peptides and proteins, such as affinity ligands, for uses in immunoassays and affinity separations. The interaction between the LCST polymer and most hydrophobic polymer surfaces is mainly due to hydrophobic interactions, and the critical surface tension ($\gamma$c) and the solubility parameter ($\delta$) of the solid polymer substrate are the most important factors which influence the LCST polymer adsorption and retention. The critical surface tension appears to correlate best with the LCST polymer adsorption levels on different substrates, while the solubility parameter correlates best with the retention of the adsorbed polymer. According to our preliminary study, n-butyl groups probably interact more strongly with the substrates than isopropyl groups because of the greater hydrophobic surface area of the former groups.},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1163/156856294X00202},
  eprint       = {https://doi.org/10.1163/156856294X00202},
  keywords     = {LCST, thermoresponsive, surface},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1163/156856294X00202},
}

@Article{Reddy2015,
  author       = {Reddy, P. Madhusudhana and Chang, Chi-Jung and Hsieh, Shih-Rong and Huang, Hsin-Chun and Lee, Ming-Ching},
  journal      = {RSC Advances},
  title        = {Overview of the effect of monomers and green solvents on thermoresponsive copolymers: phase transition temperature and surface properties},
  year         = {2015},
  pages        = {86901--86909},
  volume       = {5},
  abstract     = {The present study explores the effect of the monomer substitution pattern of different copolymers on their volume phase transition temperature (VPTT) and surface wetting properties (SWPs) with the aid of differential scanning calorimetry (DSC){,} contact angle (CA){,} scanning electron microscopy (SEM) and Fourier transform-infrared spectroscopy (FT-IR) measurements. The present experimental results unveil that the VPTT and SWPs were greatly governed by the ability of the neighboring side chains to form intramolecular hydrogen bonds and the hydrophobic--hydrophilic balance of the polymer. The substitution of some of the acrylic acid (AA) monomers in the copolymer hydrogel P(NIPAM-co-AA) by the polyethyleneglycolmethacrylate (PEGMA) monomer resulted in the copolymer hydrogel{,} P(NIPAM-co-PEGMA-co-AA). The PEGMA in P(NIPAM-co-PEGMA-co-AA) can promote the intermolecular hydrogen bonds of the copolymer with the water molecules and thus hinders the formation of the intramolecular hydrogen bonds. Consequently{,} the VPTT of the P(NIPAM-co-PEGMA-co-AA) occurs at higher temperatures when compared to the P(NIPAM-co-AA) and P(NIPAM-co-PEGMA) systems. Further{,} in view of the potential applications of ionic liquids (IL) in polymer science{,} the effect of IL on the VPTT and SWP of the copolymers was investigated. The knowledge from this study can pave the way to engineer stimuli responsive polymers for a wide range of applications in the modern era.},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1039/C5RA18246H},
  issue        = {106},
  keywords     = {green solvent, thermoresponsive, DSC, application focused, contact angle, scanning electron microscopy, SEM, infrared, FTIR, volume phase transition, application-focused},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C5RA18246H},
}

@Article{Deshmukh2009,
  author       = {Deshmukh, Sanket and Mooney, Damian A. and McDermott, Thomas and Kulkarni, Savita and Don MacElroy, J. M.},
  journal      = {Soft Matter},
  title        = {Molecular modeling of thermo-responsive hydrogels: observation of lower critical solution temperature},
  year         = {2009},
  pages        = {1514--1521},
  volume       = {5},
  abstract     = {Stimuli-sensitive hydrogels offer enormous potential as {\textquoteleft}intelligent{\textquoteright} drug delivery vehicles{,} i.e. ones which are targeted and responsive to symptomatic needs. In particular{,} temperature sensitive hydrogels exhibit a dramatic{,} but well defined{,} volume phase transition (lower critical solution temperature (LCST)){,} which depending upon the hydrogel{,} results in either an expansion or shrinkage of the hydrogel. The exact mechanism of the LCST is not fully understood{,} weakening the ability to design devices a priori. Here{,} molecular simulation techniques are used to model the hydrogel poly (N-isopropyl acrylamide) (PNIPAM) above{,} below and at the LCST to probe the molecular level mechanisms governing its origin and transport mechanisms within the hydrogel under NPT ensembles.},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1039/B816443F},
  file         = {:Deshmukh2009 - Molecular Modeling of Thermo Responsive Hydrogels_ Observation of Lower Critical Solution Temperature.pdf:PDF},
  issue        = {7},
  keywords     = {PNIPAM, simulation, LCST, hydrogel},
  publisher    = {The Royal Society of Chemistry},
  ranking      = {rank5},
  url          = {http://dx.doi.org/10.1039/B816443F},
}

@Article{Kourilova2013,
  author       = {Kou{{\v{r}}}ilov{\'{a}}, Hana and Sp{\v{e}}v{\'{a}}{\v{c}}ek, Ji{{\v{r}}}{\'{i}} and Hanykov{\'{a}}, Lenka},
  journal      = {Polymer Bulletin},
  title        = {1H NMR study of temperature-induced phase transitions in aqueous solutions of poly(N-isopropylmethacrylamide)/poly(N-vinylcaprolactam) mixtures},
  year         = {2013},
  creationdate = {2021-03-08T00:00:00},
  doi          = {10.1007/s00289-012-0831-x},
  keywords     = {1H, NMR, thermoresponsive, PNIPMAM, PNVC},
}

@Article{Ptitsyn1967,
  author       = {Ptitsyn, O. B. and Kron, A. K. and Eizner, Yu. Ye.},
  journal      = {Journal of Polymer Science Part C: Polymer Symposia},
  title        = {The models of the denaturation of globular proteins. I. Theory of globula--coil transitions in macromolecules},
  year         = {1967},
  number       = {6},
  pages        = {3509--3517},
  volume       = {16},
  abstract     = {The theory of long-range interactions in macromolecules is proposed for the region where the attraction forces predominate (that is below $\tau$-point). In an approximate analytical variant of the theory the free energy of segment--segment interactions is calculated without taking into account their bonding in the single chain, that is, by means of strict and approximate equation for the free energy of interaction of real gas molecules. The theory predicts that under some conditions the macromolecule undergoes below the $\tau$-point, during the change of temperature or solvent composition, the first-order phase transition from the statistically coiled state to the compact (globular) state. The transition predicted by the theory is similar to the condensation of the real gas cloud to the liquid drop. This result is confirmed by the more strict Monte Carlo calculation which takes into account the bonding of the segments in a single chain. This calculation not only confirms the existence of a drastic compression of the macromolecule, when the attractive forces between its segments increase, but show also that, in the transition region, the macromolecules divide into poorly coiled chains (statistical coils) and highly coiled chains (globula), which directly prove the phase character of the transition. In common macromolecules the {\textquotedblleft}intramolecular condensation{\textquotedblright} predicted by the theory must occur near to the point of intermolecular condensation so it is difficult to observe it experimentally. However, in macromolecules containing both lyophobic and lyophilic groups the intramolecular condensation may well occur due to the mutual attraction of lyophobic groups and lyophilic groups covering the surfaces of obtained globulas may prevent them from aggregation. In these macromolecules one can observe the intermolecular globula--coil phase transitions by changing the temperature or the solvent composition. It is most likely that the denaturation (and renaturation) of the globular proteins are the examples of such transitions.},
  creationdate = {2021-03-09T00:00:00},
  doi          = {10.1002/polc.5070160644},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polc.5070160644},
  keywords     = {Theory, denaturation, proteins, theta temperature, theta point},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polc.5070160644},
}

@Article{Mukherji2013,
  author       = {Mukherji, Debashish and Kremer, Kurt},
  journal      = {Macromolecules},
  title        = {Coil--Globule--Coil Transition of PNIPAm in Aqueous Methanol: Coupling All-Atom Simulations to Semi-Grand Canonical Coarse-Grained Reservoir},
  year         = {2013},
  number       = {22},
  pages        = {9158--9163},
  volume       = {46},
  abstract     = {Conformational transitions of (bio)macromolecules in aqueous mixtures are intimately linked to local concentration fluctuations of different solvent components. Though computer simulations are ideally suited to investigate such phenomena, in conventional setups the excess of one cosolvent close to the solute leads to depletion elsewhere, requiring very large simulation domains to avoid system size effects. We, here, propose an approach to overcome this depletion effect, which combines the adaptive resolution scheme (AdResS) with a Metropolis particle exchange criterion. In AdResS, a small all-atom region, containing the solute, is coupled to a coarse-grained reservoir, where the particle exchange is performed. The particle exchange would be almost impossible had they been performed in an all-atom setup of a dense molecular liquid. As a first application of the method, we study the concentration driven reentrant collapse and swelling transition of poly(N-isopropylacrylamide) (PNIPAm) in aqueous methanol and demonstrate the role of the delicate interplay of the different intermolecular interactions.},
  creationdate = {2021-03-09T00:00:00},
  doi          = {10.1021/ma401877c},
  eprint       = {https://doi.org/10.1021/ma401877c},
  file         = {:Mukherji2013 - Coil Globule Coil Transition of PNIPAm in Aqueous Methanol_ Coupling All Atom Simulations to Semi Grand Canonical Coarse Grained Reservoir.pdf:PDF;:CoilGlobuleCoilTransitionOfPNIPAMInAqueousMethanol-CouplingAllAtomSimulationsToSemiGrandCanonicalGrainedReservoir-SI_MukherjiEtAl_Macromol2013.pdf:PDF},
  keywords     = {simulation,PNIPAM,cononsolvency,LSCT,UCST,aqueous alcohol,methanol},
  url          = {https://doi.org/10.1021/ma401877c},
}

@Article{Hirano2006,
  author       = {Hirano, Tomohiro and Okumura, Yuya and Kitajima, Hiroko and Seno, Makiko and Sato, Tsuneyuki},
  journal      = {Journal of Polymer Science Part A: Polymer Chemistry},
  title        = {Dual roles of alkyl alcohols as syndiotactic-specificity inducers and accelerators in the radical polymerization of N-isopropylacrylamide and some properties of syndiotactic poly(N-isopropylacrylamide)},
  year         = {2006},
  number       = {15},
  pages        = {4450--4460},
  volume       = {44},
  abstract     = {The effects of simple alkyl alcohols on the radical polymerization of N-isopropylacrylamide in toluene at low temperatures were investigated. We succeeded in the induction of syndiotactic specificity and the acceleration of polymerization reactions at the same time by adding simple alkyl alcohols such as 3-methyl-3-pentanol (3Me3PenOH) to N-isopropylacrylamide polymerizations. The dyad syndiotacticity increased with a decrease in the temperature and an increase in the bulkiness of the added alcohol and reached up to 71\% at $-$60 {$^{\circ}$}C in the presence of 3Me3PenOH. With the assistance of NMR analysis, it was revealed that the alcohol compounds played dual roles in this polymerization system; an alcohol compound coordinating to the N-H proton induced syndiotactic specificity, and that hydrogen-bonded to the C=O oxygen accelerated the polymerization reaction. The effect of syndiotacticity on the properties of poly(N-isopropylacrylamide)s was also examined in some detail. {\copyright} 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4450--4460, 2006},
  creationdate = {2021-03-09T00:00:00},
  doi          = {https://doi.org/10.1002/pola.21546},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/pola.21546},
  file         = {:Hirano2006 - Dual Roles of Alkyl Alcohols As Syndiotactic Specificity Inducers and Accelerators in the Radical Polymerization of N Isopropylacrylamide and Some Properties of Syndiotactic Poly(N Isopropylacrylamide).pdf:PDF},
  keywords     = {alcohol, hydrogen bond, lower critical solution temperature, LCST, N-isopropylacrylamide, pNIPAM, radical polymerization, stimuli-sensitive polymers, syndiotactic-specific, synthesis, tacticity},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/pola.21546},
}

@Article{Ma2012,
  author       = {Ma, Xiang and Sun, Cheng and Huang, Jiaxin and Boutis, Gregory S.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Thermal Hysteresis in the Backbone and Side-Chain Dynamics of the Elastin Mimetic Peptide [VPGVG]3 Revealed by 2H NMR},
  year         = {2012},
  note         = {PMID: 22142235},
  number       = {1},
  pages        = {555--564},
  volume       = {116},
  abstract     = {We report on experimental measurements of the backbone and side-chain dynamics of the elastin mimetic peptide [VPGVG]3 by 2H NMR echo spectroscopy and 2D T1--T2 correlation relaxometry. The T1 and T2 relaxation times of the Gly $\alpha$-deuterons and Val $\alpha$-, $\beta$-, and $\gamma$-deuterons of a hydrated sample reveal a thermal hysteresis when the temperature is raised from $-$10 to 45 {$^{\circ}$}C and then subsequently cooled back to $-$10 {$^{\circ}$}C. In addition, near 30 {$^{\circ}$}C we observe a reduction in the slope of the T1(T) and T2(T) heating curves, indicating a structural change that appears to be correlated well to the known inverse temperature transition of this peptide. The thermal dependence of the correlation times of the Gly $\alpha$-deuterons are well fit by an Arrhenius Law, from which we measured Eact = (20.0 $\pm$ 3.1) kJ/mol when the sample is heated and Eact = (10.9 $\pm$ 2.8) kJ/mol when cooled. Molecular dynamics simulations support the notion that the measured activation energy is determined largely by the extent of localized water, which is observed to decrease with increasing temperature from approximately 25 to 42 {$^{\circ}$}C.},
  creationdate = {2021-03-10T00:00:00},
  doi          = {10.1021/jp208966k},
  eprint       = {https://doi.org/10.1021/jp208966k},
  keywords     = {NMR, T1-T2 correlation, 2H, Peptide, elastin, T1, T2, spin-lattice, spin-spin, relaxation},
  url          = {https://doi.org/10.1021/jp208966k},
}

@Article{Zeng1997,
  author       = {Fang Zeng and Zhen Tong and Hanqiao Feng},
  journal      = {Polymer},
  title        = {N.m.r. investigation of phase separation in poly(N-isopropyl acrylamide)/water solutions},
  year         = {1997},
  issn         = {0032-3861},
  number       = {22},
  pages        = {5539--5544},
  volume       = {38},
  abstract     = {1H and 13C n.m.r. spectra of poly(N-isopropyl acrylamide) (PNIPA) in D2O and CDCl3 were measured at several temperatures encompassing the lower critical solution temperature (LCST) about 32{$^{\circ}$}C of the PNIPA/water solution, using a high resolution n.m.r. spectrometer (500 MHz for proton). The PNIPA/CDCl3 is homogeneous in the temperature ranging from 16 to 36{$^{\circ}$}C and the hydrogen bonds of the amide groups are weakened by the solvation of CDCl3 and broken by heating. In the PNIPA/D2O solution, the proton and 13C spectra are well resolved below the LCST. Whereas at temperatures above the LCST, all the resonance peaks except that for water proton became broad and the spectra lost their fine structure. The integral intensity of the water proton relative to that of the lone proton in the isopropyl group increases with increasing temperature, suggesting that some water molecules appear to be released out of the hydrated shells around the polymer chains. When the solution was heated from 22 to 35{$^{\circ}$}C, the spin-lattice relaxation time T1 for the proton of the methyl group in the isopropyl residue increased, while that for the protons of the methylene and methyne groups of the backbone chain decreased. This indicates that during heating the relaxation of the isopropyl side chain slows down and that of the main chain speeds up. The phase separation was qualitatively interpreted with the Nemethy-Scheraga model for the hydrophobic bonding.},
  comment      = {Elsevier Paper - no full access},
  creationdate = {2021-03-10T00:00:00},
  doi          = {https://doi.org/10.1016/S0032-3861(97)00118-3},
  file         = {:Zeng1997 - N.m.r. Investigation of Phase Separation in Poly(N Isopropyl Acrylamide)_water Solutions.pdf:PDF},
  keywords     = {poly(N-isopropyl acrylamide), PNIPAM, phase transition, hydrophobic interaction, NMR, LCST, 1H, 13C, spin-lattice relaxation, T1, spectrum},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386197001183},
}

@Article{Wang2016,
  author       = {Wang, Jian and Liu, Biaolan and Ru, Geying and Bai, Jia and Feng, Jiwen},
  journal      = {Macromolecules},
  title        = {Effect of Urea on Phase Transition of Poly(N-isopropylacrylamide) and Poly(N,N-diethylacrylamide) Hydrogels: A Clue for Urea-Induced Denaturation},
  year         = {2016},
  number       = {1},
  pages        = {234--243},
  volume       = {49},
  abstract     = {1H MAS NMR spectroscopy has been applied to study the urea effect on phase transition of two similar thermosensitive polymer hydrogels: poly(N-isopropylacrylamide) (PNIPAM) and poly(N,N-diethylacrylamide) (PDEA). It is found that urea influences the phase transition of the hydrogels in opposite ways: lowering the lower critical solution temperature (LCST) of PNIPAM and hence stabilizing its globular structure, whereas raising the LCST of PDEA and destabilizing the globular structure. The self-diffusion coefficient and urea--polymer nuclear Overhauser effect (NOE) measurement reveal that urea has a stronger interaction with PNIPAM than with PDEA. Moreover, the enhanced positive water--PNIPAM NOE suggests that urea not only interacts directly with PNIPAM via hydrogen bond but also intensifies the hydrogen bonding interaction between water and PNIPAM. We suggest that different urea--polymer hydrogen bonding interaction due to the presence or absence of amide hydrogen is correlated with the distinct LCST variation of PNIPAM and PDEA.},
  creationdate = {2021-03-10T00:00:00},
  doi          = {10.1021/acs.macromol.5b01949},
  eprint       = {https://doi.org/10.1021/acs.macromol.5b01949},
  file         = {:/autohome/saeckech/Promotion/Literatur/Cononsolvency/EffectOfUreaOnPhaseTransitionOfPolyNIsopropylacrylamideAndPolyNNDiethylacrylamideHydrogels-AClueForUreaInducedDenaturation_WangEtAl_Macromol2016.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Cononsolvency/EffectOfUreaOnPhaseTransitionOfPolyNIsopropylacrylamideAndPolyNNDiethylacrylamideHydrogels-AClueForUreaInducedDenaturation_WangEtAl_Macromol2016_SI.pdf:PDF},
  keywords     = {1H, NMR, MAS, PNIPAM, urea, PDEA, LCST},
  url          = {https://doi.org/10.1021/acs.macromol.5b01949},
}

@Article{Gorelov1997,
  author       = {A. V. Gorelov and A. {Du Chesne} and K. A. Dawson},
  journal      = {Physica A: Statistical Mechanics and its Applications},
  title        = {Phase separation in dilute solutions of poly (N-isopropylacrylamide)},
  year         = {1997},
  issn         = {0378-4371},
  number       = {3},
  pages        = {443--452},
  volume       = {240},
  abstract     = {The appearance of spherical particles resulting from phase separation in dilute solutions of poly(N-isopropylacrylamide) has been observed by dynamic light scattering (DLS). The particles have a relatively narrow size distribution. The size of particles increases with increasing concentration of polymer, and decreasing heating speed. Electron microscopy confirms the existence of spherical particles with size and polydispersity in agreement with DLS.},
  creationdate = {2021-03-10T00:00:00},
  doi          = {https://doi.org/10.1016/S0378-4371(97)00192-1},
  file         = {:Gorelov1997 - Phase Separation in Dilute Solutions of Poly (N Isopropylacrylamide).pdf:PDF},
  keywords     = {Polymer solution, Aggregate, Collapse, Phase coexistence, PNIPAM, DLS},
  url          = {https://www.sciencedirect.com/science/article/pii/S0378437197001921},
}

@Article{Wu2004,
  author       = {Wu, Chi and Li, Wei and Zhu, Xiao Xia},
  journal      = {Macromolecules},
  title        = {Viscoelastic Effect on the Formation of Mesoglobular Phase in Dilute Solutions},
  year         = {2004},
  number       = {13},
  pages        = {4989--4992},
  volume       = {37},
  abstract     = {In dilute heteropolymer solutions, a limited number of the chains, just like proteins, could collapse and associate to form a stable/metastable mesoglobular phase between single-chain globules and macroscopic precipitates. Recently, we found that inserting more hydrophobic comonomers into a thermally sensitive chain backbone surprisingly led to the formation of smaller mesoglobules in water. This apparent contradiction to our conventional wisdom can be satisfactorily explained in terms of the overlooked viscoelastic effect; namely, hydrophobic association inside each mesoglobule increases the chain relaxation time ($\tau$e). When it becomes much longer than the interaction time ($\tau$c) of two colliding mesoglobules, each mesoglobule behaves like a tiny nonadhesive {\textquotedblleft}glass{\textquotedblright} ball. This stabilization mechanism is completely different from thermodynamic consideration in which one normally tries to make the particle surface hydrophilic so that $\tau$c is reduced.},
  creationdate = {2021-03-10T00:00:00},
  doi          = {10.1021/ma049556n},
  eprint       = {https://doi.org/10.1021/ma049556n},
  file         = {:Wu2004 - Viscoelastic Effect on the Formation of Mesoglobular Phase in Dilute Solutions.pdf:PDF},
  keywords     = {viscoelastic,thermoresponsive,pNIPAM,aggregation},
  url          = {https://doi.org/10.1021/ma049556n},
}

@Article{Aseyev2005a,
  author       = {Vladimir Aseyev and Sami Hietala and Antti Laukkanen and Markus Nuopponen and Ondine Confortini and Filip E. {Du Prez} and Heikki Tenhu},
  journal      = {Polymer},
  title        = {Mesoglobules of thermoresponsive polymers in dilute aqueous solutions above the LCST},
  year         = {2005},
  issn         = {0032-3861},
  note         = {Stimuli Responsive Polymers},
  number       = {18},
  pages        = {7118--7131},
  volume       = {46},
  abstract     = {The colloidal stability and characteristics of particles formed by homopolymers of poly(N-vinyl caprolactam), poly(N-isopropyl acrylamide) and poly(vinyl methyl ether) in dilute aqueous solutions above the lower critical solution temperature, LCST, was followed by means of dynamic and static light scattering. Depending on the solution concentration, the homopolymers precipitate or form stable dispersions of monodisperse spherical particles. To obtain colloidally stable aggregates, also called mesoglobules, no stabilising agent was added. The stability of the mesoglobules upon time and dilution at temperatures above the LCST suggests that the particle surfaces possess a hydrophilic character. The size of the formed particles depends on the concentration and the heating rate of the solutions. However, internal structure and shape of mesoglobules are affected neither by the way, how the mesoglobules were prepared, nor by molar mass of individual macromolecules. Mesoglobules of PNIPAM obey the M$\propto$R2.7 scaling law. Origin of stability of the dispersions vs. expected precipitation is discussed.},
  creationdate = {2021-03-10T00:00:00},
  doi          = {https://doi.org/10.1016/j.polymer.2005.05.097},
  file         = {:Aseyev2005a - Mesoglobules of Thermoresponsive Polymers in Dilute Aqueous Solutions above the LCST.pdf:PDF},
  keywords     = {Thermally responsive polymer, thermoresponsive, Aggregation, Mesoglobule, thermoresponsive, PNVC, PVCL, PVME, PNIPAM, LCST, DLS, SLS, light scattering, scaling},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386105007482},
}

@Article{Jerschow1997,
  author       = {Alexej Jerschow and Norbert M{\"{u}}ller},
  journal      = {Journal of Magnetic Resonance},
  title        = {Suppression of Convection Artifacts in Stimulated-Echo Diffusion Experiments. Double-Stimulated-Echo Experiments},
  year         = {1997},
  issn         = {1090-7807},
  number       = {2},
  pages        = {372--375},
  volume       = {125},
  creationdate = {2021-03-10T00:00:00},
  doi          = {https://doi.org/10.1006/jmre.1997.1123},
  keywords     = {NMR, diffusion, convection artifact suppression, double stimulated echo},
  url          = {https://www.sciencedirect.com/science/article/pii/S109078079791123X},
}

@Article{Cao2005,
  author       = {Zhiqiang Cao and Wenguang Liu and Peng Gao and Kangde Yao and Hexian Li and Guochang Wang},
  journal      = {Polymer},
  title        = {Toward an understanding of thermoresponsive transition behavior of hydrophobically modified N-isopropylacrylamide copolymer solution},
  year         = {2005},
  issn         = {0032-3861},
  number       = {14},
  pages        = {5268--5277},
  volume       = {46},
  abstract     = {Poly(N-isopropylacrylamide-co-vinyl laurate)(PNIPAAm-co-VL) copolymers were prepared at various feed ratios via conventional radical random copolymerization. The formation, composition ratios and molecular weight of copolymers were examined. The thermoresponsive behaviors of PNIPAAm and PNIPAAm-co-VL solutions at low and high concentrations were intensively investigated by turbidity measurement, Micro-DSC, temperature-variable state fluorescence, 1H NMR and dynamic light scattering (DLS). Several important results were obtained that (1) incorporation of PVL results in much lower and broader LCST regions of the copolymer solutions, and facilitates the formation of hydrophobic microdomains far below LCST, causing a pronounced aggregation in solutions (2) temperature-variable 1H NMR spectra shows that during the phase transition, the {\textquoteleft}penetration{\textquoteright} of PNIPAAm into the hydrophobic core is a process accompanied with a transition of isopropyl from hydration to dehydration as well as a self-aggregation of hydrophobic chains at different temperature stages (3) according to the 1H NMR spectra of polymer solutions obtained at varied temperatures, the microdomains from hydrophobic VL moieties have a different accessibility for isopropyl groups and the entire chains during phase transition (4) temperature-variable DLS demonstrates that the temperature-induced transition behavior of copolymers is supposedly divided into three stages: pre-LCST aggregation (25{$^{\circ}$}C).},
  creationdate = {2021-03-10T00:00:00},
  doi          = {https://doi.org/10.1016/j.polymer.2005.04.050},
  file         = {:Cao2005 - Toward an Understanding of Thermoresponsive Transition Behavior of Hydrophobically Modified N Isopropylacrylamide Copolymer Solution.pdf:PDF},
  keywords     = {Poly(-isopropylacrylamide), PNIPAM, Vinyl laurate, Thermoresponsive, micro-DSC, turbidity, fluorescence, 1H NMR, DLS, PVL, LCST, copolymer solution, coil-globule transition},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386105004957},
}

@Article{Wang1998,
  author       = {Wang, Xiaohui and Qiu, Xingping and Wu, Chi},
  journal      = {Macromolecules},
  title        = {Comparison of the Coil-to-Globule and the Globule-to-Coil Transitions of a Single Poly(N-isopropylacrylamide) Homopolymer Chain in Water},
  year         = {1998},
  number       = {9},
  pages        = {2972--2976},
  volume       = {31},
  abstract     = {Using a newly prepared nearly monodisperse (Mw/Mn  1.05) high molar mass (Mw = 1.3 $\times$ 107 g/mol) poly(N-isopropylacrylamide) (PNIPAM) sample, we successfully, for the first time, made the conformation of individual PNIPAM chains change from a coil to a fully collapsed thermodynamically stable single chain globule and then back to a coil in an extremely dilute aqueous solution ($\sim$6.7 $\times$ 10-7 g/mL). The average chain density in the globule state is $\sim$0.34 g/mL, close to 0.40 g/cm3 predicted on the basis of a space-filling model, indicating that the globule still contains $\sim$66\% water even in its fully collapsed state. At a given temperature around the lower critical solution temperature, the chains are smaller in the globule-to-coil transition than in the coil-to-globule transition, revealing that the coil-to-globule transition is an irreversible process. The hysteresis can be attributed to the formation of intrachain structures, presumably the intrachain hydrogen bonding, in the globule state. We confirmed the existence of the crumpled coil and the molten globule states between the random coil and the collapsed globule states. The coil-to-crumpled coil transition can be reasonably described by the Birshtein and Pryamitsyn theory.},
  creationdate = {2021-03-10T00:00:00},
  doi          = {10.1021/ma971873p},
  eprint       = {https://doi.org/10.1021/ma971873p},
  file         = {:Wang1998 - Comparison of the Coil to Globule and the Globule to Coil Transitions of a Single Poly(N Isopropylacrylamide) Homopolymer Chain in Water.pdf:PDF},
  keywords     = {PNIPAM, hysteresis, dilute, high molar mass, LCST, irreversible, crumpled coil, molten globule, DLS, SLS, light scattering},
  url          = {https://doi.org/10.1021/ma971873p},
}

@Article{Plummer2006,
  author       = {Plummer, Ronda and Hill, David J. T. and Whittaker, Andrew K.},
  journal      = {Macromolecules},
  title        = {Solution Properties of Star and Linear Poly(N-isopropylacrylamide)},
  year         = {2006},
  number       = {24},
  pages        = {8379--8388},
  volume       = {39},
  abstract     = {The LCST transitions of novel N-isopropylacrylamide (NIPAM) star polymers, prepared using the four-armed RAFT agent pentaerythritoltetrakis(3-(S-benzyltrithiocarbonyl)propionate) (PTBTP) and their hydrolyzed linear arms were studied using 1H NMR, PFG-NMR, and DLS. The aim was to determine the effect of polymer architecture and the presence of end groups derived from RAFT agents on the LCST. The LCST transitions of star PNIPAM were significantly depressed by the presence of the hydrophobic star core and possibly the benzyl end groups. The effect was molecular weight dependent and diminished once the number of repeating units per arm $\geq$70. The linear PNIPAM exhibited an LCST of 35 {$^{\circ}$}C, regardless of molecular weight; the presence of both hydrophilic and hydrophobic end groups after hydrolysis from the star core was suggested to cancel effects on the LCST. A significant decrease in RH was observed below the LCST for star and linear PNIPAM and was attributed to the formation of n-clusters. Application of a scaling law to the linear PNIPAM data indicated the cluster size n = 6. Tethering to the hydrophobic star core appeared to inhibit n-cluster formation in the lowest molecular weight stars; this may be due to enhanced stretching of the polymer chains, or the presence of larger numbers of n-clusters at temperatures below those measured.},
  creationdate = {2021-03-11T00:00:00},
  doi          = {10.1021/ma0614545},
  eprint       = {https://doi.org/10.1021/ma0614545},
  file         = {:Plummer2006 - Solution Properties of Star and Linear Poly(N Isopropylacrylamide).pdf:PDF},
  keywords     = {LCST, PNIPAM, star, RAFT, 1H, NMR, PFG, DLS, molecular weight, n-cluster, scaling},
  url          = {https://doi.org/10.1021/ma0614545},
}

@Article{Burba2008,
  author       = {Burba, Christopher M. and Carter, Shawn M. and Meyer, Kevin J. and Rice, Charles V.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Salt Effects on Poly(N-isopropylacrylamide) Phase Transition Thermodynamics from NMR Spectroscopy},
  year         = {2008},
  note         = {PMID: 18681469},
  number       = {34},
  pages        = {10399--10404},
  volume       = {112},
  abstract     = {NMR spectra were collected for cross-linked poly(N-isopropylacrylamide), poly(NIPAM), hydrogels in the presence of NaCl and CaCl2 aqueous solutions. Intensity variations in the 1H NMR signals of the polymer provide insight into the phase transition process. These data were used to observe a two-stage phase transition process. Thermodynamic quantities were obtained from a van{\textquoteright}t Hoff analysis of the temperature-dependent equilibrium constants, which were derived from the NMR data. The {{$\Delta$}}H{$^{\circ}$} and {{$\Delta$}}S{$^{\circ}$} values for the hydrogel in D2O are 3.4 kJ/mol and 11.2 J/mol$\cdot$K for stage I, which is attributed to the formation of hydrophobic bonds between neighboring isopropyl groups. The formation of hydrogen bonds during stage II yielded {{$\Delta$}}H{$^{\circ}$} and {{$\Delta$}}S{$^{\circ}$} values of 14.8 kJ/mol and 48.4 J/mol$\cdot$K in D2O. However, the corresponding {{$\Delta$}}H{$^{\circ}$} values in 150 mM NaCl and 150 mM CaCl2 are reduced to 1.5 and 1.8 kJ/mol for stage I of the dehydration process. This corresponds to the known effect of salts on hydrophobic bond energetics. The value of {{$\Delta$}}S{$^{\circ}$} also decreased to 4.9 and 5.9 J/mol$\cdot$K in NaCl and CaCl2 solutions, respectively. However, the thermodynamic values during stage II were only slightly affected by the salts. The lower temperatures required to induce spontaneous precipitation implies that {{$\Delta$}}G{$^{\circ}$} of precipitation is reduced. With our measurement of equilibrium thermodynamics, we see that 150 mM NaCl and CaCl2 solutions have a greater effect on hydrophobic bond formation associated with the phase transition process. In this manner, these salts aid in solvent reorganization necessary to form the hydrophobic bond, and this suggests that the formation of hydrophobic bonds is a strong determining factor in the stability of poly(NIPAM) hydrogels in water.},
  creationdate = {2021-03-11T00:00:00},
  doi          = {10.1021/jp8005553},
  eprint       = {https://doi.org/10.1021/jp8005553},
  file         = {:Burba2008 - Salt Effects on Poly(N Isopropylacrylamide) Phase Transition Thermodynamics from NMR Spectroscopy.pdf:PDF},
  keywords     = {NMR, 1H, PNIPAM, hydrogel, salt, two-stage phase transition, vant Hoff, thermodynamics},
  url          = {https://doi.org/10.1021/jp8005553},
}

@Article{Maccarrone2014,
  author     = {Maccarrone, Simona and Scherzinger, Christine and Holderer, Olaf and Lindner, Peter and Sharp, Melissa and Richtering, Walter and Richter, Dieter},
  journal    = {Macromolecules},
  title      = {Cononsolvency Effects on the Structure and Dynamics of Microgels},
  year       = {2014},
  number     = {17},
  pages      = {5982--5988},
  volume     = {47},
  abstract   = {Sensitive microgels are submicrometer sized, cross-linked polymer particles with a unique swelling behavior changing in response to surrounding conditions like temperature, pH and ionic strength. In this study we influence the swelling capability of thermosensitive microgels microgel by the composition of the solvent (cononsolvency). In particular, we investigate the effects on the structure and dynamics of poly(N-isopropylacrylamide) (PNIPAM) and poly(N,N-diethylacrylamide) (PDEAAM) microgels with different degree of swelling in MeOD/D2O solvent mixture at 10 {$^{\circ}$}C using a combination of small angle neutron scattering (SANS) and neutron spin echo (NSE) spectroscopy at nanoseconds scales in the range of several nanometers. The structural characterization including size and density profiles was determined by fitting SANS data. The dynamical behavior of partially collapsed and swollen microgels is comprehensively described within the theory of semidilute polymers in solutions where hydrodynamic interactions are dominant. The partially collapsed PNIPAM microgel particles are not solid diffusing objects but they have relevant contributions from internal motions. Thus, Zimm segmental dynamics can be detected with elevated apparent viscosity. The swollen PDEAAM microgel particles have a faster internal dynamics compared to the partially collapsed PNIPAM. It can also be explained by Zimm-like relaxations with relatively high apparent viscosity and an additional diffusive contribution coming from the cross-linkers.},
  doi        = {10.1021/ma500954t},
  eprint     = {https://doi.org/10.1021/ma500954t},
  file       = {:Maccarrone2014 - Cononsolvency Effects on the Structure and Dynamics of Microgels.pdf:PDF},
  keywords   = {PNIPAM, PDEAAM, cononsolvency, SANS, NSE, neutron, hydrodynamic radius, diffusion coefficient, surface roughness},
  printed    = {printed},
  ranking    = {rank3},
  readstatus = {read},
  url        = {https://doi.org/10.1021/ma500954t},
}

@Article{PerezRamirez2019,
  author     = {P{\'{e}}rez-Ram{\'{i}}rez, H. A. and Haro-P{\'{e}}rez, C. and Odriozola, G.},
  journal    = {ACS Applied Polymer Materials},
  title      = {Effect of Temperature on the Cononsolvency of Poly(N-isopropylacrylamide) (PNIPAM) in Aqueous 1-Propanol},
  year       = {2019},
  number     = {11},
  pages      = {2961--2972},
  volume     = {1},
  abstract   = {The wide range of applications of poly(N-isopropylacrylamide) (PNIPAM) is based on the temperature dependence of its coil-to-globule transition, which strongly relies on the solvent. Here, we focus on the cononsolvency effect of PNIPAM oligomers in aqueous 1-propanol mixtures that is studied by molecular dynamics simulations of single chains and membrane-like arrangements. The complete phase diagram is sketched from the radius of gyration of the simulated oligomers, and it is compared to that obtained from the hydrodynamic radius of PNIPAM microgels, finding a good agreement. At the water-rich region, the decrease of the lower critical solution temperature (LCST) with increasing cosolvent concentration is independent of the polymer length and concentration. In this region, the radius of gyration of our simulated oligomer is strongly temperature dependent and a coil--globule transition temperature is easily captured. Conversely, at the alcohol-rich region, simulations show a monotonically increasing radius of gyration of the oligomer with alcohol concentration, a radius that is practically independent of temperature. This finding is in line with a polymer phase separation, showing an upper critical solution temperature (UCST) for a small cosolvent concentration window, which depends on the polymer length and concentration. Hence, in this case, polymer--polymer effective interactions are key to phase separation instead of its single chain conformation, contrasting with the coil--globule transition. Indeed, we find a soft-coil like structure for the simulated oligomer around a propanol molar fraction of 0.24, which is close to the mixture composition where the UCST phase transition is detected. Finally, in line with an UCST scenario, our simulated membrane turns unstable at high temperature and alcohol concentration.},
  doi        = {10.1021/acsapm.9b00665},
  eprint     = {https://doi.org/10.1021/acsapm.9b00665},
  file       = {:PerezRamirez2019 - Effect of Temperature on the Cononsolvency of Poly(N Isopropylacrylamide) (PNIPAM) in Aqueous 1 Propanol.pdf:PDF},
  keywords   = {PNIPAM, cononsolvency, 1-propanol, simulation, binary mixture, alcohol, LCST, UCST},
  printed    = {printed},
  readstatus = {read},
  url        = {https://doi.org/10.1021/acsapm.9b00665},
}

@Article{Wang2009,
  author   = {Wang, Nian and Ru, Geying and Wang, Liying and Feng, Jiwen},
  journal  = {Langmuir},
  title    = {1H MAS NMR Studies of the Phase Separation of Poly(N-isopropylacrylamide) Gel in Binary Solvents},
  year     = {2009},
  note     = {PMID: 19334692},
  number   = {10},
  pages    = {5898--5902},
  volume   = {25},
  abstract = {Preferential interactions of solvents with poly(N-isopropylacrylamide) (PNIPAM) gel networks in binary water/alcohol (water/methanol and water/ethanol) mixtures have been investigated using variable-temperature high-resolution 1H MAS NMR. NMR results for PNIPAM gel in the binary solvents reveal the existence of two distinct types of water/alcohol mixtures above the LCST: confined binary solvents bound inside the gel, and free binary solvents expelled from the gel. It is interesting to find that the alcohol concentration in confined solution is significantly higher than that in free solution. Moreover, of the two alcohols, ethanol is more significantly concentrated in the confined solution. These results demonstrate that the polymer preferentially interacts with alcohol molecules over water and that the alcohol with higher hydrophobicity exhibits higher preferential absorption on PNIPAM. Our results also show that 1H NMR measurements made on two distinct types of solution provide a convenient, direct means of characterizing the preferential adsorption of solvent on polymer.},
  doi      = {10.1021/la8038363},
  eprint   = {https://doi.org/10.1021/la8038363},
  file     = {:Wang2009 - 1H MAS NMR Studies of the Phase Separation of Poly(N Isopropylacrylamide) Gel in Binary Solvents.pdf:PDF},
  keywords = {PNIPAM, microgel, 1H NMR, MAS, binary solvent, cononsolvency, LCST, methanol, chemical shift},
  printed  = {printed},
  ranking  = {rank5},
  url      = {https://doi.org/10.1021/la8038363},
}

@Article{Pelton2000,
  author   = {Robert Pelton},
  journal  = {Advances in Colloid and Interface Science},
  title    = {Temperature-sensitive aqueous microgels},
  year     = {2000},
  issn     = {0001-8686},
  number   = {1},
  pages    = {1--33},
  volume   = {85},
  abstract = {An account of the preparation and characterization of temperature-sensitive aqueous microgels based on poly(N-isopropylacrylamide) was first published in 1986. Since then there has been a steady increase in the number of publications describing preparation, characterization and applications of temperature-sensitive microgels. This paper reviews the important developments in the area of temperature-sensitive aqueous microgels over the last decade. Although most of the work involves gels based on poly(N-isopropylacrylamide), other polymers are also considered. Core--shell latex particles exhibiting temperature-sensitive properties are also described.},
  doi      = {https://doi.org/10.1016/S0001-8686(99)00023-8},
  file     = {:Pelton2000 - Temperature Sensitive Aqueous Microgels.pdf:PDF},
  keywords = {thermoresponsive, PNIPAM, review, synthesis, Thermal sensitive microgels, Temperature-sensitive microgels, Latexes, Colloids, Swelling, Polymer--surfactant interactions},
  url      = {https://www.sciencedirect.com/science/article/pii/S0001868699000238},
}

@Article{Kratz2001,
  author     = {Karl Kratz and Thomas Hellweg and Wolfgang Eimer},
  journal    = {Polymer},
  title      = {Structural changes in PNIPAM microgel particles as seen by SANS, DLS, and EM techniques},
  year       = {2001},
  issn       = {0032-3861},
  number     = {15},
  pages      = {6631--6639},
  volume     = {42},
  abstract   = {Thermo-sensitive poly(N-isopropylacrylamide) (PNIPAM) microgels with different cross-linker density have been investigated by complementary scattering methods and high-resolution imaging techniques. The swelling behavior of the colloidal particles as probed by dynamic light scattering (DLS), is discussed together with information on local structure and dynamics of the particles as obtained from small angle neutron scattering (SANS). Below the volume phase transition the static structure factor reveals liquid-like contributions. This is similar to macroscopic gels, but for low q the scattering behavior is different because of the influence of the particle form factor P(q). Beyond the phase transition temperature, Tc, the system becomes completely phase separated and interfacial scattering dominates the measured SANS profiles (I(q)$\propto$q$-$4). Slight deviations from the ideal Porod behavior can be interpreted in terms of surface roughness of the collapsed particles. This corresponds to structures visible on AFM micrographs.},
  doi        = {https://doi.org/10.1016/S0032-3861(01)00099-4},
  file       = {:Kratz2001 - Structural Changes in PNIPAM Microgel Particles As Seen by SANS, DLS, and EM Techniques.pdf:PDF},
  keywords   = {Colloidal microgel, Poly(-isopropylacrylamide), Volume phase transition, PNIPAM, SANS, neutron, DLS},
  printed    = {printed},
  readstatus = {read},
  url        = {https://www.sciencedirect.com/science/article/pii/S0032386101000994},
}

@Article{Tanaka2009,
  author   = {Tanaka, Fumihiko and Koga, Tsuyoshi and Kojima, Hiroyuki and Winnik, Fran{\c{c}}oise M.},
  journal  = {Macromolecules},
  title    = {Temperature- and Tension-Induced Coil$-$Globule Transition of Poly(N-isopropyl\-acrylamide) Chains in Water and Mixed Solvent of Water/Methanol},
  year     = {2009},
  number   = {4},
  pages    = {1321--1330},
  volume   = {42},
  abstract = {The concept of cooperative dehydration, defined as the simultaneous dissociation of the water molecules bound in correlated sequences to a polymer chain, has been applied to study the collapse of a poly(N-isopropylacrylamide) (PNIPAM) chain upon heating in aqueous solutions. We examined the applicability of this concept in three situations: (i) PNIPAM in water (in the absence of added force), (ii) PNIPAM in water subjected to a tension applied to the chain ends, and (iii) PNIPAM in a mixed solvent of water and a second water-miscible solvent. The transition becomes sharper as the cooperativity parameter of hydration increases. The tension$-$elongation curve of a hydrated chain at various temperatures, calculated following an approach similar to the classical theory of coil$-$helix transition, presents a flat plateau corresponding to the tension for which collapsed segments reel out of the globules. The reeled-out segments are hydrated immediately upon exposure to water. The calculations suggest a possible shift to higher temperatures of the cloud points of aqueous PNIPAM solutions under shear flow. The reentrant coil$-$globule$-$coil transition in mixed solvent of water and methanol is studied from the viewpoint of competitive hydrogen bonds between polymer$-$water and polymer$-$methanol.},
  doi      = {10.1021/ma801982e},
  eprint   = {https://doi.org/10.1021/ma801982e},
  keywords = {PNIPAM, cooperatuve hydration, thermoresponsive, cononsolvency, methanol},
  printed  = {printed},
  url      = {https://doi.org/10.1021/ma801982e},
}

@Article{Siemes2018,
  author   = {Siemes, Eric and Nevskyi, Oleksii and Sysoiev, Dmytro and Turnhoff, Sarah K. and Oppermann, Alex and Huhn, Thomas and Richtering, Walter and W{\"{o}}ll, Dominik},
  journal  = {Angewandte Chemie International Edition},
  title    = {Nanoscopic Visualization of Cross-Linking Density in Polymer Networks with Diarylethene Photoswitches},
  year     = {2018},
  number   = {38},
  pages    = {12280--12284},
  volume   = {57},
  abstract = {The in\hspace{0.25em}situ nanoscopic imaging of soft matter polymer structures is of importance to gain knowledge of the relationship between structure, properties, and functionality on the nanoscopic scale. Cross-linking of polymer chains effects the viscoelastic properties of gels. The correlation of mechanical properties with the distribution and amount of cross-linkers is relevant for applications and for a detailed understanding of polymers on the molecular scale. We introduce a super-resolution fluorescence-microscopy-based method for visualizing and quantifying cross-linker points in polymer systems. A novel diarylethene-based photoswitch with a highly fluorescent closed and a non-fluorescent open form is used as a photoswitchable cross-linker in a polymer network. As an example for its capability to nanoscopically visualize cross-linking, we investigate pNIPAM microgels as a system known with variations in internal cross-linking density.},
  doi      = {https://doi.org/10.1002/anie.201807741},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201807741},
  file     = {:Siemes2018 - Nanoscopic Visualization of Cross Linking Density in Polymer Networks with Diarylethene Photoswitches.pdf:PDF;:NanoscopicVisualizationOfCrossLinkingDensityInPolymerNetworksWithDiarylethenePhotoswitches_SiemesEtAl_AngewChemieCommunications2018_information.pdf:PDF;:NanoscopicVisualizationOfCrossLinkingDensityInPolymerNetworksWithDiarylethenePhotoswitches_SiemesEtAl_AngewChemieCommunications2018_movie.avi:avi},
  keywords = {cross-linker,microgels,photoswitch,soft matter,super-resolution fluorescence microscopy,cross-linker distribution,fluorescence,pNIPAM},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201807741},
}

@Article{Andersson2006,
  author     = {Mirja Andersson and Sirkka Liisa Maunu},
  journal    = {Colloid and Polymer Science},
  title      = {Volume phase transition and structure of poly(N-isopropylacrylamide) microgels studied with $^1$H-NMR spectroscopy in D$_2$O},
  year       = {2006},
  pages      = {293--303},
  volume     = {285},
  abstract   = {Thermoresponsive colloidal microgels were prepared by polymerisation of N-isopropylacrylamide (NIPAM) with varying concentration of a cross-linking monomer, N,N-methylenebisacrylamide (MBA), in water with either 0.4 or 6.7 mM concentration of an anionic surfactant, sodium dodecylsulphate (SDS). Volume phase transitions of the prepared microgels were studied in D 2 O by 1 H-NMR spectroscopy including the measurements of spin--lattice (T1) and spin--spin (T2) relaxation times for the protons of poly(N-isopropylacrylamide) (PNIPAM) at temperature range 22--50 {$^{\circ}$}C. In addition, microcalorimetry, turbidometry, dynamic light scattering and electrophoretic mobility measurements were used to characterise the aqueous microgels. The results from the different characterisation methods indicated that PNIPAM microgels prepared in 6.7 mM SDS concentration are structurally different compared to their correspondences prepared in 0.4 mM concentration. Increasing MBA concentration in the microgel synthesis appears to increase the structural heterogeneity in both cases of SDS concentration. PNIPAM structures with significantly higher molecular mobilities at temperatures above 35 {$^{\circ}$}C were observed in the microgels prepared in 0.4 mM SDS concentration, as indicated by the 1 H NMR relaxation times of different PNIPAM protons. We conclude that the high mobilities measured with NMR at elevated temperatures and also the clearly negative values of zeta potential are in connection to a fairly mobile surface layer with polyelectrolyte nature and a consequent high local lower critical solution temperature.},
  file       = {:Andersson2006 - Volume Phase Transition and Structure of Poly(N Isopropylacrylamide) Microgels Studied with $^1$H NMR Spectroscopy in D$_2$O.pdf:PDF},
  keywords   = {PNIPAM, NMR, microgel, cross-linking density, structure, thermoresponsive},
  printed    = {printed},
  ranking    = {rank4},
  readstatus = {read},
  url        = {https://doi.org/10.1007/s00396-006-1563-y},
}

@Article{Scheffold2020,
  author   = {Frank Scheffold},
  journal  = {nature communications},
  title    = {Pathways and challenges towards a complete characterization of microgels},
  year     = {2020},
  pages    = {4315},
  volume   = {11},
  abstract = {Due to their controlled size, sensitivity to external stimuli, and ease-of-use, microgel colloids are unique building blocks for soft materials made by crosslinking polymers on the micrometer scale. Despite the plethora of work published, many questions about their internal structure, interactions, and phase behavior are still open. The reasons for this lack of understanding are the challenges arising from the small size of the microgel particles, complex pairwise interactions, and their solvent permeability. Here we describe pathways toward a complete understanding of microgel colloids based on recent experimental advances in nanoscale characterization, such as super-resolution microscopy, scattering methods, and modeling.},
  keywords = {microgel, review},
  url      = {https://doi.org/10.1038/s41467-020-17774-5},
}

@Article{Backes2017,
  author     = {Backes, Sebastian and Krause, Patrick and Tabaka, Weronika and Witt, Marcus U. and Mukherji, Debashish and Kremer, Kurt and von Klitzing, Regine},
  journal    = {ACS Macro Letters},
  title      = {Poly(N-isopropylacrylamide) Microgels under Alcoholic Intoxication: When a LCST Polymer Shows Swelling with Increasing Temperature},
  year       = {2017},
  number     = {10},
  pages      = {1042--1046},
  volume     = {6},
  abstract   = {Poly(N-isopropylacrylamide) (PNIPAM) microgel is a smart polymer that shows a volume phase transition temperature (VPTT) at around 32 {$^{\circ}$}C in aqueous solutions, above which it collapses. In this work, combining experiments and molecular simulations, it is shown that PNIPAM microgels do not always exhibit a collapsed structure above the VPTT. Instead, PNIPAM in aqueous alcohol mixtures shows a two-step conformational transition, i.e., a collapse at low temperatures (T  50 {$^{\circ}$}C. The present analysis indicates that delicate microscopic interaction details, together with the bulk solution properties, play a key role in dictating the reswelling behavior. Even when PNIPAM microgels swell with increasing T, this is not a standard upper critical solution behavior.},
  doi        = {10.1021/acsmacrolett.7b00557},
  eprint     = {https://doi.org/10.1021/acsmacrolett.7b00557},
  file       = {:Backes2017 - Poly(N Isopropylacrylamide) Microgels under Alcoholic Intoxication_ When a LCST Polymer Shows Swelling with Increasing Temperature.pdf:PDF},
  keywords   = {PNIPAM, thermoresponsive, simulation, cononsolvency, DLS},
  ranking    = {rank5},
  readstatus = {read},
  url        = {https://doi.org/10.1021/acsmacrolett.7b00557},
}

@Article{Pang2010,
  author   = {Pang, Juan and Yang, Hu and Ma, Jing and Cheng, Rongshi},
  journal  = {The Journal of Physical Chemistry B},
  title    = {Solvation Behaviors of N-Isopropylacrylamide in Water/Methanol Mixtures Revealed by Molecular Dynamics Simulations},
  year     = {2010},
  note     = {PMID: 20550151},
  number   = {26},
  pages    = {8652--8658},
  volume   = {114},
  abstract = {Solvation behaviors of N-isopropylacrylamide (NIPAM) in water/methanol mixtures are investigated by molecular dynamics simulations. The results indicate that NIPAM$-$solvent interactions are weakened with the increase of methanol mole fractions (xmethanol) from 0.25 to 0.80, rationalizing the reentrant coil-to-globule-to-coil transition behaviors of poly(N-isopropylacrylamide) in the mixed solvents. Interestingly, hydrogen-bonded water/methanol clusters are abundant in binary mixed solvents, leading to the decrement of NIPAM$-$solvent interactions. To better understand the intermolecular interactions in the water/methanol complex clusters, the structures of pure water and methanol clusters are also studied for a comparison. Although the amount of water clusters decreases with an increase in xmethanol, the structure of water clusters stays stable, and hydrogen-bonded networks are not essentially disrupted. As for methanol molecules, they prefer to form short nonbranched chainlike hydrogen-bonded clusters. However, most of the chainlike hydrogen-bonded methanol clusters are broken in water-rich solutions, leaving the little probability for the formation of dimeric and trimeric methanol clusters.},
  doi      = {10.1021/jp100743k},
  eprint   = {https://doi.org/10.1021/jp100743k},
  file     = {:Pang2010 - Solvation Behaviors of N Isopropylacrylamide in Water_Methanol Mixtures Revealed by Molecular Dynamics Simulations.pdf:PDF},
  keywords = {PNIPAM, simulation, cononsolvency, methanol},
  url      = {https://doi.org/10.1021/jp100743k},
}

@Article{Bolisetty2009,
  author   = {Bolisetty, S. and Hoffmann, M. and Lekkala, S. and Hellweg, Th. and Ballauff, M. and Harnau, L.},
  journal  = {Macromolecules},
  title    = {Coupling of Rotational Motion with Shape Fluctuations of Core$-$Shell Microgels Having Tunable Softness},
  year     = {2009},
  number   = {4},
  pages    = {1264--1269},
  volume   = {42},
  abstract = {The influence of shape fluctuations on deformable thermosensitive microgels in aqueous solution is investigated by dynamic light scattering (DLS) and depolarized dynamic light scattering (DDLS). The systems under study consist of a solid core of polystyrene and a thermosensitive shell of cross-linked poly(N-isopropylacrylamide) (PNIPA) without and with embedded palladium nanoparticles. PNIPA is soluble in water but has a lower critical solution temperature at (LCST). Below the LCST the PNIPA shell is swollen. Here we find that besides translational and rotational diffusion, the particles exhibit additional dynamics resulting from shape fluctuations. This leads to a pronounced apparent increase of the rotational diffusion coefficient. Above the transition temperature the shell collapses and provides a rather tight envelope of the core. In this state the dynamics of the shell is frozen, and the core$-$shell particles behave like hard spheres. A simple physical model is presented to capture and explain the essentials of the coupling of rotational motion and shape fluctuations.},
  doi      = {10.1021/ma8022603},
  eprint   = {https://doi.org/10.1021/ma8022603},
  keywords = {microgel, DLS, DDLS, PNIPAM, PS, polystyrene, nanoparticles, thermoresponsive},
  url      = {https://doi.org/10.1021/ma8022603},
}

@Article{Wu1996,
  author   = {Wu, Chi and Zhou, Shuiqin},
  journal  = {Macromolecules},
  title    = {Internal Motions of both Poly(N-isopropylacrylamide) Linear Chains and Spherical Microgel Particles in Water},
  year     = {1996},
  number   = {5},
  pages    = {1574--1578},
  volume   = {29},
  abstract = {Poly(N-isopropylacrylamide) (PNIPAM) linear chains and spherical microgel particles in very dilute aqueous solutions were studied by dynamic laser light scattering (LLS) over a wide range of scattering angles (6$-$154{$^{\circ}$}). For the linear chains, at x  1, only one peak related to diffusion was observed in the line-width distribution G({{$\Gamma$}}), while for x > 1, we detected a second peak related to internal motions, where x = (qRg)2 with q and Rg the scattering vector and the radius of gyration, respectively. The average line width of the second peak can be related to some internal motions predicted in the nondraining bead-and-spring model, but other predicted internal motions are not observable. In the swollen microgel particles (Rg $\sim$ 160 nm), the internal motions were only observed at x $\geq$ 13 (1/q $\geq$ 44 nm). At very high x, in both the chains and particles, the two peaks merge into one broad peak and the plot of 〈{{$\Gamma$}}〉/q3 vs x1/2 approaches two different plateaus, where 〈{{$\Gamma$}}〉 = $\int$0$\infty$G({{$\Gamma$}}){{$\Gamma$}} d{{$\Gamma$}}. Both of the plateaus are lower than predicted in the bead-and-spring model. The plateau of the particles is much lower than that of the chains. Energetically favorable internal motions may not be observable in dynamic LLS, possibly due to the observation length scale (1/q).},
  doi      = {10.1021/ma950677k},
  eprint   = {https://doi.org/10.1021/ma950677k},
  file     = {:Wu1996 - Internal Motions of Both Poly(N Isopropylacrylamide) Linear Chains and Spherical Microgel Particles in Water.pdf:PDF},
  keywords = {PNIPAM, microgel, DLS},
  url      = {https://doi.org/10.1021/ma950677k},
}

@Article{Hellweg2002,
  author   = {Thomas Hellweg and Karl Kratz and Stephanie Pouget and Wolfgang Eimer},
  journal  = {Colloids and Surfaces A: Physicochemical and Engineering Aspects},
  title    = {Internal dynamics in colloidal PNIPAM microgel particles immobilised in mesoscopic crystals},
  year     = {2002},
  issn     = {0927-7757},
  number   = {2},
  pages    = {223--232},
  volume   = {202},
  abstract = {Internal dynamics of colloidal microgels based on N-isopropyl-acrylamide is investigated by means of neutron spin-echo spectroscopy. To avoid interference of the relaxation of interest with the centre of mass diffusion, the microgels were immobilised in a colloidal crystal. Due to the q-range used in these quasi-elastic neutron scattering experiments, it is possible to obtain nearly completely decaying ensemble averaged intermediate scattering functions 〈ISF〉E. These can be fitted by single exponential forms, simplifying largely the data analysis compared with photon correlation spectroscopy. This is due to the fact that for light q2〈$\xi$2〉$\rightarrow\infty$ can not be reached, whereas for neutrons this condition is approximately fulfilled. The obtained network diffusion coefficients decrease linearly with increasing cross-linker concentration. This is in contrast to previous results from photon correlation spectroscopy obtained for macroscopic poly(N-isopropyl-acrylamide) gels [Macromolecules, 29 (1996) 8746].},
  doi      = {https://doi.org/10.1016/S0927-7757(01)01077-9},
  file     = {:Hellweg2002 - Internal Dynamics in Colloidal PNIPAM Microgel Particles Immobilised in Mesoscopic Crystals.pdf:PDF},
  keywords = {DLS, Microgels, Colloidal particles, Network, Non-ergodicity, NSE, PNIPAM, neutron spin echo, QENS, PCS, diffusion, cross-linker},
  url      = {https://www.sciencedirect.com/science/article/pii/S0927775701010779},
}

@Article{Gu2020,
  author   = {Gu, Yuwei and Zhao, Julia and Johnson, Jeremiah A.},
  journal  = {Angewandte Chemie International Edition},
  title    = {Polymer Networks: From Plastics and Gels to Porous Frameworks},
  year     = {2020},
  number   = {13},
  pages    = {5022--5049},
  volume   = {59},
  abstract = {Polymer networks, which are materials composed of many smaller components---referred to as {\textquotedblleft}junctions{\textquotedblright} and {\textquotedblleft}strands{\textquotedblright}---connected together via covalent or non-covalent/supramolecular interactions, are arguably the most versatile, widely studied, broadly used, and important materials known. From the first commercial polymers through the plastics revolution of the 20th century to today, there are almost no aspects of modern life that are not impacted by polymer networks. Nevertheless, there are still many challenges that must be addressed to enable a complete understanding of these materials and facilitate their development for emerging applications ranging from sustainability and energy harvesting/storage to tissue engineering and additive manufacturing. Here, we provide a unifying overview of the fundamentals of polymer network synthesis, structure, and properties, tying together recent trends in the field that are not always associated with classical polymer networks, such as the advent of crystalline {\textquotedblleft}framework{\textquotedblright} materials. We also highlight recent advances in using molecular design and control of topology to showcase how a deep understanding of structure--property relationships can lead to advanced networks with exceptional properties.},
  doi      = {https://doi.org/10.1002/anie.201902900},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201902900},
  file     = {:Gu2020 - Polymer Networks_ from Plastics and Gels to Porous Frameworks.pdf:PDF},
  keywords = {gels, microporous polymers, polymer networks, polymers, review, microgel, synthesis, structure},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201902900},
}

@Article{Daly2000,
  author    = {Daly, Emma and Saunders, Brian R.},
  journal   = {Physical Chemistry Chemical Physics},
  title     = {Temperature--dependent electrophoretic mobility and hydrodynamic radius measurements of poly(N-isopropylacrylamide) microgel particles: structural insights},
  year      = {2000},
  pages     = {3187--3193},
  volume    = {2},
  abstract  = {Electrophoretic mobility and hydrodynamic radius measurements of poly(-isopropylacrylamide) [poly(NIPAM)] microgel particles dispersed in water were made as a function of temperature and ionic strength. The data reveal differences between the temperatures at which the particle volume and electrophoretic mobility undergo significant changes. The temperature at which the volume phase transition (VPTT) occurred was 5--6{$^{\circ}$}C lower than the temperature at which pronounced electrophoretic mobility changes occurred. The data appear to be consistent with three stages of collapse for the microgel particles over the temperature range 25--50{$^{\circ}$}C. Ohshima{'}s equations for the electrophoretic mobility of particles covered by an ion-impenetrable surface charge layer were successfully used to fit the data. Electrokinetic equations for hard-sphere systems could not be used for our system. The successful application of the Ohshima theory is evidence that poly(NIPAM) microgel particles prepared by surfactant-free emulsion polymerisation consist of a core--shell structure. It is proposed that the core is relatively highly cross-linked and has a low concentration of ionic groups; whereas{,} the shell is lightly cross-linked and can be considered as a polyelectrolyte layer. The softness parameter obtained from fitting the Ohshima model to data obtained at 46{$^{\circ}$}C was much higher than expected for a rigid particle and suggests incomplete collapse of the shell at this temperature.},
  doi       = {10.1039/B002678F},
  issue     = {14},
  keywords  = {PNIPAM,core-shell,polyelectrolyte,tension,methanol,microgel},
  printed   = {printed},
  publisher = {The Royal Society of Chemistry},
  url       = {http://dx.doi.org/10.1039/B002678F},
}

@Article{Brugnoni2019,
  author    = {Brugnoni, Monia and Nickel, Anne C. and Kr{\"{o}}ger, Leif C. and Scotti, Andrea and Pich, Andrij and Leonhard, Kai and Richtering, Walter},
  journal   = {Polymer Chemistry},
  title     = {Synthesis and structure of deuterated ultra-low cross-linked poly(N-isopropylacrylamide) microgels},
  year      = {2019},
  pages     = {2397--2405},
  volume    = {10},
  abstract  = {Ultra-low cross-linked (ULC) microgels are extremely soft polymers with advanced material properties exhibiting a colloid-to-polymer transition. Poly(N-isopropylacrylamide) (pNIPAM) microgels are commonly synthesized by radical precipitation polymerization of the fully protonated monomer N-isopropylacrylamide (NIPAM). Analogous deuterated monomers arouse interest regarding their varying scattering length densities in small-angle neutron scattering (SANS). An isotope substitution in the main monomer of a microgel changes its scattering length density{,} which enables the exploitation of the technique of contrast variation in SANS. Here{,} we demonstrate that the synthesis of the deuterated pNIPAM ULC microgels encounters challenges related to the self-cross-linking mechanism of the polymer chains. The location of the deuterium isotopes is crucial for the generation of deuterated pNIPAM ULC microgels: when the isopropyl group of NIPAM is deuterated{,} the cross-linking is strongly restrained and the formation of microgels is precluded. However{,} the deuteration of the vinyl group of NIPAM{,} ending as backbone in the pNIPAM chains{,} allows the self-cross-linking. Ab initio calculations of the bond dissociation enthalpies endorse that the cross-linking of the pNIPAM chains occurs via hydrogen atom abstraction at the tertiary carbon atom of the isopropyl group. Additionally{,} we show that the deuteration of the vinyl group barely shifts the transition temperature of the polymer compared to protonated pNIPAM{,} whereas deuteration of the isopropyl group results in a significant shift of the transition temperature toward higher temperatures. Finally{,} the deuterated ULC micro- and nanogels reveal a stronger cross-linked network with lower swelling ability compared to the protonated microgels.},
  doi       = {10.1039/C8PY01699B},
  file      = {:Brugnoni2019 - Synthesis and Structure of Deuterated Ultra Low Cross Linked Poly(N Isopropylacrylamide) Microgels.pdf:PDF},
  issue     = {19},
  keywords  = {deuterated PNIPAM, microgel, ultra low cross-link, SANS, DLS, UV-Vis, calculation, synthesis},
  publisher = {The Royal Society of Chemistry},
  url       = {http://dx.doi.org/10.1039/C8PY01699B},
}

@Article{Andersson2006a,
  author   = {Mirja Andersson and Sami Hietala and Heikki Tenhu and Sirkka Liisa Maunu},
  journal  = {Colloid and Polymer Science},
  title    = {Polystyrene latex particles coated with crosslinked poly(N-isopropylacrylamide)},
  year     = {2006},
  pages    = {1255--1263},
  volume   = {284},
  doi      = {10.1007/s00396-006-1470-2},
  file     = {:Andersson2006a - Polystyrene Latex Particles Coated with Crosslinked Poly(N Isopropylacrylamide).pdf:PDF},
  keywords = {Poly(N-isopropylacrylamide), microgel, core-shell, 1H NMR, microcalorimetry, PNIPAM, calorimetry, DLS, T1, T2, relaxation, spin-lattice, spin-spin},
  printed  = {printed},
}

@Article{Deshmukh2000,
  author   = {M. V. Deshmukh and A. A. Vaidya and M. G. Kulkarni and P. R. Rajamohanan and S. Ganapathy},
  journal  = {Polymer},
  title    = {LCST in poly(N-isopropylacrylamide) copolymers: high resolution proton NMR investigations},
  year     = {2000},
  issn     = {0032-3861},
  number   = {22},
  pages    = {7951--7960},
  volume   = {41},
  abstract = {A series of copolymers of N-isopropylacrylamide (NIPA) and acryloyl amino acids were synthesized and conjugated with p-aminobenzamidine (PABA). The values of lower critical solution temperatures (LCSTs) of these polymers estimated by 1H NMR were in agreement with those estimated by the turbidometric methods. The apparent shifts in the peak positions for the polymer with increasing temperature reported in the past are shown to be artifacts resulting from the deuterium lock experiment. The 1H--1H NOESY experiments were carried out to distinguish the interactions between the protons in: (a) 6-amino caproic acid (6ACA) and NIPA and (b) PABA and NIPA. These explain the variation in the LCST of the polymers based on the contributions of the two monomers to the magnitude of the polymer--polymer interactions. The findings are further supported by proton spin--lattice relaxation time measurements.},
  doi      = {https://doi.org/10.1016/S0032-3861(00)00174-9},
  file     = {:Deshmukh2000 - LCST in Poly(N Isopropylacrylamide) Copolymers_ High Resolution Proton NMR Investigations.pdf:PDF},
  keywords = {N-isopropylacrylamide,PNIPAM, Lower critical solution temperature, LCST, 1H NMR, NOESY, T1, spin-lattice relaxation},
  url      = {https://www.sciencedirect.com/science/article/pii/S0032386100001749},
}

@Article{Durand2000,
  author   = {Durand, Alain and Hourdet, Dominique and Lafuma, Fran{\c{c}}oise},
  journal  = {The Journal of Physical Chemistry B},
  title    = {Thermoassociative Graft Copolymers:\hspace{0.167em} NMR Investigation and Comparison with Rheological Behaviour},
  year     = {2000},
  number   = {40},
  pages    = {9371--9377},
  volume   = {104},
  abstract = {The thermoassociative properties of semidilute solutions of graft copolymers containing poly(N-isopropylacrylamide) (PNIPA) side chains are studied by 1H NMR. Upon heating, the PNIPA grafts self-aggregate into hydrophobic microdomains and their 1H NMR signal is no longer detectable. This phenomenon is attributed to the glassy structure of the aggregates' core and allows a direct detection of the aggregation process. On this basis it becomes possible to detect the formation of the microdomains by salting-out (with potassium carbonate) or their dissociation by adding an anionic surfactant (sodium dodecyl sulfate). The 1H NMR observations are compared to the rheological data previously obtained and to small-angle neutron scattering measurements performed in similar conditions. A good correlation is evidenced between the macroscopic and microscopic transitions probed by the different techniques.},
  doi      = {10.1021/jp993769a},
  eprint   = {https://doi.org/10.1021/jp993769a},
  file     = {:Durand2000 - Thermoassociative Graft Copolymers_ NMR Investigation and Comparison with Rheological Behaviour.pdf:PDF},
  keywords = {PNIPAM, rheology, 1H NMR, copolymers, salt, surfactant, SANS},
  url      = {https://doi.org/10.1021/jp993769a},
}

@Article{Krynicki1966,
  author   = {K. Krynicki},
  journal  = {Physica},
  title    = {Proton spin-lattice relaxation in pure water between 0{$^{\circ}$}C and 100{$^{\circ}$}C},
  year     = {1966},
  issn     = {0031-8914},
  number   = {1},
  pages    = {167--178},
  volume   = {32},
  abstract = {Proton spin-lattice relaxation times, T1, at 28 MHz by a recovery from saturation, are reported for very pure water between 0 and 100{$^{\circ}$}C. Our experimental T1 values for water are the longest values which have been observed. In this temperature region the most effective spin-lattice relaxation mechanism in water is by proton dipole-dipole intra- and intermolecular interactions modulated by thermal molecular motion. Measurements for water of dielectric relaxation, X ray diffraction, self diffusion, viscosity and slow neutron inelastic scattering are used in the interpretation of the proton T1 results. The intermolecular contribution to T-11 has been determined with the aid of X ray radial distribution curves and Hubbard's correction for the off-centre proton effect. There is excellent agreement between the temperature dependence of the experimental proton spin-lattice relaxation times and the reciprocals of the dielectric relaxation times. The ratio of the dielectric relaxation time to the molecular reorientation NMR correlation time is found independent of temperature and equal to 3.7 instead of the expected value, three. This result provides an evidence for a small value of the single jump angle in the Brownian reorientation of water molecules and may be accounted for by an internal field correction factor of 0.81. This compares with the value 0.69 obtained for water from the Powles formula.},
  doi      = {https://doi.org/10.1016/0031-8914(66)90113-3},
  keywords = {1H NMR, reference, spin-lattice relaxation, T1, H2O, water},
  url      = {https://www.sciencedirect.com/science/article/pii/0031891466901133},
}

@Article{Graf1980,
  author   = {Graf, V. and Noack, F. and B{\'{e}}n{\'{e}}, G. J.},
  journal  = {The Journal of Chemical Physics},
  title    = {Proton spin T1 relaxation dispersion in liquid H2O by slow proton-exchange},
  year     = {1980},
  number   = {2},
  pages    = {861--863},
  volume   = {72},
  doi      = {10.1063/1.439240},
  eprint   = {https://doi.org/10.1063/1.439240},
  keywords = {H2O, nmr, relaxation dispersion, reference},
  url      = {https://doi.org/10.1063/1.439240},
}

@Article{Yang2017,
  author     = {Yang, Man and Liu, Chunyan and Zhao, Kongshuang},
  journal    = {Physical Chemistry Chemical Physics},
  title      = {Concentration dependent phase behavior and collapse dynamics of PNIPAM microgel by dielectric relaxation},
  year       = {2017},
  pages      = {15433--15443},
  volume     = {19},
  abstract   = {The dielectric behavior of thermo-sensitive poly-(N-isopropylacrylamide) (PNIPAM) microgel with three different concentrations was investigated for the frequencies ranging from 40 Hz to 110 MHz as a function of temperature from 10 to 60 {$^{\circ}$}C. Two remarkable and temperature-dependent relaxation processes were observed. The slow relaxation originates from the segmental motion over the whole temperature range. The fast relaxation is due to the fluctuation of counterions below the lower critical solution temperature (LCST) and the interfacial polarization above the LCST. It was concluded from the temperature-dependent dielectric parameters that the microgel concentration will not influence the LCST but affects the phase behavior of the microgel suspension: the dense system experienced a colloidal crystal-to-liquid transition and volume phase transition{,} while the dilute system only underwent a volume phase transition. Based on the interfacial polarization theory{,} the electrical parameters for the constituent phases (permittivity{,} conductivity{,} and volume fraction of the microgel ($\epsilon$p{,} $\kappa$p{,} ϕ) and the conductivity of water $\kappa$a) and the water content in the microgel (fw) were calculated using Hanai{'}s equation. In addition{,} the thermodynamics parameters of the two relaxations were calculated from the Eyring equation. The electrical and thermodynamic parameters indicate that the microgel concentration influences the volume{,} charge density{,} thickness of the electric double layer{,} and degrees of freedom of the segments of the microgel{,} thereby resulting in the differences in collapse dynamics.},
  comment    = {ethanol-water: see url},
  doi        = {10.1039/C7CP01378G},
  file       = {:Yang2017 - Concentration Dependent Phase Behavior and Collapse Dynamics of PNIPAM Microgel by Dielectric Relaxation.pdf:PDF},
  issue      = {23},
  keywords   = {PNIPAM, dielectric, concentration},
  printed    = {printed},
  publisher  = {The Royal Society of Chemistry},
  ranking    = {rank3},
  readstatus = {skimmed},
  url        = {http://ddbonline.ddbst.com/DDBSearch/onlineddboverview.exe?submit=Details&systemcomplist=11,174},
}

@Misc{jpdatabase,
  howpublished = {National Institute of Advanced Industrial Science and Technology (AIST)},
  abstract     = {[Japanese] National Institute of Advanced Industrial Science and Technology (AIST)},
  keywords     = {chemical shift, nmr, database},
  ranking      = {rank5},
  url          = {https://sdbs.db.aist.go.jp/sdbs/cgi-bin/direct_frame_top.cgi},
}

@Article{Sergeyev2014,
  author   = {N. M. Sergeyev and S. M. Gerdov and Yu. K. Grishin and V. A. Roznyatovsky},
  journal  = {Moscow University Chemistry Bulletin},
  title    = {High Resolution $^2$H NMR Spectroscopy at the Natural Abundance Level of Deuterium},
  year     = {2014},
  pages    = {202--209},
  volume   = {69},
  comment  = {Is OH in the spectra actually OD?},
  doi      = {10.3103/S0027131414050071},
  file     = {:Sergeyev2014 - High Resolution $^2$H NMR Spectroscopy at the Natural Abundance Level of Deuterium.pdf:PDF},
  keywords = {2H-NMR, ethanol, T1, spin-lattice relaxation, propanol, 2h-chemical shift, {1,4-dioxane}, {1,2-dichloroethane}},
  url      = {https://doi.org/10.3103/S0027131414050071},
}

@Article{Roessler1984,
  author   = {E. R{\"{o}}ssler and H. Sillescu},
  journal  = {Chemical Physics Letters},
  title    = {2H NMR Study of supercooled toluene},
  year     = {1984},
  issn     = {0009-2614},
  number   = {1},
  pages    = {94--98},
  volume   = {112},
  abstract = {Deuteron spin relaxation times T1, T2, solid echoes and spin-alignment echoes have been investigated in toluene-d3 and toluene-d5, respectively. Whereas a Cole---Davidson distribution of correlation times accounts for T1 and T2 at higher temperatures, there are indications that a non-exponential correlation function for molecular reorientation is more appropriate at low temperatures close to the glass transition.},
  doi      = {https://doi.org/10.1016/0009-2614(84)87048-7},
  file     = {:Roessler1984 - 2H NMR Study of Supercooled Toluene.pdf:PDF},
  keywords = {toluene, toluol, 2H NMR, spin-lattice relaxation, spin-spin relaxation, T1, T2},
  url      = {https://www.sciencedirect.com/science/article/pii/0009261484870487},
}

@Article{Huang2020,
  author   = {Huang, Yuqing and Zhan, Haolin and You, Xueqiu and Yang, Yu and Li, Chen and Cai, Shuhui and Chen, Zhong},
  journal  = {IEEE Transactions on Instrumentation and Measurement},
  title    = {A Pure Shift-Based NMR Method for Transverse Relaxation Measurements on Complex Samples},
  year     = {2020},
  number   = {1},
  pages    = {201--211},
  volume   = {69},
  doi      = {10.1109/TIM.2019.2894047},
  file     = {:Huang2020 - A Pure Shift Based NMR Method for Transverse Relaxation Measurements on Complex Samples.pdf:PDF},
  keywords = {chemical shift, T2, spin-spin relaxation, CPMG, NMR},
}

@Article{Bharadwaj2019,
  author     = {Bharadwaj, Swaminath and van der Vegt, Nico F. A.},
  journal    = {Macromolecules},
  title      = {Does Preferential Adsorption Drive Cononsolvency?},
  year       = {2019},
  number     = {11},
  pages      = {4131--4138},
  volume     = {52},
  abstract   = {Cononsolvency refers to the effect in which a polymer chain in good solvent collapses when it is mixed with an increasing concentration of a second good solvent. An important question is if universality of nonspecific attraction between monomers and cosolvent explains the cononsolvency phenomenon. We report results obtained with computer simulations of coarse-grained models and show that the above universality does not exist. We demonstrate that cononsolvency can occur with or without the preferential adsorption of the cosolvent on the polymer chain and discuss experimental systems corresponding to these cases.},
  doi        = {10.1021/acs.macromol.9b00575},
  eprint     = {https://doi.org/10.1021/acs.macromol.9b00575},
  file       = {:Bharadwaj2019 - Does Preferential Adsorption Drive Cononsolvency_.pdf:PDF},
  keywords   = {cononsolvency, simulation, Michaels Empfehlung, preferential adsorption, van der Vegt},
  printed    = {printed},
  ranking    = {rank4},
  readstatus = {read},
  url        = {https://doi.org/10.1021/acs.macromol.9b00575},
}

@Article{Guettari2017,
  author  = {Moez Guettari and Amal Belaidi and Stephane Abel and Tahar Tajouri},
  journal = {Journal of Solution Chemistry},
  title   = {Polyvinylpyrrolidone Behavior in Water/Ethanol Mixed Solvents: Comparison of Modeling Predictions with Experimental Results},
  year    = {2017},
  pages   = {1404--1417},
  volume  = {46},
  file    = {:Guettari2017 - Polyvinylpyrrolidone Behavior in Water_Ethanol Mixed Solvents_ Comparison of Modeling Predictions with Experimental Results.pdf:PDF},
  url     = {https://doi.org/10.1007/s10953-017-0649-0},
}

@Article{Tanaka2011,
  author   = {Tanaka, Fumihiko and Koga, Tsuyoshi and Kojima, Hiroyuki and Xue, Na and Winnik, Fran{\c{c}}oise M.},
  journal  = {Macromolecules},
  title    = {Preferential Adsorption and Co-nonsolvency of Thermoresponsive Polymers in Mixed Solvents of Water/Methanol},
  year     = {2011},
  number   = {8},
  pages    = {2978--2989},
  volume   = {44},
  abstract = {If two good solvents become poor for a polymer when mixed, the solvent pair is called a co-nonsolvent pair for the polymer. The sharp depression of the LCST by the co-nonsolvency in solutions of poly(N-isopropylacrylamide) in the mixed solvent of water and methanol is shown to be caused by the competitive hydrogen bonding of water and methanol molecules onto the polymer chains. On the basis of a new statistical-mechanical model for competitive hydrogen bonds, the degree of hydration $\theta$(w) and of methanol binding $\theta$(m), excess degree {{$\Delta$}}$\theta$E of solvent binding, preferential adsorption coefficients {{$\Gamma$}}, LCST spinodal lines, and cloud-point depression {{$\Delta$}}Tcl are theoretically calculated and compared with the experimental results. The optimal composition xm(M) of methanol at which LCST takes the minimum value is studied as a function of the polymer molecular weight M. In the high molecular weight limit, it takes xm $\simeq$ 0.35. The solution recovers a uniform state in the region of higher methanol composition. Such a peculiar phase separation is caused by the dehydration of the polymer chains by the mixed methanol molecules in a cooperative way.},
  doi      = {10.1021/ma102695n},
  eprint   = {https://doi.org/10.1021/ma102695n},
  file     = {:Tanaka2011 - Preferential Adsorption and Co Nonsolvency of Thermoresponsive Polymers in Mixed Solvents of Water_Methanol.pdf:PDF},
  keywords = {cononsolvency,co-nonsolvency,PNIPAM,methanol,water,LCST,theory,mean-field,ternary flory-huggins},
  printed  = {printed},
  ranking  = {rank5},
  url      = {https://doi.org/10.1021/ma102695n},
}

@Article{Xu2020,
  author   = {Xiaomin Xu and Yang Liu and Wenbo Fu and Mingyu Yao and Zhan Ding and Jiaming Xuan and Dongxiang Li and Shenjie Wang and Yongqing Xia and Meiwen Cao},
  journal  = {Polymers},
  title    = {Poly(N-isopropylacrylamide)-Based Thermoresponsive Composite Hydrogels for Biomedical Applications},
  year     = {2020},
  pages    = {580},
  volume   = {12},
  file     = {:Xu2020 - Polye(N Isopropylacrylamide) Based Thermoresponsive Composite Hydrogels for Biomedical Applications.pdf:PDF},
  keywords = {application focused, PNIPAM, microgel, review, application-focused},
  url      = {https://doi.org/10.3390/polym12030580},
}

@Article{Thorne2011,
  author   = {Johanna B. Thorne and George J. Vine and Martin J. Snowden},
  journal  = {Colloid and Polymer Science},
  title    = {Microgel applications and commercial consideratinos},
  year     = {2011},
  pages    = {625},
  volume   = {289},
  file     = {:Thorne2011 - Microgel Applications and Commercial Consideratinos.pdf:PDF},
  keywords = {PNIPAM, review, application focused, microgel, application-focused},
  url      = {https://doi.org/10.1007/s00396-010-2369-5},
}

@Article{Yemloul2011,
  author   = {Yemloul, Mehdi and Steiner, Emilie and Robert, Anthony and Bouguet-Bonnet, Sabine and Allix, Florent and Jamart-Gr{\'{e}}goire, Brigitte and Canet, Daniel},
  journal  = {The Journal of Physical Chemistry B},
  title    = {Solvent Dynamical Behavior in an Organogel Phase As Studied by NMR Relaxation and Diffusion Experiments},
  year     = {2011},
  note     = {PMID: 21355595},
  number   = {11},
  pages    = {2511--2517},
  volume   = {115},
  abstract = {An organogelation process depends on the gelator$-$solvent pair. This study deals with the solvent dynamics once the gelation process is completed. The first approach used is relaxometry, i.e., the measurement of toluene proton longitudinal relaxation time T1 as a function of the proton NMR resonance frequency (here in the 5kHz to 400 MHz range). Pure toluene exhibits an unexpected T1 variation, which has been identified as paramagnetic relaxation resulting from an interaction of toluene with dissolved oxygen. In the gel phase, this contribution is retrieved with, in addition, a strong decay at low frequencies assigned to toluene molecules within the gel fibers. Comparison of dispersion curves of pure toluene and toluene in the gel phase leads to an estimate of the proportion of toluene embedded within the organogel (found around 40\%). The second approach is based on carbon-13 T1 and nuclear Overhauser effect measurements, the combination of these two parameters providing direct information about the reorientation of C$-$H bonds. It appears clearly that reorientation of toluene is the same in pure liquid and in the gel phase. The only noticeable changes in carbon-13 longitudinal relaxation times are due to the so-called chemical shift anisotropy (csa) mechanism and reflect slight modifications of the toluene electronic distribution in the gel phase. NMR diffusion measurements by the pulse gradient spin-echo (PGSE) method allow us to determine the diffusion coefficient of toluene inside the organogel. It is roughly two-thirds of the one in pure toluene, thus indicating that self-diffusion is the only dynamical parameter to be slightly affected when the solvent is inside the gel structure. The whole set of experimental observations leads to the conclusion that, once the gel is formed, the solvent becomes essentially passive, although an important fraction is located within the gel structure.},
  doi      = {10.1021/jp200281f},
  eprint   = {https://doi.org/10.1021/jp200281f},
  file     = {:Yemloul2011 - Solvent Dynamical Behavior in an Organogel Phase As Studied by NMR Relaxation and Diffusion Experiments.pdf:PDF},
  keywords = {toluol, toluene, NMR, spin-spin relaxation, T1},
  url      = {https://doi.org/10.1021/jp200281f},
}

@Article{Crowther1998,
  author   = {H. M. Crowther and B. Vincent},
  journal  = {Colloid and Polymer Science},
  title    = {Swelling behaviour of poly-N-isopropylacrylamide microgels particles in alcoholic solutions},
  year     = {1998},
  pages    = {46--51},
  volume   = {276},
  file     = {:Crowther1998 - Swelling Behaviour of Poly N Isopropylacrylamide Microgels Particles in Alcoholic Solutions.pdf:PDF},
  keywords = {PNIPAM, microgel, cononsolvency, co-nonsolvency, methanol, ethanol, propanol},
  printed  = {printed},
  ranking  = {rank5},
  url      = {https://doi.org/10.1007/s003960050207},
}

@Article{Spevacek2017,
  author   = {Ji{{\v{r}}}{\'{i}} Sp{\v{e}}v{\'{a}}{\v{c}}ek and Rafa{{\l}} Konefa{{\l}} and Ji{{\v{r}}}{\'{i}} Dybal and Eva {{\v{C}}}adov{\'{a}} and Jana Kov{\'{a}}{{\v{r}}}ov{\'{a}}},
  journal  = {European Polymer Journal},
  title    = {Thermoresponsive behavior of block copolymers of PEO and PNIPAm with different architecture in aqueous solutions: A study by NMR, FTIR, DSC and quantum-chemical calculations},
  year     = {2017},
  issn     = {0014-3057},
  pages    = {471--483},
  volume   = {94},
  abstract = {Temperature behavior of D2O solutions of thermoresponsive diblock poly(ethylene oxide) (PEO)-b-poly(N-isopropylacrylamide) (PNIPAm) copolymers and Y-shape triblock PEO-b-(PNIPAm)2 copolymers was investigated and compared with the phase transition of the PNIPAm homopolymer by combination of NMR and ATR FTIR spectroscopy, DSC and model quantum-chemical calculations. It is shown that the phase transition and structures of PNIPAm component (forming micellar cores) are significantly affected not only by the presence of the PEO block but also by copolymer architecture. Both these factors affect energetics of the phase transition, influence of the polymer concentration and behavior of bound water at elevated temperatures. They also affect the degree of dehydration of PNIPAm segments (CO groups) at temperatures above the phase transition which is higher for block copolymers (especially for the diblock) in comparison with PNIPAm homopolymer. NOESY NMR spectra likewise revealed influence of the architecture of the block copolymer on its conformational behavior in the pretransition region.},
  doi      = {https://doi.org/10.1016/j.eurpolymj.2017.07.034},
  file     = {:Spevacek2017 - Thermoresponsive Behavior of Block Copolymers of PEO and PNIPAm with Different Architecture in Aqueous Solutions_ a Study by NMR, FTIR, DSC and Quantum Chemical Calculations.pdf:PDF},
  keywords = {Thermoresponsive polymer, Diblock copolymer PEO--PNIPAm, Y-shape triblock copolymer PEO--(PNIPAm), Aqueous solution, NMR, FTIR, PNPIAM, spin-spin relaxation, T2, D2O},
  url      = {https://www.sciencedirect.com/science/article/pii/S0014305717309321},
}

@Article{Scherzinger2014,
  author     = {Christine Scherzinger and Annett Schwarz and Andr{\'{e}} Bardow and Kai Leonhard and Walter Richtering},
  journal    = {Current Opinion in Colloid \& Interface Science},
  title      = {Cononsolvency of poly-N-isopropyl acrylamide (PNIPAM): Microgels versus linear chains and macrogels},
  year       = {2014},
  issn       = {1359-0294},
  number     = {2},
  pages      = {84--94},
  volume     = {19},
  abstract   = {Poly-N-isopropyl acryl amide (PNIPAM) is swollen in both pure water and pure methanol but collapses in mixtures of these solvents. In this review, this cononsolvency of PNIPAM in water/methanol mixtures is discussed. Experimental studies of linear PNIPAM chains and macrogels are compared to microgels. Theoretical studies are presented based on molecular dynamics simulation and quantum mechanical calculations as well as semi-empirical models. The different explanations for the cononsolvency available in the literature are introduced. Experiments show that all PNIPAM species collapse and re-swell at comparable methanol fraction in the mixture. Cross-linker density of macrogels and microgels has only slight influence on cononsolvency, whereas chain length of linear chains has a significant influence. Microgels provide advantages to study cononsolvency by enabling a broader experimental approach. Furthermore, multi-sensitive microgels can be prepared, which contain compartments sensitive to different stimuli.},
  doi        = {https://doi.org/10.1016/j.cocis.2014.03.011},
  file       = {:Scherzinger2014 - Cononsolvency of Poly N Isopropyl Acrylamide (PNIPAM)_ Microgels Versus Linear Chains and Macrogels.pdf:PDF},
  keywords   = {Microgels, Poly-N-isopropyl acryl amide, PNIPAM, Cononsolvency, Methanol, Computer simulation, review},
  printed    = {printed},
  ranking    = {rank5},
  readstatus = {read},
  url        = {https://www.sciencedirect.com/science/article/pii/S1359029414000351},
}

@Article{Martinez2018,
  author   = {Martinez, Mar{\'{i}}a V. and Molina, Maria and Barbero, Cesar A.},
  journal  = {The Journal of Physical Chemistry B},
  title    = {Poly(N-isopropylacrylamide) Cross-Linked Gels as Intrinsic Amphiphilic Materials: Swelling Properties Used to Build Novel Interphases},
  year     = {2018},
  note     = {PMID: 30130119},
  number   = {38},
  pages    = {9038--9048},
  volume   = {122},
  abstract = {The hydrophilic nature of hydrogels allows their swelling in aqueous solutions. In that way, any substance loaded inside the gel is exposed to the aqueous media and could be released if it is soluble in water. However, only substances that are soluble in water can be loaded inside a gel, which can be swelled only in water. In this work, we studied the swelling of poly(N-isopropylacrylamide) (PNIPAM) gels in nonaqueous solvents and their solutions with water. PNIPAM gels swell strongly in highly polar solvents, but they do not swell in slightly polar solvents (e.g., toluene). However, it is possible to swell the gel in mixtures containing toluene. The observed properties of PNIPAM gels allow describing them both as solvogels or amphigels. When the loaded substance is soluble in one solvent (e.g., water) and not in another (e.g., chloroform), the substance is not released but exposed to the new media. As a proof of concept, a colorimetric pH sensor active in CHCl3 and a Cu1+ sensor in water were built. Moreover, using a ternary solution containing toluene linear polystyrene can be loaded inside the gel, making a semi-interpenetrated network. Because PNIPAM swells in water and solvents immiscible in water, a liquid/liquid interphase can be set inside a gel. A near-infrared absorbing dye (soluble in CHCl3) is loaded in only half of a thermoresponsive PNIPAM gel. Upon near-infrared irradiation, only the region where the dye is loaded heats up driving the phase transition of PNIPAM.},
  doi      = {10.1021/acs.jpcb.8b07625},
  eprint   = {https://doi.org/10.1021/acs.jpcb.8b07625},
  file     = {:Martinez2018 - Poly(N Isopropylacrylamide) Cross Linked Gels As Intrinsic Amphiphilic Materials_ Swelling Properties Used to Build Novel Interphases.pdf:PDF},
  keywords = {swelling kinetics, PNIPAM, ethanol, chloroform, tetrahydrofluran, THF, H2O, water, N-methyl pyrrolidone, NMP, hydrogen bond},
  url      = {https://doi.org/10.1021/acs.jpcb.8b07625},
}

@Article{Hofmann2013,
  author     = {Hofmann, Christian H. and Plamper, Felix A. and Scherzinger, Christine and Hietala, Sami and Richtering, Walter},
  journal    = {Macromolecules},
  title      = {Cononsolvency Revisited: Solvent Entrapment by N-Isopropyl\-acrylamide and N,N-Diethyl\-acrylamide Microgels in Different Water/Methanol Mixtures},
  year       = {2013},
  number     = {2},
  pages      = {523--532},
  volume     = {46},
  abstract   = {Aqueous dispersions of homo- and copolymer microgels of N-isopropylacrylamide (NiPAm) and N,N-diethylacrylamide (DEAm) with different compositions are temperature-dependently studied by means of proton nuclear magnetic resonance spectroscopy (1H NMR) and differential scanning calorimetry (DSC). Furthermore, the effect of varying the solvent composition by adding methanol is investigated. Methanol addition leads to a broadening of the thermally induced volume phase transition in case of NiPAm-containing samples, as confirmed by DSC. At the same time, the width of transition approaches the one of neat PDEAm. Two different solvent species, namely bulk-like and restricted solvent, are observed as separate lines in 1H NMR experiments when the gels deswell. The restricted nature of the second species is affirmed by pulsed field gradient (PFG) NMR self-diffusion experiments. The temperature Tsplit from which on the restricted species is found cannot be directly related to the volume phase transition temperature determined by DSC. The difference between Tsplit and the DSC peak temperature changes depending on the NiPAm-content of the microgel. An increase in the shift difference between the two solvent signals with temperature indicates a continuous change of the restricted solvent environment. At even higher temperature, the shift difference of restricted and bulk solvent approaches asymptotically a constant value. In general, the observed effects of methanol addition are consistent with an increasing complexation of the amide protons of the microgel (originating from the NiPAm units) with methanol. In contrast, poly(DEAm) does not show any anomaly concerning transition width and Tsplit upon methanol addition. This is attributed to the lack of amide protons. The results indicate that the presence of cononsolvency can be explained by the presence of the amide proton.},
  doi        = {10.1021/ma302384v},
  eprint     = {https://doi.org/10.1021/ma302384v},
  file       = {:Hofmann2013 - Cononsolvency Revisited_ Solvent Entrapment by N Isopropylacrylamide and N,N Diethylacrylamide Microgels in Different Water_Methanol Mixtures.pdf:PDF;:CononsolvencyRevisited-SolventEntrapmentByNIsopropylacrylamideAndNNDiethylacrylamideMicrogelsInDifferentWaterMethanolMixtures_HofmannEtAl_Macromolecules2013_SI.pdf:PDF},
  keywords   = {PNIPAM, cononsolvency, methanol, NMR, DSC, PDEAm},
  printed    = {printed},
  ranking    = {rank4},
  readstatus = {read},
  url        = {https://doi.org/10.1021/ma302384v},
}

@Article{Hirotsu1987,
  author   = {Hirotsu, Shunsuke},
  journal  = {Journal of the Physical Society of Japan},
  title    = {Phase Transition of a Polymer Gel in Pure and Mixed Solvent Media},
  year     = {1987},
  number   = {1},
  pages    = {233--242},
  volume   = {56},
  abstract = {A volume phase transition of poly-N-isopropylacrylamide (NIPA) gel immersed in some pure and mixed solvents has been investigated experimentally. A slightly discontinuous transition of NIPA get in water changed to a more distinctly first-order transition on adding a small amount (20%) of alcohols to water. As the concentration of alcohols in the mixed solvent increased further, the volume transition blurred and eventually disappeared. Analyzing the experimental results on the basis of the mean field theory of polymer solution, it has been shown that the polymer-solvent interaction parameter $\chi$ exhibits a drastic change at the volume transitions. This indicates that the enthalpy and entropy of solution depend strongly on polymer concentration.},
  doi      = {10.1143/JPSJ.56.233},
  eprint   = {https://doi.org/10.1143/JPSJ.56.233},
  file     = {:Hirotsu1987 - Phase Transition of a Polymer Gel in Pure and Mixed Solvent Media.pdf:PDF},
  keywords = {PNIPAM, macrogel, water, methanol, ethanol, iso-propanol, cononsolvency, co-nonsolvency, no access},
  ranking  = {rank5},
  url      = {https://doi.org/10.1143/JPSJ.56.233},
}

@Article{Kojima2013,
  author   = {Kojima, Hiroyuki and Tanaka, Fumihiko and Scherzinger, Christine and Richtering, Walter},
  journal  = {Journal of Polymer Science Part B: Polymer Physics},
  title    = {Temperature dependent phase behavior of PNIPAM microgels in mixed water/methanol solvents},
  year     = {2013},
  number   = {14},
  pages    = {1100--1111},
  volume   = {51},
  abstract = {Temperature dependent phase behavior of poly(N-isopropylacylamide) (PNIPAM) microgels in water/methanol mixtures of different composition was studied with dynamic light scattering (DLS) and small-angle neutron scattering (SANS). Using DLS, it is possible to measure the diffusion coefficient, and thus the size of particles exactly and directly; the variation of the phase transition temperature in the different solvents is also easy to detect by this method. With SANS measurements in D2O/MeOD mixtures, some of the DLS results were confirmed. Moreover, SANS measurements give valuable information on the particle structure in different solvents. The experiments were compared with the theory of competitive hydration introduced by Tanaka et al. We found a good agreement of theory and experiment, and obtained the theoretical predictions: around the transition temperature, the composition of the bound methanol along the chains is higher than that of the outer solution, while the whole methanol composition inside the gel is lower. {\copyright} 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym. Phys. 2013, 51, 1100--1111},
  doi      = {https://doi.org/10.1002/polb.23194},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.23194},
  file     = {:Kojima2013 - Temperature Dependent Phase Behavior of PNIPAM Microgels in Mixed Water_methanol Solvents.pdf:PDF},
  keywords = {competitive hydrogen bonds, cononsolvency, co-nonsolvency, water, methanol, dynamic light scattering, DLS, microgels, neutron scattering, SANS, poly(N-isopropylacylamide), PNIPAM, solvent excess adsorption, solvent excess binding},
  ranking  = {rank4},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.23194},
}

@Article{Wu1998a,
  author   = {Chi Wu},
  journal  = {Polymer},
  title    = {A comparison between the `coil-to-globule' transition of linear chains and the {\textquotedblleft}volume phase transition{\textquotedblright} of spherical microgels},
  year     = {1998},
  issn     = {0032-3861},
  number   = {19},
  pages    = {4609--4619},
  volume   = {39},
  abstract = {The coil-to-globule transition of individual poly(N-isopropylacrylamide) (PNIPAM) linear chains and the volume phase transition of spherical PNIPAM microgels were studied by a combination of static and dynamic laser light scattering. The thermodynamically stable collapsed single-chain globule was observed for the first time. The ratio of Rg/Rh lower than 0.774, predicted for a uniform sphere, indicates that the coil-to-globule transition is not an `all-or-nothing' process, where Rg and Rh are the gyration and hydrodynamic radii, respectively. The time scale less than 100s observed in the coil-to-globule transition is too short to support a suggested high chain-knotting density inside the globule. At the collapsing limit, the single-chain globule and microgel particle still contain 80% and 70% of water respectively in their hydrodynamic volumes. As for the volume phase transition, our results indicated that the volume change of the microgels is practically continuous, in contrast to the discontinuous volume phase transition observed in bulk PNIPAM gels. The discrepancy between a microgel and a bulk gel can be attributed to shear modulus.},
  doi      = {https://doi.org/10.1016/S0032-3861(97)10130-6},
  keywords = {coil-to-globule transition, volume phase transition, spherical microgels, PNIPAM, DLS, SLS, LLS, kinetics},
  url      = {https://www.sciencedirect.com/science/article/pii/S0032386197101306},
}

@Article{Walter2012,
  author   = {Walter, Jonathan and Sehrt, Jan and Vrabec, Jadran and Hasse, Hans},
  journal  = {The Journal of Physical Chemistry B},
  title    = {Molecular Dynamics and Experimental Study of Conformation Change of Poly(N-isopropylacrylamide) Hydrogels in Mixtures of Water and Methanol},
  year     = {2012},
  note     = {PMID: 22432852},
  number   = {17},
  pages    = {5251--5259},
  volume   = {116},
  abstract = {The conformation transition of poly(N-isopropylacrylamide) hydrogel as a function of the methanol mole fraction in water/methanol mixtures is studied both experimentally and by atomistic molecular dynamics simulation with explicit solvents. The composition range in which the conformation transition of the hydrogel occurs is determined experimentally at 268.15, 298.15, and 313.15 K. In these experiments, cononsolvency, i.e., collapse at intermediate methanol concentrations while the hydrogel is swollen in both pure solvents, is observed at 268.15 and 298.15 K. The composition range in which cononsolvency is present does not significantly depend on the amount of cross-linker. The conformation transition of the hydrogel is caused by the conformation transition of the polymer chains of its backbone. Therefore, conformation changes of single backbone polymer chains are studied by massively parallel molecular dynamics simulations. The hydrogel backbone polymer is described with the force field OPLS-AA, water with the SPC/E model, and methanol with the model of the GROMOS-96 force field. During simulation, the mean radius of gyration of the polymer chains is monitored. The conformation of the polymer chains is studied at 268, 298, and 330 K as a function of the methanol mole fraction. Cononsolvency is observed at 268 and 298 K, which is in agreement with the present experiments. The structure of the solvent around the hydrogel backbone polymer is analyzed using H-bond statistics and visualization. It is found that cononsolvency is caused by the fact that the methanol molecules strongly attach to the hydrogel{\textquoteright}s backbone polymer, mainly with their hydroxyl group. This leads to the effect that the hydrophobic methyl groups of methanol are oriented toward the bulk solvent. The hydrogel+solvent shell hence appears hydrophobic and collapses in water-rich solvents. As more methanol is present in the solvent, the effect disappears again.},
  comment  = {concentration-dependence shown in Fig 4},
  doi      = {10.1021/jp212357n},
  eprint   = {https://doi.org/10.1021/jp212357n},
  file     = {:Walter2012 - Molecular Dynamics and Experimental Study of Conformation Change of Poly(N Isopropylacrylamide) Hydrogels in Mixtures of Water and Methanol.pdf:PDF},
  keywords = {PNIPAM,microgel,cononsolvency,co-nonsolvency,simulation,methanol,cross-linker concentration,cross-linker density,aqueous alcohol,aqueous methanol},
  printed  = {printed},
  ranking  = {rank5},
  url      = {https://doi.org/10.1021/jp212357n},
}

@Article{Huether2004,
  author   = {Andreas H{\"{u}}ther and Xiaoping Xu and Gerd Maurer},
  journal  = {Fluid Phase Equilibria},
  title    = {Swelling of n-isopropyl acrylamide hydrogels in water and aqueous solutions of ethanol and acetone},
  year     = {2004},
  issn     = {0378-3812},
  number   = {2},
  pages    = {231--244},
  volume   = {219},
  abstract = {Hydrogels are three-dimensional networks of hydrophilic polymer chains with properties in between liquids and solids. One of the most interesting features is their capability to swell as well as to shrink depending on their surroundings. This paper deals with experimental investigations of the swelling behavior of nonionic synthetic hydrogels of n-isopropyl acrylamide. The swelling of some hydrogels differing in, e.g. the cross-linking density and the length of the polymer chains, in aqueous solutions of ethanol as well as of acetone was investigated at 298K. The experimental results are presented and discussed also with respect to the phenomenon of {\textquotedblleft}multiple phase transitions{\textquotedblright}. Typically, the amount of absorbed material depends on the composition of the solvent showing a considerable decrease at around 20--40mass% of the organic solvent component. In aqueous solutions of ethanol, some hydrogels reveal a phase transition from a swollen into a shrunken state at a certain ethanol concentration. {\textquotedblleft}Multiple phase transitions{\textquotedblright} (i.e. several transitions at different ethanol concentrations) were also observed, but they proved to be caused by the kinetics of the swelling/shrinking process which can result in heterogeneous gel structures. The equilibrium properties are correlated with a thermodynamic model which combines an expression for the Gibbs energy of a liquid with an expression for the Helmholtz energy of an elastic network. The compositions of the coexisting phases (gel phase and surrounding liquid solution) were also determined. As long as the gel absorbs a large amount of solvent, there are only small differences between the solvent concentrations in the gel and in the surrounding liquid. When the gel is in a shrunken state, there are (small) differences in the composition which are reliably predicted.},
  doi      = {https://doi.org/10.1016/j.fluid.2003.08.002},
  file     = {:Huether2004 - Swelling of N Isopropyl Acrylamide Hydrogels in Water and Aqueous Solutions of Ethanol and Acetone.pdf:PDF},
  keywords = {Synthetic chemically cross-linked hydrogels, -Isopropyl acrylamide, PNIPAM, Swelling equilibrium in water and aqueous solutions, Experimental data, Modeling, cononsolvency, co-nonsolvency, ethanol, acetone},
  url      = {https://www.sciencedirect.com/science/article/pii/S0378381203003893},
}

@Article{Hirotsu1995,
  author   = {Shunsuke Hirotsu and Takaharu Okajima and Tatsuyuki Yamamoto},
  journal  = {Macromolecules},
  title    = {Anomalous Aggregation Pattern Observed on Gels in Mixed Solvent},
  year     = {1995},
  pages    = {775--777},
  volume   = {28},
  abstract = {Permanent gels swell extensively in good solvent and shrink into a compact form in poor solvent. If the quality of solvent is somehow changed from good to poor, a phase separation takes place. So far, however, studies of phase separation of gels have been quite scarce as compared with extensive studies on polymer blends. We know only a few previous studies1-3 on the phase separation of permanent gels, most of which have been made by light scattering measurement under the shallow quench condition. We note that the phase separation of gels has a notable feature as compared with that of polymer blends or solutions. It is frequently observed that the phase separation creates a stable heterogeneous structure within gels, and the process stops at some intermediate stage. In other words, the phase separation of gels often fails to go to completion on a macroscopic scale. Usually gels in the incompletely phase-separated state are opaque, so that it has been deduced that the structure consists of alternating polymer-rich and solvent-rich regions with spacing on the order of the wavelength of light. The term ``microsyneresis'' has often been used4 to represent this heterogeneity in gels. Although microsyneresis has long been known to occur in various gels, the structure of a gel network trapped in this state has not been studied in detail. In the course of studying the inhomogeneity of phaseseparated gels, we have recently met with a very peculiar aggregation pattern. The pattern is formed in the bulk of gel in the course of phase separation and, thus, is quite different from the pattern appearing on the surface of swelling gels reported previously.5 The present paper is a preliminary report of this new finding. The pattern was observed on polyC/V-isopropylacrylamide) (NIPA) gels in water-ethanol mixtures when the composition of the solvent was changed abruptly. Qualitatively the same results were observed also with water-methanol and water---n-propanol mixtures. Neutral NIPA gel in a water---ethanol mixture has been known to show a reentrant-type behavior between the swollen and the shrunken phases as a function of solvent composition.6,7 Figure 1 shows the equilibrium swelling ratio a of NIPA gel as a function of solvent composition x (the volume fraction of ethanol) at a few temperatures. We define the swelling ratio a by a = (WVo)1/3 = (0o/0)1/3 where V is the volume and  is the concentration of the gel. The subscript 0 means the value of the relaxed network. It is to be noted that the gel swells extensively in pure water as wel as in pure ethanol, whereas it collapses in the intermediate composition region. The transition between the swollen and the shrunken phases is discontinuous in the water-rich region, whereas it is continuous in the alcohol-rich region},
  file     = {:Hirotsu1995 - Anomalous Aggregation Pattern Observed on Gels in Mixed Solvent.pdf:PDF},
  keywords = {macrogel, PNIPAM, cononsolvency, co-nonsolvency, water, ethanol, methanol, n-propanol},
}

@Article{LopezLeon2010,
  author   = {L{\'{o}}pez-Le{\'{o}}n, Teresa and Bastos-Gonz{\'{a}}lez, Delfina and Ortega-Vinuesa, Juan Luis and Ela{\"{i}}ssari, Abdelhamid},
  journal  = {ChemPhysChem},
  title    = {Salt Effects in the Cononsolvency of Poly(N-isopropylacrylamide) Microgels},
  year     = {2010},
  number   = {1},
  pages    = {188--194},
  volume   = {11},
  abstract = {Poly(N-isopropylacrylamide) (PNIPAM) is well known to exhibit reentrant behavior or cononsolvency in response to the composition of a mixed solvent consisting of water and a low-chain alcohol. Since the solvent structure plays an important role in this phenomenon, the presence of structure-breaking/structure-making ions in solution is expected to have a dramatic effect on the cononsolvency of PNIPAM. The present work examines the way that the presence of different salts can modify the reentrant-phase diagram displayed by a cationic PNIPAM microgel in the mixed ethanol/water solvent. The effects of four Hofmeister anions---SO42$-$, Cl$-$, NO3$-$ and SCN$-$---with different abilities to modify the solvent structure are analyzed. The species with kosmotropic or structure-making character show a clear competition with ethanol for the water molecules, intensifying the nonsolvency of the PNIPAM with the EtOH volume fraction (ϕe). However, striking results are found with the most chaotropic or structure-breaking anion, SCN$-$. In contrast to what happens in water-rich solutions, the presence of SCN$-$ in alcohol-rich solvents enhances the solubility of the polymer, which macroscopically results in the microgel swelling. Moreover, this ion displays great stabilizing properties when ϕe> is 0.2. These results have been explained by considering how chaotropic or structure-breaking ions interact with water and ethanol molecules.},
  doi      = {https://doi.org/10.1002/cphc.200900491},
  eprint   = {https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/cphc.200900491},
  file     = {:LopezLeon2010 - Salt Effects in the Cononsolvency of Poly(N Isopropylacrylamide) Microgels.pdf:PDF},
  keywords = {colloids, gels, nanoparticles, salt effects, solvent effects, cononsolvency, co-nonsolvency, water, ethanol, PNIPAM, microgel, Hofmeister},
  ranking  = {rank5},
  url      = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/cphc.200900491},
}

@Article{Orakdogen2006,
  author   = {Nermin Orakdogen and Oguz Okay},
  journal  = {Polymer},
  title    = {Reentrant conformation transition in poly(N,N-dimethylacrylamide) hydrogels in water--organic solvent mixtures},
  year     = {2006},
  issn     = {0032-3861},
  number   = {2},
  pages    = {561--568},
  volume   = {47},
  abstract = {Conformational changes in poly(N,N-dimethylacrylamide) (PDMA) networks swollen in aqueous solutions of organic solvents are studied both experimentally and theoretically. PDMA hydrogels of various charge densities were prepared by free-radical crosslinking copolymerization. Swelling behavior of the hydrogels was investigated in aqueous organic solvent mixtures as functions of solvent species and the concentration. With increasing volume fraction ϕ of acetone, tetrahydrofuran, or 1,4-dioxane in the aqueous solution, PDMA hydrogels exhibit reentrant conformation transition. During this transition, the gel first deswells in the range of ϕ between 0.4 and 0.9, and then rapidly reswells if ϕ is monotonically increased. The reswelling of the collapsed PDMA gel occurs in a narrow of ϕ above ϕ=0.97. It was shown that the reentrant transition in PDMA gels requires moderate hydrogen bonding organic solvents, so that the hydrophobic interactions between PDMA and the organic solvent dominate the swelling process. The results were interpreted using the theory of equilibrium swelling. The interaction parameters in the gel system as well as the partition parameter of the organic solvent between the gel and the solution phases were calculated.},
  doi      = {https://doi.org/10.1016/j.polymer.2005.11.066},
  keywords = {Hydrogels, Reentrant transition, Hydrophobic interactions, cononsolvency, co-nonsolvency, acetone, tetrahydrofuran, THF, dioxane, water, methanol,ethanol, propanol, butanol, DMSO, macrogel},
  printed  = {printed},
  ranking  = {rank4},
  url      = {https://www.sciencedirect.com/science/article/pii/S0032386105017179},
}

@Article{Arndt2012,
  author   = {Arndt, Markus C. and Sadowski, Gabriele},
  journal  = {Macromolecules},
  title    = {Modeling Poly(N-isopropylacrylamide) Hydrogels in Water/Alcohol Mixtures with PC-SAFT},
  year     = {2012},
  number   = {16},
  pages    = {6686--6696},
  volume   = {45},
  abstract = {The PC-SAFT equation of state is used for thermodynamic modeling of poly(N-isopropylacrylamide) PNIPAAm in water and alcohols (methanol, ethanol, 1-propanol, and 2-propanol). For calculating the swelling behavior of cross-linked PNIPAAm gels, an additional contribution to the Helmholtz energy considering elastic forces is implemented and the resulting pressure difference in the gel is taken into account. The model is used to describe the gel-phase composition and the degree of swelling as a function of both the temperature and the solvent composition in good agreement with experimental data. In particular, the re-entrant phenomenon of the swelling transition in the ternary mixtures is modeled correctly and data from the literature correspond well with the computed results, suggesting a significant predictive capability of the model.},
  doi      = {10.1021/ma300683k},
  eprint   = {https://doi.org/10.1021/ma300683k},
  file     = {:Arndt2012 - Modeling Poly(N Isopropylacrylamide) Hydrogels in Water_Alcohol Mixtures with PC SAFT.pdf:PDF},
  keywords = {PNIPAM, gel, cononsolvency, co-nonsolvency, water, methanol, ethanol, 1-propanol, 2-propanol, theory, model},
  ranking  = {rank4},
  url      = {https://doi.org/10.1021/ma300683k},
}

@Book{Mehring1983,
  author    = {Michael Mehring},
  publisher = {Springer, Berlin-Heidelberg},
  title     = {Principles of High Resolution NMR in Solids},
  year      = {1983},
  isbn      = {978-3-642-68756-3},
  doi       = {https://doi.org/10.1007/978-3-642-68756-3_6},
  file      = {:Mehring1983 - Principles of High Resolution NMR in Solids.pdf:PDF},
  keywords  = {NMR, book, theory},
}

@Article{Yang2017a,
  author    = {Yang, Man and Liu, Chunyan and Lian, Yiwei and Zhao, Kongshuang and Zhu, Dan and Zhou, Jianfeng},
  journal   = {Soft Matter},
  title     = {Relaxations and phase transitions during the collapse of a dense PNIPAM microgel suspension---thorough insight using dielectric spectroscopy},
  year      = {2017},
  pages     = {2663--2676},
  volume    = {13},
  abstract  = {The dielectric behavior of a thermo-sensitive poly-(N-isopropylacrylamide) (PNIPAM) microgel suspension with a dense concentration was investigated over the frequency range of 40 Hz to 110 MHz in a wide temperature window of 10--60 {$^{\circ}$}C. By successfully removing the electrode polarization effect from the original data{,} two remarkable and temperature-dependent relaxation processes were observed. Both of the two-phase transition processes{,} i.e.{,} the colloidal crystal-to-liquid transition{,} which has not yet been detected by dielectric spectroscopy before{,} as well as the volume phase transition{,} were detected by the relaxation parameters. Based on the three physical states of the microgel suspension{,} the relaxation mechanisms are discussed in detail. The slow relaxation originates from the segmental motion and the counterion motion along the polymer chain over the whole temperature range. It was found that when the system is in the colloidal crystal and liquid state{,} the segmental motion is cooperative with side chain and hydrogen bonding networks{,} while in the phase separation state (at temperatures above the lower critical solution temperature (LCST)){,} the cooperative interaction disappears. The fast relaxation is due to the fluctuation of counterions below the LCST and the interfacial polarization above the LCST. Based on interfacial polarization theory{,} which describes the dielectric model of a conventional particle dispersion{,} the temperature dependence of the electrical properties for the constituent phases (the permittivity{,} conductivity and volume fraction of the microgel ($\epsilon$p{,} $\kappa$p{,} ϕ); the conductivity of the medium water ($\kappa$a); the water content in the PNIPAM microgel (fw)) were calculated using the Hanai equation. The water content is close to the result obtained using light scattering{,} indicating that the dielectric model for a conventional particle dispersion is also applicable to a soft atypical colloidal dispersion.},
  doi       = {10.1039/C7SM00144D},
  issue     = {14},
  keywords  = {BDS, dielectric spectroscopy, PNIPAM, microgel},
  publisher = {The Royal Society of Chemistry},
  url       = {http://dx.doi.org/10.1039/C7SM00144D},
}

@Article{Gao2002,
  author   = {Gao, Jun and Hu, Zhibing},
  journal  = {Langmuir},
  title    = {Optical Properties of N-Isopropylacrylamide Microgel Spheres in Water},
  year     = {2002},
  number   = {4},
  pages    = {1360--1367},
  volume   = {18},
  abstract = {Optical properties of N-isopropylacrylamide (NIPA) microgel spheres in water have been investigated using light-scattering and turbidity methods. Two batches of NIPA microgel spheres with hydrodynamic radii of 132 and 216 nm were synthesized in water at 25 {$^{\circ}$}C. Concentrations ranging from $\sim$0.01 to $\sim$14 wt \% were obtained by dilution$-$condensation of the dispersions. The hydrodynamic radius distribution, the radius of gyration, and the molar mass of the microgel spheres were determined by combining dynamic and static light scattering. As the polymer concentration increases, the microgel spheres in dispersions exist in the liquid, crystalline, and glass states, while the optical appearance of the dispersions changes progressively from transparent to cloudy to colored (pink, green, blue, and purple gradually) and to transparent. The formation of large colloidal crystals in a very narrow concentration range (ca. 3$\sim$5 wt \%) at room temperature ($\sim$18$-$22 {$^{\circ}$}C) yields iridescent patterns from typical Bragg diffraction. For a colored dispersion, the turbidity exhibits a sharp shoulder-shaped increase at a certain wavelength $\lambda$c that decreases linearly with decreasing interparticle distance. It is found that for a dilute dispersion light scattering is the main cause of the turbidity, while for a concentrated dispersion in which microgel spheres are close-packed, interparticle interference becomes dominant. Heating a concentrated NIPA microgel dispersion from room temperature to 35 {$^{\circ}$}C leads to a continuous increase of turbidity. The ordered structure of microgel spheres was melted and transformed into a disordered liquid state at about 30 {$^{\circ}$}C, which was lower than the volume phase-transition temperature of $\sim$34 {$^{\circ}$}C. Phase inversion can be obtained either by condensation of the sample at room temperature or by heating a concentrated sample.},
  doi      = {10.1021/la011405f},
  eprint   = {https://doi.org/10.1021/la011405f},
  file     = {:Gao2002 - Optical Properties of N Isopropylacrylamide Microgel Spheres in Water.pdf:PDF},
  keywords = {PNIPAM, microgel, concentration, DLS, light scattering, trubidity},
  url      = {https://doi.org/10.1021/la011405f},
}

@Article{Wilbur1976,
  author   = {Wilbur, D. J. and DeFries, T. and Jonas, J.},
  journal  = {The Journal of Chemical Physics},
  title    = {Self-diffusion in compressed liquid heavy water},
  year     = {1976},
  number   = {5},
  pages    = {1783--1786},
  volume   = {65},
  doi      = {10.1063/1.433324},
  eprint   = {https://doi.org/10.1063/1.433324},
  keywords = {NMR, diffusion, heavy water, d2o, gradient calibration, pressure},
  url      = {https://doi.org/10.1063/1.433324},
}

@Article{Holz2000,
  author    = {Holz, Manfred and Heil, Stefan R. and Sacco, Antonio},
  journal   = {Physical Chemistry Chemical Physics},
  title     = {Temperature-dependent self-diffusion coefficients of water and six selected molecular liquids for calibration in accurate 1H NMR PFG measurements},
  year      = {2000},
  pages     = {4740--4742},
  volume    = {2},
  abstract  = {Pulsed magnetic field gradient (PFG) NMR is today a routine method for the determination of self-diffusion coefficients{,} D. However{,} a remaining goal is the improvement of the precision of the method. The best procedure for the determination of accurate diffusion coefficients by PFG NMR is a calibration with a sample of precisely known D-value. In continuation of our previous work on calibration at 25{$^{\circ}$}C (M. Holz and H. Weing{\"{a}}rtner{,} J. Magn. Reson.{,} 1991{,} 92{,} 115) we present reference data as a function of temperature. Since H2O plays an outstanding role as liquid and as primary standard{,} we carefully measured self-diffusion coefficients of water by 1H PFG NMR in the temperature range from + 5 to + 55{$^{\circ}$}C and added literature data obtained from tracer methods in the range between 0 and + 100{$^{\circ}$}C. This comparatively large collection of data could then be fitted to a Speedy--Angell power law{,} showing the excellent congruence of the results of two completely different methods and proofing the certainty of the absolute values for water. In this manner reliable primary standard values with error limits of 1% were obtained{,} allowing us to adapt the temperature of the standard water to the sample temperature of interest. We further give 1H PFG NMR self-diffusion reference data in the range from + 5 to + 55{$^{\circ}$}C for six easily accessible solvents{,} which we propose as secondary calibration standards{,} namely cyclohexane{,} dioxane{,} dodecane{,} DMSO{,} tetradecane and pentanol{,} covering a large range of absolute D-values and allowing us to match in addition the absolute D-values of calibration sample and sample under investigation. Furthermore{,} the gained accurate self-diffusion data are suited for an elaborate check of theoretical approaches in the physics of molecular liquids.},
  doi       = {10.1039/B005319H},
  file      = {:Holz2000 - Temperature Dependent Self Diffusion Coefficients of Water and Six Selected Molecular Liquids for Calibration in Accurate 1H NMR PFG Measurements.pdf:PDF},
  issue     = {20},
  keywords  = {NMR, diffusion, water, h2o, gradient calibration, PFG},
  publisher = {The Royal Society of Chemistry},
  url       = {http://dx.doi.org/10.1039/B005319H},
}

@Article{Kaerger2021,
  author   = {J{\"{o}}rg K{\"{a}}rger and Marija Avramovska and Dieter Freude and J{\"{u}}rgen Haase and Senugtaik Hwang and Rustem Valiullin},
  journal  = {Adsorption},
  title    = {Pulsed field gradient NMR diffusion measurement in nanoporous materials},
  year     = {2021},
  volume   = {27},
  file     = {:Kaerger2021 - Pulsed Field Gradient NMR Diffusion Measurement in Nanoporous Materials.pdf:PDF},
  keywords = {NMR, pfg, diffusion, nanopores, review, michael},
  url      = {https://doi.org/10.1007/s10450-020-00290-9},
}

@Article{Costa2002,
  author   = {Ricardo O. R. Costa and Roberto F. S. Freitas},
  journal  = {Polymer},
  title    = {Phase behavior of poly(N-iso\-propyl\-acryl\-amide) in binary aqueous solutions},
  year     = {2002},
  issn     = {0032-3861},
  number   = {22},
  pages    = {5879--5885},
  volume   = {43},
  abstract = {In this work, the phase behavior of linear poly(N-isopropylacrylamide) (PNIPA) in water--solvent mixtures was investigated. Several solvents, including low molecular weight alcohols, were selected and phase separation temperatures were determined through cloud point measurements. All the studied systems exhibited the cononsolvency effect, i.e. lower PNIPA compatibility within definite ranges of composition in water-rich mixtures. However, it was first detected that the coexistence of phase separation temperatures---a lower critical solution temperature (LCST) with an upper critical solution temperature (UCST)---at higher solvent concentrations in most systems, depend on the hydrophobic nature of the solvent. The change from a LCST to a UCST was correlated with the competition between polymer--water and polymer--solvent interactions mediated by compositional factors. The effects produced by the different solvents tested were qualitatively compared, considering aspects related to their particular molecular structures, such as the potential to form hydrogen bonds and the implications of the size and shape of non-polar groups for hydrophobic hydration.},
  doi      = {https://doi.org/10.1016/S0032-3861(02)00507-4},
  file     = {:Costa2002 - Phase Behavior of Poly(N Isopropylacrylamide) in Binary Aqueous Solutions.pdf:PDF},
  keywords = {Hydrophobic hydration, Lower critical solution temperature, LCST, Thermoreversible hydrogel, thermosensitive, PNIPAM, aqueous alcohol, UCST, cloud point, cononsolvency, chain length, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate},
  url      = {https://www.sciencedirect.com/science/article/pii/S0032386102005074},
}

@Article{Modesti2009,
  author   = {Modesti, Giorgio and Zimmermann, Boris and B{\"{o}}rsch, Michael and Herrmann, Andreas and Saalw{\"{a}}chter, Kay},
  journal  = {Macromolecules},
  title    = {Diffusion in Model Networks as Studied by NMR and Fluorescence Correlation Spectroscopy},
  year     = {2009},
  note     = {PMID: 19812716},
  number   = {13},
  pages    = {4681--4689},
  volume   = {42},
  abstract = {We have studied the diffusion of small solvent molecules (octane) and larger hydrophobic dye probes in octane-swollen poly(dimethyl siloxane) linear-chain solutions and end-linked model networks, using pulsed-gradient nuclear magnetic resonance (NMR) and fluorescence correlation spectroscopy (FCS), respectively, focusing on diffusion in the bulk polymer up to the equilibrium degree of swelling of the networks, that is, 4.8 at most. The combination of these results allows for new conclusions on the feasibility of different theories describing probe diffusion in concentrated polymer systems. While octane diffusion shows no cross-link dependence, the larger dyes are increasingly restricted by fixed chemical meshes. The simple Fujita free-volume theory proved most feasible to describe probe diffusion in linear long-chain solutions with realistic parameters, while better fits were obtained assuming a stretched exponential dependence on concentration. Importantly, we have analyzed the cross-link specific effect on probe diffusion independently of any specific model by comparing the best-fit interpolation of the solution data with the diffusion in the networks. The most reasonable description is obtained by assuming that the cross-link effect is additive in the effective friction coefficient of the probes. The concentration dependences as well as the data compared at the equilibrium degrees of swelling indicate that swelling heterogeneities and diffusant shape have a substantial influence on small-molecule diffusion in networks.},
  doi      = {10.1021/ma900614j},
  eprint   = {https://doi.org/10.1021/ma900614j},
  file     = {:Modesti2009 - Diffusion in Model Networks As Studied by NMR and Fluorescence Correlation Spectroscopy.pdf:PDF},
  keywords = {Diffusion, NMR, model, FCS, polymer network},
  url      = {https://doi.org/10.1021/ma900614j},
}

@Article{Bonetto2006,
  author   = {Bonetto, F. and Anoardo, E. and Polello, M.},
  journal  = {Concepts in Magnetic Resonance Part B},
  title    = {Saddle coils for uniform static magnetic field generation in NMR experiments},
  year     = {2006},
  number   = {1},
  pages    = {9--19},
  volume   = {29B},
  abstract = {The magnetic flux density field (called, henceforth, {\textquotedblleft}magnetic field,{\textquotedblright} for the sake of simplicity) generated by a saddle coil system is numerically calculated in the whole space and experimentally tested in two different spatial planes. The uniformity of the magnetic field is studied using Taylor series expansions of the three components separately. The optimum geometry is revised and obtained from the second-order Taylor expansions. The most favorable relationship between saddle coil geometric parameters is determined in case the optimum geometry cannot be achieved (because of experimental restrictions). Approximated manipulable analytical expressions are obtained via fourth-order Taylor expansions of the three components of the magnetic field and compared with exact expressions. They were found to differ in less than 10$-$3\% within a sample region, when typical sample and coil dimensions are considered. Deviations of the magnetic field produced by an optimum-compensating saddle coil system were contrasted with typical NMR field-cycling magnetic field inhomogeneities. Possible influences of such deviations in NMR experiments are discussed. {\copyright} 2006 Wiley Periodicals, Inc. Concepts Magn Reson Part B (Magn Reson Engineering) 29B: 9--19, 2006},
  doi      = {https://doi.org/10.1002/cmr.b.20057},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.b.20057},
  file     = {:Bonetto2006 - Saddle Coils for Uniform Static Magnetic Field Generation in NMR Experiments.pdf:PDF},
  keywords = {saddle coils, magnetic field uniformity, field-cycling NMR, setup},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.b.20057},
}

@Article{Chu2007,
  author   = {Liang-Yin Chu and Jin-Woong Kim and Rhutesh K. Shah and David A. Weitz},
  journal  = {Advanced Functional Materials},
  title    = {Monodisperse Thermoresponsive Microgels with Tunable Volume-Phase Transition Kinetics},
  year     = {2007},
  number   = {17},
  pages    = {3499--3504},
  volume   = {17},
  abstract = {A facile method to control the volume-phase transition kinetics of thermo-sensitive poly(N-isopropylacrylamide) (PNIPAM) microgels is presented. Monodisperse PNIPAM microgels with spherical voids are prepared using a microfluidic device. The swelling and shrinking responses of these microgels with spherical voids to changes in temperature are compared with those of voidless microgels of the same size and chemical composition prepared using the same microfluidic device. It is shown that the PNIPAM microgels with voids respond faster to changes in temperature as compared with their voidless counterparts. Also, the induced void structure does not have a detrimental effect on the equilibrium volume change of the microgels. Thus, the volume phase transition kinetics of the microgels can be finely tuned by controlling the number and size of the voids. The flexibility, control, and simplicity in fabrication rendered by this approach make these microgels appealing for applications that range from drug delivery systems and chemical separations to chemical/biosensing and actuators.},
  doi      = {https://doi.org/10.1002/adfm.200700379},
  eprint   = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/adfm.200700379},
  file     = {:Chu2007 - Monodisperse Thermoresponsive Microgels with Tunable Volume Phase Transition Kinetics.pdf:PDF},
  keywords = {Hydrogels, Microgels, Microspheres, Poly(N-isopropylacrylamide), PNIPAM, Stimuli-responsive materials, VPT},
  url      = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.200700379},
}

@Article{Burmistrova2011,
  author     = {Anna Burmistrova and Marcel Richter and Cagri Uzum and Regine von Klitzing},
  journal    = {Colloid and Polymer Science},
  title      = {Effect of cross-linker density of P(NIPAM-co-AAc) microgels at solid surfaces on the swelling/shrinking behaviour and the Young's modulus},
  year       = {2011},
  abstract   = {The effect of the amount of cross-linker in poly(N-isopropylacrylamide-co-acrylic acid) microgel particles on the swelling behaviour and their elasticity is studied. The distribution of the stiffness through the particle is also investigated. Therefore, the swelling ratio obtained from dynamic light scattering measure- ments in aqueous solutions is compared with the one after adsorption at polycation-coated silicon wafers. The studies of the swelling behaviour at the surface are carried out with scanning force microscopy (SFM) against liquid. The Young{\textquoteright}s modulus is determined by indentation experiments with an SFM. With increasing amount of cross-linker, the ability to shrink as well as the shift in the lower critical solution temperature and in particle size (hysteresis) during the heating and cooling processes decreases. In addition, the particles at the surface preserve their height/width ratio at high amount of cross-linker, while at low amounts the shrinking and swelling mainly takes place with respect to changes in height. The particles show their highest Young{\textquoteright}s mod- ulus in the centre of the particles and become stiffer with increasing the amount of cross-linker and the temperature.},
  doi        = {10.1007/s00396-011-2383-2},
  file       = {:Burmistrova2011 - Effect of Cross Linker Density of P(NIPAM Co AAc) Microgels at Solid Surfaces on the Swelling_shrinking Behaviour and the Young's Modulus.pdf:PDF},
  keywords   = {PNIPAM, microgel, hysteresis, von Klitzing, DLS, dynamic light scattering, SFM, scanning force microscopy, AFM, atomic force microscopy},
  printed    = {printed},
  ranking    = {rank5},
  readstatus = {read},
}

@Article{Cheng2006,
  author     = {Cheng, He and Shen, Lei and Wu, Chi},
  journal    = {Macromolecules},
  title      = {LLS and FTIR Studies on the Hysteresis in Association and Dissociation of Poly(N-isopropylacrylamide) Chains in Water},
  year       = {2006},
  number     = {6},
  pages      = {2325--2329},
  volume     = {39},
  abstract   = {Using a combination of static and dynamic laser scattering, we examined the association and dissociation of linear poly(N-isopropylacrylamide) (PNIPAM) chains in dilute aqueous solutions. There exists a hysteresis in the temperature dependence of the average hydrodynamic radius (〈Rh〉), average radius of gyration (〈Rg〉), and apparent weight-average molar mass (Mw,app) in one heating-and-cooling cycle. In the heating process, the chains first undergo intrachain contraction before interchain association to form stable aggregates at temperatures much higher than the lower critical solution temperature (LCST $\sim$ 32 {$^{\circ}$}C) of PNIPAM in water. In the cooling process before the solution temperature approaches the LCST, Mw,app remains a constant and both 〈Rg〉 and 〈Rh〉 increase, but the ratio of 〈Rg〉/〈Rh〉 decreases. In other words, the aggregates undergo an unevenly swelling; namely, the periphery swells more than the center, and there is no chain dissociation. FTIR spectra reveal that as the temperature increases, the adsorption peak area related to the hydrogen bonding 〉CO$\cdot\cdot\cdot$H$-$O$-$H decreases, but the adsorption peak related to the hydrogen bonding 〉CO$\cdot\cdot\cdot$H$-$N〈 appears when the temperature is higher than the LCST, reflecting the dehydration and the formation of some additional intersegment hydrogen bonds in the collapsed state during the heating. Therefore, the chain contraction is entropy-driven, and the hysteresis can be attributed to these additional hydrogen bonds that act as the {\textquotedblleft}cross-linking{\textquotedblright} points to make the chain aggregates behave like a {\textquotedblleft}gel{\textquotedblright}. The chain dissociation only occurs when the temperature is much lower than the LCST, at which water becomes a very good solvent for PNIPAM.},
  doi        = {10.1021/ma052561m},
  eprint     = {https://doi.org/10.1021/ma052561m},
  file       = {:Cheng2006 - LLS and FTIR Studies on the Hysteresis in Association and Dissociation of Poly(N Isopropylacrylamide) Chains in Water.pdf:PDF},
  keywords   = {PNIPAM, hysteresis, light scattering, DLS, LLS, von Klitzing},
  printed    = {printed},
  ranking    = {rank5},
  readstatus = {read},
  url        = {https://doi.org/10.1021/ma052561m},
}

@Article{Backes2017a,
  author     = {Backes, Sebastian and Krause, Patrick and Tabaka, Weronika and Witt, Marcus U. and von Klitzing, Regine},
  journal    = {Langmuir},
  title      = {Combined Cononsolvency and Temperature Effects on Adsorbed PNIPAM Microgels},
  year       = {2017},
  note       = {PMID: 29166032},
  number     = {50},
  pages      = {14269--14277},
  volume     = {33},
  abstract   = {The present study addresses the multiresponsive behavior of poly(N-isopropylacrylamide) (PNIPAM) microgels adsorbed to interfaces. The microgels react to changes in temperature by shrinking in aqueous solution above their volume phase transition temperature (VPTT). Additionally, they shrink in mixtures of water and ethanol, although both individual liquids are good solvents for PNIPAM. The combination of this so-called cononsolvency effect and the temperature response of adsorbed microgels is studied by atomic force microscopy (AFM). Adsorbed microgels are of special interest because they are compressed considerably compared to those in bulk solution. It is shown that the impact of adsorption on swelling depends on the specific surface details, as well as the sample preparation. Thereby, the microgels are deposited on two different kinds of surfaces: on gold surface and on polycation (PAH) coating which show different interactions with the microgels in terms of electrostatic interaction and wettability. In addition, the microgels were deposited from different solvent mixtures. This influences the microgel structure and thereby the swelling properties. Nanorheology studies by dynamic AFM measurements lead to surprising results which are explained by the fact that not only polymer density but a subtle interaction between polymer and solvent might dominate the rheological properties. This work supports the view that preferential adsorption of ethanol at PNIPAM drives cononsolvency, while the shrinking at T > VPTT is caused by general breaking of hydrogen bonds between solvents and PNIPAM.},
  doi        = {10.1021/acs.langmuir.7b02903},
  eprint     = {https://doi.org/10.1021/acs.langmuir.7b02903},
  file       = {:Backes2017a - Combined Cononsolvency and Temperature Effects on Adsorbed PNIPAM Microgels.pdf:PDF},
  keywords   = {PNIPAM, co-nonsolvency, von Klitzing, microgel, VPT, AFM},
  printed    = {printed},
  ranking    = {rank3},
  readstatus = {read},
  url        = {https://doi.org/10.1021/acs.langmuir.7b02903},
}

@Article{Takaizumi2005,
  author   = {Katsuko Takaizumi},
  journal  = {Journal of Solution Chemistry},
  title    = {A Curious Phenomenon in the Freezing-Thawing Process of Aqueous Ethanol Solution},
  year     = {2005},
  pages    = {597--612},
  volume   = {34},
  abstract = {The freezing--thawing process of aqueous ethanol solutions has been studied by differential scanning calorimetry (DSC) in an intermediate concentration range higher than about 30 wt% of the alcohol. Two kinds of ethanol hydrate solid were confirmed to exist: EtOH$\cdot$4.67H2O with a melting peak (D1$\ast$) at $-$64.5◦C and EtOH$\cdot$4.75H2O with a melting peak (D2$\ast$) at $-$63.1◦C. The peak D1$\ast$ appears just after mixing ethanol and water. However, the peak curiously shifts to the D2$\ast$ peak after storage for a few days or more at room temperature. The phenomenon was accelerated by heating or by repetition of the freezing--thawing process. The origin of the phenomenon has been discussed in relation to the state of solution.},
  file     = {:Takaizumi2005 - A Curious Phenomenon in the Freezing Thawing Process of Aqueous Ethanol Solution.pdf:PDF},
  keywords = {ethanol,freezing,DSC,aqueous alcohol},
  url      = {https://doi.org/10.1007/s10953-005-5595-6},
}

@Article{Eguchi1980,
  author    = {Taro Eguchi and Gen Soda and Hideaki Chihara},
  journal   = {Molecular Physics},
  title     = {Molecular motions in polymorphic forms of ethanol as studied by nuclear magnetic resonance},
  year      = {1980},
  number    = {3},
  pages     = {681--696},
  volume    = {40},
  abstract  = {Measurements were made of the temperature dependence of the N.M.R. lineshape between 32 and 159 K and the spin-lattice relaxation time T 1 between 56 and 190 K at 10 MHz to study the molecular motion in various states of ethanol and ethanol-D. The methyl group reorientation about C 3 axis is the main relaxation mechanism in the stable crystalline phase, having an activation energy of 12$\cdot$6 kJ mol-1 and $\tau$c 0 = 3$\cdot$3 $\times$ 10-13 s. The molecular tumbling together with rapid methyl rotation is responsible for the dominant relaxation mechanism in the undercooled liquid and the metastable plastic phase. On the other hand, T 1 in the glassy liquid and the glassy crystal may be described by a quantum picture, i.e. the tunnelling rotation of the methyl group. The slope of the T 1 curve for these glassy states corresponds to the separation between the ground and the first excited torsional levels, which is 1$\cdot$9 kJ mol-1. The tunnelling splitting was deduced to be 15 $\pm$ 5 MHz and the barrier height 8 $\pm$ 1 kJ mol-1.},
  doi       = {10.1080/00268978000101791},
  eprint    = {https://doi.org/10.1080/00268978000101791},
  file      = {:Eguchi1980 - Molecular Motions in Polymorphic Forms of Ethanol As Studied by Nuclear Magnetic Resonance.pdf:PDF},
  keywords  = {nmr, ethanol, ethanol-d, spin-lattice relaxation, t1, lineshape},
  publisher = {Taylor \& Francis},
  url       = {https://doi.org/10.1080/00268978000101791},
}

@PhdThesis{Kyriakos2015,
  author   = {Konstantinos Kyriakos},
  school   = {Technische Universit{\"{a}}t M{\"{u}}nchen},
  title    = {Cononsolvency of PNIPAM in water / alcohol mixtures - A neutron scattering study},
  year     = {2015},
  month    = feb,
  type     = {phdthesis},
  abstract = {Thermoresponsive polymers are possible cornerstones for designing numerous smart materials with applications in a wide range of disciplines. In this dissertation the focus is on
the properties of the thermoresponsive poly(N-isopropyl acrylamide), in homopolymers and amphiphilic block copolymers, in solutions of mixed solvents of water and a short chain alcohol (e.g. methanol). By means of time-resolved small angle neutron scattering (TR-SANS) we study the micellar structure and follow the aggregation triggered by the phase transition, at a mesoscopic length scale, by two different pathways. We observe a strong influence of the solvation environment on the the aggregation kinetics and use different models to quantify the findings. By means of quasi-elastic neutron scattering (QENS) we focus on the local polymer-solvent and solvent-solvent interactions and reveal the solvation mechanism at the molecular level. In the appendix of this work some results on the novel thermoresponsive polymer poly(methoxy diethylene glycol) are presented.},
  file     = {:Kyriakos2015 - Cononsolvency of PNIPAM in Water _ Alcohol Mixtures a Neutron Scattering Study.pdf:PDF},
  url      = {https://mediatum.ub.tum.de/doc/1239016/1239016.pdf},
}

@Article{Versmold1974,
  author       = {Versmold, H.},
  journal      = {Berichte der Bunsen-Gesellschaft für physikalische Chemie},
  title        = {NMR Studies of Reorientational Motion in Ethanol and Ethanol Glycerol Mixtures},
  year         = {1974},
  number       = {12},
  pages        = {1318--1327},
  volume       = {78},
  abstract     = {Deuteron nuclear magnetic relaxation rates 1/T1 have been measured as a function of temperature for the three labelled ethanols CH3CH2OD, CH3CD2OH and CD3CH2OH. In the supercooled region relaxation rate maxima for the different species were found. The data are discussed in terms of a rotational diffusion model for the overall and the internal reorientations. The slowest motion is performed by the hydroxyl group. Faster reorientation occurs for the ethyl group which behaves as a rather rigid entity in pure ethanol. The internal reorientation of the methyl group has further been studied in ethanol glycerol mixtures. With increasing glycerol content the motion of the ethanol skeleton is slowed down but the internal motion of the CD3 group about its C3 symmetry axis maintains its rate. This leads to two relaxation rate steps for the deuterons of the methyl group in these mixtures. The first due to the reorientational motion of the symmetry axis of the CD3 group occurs in the same temperature range as the relaxation rate maximum of the methylene group. The second step was found at lower temperatures. It belongs to the spinning of the methyl group about its symmetry axis.},
  creationdate = {2021-10-19T00:00:00},
  doi          = {10.1002/bbpc.19740781206},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/bbpc.19740781206},
  file         = {:Versmold1974 - NMR Studies of Reorientational Motion in Ethanol and Ethanol Glycerol Mixtures.pdf:PDF},
  keywords     = {Magnetische Kernresonanz, NMR, Molek{\"{u}}lstruktur, Rotation, Zwischenmolekulare Wechselwirkungen, ethanol, T1, spin-lattice relaxation SLR},
  printed      = {printed},
  url          = {https://onlinelibrary.wiley.com/doi/10.1002/bbpc.19740781206},
}

@Article{Dixit2002,
  author       = {S. Dixit and J. Crain and W. C. K. Poon and J. L. Finney and A. K. Soper},
  journal      = {Nature},
  title        = {Molecular segregation observed in a concentrated alcohol-water solution},
  year         = {2002},
  pages        = {829--832},
  volume       = {416},
  abstract     = {When a simple alcohol such as methanol or ethanol is mixed with water1,2, the entropy of the system increases far less than expected for an ideal solution of randomly mixed molecules3. This well-known effect has been attributed to hydrophobic headgroups creating ice-like or clathrate-like structures in the surrounding water4, although experimental support for this hypothesis is scarce5,6,7. In fact, an increasing amount of experimental and theoretical work suggests that the hydrophobic headgroups of alcohol molecules in aqueous solution cluster together2,8,9,10. However, a consistent description of the details of this self-association is lacking11,12,13. Here we use neutron diffraction with isotope substitution to probe the molecular-scale structure of a concentrated alcohol--water mixture (7:3 molar ratio). Our data indicate that most of the water molecules exist as small hydrogen-bonded strings and clusters in a {\textquoteleft}fluid{\textquoteright} of close-packed methyl groups, with water clusters bridging neighbouring methanol hydroxyl groups through hydrogen bonding. This behaviour suggests that the anomalous thermodynamics of water--alcohol systems arises from incomplete mixing at the molecular level and from retention of remnants of the three-dimensional hydrogen-bonded network structure of bulk water.},
  creationdate = {2021-11-02T00:00:00},
  file         = {:Dixit2002 - Molecular Segregation Observed in a Concentrated Alcohol Water Solution.pdf:PDF},
  keywords     = {cononsolvency, neutron scattering, alcohol solution, ethanol, methanol, water, h2o},
  printed      = {printed},
  ranking      = {rank5},
  url          = {https://doi.org/10.1038/416829a},
}

@Misc{DDB,
  comment      = {Dortmund University Database},
  creationdate = {2021-11-04T00:00:00},
  keywords     = {solubility},
  ranking      = {rank5},
  url          = {http://www.ddbst.com/ddb-search.html},
}

@Article{BevanOtt1979,
  author       = {J. {Bevan Ott} and J. {Rex Goates} and Boyd A. Waite},
  journal      = {Journal of Chemical Thermodynamics},
  title        = {(Solid + liquid) phase equilibria and solid-hydrate formation in water + methyl, + ethyl, + isopropyl, and + tertiary butyl alcohols},
  year         = {1979},
  issn         = {0021-9614},
  number       = {8},
  pages        = {739--746},
  volume       = {11},
  abstract     = {(Solid + liquid) phase diagrams have been obtained from time-temperature melting curves for water + methyl, + ethyl, + isopropyl, and + tertiary butyl alcohols. Incongruently melting hydrates form in all four systems. In addition, water + t-butyl alcohol has a congruently melting compound. Correlations between inflexions found in the water-rich compositions of the (solid + liquid) equilibrium lines and the size of the alkyl groups of the alcohols are noted, and a possible interpretation is given.},
  creationdate = {2021-11-04T00:00:00},
  doi          = {https://doi.org/10.1016/0021-9614(79)90005-3},
  file         = {:BevanOtt1979 - (Solid + Liquid) Phase Equilibria and Solid Hydrate Formation in Water + Methyl, + Ethyl, + Isopropyl, and + Tertiary Butyl Alcohols.pdf:PDF},
  keywords     = {phase diagram, alcohol solution, ethanol, water},
  url          = {https://www.sciencedirect.com/science/article/pii/0021961479900053},
}

@Article{Ghosh2019,
  author       = {Ghosh, Ashesh and Chaudhary, Gaurav and Kang, Jin Gu and Braun, Paul V. and Ewoldt, Randy H. and Schweizer, Kenneth S.},
  journal      = {Soft Matter},
  title        = {Linear and nonlinear rheology and structural relaxation in dense glassy and jammed soft repulsive pNIPAM microgel suspensions},
  year         = {2019},
  pages        = {1038--1052},
  volume       = {15},
  abstract     = {We present an integrated experimental and quantitative theoretical study of the mechanics of self-crosslinked{,} slightly charged{,} repulsive pNIPAM microgel suspensions over a very wide range of concentrations (c) that span the fluid{,} glassy and putative {\textquotedblleft}soft jammed{\textquotedblright} regimes. In the glassy regime we measure a linear elastic dynamic shear modulus over 3 decades which follows an apparent power law concentration dependence G$\prime$ $\sim$ c5.64{,} a variation that appears distinct from prior studies of crosslinked ionic microgel suspensions. At very high concentrations there is a sharp crossover to a nearly linear growth of the modulus. To theoretically understand these observations{,} we formulate an approach to address all three regimes within a single conceptual Brownian dynamics framework. A minimalist single particle description is constructed that allows microgel size to vary with concentration due to steric de-swelling effects. Using a Hertzian repulsion interparticle potential and a suite of statistical mechanical theories{,} quantitative predictions under quiescent conditions of microgel collective structure{,} dynamic localization length{,} elastic modulus{,} and the structural relaxation time are made. Based on a constant inter-particle repulsion strength parameter which is determined by requiring the theory to reproduce the linear elastic shear modulus over the entire concentration regime{,} we demonstrate good agreement between theory and experiment. Testable predictions are then made. We also measured nonlinear rheological properties with a focus on the yield stress and strain. A theoretical analysis with no adjustable parameters predicts how the quiescent structural relaxation time changes under deformation{,} and how the yield stress and strain change as a function of concentration. Reasonable agreement with our observations is obtained. To the best of our knowledge{,} this is the first attempt to quantitatively understand structure{,} quiescent relaxation and shear elasticity{,} and nonlinear yielding of dense microgel suspensions using microscopic force based theoretical methods that include activated hopping processes. We expect our approach will be useful for other soft polymeric particle suspensions in the core--shell family.},
  creationdate = {2021-11-16T00:00:00},
  doi          = {10.1039/C8SM02014K},
  file         = {:Ghosh2019 - Linear and Nonlinear Rheology and Structural Relaxation in Dense Glassy and Jammed Soft Repulsive PNIPAM Microgel Suspensions.pdf:PDF},
  issue        = {5},
  keywords     = {concentration-dependence, PNIPAM, microgel, rheology},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C8SM02014K},
}

@Article{Virtanen2019,
  author       = {Virtanen, Otto L. J. and Kather, Michael and Meyer-Kirschner, Julian and Melle, Andrea and Radulescu, Aurel and Viell, J{\"{o}}rn and Mitsos, Alexander and Pich, Andrij and Richtering, Walter},
  journal      = {ACS Omega},
  title        = {Direct Monitoring of Microgel Formation during Precipitation Polymerization of N-Isopropylacrylamide Using in Situ SANS},
  year         = {2019},
  number       = {2},
  pages        = {3690--3699},
  volume       = {4},
  abstract     = {Poly(N-isopropylacrylamide) microgels have found various uses in fundamental polymer and colloid science as well as in different applications. They are conveniently prepared by precipitation polymerization. In this reaction, radical polymerization and colloidal stabilization interact with each other to produce well-defined thermosensitive particles of narrow size distribution. However, the underlying mechanism of precipitation polymerization has not been fully understood. In particular, the crucial early stages of microgel formation have been poorly investigated so far. In this contribution, we have used small-angle neutron scattering in conjunction with a stopped-flow device to monitor the particle growth during precipitation polymerization in situ. The average particle volume growth is found to follow pseudo-first order kinetics, indicating that the polymerization rate is determined by the availability of the unreacted monomer, as the initiator concentration does not change considerably during the reaction. This is confirmed by calorimetric investigation of the polymerization process. Peroxide initiator-induced self-crosslinking of N-isopropylacrylamide and the use of the bifunctional crosslinker N,N$\prime$-methylenebisacrylamide are shown to decrease the particle number density in the batch. The results of the in situ small-angle neutron scattering measurements indicate that the particles form at an early stage in the reaction and their number density remains approximately the same thereafter. The overall reaction rate is found to be sensitive to monomer and initiator concentration in accordance with a radical solution polymerization mechanism, supporting the results from our earlier studies.},
  creationdate = {2021-11-16T00:00:00},
  doi          = {10.1021/acsomega.8b03461},
  eprint       = {https://doi.org/10.1021/acsomega.8b03461},
  file         = {:Virtanen2019 - Direct Monitoring of Microgel Formation during Precipitation Polymerization of N Isopropylacrylamide Using in Situ SANS.pdf:PDF},
  keywords     = {neutron, SANS, PNIPAM, microgel, synthesis},
  url          = {https://doi.org/10.1021/acsomega.8b03461},
}

@Article{Benetis1983,
  author       = {Nikolas Benetis and Jozef Kowalewski and Lars Nordenski{\"{o}}ld and H{{\aa}}kan Wennerstr{\"{o}}m and Per-Olof Westlund},
  journal      = {Molecular Physics},
  title        = {Dipole-dipole nuclear spin relaxation},
  year         = {1983},
  number       = {3},
  pages        = {515--530},
  volume       = {50},
  abstract     = {The transverse spin relaxation of a spin I in a IS pair is analysed for the dipole-dipole relaxation mechanism. It is shown that, when for the S-spin there is an additional efficient relaxation mechanism, which is of a second order tensorial rank, there can exist substantial corrections to the Solomon-Bloembergen equation for T 2. The correction terms are found to be non-negligible in the non-extreme narrowing limit. The correction terms are due to a cross correlation effect between the dipole-dipole interaction and the interaction causing the efficient relaxation of the S spin. As shown in the Appendix the correction appears as a near divergence of a fourth order term in the Redfield type expansion of the equation of motion of the density matrix. The explicit expressions for T 2 are, however, derived using a Liouville operator formalism combined with a perturbation expansion. For the relaxation of the S-spin a zero field splitting term is considered for a paramagnetic system with S $\geq$ 1. Similarly for a nuclear spin S the quadrupolar interaction provides an efficient relaxation mechanism when S $\geq$ 1. For these cases explicit examples are worked out and for example if S = 1 and the principal axis system of the zero field splitting term or the quadrupolar interaction coincides with the dipole-dipole vector the cross correlation corrections are such that the high field value of T 2 is 2$\cdot$5 times the value given by the Solomon-Bloembergen equation. It is also argued that a similar cross correlation effect can appear in spin one half systems if three or more spins are involved. It thus appears that the quantitative analysis of T 2 data for systems outside the extreme narrowing regime is even more complicated than has previously been appreciated.},
  creationdate = {2021-11-17T00:00:00},
  doi          = {10.1080/00268978300102521},
  eprint       = {https://doi.org/10.1080/00268978300102521},
  file         = {:Benetis1983 - Dipole Dipole Nuclear Spin Relaxation.pdf:PDF},
  keywords     = {nmr, theory, solomon bloembergen morgan, SBM, T1, T2, relaxation},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/00268978300102521},
}

@Article{Beckmann1988,
  author       = {Peter A. Beckmann},
  journal      = {Physics Reports},
  title        = {Spectral densities and nuclear spin relaxation in solids},
  year         = {1988},
  issn         = {0370-1573},
  number       = {3},
  pages        = {85--128},
  volume       = {171},
  abstract     = {We investigate the properties of ten spectral densities relevant for nuclear spin relaxation studies in solids. This is preceded by a brief review of nuclear spin relaxation in solids which includes a discussion of the appropriate spin-dependent interactions and the various relaxation rates which can be measured. Also, the link between nuclear spin relaxation and dielectric relaxation is discussed. Where possible and/or appropriate each of the spectral densities is expressed as a continuous distribution of Bloembergen-Purcell-Pound (or Debye) spectral densities 2$\xi$ /(1 + $\xi$2 $\omega$2) for nuclear Larmor angular frequency $\omega$ and correlation time $\xi$. The spectral densities are named after their originators or the shape of the distributions of correlation times or both and are (1) Bloembergen-Purcell-Pound or $\delta$-function, (2) Havriliak-Negami, (3) Cole-Cole, (4) Davidson-Cole, (5) Fang, (6) Fuoss-Kirkwood, (7) Bryn Mawr, (8) Wagner or log-Gaussian, (9) log-Lorentzian, and (10) Fr{\"{o}}hlich or energy box. The Havriliak-Negami spectral density is related to the Dissado-Hill theory for dielectric relaxation. The spectral densities are expressed in a way which makes them easy to compare with each other and with experimental data. Many plots of the distributions of correlation times and of the spectral densities vs. various correlation times characterizing the distributions are given.},
  creationdate = {2021-11-17T00:00:00},
  doi          = {https://doi.org/10.1016/0370-1573(88)90073-7},
  file         = {:Beckmann1988 - Spectral Densities and Nuclear Spin Relaxation in Solids.pdf:PDF},
  keywords     = {nmr, theory, spectral density},
  url          = {https://www.sciencedirect.com/science/article/pii/0370157388900737},
}

@Article{Jukic2020,
  author       = {Juki{\'{c}}, Ivo and Po{\v{z}}ar, Martina and Lovrin{\v{c}}evi{\'{c}}, Bernarda},
  journal      = {Physical Chemistry Chemical Physics},
  title        = {Comparative analysis of ethanol dynamics in aqueous and non-aqueous solutions},
  year         = {2020},
  pages        = {23856--23868},
  volume       = {22},
  abstract     = {In this study{,} we compare the results for vibrational{,} reorientational and hydrogen bond dynamics of ethanol in water and in hexane across the whole concentration range. Water and hexane are both commonly used as solvents{,} but so far{,} it has been unclear to what extent they modify the solute dynamics. Ethanol is chosen as the solute because it is an aliphatic molecule that is miscibile with both solvents. It is known that ethanol forms micelle-like domains in water and cyclic clusters resembling loops in hexane. This structural micro-heterogeneity is well known both in experiments and in simulations. The main question we raise here is: is there a signature of micro-heterogeneity in the dynamical quantities of ethanol? We focus on quantities such as the vibrational spectra{,} the reorientational correlation functions{,} the self-diffusion coefficients{,} the ethanol--ethanol hydrogen bond correlation functions and the corresponding hydrogen bond histograms. For the first time ever{,} we compute the van Hove functions to reveal the dynamical variations of spatial correlations in these systems. All these results complement each other and provide a unifying dynamical description of ethanol in binary mixtures.},
  creationdate = {2021-11-18T00:00:00},
  doi          = {10.1039/D0CP03160G},
  file         = {:Jukic2020 - Comparative Analysis of Ethanol Dynamics in Aqueous and Non Aqueous Solutions.pdf:PDF},
  issue        = {41},
  keywords     = {ethanol, water, hexane, correlation time, self-diffusion, binary mixture, simulation},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D0CP03160G},
}

@Article{Laenen1997,
  author       = {R. Laenen and C. Rauscher},
  journal      = {Chemical Physics Letters},
  title        = {Time-resolved infrared spectroscopy of ethanol monomers in liquid solution: molecular reorientation and energy relaxation times},
  year         = {1997},
  issn         = {0009-2614},
  number       = {1},
  pages        = {63--70},
  volume       = {274},
  abstract     = {Two-color pump-probe spectroscopy has been performed with subpicosecond time resolution in the CH- and OH-stretching regions of ethanol monomers dissolved in carbon tetrachloride in the temperature range from 259 to 333 K. From the isotropic component of the probe transmission signal we deduce the lifetime of the OH-stretching vibration to be T1 = 8 $\pm$ 1 ps while the molecular reorientation is directly observed from the anisotropic signal to occur with $\tau$or = 2 $\pm$ 0.5 ps at room temperature. Additional information on the relaxation pathway of the excited OH-strecthing and on the asymmetric CH3-stretching vibration of ethanol is presented as well as evidence for an inhomogeneous broadening of the monomeric OH-vibration.},
  creationdate = {2021-11-18T00:00:00},
  doi          = {https://doi.org/10.1016/S0009-2614(97)00644-1},
  file         = {:Laenen1997 - Time Resolved Infrared Spectroscopy of Ethanol Monomers in Liquid Solution_ Molecular Reorientation and Energy Relaxation Times.pdf:PDF},
  keywords     = {ethanol, rotational correlation times, two-color pump-probe spectrocopy},
  url          = {https://www.sciencedirect.com/science/article/pii/S0009261497006441},
}

@Article{Chen1975,
  author       = {Chen, Teng ko and Beyerlein, A. L. and Savitsky, G. B.},
  journal      = {The Journal of Chemical Physics},
  title        = {Rotational correlation times for ethanol by deuteron magnetic spin--lattice relaxation},
  year         = {1975},
  number       = {7},
  pages        = {3176--3177},
  volume       = {63},
  abstract     = {The deuterium T1 relaxation times of perdeuterated ethanol in CCl4, benzene, and water solutions have been measured. The results are compared with theoretical determinations of the rotational correlation time. (AIP)},
  creationdate = {2021-11-19T00:00:00},
  doi          = {10.1063/1.431717},
  eprint       = {https://aip.scitation.org/doi/pdf/10.1063/1.431717},
  keywords     = {ethanol, rotational correlation time, SLR, concentration},
  url          = {https://aip.scitation.org/doi/abs/10.1063/1.431717},
}

@Article{Uedaira1980,
  author       = {H. Uedaira},
  journal      = {Inorganica Chimica Acta},
  title        = {Rotational correlation times and self-diffusion coefficients in methanol--ethanol system},
  year         = {1980},
  issn         = {0020-1693},
  pages        = {X104--X105},
  volume       = {40},
  abstract     = {It is well known that rotational motion is strongly correlated with translational motion in polar liquids [1] and aqueous solutions of non-electrolytes [2]. The investigation on the correlation of these motions is one of the usefull approach for elucidating the structure in the mixture of polar liquids. In this report we investigate the concentration dependence of the deuteron relaxation rate 1/T1 of the partially deuterated alcohols CD3OH, CD3CH2OH, and CH3CD2OH and the self-diffusion coefficients in methanol--ethanol system at 25 {$^{\circ}$}C. The measurements of the spin-lattice relaxation times and the self-diffusion coefficients have been performed with a spin-echo spectrometer JNM-FSE 60A and a S/N Booster JNM-3B-SB(JEOL). The resonance frequencies for 1H and 2H are 60 and 9.2 MHz, respectively. All samples were degassed and sealed. In Fig. 1 is shown the concentration dependence of the self-diffusion coefficients of methanol and ethanol in the methanol--ethanol mixture. A minimum of self-diffusion coefficient of methanol appears at higher concentration than that of ethanol. The concentration dependence of the deuteron relaxation rate 1/t1 of CD3OH in C2H5OH is shown in Fig. 2. The deuterion relaxation rate shows a maximum at 11 mol% of methanol. In the case of methanol, therefore, the self-diffusion coefficient correlates with relaxation rate. In the case of ethanol, however, both the relaxation rates of --CD3 and --CD2 did not show the maximum but decreased with increasing the concentration of methanol.},
  creationdate = {2021-11-19T00:00:00},
  doi          = {https://doi.org/10.1016/S0020-1693(00)92195-9},
  keywords     = {methanol, ethaol, self-diffusion coefficient, T1, SLR, spin-lattice relaxation, concentration-dependent},
  url          = {https://www.sciencedirect.com/science/article/pii/S0020169300921959},
}

@Article{Ludwig1994,
  author       = {R. Ludwig and M. D. Zeidler},
  journal      = {Molecular Physics},
  title        = {NMR relaxation in ethanol and propanol and in their binary mixtures with carbon tetrachloride},
  year         = {1994},
  number       = {2},
  pages        = {313--323},
  volume       = {82},
  abstract     = {NMR proton, deuteron and oxygen-17 relaxation rates were measured in different isotopic species of liquid ethanol and propanol and in their mixtures with carbon tetrachloride. For the pure alcohols a large temperature range could be covered and the relaxation rate maxima were obtained. Evaluation of the rates yielded rotational correlation times, the OH bond length and quadrupole coupling constants for the deuteron and for oxygen-17.},
  creationdate = {2021-11-19T00:00:00},
  doi          = {10.1080/00268979400100234},
  eprint       = {https://doi.org/10.1080/00268979400100234},
  file         = {:Ludwig1994 - NMR Relaxation in Ethanol and Propanol and in Their Binary Mixtures with Carbon Tetrachloride.pdf:PDF},
  keywords     = {ethanol, nmr, SLR, spin-lattice relaxation, rotational correlation time},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/00268979400100234},
}

@Article{Ansari1984,
  author       = {M. S. Ansari and H. G. Hertz},
  journal      = {Journal of Solution Chemistry},
  title        = {Effect of ion-solvation on the internal dynamics of the ethanol molecule as studied using NMRB' coefficients},
  year         = {1984},
  pages        = {877--906},
  volume       = {13},
  abstract     = {The modification of reorientational correlation times for the various kinds of chemically non-equivalent protons of the ethanol molecule as a result of ionsolvation has been investigated with the help of NMR B$\prime$ coefficients. For this purpose, the proton spin-lattice relaxation times of specifically deuterated ethanols, containing only one type of chemically equivalent protons were measured in neat ethanols and their lithium chloride and iodide solutions at a number of concentrations. The measurements were also extended over a wide temperature range below room temperature. Some results of various other chlorides were also included for comparison. The results are discussed in the light of pertinent theories available at present. At 250 K the rotational correlation time of the molecule in pure ethanol is 64 ps and the correlation times of the CH2 and CH3 groups are 8 and 3 ps, respectively. In the solvation sphere of Li+ the correlation times for the molecule and the respective groups are about 4, 7, and 4 times as long. However, the internal reorientation times are found, in some cases, to be virtually zero which we take as an indication that the description of the internal motion by current theories is not satisfactory.},
  creationdate = {2021-11-19T00:00:00},
  file         = {:Ansari1984 - Effect of Ion Solvation on the Internal Dynamics of the Ethanol Molecule As Studied Using NMRB' Coefficients.pdf:PDF},
  keywords     = {nmr, ethanol, reorientational correlation times, ionic strength},
  url          = {https://doi.org/10.1007/BF00645334},
}

@Article{Meckl1988,
  author       = {S. Meckl and M. D. Zeidler},
  journal      = {Molecular Physics},
  title        = {Self-diffusion measurements of ethanol and propanol},
  year         = {1988},
  number       = {1},
  pages        = {85--95},
  volume       = {63},
  abstract     = {Self-diffusion coefficients of ethanol and 1-propanol were measured by the N.M.R. spin-echo technique over the temperature range 285 K $\leqslant$- T $\leqslant$- 320 K and the pressure range 0$\cdot$1 MPa $\leqslant$- P $\leqslant$- 400 MPa. The results are interpreted on the basis of the rough hard-sphere model. A test of the Stokes-Einstein relation is performed and a modification of it is proposed.},
  creationdate = {2021-11-19T00:00:00},
  doi          = {10.1080/00268978800100081},
  eprint       = {https://doi.org/10.1080/00268978800100081},
  file         = {:Meckl1988 - Self Diffusion Measurements of Ethanol and Propanol.pdf:PDF},
  keywords     = {ethanol, self-diffusion, pressure-dependent},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/00268978800100081},
}

@Article{Liu2005,
  author       = {Mingzhu Liu and Fengling Bian and Fenling Sheng},
  journal      = {European Polymer Journal},
  title        = {FTIR study on molecular structure of poly(N-isopropylacrylamide) in mixed solvent of methanol and water},
  year         = {2005},
  issn         = {0014-3057},
  number       = {2},
  pages        = {283--291},
  volume       = {41},
  abstract     = {The intrachain and interchain hydrogen bonding of poly(N-isopropylacrylamide) (PNIPA) and intermolecular hydrogen bonding between PNIPA chains and the solvent molecules in the mixed solvent of methanol and water have been quantitatively investigated by using Fourier transform infrared (FTIR) spectroscopy at 25{$^{\circ}$}C. In this spectroscopic system with curve fitting program, we found that in the C--H stretching region, both the N-isopropyl group and the backbone underwent conformational change upon the solvent composition. An analysis of the amide I band suggested that the amide groups of PNIPA were mainly involved in intermolecular hydrogen bonding with water molecules, and the polymer chains were flexible and disordered in the mixed solvent when the methanol volume fraction ($\chi$v) was lower than 15%. While $\chi$v was in the range of 15--65%, about 30% of these intermolecular hydrogen bonding between the polymer and water were replaced by intrachain and interchain hydrogen bonding, consequently, PNIPA shrinked as aggregates. If $\chi$v was above 65%, the interchain hydrogen bonding became predominant due to the solubility characteristics of amphiphilic methanol, and the PNIPA system was homogeneous solution again. We believe that the reentrant transition is related to the weaker interaction between PNIPA molecules and methanol--water complexes, (H2O)m(CH3OH)n (m/n=5/1, 5/2, 5/3, 5/4, 5/5) as compared to that between PNIPA and free water or free methanol.},
  creationdate = {2021-11-22T00:00:00},
  doi          = {https://doi.org/10.1016/j.eurpolymj.2004.09.008},
  file         = {:Liu2005 - FTIR Study on Molecular Structure of Poly(N Isopropylacrylamide) in Mixed Solvent of Methanol and Water.pdf:PDF},
  keywords     = {Poly(-isopropylacrylamide), PNIPAM, Fourier transform infrared, FTIR, Lower critical solution temperature, LCST, Conformational analysis, Hydrogen bonding, cononsolvency, methanol, alcohol complex},
  ranking      = {rank5},
  url          = {https://www.sciencedirect.com/science/article/pii/S0014305704003271},
}

@Book{Saito2007,
  author       = {Hazime Saito and Isao Ando and Akira Naito},
  publisher    = {Springer e-Books},
  title        = {Solid State NMR Spectroscopy for Biopolymers: Principles and Applications},
  year         = {2007},
  isbn         = {9781402043024},
  creationdate = {2021-11-23T00:00:00},
  keywords     = {book},
}

@InBook{Levitt2007,
  author       = {Levitt, Malcolm H.},
  publisher    = {John Wiley \& Sons, Ltd},
  title        = {Composite Pulses},
  year         = {2007},
  isbn         = {9780470034590},
  booktitle    = {eMagRes},
  creationdate = {2021-11-23T00:00:00},
  doi          = {https://doi.org/10.1002/9780470034590.emrstm0086},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/9780470034590.emrstm0086},
  file         = {:Levitt2007 - Composite Pulses.pdf:PDF},
  keywords     = {nmr, book, composite pulse, finite pulse},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/9780470034590.emrstm0086},
}

@PhdThesis{Urban2004,
  author       = {Jeffrey Todd Urban},
  school       = {University of California, Berkley},
  title        = {Nuclear Magnetic Resonance Studies of Quadrupolar Nuclei and Dipolar Field Effects},
  year         = {2004},
  type         = {phdthesis},
  creationdate = {2021-11-24T00:00:00},
  file         = {:Urban2004 - Nuclear Magnetic Resonance Studies of Quadrupolar Nuclei and Dipolar Field Effects.pdf:PDF},
  keywords     = {nmr, theory, dissertation},
  url          = {https://www.osti.gov/servlets/purl/836811},
}

@Article{Westlund2000,
  author       = {Westlund, P.-O.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Line Shape Analysis of NMR Powder Spectra of 2H2O in Lipid Bilayer Systems},
  year         = {2000},
  number       = {25},
  pages        = {6059--6064},
  volume       = {104},
  abstract     = {A NMR line shape/spin relaxation model is developed for 2H2O studies of structure and dynamics of the lipid$-$water interfaces of phosphatidylcholine bilayers. A line shape function describing the orientational dependence of 2H2O is derived. In addition, also expressions of the observed quadrupole splitting and the spin$-$lattice relaxation rate are derived within the same dynamic model. The model comprises two chemically interchanging fractions of water namely, {\textquotedblleft}free{\textquotedblright}, and {\textquotedblleft}bound{\textquotedblright}. There are four molecular parameters characterizing the {\textquotedblleft}bound{\textquotedblright} water of the lipid water interface, namely, (1) the fraction water molecules bound to lipid molecules, (2) the local water order parameter , (3) the order parameter which describes the averaged {\textquotedblleft}bound{\textquotedblright} water, and an effective correlation time (4) $\tau$c, characterizing water translational diffusion at the interface. This model allows for analyzing quadrupole splittings, spin$-$lattice relaxation rates, and water powder line shapes. Thus, dynamics as well as structural information about the water molecules residing in the water lipid interface may be extracted. In the reinterpretation of 2H2O powder spectra obtained for lamellar phases of dipalmitoylphosphatidylcholine (DPPC), the results clearly indicate that (L$\alpha$) > (L$\beta${\textquoteleft}) when comparing the liquid crystalline phase with 10$-$11 water molecules per lipid molecule and the gel phase with 3.5$-$4.2 water molecules per lipid molecule. Whereas the order of the perturbed water is similar in both phases, (L$\alpha$) $\approx$ (L$\beta${\textquoteleft}). The lateral diffusion is characterized by a correlation time $\tau$c > 60 ns but cannot be determined without measuring the spin$-$lattice relaxation measurements.},
  creationdate = {2021-11-24T00:00:00},
  doi          = {10.1021/jp994037l},
  eprint       = {https://doi.org/10.1021/jp994037l},
  file         = {:Westlund2000 - Line Shape Analysis of NMR Powder Spectra of 2H2O in Lipid Bilayer Systems.pdf:PDF},
  keywords     = {nmr, line shape, pake, theory, exchange},
  url          = {https://doi.org/10.1021/jp994037l},
}

@Article{Sanzari2020,
  author       = {Ilaria Sanzari and Elena Buratti and Ruomeng Huang and Camelia G. Tusan and Franco Dinelli and Nicholas D. Evans and Themistoklis Prodromakis and Monica Bertoldo},
  journal      = {Scientific Reports},
  title        = {Poly(N-isopropylacrylamide) based thin microgel films for use in cell culture applications},
  year         = {2020},
  volume       = {10},
  abstract     = {Poly(N-isopropylacrylamide) (PNIPAm) is widely used to fabricate cell sheet surfaces for cell culturing, however copolymer and interpenetrated polymer networks based on PNIPAm have been rarely explored in the context of tissue engineering. Many complex and expensive techniques have been employed to produce PNIPAm-based films for cell culturing. Among them, spin coating has demonstrated to be a rapid fabrication process of thin layers with high reproducibility and uniformity. In this study, we introduce an innovative approach to produce anchored smart thin films both thermo- and electro-responsive, with the aim to integrate them in electronic devices and better control or mimic different environments for cells in vitro. Thin films were obtained by spin coating of colloidal solutions made by PNIPAm and PAAc nanogels. Anchoring the films to the substrates was obtained through heat treatment in the presence of dithiol molecules. From analyses carried out with AFM and XPS, the final samples exhibited a flat morphology and high stability to water washing. Viability tests with cells were finally carried out to demonstrate that this approach may represent a promising route to integrate those hydrogels films in electronic platforms for cell culture applications.},
  creationdate = {2021-11-24T00:00:00},
  file         = {:Sanzari2020 - Poly(N Isopropylacrylamide) Based Thin Microgel Films for Use in Cell Culture Applications.pdf:PDF},
  keywords     = {pnipam, afm, xps, application focused, tissue engineering, application-focused},
  url          = {https://doi.org/10.1038/s41598-020-63228-9},
}

@Article{Curtis1986,
  author       = {Curtis, Janet and Dalling, Don K. and Grant, David M.},
  journal      = {Journal of Organic Chemistry},
  title        = {Deuterium chemical shifts and chemical shift parameters in methylcyclohexanes},
  year         = {1986},
  number       = {2},
  pages        = {136--142},
  volume       = {51},
  abstract     = {Natural-abundance, proton-decoupled deuterium NMR spectra were used in conjunction with proton spectra to simplify the hydrogen chemical shift assignments in 17 methylcyclohexanes. The simple deuterium spectra were interpreted by use of symmetry, hydrogen-scalar coupling information, and linear parameters obtained with a multiple regression analysis. The nonnegligible parameters primarily were those with either structural or spatial proximity between the ring hydrogen and methyl substituent. Three compounds which appear to have substantial nonchair contributions to their conformational equilibria are identified and discussed. The possible origin of four highly unique, vicinal methyl-hydrogen parameters is suggested.},
  creationdate = {2022-01-03T00:00:00},
  doi          = {10.1021/jo00352a003},
  eprint       = {https://doi.org/10.1021/jo00352a003},
  file         = {:Curtis1986 - Deuterium Chemical Shifts and Chemical Shift Parameters in Methylcyclohexanes.pdf:PDF},
  url          = {https://doi.org/10.1021/jo00352a003},
}

@Article{Chechko2013,
  author       = {Chechko and Gotsulsky and Malomuzh},
  journal      = {Condensed Matter Physics},
  title        = {Peculiar points in the phase diagram of the water-alcohol solutions},
  year         = {2013},
  issn         = {1607-324X},
  number       = {2},
  pages        = {23006},
  volume       = {16},
  abstract     = {The work is devoted to the investigation of nontrivial behavior of dilute water-alcohol solutions. The temperature and concentration dependencies of the contraction for aqueous solutions of ethanol and methanol are analyzed. The existence of a speciﬁc point, the so-called peculiar point, was established. It is shown that water–alcohol solutions of different types obey the principle of corresponding states if temperature and volume fraction are used as principal coordinates. In this case, the concentration of the peculiar point for different solutions is close to x ν = 0.28. Several predictions are made.},
  creationdate = {2022-01-04T00:00:00},
  doi          = {10.5488/cmp.16.23006},
  file         = {:Chechko2013 - Peculiar Points in the Phase Diagram of the Water Alcohol Solutions.pdf:PDF},
  keywords     = {cononsolvency, aqueous ethanol, aqueous methanol, alcohol solution, phase diagram},
  publisher    = {Institute for Condensed Matter Physics},
  url          = {http://dx.doi.org/10.5488/CMP.16.23006},
}

@Article{Cooper2012,
  author       = {Cooper, Catherine L. and Cosgrove, Terence and van Duijneveldt, Jeroen S. and Murray, Martin and Prescott, Stuart W.},
  journal      = {Langmuir},
  title        = {Colloidal Particles in Competition for Stabilizer: A Solvent Relaxation NMR Study of Polymer Adsorption and Desorption},
  year         = {2012},
  note         = {PMID: 23137265},
  number       = {48},
  pages        = {16588--16595},
  volume       = {28},
  abstract     = {The competitive adsorption of poly(vinylpyrrolidone) onto silica and alumina-modified silica particles was studied using solvent relaxation nuclear magnetic resonance. The additive nature of the measured relaxation rate enabled predictions to be made of the relaxation rate in different polymer adsorption scenarios. Preferential adsorption of the poly(vinylpyrrolidone) onto the unmodified silica particles occurred when there was insufficient polymer in the system to coat the entire available surface area. Desorption was also found to occur when the polymer was initially adsorbed upon the alumina-modified particle and silica particles were added.},
  creationdate = {2022-01-20T00:00:00},
  doi          = {10.1021/la303864h},
  eprint       = {https://doi.org/10.1021/la303864h},
  file         = {:Cooper2012 - Colloidal Particles in Competition for Stabilizer_ a Solvent Relaxation NMR Study of Polymer Adsorption and Desorption.pdf:PDF},
  keywords     = {nmr, colloid stabilization, polymer, silica particles, adsorption},
  url          = {https://doi.org/10.1021/la303864h},
}

@Article{Watanabe2014,
  author       = {Eiji Watanabe and Gregory S. Boutis and Hiroko Sato and Sokei Sekine and Tetsuo Asakura},
  journal      = {Polymer},
  title        = {NMR studies of thermo-responsive behavior of an amphiphilic poly(asparagine) derivative in water},
  year         = {2014},
  issn         = {0032-3861},
  note         = {Special issue: Porous Polymers},
  number       = {1},
  pages        = {278--286},
  volume       = {55},
  abstract     = {The thermo-responsive behavior of a unique biocompatible polymer, poly(N-substituted $\alpha$/$\beta$-asparagine) derivative (PAD), has been studied with several NMR methods. The 1H and 13C solution NMR measurements of the PAD in DMSO-d6 were used to investigate the isolated polymer and perform spectral assignments. By systematic addition of D2O we have tracked structural changes due to aggregation and observed contraction of hydrophilic side chains. Solution and cross polarization/magic angle spinning (CP/MAS) 13C NMR approaches were implemented to investigate the aggregates of the PAD aqueous solution during the liquid to gel transition as the temperature was increased. At temperatures near 20{~}{$^{\circ}$}C, all of the peaks from the PAD were observed in the 13C CP/MAS and 13C solution NMR spectra, indicating the presence of polymer chain nodes. Increasing the temperature to 40{~}{$^{\circ}$}C resulted in a partial disentanglement of the nodes due to thermal agitation and further heating resulted in little to no additional structural changes. Deuterium T1--T2 and T2--T2 two-dimensional relaxation spectroscopies using an inverse Laplace transform, were also implemented to monitor the water--PAD interaction during the phase transition. At temperatures near 20{~}{$^{\circ}$}C the dynamical characteristics of water were manifested into one peak in the deuterium T1--T2 map. Increasing the temperature to 40{~}{$^{\circ}$}C resulted in several distinguishable reservoirs of water with different dynamical characteristics. The observation of several reservoirs of water at the temperature of gel formation at 40{~}{$^{\circ}$}C is consistent with a physical picture of a gel involving a network of interconnected polymer chains trapping a fluid. Further increase in temperature to 70{~}{$^{\circ}$}C resulted in two non-exchanging water reservoirs probed by deuterium T2--T2 measurements.},
  creationdate = {2022-01-24T00:00:00},
  doi          = {https://doi.org/10.1016/j.polymer.2013.11.015},
  file         = {:Watanabe2014 - NMR Studies of Thermo Responsive Behavior of an Amphiphilic Poly(asparagine) Derivative in Water.pdf:PDF},
  keywords     = {NMR, Stimuli-responsive polymer, 2H relaxation, T1, T2, solvent relaxation},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386113010537},
}

@Article{Aravopoulou2018,
  author       = {Aravopoulou, Dionysia and Kyriakos, Konstantinos and Miasnikova, Anna and Laschewsky, Andr{\'{e}} and Papadakis, Christine M. and Kyritsis, Apostolos},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Comparative Investigation of the Thermoresponsive Behavior of Two Diblock Copolymers Comprising PNIPAM and PMDEGA Blocks},
  year         = {2018},
  note         = {PMID: 29420029},
  number       = {9},
  pages        = {2655--2668},
  volume       = {122},
  abstract     = {The thermoresponsive behavior of two diblock copolymers PS-b-PNIPAM and PS-b-PMDEGA, which both comprise a hydrophobic polystyrene (PS) block but different thermoresponsive blocks, also differing in length, poly(N-isopropylacrylamide) (PNIPAM) and poly(methoxy diethylene glycol acrylate) (PMDEGA), respectively, was comparatively investigated in a wide temperature range. Concentrated aqueous solutions containing 25 wt \% polymer were studied by small-angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), and broadband dielectric spectroscopy (BDS). DSC measurements show that, during the demixing phase transition, the hydration number per oligo(ethylene glycol) side chain in the PS-b-PMDEGA solution decreases rather gradually, even up to 20 {$^{\circ}$}C above the onset of the transition, i.e., the cloud point (CP). In contrast, the PS-b-PNIPAM solution exhibits an abrupt, stepwise dehydration behavior at its CP, indicated by the sharp, narrow endothermic peak. BDS measurements suggest that the organization of the expelled water during the phase transition and the subsequent evolution of the micellar aggregates are different for the two copolymers. In the PS-b-PMDEGA solution, the long-range charge transport process changes significantly at its CP and strong interfacial polarization processes appear, probably due to charge accumulation at the interfaces between the micellar aggregates and the aqueous medium. On the contrary, in the PS-b-PNIPAM solution, the phase transition has only a marginal effect on the long-range conduction process and is accompanied by a reduction in the high-frequency (1 MHz) dielectric permittivity, $\epsilon\prime$. The latter effect is attributed to the reduced polarization strength of local chain modes due to an enhancement of intra- and interchain hydrogen bonds (HBs) in the polymer-rich phase during the water detaching process. Surprisingly, our BDS measurements indicate that prior to both the demixing and remixing processes the local chain mobility increases temporally. Our dielectric studies suggest that for PS-b-PNIPAM the water detaching process initiates a few degrees below CP and that the local chain mobility and intra- and/or interchain HBs of the PNIPAM blocks may control its thermoresponsive behavior. Dielectric {\textquotedblleft}jump{\textquotedblright} experiments show that the kinetics of micellar aggregation in the PS-b-PMDEGA solution is slower than that in the PS-b-PNIPAM solution and is independent of the target temperature within the two-phase region. From the experimental point of view, it is shown that the dielectric susceptibility, especially, the dielectric permittivity, $\epsilon\prime$, is a well-suited probe for monitoring both the reversible changes in the molecular dipolar bond polarizability and the long-range interfacial polarization at the phase transition.},
  creationdate = {2022-01-24T00:00:00},
  doi          = {10.1021/acs.jpcb.7b09647},
  eprint       = {https://doi.org/10.1021/acs.jpcb.7b09647},
  file         = {:Aravopoulou2018 - Comparative Investigation of the Thermoresponsive Behavior of Two Diblock Copolymers Comprising PNIPAM and PMDEGA Blocks.pdf:PDF},
  keywords     = {PNPIAM, Polystyrene, PMDEGA, thermoresponsive, BDS, SAXS, DSC, blockcopolymer},
  ranking      = {rank4},
  url          = {https://doi.org/10.1021/acs.jpcb.7b09647},
}

@Article{Wang2017,
  author       = {Wang, Jian and Wang, Nian and Liu, Biaolan and Bai, Jia and Gong, Pei and Ru, Geying and Feng, Jiwen},
  journal      = {Physical Chemistry Chemical Physics},
  title        = {Preferential adsorption of the additive is not a prerequisite for cononsolvency in water-rich mixtures},
  year         = {2017},
  pages        = {30097--30106},
  volume       = {19},
  abstract     = {Cononsolvency of poly(N-isopropylacrylamide) (PNIPAM) gels in binary mixed solvents (water--acetone and water--DMSO) has been comparatively investigated by 1H HR-MAS NMR spectroscopy. The results demonstrate that{,} although the addition of both acetone and DMSO gives rise to cononsolvency behavior{,} PNIPAM preferentially interacts with acetone rather than DMSO in a water-rich regime{,} regardless of whether the temperature is above or below the volume phase transition temperature (VPTT). It suggests that the preferential adsorption of the additive cannot be deemed as a prerequisite for the cononsolvency in water-rich mixtures. The underlying molecular mechanism of cononsolvency involves a delicate balance between polymer--solvent and solvent--solvent interactions. Moreover{,} a new NOE-based NMR approach has been proposed to study the preferential adsorption in this work{,} which can be extensively adopted to study other relevant processes{,} including protein hydration{,} ligand binding{,} enzyme catalysis{,} etc.},
  creationdate = {2022-01-24T00:00:00},
  doi          = {10.1039/C7CP04384H},
  file         = {:Wang2017 - Preferential Adsorption of the Additive Is Not a Prerequisite for Cononsolvency in Water Rich Mixtures.pdf:PDF},
  issue        = {44},
  keywords     = {cononsolvency, 1H NMR, DMSO, PNIPAM, acetone, VPTT, polymer gel},
  publisher    = {The Royal Society of Chemistry},
  ranking      = {rank4},
  url          = {http://dx.doi.org/10.1039/C7CP04384H},
}

@Article{Stuart2010,
  author       = {Martien A. Cohen Stuart and Wilhelm T. S. Huck and Jan Genzer and Marcus M{\"{u}}ller and Christopher Ober and Manfred Stamm and Gleb B. Sukhorukov and Igal Szleifer and Vladimir V. Tsukruk and Marek Urban and Francoise Winnik and Stefan Zauscher and Igor Luzinov and Sergiy Minko},
  journal      = {Nature Materials},
  title        = {Emerging applications of stimuli-responsive polymer materials},
  year         = {2010},
  pages        = {101--113},
  volume       = {9},
  creationdate = {2022-01-24T00:00:00},
  doi          = {https://doi.org/10.1038/nmat2614},
  file         = {:Stuart2010 - Emerging Applications of Stimuli Responsive Polymer Materials.pdf:PDF},
  keywords     = {PNIPAM, thermoresponsive, application-focused, application focused},
}

@InProceedings{Tanaka2009a,
  author       = {Tanaka, Fumihiko and Koga, Tsuyoshi and Winnik, Fran{\c{c}}oise M.},
  booktitle    = {Gels: Structures, Properties, and Functions},
  title        = {Competitive Hydrogen Bonds and Cononsolvency of Poly(N-isopropylacrylamide)s in Mixed Solvents of Water/Methanol},
  year         = {2009},
  address      = {Berlin, Heidelberg},
  editor       = {Tokita, Masayuki and Nishinari, Katsuyoshi},
  pages        = {1--7},
  publisher    = {Springer Berlin Heidelberg},
  abstract     = {Collapse of a poly(N-isopropylacrylamide) (PNIPAM) chain upon heating in aqueous solutions is theoretically studied on the basis of cooperative dehydration (simultaneous dissociation of bound water molecules in a group of correlated sequence), and compared with the experimental observation of temperature-induced coil-globule transition by light scattering methods. The transition becomes sharper with the cooperativity parameter $\sigma$ of hydration. Phase diagrams with very flat LCST phase separation line for aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions are theoretically derived on the basis of sequential hydrogen bond formation between polymer chains and water molecules (cooperative hydration), and compared with experimental spinodal curves. The two-phase region systematically changes its shape with the cooperativity parameter $\sigma$, and the spinodals turned out to be almost independent of the polymer molecular weight for strongly cooperative hydration (small $\sigma$) as observed in PNIPAM solutions. Reentrant coil-globule-coil transition in mixed solvent of water and methanol is also studied from the viewpoint of competitive hydrogen bonds between polymer-water and polymer-methanol. The downward shift of the cloud-point curves (LCST cononsolvency) with the mol fraction of methanol due to the competition is calculated and compared with the experimental data.},
  comment      = {questionable assumptions:
-They assume a monomer unit occupies the same volume as a water molecule, but they factor in a volume difference of a water molecule and a methanol molecule.
-The solvent-solvent interaction is assumed to be weak compared to the solvent-polymer interaction.
-Despite setting the same parameters for water and methanol and supressing cooperativity, the chains are calculated to be smallest for a 1:1 mixture of water and methanol. But if solvent size and binding energy of water and methanol are the same and there is no cooperativity, why would the chain care what the solvent ratio is?},
  creationdate = {2022-01-25T00:00:00},
  doi          = {10.1007/2882_2009_1},
  file         = {:Tanaka2009a - Competitive Hydrogen Bonds and Cononsolvency of Poly(N Isopropylacrylamide)s in Mixed Solvents of Water_Methanol.pdf:PDF},
  isbn         = {978-3-642-00865-8},
  keywords     = {PNIPAM, cononsolvency, cooperative hydration, methanol, UCST},
  url          = {\url{https://books.google.de/books?id=hFu7BQAAQBAJ&pg=PA1&lpg=PA1&dq=DOI 10.1007/2882_2009_1&source=bl&ots=KjntXrdT2g&sig=ACfU3U2CLVHcnb-5if-KqywGwhoA55u__g&hl=de&sa=X&ved=2ahUKEwjv-cyFwtv1AhXCh_0HHax_CHsQ6AF6BAgCEAM#v=onepage&q&f=true}},
}

@Article{Okada2005,
  author       = {Okada, Yukinori and Tanaka, Fumihiko},
  journal      = {Macromolecules},
  title        = {Cooperative Hydration, Chain Collapse, and Flat LCST Behavior in Aqueous Poly(N-isopropylacrylamide) Solutions},
  year         = {2005},
  number       = {10},
  pages        = {4465--4471},
  volume       = {38},
  abstract     = {Phase diagrams with very flat LCST phase separation line for aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions are theoretically derived on the basis of sequential hydrogen bond formation between polymer chains and water molecules (cooperative hydration) and compared with experimental spinodal curves. The two-phase region systematically changes its shape with the cooperativity parameter $\sigma$, and the spinodals turned out to be almost independent of the polymer molecular weight for strongly cooperative hydration (small $\sigma$) as observed in PNIPAM solutions. Hydration takes place sharply within a very narrow temperature region. The number of hydrogen-bonded water molecules on a chain is calculated as a function of the temperature and the polymer concentration.},
  comment      = {see also Tanaka et al., Springer Berlin Heidelberg 2009},
  creationdate = {2022-01-25T00:00:00},
  doi          = {10.1021/ma0502497},
  eprint       = {https://doi.org/10.1021/ma0502497},
  file         = {:Okada2005 - Cooperative Hydration, Chain Collapse, and Flat LCST Behavior in Aqueous Poly(N Isopropylacrylamide) Solutions.pdf:PDF},
  keywords     = {cononsolvency, PNIPAM, LCST, cooperative hydration},
  ranking      = {rank4},
  readstatus   = {skimmed},
  url          = {https://doi.org/10.1021/ma0502497},
}

@Book{Rubinstein2004,
  author       = {Michael Rubinstein and Ralph H. Colby},
  publisher    = {Oxford University Press},
  title        = {Polymer Physics},
  year         = {2004},
  isbn         = {019852059x},
  creationdate = {2022-01-31T00:00:00},
}

@Article{Nishi2013,
  author       = {Nishi, Kengo and Hiroi, Takashi and Hashimoto, Kei and Fujii, Kenta and Han, Young-Soo and Kim, Tae-Hwan and Katsumoto, Yukiteru and Shibayama, Mitsuhiro},
  journal      = {Macromolecules},
  title        = {SANS and DLS Study of Tacticity Effects on Hydrophobicity and Phase Separation of Poly(N-isopropylacrylamide)},
  year         = {2013},
  number       = {15},
  pages        = {6225--6232},
  volume       = {46},
  abstract     = {The tacticity effect on phase separation process of poly(N-isopropylacrylamide) (PNiPAM) aqueous solutions was investigated by dynamic light scattering (DLS) and small angle neutron scattering (SANS) measurements. SANS measurement revealed that hydrophobicity of PNiPAM consisting of meso- and racemo-isomers increased with increasing the meso-content. This result is in accordance with the result of the previous experimental and simulation study on NiPAM dimers (DNiPAM) and trimers (TNiPAM) [Katsumoto, Y.; J. Phys. Chem. B 2010, 114, 13312−13318, and Autieri, E.; J. Phys. Chem. B 2011, 115, 5827–5839]; i.e., meso-diad is more hydrophobic than racemo-diad. In addition, a series of scattering experiments revealed that the ratio of meso-diad does not affect the static structure or the shrinking behavior of a single chain, but strongly affects the aggregation behavior. The PNiPAMs with low meso-content suddenly associate around the phase separation temperature, while that of the high meso-content gradually aggregate with increasing temperature. We propose that phase transition behavior of PNiPAM aqueous solutions can be controlled by changing the stereoregularity of the polymer chain.},
  creationdate = {2022-02-04T00:00:00},
  doi          = {10.1021/ma401349v},
  eprint       = {https://doi.org/10.1021/ma401349v},
  file         = {:Nishi2013 - SANS and DLS Study of Tacticity Effects on Hydrophobicity and Phase Separation of Poly(N Isopropylacrylamide).pdf:PDF},
  keywords     = {tacticity, PNIPAM, SANS, DLS},
  url          = {https://doi.org/10.1021/ma401349v},
}

@Article{Tavagnacco2018,
  author       = {Tavagnacco, L. and Zaccarelli, E. and Chiessi, E.},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {On the molecular origin of the cooperative coil-to-globule transition of poly(N-isopropylacrylamide) in water},
  year         = {2018},
  pages        = {9997--10010},
  volume       = {20},
  abstract     = {By means of atomistic molecular dynamics simulations we investigate the behaviour of poly(N-isopropylacrylamide){,} PNIPAM{,} in water at temperatures below and above the lower critical solution temperature (LCST){,} including the undercooled regime. The transition between water soluble and insoluble states at the LCST is described as a cooperative process involving an intramolecular coil-to-globule transition preceding the aggregation of chains and the polymer precipitation. In this work we investigate the molecular origin of such cooperativity and the evolution of the hydration pattern in the undercooled polymer solution. The solution behaviour of an atactic 30-mer at high dilution is studied in the temperature interval from 243 to 323 K with a favourable comparison to available experimental data. In the water soluble states of PNIPAM we detect a correlation between polymer segmental dynamics and diffusion motion of bound water{,} occurring with the same activation energy. Simulation results show that below the coil-to-globule transition temperature PNIPAM is surrounded by a network of hydrogen bonded water molecules and that the cooperativity arises from the structuring of water clusters in proximity to hydrophobic groups. Differently{,} the perturbation of the hydrogen bond pattern involving water and amide groups occurs above the transition temperature. Altogether these findings reveal that even above the LCST PNIPAM remains largely hydrated and that the coil-to-globule transition is related with a significant rearrangement of the solvent in the proximity of the surface of the polymer. The comparison between the hydrogen bonding of water in the surrounding of PNIPAM isopropyl groups and in the bulk displays a decreased structuring of solvent at the hydrophobic polymer–water interface across the transition temperature{,} as expected because of the topological extension along the chain of such interface. No evidence of an upper critical solution temperature behaviour{,} postulated in theoretical and thermodynamics studies of PNIPAM aqueous solution{,} is observed in the low temperature domain.},
  creationdate = {2022-02-04T00:00:00},
  doi          = {10.1039/C8CP00537K},
  file         = {:Tavagnacco2018 - On the Molecular Origin of the Cooperative Coil to Globule Transition of Poly(N Isopropylacrylamide) in Water.pdf:PDF},
  issue        = {15},
  keywords     = {molecular dynamics simulation, PNIPAM, cooperative hydration, cononsolvency, LCST, tacticity, atactic, UCST, polyl-leucine, PL, polyn-vinylisobutyramide PNVIBA},
  publisher    = {The Royal Society of Chemistry},
  ranking      = {rank4},
  url          = {http://dx.doi.org/10.1039/C8CP00537K},
}

@Article{Ono2007,
  author       = {Ono, Yousuke and Shikata, Toshiyuki},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Contrary Hydration Behavior of N-Isopropyl\-acrylamide to its Polymer, P(NIPAm), with a Lower Critical Solution Temperature},
  year         = {2007},
  note         = {PMID: 17266365},
  number       = {7},
  pages        = {1511--1513},
  volume       = {111},
  abstract     = {The number of hydrated water molecules per N-isopropylacrylamide in homogeneous aqueous solution was determined to be a constant with a value of 5−6 below and above the lower critical solution temperature, LCST (32 °C), of its polymer, poly(N-isopropylacrylamide), by high-frequency dielectric relaxation techniques.},
  comment      = {- Data evaluation already assumed exactly three contributions to the signal ("deconvoluted into three Debye-type relaxation modes")
- How can more than 2 water molecules be "directly" hydrated to the isopropylgroup?
- How can there be an exchange process in pure water?},
  creationdate = {2022-02-04T00:00:00},
  doi          = {10.1021/jp068954k},
  eprint       = {https://doi.org/10.1021/jp068954k},
  file         = {:Ono2007 - Contrary Hydration Behavior of N Isopropylacrylamide to Its Polymer, P(NIPAm), with a Lower Critical Solution Temperature.pdf:PDF},
  keywords     = {cooperative hydration, PNIAPM, NIPAM, BDS, dielectric, LCST, exchange, NMR},
  priority     = {prio1},
  ranking      = {rank4},
  readstatus   = {read},
  relevance    = {relevant},
  url          = {https://doi.org/10.1021/jp068954k},
}

@Article{Ahmed2009,
  author       = {Ahmed, Zeeshan and Gooding, Edward A. and Pimenov, Konstantin V. and Wang, Luling and Asher, Sanford A.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {UV Resonance Raman Determination of Molecular Mechanism of Poly(N-isopropylacrylamide) Volume Phase Transition},
  year         = {2009},
  note         = {PMID: 19260666},
  number       = {13},
  pages        = {4248--4256},
  volume       = {113},
  abstract     = {Poly(N-isopropylacrylamide) (PNIPAM) is the premier example of a macromolecule that undergoes a hydrophobic collapse when heated above its lower critical solution temperature (LCST). Here we utilize dynamic light scattering, H-NMR, and steady-state and time-resolved UVRR measurements to determine the molecular mechanism of PNIPAM’s hydrophobic collapse. Our steady-state results indicate that in the collapsed state the amide bonds of PNIPAM do not engage in interamide hydrogen bonding, but are hydrogen bonded to water molecules. At low temperatures, the amide bonds of PNIPAM are predominantly fully water hydrogen bonded, whereas, in the collapsed state one of the two normal C═O hydrogen bonds is lost. The NH−water hydrogen bonding, however, remains unperturbed by the PNIPAM collapse. Our kinetic results indicate a monoexponential collapse with τ ∼ 360 (±85) ns. The collapse rate indicates a persistence length of n ∼ 10. At lengths shorter than the persistence length the polymer acts as an elastic rod, whereas at lengths longer than the persistence length the polymer backbone conformation forms a random coil. On the basis of these results, we propose the following mechanism for the PNIPAM volume phase transition. At low temperatures PNIPAM adopts an extended, water-exposed conformation that is stabilized by favorable NIPAM−water solvation shell interactions which stabilize large clusters of water molecules. As the temperature increases an increasing entropic penalty occurs for the water molecules situated at the surface of the hydrophobic isopropyl groups. A cooperative transition occurs where hydrophobic collapse minimizes the exposed hydrophobic surface area. The polymer structural change forces the amide carbonyl and N−H to invaginate and the water clusters cease to be stabilized and are expelled. In this compact state, PNIPAM forms small hydrophobic nanopockets where the (i, i + 3) isopropyl groups make hydrophobic contacts. A persistent length of n ∼ 10 suggests a cooperative collapse where hydrophobic interactions between adjacent hydrophobic pockets stabilize the collapsed PNIPAM.},
  comment      = {"the collapsed PNIPAM does not significantly
hinder diffusion of D 2 O into the collapsed particle"},
  creationdate = {2022-02-04T00:00:00},
  doi          = {10.1021/jp810685g},
  eprint       = {https://doi.org/10.1021/jp810685g},
  file         = {:Ahmed2009 - UV Resonance Raman Determination of Molecular Mechanism of Poly(N Isopropylacrylamide) Volume Phase Transition.pdf:PDF},
  keywords     = {PNIPAM, LCST, 1H-NMR, DLS, Ultra Violet Resonance Raman, UVRR, transition kinetics, deuterated pNIPAM-d},
  ranking      = {rank4},
  readstatus   = {skimmed},
  url          = {https://doi.org/10.1021/jp810685g},
}

@Article{Maeda2000,
  author       = {Maeda, Yasushi and Higuchi, Tomomi and Ikeda, Isao},
  journal      = {Langmuir},
  title        = {Change in Hydration State during the Coil$-$Globule Transition of Aqueous Solutions of Poly(N-isopropylacrylamide) as Evidenced by FTIR Spectroscopy},
  year         = {2000},
  number       = {19},
  pages        = {7503--7509},
  volume       = {16},
  abstract     = {Coil$-$globule transition of poly(N-isopropylacrylamide) (PIPA), followed by intermolecular association in H2O and D2O, was investigated by Fourier transform infrared (FTIR) spectroscopy. IR spectra of the solutions were measured as a function of temperature, and spectral changes induced by the transition were observed. The intensities of the difference IR bands due to the vibrational modes of isopropyl and amide groups critically increased at the lower critical solution temperature (LCST). Heating of the PIPA solutions above the LCST led shifts of the amide II, C$-$H-stretching, and C$-$H-bending bands to lower wavenumbers during a shift of the amide I band to a higher wavenumber. The amide I band of the PIPA observed below the LCST could be fitted with a single component centered at 1625 cm-1, whereas two components (1625 and 1650 cm-1) were necessary to fit the band above the LCST. These components may be assigned to the CO group which is bound to water molecules as the solvent (1625 cm-1) and to the N$-$H in the side chain (1650 cm-1) via hydrogen bonding. About 13\% of the CO group is estimated to form the intra- or interchain hydrogen bonding, and the remaining CO group forms a hydrogen bond with water in the globule state. Red shifts of the antisymmetric and symmetric C$-$H-stretching bands for the isopropyl group also indicate dehydration of the hydrophobic moiety during the transition. A mechanistic hypothesis of the coil$-$globule transition, insisting that above the LCST the polymer chain is dehydrated and hydrophobic interaction between isopropyl groups induces the collapse of the chain, is strongly supported. Though the presence of metal halides (NaCl, KCl, KBr, KI) lowered the LCST, the profiles of IR difference spectra of the PIPA in those solutions were similar to those measured in pure water. Specific interactions between the amide groups on the polymer chain and the ions were unlikely. Importance of the structure and properties of water in the solution to determine the LCST of the polymer solutions is suggested.},
  creationdate = {2022-02-04T00:00:00},
  doi          = {10.1021/la0001575},
  eprint       = {https://doi.org/10.1021/la0001575},
  file         = {:Maeda2000 - Change in Hydration State during the Coil−Globule Transition of Aqueous Solutions of Poly(N Isopropylacrylamide) As Evidenced by FTIR Spectroscopy.pdf:PDF},
  keywords     = {PNIPAM, FTIR, LCST, hydrogen bond, hydration, ionic strength, salt},
  ranking      = {rank4},
  url          = {https://doi.org/10.1021/la0001575},
}

@Article{Ropp2001,
  author       = {Ropp, J. and Lawrence, C. and Farrar, T. C. and Skinner, J. L.},
  journal      = {Journal of the American Chemical Society},
  title        = {Rotational Motion in Liquid Water Is Anisotropic:  A Nuclear Magnetic Resonance and Molecular Dynamics Simulation Study},
  year         = {2001},
  note         = {PMID: 11506561},
  number       = {33},
  pages        = {8047--8052},
  volume       = {123},
  abstract     = {Experimental NMR measurements of the deuterium and 17O T1 relaxation times in deuterium-enriched liquid water have been performed from 275 to 350 K. These relaxation times can yield rotational correlation times of appropriate molecule-fixed unit vectors if the quadrupole coupling constants and asymmetry parameters are known. We determine the latter from ab initio studies of water clusters and experimental chemical shift measurements. We find that the rotational correlation time for the OD bond vector in D216O varies from 5.8 ps at 275 K to 0.86 ps at 350 K, and that the rotational correlation time for the out-of-plane vector of dilute D217O in D216O varies from 4.4 ps at 275 K to 0.64 ps at 350 K. These results indicate that the rotational motion of water is anisotropic. Molecular dynamics simulations of liquid water are in good agreement with these experiments at the higher temperatures, but the simulation results are considerably faster than experiment at the lower temperatures.},
  creationdate = {2022-02-15T00:00:00},
  doi          = {10.1021/ja010312h},
  eprint       = {https://doi.org/10.1021/ja010312h},
  file         = {:Ropp2001 - Rotational Motion in Liquid Water Is Anisotropic_ a Nuclear Magnetic Resonance and Molecular Dynamics Simulation Study.pdf:PDF},
  keywords     = {NMR, H2O, water, 17O, relaxation, rotational correlation times, simulation},
  url          = {https://doi.org/10.1021/ja010312h},
}

@Article{Roessler1991,
  author       = {Ernst Rössler},
  journal      = {Journal of Non-Crystalline Solids},
  title        = {Experimental results revealing a change of diffusion mechanism above Tg},
  year         = {1991},
  issn         = {0022-3093},
  note         = {Proceedings of the International Discussion Meeting on Relaxations in Complex Systems},
  pages        = {242--247},
  volume       = {131-133},
  abstract     = {Indications are presented which substantiate a change of diffusion mechanism in simple supercooled liquids at a temperature Tc > Tg. (i) Two dynamic regimes are observed by applying a corresponding states analysis of viscosity data. (ii) A check of the Stokes-Einstein relations for NMR correlation times and diffusion coefficients shows a failure below Tc. (iii) The bifurcation of α- and β-processes are observed by NMR and dielectric relaxation occurs near Tc. Applying predictions of mode-coupling theory a temperature-dependent amplitude on the β-processes in connection with a Cole-Cole susceptibility is introduced providing a consistent picture of the NMR and dielectric β-process. Altogether, the crossover is identified at Tc/Tg = 1.18–1.26, which is close to the crossover reported by the anomaly of the Debye-Waller factor.},
  creationdate = {2022-02-17T00:00:00},
  doi          = {https://doi.org/10.1016/0022-3093(91)90310-3},
  file         = {:Roessler1991 - Experimental Results Revealing a Change of Diffusion Mechanism above Tg.pdf:PDF},
  keywords     = {diffusion, stokes-einstein-debye, SED, nmr},
  url          = {https://www.sciencedirect.com/science/article/pii/0022309391903103},
}

@Article{Yoshida2006,
  author       = {Koji Yoshida and Ayuko Kitajo and Toshio Yamaguchi},
  journal      = {Journal of Molecular Liquids},
  title        = {17O NMR relaxation study of dynamics of water molecules in aqueous mixtures of methanol, ethanol, and 1-propanol over a temperature range of 283–403 K},
  year         = {2006},
  issn         = {0167-7322},
  note         = {Complex Liquids},
  number       = {2},
  pages        = {158--163},
  volume       = {125},
  abstract     = {17O NMR spin-lattice relaxation time (T1) of water molecules was measured in aqueous mixtures of methanol, ethanol, and 1-propanol over a temperature range of 283–403 K. At temperatures below ∼303 K, the relaxation rate R1 (=1/T1) in the aqueous mixtures of methanol and ethanol sharply increased with increasing alcohol concentration up to characteristic alcohol mole fractions xMe and xEt of ∼0.3 and ∼0.2, respectively, showing that the rotation of water molecules is gradually retarded in the water-rich region due to hydrophobic hydration. With increasing xMe and xEt up to ∼0.7 the R1 values slightly decreased and/or remained almost constant, and then increased again when xEt>0.7. With increasing temperature, the degree of the retardation in the water-rich region became insignificant, and the R1 values monotonously increased with increasing alcohol concentration. The relaxation rates in the 1-propanol–water mixtures monotonously increased with increasing alcohol content at all temperatures investigated. These results are discussed in view of microscopic structure of the alcohol–water mixtures previously obtained from X-ray diffraction measurements.},
  creationdate = {2022-02-17T00:00:00},
  doi          = {https://doi.org/10.1016/j.molliq.2005.11.009},
  keywords     = {17O NMR, spin-lattice relaxation, T1, Alcohol–water mixture, Rotational motion, Liquid structure, ethanol, qcc, quadrupole, katharina, michael},
  ranking      = {rank5},
  url          = {https://www.sciencedirect.com/science/article/pii/S0167732205001625},
}

@Article{VonGoldammer1970,
  author       = {Von Goldammer, E. and Hertz, H. G.},
  journal      = {The Journal of Physical Chemistry},
  title        = {Molecular motion and structure of aqueous mixtures with nonelectrolytes as studied by nuclear magnetic relaxation methods},
  year         = {1970},
  number       = {21},
  pages        = {3734--3755},
  volume       = {74},
  creationdate = {2022-02-17T00:00:00},
  doi          = {10.1021/j100715a008},
  eprint       = {https://doi.org/10.1021/j100715a008},
  file         = {:VonGoldammer1970 - Molecular Motion and Structure of Aqueous Mixtures with Nonelectrolytes As Studied by Nuclear Magnetic Relaxation Methods.pdf:PDF},
  keywords     = {aqueous ethanol, nmr, relaxation},
  url          = {https://doi.org/10.1021/j100715a008},
}

@Article{Harris1998,
  author       = {Harris, Kenneth R. and J. Newitt, Paula and J. Derlacki, Z.},
  journal      = {J. Chem. Soc.{,} Faraday Trans.},
  title        = {Alcohol tracer diffusion, density, NMR and FTIR studies of aqueous ethanol and 2,2,2-trifluoroethanol solutions at 25$^\circ$C},
  year         = {1998},
  pages        = {1963--1970},
  volume       = {94},
  abstract     = {New measurements have been made of the tracer diffusion coefficients of ethanol and 2{,}2{,}2-trifluoroethanol (TFE) in aqueous solution at 25^\circC across the whole composition range. The limiting values at infinite dilution of these alcohols and the series of primary alcohols from methanol to heptanol{,} the isomeric propanols and butanols and 2-butoxyethanol are found to vary as the alcohol limiting partial molar volume raised to the power -0.56. The self-diffusion coefficient of water lies on the same curve{,} suggesting that the rate-determining step for diffusion is the same for these alcohols at infinite dilution as it is for water. H{,} F and C chemical shift and density measurements have been made and apparent molar volumes obtained from the latter. The composition dependence of the ν bending vibration band of water in water–TFE at 1640 cm has been examined. The chemical shift and water IR measurements show that water–TFE behaves like other aqueous halogenoethanol solutions with water and hydroxyl proton shifts moving to higher field with increasing alcohol concentration. The results are consistent with thermodynamic data indicating some degree of microheterogeneity in the TFE-rich region of this system and a strengthening of water–TFE H-bonding on dilution of TFE. This is the opposite of what is observed for water–ethanol. We were unable to find any evidence from the diffusion data for the formation of water adducts to ethanol chains at high ethanol concentration in water–ethanol mixtures as has been suggested in the literature.},
  creationdate = {2022-02-18T00:00:00},
  doi          = {10.1039/A802567C},
  file         = {:R.Harris1998 - Alcohol Tracer Diffusion, Density, NMR and FTIR Studies of Aqueous Ethanol and 2,2,2 Trifluoroethanol Solutions at 25°C.pdf:PDF},
  issue        = {14},
  keywords     = {aqueous ethanol, diffusion, tracer, nmr, FTIR, TFE},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/A802567C},
}

@Article{Price2003,
  author       = {Price, William S. and Ide, Hiroyuki and Arata, Yoji},
  journal      = {The Journal of Physical Chemistry A},
  title        = {Solution Dynamics in Aqueous Monohydric Alcohol Systems},
  year         = {2003},
  number       = {24},
  pages        = {4784--4789},
  volume       = {107},
  abstract     = {The associative behavior of aqueous methanol, ethanol, and tert-butyl alcohol solutions at mole fractions ranging from 0 to 1 at 273, 283, and 298 K was examined using PGSE NMR measurements of the self-diffusion coefficients of the alkyl group, water and, depending on the exchange rate, hydroxyl protons. The results show that tert-butyl alcohol has the greatest ability to stabilize water through hydrophobic hydration than methanol or ethanol due to the more ideal fit of the tert-butyl group to the structure of water. However, at higher concentrations tert-butyl alcohol is the least able to cohesively interact with water through hydrogen bonding. The results provide compelling evidence for alcohol self-association (methanol < ethanol < tert-butyl alcohol) in very dilute solution. The alcohol molecules can be likened to very short lipid molecules undergoing complicated solution interactions due to their amphiphilic nature.},
  comment      = {Daten teilweise überinterpretiert. Auswertung stützt sich auf Trennung der Komponenten durch chemische Verschiebung, es wird aber kein Spektrum (chem. shift im PFG) gezeigt.},
  creationdate = {2022-02-18T00:00:00},
  doi          = {10.1021/jp027257z},
  eprint       = {https://doi.org/10.1021/jp027257z},
  file         = {:Price2003 - Solution Dynamics in Aqueous Monohydric Alcohol Systems.pdf:PDF},
  keywords     = {aqueous alcohol, aqueous methanol, aqueous ethanol, nmr, pfg, diffusion, katharina, michael},
  ranking      = {rank4},
  readstatus   = {skimmed},
  url          = {https://doi.org/10.1021/jp027257z},
}

@Article{Sacco1997,
  author       = {Sacco, Antonio and Holz, Manfred},
  journal      = {J. Chem. Soc., Faraday Trans.},
  title        = {NMR studies on hydrophobic interactions in solution Part 2.—Temperature and urea effect on the self-association of ethanol in water},
  year         = {1997},
  pages        = {1101--1104},
  volume       = {93},
  abstract     = {The self-association of ethanol has been investigated in binary aqueous mixtures and in mixtures containing urea as a third component by the application of NMR. We obtain the so-called association parameter A22 by means of the measurement of intermolecular 1H–1H dipole–dipole relaxation rates and of self-diffusion coefficients of the ethanol molecules. The composition dependence of A22 shows a surprisingly high self-association of ethanol. This result is in agreement with that found recently from other authors using different experimental methods. Addition of urea further increases the self-association of ethanol. For the first time we measure the A22 parameter as a function of temperature{,} ranging from 10 to 40°C. We observe that the association of ethanol increases with increasing temperature in agreement with theoretical predictions. The structure breaking effect of urea obviously acts on the hydrophobic association in the same way as an increase of temperature.},
  creationdate = {2022-02-18T00:00:00},
  doi          = {10.1039/A605867A},
  file         = {:Sacco1997 - NMR Studies on Hydrophobic Interactions in Solution Part 2.—Temperature and Urea Effect on the Self Association of Ethanol in Water.pdf:PDF},
  issue        = {6},
  keywords     = {nmr, aqueous ethanol, diffusion, relaxation, association},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/A605867A},
}

@Article{Kubo1954,
  author       = {Kubo, Ryogo and Tomita, Kazuhisa},
  journal      = {Journal of the Physical Society of Japan},
  title        = {A General Theory of Magnetic Resonance Absorption},
  year         = {1954},
  number       = {6},
  pages        = {888--919},
  volume       = {9},
  creationdate = {2022-02-22T00:00:00},
  doi          = {10.1143/JPSJ.9.888},
  eprint       = {https://doi.org/10.1143/JPSJ.9.888},
  file         = {:Kubo1954 - A General Theory of Magnetic Resonance Absorption.pdf:PDF},
  keywords     = {nmr, theory, T1},
  printed      = {printed},
  url          = {https://doi.org/10.1143/JPSJ.9.888},
}

@PhdThesis{AdjeiAcheamfour2016,
  author       = {Mischa Adjei-Acheamfour},
  school       = {Technische Universität Dortmund},
  title        = {17O-Zentrallinien-NMR-Untersuchungen der ultralangsamen Wassermoleküldynamik in Tetrahydrofuran-Clathrat-Hydrat und hexagonalem Eis},
  year         = {2016},
  month        = may,
  type         = {phdthesis},
  creationdate = {2022-02-22T00:00:00},
  file         = {:AdjeiAcheamfour2016 - 17O Zentrallinien NMR Untersuchungen Der Ultralangsamen Wassermoleküldynamik in Tetrahydrofuran Clathrat Hydrat Und Hexagonalem Eis.pdf:PDF},
  keywords     = {nmr, 17O, dissertation},
  url          = {https://eldorado.tu-dortmund.de/handle/2003/35143},
}

@Article{Ludwig1995,
  author       = {Ludwig, R. and Weinhold, F. and Farrar, T. C.},
  journal      = {The Journal of Chemical Physics},
  title        = {Experimental and theoretical determination of the temperature dependence of deuteron and oxygen quadrupole coupling constants of liquid water},
  year         = {1995},
  number       = {16},
  pages        = {6941--6950},
  volume       = {103},
  creationdate = {2022-02-22T00:00:00},
  doi          = {10.1063/1.470371},
  eprint       = {https://doi.org/10.1063/1.470371},
  file         = {:Ludwig1995 - Experimental and Theoretical Determination of the Temperature Dependence of Deuteron and Oxygen Quadrupole Coupling Constants of Liquid Water.pdf:PDF},
  keywords     = {nmr, 17O, water, 2h, simulation, quadrupole coupling constant},
  ranking      = {rank3},
  readstatus   = {read},
  url          = {https://doi.org/10.1063/1.470371},
}

@InProceedings{Urayama2009,
  author       = {Urayama K. and Murata N. and Nosaka S. and Kojima M. and Takigawa T.},
  booktitle    = {Gels: Structures, Properties, and Functions},
  title        = {Revisit to Swelling Kinetics of Gels},
  year         = {2009},
  address      = {Berlin, Heidelberg},
  editor       = {Tokita, Masayuki and Nishinari, Katsuyoshi},
  publisher    = {Springer Berlin Heidelberg},
  abstract     = {The swelling and shrinking dynamics of the gels with a wide variety of aspect ratios is experimentally investigated. As the aspect ratio becomes sufficiently larger or smaller than unity, the swelling kinetics asymptotically approaches that of infinitely long cylinders or infinitely large disks, respectively. The characteristic times of the infinitely long cylinders and infinitely large disks are compared to the predictions of the classical Li-Tanaka model and its modified models.},
  creationdate = {2022-02-22T00:00:00},
  doi          = {https://doi.org/10.1007/978-3-642-00865-8_15},
  file         = {:Urayama2009 - Revisit to Swelling Kinetics of Gels.pdf:PDF},
  keywords     = {gel, kinetics, PNIPAM, BIS},
}

@Article{Gerothanassis1996,
  author       = {Gerothanassis, I. P. and Tsanaktsidis, C. G.},
  journal      = {Concepts in Magnetic Resonance},
  title        = {Nuclear electric quadrupole relaxation},
  year         = {1996},
  number       = {1},
  pages        = {63--74},
  volume       = {8},
  abstract     = {Nuclei with spin quantum number 1 ≥ 1 have an asymmetric charge distribution and thus possess an electric quadrupole moment eQ. The interaction of the electric quadrupole moment with the electric field gradient of the bonding electrons provides the dominant relaxation mechanism of the quadrupolar nuclei, which are approximately three-quarters of the naturally occurring magnetic nuclei. This review summarizes the basic principles of nuclear electric quadrupolar relaxation. Particular emphasis is given to the effects of the magnitude of the quadrupole moment, the spin quantum number, the linewidth factor, the electric field gradient (which originates from charge density variations of the bonding electrons near the nucleus), and the effective correlation time for molecular tumbling. Relaxation outside the extreme narrowing condition for integer and half-integer spins is examined and experimental examples are provided. Modulation of the electric field gradient due to time-dependent intermolecular interactions and chemical exchange are discussed briefly, together with the effects of relaxation mechanisms other than quadrupolar. © 1996 John Wiley \& Sons, Inc.},
  creationdate = {2022-02-22T00:00:00},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/%28SICI%291099-0534%281996%298%3A1%3C63%3A%3AAID-CMR5%3E3.0.CO%3B2-N},
  file         = {:Gerothanassis1996 - Nuclear Electric Quadrupole Relaxation.pdf:PDF},
  keywords     = {nmr, quadrupole relaxation},
  printed      = {printed},
  ranking      = {rank5},
  readstatus   = {read},
  url          = {https://doi.org/10.1002/(SICI)1099-0534(1996)8:1<63::AID-CMR5>3.0.CO;2-N},
}

@Book{Job2021,
  author       = {Georg Job and Regina R{\"u}ffler},
  publisher    = {Springer Spektrum, Wiesbaden},
  title        = {Physikalische Chemie - Eine Einf{\"u}hrung nach neuem Konzept mit zahlreichen Experimenten},
  year         = {2021},
  edition      = {Second},
  isbn         = {978-3-658-32936-5},
  series       = {Studienbücher Chemie},
  creationdate = {2022-03-01T00:00:00},
  file         = {:Job2021 - Physikalische Chemie Eine Einführung Nach Neuem Konzept Mit Zahlreichen Experimenten.pdf:PDF},
  keywords     = {book, chemistry},
  url          = {https://doi.org/10.1007/978-3-658-32936-5},
}

@Book{Seiffert2020,
  editor       = {Sebastian Seiffert and Claudia Kummerl{\"o}we and Norbert Vennemann},
  publisher    = {Springer Spektrum, Berlin, Heidelberg},
  title        = {Makromolekulare Chemie - Ein Lehrbuch für Chemiker, Physiker, Materialwissenschaftler und Verfahrenstechniker},
  year         = {2020},
  edition      = {Six},
  isbn         = {978-3-662-61109-8},
  creationdate = {2022-03-01T00:00:00},
  file         = {:Seiffert2020 - Makromolekulare Chemie Ein Lehrbuch Für Chemiker, Physiker, Materialwissenschaftler Und Verfahrenstechniker.pdf:PDF},
  keywords     = {book, chemistry},
  url          = {https://doi.org/10.1007/978-3-662-61109-8},
}

@Article{Hore2013,
  author       = {Hore, Michael J. A. and Hammouda, Boualem and Li, Yuyan and Cheng, He},
  journal      = {Macromolecules},
  title        = {Co-Nonsolvency of Poly(n-isopropylacrylamide) in Deuterated Water/Ethanol Mixtures},
  year         = {2013},
  number       = {19},
  pages        = {7894--7901},
  volume       = {46},
  abstract     = {Small-angle neutron scattering was used to investigate poly(N-isopropylacrylamide) (PNIPAM) polymer solutions in d-water/d-ethanol mixtures. A wide poor-solvent region was observed for mixtures near 60\% d-water/40\% d-ethanol mixture. Spinodal lines were determined, permitting a mapping of the mixing/demixing regions of the phase diagram which comprises two main branches: the left branch (with mostly d-ethanol) where phase separation occurs upon cooling (UCST) and the right branch (with mostly d-water) where phase separation occurs upon heating (LCST). The ternary random phase approximation model was used to analyze SANS data. Three Flory–Huggins interaction parameters (PNIPAM/d-water, PNIPAM/d-ethanol and d-water/d-ethanol) were obtained. These display the reassuring 1/T behavior but show strong dependence on d-water/d-ethanol fraction. The conformation of polymer chains was determined by monitoring of the radius of gyration. Chains tend to swell with increasing temperature except close to the boundary of the left branch of the phase diagram (40\% d-water) where they are observed to shrink.},
  comment      = {Empirical models, extrapolations and lots of guesswork. However, cited by 70 other articles!},
  creationdate = {2022-03-12T00:00:00},
  doi          = {10.1021/ma401665h},
  eprint       = {https://doi.org/10.1021/ma401665h},
  file         = {:Hore2013 - Co Nonsolvency of Poly(n Isopropylacrylamide) in Deuterated Water_Ethanol Mixtures.pdf:PDF},
  keywords     = {PNIPAM,cononsolvency,SANS,UCST,LCST,phase diagram,aqueous ethanol,flory-huggins,radius of gyration,aqueous alcohol,ethanol},
  ranking      = {rank2},
  url          = {https://doi.org/10.1021/ma401665h},
}

@Article{Wang2014,
  author       = {Wang, Mi and Gao, Yanfeng and Cao, Chuanxiang and Chen, Kaimin and Wen, Yicun and Fang, Dingye and Li, Li and Guo, Xuhong},
  journal      = {Industrial \& Engineering Chemistry Research},
  title        = {Binary Solvent Colloids of Thermosensitive Poly(N-isopropylacrylamide) Microgel for Smart Windows},
  year         = {2014},
  number       = {48},
  pages        = {18462--18472},
  volume       = {53},
  abstract     = {Thermosensitive poly(N-isopropylacrylamide) (PNIPAAm) microgel colloids were prepared by using water and high-boiling alcohol as binary solvent. Their thermosensitive behavior and solar modulation ability were studied by differential scanning calorimetery, ultraviolet–visible–near-infrared spectrophotometery, dynamic light scattering, and rheology. Effects of alcohol content and cross-linker dose on their microstructures and optical properties were investigated. A model house was constructed to test their energy-saving performance in smart windows. It was found that the solar modulation ability of PNIPAAm microgel colloids decreased with increasing N,N′-methylenebis(acrylamide) (BIS) dose or alcohol content. Compared to glycol, glycerol showed better compatibility with PNIPAAm hydrogels, inducing less deterioration of the solar modulation ability. With 0.1 wt \% (of NIPA) BIS, when glycerol was added as a cosolvent, the prepared PNIPAAm microgel colloids exhibited spherical morphology, controllable LCST, short response time, suitable viscosity, low freezing point, restrained evaporation rate, and excellent energy-saving performance, which makes them much better candidates for application in smart windows than those using a single solvent.},
  creationdate = {2022-03-14T00:00:00},
  doi          = {10.1021/ie502828b},
  eprint       = {https://doi.org/10.1021/ie502828b},
  file         = {:Wang2014 - Binary Solvent Colloids of Thermosensitive Poly(N Isopropylacrylamide) Microgel for Smart Windows.pdf:PDF},
  keywords     = {pnipam, lcst, cononsolvency, dsc, dls, rheology, microgel, application-focused, application focused},
  url          = {https://doi.org/10.1021/ie502828b},
}

@Article{Wensink2003,
  author       = {Wensink, Erik J. W. and Hoffmann, Alex C. and van Maaren, Paul J. and van der Spoel, David},
  journal      = {The Journal of Chemical Physics},
  title        = {Dynamic properties of water/alcohol mixtures studied by computer simulation},
  year         = {2003},
  number       = {14},
  pages        = {7308--7317},
  volume       = {119},
  creationdate = {2022-03-14T00:00:00},
  doi          = {10.1063/1.1607918},
  eprint       = {https://doi.org/10.1063/1.1607918},
  file         = {:Wensink2003 - Dynamic Properties of Water_alcohol Mixtures Studied by Computer Simulation.pdf:PDF},
  keywords     = {aqueous ethanol, simulation, hydrodynamic radius, rotational correlation times, diffusion, cononsolvency},
  url          = {https://doi.org/10.1063/1.1607918},
}

@Book{Solyom2007,
  author       = {Solyom, Jeno},
  publisher    = {Springer Berlin Heidelberg},
  title        = {Fundamentals of the Physics of Solids - Structure and Dynamics},
  year         = {2007},
  edition      = {First},
  isbn         = {978-3-540-72599-2},
  volume       = {1},
  creationdate = {2022-03-29T00:00:00},
  file         = {:Solyom2007 - Fundamentals of the Physics of Solids.pdf:PDF},
  keywords     = {book},
}

@Book{Solyom2009,
  author       = {Solyom, Jeno},
  publisher    = {Springer Berlin Heidelberg},
  title        = {Fundamentals of the Physics of Solids - Electronic Properties},
  year         = {2009},
  edition      = {First},
  isbn         = {978-3-540-85315-2},
  volume       = {2},
  creationdate = {2022-03-29T00:00:00},
  file         = {:Solyom2009 - Fundamentals of the Physics of Solids.pdf:PDF},
  keywords     = {book},
}

@Book{Solyom2010,
  author       = {Jeno Solyom},
  publisher    = {Springer Berlin Heidelberg},
  title        = {Fundamentals of the Physics of Solids - Normal, Broken-Symmetry, and Correlated Systems},
  year         = {2010},
  isbn         = {978-3-642-04517-2},
  volume       = {3},
  creationdate = {2022-03-29T00:00:00},
  doi          = {10.1007/978-3-642-04518-9},
  file         = {:Solyom2010 - Fundamentals of the Physics of Solids Normal, Broken Symmetry, and Correlated Systems.pdf:PDF},
  keywords     = {book},
}

@Book{Price2009,
  author       = {Price, William S.},
  publisher    = {Cambridge University Press},
  title        = {NMR Studies of Translational Motion: Principles and Applications},
  year         = {2009},
  series       = {Cambridge Molecular Science},
  collection   = {Cambridge Molecular Science},
  creationdate = {2022-03-29T00:00:00},
  doi          = {10.1017/CBO9780511770487},
  file         = {:Price2009 - NMR Studies of Translational Motion_ Principles and Applications.pdf:PDF;:02.0_pp_v_viii_Contents.pdf:PDF;:03.0_pp_ix_xiii_Preface.pdf:PDF;:04.0_pp_xiv_xiv_Acknowledgements.pdf:PDF;:05.0_pp_xv_xxii_Abbreviations.pdf:PDF;:06.0_pp_1_68_Diffusion_and_its_measurement.pdf:PDF;:07.0_pp_69_119_Theory_of_NMR_diffusion_and_flow_measurements.pdf:PDF;:08.0_pp_120_146_PGSE_measurements_in_simple_porous_systems.pdf:PDF;:09.0_pp_147_184_PGSE_measurements_in_complex_and_exchanging_systems.pdf:PDF;:10.0_pp_185_197_PGSE_hardware.pdf:PDF;:11.0_pp_198_220_Setup_and_analysis_of_PGSE_experiments.pdf:PDF;:12.0_pp_221_255_PGSE_hardware_and_sample_problems.pdf:PDF;:13.0_pp_256_295_Specialised_PGSE_and_related_techniques.pdf:PDF;:14.0_pp_296_307_NMR_imaging_studies_of_translational_motion.pdf:PDF;:15.0_pp_308_312_B1_gradient_methods.pdf:PDF;:16.0_pp_313_368_Applications.pdf:PDF;:17.0_pp_369_376_Appendix.pdf:PDF;:18.0_pp_377_393_Index.pdf:PDF},
  keywords     = {book,NMR},
  place        = {Cambridge},
}

@InCollection{Canet2018,
  author       = {Canet, Daniel},
  booktitle    = {Cross-relaxation and Cross-correlation Parameters in NMR: Molecular Approaches},
  publisher    = {The Royal Society of Chemistry},
  title        = {Chapter 1 Introduction to Nuclear Spin Cross-relaxation and Cross-correlation Phenomena in Liquids},
  year         = {2018},
  isbn         = {978-1-84973-913-9},
  pages        = {1--60},
  abstract     = {This chapter deals with nuclear spin relaxation phenomena. It is{,} however{,} limited to nuclei of spin 1/2. It starts with a semi-classical survey of the relaxation mechanisms and the so-called ‘spectral densities’ in terms of which will be expressed for all relaxation parameters. To go further{,} the fundamentals of spin 1/2 quantum mechanics are presented with an emphasis on the so-called ‘product-operators’. Within the Bloch–Wangsness–Redfield theory{,} it is explained how the various spin states can be coupled by relaxation parameters{,} this coupling terms being arranged in the so-called ‘relaxation matrix’. The relaxation parameters include the classical relaxation rates (inverse of T1 and T2) and the cross-relaxation and cross-correlation rates. An original method{,} based on product-operators and spherical harmonics{,} leads{,} in a straightforward manner{,} to the calculation of the elements of the relaxation matrix.},
  creationdate = {2022-03-30T00:00:00},
  doi          = {10.1039/9781782622475-00001},
  file         = {:Canet2018 - Chapter 1 Introduction to Nuclear Spin Cross Relaxation and Cross Correlation Phenomena in Liquids.pdf:PDF;:CrossRelaxationAndCrossCorrelationParametersInNMR-MolecularApproaches_Index_CanetEtAl_RSC2018.pdf:PDF;:CrossCorrelationInBiomolecules_FerrageEtAl_RSC2018.pdf:PDF;:HeteronuclearCrossRelaxation_Ancian_RSC2018.pdf:PDF;:HomonuclearCrossRelaxationAndCrossCorrelationInSmallMoleculesAndInSoftMatter_Dorai_RSC2018.pdf:PDF},
  keywords     = {nmr, theory, relaxation, cross-relaxation, cross-correlation},
  ranking      = {rank5},
  readstatus   = {skimmed},
  url          = {http://dx.doi.org/10.1039/9781782622475-00001},
}

@InCollection{Dorai2018,
  author       = {Dorai, Kavita},
  booktitle    = {Cross-relaxation and Cross-correlation Parameters in NMR: Molecular Approaches},
  publisher    = {The Royal Society of Chemistry},
  title        = {Chapter 2 Homonuclear Cross-relaxation and Cross-correlation in Small Molecules and in Soft Matter},
  year         = {2018},
  isbn         = {978-1-84973-913-9},
  pages        = {61--165},
  abstract     = {This chapter describes spin relaxation experiments on small or medium-sized molecules or in soft matter{,} with a handy overview of the possible experimental schemes{,} along with their advantages and limitations. The chapter begins with a description of several one-dimensional (1D) and two-dimensional (2D) nuclear Overhauser effect (NOE) and rotating-frame Overhauser enhancement (ROE) cross-relaxation sequences and gives examples of several interesting applications. Cross-correlation experiments are then described{,} starting with 1D and 2D longitudinal and transverse cross-correlations{,} experimental dynamic frequency shifts{,} cross-correlations in paramagnetic and quadrupolar systems{,} underlying motional models and concluding with a section on the wealth of information about structure{,} conformation and dynamics that can be obtained using these experiments. A highlight of this chapter is the organization of the cross-correlated pulse sequences according to the type of cross-correlations being explored. This helps the reader to explore connections amongst these related experiments{,} from a phenomenological perspective. This chapter will interest researchers who are looking for a broad-based overview of experimental research in the area of NMR cross-relaxation and cross-correlation. NMR experimentalists who want to design the optimal cross-relaxation or cross-correlation pulse sequences{,} will also find this chapter useful.},
  creationdate = {2022-04-01T00:00:00},
  doi          = {10.1039/9781782622475-00061},
  file         = {:Dorai2018 - Chapter 2 Homonuclear Cross Relaxation and Cross Correlation in Small Molecules and in Soft Matter.pdf:PDF},
  url          = {http://dx.doi.org/10.1039/9781782622475-00061},
}

@InCollection{Ancian2018,
  author       = {Ancian, Bernard},
  booktitle    = {Cross-relaxation and Cross-correlation Parameters in NMR: Molecular Approaches},
  publisher    = {The Royal Society of Chemistry},
  title        = {Chapter 3 Heteronuclear Cross-relaxation},
  year         = {2018},
  isbn         = {978-1-84973-913-9},
  pages        = {166--238},
  abstract     = {Heteronuclear cross-relaxation is the dynamical process by which two distinct nuclear spins interact through space by a dipole–dipole mechanism{,} modulated by the re-orientational correlation time of their connection vector. Because of its inverse power six with the nuclei separation{,} it is a short distance effect (generally no more than 3 Å). In the intramolecular field{,} it appears as a very useful auxiliary means for structural analysis. In intermolecular effects{,} it is one of the most important keys for probing close approaches in solute–solvent interactions. A great emphasis is given here in this topic of solution chemistry with numerous examples in general chemistry (ionic liquids{,} ion pairs{,} aggregates) and in biology (hydration of biomolecules). In addition{,} all the relevant sequences used to measure this interaction are examined{,} as per their advantages and disadvantages. Finally{,} a theoretical insight in intermolecular effects is discussed{,} as per the so-called ‘force-free hard sphere diffusion model’ to extract both the right dependence with the relative diffusion of the species in solution and their separation distance to eradicate some wrong common misinterpretations.},
  creationdate = {2022-04-01T00:00:00},
  doi          = {10.1039/9781782622475-00166},
  file         = {:Ancian2018 - Chapter 3 Heteronuclear Cross Relaxation.pdf:PDF},
  url          = {http://dx.doi.org/10.1039/9781782622475-00166},
}

@InCollection{Ferrage2018,
  author       = {Ferrage, Fabien and Dorai, Kavita},
  booktitle    = {Cross-relaxation and Cross-correlation Parameters in NMR: Molecular Approaches},
  publisher    = {The Royal Society of Chemistry},
  title        = {Chapter 4 Cross-correlation in Biomolecules},
  year         = {2018},
  isbn         = {978-1-84973-913-9},
  pages        = {239--315},
  abstract     = {This chapter focuses on the methods used to quantitatively measure auto- and cross-correlated cross-relaxation relaxation rates in biomolecules and interpret these rates in terms of structure and dynamics. A theoretical description of average Liouvillian theory is presented in the beginning{,} to set the stage for understanding various experiments used to measure cross-relaxation in biomolecules. A series of multidimensional experiments to measure CSA–dipole{,} dipole–dipole{,} and CSA–CSA cross-correlations in large biomolecules such as proteins are discussed. Cross-correlated nuclear spin relaxation rates provide rich information about slow correlated motions as well as fast and slow internal motions in proteins. The next part of this chapter deals with motional models used to quantify cross-correlations. The model-free formalism and correlated internal motions are described in detail. A highlight of this chapter is an overview of the different cross-correlation parameters that can be obtained from dynamics studies. Several examples of applications of measurements of cross-correlation rates are then described{,} with special attention to proteins{,} nucleic acids and ligand-binding studies. The chapter concludes with a description of the famous TROSY experiments in biomolecules{,} which are based on CSA–dipole and dipole–dipole cross-correlations.},
  creationdate = {2022-04-01T00:00:00},
  doi          = {10.1039/9781782622475-00239},
  file         = {:Ferrage2018 - Chapter 4 Cross Correlation in Biomolecules.pdf:PDF},
  url          = {http://dx.doi.org/10.1039/9781782622475-00239},
}

@Article{Bodenhausen1980,
  author       = {Geoffrey Bodenhausen},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {Multiple-quantum NMR},
  year         = {1980},
  issn         = {0079-6565},
  number       = {3},
  pages        = {137--173},
  volume       = {14},
  creationdate = {2022-04-01T00:00:00},
  doi          = {https://doi.org/10.1016/0079-6565(80)80007-0},
  file         = {:Bodenhausen1980 - Multiple Quantum NMR.pdf:PDF},
  keywords     = {nmr, theory},
  url          = {https://www.sciencedirect.com/science/article/pii/0079656580800070},
}

@Article{Nilsson2012,
  author       = {Nilsson, Tomas and Halle, Bertil},
  journal      = {The Journal of Chemical Physics},
  title        = {Nuclear magnetic relaxation induced by exchange-mediated orientational randomization: Longitudinal relaxation dispersion for spin I = 1},
  year         = {2012},
  number       = {5},
  pages        = {054503},
  volume       = {137},
  creationdate = {2022-04-01T00:00:00},
  doi          = {10.1063/1.4739297},
  eprint       = {https://doi.org/10.1063/1.4739297},
  file         = {:Nilsson2012 - Nuclear Magnetic Relaxation Induced by Exchange Mediated Orientational Randomization_ Longitudinal Relaxation Dispersion for Spin I = 1.pdf:PDF},
  keywords     = {nmr, theory, exchange, relaxation},
  url          = {https://doi.org/10.1063/1.4739297},
}

@Article{AdjeiAcheamfour2014,
  author       = {Mischa Adjei-Acheamfour and Roland B{\"o}hmer},
  journal      = {Journal of Magnetic Resonance},
  title        = {Second-order quadrupole interaction based detection of ultra-slow motions: Tensor operator framework for central-transition spectroscopy and the dynamics in hexagonal ice as an experimental example},
  year         = {2014},
  issn         = {1090-7807},
  pages        = {141--149},
  volume       = {249},
  abstract     = {The second-order quadrupolar broadening of the central transition of nuclear probes with half-integer spins I is demonstrated to be useful to detect ultraslow molecular motions. On the basis of density matrix calculations explicit expressions are derived for quadrupolarly modulated sin–sin and cos–cos signals of selectively excited nuclei with I=3/2, 5/2, 7/2, and 9/2. These correlation functions are suitable for implementation in two-dimensional exchange spectroscopy as well as for stimulated-echo experiments. As an application, 17O measurements of the reorientational correlation function of water molecules in hexagonal ice are presented.},
  creationdate = {2022-04-04T00:00:00},
  doi          = {https://doi.org/10.1016/j.jmr.2014.09.019},
  file         = {:AdjeiAcheamfour2014 - Second Order Quadrupole Interaction Based Detection of Ultra Slow Motions_ Tensor Operator Framework for Central Transition Spectroscopy and the Dynamics in Hexagonal Ice As an Experimental Example.pdf:PDF},
  keywords     = {Central line, Second-order quadrupole coupling, Stimulated-echo, Oxygen-17, nmr, phase cycle, 5/2},
  ranking      = {rank5},
  url          = {https://www.sciencedirect.com/science/article/pii/S109078071400264X},
}

@InBook{Man2011,
  author       = {Man, Pascal P.},
  publisher    = {John Wiley \& Sons, Ltd},
  title        = {Quadrupolar Interactions},
  year         = {2011},
  isbn         = {9780470034590},
  abstract     = {Most nuclei in the Periodic Table are submitted to the quadrupolar interaction. Their NMR powder patterns allow us to determine their local environment symmetry. The analytical expressions of the first- and second-order of this interaction are provided. The second-order quadrupole shifts for static solids and solids rotating at the magic angle with high speed are deduced; conventions such as the asymmetry parameter and the Euler angles used in the literature are presented and discussed. The critical points of the central-line powder pattern and simulated powder patterns are provided, which allows the determination of quadrupole parameters from experimental spectra.},
  booktitle    = {eMagRes},
  creationdate = {2022-04-04T00:00:00},
  doi          = {https://doi.org/10.1002/9780470034590.emrstm0429.pub2},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/9780470034590.emrstm0429.pub2},
  file         = {:Man2011 - Quadrupolar Interactions.pdf:PDF},
  keywords     = {nmr, Crystal, MAS, powder, quadrupolar, rotation, spectrum, spherical, static, tensor, Wigner, oxygen 17O},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/9780470034590.emrstm0429.pub2},
}

@InBook{Werbelow2011,
  author       = {Werbelow, Lawrence G.},
  publisher    = {John Wiley \& Sons, Ltd},
  title        = {Relaxation Theory for Quadrupolar Nuclei},
  year         = {2011},
  isbn         = {9780470034590},
  abstract     = {Given the typical interaction strength between the nuclear electric quadrupole moment and non-vanishing local, extranuclear field gradients, the electric quadrupole relaxation mechanism is usually dominant for all spin-one or greater nuclei. In general, various quadrupolar relaxation rates can be written in simple, closed form, and features associated with relaxation-induced polarization and coherence transfer are quenched. Such expressions are summarized in the first few sections of this article. Also discussed are consequences associated with the failure of the extreme narrowing approximation that results in multiexponential relaxation. The quadrupolar interaction is traceless and in the motionally narrowed regime, averages to zero. Thus, only line broadening and not line positions are affected. However, the Zeeman and quadrupolar interactions do not commute and second-order (and higher order) corrections may become important. Thus, a discussion of the dynamic frequency shift in quadrupolar spin systems is provided. Finally, it is recognized that efficiently relaxed quadrupolar nuclei influence scalar-coupled spin one-half nuclei. Features associated with this phenomenon are developed in the last section of this article.},
  booktitle    = {eMagRes},
  creationdate = {2022-04-04T00:00:00},
  doi          = {https://doi.org/10.1002/9780470034590.emrstm0464.pub2},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/9780470034590.emrstm0464.pub2},
  file         = {:Werbelow2011 - Relaxation Theory for Quadrupolar Nuclei.pdf:PDF},
  keywords     = {nuclear spin relaxation, quadrupolar relaxation, adiabatic linewidth parameter, spectral density functions, multispin order, dynamic frequency shift, nmr, oxygen 17O},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/9780470034590.emrstm0464.pub2},
}

@Article{Chung1992,
  author       = {Chun-Wa Chung and Stephen Wimperis},
  journal      = {Molecular Physics},
  title        = {Measurement of spin-5/2 relaxation in biological and macromolecular systems using multiple-quantum NMR techniques},
  year         = {1992},
  number       = {1},
  pages        = {47--81},
  volume       = {76},
  abstract     = {Filtration of the NMR signal through a state of three- or five-quantum coherence is shown to facilitate quadrupolar relaxation studies of spin-5/2 nuclei in biological and macromolecular systems. The results of these multiple-quantum filtration experiments are analysed by directly fitting correlation times and quadrupolar coupling constants to the experimentally observed trilorentzian lineshapes or triexponential decays. Other experimental techniques are used to measure the exponential relaxation of four- and five-quantum coherences and provide an alternative and straightforward method of obtaining spin-5/2 motional parameters outside the extreme-narrowing limit. Irreducible spherical tensor operators are used to describe both the spin-5/2 quadrupolar relaxation and the multiple-quantum NMR techniques. Results are drawn from 25Mg NMR of magnesium ions binding to a large protein (bovine albumin) in aqueous solution, although the experimental techniques and fitting procedures are applicable to other spin-5/2 nuclei, such as 17O and 27Al.},
  creationdate = {2022-04-04T00:00:00},
  doi          = {10.1080/00268979200101161},
  eprint       = {https://doi.org/10.1080/00268979200101161},
  file         = {:Chung1992 - Measurement of Spin 5_2 Relaxation in Biological and Macromolecular Systems Using Multiple Quantum NMR Techniques.pdf:PDF},
  keywords     = {nmr, quadrupole, relaxation, oxygen 17O, theory, irreducible spherical tensor operators, spin 5/2},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/00268979200101161},
}

@Article{Boehmer2014,
  author       = {Roland B{\"o}hmer and Catalin Gainaru and Ranko Richert},
  journal      = {Physics Reports},
  title        = {Structure and dynamics of monohydroxy alcohols—Milestones towards their microscopic understanding, 100 years after Debye},
  year         = {2014},
  issn         = {0370-1573},
  note         = {Structure and dynamics of monohydroxy alcohols—Milestones towards their microscopic understanding, 100 years after Debye},
  number       = {4},
  pages        = {125--195},
  volume       = {545},
  abstract     = {In 1913 Debye devised a relaxation model for application to the dielectric properties of water and alcohols. These hydrogen-bonded liquids continue to be studied extensively because they are vital for biophysical processes, of fundamental importance as solvents in industrial processes, and in every-day use. Nevertheless, the way to a microscopic understanding of their properties has been beset with apparently conflicting observations and conceptual difficulties. Much of this remains true for water, but fortunately the situation for monohydroxy alcohols is different. Here, with the experimental progress witnessed in recent years and with the growing recognition of the importance of specific supramolecular structures, a coherent microscopic understanding of the structure and dynamics of these hydrogen-bonded liquids is within reach.},
  creationdate = {2022-04-20T00:00:00},
  doi          = {https://doi.org/10.1016/j.physrep.2014.07.005},
  file         = {:Boehmer2014 - Structure and Dynamics of Monohydroxy Alcohols—Milestones Towards Their Microscopic Understanding, 100 years After Debye.pdf:PDF},
  keywords     = {Monohydroxy alcohols, Structure and dynamics, Review, ethanol, 1-propanol, nmr, dielectric spectroscopy, bds},
  url          = {https://www.sciencedirect.com/science/article/pii/S0370157314002622},
}

@Article{Rathbun1961,
  author       = {Rathbun, R. E. and Babb, A. L.},
  journal      = {The Journal of Physical Chemistry},
  title        = {SELF-DIFFUSION IN LIQUIDS. III. TEMPERATURE DEPENDENCE IN PURE LIQUIDS1},
  year         = {1961},
  number       = {6},
  pages        = {1072--1074},
  volume       = {65},
  creationdate = {2022-04-20T00:00:00},
  doi          = {10.1021/j100824a520},
  eprint       = {https://doi.org/10.1021/j100824a520},
  file         = {:Rathbun1961 - SELF DIFFUSION iN LIQUIDS. III. TEMPERATURE DEPENDENCE iN PURE LIQUIDS1.pdf:PDF},
  keywords     = {ethanol, diffusion},
  url          = {https://doi.org/10.1021/j100824a520},
}

@Article{Scherzinger2012,
  author       = {Scherzinger, C. and Holderer, O. and Richter, D. and Richtering, W.},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Polymer dynamics in responsive microgels: influence of cononsolvency and microgel architecture},
  year         = {2012},
  pages        = {2762--2768},
  volume       = {14},
  abstract     = {The dynamics of polymers on the nm and ns scales inside responsive microgels was probed by means of Neutron Spin Echo (NSE) experiments. Four different microgels were studied: poly(N-isopropylacrylamide) (PNIPAM) and poly(N{,}N-diethylacrylamide) (PDEAAM) microgels{,} a P(NIPAM-co-DEAAM) copolymer microgel and a core–shell microgel with a PDEAAM core and a PNIPAM shell. These four different microgel systems were investigated in a D2O/CD3OD solvent mixture with a molar CD3OD fraction of xMeOD = 0.2 at 10 °C. The PNIPAM and the P(NIPAM-co-DEAAM) microgels are in the collapsed state under these conditions. They behave as solid diffusing objects with only very small additional contributions from internal motions. The PDEAAM particle is swollen under these conditions and mainly Zimm segmental dynamics can be detected in the intermediate scattering function at high momentum transfer. A cross-over to a collective diffusive motion is found for smaller q-values. The shell of the PDEAAM-core–PNIPAM-shell particle is collapsed{,} which leads to a static contribution to S(q{,}t); the core{,} however{,} is swollen and Zimm segmental dynamics are observed. However{,} the contributions of the Zimm segmental dynamics to the scattering function are smaller as compared to the pure PDEAAM particle. Interestingly the values of the apparent solvent viscosities inside the microgels as obtained from the NSE experiments are higher than for the bulk solvent. In addition different values were obtained for the PDEAAM microgel{,} and the PDEAAM-core of the PDEAAM-core–PNIPAM-shell particle{,} respectively. We attribute the strongly increased viscosity in the PDEAAM particle to enhanced inhomogeneities{,} which are induced by the swelling of the particle. The different viscosity inside the PDEAAM-core of the PDEAAM-core–PNIPAM-shell microgel could be due to a confinement effect: the collapsed PNIPAM-shell restricts the swelling of the PDEAAM-core and may modify the hydrodynamic interactions in this restricted environment inside the microgel.},
  creationdate = {2022-04-20T00:00:00},
  doi          = {10.1039/C2CP23328B},
  file         = {:Scherzinger2012 - Polymer Dynamics in Responsive Microgels_ Influence of Cononsolvency and Microgel Architecture.pdf:PDF},
  issue        = {8},
  keywords     = {cononsolvency,microgel,PNIPAM,PDEAAM,copolymer,core-shell microgel,neutron spin echo NSE,methanol,Zimm segemental dynamics,viscosity,inhomogeneities,confinement},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C2CP23328B},
}

@Article{Zhang2001,
  author       = {Zhang, Guangzhao and Wu, Chi},
  journal      = {Phys. Rev. Lett.},
  title        = {Reentrant Coil-to-Globule-to-Coil Transition of a Single Linear Homopolymer Chain in a Water $/$Methanol Mixture},
  year         = {2001},
  month        = jan,
  pages        = {822--825},
  volume       = {86},
  creationdate = {2022-04-21T00:00:00},
  doi          = {10.1103/PhysRevLett.86.822},
  file         = {:Zhang2001 - Reentrant Coil to Globule to Coil Transition of a Single Linear Homopolymer Chain in a Water $_$Methanol Mixture.pdf:PDF},
  issue        = {5},
  keywords     = {pnipam, cononsolvency, linear homopolymer, methanol, LLS, DLS, SLS},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.86.822},
}

@Article{Chee2011,
  author       = {Chee, Choong Kooi and Hunt, Barry J. and Rimmer, Stephen and Soutar, Ian and Swanson, Linda},
  journal      = {Soft Matter},
  title        = {Time-resolved fluorescence anisotropy studies of the cononsolvency of poly(N-isopropyl acrylamide) in mixtures of methanol and water},
  year         = {2011},
  pages        = {1176--1184},
  volume       = {7},
  abstract     = {Time-resolved anisotropy measurements (TRAMS) have provided invaluable information concerning the molecular interactions responsible for cononsolvency in the poly(N-isopropylacrylamide){,} PNIPAM{,} H2O{,} and methanol ternary system. TRAMS have successfully monitored the intramolecular segmental dynamics of an acenaphthylene labelled sample{,} ACE–PNIPAM{,} revealing details about the conformation adopted by the polymer constituent as a function of both alcohol composition and temperature of the system. In pure aqueous solution{,} ACE–PNIPAM undergoes a conformational transition from an expanded solvent swollen structure to a compact globule at the lower critical solution temperature (LCST). With increasing alcohol content up to 55% v/v of methanol there is both a reduction in the magnitude and an onset temperature of the LCST of ACE–PNIPAM. From 57.5–65% v/v methanol{,} ACE–PNIPAM forms an extended solvent swollen structure: observation of an LCST at higher polymer concentrations (e.g.{,} 0.1 wt%) is a consequence of intermolecular aggregation between expanded chains.},
  creationdate = {2022-04-21T00:00:00},
  doi          = {10.1039/C0SM00836B},
  file         = {:Chee2011 - Time Resolved Fluorescence Anisotropy Studies of the Cononsolvency of Poly(N Isopropyl Acrylamide) in Mixtures of Methanol and Water.pdf:PDF},
  issue        = {3},
  keywords     = {pnipam, cononsolvency, methanol, time-resolved fluorescence anisotropy, TRAM},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C0SM00836B},
}

@Article{Belda2004,
  author       = {R. Belda and J. V. Herraez and O. Diez},
  journal      = {Physics and Chemistry of Liquids},
  title        = {Rheological study and thermodynamic analysis of the binary system (water/ethanol): Influence of concentration},
  year         = {2004},
  number       = {5},
  pages        = {467--479},
  volume       = {42},
  abstract     = {Water is the most widely used solvent in the chemical and pharmaceutical industry, since it is the most physiological and best tolerated excipient. However, in some cases water cannot be used as a solvent because the active substance or solute is insoluble or only slightly soluble in water. For this and other reasons, nonwater solvents may be used possessing the common characteristic of being soluble or mixable in water; as a result, such solvents can be used to prepare binary or tertiary mixtures, etc., with different purposes such as increasing water solubility, or modifying the viscosity or absorption of the dissolved substance, for example. Ethanol, along with other alcohols either alone or in water–alcohol solutions involving different proportions, are widely used in the pharmaceutical industry as excipients in different formulations, or as solvents. Ethanol–water systems are characterized by the so-called volume contraction phenomenon, which is in turn accompanied by a considerable increase in the viscosity of the system. This is attributed to the increase in size of the molecular package secondary to solvation or the formation of hydrogen bonds between the alcohol and water – a phenomenon referred to as viscous synergy. The formation of hydrogen bonds between alcohol and water modifies with temperature, thus leading to variations in the viscosity of the system. The present study investigates the viscous synergy of systems comprising pure alcohol in water at different concentrations, determining the proportion of alcohol–water at which maximum viscous synergy occurs, along with the correlation between the viscosity increments and density. The ratio between the maximum viscosity reached by the mixture and the viscosity of pure alcohol is expressed by the enhancement index defined as: E η  = ηmax/η o . Likewise, and since the viscosity of these systems varies with temperature, a thermodynamic study has been made to determine the activation energy of the ethanol–water mixture as a function of concentration.},
  creationdate = {2022-04-21T00:00:00},
  doi          = {10.1080/00319100410001700850},
  eprint       = {https://doi.org/10.1080/00319100410001700850},
  file         = {:Belda2004 - Rheological Study and Thermodynamic Analysis of the Binary System (water_ethanol)_ Influence of Concentration.pdf:PDF},
  keywords     = {ethanol, water, viscosity, density, activation energy, cononsolvency, rheology, thermoddynamics},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/00319100410001700850},
}

@Article{Zhou2008,
  author       = {Zhou, Kejin and Lu, Yijie and Li, Junfang and Shen, Lei and Zhang, Guangzhao and Xie, Zuowei and Wu, Chi},
  journal      = {Macromolecules},
  title        = {The Coil-to-Globule-to-Coil Transition of Linear Polymer Chains in Dilute Aqueous Solutions: Effect of Intrachain Hydrogen Bonding},
  year         = {2008},
  number       = {22},
  pages        = {8927--8931},
  volume       = {41},
  abstract     = {Our previous studies of the captioned transition have shown that thermally sensitive poly(N-isopropylacrylamide) (PNIPAM) in water can form stable individual single-chain globules, but not for polystyrene (PS) in cyclohexane. In the current study, using poly(N,N-diethylacrylamide) (PDEAM) (Mw = 1.7 × 107 g/mol and Mw/Mn = 1.06) with no hydrogen donator site, we intend to find whether the intrachain hydrogen bonding plays a role in stabilizing individual collapsed PNIPAM single-chain globules. We found that PDEAM can also form stable single-chain globules in water even though the transition is less sharp. The resultant individual PDEAM single-chain globules are less compact, reflecting in a lower chain density and a higher ratio of the radius of gyration to hydrodynamic radius, presumably due to the lack of intrachain hydrogen bonding. Our result also shows that, unlike PNIPAM, there is no hysteresis in the transition, indirectly supporting our previous assumption that the hysteresis observed for PNIPAM is due to the formation of some intrachain additional hydrogen bonds formed in the collapsed state.},
  creationdate = {2022-04-21T00:00:00},
  doi          = {10.1021/ma8019128},
  eprint       = {https://doi.org/10.1021/ma8019128},
  file         = {:Zhou2008 - The Coil to Globule to Coil Transition of Linear Polymer Chains in Dilute Aqueous Solutions_ Effect of Intrachain Hydrogen Bonding.pdf:PDF},
  keywords     = {PDEAAM, PDEAM, PNIPAM, thermoresponsive},
  url          = {https://doi.org/10.1021/ma8019128},
}

@Article{Scherzinger2010,
  author       = {Scherzinger, Christine and Lindner, Peter and Keerl, Martina and Richtering, Walter},
  journal      = {Macromolecules},
  title        = {Cononsolvency of Poly(N,N-diethyl\-acrylamide) (PDEAAM) and Poly(N-isopropyl\-acrylamide) (PNIPAM) Based Microgels in Water/Methanol Mixtures: Copolymer vs Core−Shell Microgel},
  year         = {2010},
  number       = {16},
  pages        = {6829--6833},
  volume       = {43},
  abstract     = {The cononsolvency effect on the swelling of different stimuli-sensitive microgels was investigated in water/methanol mixtures. Poly(N,N-diethylacrylamide) (PDEAAM) and poly(N-isopropylacrylamide) (PNIPAM) homopolymer microgels, a PDEAAM-core−PNIPAM-shell microgel, and a poly(N,N-diethylacrylamide-co-N-isopropylacrylamide) (P(DEAAM−NIPAM)) microgel have been synthesized. The core−shell and the copolymer microgel have similar compositions; the PDEAAM core of the PDEAAM-core−PNIPAM-shell particle contributes 80\% to the total mass, and the copolymer consists of 75\% DEAAM and 25\% PNIPAM. They were characterized with dynamic light scattering (DLS) and small-angle neutron scattering (SANS). Microgels containing PNIPAM show the cononsolvency effect, and the particle size reaches a minimum at a methanol fraction of xmethanol = 0.2. Moreover, in core−shell microgels, the cononsolvency effect can be limited to one compartment of the particle. A core−shell microgel with a PDEAAM core and PNIPAM shell reveals a sharp surface at xmethanol = 0.2; i.e., the PNIPAM shell is collapsed, and the PDEAAM core is swollen in the solvent mixture. The results demonstrate how responsive swelling properties of such polymers in solvent mixtures can be tuned via microgel morphology. Core−shell microgels provide new opportunities for encapsulation of guest molecules.},
  creationdate = {2022-04-21T00:00:00},
  doi          = {10.1021/ma100422e},
  eprint       = {https://doi.org/10.1021/ma100422e},
  file         = {:Scherzinger2010 - Cononsolvency of Poly(N,N Diethylacrylamide) (PDEAAM) and Poly(N Isopropylacrylamide) (PNIPAM) Based Microgels in Water_Methanol Mixtures_ Copolymer Vs Core−Shell Microgel.pdf:PDF},
  keywords     = {PNIPAM, PDEAM, PDEAAM, cononsolvency, methanol, microgel, core-shell, copolymer, LLS, DLS, SANS},
  url          = {https://doi.org/10.1021/ma100422e},
}

@Article{Khattab2012,
  author       = {Khattab, Ibrahim Sadek and Bandarkar, Farzana and Fakhree, Mohammad Amin Abolghassemi and Abolghasem Jouyban},
  journal      = {Korean J. Chem. Eng.},
  title        = {Density, viscosity, and surface tension of water+ethanol mixtures from 293K to 323K},
  year         = {2012},
  pages        = {812--817},
  volume       = {29},
  creationdate = {2022-04-22T00:00:00},
  doi          = {10.1007/s11814-011-0239-6},
  file         = {:Khattab2012 - Density, Viscosity, and Surface Tension of Water+ethanol Mixtures from 293K to 323K.pdf:PDF},
  keywords     = {ethanol, viscosity},
  url          = {https://doi.org/10.1007/s11814-011-0239-6},
}

@Article{Tanaka1977,
  author       = {Tanaka, Yoshiyuki and Yamamoto, Takeshi and Satomi, Yoshimasa and Kubota, Hironobu and Makita, Tadashi},
  journal      = {The Review of Physical Chemistry of Japan},
  title        = {Specific volume and viscosity of ethanol-water mixtures under high pressure},
  year         = {1977},
  month        = jul,
  number       = {1},
  volume       = {47},
  abstract     = {The specific volume and the viscosity of enthanol-water mixtures at 25° (298.15K) and 50℃ (323.15k) have been measured under pressures up to 3200 and 800 bar (10^5 Pa), respectively. The measurements were performed by a modified Adams piezometer and a falling-cylinder viscometer. The maximum uncertainties are estimated to be 0.05% for the specific volume and 2% for the viscosity. The specific volume of the pure components and their mixtures is found to decrease monotonously with increasing pressure. The results obtained are compared with several sets of literature values. The numerical data at each temperature and composition are correlated satisfactorily as a function of pressure by both polynomial and the Tait equations. It is also found that a definite minimum appears on the isothermal compressibility versus composition isobars, arising from the complex interactions between hydrogen-bonded water and alcohol molecules. The viscosity of pure ethanol and mixtures is found to increase almost linearly with increasing pressure, whereas that of water is nearly independent of pressure in these experimental conditions. The viscosity isotherms can be formulated by a quadratic equation of pressure within the experimental error. As for the composition dependence of the viscosity, a distinct maximum appears near 0.3 mole fraction of ethanol on all isobars at both experimental temperatures.},
  creationdate = {2022-04-22T00:00:00},
  file         = {:TanY_1977 - Specific Volume and Viscosity of Ethanol Water Mixtures under High Pressure.pdf:PDF},
  keywords     = {ethanol, viscosity},
  publisher    = {The Physico-Chemical Society of Japan},
  url          = {http://hdl.handle.net/2433/47042},
}

@Article{Huerlimann2002,
  author       = {M.D Hürlimann and L Venkataramanan},
  journal      = {Journal of Magnetic Resonance},
  title        = {Quantitative Measurement of Two-Dimensional Distribution Functions of Diffusion and Relaxation in Grossly Inhomogeneous Fields},
  year         = {2002},
  issn         = {1090-7807},
  number       = {1},
  pages        = {31--42},
  volume       = {157},
  abstract     = {We demonstrate the quantitative extraction of multidimensional distribution functions in the presence of grossly inhomogeneous fields. Examples are shown for diffusion—T2 distribution functions and T1−T2 distribution functions. The pulse sequences consist of an initial editing sequence followed by a long series of nominal 180° pulses. They are designed such that the kernels describing the relationships between the distribution functions and the measured data are separable. The required phase cycling is discussed. We analyze in detail the extra spin dynamics effects due to the strong field inhomogeneities including the effects on diffusion and relaxation. A recently developed algorithm is used to invert the data and extract stable multidimensional distribution functions in an efficient manner. We present examples for several applications of this new technique. Diffusion–relaxation distribution functions can be used for fluid identification and for the characterization of pore geometry of porous media based on the effects of restricted diffusion. We have also determined T1−T2 distribution functions of water saturated sedimentary rock and find excellent agreement with previous measurements performed in homogeneous fields.},
  creationdate = {2022-05-05T00:00:00},
  doi          = {https://doi.org/10.1006/jmre.2002.2567},
  file         = {:Huerlimann2002 - Quantitative Measurement of Two Dimensional Distribution Functions of Diffusion and Relaxation in Grossly Inhomogeneous Fields.pdf:PDF},
  keywords     = {nmr, phase cycle, diffusion, stimulated echo},
  url          = {https://www.sciencedirect.com/science/article/pii/S109078070292567X},
}

@Article{Kanert1982,
  author       = {O. Kanert},
  journal      = {Physics Reports},
  title        = {Dynamical properties of defects in solids},
  year         = {1982},
  issn         = {0370-1573},
  number       = {4},
  pages        = {183--232},
  volume       = {91},
  abstract     = {In recent years a considerable amount of effort has been focussed on microscopic mechanisms of motion of defects in solids. In this review, from the very large number of investigations three selected examples will be presented: (i) Translational defect motion, (ii) Localized motion of defects at low temperatures, (iii) Motion of dislocations in solids. Various experimental techniques have been used for the study of defect motion but the most widely applied method seems to be nuclear spin relaxation based on recent progress in pulsed nuclear magnetic resonance technique as well as on recent developments in the analysis of nuclear spin relaxation data. Consequently, a large part of the article is focussed on the application of nuclear spin relaxation for studying defect motion. But, it will be shown that a detailed description of the microscopic mechanism of defect motion is only possible if comparison is made between experimental results obtained from different experimental techniques.},
  creationdate = {2022-05-05T00:00:00},
  doi          = {https://doi.org/10.1016/0370-1573(82)90097-7},
  file         = {:Kanert1982 - Dynamical Properties of Defects in Solids.pdf:PDF},
  keywords     = {nmr, relaxation, theory, review, t1 rho},
  url          = {https://www.sciencedirect.com/science/article/pii/0370157382900977},
}

@Article{Halle1981,
  author       = {Halle, Bertil and Wennerström, Håkan},
  journal      = {The Journal of Chemical Physics},
  title        = {Interpretation of magnetic resonance data from water nuclei in heterogeneous systems},
  year         = {1981},
  number       = {4},
  pages        = {1928--1943},
  volume       = {75},
  creationdate = {2022-05-10T00:00:00},
  doi          = {10.1063/1.442218},
  eprint       = {https://doi.org/10.1063/1.442218},
  file         = {:Halle1981 - Interpretation of Magnetic Resonance Data from Water Nuclei in Heterogeneous Systems.pdf:PDF},
  keywords     = {NMR},
  url          = {https://doi.org/10.1063/1.442218},
}

@Article{doi:10.1021/ja00407a012,
  author       = {Gall, C. M. and DiVerdi, J. A. and Opella, S. J.},
  journal      = {Journal of the American Chemical Society},
  title        = {Phenylalanine ring dynamics by solid-state deuterium NMR},
  year         = {1981},
  number       = {17},
  pages        = {5039--5043},
  volume       = {103},
  creationdate = {2022-05-10T00:00:00},
  doi          = {10.1021/ja00407a012},
  eprint       = {https://doi.org/10.1021/ja00407a012},
  file         = {:doi_10.1021_ja00407a012 - Phenylalanine Ring Dynamics by Solid State Deuterium NMR.pdf:PDF},
  keywords     = {pake spectrum, nmr, quadrupole coupling constant, qcc},
  url          = {https://doi.org/10.1021/ja00407a012},
}

@Article{Balachandar2022,
  author       = {Balachandar, Vijayakumar and Takatsuka, Masanobu and Kita, Rio and Shinyashiki, Naoki and Yagihara, Shin and Rathinasabapathy, Sampathkumar},
  journal      = {Macromolecules},
  title        = {Dynamics of the Poly(N-Isopropylacrylamide) Microgel Aqueous Suspension Investigated by Dielectric Relaxation Spectroscopy},
  year         = {2022},
  number       = {4},
  pages        = {1218--1229},
  volume       = {55},
  abstract     = {Free-radical precipitation polymerization was used to make non-ionic poly(N-isopropylacrylamide) (PNIPAM) microgel particles. On the synthesized PNIPAM microgel particles, a dynamic light scattering experiment was performed, and hydrodynamic radii were determined to be roughly 240 and 125 nm for temperatures of 298 and 313 K, respectively. Dielectric experiments were carried out on a 10 wt \% PNIPAM microgel aqueous suspension at temperatures extending from 288 to 323 K, including volume phase transition temperature (VPTT) at 305 K in the frequency range of 40 Hz to 50 GHz. At frequencies of about 3–5 MHz and 16–18 GHz, two distinct relaxation processes were detected, in addition to electrode polarization and the contribution of dc conductivity. The local chain motion of PNIPAM (p-process) and the average relaxation mode of water located at the bulk solution and also within the microgel (w-process) are assumed to be the origins of the two relaxation processes. Furthermore, based on the idea of two kinds of water models, contributions of each of the two kinds of water, both free water outside the microgel (w1, with its relaxation time of τw1) and confined water within the microgel (w2, with its relaxation time of τw2), to the high-frequency relaxation spectrum were evaluated. The τw2 is only 2–2.7 times larger than τw1 above VPTT. This means that rotational motion of water molecules is not significantly constrained inside the microgel particle even above VPTT. The NMR rotational correlation time τc, which is comparable to the dielectric relaxation time, was estimated using Bloembergen–Purcell–Pound (BPP) theory. The 3τc value for the microgel suspension obeys BPP theory only up to VPTT; above that, due to anisotropy and/or loss of translational mobility of water induced by microgel shrinkage, precondition of BPP theory is broken. Furthermore, we obtained the concentration of PNIPAM in microgel particles using both the relaxation times and relaxation strengths of w1 and w2 above and below VPTT. Below VPTT, the p-process locates at the MHz region, and it shifts toward the lower-frequency side above VPTT due to the hindrance by microgel structural changes. The dynamics of the polymer and water inside and outside microgel particles in the solution bulk are observed simultaneously by the same physical quantities through the volume phase transition.},
  comment      = {uses two debye processes for bound and free water. Both first and last author names may have given name and familiy name mixed up. Citation key changed from Vijayakumar2022 to Balachandar 2022 on 2025-02-12},
  creationdate = {2022-05-12T00:00:00},
  doi          = {10.1021/acs.macromol.1c02083},
  eprint       = {https://doi.org/10.1021/acs.macromol.1c02083},
  file         = {:Vijayakumar2022 - Dynamics of the Poly(N Isopropylacrylamide) Microgel Aqueous Suspension Investigated by Dielectric Relaxation Spectroscopy.pdf:PDF},
  keywords     = {PNIPAM, dielectric, hydrodynamic radius, DLS, light scattering, VPT, microgel, correlation time, BPP, spectral density},
  readstatus   = {read},
  url          = {https://doi.org/10.1021/acs.macromol.1c02083},
}

@Article{Fuellbrandt2014,
  author       = {F{\"u}llbrandt, Marieke and Ermilova, Elena and Asadujjaman, Asad and H{\"o}lzel, Ralph and Bier, Frank F. and von Klitzing, Regine and Sch{\"o}nhals, Andreas},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Dynamics of Linear Poly(N-isopropylacrylamide) in Water around the Phase Transition Investigated by Dielectric Relaxation Spectroscopy},
  year         = {2014},
  note         = {PMID: 24592989},
  number       = {13},
  pages        = {3750--3759},
  volume       = {118},
  abstract     = {The molecular dynamics of linear poly(N-isopropylacrylamide) (pNIPAM) in aqueous media at temperatures below and above the lower critical solution temperature (LCST) are investigated using broadband dielectric relaxation spectroscopy in a frequency range from 10–1 to 1011 Hz. Below the LCST, two relaxation processes are observed in the megahertz and gigahertz region assigned to the reorientation of dipoles of the solvated polymer segments (p-process) and water molecules (w-process), respectively. Both relaxation processes are analyzed using the Havriliak–Negami (HN) function, taking special attention to the w-process. Above the LCST, the dielectric spectra of the pNIPAM solutions resemble that of pure water, showing only the high frequency relaxation process of the water molecules with a more or less Debye-type behavior. The non-Debye behavior of the w-process below the LCST is mainly induced by the interactions between water and pNIPAM chains via hydrogen bonding. The relaxation time and strength of the w-process is studied with dependence on the concentration, temperature, and the polymer chain length (molecular weight). The information obtained is useful for a deeper understanding of the dehydration behavior at the phase transition. The suggestion of dehydration of the pNIPAM chains at the LCST is confirmed by calculating a dehydration number.},
  creationdate = {2022-05-16T00:00:00},
  doi          = {10.1021/jp501325x},
  eprint       = {https://doi.org/10.1021/jp501325x},
  file         = {:Fuellbrandt2014 - Dynamics of Linear Poly(N Isopropylacrylamide) in Water around the Phase Transition Investigated by Dielectric Relaxation Spectroscopy.pdf:PDF},
  keywords     = {aqueous PNIPAM, LCST, dielectric, BDS, von Klitzing, spectral density},
  readstatus   = {skimmed},
  url          = {https://doi.org/10.1021/jp501325x},
}

@Article{Ono2006,
  author       = {Ono, Yousuke and Shikata, Toshiyuki},
  journal      = {Journal of the American Chemical Society},
  title        = {Hydration and Dynamic Behavior of Poly(N-isopropylacrylamide)s in Aqueous Solution:  A Sharp Phase Transition at the Lower Critical Solution Temperature},
  year         = {2006},
  note         = {PMID: 16881629},
  number       = {31},
  pages        = {10030--10031},
  volume       = {128},
  abstract     = {The number of hydrated water molecules per poly(N-isopropylacrylamide) monomer unit in homogeneous aqueous solution was determined to be 11 exactly and anew below the lower critical solution temperature of 32 °C employing high-frequency dielectric relaxation techniques.},
  comment      = {drei(!) Debyes für den breiten Prozess?! Der Rest vom Paper ist auch eher Spekulation....},
  creationdate = {2022-05-16T00:00:00},
  doi          = {10.1021/ja063990i},
  eprint       = {https://doi.org/10.1021/ja063990i},
  file         = {:Ono2006 - Hydration and Dynamic Behavior of Poly(N Isopropylacrylamide)s in Aqueous Solution_ a Sharp Phase Transition at the Lower Critical Solution Temperature.pdf:PDF},
  keywords     = {PNIPAM, dielectric, BDS, hydration number, LCST, exchange},
  url          = {https://doi.org/10.1021/ja063990i},
}

@Article{Yanase2020,
  author       = {Keiichi Yanase and Richard Buchner and Takaaki Sato},
  journal      = {Journal of Molecular Liquids},
  title        = {Microscopic insights into the phase transition of poly(N-isopropylacrylamide) in aqueous media: Effects of molecular weight and polymer concentration},
  year         = {2020},
  issn         = {0167-7322},
  pages        = {112025},
  volume       = {302},
  abstract     = {We study a temperature (T)-induced phase transition of semi-dilute poly(N-isopropylacrylamide) (pNIPAm) in H2O and D2O, focusing on effects of molecular weight and polymer concentration. We use simultaneous small- and wide-angle x-ray scattering (SWAXS) and dielectric relaxation spectroscopy (DRS). The hydration number Zhyd of pNIPAm is determined by DRS. We observe a gradual decrease of Zhyd with increasing T below TS − 6 K, where TS is the spinodal temperature, and its subsequent steep decrease on approaching TS. This eccentric two-mode dehydration behavior implies strong cooperative nature of hydration/dehydration of the pNIPAm chains. Furthermore, the observed dehydration is coupled to the critical fluctuations manifested by a power-law divergence of the correlation length ξ. The emergence of a low-q interference peak provides evidence that high-density microglobules are formed even far below Ts, where a swollen coil state of polymer chains is generally considered to be predominant. The local number density of the microglobules is almost unchanged below Ts, but then exhibits a step-like increase just above Ts, where most pNIPAm chains are already collapsed. This observation suggests that in addition to the ordinary (macroscopic) density order parameter, the local number density of the microglobules should serve as an additional order parameter monitoring the phase transition of aqueous pNIPAm. The correlation length significantly decreases at higher polymer concentration because of the stronger interpenetration effect between different chains. At higher concentration, ξ converges to similar values independent of molecular weight, which indicates an already congested state of the pNIPAm chains. Lowering averaged molecular weight leads to a stronger tendency of inter-chain aggregation and interface formation especially at high T.},
  creationdate = {2022-05-16T00:00:00},
  doi          = {https://doi.org/10.1016/j.molliq.2019.112025},
  file         = {:Yanase2020 - Microscopic Insights into the Phase Transition of Poly(N Isopropylacrylamide) in Aqueous Media_ Effects of Molecular Weight and Polymer Concentration.pdf:PDF},
  keywords     = {Phase transition,Critical behavior,LCST,poly(N-isopropylacrylamide),PNIPAM,Small- and wide-angle x-ray scattering (SWAXS),SAXS,Dielectric relaxation spectroscopy,BDS,H2O,D2O,concentration,molecular weight,three state model,cooperativity,cooperative hydration,spinodal,pre-shrinking},
  readstatus   = {read},
  url          = {https://www.sciencedirect.com/science/article/pii/S0167732219324262},
}

@Article{Fukasawa2005,
  author       = {Fukasawa, Toshiko and Sato, Takaaki and Watanabe, Junji and Hama, Yoshimasa and Kunz, Werner and Buchner, Richard},
  journal      = {Phys. Rev. Lett.},
  title        = {Relation between Dielectric and Low-Frequency Raman Spectra of Hydrogen-Bond Liquids},
  year         = {2005},
  month        = nov,
  pages        = {197802},
  volume       = {95},
  creationdate = {2022-05-17T00:00:00},
  doi          = {10.1103/PhysRevLett.95.197802},
  file         = {:Fukasawa2005 - Relation between Dielectric and Low Frequency Raman Spectra of Hydrogen Bond Liquids.pdf:PDF},
  issue        = {19},
  keywords     = {dielectric spectroscopy, BDS, Raman, theory},
  numpages     = {4},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.95.197802},
}

@Article{Nakano2012,
  author       = {Nakano, Shinya and Sato, Yasuhiro and Kita, Rio and Shinyashiki, Naoki and Yagihara, Shin and Sudo, Seiichi and Yoneyama, Masaru},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Molecular Dynamics of Poly(N-isopropylacrylamide) in Protic and Aprotic Solvents Studied by Dielectric Relaxation Spectroscopy},
  year         = {2012},
  note         = {PMID: 22172006},
  number       = {2},
  pages        = {775--781},
  volume       = {116},
  abstract     = {We report the experimental results of dielectric relaxation spectroscopy for the systems of poly(N-isopropylacrylamide) [PNiPAM] in various solvents in the frequency range of 40 kHz to 20 GHz at the solution temperature of 25.0 °C. The solvents used in this study were protic solvents (water, methanol, ethanol, and 1-propanol) and aprotic solvents (acetone, methyl ethyl ketone, and dimethyl sulfoxide). Two relaxation processes were observed at frequencies of approximately 1 MHz and 10 GHz in all the solutions. The origins of the two relaxation processes are considered to be the reorientation of dipoles of the PNiPAM chains at middle frequencies (m-process) and that of solvent molecules at higher frequencies (h-process). For the PNiPAM solutions composed of protic solvents except for 1-propanol, the relaxation time of the h-process increased with increasing PNiPAM concentration, whereas that of the h-process for the 1-propanol decreased with increasing PNiPAM concentration. In contrast, the relaxation times of the h-process for the aprotic solvents were independent of the density of hydrogen-bonding sites. For the m-process, which is attributed to the local chain motion of PNiPAM, the extrapolated relaxation time to zero polymer concentration τm0 was scaled by the solvent viscosity for all the protic solvents, whereas for the aprotic solvents τm0 showed no correlation with the solvent viscosity. The dynamics of polymer chains and solvent molecules in their solution state are clarified in terms of cooperative motion, which is associated with the interactions through hydrogen bonding at the molecular level.},
  creationdate = {2022-05-18T00:00:00},
  doi          = {10.1021/jp210376u},
  eprint       = {https://doi.org/10.1021/jp210376u},
  file         = {:Nakano2012 - Molecular Dynamics of Poly(N Isopropylacrylamide) in Protic and Aprotic Solvents Studied by Dielectric Relaxation Spectroscopy.pdf:PDF},
  keywords     = {dielectric spectroscopy, BDS, PNIPAM, concentration dependence},
  url          = {https://doi.org/10.1021/jp210376u},
}

@Article{Yang2017b,
  author       = {Yang, Man and Su, Wenjuan and Zhao, Kongshuang},
  journal      = {Journal of Polymer Science Part B: Polymer Physics},
  title        = {Quantification of solvent water and hydration dynamic of thermo-sensitive microgel by dielectric spectroscopy},
  year         = {2017},
  number       = {24},
  pages        = {1859--1864},
  volume       = {55},
  abstract     = {The hydration of natural or synthetic macromolecules is of fundamental importance in our understanding of their structure and stability. Quantification of hydration water can promote the understanding to many complex biological mechanisms such as protein folding, as well as the dynamics and conformation of polymers. An approach to quantification of solvent water was developed by dielectric spectroscopy. Dielectric behaviors of PNIPAM microgels with different crosslink density distribution were measured in the range of 0.5–40 GHz and 15–50. An obvious relaxation process caused by free and bound water was found. Dielectric parameters of free and bound water show that the crosslink density distribution does not affect the volume phase transition temperature of microgels, but significantly influence the orientation dynamics of the solvent water. We found that the three kinds of microgel can be distinguished by the dielectric parameters of the bound water. In addition, the number of water in and outside microgel during the volume phase transition process was quantitatively calculated for the first time. This study provides the possibility for the quantification of water in complex biological process. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1859–1864},
  creationdate = {2022-05-18T00:00:00},
  doi          = {https://doi.org/10.1002/polb.24513},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.24513},
  file         = {:Yang2017b - Quantification of Solvent Water and Hydration Dynamic of Thermo Sensitive Microgel by Dielectric Spectroscopy.pdf:PDF},
  keywords     = {bound water, dielectric properties, dielectric relaxation spectroscopy, BDS, hydration dynamics, microgels, phase separation, LCST, VPT, quantification, relaxation, stimuli-sensitive polymers, swelling, PNIPAM, cross-linker distribution},
  priority     = {prio1},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.24513},
}

@Article{Schroeter1998,
  author       = {Schröter, K. and Unger, R. and Reissig, S. and Garwe, F. and Kahle, S. and Beiner, M. and Donth, E.},
  journal      = {Macromolecules},
  title        = {Dielectric Spectroscopy in the $\alpha\beta$ Splitting Region of Glass Transition in Poly(ethyl methacrylate) and Poly(n-butyl methacrylate):  Different Evaluation Methods and Experimental Conditions},
  year         = {1998},
  number       = {25},
  pages        = {8966--8972},
  volume       = {31},
  abstract     = {Stability of the dielectric parameters in the αβ splitting region against methodical variations is demonstrated. The Williams product ansatz for correlation functions and an additive ansatz for dielectric functions are compared for poly(ethyl methacrylate). Both evaluation methods give a diminishing α intensity with increasing temperature, and a separate trace for the α relaxation different from both the secondary β relaxation below and the high-temperature a process above the crossover. Furthermore, measurements on different poly(n-butyl methacrylate) samples and evaluation results of different experimentalists are compared. The intensity onset of the cooperative α relaxation, starting from zero at a characteristic temperature Ton in the crossover region, and the parallel course of α and β relaxations below Ton, separated by about one frequency decade in an Arrhenius diagram, remain stable against measurement and evaluation variations.},
  creationdate = {2022-05-20T00:00:00},
  doi          = {10.1021/ma9713318},
  eprint       = {https://doi.org/10.1021/ma9713318},
  file         = {:Schroeter1998 - Dielectric Spectroscopy in the Αβ Splitting Region of Glass Transition in Poly(ethyl Methacrylate) and Poly(n Butyl Methacrylate)_ Different Evaluation Methods and Experimental Conditions.pdf:PDF},
  keywords     = {dielectric spectroscopy, BDS, theory, spectral density},
  url          = {https://doi.org/10.1021/ma9713318},
}

@Article{ContiNibali2020,
  author       = {Conti Nibali, V. and Pezzotti, S. and Sebastiani, F. and Galimberti, D. R. and Schwaab, G. and Heyden, M. and Gaigeot, M.-P. and Havenith, M.},
  journal      = {The Journal of Physical Chemistry Letters},
  title        = {Wrapping Up Hydrophobic Hydration: Locality Matters},
  year         = {2020},
  note         = {PMID: 32459100},
  number       = {12},
  pages        = {4809--4816},
  volume       = {11},
  abstract     = {Water, being the universal solvent, acts as a competing agent in fundamental processes, such as folding, aggregation or biomolecular recognition. A molecular understanding of hydrophobic hydration is of central importance to understanding the subtle free energy differences, which dictate function. Ab initio and classical molecular dynamics simulations yield two distinct hydration water populations in the hydration shell of solvated tert-butanol noted as “HB-wrap” and “HB-hydration2bulk”. The experimentally observed hydration water spectrum can be dissected into two modes, centered at 164 and 195 cm–1. By comparison to the simulations, these two bands are attributed to the “HB-wrap” and “HB-hydration2bulk” populations, respectively. We derive a quantitative correlation between the population in each of these two local water coordination motifs and the temperature dependence of the solvation entropy. The crossover from entropy to enthalpy dominated solvation at elevated temperatures, as predicted by theory and observed experimentally, can be rationalized in terms of the distinct temperature stability and thermodynamic signatures of “HB-wrap” and “HB-hydration2bulk”.},
  creationdate = {2022-05-20T00:00:00},
  doi          = {10.1021/acs.jpclett.0c00846},
  eprint       = {https://doi.org/10.1021/acs.jpclett.0c00846},
  file         = {:ContiNibali2020 - Wrapping up Hydrophobic Hydration_ Locality Matters.pdf:PDF;:WrappingUpHydrophobicHydration-LocalityMatters_NibaliEtAl_JPCLett2020_SI.pdf:PDF},
  keywords     = {hydrophobic hydration, simulation, theory, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://doi.org/10.1021/acs.jpclett.0c00846},
}

@Article{Kita2007,
  author       = {Kita, Rio and Polyakov, Pavel and Wiegand, Simone},
  journal      = {Macromolecules},
  title        = {Ludwig−Soret Effect of Poly(N-isopropylacrylamide):  Temperature Dependence Study in Monohydric Alcohols},
  year         = {2007},
  number       = {5},
  pages        = {1638--1642},
  volume       = {40},
  abstract     = {We report the experimental results of the Ludwig−Soret effect for poly(N-isopropylacrylamide) (PNiPAM) in alcohols measured in the temperature range from 20 to 45 °C by means of thermal diffusion forced Rayleigh scattering (TDFRS). Alcohols, used in this study as solvent, are monohydric alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and tert-butanol). In the studied temperature range, PNiPAM in methanol shows a positive Soret coefficient, whereas PNiPAM has a negative Soret coefficient in larger alcohols, i.e., 1-propanol, 2-propanol, 1-butanol, and tert-butanol. In ethanol the temperature dependence of the Soret coefficient of PNiPAM shows a sign change from positive to negative with increasing temperature at T = 34 °C. The temperature dependence of the Soret coefficients for these alcohol solutions is discussed in terms of cohesive energies such as the Hildebrand solubility parameter. It is indicated that the balance between the hydrogen-bonding capability and the hydrophobic association plays a dominant role for the sign change in the Soret coefficient and the thermal diffusion coefficient of PNiPAM.},
  creationdate = {2022-05-20T00:00:00},
  doi          = {10.1021/ma0621831},
  eprint       = {https://doi.org/10.1021/ma0621831},
  file         = {:doi_10.1021_ma0621831 - Ludwig−Soret Effect of Poly(N Isopropylacrylamide)_ Temperature Dependence Study in Monohydric Alcohols.pdf:PDF},
  keywords     = {PNIPAM, diffusion, alcohol, ethanol, methanol, propanol, 1-butanol, tert-butanol},
  url          = {https://doi.org/10.1021/ma0621831},
}

@Article{Dai2010,
  author       = {Dai, Zhuojun and Wu, Chi},
  journal      = {Macromolecules},
  title        = {Internal Motions of Linear Chains and Spherical Microgels in Θ and Poor Solvents},
  year         = {2010},
  number       = {23},
  pages        = {10064--10070},
  volume       = {43},
  abstract     = {Internal motions of narrowly poly(N-isopropylacrylamide) (PNIPAM) linear chains and spherical microgels in a very dilute aqueous solution and dispersion were studied under the Θ and poor solvent conditions by dynamic laser light scattering (LLS) over a wide range of scattering angles. As expected, only one narrow peak related to the translational diffusion was observed in the line-width distribution G(Γ) of both linear chains and spherical microgels when x < 1, where x = (qRg)2 with q and Rg the scattering vector and the radius of gyration, respectively. As x increases to approach 1, we start to see a second peak related to fast internal motions of linear chains, whose average line width is related to some of the internal motions (normal modes) predicted in the nondraining bead-and-spring model. However, for swollen microgels, the second peak related to the internal motions only appears when x is much higher (1/q ∼ 50 nm), indicating that thermal energy is not able to excite the entire microgel but only a small portion of the gel network. As the solvent quality changes from good to poor, the shrinking of a linear chain or subchains in the gel network gradually suppresses the internal motions, presumably due to stronger intersegment interaction. Surprisingly, we found that the relative contribution of the second peak makes a turning near the Θ temperature, leading to a new way to estimate the Θ condition of a given polymer solution.},
  creationdate = {2022-05-23T00:00:00},
  doi          = {10.1021/ma1017814},
  eprint       = {https://doi.org/10.1021/ma1017814},
  file         = {:Dai2010 - Internal Motions of Linear Chains and Spherical Microgels in Θ and Poor Solvents.pdf:PDF},
  keywords     = {linear PNIPAM, microgel, LLS, internal motion, model, radius of gyration, hydrodynamic radius},
  url          = {https://doi.org/10.1021/ma1017814},
}

@Article{Mukae1993,
  author       = {Mukae, Katsuya and Sakurai, Masao and Sawamura, Seiji and Makino, Kimiko and Kim, Sung Wan and Ueda, Issaku and Shirahama, Keishiro},
  journal      = {The Journal of Physical Chemistry},
  title        = {Swelling of poly(N-isopropylacrylamide) gels in water-alcohol (C1-C4) mixed solvents},
  year         = {1993},
  number       = {3},
  pages        = {737--741},
  volume       = {97},
  abstract     = {The swelling volume of poly(TV-isopropylacrylamide) gels in alcohol-water mixtures (C1-C4) was measured at 25C. The swollen gel in water shrank first with addition of a small amount of alcohol and then reswelled on further addition of alcohol showing a typical reentrant transition. The swelling behavior of the gels was correlated with the properties of the aqueous alcohol mixtures (i.e., the change of alcohol molar volume and thermodynamic activities of alcohol and water). The uptake of ethanol and water in the equilibrated gels was measured at 25 °C. Ethanol was found to be selectively taken up in all aqueous alcohol mixtures. The strength of hydrogen bonding around amide groups of the linear polymer in aqueous ethanol solution was examined by Fourier transform infrared spectroscopy (FT-IR). Stretching frequencies of the carbonyl group (amide I) of the polymer were sensitive to hydrogen bond strength which depended on the alcohol composition. These FT-IR spectroscopic studies suggested that the polymer networks may take a compact conformation in the reentrant transition region where the PIPAAm chains interact with themselves through hydrogen bonding.},
  creationdate = {2022-05-23T00:00:00},
  doi          = {10.1021/j100105a034},
  eprint       = {https://doi.org/10.1021/j100105a034},
  file         = {:Mukae1993 - Swelling of Poly(N Isopropylacrylamide) Gels in Water Alcohol (C1 C4) Mixed Solvents.pdf:PDF},
  keywords     = {PNIPAM, cononsolvency, methanol, ethanol, propanol, butanol, hydrogel, hydrogen bond, FTIR, infrared, gel, uptake},
  priority     = {prio1},
  url          = {https://doi.org/10.1021/j100105a034},
}

@Article{Hindman1971,
  author       = {Hindman,J. C. and Zielen,A. J. and Svirmickas,A. and Wood,M.},
  journal      = {The Journal of Chemical Physics},
  title        = {Relaxation Processes in Water. The Spin–Lattice Relaxation of the Deuteron in D2O and Oxygen‐17 in H217O},
  year         = {1971},
  number       = {2},
  pages        = {621--634},
  volume       = {54},
  comment      = {Does not state if relaxation curves are stretched. They are probably not.},
  creationdate = {2022-05-23T00:00:00},
  doi          = {10.1063/1.1674887},
  eprint       = {https://doi.org/10.1063/1.1674887},
  file         = {:Hindman1971 - Relaxation Processes in Water. the Spin–Lattice Relaxation of the Deuteron in D2O and Oxygen‐17 in H217O.pdf:PDF},
  keywords     = {2h-nmr,17o-nmr,water,d2o,h217o,t1,spin-lattice relaxation,thermodynamics,entropy,enthalpy,SED,quadrupole coupling constant,qcc,H2O,nmr},
  url          = {https://doi.org/10.1063/1.1674887},
}

@Article{Fumino1995,
  author       = {Koichi Fumino and Akio Shimizu and Yoshihiro Taniguchi},
  journal      = {Denki Kagaku oyobi Kogyo Butsuri Kagaku},
  title        = {Temperature Effects on the Rotational Motion of the Coordinated D2O Molecules in LiBr Aqueous Solutions Studies by 2D and 17O NMR Relaxation},
  year         = {1995},
  number       = {1},
  pages        = {54--62},
  volume       = {63},
  creationdate = {2022-05-23T00:00:00},
  doi          = {10.5796/kogyobutsurikagaku.63.54},
  file         = {:Fumino1995 - Temperature Effects on the Rotational Motion of the Coordinated D_sub_2__sub_O Molecules in LiBr Aqueous Solutions Studies by _sup_2__sup_D and _sup_17__sup_O NMR Relaxation.pdf:PDF},
  keywords     = {NMR, T1, spin-lattice relaxation, 2H, 17O, salt concentration, activation energy},
  url          = {https://doi.org/10.5796/kogyobutsurikagaku.63.54},
}

@Article{Fumino1998,
  author       = {Koichi Fumino and Kenichi Yukiyasu and Akio Shimizu and Yoshihiro Taniguchi},
  journal      = {Journal of Molecular Liquids},
  title        = {NMR studies on dynamic behavior of water molecules in tetraalkylammonium bromide-D2O solutions at 5–25°C+},
  year         = {1998},
  issn         = {0167-7322},
  number       = {1},
  pages        = {1--12},
  volume       = {75},
  abstract     = {The spin-lattice relaxation times (T1) of D and 17O nuclei of D2O molecules in tetraalkylammonium bromides (R4NBr; R=Me, Et, Pr, Bu), dilute aqueous solutions were measured at the concentration of 0.2 to 1.0 mol/kg and at the temperature of 5 to 25 °C. The relative spin-lattice relaxation rate, R1/R10 (R1=1/T1) at 25 °C increased linearly with increasing concentration of tetraalkylammonium bromide solutions. But, it varied nonlinearly against the concentration below 20 °C and the deviation increased with decreasing temperature. The dynamic hydration number (nDHN) of D and 17O nuclei of a D2O molecule in the hydration sphere of tetraalkylammonium ions had good correlation with the molecular size, except for the Bu4N+ ion. The deviation of nDHN of Bu4N+ ion at low temperature reflected the caging effect due to the association through hydrogen bonding among water molecules as the association increases at lower temperature. It was suggested that the rotational anisotropy (τ+D/τ+170) of water molecules can be used as a new indicator to classify three types of hydration; negative, positive, and hydrophobic hydrations.},
  creationdate = {2022-05-25T00:00:00},
  doi          = {https://doi.org/10.1016/S0167-7322(97)00020-2},
  file         = {:Fumino1998 - NMR Studies on Dynamic Behavior of Water Molecules in Tetraalkylammonium Bromide D2O Solutions at 5–25°C+.pdf:PDF},
  keywords     = {nmr, water, h2o, d2o, coupling constant, 2H, 17O, salt, ion},
  url          = {https://www.sciencedirect.com/science/article/pii/S0167732297000202},
}

@Article{Struis1987,
  author       = {Struis, R. P. W. J. and De Bleijser, J. and Leyte, J. C.},
  journal      = {The Journal of Physical Chemistry},
  title        = {An NMR contribution to the interpretation of the dynamical behavior of water molecules as a function of the magnesium chloride concentration at 25.degree.C},
  year         = {1987},
  number       = {24},
  pages        = {6309--6315},
  volume       = {91},
  creationdate = {2022-05-25T00:00:00},
  doi          = {10.1021/j100308a045},
  eprint       = {https://doi.org/10.1021/j100308a045},
  file         = {:Struis1987 - An NMR Contribution to the Interpretation of the Dynamical Behavior of Water Molecules As a Function of the Magnesium Chloride Concentration at 25.degree.C.pdf:PDF},
  keywords     = {nmr, waster, h2o, d2o, 17o, 2h, coupling constant, relaxation, self-diffusion},
  url          = {https://doi.org/10.1021/j100308a045},
}

@Article{Struis1987a,
  author       = {Struis, R. P. W. J. and De Bleijser, J. and Leyte, J. C.},
  journal      = {The Journal of Physical Chemistry},
  title        = {Dynamic behavior and some of the molecular properties of water molecules in pure water and in magnesium chloride solutions},
  year         = {1987},
  number       = {6},
  pages        = {1639--1645},
  volume       = {91},
  creationdate = {2022-05-25T00:00:00},
  doi          = {10.1021/j100290a069},
  eprint       = {https://doi.org/10.1021/j100290a069},
  file         = {:Struis1987a - Dynamic Behavior and Some of the Molecular Properties of Water Molecules in Pure Water and in Magnesium Chloride Solutions.pdf:PDF},
  keywords     = {nmr, relaxation, 2h, 1h, 17o,},
  url          = {https://doi.org/10.1021/j100290a069},
}

@Article{Qvist2012,
  author       = {Qvist,Johan and Mattea,Carlos and Sunde,Erik P. and Halle,Bertil},
  journal      = {The Journal of Chemical Physics},
  title        = {Rotational dynamics in supercooled water from nuclear spin relaxation and molecular simulations},
  year         = {2012},
  number       = {20},
  pages        = {204505},
  volume       = {136},
  abstract     = {Structural dynamics in liquid water slow down dramatically in the supercooled regime. To shed further light on the origin of this super-Arrhenius temperature dependence, we report high-precision 17O and 2H NMR relaxation data for H2O and D2O, respectively, down to 37 K below the equilibrium freezing point. With the aid of molecular dynamics (MD) simulations, we provide a detailed analysis of the rotational motions probed by the NMR experiments. The NMR-derived rotational correlation time τ R is the integral of a time correlation function (TCF) that, after a subpicosecond librational decay, can be described as a sum of two exponentials. Using a coarse-graining algorithm to map the MD trajectory on a continuous-time random walk (CTRW) in angular space, we show that the slowest TCF component can be attributed to large-angle molecular jumps. The mean jump angle is ∼48◦ at all temperatures and the waiting time distribution is non-exponential, implying dynamical heterogeneity. We have previously used an analogous CTRW model to analyze quasielastic neutron scattering data from supercooled water. Although the translational and rotational waiting times are of similar magnitude, most translational jumps are not synchronized with a rotational jump of the same molecule. The rotational waiting time has a stronger temperature dependence than the translation one, consistent with the strong increase of the experimentally derived product τ R DT at low temperatures. The present CTRW jump model is related to, but differs in essential ways from the extended jump model proposed by Laage and co-workers. Our analysis traces the super-Arrhenius temperature dependence of τ R to the rotational waiting time. We present arguments against interpreting this temperature dependence in terms of mode-coupling theory or in terms of mixture models of water structure.},
  creationdate = {2022-05-25T00:00:00},
  doi          = {10.1063/1.4720941},
  eprint       = {https://doi.org/10.1063/1.4720941},
  file         = {:Qvist2012 - Rotational Dynamics in Supercooled Water from Nuclear Spin Relaxation and Molecular Simulations.pdf:PDF;:Qvist2012 - Rotational Dynamics in Supercooled Water from Nuclear Spin Relaxation and Molecular Simulations_SI.pdf:PDF},
  keywords     = {NMR, relaxation, water, h2o, d2o, 2h, 17o, simulation},
  url          = {https://doi.org/10.1063/1.4720941},
}

@Article{MathurDeVre1980,
  author       = {R. {Mathur-De Vré}},
  journal      = {Progress in Biophysics and Molecular Biology},
  title        = {The NMR studies of water in biological systems},
  year         = {1980},
  issn         = {0079-6107},
  pages        = {103--134},
  volume       = {35},
  creationdate = {2022-05-27T00:00:00},
  doi          = {https://doi.org/10.1016/0079-6107(80)90004-8},
  file         = {:MathurDeVre1980 - The NMR Studies of Water in Biological Systems.pdf:PDF},
  keywords     = {nmr, theory, 1h, 2h, 17o, water, polymer},
  url          = {https://www.sciencedirect.com/science/article/pii/0079610780900048},
}

@Article{Holz1996,
  author       = {Holz,Manfred and Mao,Xi‐an and Seiferling,Dieter and Sacco,Antonio},
  journal      = {The Journal of Chemical Physics},
  title        = {Experimental study of dynamic isotope effects in molecular liquids: Detection of translation‐rotation coupling},
  year         = {1996},
  number       = {2},
  pages        = {669--679},
  volume       = {104},
  abstract     = {How and to what extent do molecular motions in a liquid depend upon the molecular mass? Since this fundamental problem could not yet be satisfactorily resolved by theoretical approaches, we present in this paper an experimental approach. In continuation of previous work from our laboratory, the effects of isotopic H–D substitution on viscosity and self-diffusion have been measured for twelve molecular liquids in a certain temperature range near room temperature. These liquids are the often used solvents: methanol, ethanol, formamide, N,N-dimethylformamide, dimethylsulfoxide, acetone, acetonitrile, pyridine, nitromethane, tetrahydrofuran, dioxane, and benzene; we have found comparatively high dynamic isotopic effects between 3% and 14%. Beside the NMR self-diffusion measurements we have, for the first time, performed measurements of the effect of mass change on the molecular rotational diffusion via 17O and 14N intramolecular quadrupole relaxation. In all the given molecular liquids, except benzene, the dynamic isotope effects on viscosity, translational, and rotational diffusion follow a square-root of the moment of inertia law, revealing strong translation-rotation coupling in these liquids. However, in the two further liquids n-octanol and n-dodecanol this coupling seems to be absent, since we find here for the dynamic isotopic effect on viscosity a square-root of mass law. We have also measured D*, the tracer-diffusion coefficients of light ~protonated! molecules in the heavy ~deuterated! liquids. Here, we find a very weak mass dependence of D*, which obviously follows a square-root of reduced mass law, as predicted from simple gas kinetic theory. A ‘‘negative’’ dynamic isotope effect for CHCl3/CDCl3 postulated in the literature could not be confirmed by our measurements. The NMR techniques used for this study turned out to be excellently suited for investigations of the mass effects on dynamic quantities in liquid systems},
  creationdate = {2022-05-27T00:00:00},
  doi          = {10.1063/1.470863},
  eprint       = {https://doi.org/10.1063/1.470863},
  file         = {:Holz1996 - Experimental Study of Dynamic Isotope Effects in Molecular Liquids_ Detection of Translation‐rotation Coupling.pdf:PDF},
  keywords     = {nmr, theory, isotope, 2h, 17o},
  url          = {https://doi.org/10.1063/1.470863},
}

@Article{Qvist2009,
  author       = {Qvist, Johan and Persson, Erik and Mattea, Carlos and Halle, Bertil},
  journal      = {Faraday Discuss.},
  title        = {Time scales of water dynamics at biological interfaces: peptides{,} proteins and cells},
  year         = {2009},
  pages        = {131--144},
  volume       = {141},
  abstract     = {Water 2H and 17O spin relaxation is used to study water dynamics in the hydration layers of two small peptides{,} two globular proteins and in living cells of two microorganisms. The dynamical heterogeneity of hydration water is characterized by performing relaxation measurements over a wide temperature range{,} extending deeply into the supercooled regime{,} or by covering a wide frequency range. Protein hydration layers can be described by a power-law distribution of rotational correlation times with an exponent close to 2. This distribution comprises a small fraction of protein-specific hydration sites{,} where water rotation is strongly retarded{,} and a dominant fraction of generic hydration sites{,} where water rotation is as fast as in the hydration shells of small peptides. The generic dynamic perturbation factor is less than 2 at room temperature and exhibits a maximum near 260 K. The dynamic perturbation is induced by H-bond constraints that interfere with the cooperative mechanism that facilitates rotation in bulk water. Because these constraints are temperature-independent{,} hydration water does not follow the super-Arrhenius temperature dependence of bulk water. Water in living cells behaves as expected from studies of simpler model systems{,} the only difference being a larger fraction of secluded (strongly perturbed) hydration sites associated with the supramolecular organization in the cell. Intracellular water that is not in direct contact with biopolymers has essentially the same dynamics as bulk water. There is no significant difference in cell water dynamics between mesophilic and halophilic organisms{,} despite the high K+ and Na+ concentrations in the latter.},
  creationdate = {2022-05-27T00:00:00},
  doi          = {10.1039/B806194G},
  file         = {:Qvist2009 - Time Scales of Water Dynamics at Biological Interfaces_ Peptides, Proteins and Cells.pdf:PDF},
  issue        = {0},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/B806194G},
}

@InCollection{Castiglione2015,
  author       = {Franca Castiglione and Andrea Mele and Guido Raos},
  publisher    = {Academic Press},
  title        = {Chapter Four - 17O NMR: A “Rare and Sensitive” Probe of Molecular Interactions and Dynamics},
  year         = {2015},
  editor       = {Graham A. Webb},
  pages        = {143--193},
  series       = {Annual Reports on NMR Spectroscopy},
  volume       = {85},
  abstract     = {This review summarizes recent developments in the area of liquid-state nuclear magnetic resonance spectroscopy of the 17O nucleus. It is structured in sections, respectively, covering (a) general background information, with special emphasis on spin relaxation phenomena for quadrupolar nuclei and in paramagnetic environments, (b) methods for the calculation of 17O NMR parameters, with illustrative results, (c) applications in chemistry and materials science, (d) application to biomolecules and biological systems, and (e) relaxation phenomena, including contrast agents for magnetic resonance imaging. The 17O nucleus emerges as a very sensitive probe of the local environment—including both bonding and nonbonding interactions—and molecular motions.},
  comment      = {Elsevier-Paper},
  creationdate = {2022-05-27T00:00:00},
  doi          = {https://doi.org/10.1016/bs.arnmr.2014.12.004},
  issn         = {0066-4103},
  keywords     = {Chemical shift, Relaxometry, Quantum chemistry, Molecular dynamics, Electric field gradient, Solvation, Imaging, Contrast agents, Quadrupolar nuclei, Oxygen-17},
  url          = {https://www.sciencedirect.com/science/article/pii/S0066410314000106},
}

@Article{Keeler2016,
  author       = {Keeler, Eric G. and Michaelis, Vladimir K. and Griffin, Robert G.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {17O NMR Investigation of Water Structure and Dynamics},
  year         = {2016},
  note         = {PMID: 27454747},
  number       = {32},
  pages        = {7851--7858},
  volume       = {120},
  abstract     = {The structure and dynamics of the bound water in barium chlorate monohydrate were studied with 17O nuclear magnetic resonance (NMR) spectroscopy in samples that are stationary and spinning at the magic-angle in magnetic fields ranging from 14.1 to 21.1 T. 17O NMR parameters of the water were determined, and the effects of torsional oscillations of the water molecule on the 17O quadrupolar coupling constant (CQ) were delineated with variable temperature MAS NMR. With decreasing temperature and reduction of the librational motion, we observe an increase in the experimentally measured CQ explaining the discrepancy between experiments and predictions from density functional theory. In addition, at low temperatures and in the absence of 1H decoupling, we observe a well-resolved 1H–17O dipole splitting in the spectra, which provides information on the structure of the H2O molecule. The splitting arises because of the homogeneous nature of the coupling between the two 1H–17O dipoles and the 1H–1H dipole.},
  creationdate = {2022-05-27T00:00:00},
  doi          = {10.1021/acs.jpcb.6b05755},
  eprint       = {https://doi.org/10.1021/acs.jpcb.6b05755},
  file         = {:Keeler2016 - 17O NMR Investigation of Water Structure and Dynamics.pdf:PDF},
  keywords     = {nmr, 17o, quadrupole coupling constant, chemical shift},
  url          = {https://doi.org/10.1021/acs.jpcb.6b05755},
}

@Article{Bhattacharyya2003,
  author       = {Bhattacharyya, Kankan},
  journal      = {Accounts of Chemical Research},
  title        = {Solvation Dynamics and Proton Transfer in Supramolecular Assemblies},
  year         = {2003},
  note         = {PMID: 12589694},
  number       = {2},
  pages        = {95--101},
  volume       = {36},
  abstract     = {Water molecules confined in a supramolecular assembly control reactivity and dynamics of biological systems in a unique way. In a confined system, water molecules display an ultraslow component of solvation which is slower than that in bulk water by 2−4 orders of magnitude. The ultraslow component arises mainly from the disruption of the hydrogen-bond network of water and the binding of water molecules to a macromolecule. The ultraslow component of solvation markedly retards polar reactions. Many examples of slow dynamics in complex systems, and their implications in biological and natural processes are discussed.},
  creationdate = {2022-06-01T00:00:00},
  doi          = {10.1021/ar020067m},
  eprint       = {https://doi.org/10.1021/ar020067m},
  file         = {:Bhattacharyya2003 - Solvation Dynamics and Proton Transfer in Supramolecular Assemblies.pdf:PDF},
  keywords     = {review, solvent, polymer, exchange},
  url          = {https://doi.org/10.1021/ar020067m},
}

@Article{Nandi1997,
  author       = {Nandi, Nilashis and Bagchi, Biman},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Dielectric Relaxation of Biological Water},
  year         = {1997},
  number       = {50},
  pages        = {10954--10961},
  volume       = {101},
  abstract     = {Dielectric relaxation and NMR spectrum of water in biological systems such as proteins, DNA, and reverse micelles can often be described by two widely different time constants, one of which is in the picosecond while the other is in the nanosecond regime. Although it is widely believed that the bimodal relaxation arises from water at the hydration shell, a quantitative understanding of this important phenomenon is lacking. In this article we present a theory of dielectric relaxation of biological water. The time dependent relaxation of biological water is described in terms of a dynamic equilibrium between the free and bound water molecules. It is assumed that only the free water molecules undergo orientational motion; the bound water contribution enters only through the rotation of the biomolecule, which is also considered. The dielectric relaxation is then determined by the equilibrium constant between the two species and the rate of conversion from bound to free state and vice versa. However, the dielectric relaxation in such complex biomolecular systems depends on several parameters such as the rotational time constant of the protein molecule, the dimension of the hydration shell, the strength of the hydrogen bond, the static dielectric constant of the water bound to the biomolecule, etc. The present theory includes all these aspects in a consistent way. The results are shown to be in very good agreement with all the known results. The present study can be helpful in understanding the solvation of biomolecules such as proteins.},
  creationdate = {2022-06-01T00:00:00},
  doi          = {10.1021/jp971879g},
  eprint       = {https://doi.org/10.1021/jp971879g},
  file         = {:Nandi1997 - Dielectric Relaxation of Biological Water.pdf:PDF},
  keywords     = {bound, water, exchange, polymer, protein, solvation, dielectric spectroscopy, nmr},
  url          = {https://doi.org/10.1021/jp971879g},
}

@Article{Glasel1970,
  author       = {Glasel, Jay A.},
  journal      = {Journal of the American Chemical Society},
  title        = {Deuteron Magnetic Relaxation Studies on the Solution Properties of Some Denaturing Agents and Surfactants},
  year         = {1970},
  note         = {PMID: 5411055},
  number       = {2},
  pages        = {372--375},
  volume       = {92},
  abstract     = {Deuteron relaxation times in D2O solutions of urea, acteone, guanidine, hydrochloride, dimethyl sulfoxide, t-butylalcohol, sodiumdodecylsulfate and several commercial surfactants are reported. The observed interaction of these with water at low concentration is analyzed and discussed. It is of the same order of magnitude as water-ion interaction. Properties of compound formation between dimethyl sulfoxide and water at high solute concentrations is also discussed. The results indicate 3H2O-DMSO as the formula of the complex and this is compared with the results of other methods.},
  creationdate = {2022-06-01T00:00:00},
  doi          = {10.1021/ja00705a602},
  eprint       = {https://doi.org/10.1021/ja00705a602},
  file         = {:Glasel1970 - Deuteron Magnetic Relaxation Studies on the Solution Properties of Some Denaturing Agents and Surfactants.pdf:PDF},
  url          = {https://doi.org/10.1021/ja00705a602},
}

@Article{Glasel1974,
  author       = {Glasel, Jay A. and Lee, K. H.},
  journal      = {Journal of the American Chemical Society},
  title        = {Interpretation of water nuclear magnetic resonance relaxation times in heterogeneous systems},
  year         = {1974},
  number       = {4},
  pages        = {970--978},
  volume       = {96},
  abstract     = {Evidence is presented for the existence of large magnetic field inhomogeneities in heterogeneous systems which make it difficult to analyze nmr wide-line and relaxation results correctly using current theoretical and experimental techniques. Spin-echo and null-point techniques have been employed to measure transverse and longitudinal relaxation times of deuterons for a series of deuterium oxide-glass bead systems. The average diameter of the beads ranged from 20 to 661 u in seven different groups. Relaxation times were affected by the existence of the larger surface area and decreased as the surface to volume ration increased. No effects of surface character on relaxation times were detected. Accepted interpreation of the results in terms of fast exchange of water molecules between bulk and surface water indicates that there is prectically no surface water in rotationally restriced form at the surface of glass beads: uncoated, coated with hydrophilic membranes, or coated with hydrophobic silicone compound. However, further analysis of the experimental results indicated that any surface effects could have been masked by the large magnetic inner field inhomogeneities creater by the heterogeneous nature of the samples. A simple model is used to show the existence of large field gradients in heterogeneous systems. Theroretical values of field inhomogeneity agree well with experimental values. It was also observed that paramagnetic substance bound at the surface of the glass beads enhanced the longitudinal relaxation rate of the deuterium over the same number of ions in an aqueous solution of the same available volume. The results have important implications for the evaluation of similar data arising from heterogeneous biological samples. It is possible, however, that measurements of relaxation times in uniform heterogeneous systems (such as the beads) could be used to determine diffusion coefficients in liquids.},
  creationdate = {2022-06-01T00:00:00},
  doi          = {10.1021/ja00811a003},
  eprint       = {https://doi.org/10.1021/ja00811a003},
  file         = {:Glasel1974 - Interpretation of Water Nuclear Magnetic Resonance Relaxation Times in Heterogeneous Systems.pdf:PDF},
  keywords     = {susceptibility, heterogeneous systems, nmr, relaxation},
  printed      = {printed},
  readstatus   = {read},
  url          = {https://doi.org/10.1021/ja00811a003},
}

@Article{Glasel1970a,
  author       = {J. Glasel},
  journal      = {Nature},
  title        = {NMR Relaxation in Heterogeneous Systems},
  year         = {1970},
  pages        = {704--705},
  volume       = {227},
  abstract     = {There has recently been some discussion of the difficulties of interpreting nuclear magnetic resonance line broadening in complex heterogeneous suspensions. The discussion has been concerned with hindered rotation of solvent species, and it has been confined to proton magnetic relaxation. We report here a study of the relaxation phenomenon in a well defined physicochemical system and contrast the results for proton and deuteron relaxation.},
  creationdate = {2022-06-01T00:00:00},
  doi          = {https://doi.org/10.1038/227704b0},
  file         = {:Glasel1970a - NMR Relaxation in Heterogeneous Systems.pdf:PDF},
  keywords     = {heterogeneous systems, nmr, intra, inter, 1h, 2h},
  readstatus   = {read},
  url          = {https://doi.org/10.1038/227704b0},
}

@Article{Glasel1970b,
  author       = {Glasel, Jay A.},
  journal      = {Journal of the American Chemical Society},
  title        = {Participation of Water in Conformational Changes of Biopolymers as Studied by Deuteron Magnetic Relaxation},
  year         = {1970},
  note         = {PMID: 5411056},
  number       = {2},
  pages        = {375--381},
  volume       = {92},
  abstract     = {deuteron magnetic spin-lattice relaxation experiments perfomed on D2O solutions of various macromolecules are described and discussed. This technique allows the interaction of water with various conformations of biopolymers to be measured quantitatively. The molecules studied are: poly(L-glutamic acid), poly(L-lysine), poly(adenylic acid), poly(uridylic acid), poly(methacrylic acid), poly(vinyloxazolidone methyl) and poly(vinyl-pyrrolidone). General classes of interactions are proposed on the basis of the results, and the effect of geometrical fluctuations of polymer conformation upon polymer-water interactions are discussed. It is concluded that the competing effects of counterion-polymer interaction (electrostatic) and polymer-water interaction (hydrogen bond) are of vital importance in mediating polymer conformation.},
  creationdate = {2022-06-01T00:00:00},
  doi          = {10.1021/ja00705a603},
  eprint       = {https://doi.org/10.1021/ja00705a603},
  file         = {:Glasel1970b - Participation of Water in Conformational Changes of Biopolymers As Studied by Deuteron Magnetic Relaxation.pdf:PDF},
  printed      = {printed},
  readstatus   = {read},
  url          = {https://doi.org/10.1021/ja00705a603},
}

@Article{Kyriakos2016,
  author       = {Kyriakos, Konstantinos and Philipp, Martine and Silvi, Luca and Lohstroh, Wiebke and Petry, Winfried and Müller-Buschbaum, Peter and Papadakis, Christine M.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Solvent Dynamics in Solutions of PNIPAM in Water/Methanol Mixtures—A Quasi-Elastic Neutron Scattering Study},
  year         = {2016},
  note         = {PMID: 27187897},
  number       = {20},
  pages        = {4679--4688},
  volume       = {120},
  abstract     = {The solvent dynamics of concentrated solutions of poly(N-isopropylacrylamide) (PNIPAM, 25 wt \%) in water/methanol mixtures (85:15 v/v) are measured with the aim of shedding light onto the cononsolvency effect. Quasi-elastic neutron scattering (QENS) with contrast variation has been carried out at temperatures below and above the cloud point by using in the first set of experiments the mixture H2O:d-MeOD (d-MeOD denotes fully deuterated methanol) as a solvent and in the second set of experiments the mixture D2O:MeOH (MeOH denotes methanol). As a reference, bulk H2O, bulk MeOH and the mixtures H2O:d-MeOD and D2O:MeOH (both 85:15 v/v) have been investigated as well. In the PNIPAM solution in H2O:d-MeOD, two water populations are identified, namely strongly and less strongly arrested water. At the cloud point, the former is partially released from PNIPAM. The diffusion coefficient of the latter one is similar to the one in the water/methanol mixture, and its residence time decreases at the cloud point. The PNIPAM solution in D2O:MeOH reveals similar dynamics to the one in H2O:d-MeOD which may reflect that the dynamics of MeOH near the PNIPAM chain is similar to the one of H2O. The similarity may, however, partially be due to H/D exchange between D2O and MeOH. In both PNIPAM solutions, the mean-square displacement of the PNIPAM chain decreases gradually above the cloud point.},
  creationdate = {2022-06-09T00:00:00},
  doi          = {10.1021/acs.jpcb.6b01200},
  eprint       = {https://doi.org/10.1021/acs.jpcb.6b01200},
  file         = {:Kyriakos2016 - Solvent Dynamics in Solutions of PNIPAM in Water_Methanol Mixtures—A Quasi Elastic Neutron Scattering Study.pdf:PDF;:SolventDynamicsInSolutionsOfPNIPAMInWaterMethanolMixtures-AQuasiElasitcNeutronScatteringStudy_KyriakosEtAl_JPC2016_SI.pdf:PDF},
  keywords     = {pnipam, quasi-elastic neutron scattering, QENS, cononsolvency, methanol},
  url          = {https://doi.org/10.1021/acs.jpcb.6b01200},
}

@Article{Haq2017,
  author       = {Muhammad Abdul Haq and Yunlan Su and Dujin Wang},
  journal      = {Materials Science and Engineering: C},
  title        = {Mechanical properties of PNIPAM based hydrogels: A review},
  year         = {2017},
  issn         = {0928-4931},
  pages        = {842--855},
  volume       = {70},
  abstract     = {Materials which adjust their properties in response to environmental factors such as temperature, pH and ionic strength are rapidly evolving and known as smart materials. Hydrogels formed by smart polymers have various applications. Among the smart polymers, thermoresponsive polymer poly(N-isopropylacrylamide)(PNIPAM) is very important because of its well defined structure and property specially its temperature response is closed to human body and can be finetuned as well. Mechanical properties are critical for the performance of stimuli responsive hydrogels in diverse applications. However, native PNIPAM hydrogels are very fragile and hardly useful for any practical purpose. Intense researches have been done in recent decade to enhance the mechanical features of PNIPAM hydrogel. In this review, several strategies including interpenetrating polymer network (IPN), double network (DN), nanocomposite (NC) and slide ring (SR) hydrogels are discussed in the context of PNIPAM hydrogel.},
  creationdate = {2022-06-09T00:00:00},
  doi          = {https://doi.org/10.1016/j.msec.2016.09.081},
  file         = {:Haq2017 - Mechanical Properties of PNIPAM Based Hydrogels_ a Review.pdf:PDF},
  keywords     = {Poly(-isopropylacrylamide), Hydrogel, Smart material, Mechanical properties, review},
  url          = {https://www.sciencedirect.com/science/article/pii/S0928493116315466},
}

@Article{Tan2010,
  author       = {B.H. Tan and R.H. Pelton and K.C. Tam},
  journal      = {Polymer},
  title        = {Microstructure and rheological properties of thermo-responsive poly(N-isopropylacrylamide) microgels},
  year         = {2010},
  issn         = {0032-3861},
  number       = {14},
  pages        = {3238--3243},
  volume       = {51},
  abstract     = {The microstructure and rheological properties of thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) microgels cross-linked with methylenebis-acrylamide (BA) were examined by dynamic light scattering and rheological techniques. As the temperature was increased from 10 to 50 °C, the particles diameter decreased by approximately two times near the volume phase transition temperature, Tv of between 30 and 35 °C. The addition of salt to the microgel dispersion provides competition for the water molecules hydrating the PNIPAM chains thus weakening the PNIPAM–H2O hydrogen bonds and the microgel progressively deswelled. The validity and limitation of the semi-empirical approach to model charged soft microgel particles developed previously were tested on this thermo-responsive system. A variable specific volume, k was introduced to convert the mass concentration to effective volume fraction. With increasing concentration, inter-particle repulsive force was enhanced, which overcame the osmotic force inside the soft particle, resulting in the expulsion of solvent from the swollen particles, and the particle shrank. The viscosity data for PNIPAM microgels at varying solution temperatures and ionic strength showed excellent agreement with the modified Krieger–Dougherty (K–D) model.},
  creationdate = {2022-06-09T00:00:00},
  doi          = {https://doi.org/10.1016/j.polymer.2010.04.059},
  file         = {:Tan2010 - Microstructure and Rheological Properties of Thermo Responsive Poly(N Isopropylacrylamide) Microgels.pdf:PDF},
  keywords     = {Thermo-responsive microgel, Viscosity, Poly(NIPAM), pnipam, salt, ionic strength, vpt, rheology, light scattering, dls, effective volume fraction},
  url          = {https://www.sciencedirect.com/science/article/pii/S003238611000385X},
}

@Article{Schild1991,
  author       = {Schild, Howard G. and Muthukumar, M. and Tirrell, David A.},
  journal      = {Macromolecules},
  title        = {Cononsolvency in mixed aqueous solutions of poly(N-isopropylacrylamide)},
  year         = {1991},
  number       = {4},
  pages        = {948--952},
  volume       = {24},
  abstract     = {The lower critical solution temperature (LCST) of poly(N-isopropylacrylamide) (PNIPAAM), prepared by an aqueous redox polymerization, was studied in the cononsolvent mixture of water and methanol by means of cloud-point and microcalorimetric measurements. The observed solution behavior was quite distinct from that of poly (vinyl methyl ether) in the same binary solvent. Other cononsolvents, including dioxane and tetrahydrofuran, yielded phase diagrams similar to those of PNIPAAM in water-methanol mixtures. Flory-Huggins ternary solution theory can explain the observed results only in terms of a change in the solvent-solvent interaction parameter ( [2) in PNIPAAM solutions. We believe this to be physically implausible in the dilute (0.04%) solutions used in this work. Furthermore, we find in comparing our work with that of Hirotsu (Hirotsu, S. J. Chem. Phys. 1988, 88, 427) that the behavior of PNIPAAM in water methanol mixtures is strikingly insensitive to á 200-fold variation in polymer concentration. We suggest that perturbation of 2 is not the origin of cononsolvency or of the gel collapse transitions reported by Hirotsu and by Tanaka and co-workers (Amiya, T.; Hirokawa, Y.; Hirose, Y.; Li, Y.; Tanaka, T. J. Chem. Phys. 1987, 86, 2375)},
  creationdate = {2022-06-09T00:00:00},
  doi          = {10.1021/ma00004a022},
  eprint       = {https://doi.org/10.1021/ma00004a022},
  file         = {:Schild1991 - Cononsolvency in Mixed Aqueous Solutions of Poly(N Isopropylacrylamide).pdf:PDF},
  keywords     = {pnipam, cononsolvency, cloud-point, microcalorimetry, lcst, flory-huggins},
  url          = {https://doi.org/10.1021/ma00004a022},
}

@Article{Tamai1996a,
  author       = {Tamai, Yoshinori and Tanaka, Hideki and Nakanishi, Koichiro},
  journal      = {Macromolecules},
  title        = {Molecular Dynamics Study of Polymer−Water Interaction in Hydrogels. 2. Hydrogen-Bond Dynamics},
  year         = {1996},
  number       = {21},
  pages        = {6761--6769},
  volume       = {29},
  abstract     = {Molecular dynamics simulations have been performed for hydrogel models of poly(vinyl alcohol) (PVA), poly(vinyl methyl ether) (PVME), and poly(N-isopropylacrylamide) (PNiPAM). The dynamics of hydrogen bonds and the translational and rotational motions of water molecules in the vicinity of the polymer segments are analyzed to investigate the properties of water molecules which are highly cooperative with the surrounding polymer chains. The characters of the hydrophilic groups which are reflected in the lifetime of hydrogen bonds, the spectral density, etc., are examined. The mobility of water molecules is significantly lowered around polymer chains for both translational and rotational motions. This is partly because of the hydrogen bonds between water and polymers around the hydrophilic groups and partly because of the structuralization of water around the hydrophobic groups.},
  creationdate = {2022-06-09T00:00:00},
  doi          = {10.1021/ma960961r},
  eprint       = {https://doi.org/10.1021/ma960961r},
  file         = {:Tamai1996 - Molecular Dynamics Study of Polymer−Water Interaction in Hydrogels. 2. Hydrogen Bond Dynamics.pdf:PDF},
  keywords     = {molecular dynamics simulation,pnipam,pva,pvme,hydrogen bond,cooperativity,spectral density,diffusion coefficient,hydrophobic hydration},
  url          = {https://doi.org/10.1021/ma960961r},
}

@Article{Sun2008,
  author       = {Sun, Bingjie and Lin, Yinan and Wu, Peiyi and Siesler, Heinz W.},
  journal      = {Macromolecules},
  title        = {A FTIR and 2D-IR Spectroscopic Study on the Microdynamics Phase Separation Mechanism of the Poly(N-isopropylacrylamide) Aqueous Solution},
  year         = {2008},
  number       = {4},
  pages        = {1512--1520},
  volume       = {41},
  abstract     = {The thermal behavior of PNIPAM in its concentrated D2O solution (20 wt \%) was studied by FTIR and 2D-IR correlation spectroscopy. The spectral data of the C−H groups and the Amide I region provide details about the changes of the hydrophobic and hydrophilic parts in the polymer respectively during a heating−cooling cycle. The reversal of peak positions of the C−H bands upon cooling indicates the reversibility of temperature-induced dehydration of the hydrophobic groups. The change in hydrogen bonding of CO···D−N constructed between dehydrated CO and N−D groups, as derived from the Amide I region, does not revert precisely in the cooling process due to the newly formed hydrogen bonds in the collapsed state, and a hysteresis phenomenon is observed. In our concentrated solution (20 wt \%), the strength of those intra- and interchain hydrogen bonds even prevent the polymers from dissociating completely below the LCST during the cooling process. The microdynamics phase separation mechanism was obtained by application of the 2D-IR analysis to the spectral data. When the temperature rises, the two-step dehydration of the CH3 groups occurs first, then the main-chain diffusion and aggregation takes place, and finally the hydrogen bond transition occurs. The dynamic sequence in the cooling process is also described.},
  creationdate = {2022-06-09T00:00:00},
  doi          = {10.1021/ma702062h},
  eprint       = {https://doi.org/10.1021/ma702062h},
  file         = {:Sun2008 - A FTIR and 2D IR Spectroscopic Study on the Microdynamics Phase Separation Mechanism of the Poly(N Isopropylacrylamide) Aqueous Solution.pdf:PDF},
  keywords     = {FTIR, pnipam, aqueous, d2o, hysteresis},
  url          = {https://doi.org/10.1021/ma702062h},
}

@Article{Fuellbrandt2012,
  author       = {F{\"u}llbrandt, Marieke and von Klitzing, Regine and Sch{\"o}nhals, Andreas},
  journal      = {Soft Matter},
  title        = {Probing the phase transition of aqueous solutions of linear low molecular weight poly(N-isopropyl\-acrylamide) by dielectric spectroscopy},
  year         = {2012},
  pages        = {12116--12123},
  volume       = {8},
  abstract     = {Aqueous solutions of linear poly(N-isopropylacrylamide) (pNIPAM) with different polymer concentrations are investigated using dielectric spectroscopy in a frequency range of 10−1 Hz to 106 Hz at temperatures from 15 °C to 50 °C. The phase transition of pNIPAM is monitored by both the temperature (T) and the frequency (f) dependence of the conductivity spectra σ*(f{,} T). First{,} the T-dependence of the DC conductivity σ′DC is investigated and the phase transition (“coil-to-globule” transition) at the lower critical solution temperature (LCST) of pNIPAM is deduced by a change in the T-dependence of σ′DC. The observed hysteresis between heating and cooling runs is discussed in detail in dependence on both the polymer concentration and the rate. Second{,} for the first time a pronounced f-dependence of the real part of conductivity σ′ is observed at temperatures above the LCST whereas at temperatures below the LCST the conductivity spectra are more or less similar to that of water (frequency independent). This f-dependence of σ′ is assigned to the formation of a kind of soft particle (“globular structure”) at the LCST which is more or less impermeable to water and ions therefore giving rise to Maxwell–Wagner–Sillars (MWS) polarization effects (blocking of charges at the soft particle). The dependence on the concentration is studied in detail.},
  creationdate = {2022-06-09T00:00:00},
  doi          = {10.1039/C2SM26826D},
  file         = {:Fuellbrandt2012 - Probing the Phase Transition of Aqueous Solutions of Linear Low Molecular Weight Poly(N Isopropylacrylamide) by Dielectric Spectroscopy.pdf:PDF},
  issue        = {48},
  keywords     = {pNIPAM, transition kinetics, dc conductivity, hysteresis},
  printed      = {printed},
  publisher    = {The Royal Society of Chemistry},
  readstatus   = {read},
  url          = {http://dx.doi.org/10.1039/C2SM26826D},
}

@Article{Kourilova2009,
  author       = {Hana Kouřilová and Lenka Hanyková and Jiří Spěváček},
  journal      = {European Polymer Journal},
  title        = {NMR study of phase separation in D2O/ethanol solutions of poly(N-isopropylmethacrylamide) induced by solvent composition and temperature},
  year         = {2009},
  issn         = {0014-3057},
  number       = {10},
  pages        = {2935--2941},
  volume       = {45},
  abstract     = {1H and 13C NMR spectroscopies were applied to investigate phase separation in solutions of poly(N-isopropylmethacrylamide) (PIPMAm) in D2O/ethanol (EtOH) mixtures induced by solvent composition (cononsolvency) and temperature. Effects of EtOH content in D2O/EtOH mixtures and temperature on the appearance and extent of the phase separation were characterized. Differences in mesoglobules formed during the phase separation induced by cononsolvency and temperature were found. For temperature-induced phase separation, 13C spin–spin relaxation times showed that besides the free EtOH expelled from the PIPMAm mesoglobules, there are also EtOH molecules bound in these mesoglobules. On the other hand, virtually no bound EtOH molecules were detected for mesoglobules formed as a consequence of the cononsolvency. For PIPMAm random copolymers containing negatively charged methacrylate units the phase separation induced by solvent composition was not observed.},
  creationdate = {2022-06-10T00:00:00},
  doi          = {10.1016/j.eurpolymj.2009.06.011},
  file         = {:Kourilova2009 - NMR Study of Phase Separation in D2O_ethanol Solutions of Poly(N Isopropylmethacrylamide) Induced by Solvent Composition and Temperature.pdf:PDF},
  keywords     = {Poly(-isopropylmethacrylamide)/DO/ethanol solutions, Phase separation, Cononsolvency, H and C NMR spectroscopy},
  printed      = {printed},
  url          = {https://www.sciencedirect.com/science/article/pii/S0014305709002766},
}

@Book{Abragam1999,
  author       = {Anatole Abragam},
  publisher    = {Oxford: University Press},
  title        = {The principles of nuclear magnetism},
  year         = {1999},
  isbn         = {019852014x},
  creationdate = {2022-07-07T00:00:00},
  file         = {:Abragam1999 - The Principles of Nuclear Magnetism.pdf:PDF},
}

@Article{Kyrey2021,
  author       = {Kyrey, Tetyana and Witte, Judith and Lutzki, Jana and Zamponi, Michaela and Wellert, Stefan and Holderer, Olaf},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Mobility of bound water in PNIPAM microgels},
  year         = {2021},
  pages        = {14252--14259},
  volume       = {23},
  abstract     = {Polymer–solvent interactions play a crucial role in the stimuli-responsive behaviour of polymer networks. They influence the swelling/deswelling behaviour as well as the dynamics of the polymer chains. Scattering experiments provide insight into the polymer–water interaction of poly(N-isopropylacrylamide) (PNIPAM) microgels cross-linked with N{,}N′-methylenebisacrylamide (BIS) in dried and humidified state. The water mobility is studied by means of neutron spin-echo spectroscopy and neutron backscattering spectroscopy. The residual water amount has been determined with Karl Fischer titration. For both degrees of humidification{,} the relaxation time of the water molecules is much larger than that of free water due to the strong interactions with the polymer network and is only weakly depending on temperature and length scale of observation. The possible influence of the water on methyl group rotations is discussed.},
  creationdate = {2022-07-07T00:00:00},
  doi          = {10.1039/D1CP01823J},
  file         = {:Kyrey2021 - Mobility of Bound Water in PNIPAM Microgels.pdf:PDF},
  issue        = {26},
  keywords     = {pNIPAM,microgel,neutron scattering,bound water,QENS,solvent dynamics},
  priority     = {prio1},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D1CP01823J},
}

@Article{Park1994,
  author       = {Park, Tae Gwan and Hoffman, Allan S.},
  journal      = {Journal of Applied Polymer Science},
  title        = {Deswelling characteristics of poly(N-isopropylacrylamide) hydrogel},
  year         = {1994},
  number       = {1},
  pages        = {85--89},
  volume       = {52},
  abstract     = {Poly(N-isopropylacrylamide) gels exhibit a lower critical solution temperature (LCST) behavior in aqueous solution. At temperatures below the LCST, the gel is more hydrated than at temperatures above the LCST. At the LCST, the volume change is sharp. It is shown here that the water content of the gel above the LCST depends upon previous states of the gel (e.g., dry or wet), the heating rate, and the gel thickness. Deswelling kinetics are also affected by the gel thickness. Caffeine release experiments indicate that microscopic water pockets are formed within the matrix during the rapid gel collapse procedure.},
  creationdate = {2022-07-07T00:00:00},
  doi          = {https://doi.org/10.1002/app.1994.070520110},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/app.1994.070520110},
  file         = {:https___doi.org_10.1002_app.1994.070520110 - Deswelling Characteristics of Poly(N Isopropylacrylamide) Hydrogel.pdf:PDF},
  keywords     = {pNIPAM, kinetics, hydrogel, gel, LCST, drug delivery, VPTT, weight},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/app.1994.070520110},
}

@Article{Mallamace2015,
  author       = {Francesco Mallamace and Carmelo Corsaro and Domenico Mallamace and Nicola Cicero and Sebastiano Vasi and Giacomo Dugo and H. Eugene Stanley},
  journal      = {Front. Phys.},
  title        = {Dynamical chances in hydration water accompanying lysozyme thermal denaturation},
  year         = {2015},
  volume       = {10},
  creationdate = {2022-07-11T00:00:00},
  doi          = {https://doi.org/10.1007/s11467-015-0486-9},
  file         = {:Mallamace2015 - Dynamical Chances in Hydration Water Accompanying Lysozyme Thermal Denaturation.pdf:PDF},
  keywords     = {1H-nmr, polymer, lysozyme, hydration water, denaturation, collapse, longitudinal relaxation, T1, self-diffusion},
  url          = {https://doi.org/10.1007/s11467-015-0486-9},
}

@Article{Hannoun1986,
  author       = {Hannoun, Betty J. M. and Stephanopoulos, Gregory},
  journal      = {Biotechnology and Bioengineering},
  title        = {Diffusion coefficients of glucose and ethanol in cell-free and cell-occupied calcium alginate membranes},
  year         = {1986},
  number       = {6},
  pages        = {829--835},
  volume       = {28},
  abstract     = {The diffusivities of glucose and ethanol in cell-free and cell-occupied membranes of calcium alginate were measured in a diffusion cell. The lag time analysis was used. Diffusivities decreased with increasing alginate concentration and were comparable with those in water for a 2\% alginate membrane. Glucose and ethanol concentrations had no effect on the respective diffusion coefficients. The ratio of ethanol diffusivity to glucose diffusivity in 2 and 4\% alginate agreed closely with the inverse ratio of the hydrodynamic raii for the two molecules in water, indicating that the hydrodynamic theory of diffusion in liquids may be applicable to diffusion in dilute alginate gels. Also, the presence of 20\% dead yeast cells had no effect on the diffusivities. The data reported can be used to study reaction and diffusion in immobilized cell reactors and cell physiology under immobilized conditions.},
  creationdate = {2022-07-11T00:00:00},
  doi          = {https://doi.org/10.1002/bit.260280609},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/bit.260280609},
  file         = {:Hannoun1986 - Diffusion Coefficients of Glucose and Ethanol in Cell Free and Cell Occupied Calcium Alginate Membranes.pdf:PDF},
  keywords     = {ethanol, hydrodynamic radius, diffusion coefficient},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/bit.260280609},
}

@Article{Lindsey1980,
  author       = {Lindsey,C. P. and Patterson,G. D.},
  journal      = {The Journal of Chemical Physics},
  title        = {Detailed comparison of the Williams–Watts and Cole–Davidson functions},
  year         = {1980},
  number       = {7},
  pages        = {3348--3357},
  volume       = {73},
  abstract     = {The distribution function of relaxation times underlying the nonexponential relaxation function of Williams and Watts is derived and compared with the analogous Cole-Davidson distribution function. In order to make the comparison between the two distribution functions, a simple empirical relationship between the Cole-Davidson and Williams-Watts parameters was determined which may be used to compare data analyzed using the two fitting functions. Although the relaxation functions are similar to each other, the distribution functions are quite dissimilar. The Cole-Davidson distribution shows a sharp long time cutoff, while the Williams-Watts distribution decays approximately exponentially at long times. Finally, several useful relations between relaxation and distribution functions are summarized or derived, and the limitations of deriving distribution functions from relaxation functions are discussed.},
  creationdate = {2022-07-20T00:00:00},
  doi          = {10.1063/1.440530},
  eprint       = {https://doi.org/10.1063/1.440530},
  file         = {:Lindsey1980 - Detailed Comparison of the Williams–Watts and Cole–Davidson Functions.pdf:PDF},
  keywords     = {spectral density, correlation time distribution, dielectric spectroscopy, theory},
  url          = {https://doi.org/10.1063/1.440530},
}

@Article{Serin2016,
  author       = {Serin, Guillaume and Nguyen, Hong Hanh and Marty, Jean-Daniel and Micheau, Jean-Claude and Gernigon, V{\'{e}}ronique and Mingotaud, Anne-Fran{\c{c}}oise and Bajon, Damienne and Soulet, Thierry and Massenot, S{\'{e}}bastien and Coudret, Christophe},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Terahertz Time-Domain Spectroscopy of Thermoresponsive Polymers in Aqueous Solution},
  year         = {2016},
  note         = {PMID: 27490372},
  number       = {36},
  pages        = {9778--9787},
  volume       = {120},
  abstract     = {The behavior of highly concentrated aqueous solutions of two thermoresponsive polymers poly(N-isopropylacrylamide) (PNIPAm) and poly(N-vinylcaprolactam) (PVCL) have been investigated by terahertz time-domain spectroscopy (THz-TDS). Measurements have been performed for concentrations up to 20 wt \%, over a frequency range from 0.3 to 1.5 THz and for temperatures from 20 to 45 {$^{\circ}$}C including the zone for lower critical solution temperature (LCST). THz-TDS enables the study of the behavior of water present in the solution (i.e., free or bound to the polymer). From these measurements, in addition to phase transition temperature, thermodynamic data such as variation of enthalpy and entropy can be inferred. Thanks to these data, further insights upon the mechanism involved during the dehydration phenomenon were obtained. These results were compared to the ones issued from dynamic light scattering, spectroscopy, or microscopy techniques to underline the interest to use THz-TDS as a powerful tool to characterize the behavior of thermoresponsive polymers in highly concentrated solutions.},
  comment      = {hysteresis in SI},
  creationdate = {2022-07-21T00:00:00},
  doi          = {10.1021/acs.jpcb.6b06859},
  eprint       = {https://doi.org/10.1021/acs.jpcb.6b06859},
  file         = {:Serin2016 - Terahertz Time Domain Spectroscopy of Thermoresponsive Polymers in Aqueous Solution.pdf:PDF;:TerahertzTimeDomainSpectroscopyOfThermoresponsivePolymersInAqueousSolution_SerinEtAl_JPC2016_SI.pdf:PDF},
  keywords     = {pnipam, PVCL, terahrtz time-domain spectroscopy, TDS, LCST, concentration, entropy, enthalpy, two-state model, dehydration, hydrogen bonds, bound water, hydration number, hysteresis},
  readstatus   = {read},
  url          = {https://doi.org/10.1021/acs.jpcb.6b06859},
}

@Article{Shiraga2015,
  author       = {Shiraga, Keiichiro and Naito, Hirotaka and Suzuki, Tetsuhito and Kondo, Naoshi and Ogawa, Yuichi},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Hydration and Hydrogen Bond Network of Water during the Coil-to-Globule Transition in Poly(N-isopropylacrylamide) Aqueous Solution at Cloud Point Temperature},
  year         = {2015},
  note         = {PMID: 25865253},
  number       = {17},
  pages        = {5576--5587},
  volume       = {119},
  abstract     = {Aqueous solutions of poly(N-isopropylacrylamide), P-NIPAAm, exhibit a noticeable temperature responsive change in molecular conformation at a cloud point temperature (Tcp). As the temperature rises above Tcp, the extended coil-like P-NIPAAm structure changes into a swollen globule-like conformation as hydration levels decrease and hydrophobic interactions increase. Though water plays an important role in this coil-to-globule transition of P-NIPAAm, the behavior of water molecules and the associated hydrogen-bond (HB) network of the surrounding bulk water are still veiled in uncertainty. In this study, we elucidate changes in the hydration state and the dynamical structure of the water HB network of P-NIPAAm aqueous solutions during the coil-to-globule transition by analyzing the complex dielectric constant in the terahertz region (0.25–12 THz), where bulk water reorientations and intermolecular vibrations of water can be selectively probed. The structural properties of the water HB network were examined in terms of the population of the non-HB water molecules (not directly engaged in the HB network or hydrated to P-NIPAAm) and the tetrahedral coordination of the water molecules engaged in the HB network. We found the hydration number below Tcp (≈10) was decreased to approximately 6.5 as temperature increased, in line with previous studies. The HB network of bulk water becomes more structured as the coil-to-globule phase transition takes place, via decreases in non-HB water and reduction in the orderliness of the tetrahedral HB architecture. Together these results indicate that the coil-to-globule transition is associated with a shift to hydrophobic-dominated interactions that drive thermoresponsive structural changes in the surrounding water molecules.},
  comment      = {Very similar polymer solutions to mine, but working with fitparameters they didnt really measure.},
  creationdate = {2022-07-21T00:00:00},
  doi          = {10.1021/acs.jpcb.5b01021},
  eprint       = {https://doi.org/10.1021/acs.jpcb.5b01021},
  file         = {:Shiraga2015 - Hydration and Hydrogen Bond Network of Water during the Coil to Globule Transition in Poly(N Isopropylacrylamide) Aqueous Solution at Cloud Point Temperature.pdf:PDF},
  keywords     = {pnipam, LCST, solvent dynamics, bound water, hydrogen bond network, dielectric spectroscopy},
  ranking      = {rank1},
  relevance    = {relevant},
  url          = {https://doi.org/10.1021/acs.jpcb.5b01021},
}

@Article{Deshmukh2012,
  author       = {Deshmukh, Sanket A. and Sankaranarayanan, Subramanian K. R. S. and Suthar, Kamlesh and Mancini, Derrick C.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Role of Solvation Dynamics and Local Ordering of Water in Inducing Conformational Transitions in Poly(N-isopropylacrylamide) Oligomers through the LCST},
  year         = {2012},
  note         = {PMID: 22296566},
  number       = {9},
  pages        = {2651--2663},
  volume       = {116},
  abstract     = {Conformational transitions in thermo-sensitive polymers are critical in determining their functional properties. The atomistic origin of polymer collapse at the lower critical solution temperature (LCST) remains a fundamental and challenging problem in polymer science. Here, molecular dynamics simulations are used to establish the role of solvation dynamics and local ordering of water in inducing conformational transitions in isotactic-rich poly(N-isopropylacrylamide) (PNIPAM) oligomers when the temperature is changed through the LCST. Simulated atomic trajectories are used to identify stable conformations of the water-molecule network in the vicinity of polymer segments, as a function of the polymer chain length. The dynamics of the conformational evolution of the polymer chain within its surrounding water molecules is evaluated using various structural and dynamical correlation functions. Around the polymer, water forms cage-like structures with hydrogen bonds. Such structures form at temperatures both below and above the LCST. The structures formed at temperatures above LCST, however, are significantly different from those formed below LCST. Short oligomers consisting of 3, 5, and 10 monomer units (3-, 5-, and 10-mer), are characterized by significantly higher hydration level (water per monomer ∼ 16). Increasing the temperature from 278 to 310 K does not perturb the structure of water around the short oligomers. In the case of 3-, 5-, and 10-mer, a distinct coil-to-globule transition was not observed when the temperature was raised from 278 to 310 K. For a PNIPAM polymer chain consisting of 30 monomeric units (30-mer), however, there exist significantly different conformations corresponding to two distinct temperature regimes. Below LCST, the water molecules in the first hydration layer (∼12) around hydrophilic groups arrange themselves in a specific ordered manner by forming a hydrogen-bonded network with the polymer, resulting in a solvated polymer acting as hydrophilic. Above LCST, this arrangement of water is no longer stable, and the hydrophobic interactions become dominant, which contributes to the collapse of the polymer. Thus, this study provides atomic-scale insights into the role of solvation dynamics in inducing coil-to-globule phase transitions through the LCST for thermo-sensitive polymers like PNIPAM.},
  creationdate = {2022-07-21T00:00:00},
  doi          = {10.1021/jp210788u},
  eprint       = {https://doi.org/10.1021/jp210788u},
  file         = {:Deshmukh2012 - Role of Solvation Dynamics and Local Ordering of Water in Inducing Conformational Transitions in Poly(N Isopropylacrylamide) Oligomers through the LCST.pdf:PDF},
  keywords     = {solvent dynamics, pnipam, LCST, oligomer, thermoresponsive, molecular dynamics simulation, bound water, network, ordering, hydrogen bond},
  url          = {https://doi.org/10.1021/jp210788u},
}

@Article{Sun2010,
  author       = {Sun, Shengtong and Hu, Jun and Tang, Hui and Wu, Peiyi},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Chain Collapse and Revival Thermodynamics of Poly(N-isopropylacrylamide) Hydrogel},
  year         = {2010},
  note         = {PMID: 20666519},
  number       = {30},
  pages        = {9761--9770},
  volume       = {114},
  abstract     = {Two-dimensional correlation infrared spectroscopy (2DIR) and a newly developed perturbation correlation moving window (PCMW) technique were employed to study the precise chain collapse and revival thermodynamic mechanism of poly(N-isopropylacrylamide) (PNIPAM) hydrogel. Both Boltzmann fitting and PCMW had figured out the volume phase transition temperature for heating and cooling processes to be about 35 and 33.5 °C, respectively, close to the results obtained from DSC. Furthermore, determination of the isosbestic points for v(CH3) and v(C═O) overlaid spectra showed that the chain collapse of PNIPAM hydrogel took place along with some intermediate states or a completely continuous phase transition while the chain revival occurred with only conversion between two single states. Finally, 2Dcos discerned all the sequence of group motions of PNIPAM hydrogel, indicating that in the heating process, PNIPAM hydrogel occurred to collapse along the backbone before water molecules were expelled outside the network, while in the sequential cooling process, PNIPAM hydrogel had water molecules diffusing into the network first before the chain revival along the backbone occurred.},
  creationdate = {2022-07-21T00:00:00},
  doi          = {10.1021/jp103818c},
  eprint       = {https://doi.org/10.1021/jp103818c},
  file         = {:Sun2010 - Chain Collapse and Revival Thermodynamics of Poly(N Isopropylacrylamide) Hydrogel.pdf:PDF},
  keywords     = {two-dimensional correlation infrared spectroscopy, 2DIR, pnipam, hydrogel, LCST, VPTT, hysteresis, thermodynamics},
  printed      = {printed},
  url          = {https://doi.org/10.1021/jp103818c},
}

@Article{Laszlo2010,
  author       = {L{\'{a}}szl{\'{o}}, Krisztina and Guillermo, Armel and Fluerasu, Andrei and Moussa{\"{i}}d, Abdellatif and Geissler, Erik},
  journal      = {Langmuir},
  title        = {Microphase Structure of Poly(N-isopropylacrylamide) Hydrogels As Seen by Small- and Wide-Angle X-ray Scattering and Pulsed Field Gradient NMR},
  year         = {2010},
  note         = {PMID: 19921858},
  number       = {6},
  pages        = {4415--4420},
  volume       = {26},
  abstract     = {Above the lower critical solution temperature Tc (ca. 34 {$^{\circ}$}C), poly(N-isopropylacrylamide) hydrogels become weakly hydrophobic and undergo microphase separation. Macroscopic deswelling, however, is extraordinarily slow, the out-of equilibrium state of the gel being conserved for many days. In this article the structure of the microphase-separated state above Tc is probed by small-angle X-ray scattering and by pulsed field gradient NMR of the protons of water, both in the water phase and in the polymer-rich phase. Above Tc the gel comprises two microphases, separated by smooth interfaces. The cavities occupied by the water phase form a connected network. The diffusion rate of the water molecules in this phase varies from one cavity to another and can be described by a Gaussian distribution. Water molecules belonging to the polymer-rich phase are also mobile, but their self-diffusion coefficient D is greatly diminished. Absence of compartmentalization of the water phase implies that the slow deswelling rate of the gel is not due to trapping of the water phase.},
  creationdate = {2022-07-21T00:00:00},
  doi          = {10.1021/la903468h},
  eprint       = {https://doi.org/10.1021/la903468h},
  file         = {:Laszlo2010 - Microphase Structure of Poly(N Isopropylacrylamide) Hydrogels As Seen by Small and Wide Angle X Ray Scattering and Pulsed Field Gradient NMR.pdf:PDF},
  keywords     = {pnipam, hydrogel, PFG, 1H NMR, x-ray, SAXS, WAXS, LCST},
  url          = {https://doi.org/10.1021/la903468h},
}

@Article{Shibayama1994,
  author       = {Shibayama, Mitsuhiro and Morimoto, Masato and Nomura, Shunji},
  journal      = {Macromolecules},
  title        = {Phase Separation Induced Mechanical Transition of Poly(N-isopropylacrylamide)/Water Isochore Gels},
  year         = {1994},
  number       = {18},
  pages        = {5060--5066},
  volume       = {27},
  abstract     = {Poly(N-isopropylacrylamide) (NIPAAm) gels immersed in water (isobar gels) are known to undergo a volume phase transition at T_c ~ 34°C. This transition, due to the release of hydrophobic hydration, leads to dramatic changes in physical properties, such as mechanical, optical, and thermal properties. We dealt with NIPAAm isochore gels, where the gels were isolated from water to keep the gel concentration, and investigated the mechanical and thermal properties of the gels as functions of temperature, cross-link density, and polymer concentration. The dynamic storage modulus, E', increased suddenly at T_c by a factor of 10 or more and  became frequency dependent with increasing temperature. The enthalpy change related to the dissociation of the hydrophobic hydration was obtained as a function of the gel concentration. It was found that about 13 water molecules were released to dehydrate one NIPAAm molecule. Attenuated total reflection (ATR) infrared absorption spectroscopy was also conducted to elucidate the local environment of the NIPAAm gel network},
  creationdate = {2022-07-21T00:00:00},
  doi          = {10.1021/ma00096a031},
  eprint       = {https://doi.org/10.1021/ma00096a031},
  file         = {:Shibayama1994 - Phase Separation Induced Mechanical Transition of Poly(N Isopropylacrylamide)_Water Isochore Gels.pdf:PDF},
  keywords     = {pnipam,VPTT,gel,hydrophobic hydration,bound water network,viscosity,enthalpy,thermodynamics,ATR infrared absorption spectroscopy,DSC,clathrate,hydration shell,infrared},
  url          = {https://doi.org/10.1021/ma00096a031},
}

@Article{Liu2014,
  author       = {Ming S. Liu and Cheryl Taylor and Bill Chong and Lihui Liu and Ante Bilic and Netsanet Shiferaw Terefe and Regine Stockmann and San H. Thang and Kirthi De Silva},
  journal      = {European Polymer Journal},
  title        = {Conformational transitions and dynamics of thermal responsive poly(N-isopropylacrylamide) polymers as revealed by molecular simulation},
  year         = {2014},
  issn         = {0014-3057},
  pages        = {153--159},
  volume       = {55},
  abstract     = {Stimuli responsive polymers (SRP) have attracted increasing interest for their unlimited potential of molecular capture, separation, purification and delivery particularly at the cutting edge of bio-nano technologies, as well as for the biotechnological, food and medical industries. However, molecular mechanisms of SRPs and their interactions with target materials are little understood at atomistic levels. Based on poly(N-isopropylacrylamide) (pNIPAAm) and poly(NIPAAm-co-AAc-co-tBAAm) polymers, we examined the SRP operating mechanisms and dynamics by all-atom molecular simulation in varying conditions of temperature and chemistry. The LCST conformational transition predicted by simulation agreed well with experimental results, and simulation results notably leads to elucidate mechanism that torsional energy of isopropyl acryl tethers and H-bond play vital roles in driving the transition in response to temperature changes. These insights are helping molecular design and virtual screening of tailor-made SRPs, and harnessing the responsive control of temperature and other stimuli factors (e.g. ions, hydrophobicity).},
  creationdate = {2022-07-21T00:00:00},
  doi          = {https://doi.org/10.1016/j.eurpolymj.2014.03.019},
  file         = {:Liu2014 - Conformational Transitions and Dynamics of Thermal Responsive Poly(N Isopropylacrylamide) Polymers As Revealed by Molecular Simulation.pdf:PDF},
  keywords     = {Stimuli responsive polymers, Poly(N-isopropylacrylamide), pnipam, Molecular dynamics simulation, LCST transition, Molecular mechanism, hydrogen bond},
  printed      = {printed},
  url          = {https://www.sciencedirect.com/science/article/pii/S0014305714000998},
}

@Article{Wittebort1988,
  author       = {Wittebort, R. J. and Usha, M. G. and Ruben, D. J. and Wemmer, D. E. and Pines, A.},
  journal      = {Journal of the American Chemical Society},
  title        = {Observation of molecular reorientation in ice by proton and deuterium magnetic resonance},
  year         = {1988},
  number       = {17},
  pages        = {5668--5671},
  volume       = {110},
  creationdate = {2022-07-26T00:00:00},
  doi          = {10.1021/ja00225a013},
  eprint       = {https://doi.org/10.1021/ja00225a013},
  file         = {:Wittebort1988 - Observation of Molecular Reorientation in Ice by Proton and Deuterium Magnetic Resonance.pdf:PDF},
  keywords     = {water, h2o, d2o, 1h nmr, 2h nmr, ice, simulation, jump rate, spectra},
  url          = {https://doi.org/10.1021/ja00225a013},
}

@Article{Sbeih2021,
  author       = {Sbeih, Suhad and Mohanty, Priti S. and Yethiraj, Anand and Morrow, Michael R.},
  journal      = {Langmuir},
  title        = {2H NMR Study of Polymer Segmental Dynamics at Varying Cross-Linking in Poly(N-isopropylacrylamide) Microgels},
  year         = {2021},
  note         = {PMID: 34767370},
  number       = {46},
  pages        = {13664--13675},
  volume       = {37},
  abstract     = {A microscopic understanding of the internal structure and dynamics of poly(N-isopropylacrylamide) (PNIPAM) chains, in microgel colloids, is developed using deuterium NMR (2H NMR) to study deuterated PNIPAM suspensions as functions of temperature and pressure for four cross-linker molar fractions (f). The PNIPAM polymers were labeled with deuterons at the backbone (d3-PNIPAM) or on side chains (d7-PNIPAM). 2H NMR spectra of the d3-PNIPAM suspensions for all cross-linker molar fractions indicated freely moving chains at low temperature and a nearly immobilized fraction above ∼35 °C. Polymer segments in the collapsed phase of the d3-PNIPAM suspension were more mobile than those in the dry powder. This is direct microscopic evidence that the polymer remains significantly hydrated in the collapsed phase, consistent with strong, indirect evidence from recent light scattering and rheology measurements from our laboratory. However, the observation of a small fraction of immobilized segments in the swollen phase for higher cross-linker molar fraction suggests that, particularly for high levels of cross-linking, some polymer is nonhydrated even in the swollen phase. Finally, variable-pressure NMR (up to 90 MPa) showed a slight increase in transition temperature with pressure for lower cross-linker molar fractions and a larger increase in transition temperature with pressure for higher cross-linker molar fractions. This is consistent with a previously reported dependence of collapse transition enthalpy on cross-linker molar fraction.},
  comment      = {- some data may be okay and valuable to use, but errors were made in their interpretation.
-they did not realize that the N-D deuteron can exchange with water O-D and instead argue that it does not contribute to the spectrum because there are fewer deuterons (1) than in the methyl groups (6) (and that intensity is spread out more because the coupling constant is slightly higher - this part they may have gotten right.)
-They talk about a T2 minimum for pNIPAM-d3, but our field cycling suggests that the spectral density re-approaches the high temperature limit. Their data could still be okay, just don't believe their analysis of which segements contribute how strongly to the signal.
- for pNIPAM-d7, based on a molar NIPAM fraction of about 9%, the expected fraction of exchangeable deuterons which are in water is 95%. Since the ratio of exchangeable to non-exchangeable deuterons is 1:6, 15% of the signal come from water and should remain visible even after pNIPAM collapse if water remains mobile. However, about 30% of the intensity remain. I'm not sure where the other 15% come from. Is there a simultaneous line shape narrowing happening?
- backbone has a lineshape transition (~125kHz) from 35°C (narrow) to 45°C (broad). Attention: CD2 may be able to flip while CD probably is not (other study).},
  creationdate = {2022-07-26T00:00:00},
  doi          = {10.1021/acs.langmuir.1c02269},
  eprint       = {https://doi.org/10.1021/acs.langmuir.1c02269},
  file         = {:Sbeih2021 - 2H NMR Study of Polymer Segmental Dynamics at Varying Cross Linking in Poly(N Isopropylacrylamide) Microgels.pdf:PDF;:2HNMRStudyofPolymerSegmentalDynamicsAtVaryingCrossLinkingInPolyNIsopropylacrylamideMicrogels_SbeihEtAl_Langmuir2021_SI.pdf:PDF},
  keywords     = {2h nmr, pnipam-d, microgel, spectra},
  priority     = {prio1},
  ranking      = {rank1},
  readstatus   = {skimmed},
  url          = {https://doi.org/10.1021/acs.langmuir.1c02269},
}

@Article{Chee1997,
  author       = {Choong Kooi Chee and Stephen Rimmer and Ian Soutar and Linda Swanson},
  journal      = {Polymer},
  title        = {Time-resolved fluorescence anisotropy studies of the temperature-induced intramolecular conformational transition of poly(N-isopropylacrylamide) in dilute aqueous solution},
  year         = {1997},
  issn         = {0032-3861},
  number       = {2},
  pages        = {483--486},
  volume       = {38},
  abstract     = {Time-resolved fluorescence anisotropy measurements have been performed upon an acenaphthylene-labelled (0.5 mol%) sample of poly(N-isopropylacrylamide), PNIPAM, in dilute solutions in both methanol and water as solvents. In methanol, segmental relaxation of PNIPAM follows an Arrhenius dependence upon temperature over the range investigated (279–323K) characterized by an ‘activation energy’ of 13.4(±0.5) kJ mol−1. This is only slightly greater (by ca 2.4 kJ mol−1) than that of solvent flow and it is likely that specific dipolar interactions between the PNIPAM and the methanol determine the macromolecular dynamics in this solvent. In aqueous solution, the segmental mobility of PNIPAM exhibits a dramatic thermoreversible discontinuity at ca 32°C. This change in conformational behaviour occurs at the polymer's lower critical solution temperature in aqueous media. This observation, supports the proposition (Winnik, F. M. Polymer 1990, 31, 2125) that the thermally-induced separation in this system occurs by a ‘dual mode’ mechanism wherein intermolecular aggregation is preceded by intramolecular conformational shrinkage of the polymer coils.},
  creationdate = {2022-07-26T00:00:00},
  doi          = {https://doi.org/10.1016/S0032-3861(96)00636-2},
  file         = {:Chee1997 - Time Resolved Fluorescence Anisotropy Studies of the Temperature Induced Intramolecular Conformational Transition of Poly(N Isopropylacrylamide) in Dilute Aqueous Solution.pdf:PDF},
  keywords     = {poly(N-isopropylacrylamide), pnipam, segmental dynamics, fluorescence, anisotropy},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386196006362},
}

@Article{Kogure2005,
  author       = {Hiroyuki Kogure and Sunao Nanami and Yuka Masuda and Yoshiharu Toyama and Kenji Kubota},
  journal      = {Colloid Polym Sci},
  title        = {Hydration and dehydration behavior of {N}-isopropylacrylamide gel particles},
  year         = {2005},
  pages        = {1163--1171},
  volume       = {283},
  abstract     = {Thermal response of N-isopropylacrylamide (NiPAM) gel particles of submicron size was investigated by means of ultrasonic velocity and density focusing on the hydration and dehydration behavior. Hydration number, defined as the number of water molecules bound to one NiPAM monomer unit, was quantitatively evaluated in the course of the volume phase transition. Hydration numbers at low and high temperatures were about 7.5 (20 °C) and 3 (40 °C), respectively. Hydration number decreases markedly near the volume phase transition temperature, and the decrease is responsible to the formation of hydrophobic bonding and dehydration. The hydration number is independent both of the size and the composition of gel particles in the shrunken state, although there exists a composition dependence in the swollen state. It was also found that the self-assemblies formed by hydrophobic interaction are more bulky compared to those in the hydrated state.},
  creationdate = {2022-08-12T00:00:00},
  doi          = {https://doi.org/10.1007/s00396-005-1303-8},
  file         = {:Kogure2005 - Hydration and Dehydration Behavior of N Isopropylacrylamide Gel Particles.pdf:PDF},
  keywords     = {pnipam, microgel, hydration, ultrasonic velocity, VPTT, self-assembly},
  url          = {https://doi.org/10.1007/s00396-005-1303-8},
}

@Article{Fujishige1987,
  author       = {Shoei Fujishige},
  journal      = {Polymer},
  title        = {Intrinsic Viscosity-Molecular Weight Relationships for Poly(N-isopropylacrylamide) Solutions},
  year         = {1987},
  number       = {3},
  pages        = {297--300},
  volume       = {19},
  creationdate = {2022-11-24T00:00:00},
  doi          = {https://doi.org/10.1295/polymj.19.297},
  file         = {:Fujishige1987 - Intrinsic Viscosity Molecular Weight Relationships for Poly(N Isopropylacrylamide) Solutions.pdf:PDF},
  keywords     = {pNIPAM, linear, intrinsic viscosity, molecular weight, fractionation, osmometry},
}

@Article{Bischofberger2014,
  author       = {Bischofberger, I. and Calzolari, D. C. E. and Trappe, V.},
  journal      = {Soft Matter},
  title        = {Co-nonsolvency of PNiPAM at the transition between solvation mechanisms},
  year         = {2014},
  pages        = {8288--8295},
  volume       = {10},
  abstract     = {We investigate the co-nonsolvency of poly-N-isopropyl acrylamide (PNiPAM) in different water–alcohol mixtures and show that this phenomenon is due to two distinct solvation contributions governing the phase behavior of PNiPAM in the water-rich and alcohol-rich regime respectively. While hydrophobic hydration is the predominant contribution governing the phase behavior of PNiPAM in the water-rich regime{,} the mixing contributions governing the phase behavior of classical polymer solutions determine the phase behavior of PNiPAM in the alcohol-rich regime. This is evidenced by distinct scaling relations denoting the energetic state of the aqueous medium as a key parameter for the phase behavior of PNiPAM in the water-rich regime{,} while the volume fractions of respectively water{,} alcohol and PNiPAM become relevant parameters in the alcohol-rich regime. Adding alcohol to water decreases the energetics of the aqueous medium{,} which gradually suppresses hydrophobic hydration{,} while adding water to alcohol decreases the solvent quality. Consequently{,} PNiPAM is insoluble in the intermediate range of solvent composition{,} where neither hydrophobic hydration nor the mixing contributions prevail. This accounts for the co-nonsolvency phenomenon observed for PNiPAM in water–alcohol mixtures.},
  creationdate = {2022-11-24T00:00:00},
  doi          = {10.1039/C4SM01345J},
  file         = {:Bischofberger2014 - Co Nonsolvency of PNiPAM at the Transition between Solvation Mechanisms.pdf:PDF;:CononsolvencyOfPNIPAMAtTheTransitionBetweenSolvationMechanisms-Corrections_BischofbergerEtAl_SoftMatter2014.pdf:PDF},
  issue        = {41},
  keywords     = {pNIPAM,linear,microgel,cononsolvency,methanol,ethanol,propanol,SLS,radius of gyration,hydrodynamic radius,aqueous alcohol,excess enthalpy},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C4SM01345J},
}

@Article{Stieger2003,
  author       = {Stieger, Markus and Richtering, Walter},
  journal      = {Macromolecules},
  title        = {Shear-Induced Phase Separation in Aqueous Polymer Solutions:  Temperature-Sensitive Microgels and Linear Polymer Chains},
  year         = {2003},
  number       = {23},
  pages        = {8811--8818},
  volume       = {36},
  abstract     = {The influence of shear flow on the phase separation of aqueous poly(N-isopropylacrylamide) (PNiPAM) microgel suspensions was investigated by means of rheo-turbidity and rheo-small angle neutron scattering (rheo-SANS) and compared to the behavior of linear PNiPAM macromolecules. The rheological behavior of concentrated microgel suspensions depends strongly on temperature, but flow and viscoelastic properties of concentrated solutions of the linear polymer are not significantly affected by temperature changes. Shear-induced phase separation was observed for both polymer architectures, although the viscoelastic properties of the two systems have different structural origins. Shear-induced demixing was found with a microgel with a cross-linking density of 1.5 mol \% only at high concentrations when the sample behaved as a viscoelastic solid near the equilibrium demixing temperature. No influence of shear flow on the miscibility gap was observed for a PNiPAM microgel with a higher cross-linking density (5.5 mol \%). This indicates that a coupling of shear stress with the concentration fluctuations leading to solvent squeezing is only possible when the particles are densely packed and sufficiently soft.},
  creationdate = {2022-11-24T00:00:00},
  doi          = {10.1021/ma034788s},
  eprint       = {https://doi.org/10.1021/ma034788s},
  file         = {:Stieger2003 - Shear Induced Phase Separation in Aqueous Polymer Solutions_ Temperature Sensitive Microgels and Linear Polymer Chains.pdf:PDF},
  keywords     = {pNIPAM, linear, microgel, viscosity, thermoresponsive, reho-turbidity, rheo-SANS, overlap concentration, SLS},
  ranking      = {rank5},
  url          = {https://doi.org/10.1021/ma034788s},
}

@Article{Geil1993,
  author       = {B. Geil and G. Hinze},
  journal      = {Chemical Physics Letters},
  title        = {Influence of data treatment on the shape of 2H NMR T1 curves},
  year         = {1993},
  issn         = {0009-2614},
  number       = {1},
  pages        = {51--55},
  volume       = {216},
  abstract     = {A new interpretation of 2H T1 data of glass-forming systems in the range of the range of the caloric glass transition temperature has been proposed. It is shown that with the traditional treatment of the data the timescale of structural relaxation has an influence on the observed spin-lattice relaxation times. Avoiding this problem with a different treatment of the experimental data, it is possible to compare the 2H T1 data directly with corresponding 1H data.},
  comment      = {'Dramatic increase of the fact[or] $\xi$ even for values of $\sigma$ which are smaller than observed in typical experiments' -> ist der beschriebene Effekt auch für typische $\sigma$ eine plausible Ursache für die Unterschiede der beiden Mittelwerte? Die Idee aus dem Paper ist quantitativ kaum zu überprüfen, da über die Verteilungen von tau und T1 zu wenig bekannt ist.},
  creationdate = {2023-01-06T00:00:00},
  doi          = {https://doi.org/10.1016/0009-2614(93)E1243-A},
  file         = {:Geil1993 - Influence of Data Treatment on the Shape of 2H NMR T1 Curves.pdf:PDF},
  keywords     = {2H-NMR, T1, rate average, time average, initial slope},
  url          = {https://www.sciencedirect.com/science/article/pii/0009261493E1243A},
}

@Article{Zimmerman1957,
  author       = {Zimmerman, J. R. and Brittin, W. E.},
  journal      = {The Journal of Physical Chemistry},
  title        = {Nuclear Magnetic Resonance Studies in Multiple Phase Systems: Lifetime of a Water Molecule in an Adsorbing Phase on Silica Gel},
  year         = {1957},
  number       = {10},
  pages        = {1328--1333},
  volume       = {61},
  abstract     = {Further evaluation studies of nuclear resonance relaxation phenomena of the hydrogen nuclei of H20 adsorbed on silica gel observed by means of radio frequency pulse techniques are  described. A stochastic theory for multiphase systems sometimes encountered in relaxation phenomena is presented. Special emphasis is directed toward a theoretical understanding of two phase systems observed in the study of water vapor adsorbed on silica gel, Adsorption experiments are discussed which directly demonstrate, for a specific x/m value, the simultaneous existence of (a) two phase behavior for transverse (Tt) relaxation measurements and (b) single phase behavior for longitudinal relaxation (T¡) data. Finally, a close estimate is obtained of the life-time of a water molecule in an adsorbing phase at low coverage on silica gel.},
  creationdate = {2023-01-09T00:00:00},
  doi          = {10.1021/j150556a015},
  eprint       = {https://doi.org/10.1021/j150556a015},
  file         = {:Zimmerman1957 - Nuclear Magnetic Resonance Studies in Multiple Phase Systems_ Lifetime of a Water Molecule in an Adsorbing Phase on Silica Gel.pdf:PDF},
  url          = {https://doi.org/10.1021/j150556a015},
}

@Article{Scherzinger2015,
  author       = {C. Scherzinger and A. Balaceanu and C.H. Hofmann and A. Schwarz and K. Leonhard and A. Pich and W. Richtering},
  journal      = {Polymer},
  title        = {Cononsolvency of mono- and di-alkyl N-substituted poly(acrylamide)s and poly(vinyl caprolactam)},
  year         = {2015},
  issn         = {0032-3861},
  pages        = {50--59},
  volume       = {62},
  abstract     = {In this comparative study we investigate the influence of the side chain substitution pattern on the volume phase transition temperature (VPTT) of thermo-sensitive polymer microgels. We especially focus on cononsolvency of water and methanol. We compare literature data for poly(N-isopropylacrylamide) (PNIPAM) that shows cononsolvency to experimental data for secondary amide poly(N-n-propylacrylamide) (PNNPAM) as well as tertiary poly(N,N-diethylacrylamide) (PDEAAM) and poly(N-vinyl-caprolactam) (PVCL). As methods we apply size determination by dynamic light scattering (DLS) as well as differential scanning calorimetry(DSC) and theoretical calculations using COSMO-RS (conductor-like screening model for real solvents). Clear differences are found for PDEAAM and PVCL in comparison to PNIPAM and PNNPAM. We ascribe the significant differences between PNIPAM and PNNPAM on the one hand and PDEAAM and PVCL on the other hand to the amide proton, which is present in PNIPAM and PNNPAM but not in the other two polymers.},
  creationdate = {2023-02-13T00:00:00},
  doi          = {https://doi.org/10.1016/j.polymer.2015.02.007},
  file         = {:Scherzinger2015 - Cononsolvency of Mono and Di Alkyl N Substituted Poly(acrylamide)s and Poly(vinyl Caprolactam).pdf:PDF},
  keywords     = {Re-entrant phase behaviour, Thermo-responsive-polymer, Nanogel, thermoresponsive, microgel, cononsolvency, methanol, pNIPAM, pNNPAM, PDEAAM, PVCL, DLS, DSC, calculation},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386115001585},
}

@Article{Bharadwaj2022,
  author       = {Bharadwaj, Swaminath and Niebuur, Bart-Jan and Nothdurft, Katja and Richtering, Walter and van der Vegt, Nico F. A. and Papadakis, Christine M.},
  journal      = {Soft Matter},
  title        = {Cononsolvency of thermoresponsive polymers: where we are now and where we are going},
  year         = {2022},
  pages        = {2884--2909},
  volume       = {18},
  abstract     = {Cononsolvency is an intriguing phenomenon where a polymer collapses in a mixture of good solvents. This cosolvent-induced modulation of the polymer solubility has been observed in solutions of several polymers and biomacromolecules{,} and finds application in areas such as hydrogel actuators{,} drug delivery{,} compound detection and catalysis. In the past decade{,} there has been a renewed interest in understanding the molecular mechanisms which drive cononsolvency with a predominant emphasis on its connection to the preferential adsorption of the cosolvent. Significant efforts have also been made to understand cononsolvency in complex systems such as micelles{,} block copolymers and thin films. In this review{,} we will discuss some of the recent developments from the experimental{,} simulation and theoretical fronts{,} and provide an outlook on the problems and challenges which are yet to be addressed.},
  creationdate = {2023-02-13T00:00:00},
  doi          = {10.1039/D2SM00146B},
  file         = {:Bharadwaj2022 - Cononsolvency of Thermoresponsive Polymers_ Where We Are Now and Where We Are Going.pdf:PDF},
  issue        = {15},
  keywords     = {review, cononsolvency, thermoresponsive},
  printed      = {printed},
  publisher    = {The Royal Society of Chemistry},
  ranking      = {rank5},
  readstatus   = {read},
  url          = {http://dx.doi.org/10.1039/D2SM00146B},
}

@Article{Budkov2018,
  author       = {Yu. A. Budkov and A. L. Kolesnikov},
  journal      = {Polymer Science, Series C},
  title        = {Models of the Conformational Behavior of Polymers in Mixed Solvents},
  year         = {2018},
  pages        = {148--159},
  volume       = {60},
  abstract     = {Theoretical models of the conformational behavior of flexible polymer chains in mixed solvents enunciated in the world literature during the last decade are critically reviewed. Models describing different mechanisms of coil-to-globule transitions in a good solvent induced by cosolvent addition are highlighted. Special attention is given to the analysis of theoretical approaches to describing the collapse of polymer chains in binary mixtures of good solvents. The review addresses researchers engaged in polymer physics and chemistry and materials scientists involved in the design of smart polymers},
  creationdate = {2023-02-13T00:00:00},
  doi          = {https://doi.org/10.1134/S1811238218020030},
  file         = {:Budkov2018 - Models of the Conformational Behavior of Polymers in Mixed Solvents.pdf:PDF},
  keywords     = {cononsolvency, polymer conformtation models, review},
  url          = {https://doi.org/10.1134/S1811238218020030},
}

@Article{Fukai2018,
  author       = {Fukai, Toshiki and Shinyashiki, Naoki and Yagihara, Shin and Kita, Rio and Tanaka, Fumihiko},
  journal      = {Langmuir},
  title        = {Phase Behavior of Co-Nonsolvent Systems: Poly(N-isopropylacrylamide) in Mixed Solvents of Water and Methanol},
  year         = {2018},
  note         = {PMID: 29412671},
  number       = {9},
  pages        = {3003--3009},
  volume       = {34},
  abstract     = {Cloud points of poly(N-isopropylacrylamide) in aqueous mixed solvents, with methanol as the cosolvent, are experimentally measured for polymer concentrations varied up to as high as the weight fraction 0.25. They are shown to form closed loops on the ternary phase plane in the temperature region between 5 and 30 °C, and hence co-nonsolvency is complete. Miscibility loops shrink by cooling, or equivalently, they exhibit lower critical solution temperature behavior. For a fixed polymer concentration, there is a composition of the mixed solvent at which the cloud-point temperature takes the lowest value. This minimum cloud-point temperature composition of the mixed solvent turned out to be almost independent of the polymer concentration, at least within the measured dilute region below the weight fraction 0.25. On the basis of the assumption that the phase separation is closely related to the preferential adsorption of the solvents by hydrogen bonding, we employ a model solution of Flory–Huggins type, augmented with direct and cooperative polymer–solvent hydrogen bonds, to construct the ternary phase diagrams. Theoretical calculation of the spinodal curves is performed, and the results are compared with the obtained experimental cloud-point data. The effect of molecular volume of the cosolvent is also studied within the same theoretical framework. Possibility for a upper critical solution temperature co-nonsolvency to appear for cosolvents with larger molecular volume is discussed.},
  creationdate = {2023-02-13T00:00:00},
  doi          = {10.1021/acs.langmuir.7b03815},
  eprint       = {https://doi.org/10.1021/acs.langmuir.7b03815},
  file         = {:Fukai2018 - Phase Behavior of Co Nonsolvent Systems_ Poly(N Isopropylacrylamide) in Mixed Solvents of Water and Methanol.pdf:PDF},
  keywords     = {cononsolvency,pNIPAM,methanol,tanaka,flory-huggins},
  url          = {https://doi.org/10.1021/acs.langmuir.7b03815},
}

@Article{Yong2020,
  author       = {Yong, Huaisong and Merlitz, Holger and Fery, Andreas and Sommer, Jens-Uwe},
  journal      = {Macromolecules},
  title        = {Polymer Brushes and Gels in Competing Solvents: The Role of Different Interactions and Quantitative Predictions for Poly(N-isopropylacrylamide) in Alcohol–Water Mixtures},
  year         = {2020},
  number       = {7},
  pages        = {2323--2335},
  volume       = {53},
  abstract     = {Cononsolvency occurs if a mixture of two good solvents causes the collapse or demixing of polymers into a polymer-rich phase in a certain range of compositions of these two solvents. The better solvent is usually called the cosolvent, and the other common solvent is called the solvent. An unsolved problem in the understanding of the cononsolvency transition of polymers is the role of various polymer–solvent and cosolvent–solvent interactions. In this work, using a mean-field model, we offer a comprehensive and quantitative theoretical study of the cononsolvency effect of neutral immobilized polymers, in particular, poly(N-isopropylacrylamide) (PNiPAAm) brushes and macrogels. Our model quantitatively describes and predicts the phase-transition behaviors of PNiPAAm brushes and gels in various aqueous alcohol solutions. We demonstrated that in addition to the dominant polymer–cosolvent preferential adsorption and monomer–cosolvent–monomer triple contact (cosolvent-assisted temporary cross-linking effect), a nonideal mixing between the polymer and solvent shifts the collapse transition to the lower-concentration region of the cosolvent, while an increase of the demixing tendency between the cosolvent and solvent reduces the width of the cononsolvency transition. Moreover, weakening of the cononsolvency transition in cosolvent-poor aqueous solutions at high hydrostatic pressure can be explained by the suppression of demixing tendencies between the cosolvent and water, and between polymer and water in the case of PNiPAAm.},
  creationdate = {2023-02-13T00:00:00},
  doi          = {10.1021/acs.macromol.0c00033},
  eprint       = {https://doi.org/10.1021/acs.macromol.0c00033},
  file         = {:Yong2020 - Polymer Brushes and Gels in Competing Solvents_ the Role of Different Interactions and Quantitative Predictions for Poly(N Isopropylacrylamide) in Alcohol–Water Mixtures.pdf:PDF;:PolymerBrushesAndGelsInCompetingSolvents-TheRoleOfDifferentInteractionsAndQUantitativePredictionsForPolyNIsopropylacrylamideInAlcoholWaterMixtures-SI_YongEtAl_Macromol2020.pdf:PDF},
  keywords     = {pNIPAM,brush,macrogel,hydrogel,cononsolvency,preferential adsorption,triple contact,mean-field,theory,calculations,enthalpic bridge,pressure dependence,model},
  url          = {https://doi.org/10.1021/acs.macromol.0c00033},
}

@Article{Zuo2019,
  author       = {Zuo, Taisen and Ma, Changli and Jiao, Guisheng and Han, Zehua and Xiao, Shiyan and Liang, Haojun and Hong, Liang and Bowron, Daniel and Soper, Alan and Han, Charles C. and Cheng, He},
  journal      = {Macromolecules},
  title        = {Water/Cosolvent Attraction Induced Phase Separation: A Molecular Picture of Cononsolvency},
  year         = {2019},
  number       = {2},
  pages        = {457--464},
  volume       = {52},
  abstract     = {Cononsolvency is a phenomenon for which the solubility of a macromolecule decreases or even vanishes in the mixture of two good solvents. Although it has been widely applied in the physicochemical, green chemical, and pharmaceutical industries, its origin is still under active debate. Here, by using combined neutron total scattering, deuterium-labeling, and all-atom molecular dynamic simulations, we demonstrated that it is the strong water/cosolvent attraction that leads to the cononsolvency, both competitive hydrogen bonding and water/cosolvent complexation are its results. The combined approach presented here has opened a new route for investigating the most probable all-atom structure in macromolecular solutions.},
  creationdate = {2023-02-13T00:00:00},
  doi          = {10.1021/acs.macromol.8b02196},
  eprint       = {https://doi.org/10.1021/acs.macromol.8b02196},
  file         = {:Zuo2019 - Water_Cosolvent Attraction Induced Phase Separation_ a Molecular Picture of Cononsolvency.pdf:PDF;:WaterCosolventAttractionInducedPhaseSeparation-AMolecularPictureOfCononsolvency-SI_ZuoEtAl_Macromol2019.pdf:PDF},
  keywords     = {cononsolvency,neutron scattering,simulation,competitive hydrogen bonding,complexation,solvent complexes},
  url          = {https://doi.org/10.1021/acs.macromol.8b02196},
}

@Article{Dudowicz2015,
  author       = {Dudowicz,Jacek and Freed,Karl F. and Douglas,Jack F.},
  journal      = {The Journal of Chemical Physics},
  title        = {Communication: Cosolvency and cononsolvency explained in terms of a Flory-Huggins type theory},
  year         = {2015},
  number       = {13},
  pages        = {131101},
  volume       = {143},
  abstract     = {Standard Flory-Huggins (FH) theory is utilized to describe the enigmatic cosolvency and cononsolvency phenomena for systems of polymers dissolved in mixed solvents. In particular, phase boundaries (specifically upper critical solution temperature spinodals) are calculated for solutions of homopolymers B in pure solvents and in binary mixtures of small molecule liquids A and C. The miscibility (or immiscibility) patterns for the ternary systems are classified in terms of the FH binary interaction parameters { χ α β } and the ratio r = φ A /φ C of the concentrations φ A and φ C of the two solvents. The trends in miscibility are compared to those observed for blends of random copolymers (A x C 1−x ) with homopolymers (B) and to those deduced for A/B/C solutions of polymers B in liquid mixtures of small molecules A and C that associate into polymeric clusters { A p C q } i , (i = 1, 2, . . . , ∞). Although the classic FH theory is able to explain cosolvency and cononsolvency phenomena, the theory does not include a consideration of the mutual association of the solvent molecules and the competitive association between the solvent molecules and the polymer. These interactions can be incorporated in refinements of the FH theory, and the present paper provides a foundation for such extensions for modeling the rich thermodynamics of polymers in mixed solvents},
  creationdate = {2023-02-13T00:00:00},
  doi          = {10.1063/1.4932061},
  eprint       = {https://aip.scitation.org/doi/pdf/10.1063/1.4932061},
  file         = {:Dudowicz2015 - Communication_ Cosolvency and Cononsolvency Explained in Terms of a Flory Huggins Type Theory.pdf:PDF},
  keywords     = {cononsolvency, flory-huggins, theory, calculation, ternary system},
  url          = {https://aip.scitation.org/doi/abs/10.1063/1.4932061},
}

@Article{Drozdov2022,
  author       = {Drozdov, Aleksey D. and de Claville Christiansen, Jesper},
  journal      = {Chemistry},
  title        = {Equilibrium Swelling of Thermo-Responsive Gels in Mixtures of Solvents},
  year         = {2022},
  issn         = {2624-8549},
  number       = {3},
  pages        = {681--700},
  volume       = {4},
  abstract     = {Thermo-responsive (TR) gels of the LCST (lower critical solution temperature) type swell in water at temperatures below their volume phase transition temperature Tc and collapse above the critical temperature. When water is partially replaced with an organic liquid, these materials demonstrate three different types of equilibrium solvent uptake diagrams at temperatures below, above, in the close vicinity of Tc. A model is developed for equilibrium swelling of TR gels in binary mixtures of solvents. It takes into account three types of phase transitions in TR gels driven by (i) aggregation of hydrophobic side groups into clusters from which solvent molecules are expelled, (ii) replacement of water with cosolvent molecules in cage-like structures surrounding these groups, and (iii) replacement of water with cosolvent as the main element of hydration shells around backbone chains. The model involves a relatively small number of material constants that are found by matching observations on covalently cross-linked poly(N-isopropylacrylamide) macroscopic gels and microgels. Good agreement is demonstrated between the experimental data and results of numerical analysis. Classification is provided of the phase transition points on equilibrium swelling diagrams.},
  creationdate = {2023-02-13T00:00:00},
  doi          = {10.3390/chemistry4030049},
  file         = {:Drozdov2022 - Equilibrium Swelling of Thermo Responsive Gels in Mixtures of Solvents.pdf:PDF},
  keywords     = {thermoresponsive,lcst,cononsolvency,pNIPAM,microgel,macrogel,theory,flory-rhener,dioxane,reentrant,flory-huggins},
  url          = {https://www.mdpi.com/2624-8549/4/3/49},
}

@Article{Budkov2016,
  author       = {Yu. A. Budkov and A. L. Kolesnikov and N. N. Kalikin and M. G. Kiselev},
  journal      = {Europhysics Letters},
  title        = {A statistical theory of coil-to-globule-to-coil transition of a polymer chain in a mixture of good solvents},
  year         = {2016},
  month        = jun,
  number       = {4},
  pages        = {46004},
  volume       = {114},
  abstract     = {We present an off-lattice statistical model of a single polymer chain in mixed-solvent media. Taking into account the polymer conformational entropy, renormalization of solvent composition near the polymer backbone, the universal intermolecular excluded-volume and van der Waals interactions within the self-consistent field theory, the reentrant coil-to-globule-to-coil transition (co-nonsolvency) has been described in this paper. For convenience we split the system volume in two parts: the volume occupied by the polymer chain and the volume of bulk solution. Considering the equilibrium between two sub-volumes, the polymer solvation free energy as a function of radius of gyration and co-solvent mole fraction within internal polymer volume has been obtained. Minimizing the free energy of solvation with respect to its arguments, we show two qulitatively different regimes of co-nonsolvency. Namely, at sufficiently high temperature the reentrant coil-to-globule-to-coil transition proceeds smoothly. On the contrary, when the temperature drops below a certain threshold value a coil-globule transition occurs in the regime of first-order phase transition, i.e., discontinuous changes of the radius of gyration and the local co-solvent mole fraction near the polymer backbone. We show that, when the collapse of the polymer chain takes place, the entropy and enthalpy contributions to the solvation free energy of the globule strongly grow. From the first principles of statistical thermodynamics we confirm earlier speculations based on the MD simulations results that the co-nonsolvency is the essentially enthalpic-entropic effect and is caused by enthalpy-entropy compensation. We show that the temperature dependences of the solution heat capacity change due to the solvation of the polymer chain are in qualitative agreement with the differential scanning calorimetry data for PNIPAM in aqueous methanol.},
  creationdate = {2023-02-13T00:00:00},
  doi          = {10.1209/0295-5075/114/46004},
  file         = {:Budkov2016 - A Statistical Theory of Coil to Globule to Coil Transition of a Polymer Chain in a Mixture of Good Solvents.pdf:PDF},
  keywords     = {cononsolvency, theory},
  publisher    = {EDP Sciences, IOP Publishing and Società Italiana di Fisica},
  url          = {https://dx.doi.org/10.1209/0295-5075/114/46004},
}

@Article{Yong2019,
  author       = {Yong, Huaisong and Bittrich, Eva and Uhlmann, Petra and Fery, Andreas and Sommer, Jens-Uwe},
  journal      = {Macromolecules},
  title        = {Co-Nonsolvency Transition of Poly(N-isopropylacrylamide) Brushes in a Series of Binary Mixtures},
  year         = {2019},
  number       = {16},
  pages        = {6285--6293},
  volume       = {52},
  abstract     = {Co-nonsolvency occurs if a mixture of two good solvents causes the collapse or demixing of polymers into a polymer-rich phase in a certain range of compositions of these two solvents. In this work, we systematically study the co-nonsolvency behavior of poly(N-isopropylacrylamide) brushes of different grafting densities in a series of alcohol–water binary mixtures with increasing hydrophobic parts ranging from methanol to 1-butanol by using ellipsometry. We report a strong collapse transition by increasing the alcohol concentration in the water-rich phase, which is enhanced for longer-chain alcohols. The analysis of the thermodynamic properties of the alcohol–water series displays that an increasing demixing tendency between alcohol and water is correlated with an enhancement of the collapse transition of the brush. The increase of grafting density weakens the transition behavior but does not shift the solvent composition point of maximum brush collapse, which is in agreement with the predictions of a recently proposed mean-field model based on the preferential adsorption concept. Among the fully miscible solvents, the most sensitive switching behavior of the brush is found for 1-propanol while 1-butanol already displays a miscibility gap at higher volume fractions.},
  creationdate = {2023-02-13T00:00:00},
  doi          = {10.1021/acs.macromol.9b01286},
  eprint       = {https://doi.org/10.1021/acs.macromol.9b01286},
  file         = {:Yong2019 - Co Nonsolvency Transition of Poly(N Isopropylacrylamide) Brushes in a Series of Binary Mixtures.pdf:PDF;:CononsolvencyTransitionOfPolyNIsopropylacrylamideBrushesInASeriesOfBinaryMixtures-SI_YongEtAl_Macromol2019.pdf:PDF},
  keywords     = {cononsolvency, pNIPAM, bruhes, methanol, ethanol, propanol, butanol, ellipsometry},
  url          = {https://doi.org/10.1021/acs.macromol.9b01286},
}

@Article{Podewitz2019,
  author       = {Podewitz, Maren and Wang, Yin and Quoika, Patrick K. and Loeffler, Johannes R. and Schauperl, Michael and Liedl, Klaus R.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Coil–Globule Transition Thermodynamics of Poly(N-isopropylacrylamide)},
  year         = {2019},
  note         = {PMID: 31545046},
  number       = {41},
  pages        = {8838--8847},
  volume       = {123},
  abstract     = {Thermosensitive polymers such as poly(N-isopropylacrylamide) (PNIPAM) undergo a phase transition in aqueous solution from a random-coil structural ensemble to a globule structural ensemble at the lower critical solution temperature (LCST). Above this temperature, PNIPAM agglomerates and becomes insoluble, whereas it is soluble below the temperature. Thus, thermosensitive polymers represent essential targets for several applications, e.g., in drug delivery. Although their ability to change structure in response to a temperature alteration is highly relevant for industrial processes, their thermodynamic properties are mostly qualitatively understood, and the quantitative thermodynamic picture is still elusive. In this study, we used a combined atomistic molecular dynamics and well-tempered metadynamics simulation approach to estimate coil–globule transition thermodynamics. An isotactic 30-mer of PNIPAM was investigated over a broad temperature range between 200 and 360 K. The transition from the globule to the random-coil structure was observed with well-tempered metadynamics. For the first time, the free energy surface of PNIPAM was estimated and it is shown that the simulation results are in line with the experimentally observed thermosensitive behavior. Below the LCST, the random-coil ensemble represents the global energy minimum and is thermodynamically favored by 21 ± 9 kJ/mol compared to the globule ensemble; both are separated by a barrier of 49 ± 14 kJ/mol. In contrast, above the LCST, the globule ensemble is thermodynamically favored by 21 ± 8 kJ/mol over the random-coil ensemble. The barrier from random-coil to globule is 17 ± 10 kJ/mol.},
  creationdate = {2023-02-13T00:00:00},
  doi          = {10.1021/acs.jpcb.9b06125},
  eprint       = {https://doi.org/10.1021/acs.jpcb.9b06125},
  file         = {:Podewitz2019 - Coil–Globule Transition Thermodynamics of Poly(N Isopropylacrylamide).pdf:PDF;:CoilGlobuleTransitionThermodynamicsOfPolyNIsopropylacrylamide-SI_PodewitzEtAl_JPC2019.pdf:PDF},
  keywords     = {pNIPAM, thermoresponsive, LCST, simulation, thermodynamics},
  url          = {https://doi.org/10.1021/acs.jpcb.9b06125},
}

@Article{Isaacson1980,
  author       = {Isaacson, J. and Lubensky, T.C.},
  journal      = {{Journal de Physique Lettres}},
  title        = {{Flory exponents for generalized polymer problems}},
  year         = {1980},
  number       = {19},
  pages        = {469--471},
  volume       = {41},
  creationdate = {2023-02-13T00:00:00},
  doi          = {10.1051/jphyslet:019800041019046900},
  file         = {:Isaacson1980 - Flory Exponents for Generalized Polymer Problems.pdf:PDF},
  hal_id       = {jpa-00231823},
  hal_version  = {v1},
  keywords     = {electrolytes, macromolecular dynamics, polymer melts, polymer solutions, Flory exponent, generalized polymer problems, upper critical dimension, mean field theory, radius of gyration, degree of polymerization, branched polymers, branched polyelectrolytes, linear polymers, linear polyelectrolytes},
  pdf          = {https://hal.science/jpa-00231823/file/ajp-jphyslet_1980_41_19_469_0.pdf},
  publisher    = {{Edp sciences}},
  url          = {https://hal.science/jpa-00231823},
}

@Article{Moore1978,
  author       = {M A Moore and A J Bray},
  journal      = {Journal of Physics A: Mathematical and General},
  title        = {On the Flory formula for the polymer size exponent ν},
  year         = {1978},
  month        = jul,
  number       = {7},
  pages        = {1353},
  volume       = {11},
  abstract     = {The average end-to-end distance RN of a flexible polymer chain of N segments in a good solvent varies as Nnu , where, according to Flory, the size exponent nu =3/(2+d) in d dimensions (1&lt;or=d&lt;or=4). The original derivation of this formula for the exponent nu has been shown by des Cloizeaux (1976) to be without foundation. The authors demonstrate that the Flory formula is valid in a model for which only a finite (but large) number of spherical harmonics are retained in the harmonic (partial wave) expansion of the propagator.},
  creationdate = {2023-02-13T00:00:00},
  doi          = {10.1088/0305-4470/11/7/023},
  file         = {:Moore1978 - On the Flory Formula for the Polymer Size Exponent Ν.pdf:PDF},
  keywords     = {flory exponent},
  url          = {https://dx.doi.org/10.1088/0305-4470/11/7/023},
}

@Article{Kolberg2019,
  author       = {Kolberg, Adrianna and Wenzel, Christiane and Hackenstrass, Klara and Schwarzl, Richard and Rüttiger, Christian and Hugel, Thorsten and Gallei, Markus and Netz, Roland R. and Balzer, Bizan N.},
  journal      = {Journal of the American Chemical Society},
  title        = {Opposing Temperature Dependence of the Stretching Response of Single PEG and PNiPAM Polymers},
  year         = {2019},
  note         = {PMID: 31240903},
  number       = {29},
  pages        = {11603--11613},
  volume       = {141},
  abstract     = {The response of switchable polymer blends and coatings to temperature variation is important for the development of high-performance materials. Although this has been well studied for bulk materials, a proper understanding at the molecular level, in particular for high stretching forces, is still lacking. Here we investigate the molecular details of the temperature-dependent elastic response of two widely used water-soluble polymers, namely, polyethylene glycol (PEG) and poly(N-isopropylacrylamide) (PNiPAM) with a combined approach using atomic force microscopy (AFM) based single molecule force spectroscopy (SMFS) experiments and molecular dynamics (MD) simulations. SMFS became possible by the covalent attachment of long and defined single polymers featuring a functional end group. Most interestingly, varying the temperature produces contrasting effects for PEG and PNiPAM. Surprising as these results might occur at first sight, they can be understood with the help of MD simulations in explicit water. We find that hydration is widely underestimated for the mechanics of macromolecules and that a polymer chain has competing energetic and entropic elastic components. We propose to use the temperature dependence to quantify the energetic behavior for high stretching forces. This fundamental understanding of temperature-dependent single polymer stretching response might lead to innovations like fast switchable polymer blends and coatings with polymer chains that act antagonistically.},
  creationdate = {2023-02-13T00:00:00},
  doi          = {10.1021/jacs.9b04383},
  eprint       = {https://doi.org/10.1021/jacs.9b04383},
  file         = {:Kolberg2019 - Opposing Temperature Dependence of the Stretching Response of Single PEG and PNiPAM Polymers.pdf:PDF;:OpposingTemperatureDependenceOfTheStretchingResponseOfSinglePEGAndPNIPAMPolymers-SI_KolbergEtAl_JAmChemSoc2019.pdf:PDF},
  keywords     = {pNIPAM, simulation, AFM, SMFS, PEG, thermoresponsive},
  url          = {https://doi.org/10.1021/jacs.9b04383},
}

@Article{Ramakrishnan2017,
  author       = {Ramakrishnan, Gopakumar and González-Jiménez, Mario and Lapthorn, Adrian J. and Wynne, Klaas},
  journal      = {The Journal of Physical Chemistry Letters},
  title        = {Spectrum of Slow and Super-Slow (Picosecond to Nanosecond) Water Dynamics around Organic and Biological Solutes},
  year         = {2017},
  note         = {PMID: 28612605},
  number       = {13},
  pages        = {2964--2970},
  volume       = {8},
  abstract     = {Water dynamics in the solvation shell of solutes plays a very important role in the interaction of biomolecules and in chemical reaction dynamics. However, a selective spectroscopic study of the solvation shell is difficult because of the interference of the solute dynamics. Here we report on the observation of heavily slowed down water dynamics in the solvation shell of different solutes by measuring the low-frequency spectrum of solvation water, free from the contribution of the solute. A slowdown factor of ∼50 is observed even for relatively low concentrations of the solute. We go on to show that the effect can be generalized to different solutes including proteins.},
  creationdate = {2023-02-13T00:00:00},
  doi          = {10.1021/acs.jpclett.7b01127},
  eprint       = {https://doi.org/10.1021/acs.jpclett.7b01127},
  file         = {:Ramakrishnan2017 - Spectrum of Slow and Super Slow (Picosecond to Nanosecond) Water Dynamics around Organic and Biological Solutes.pdf:PDF;:SpectrumOfSlowAndSuperSlowPicosecondToNanosecondWaterDynamicsAroundOrganicAndBiologicalSolutes-SI_RamakrishnanEtAl_JPCLett2017.pdf:PDF},
  keywords     = {solvation shell, optical kerr effect, water dynamics, poylmer, protein},
  url          = {https://doi.org/10.1021/acs.jpclett.7b01127},
}

@Article{Tavagnacco2020,
  author       = {Letizia Tavagnacco and Emanuela Zaccarelli and Ester Chiessi},
  journal      = {Journal of Molecular Liquids},
  title        = {Molecular description of the coil-to-globule transition of Poly(N-isopropylacrylamide) in water/ethanol mixture at low alcohol concentration},
  year         = {2020},
  issn         = {0167-7322},
  pages        = {111928},
  volume       = {297},
  abstract     = {Poly (N-isopropylacrylamide), PNIPAM, is a widely studied polymer, which serves as a key constituent of nanostructured soft materials with responsive properties. Upon increasing temperature the PNIPAM polymer chain undergoes a reversible coil-to-globule transition at T~305 K, which is reflected by a volume phase transition in cross-linked architectures, such as microgels, valuable for many practical applications. The addition of a cosolvent is a simple method to tune the transition temperature according to the specific purpose. In this study, we use atomistic molecular dynamics simulations to explore the solution behavior of a PNIPAM chain in a mixture of water and ethanol, acting as cosolvent, at low alcohol concentration. Our simulations reproduce the occurrence of the coil-to-globule transition of the polymer chain at 289 K, a temperature lower than that measured in water, in full agreement with experimental findings. By monitoring the temperature evolution of structural and dynamical properties of the PNIPAM-water-ethanol ternary system, we detect a localization of ethanol molecules at the polymer interface, mainly due to interactions between isopropyl and ethyl groups. We observe that the transition occurs without a release of adsorbed ethanol molecules, but with a loss of water molecules from the surrounding of PNIPAM hydrophobic moieties that favours the aggregation of ethanol molecules close to the polymer. Our results support the idea that both the decreased chemical potential of water in the bulk of the mixture and the competition between water and ethanol molecules in the interactions with the polymer play a driving role in the transition.},
  creationdate = {2023-02-14T00:00:00},
  doi          = {10.1016/j.molliq.2019.111928},
  file         = {:Tavagnacco2020 - Molecular Description of the Coil to Globule Transition of Poly(N Isopropylacrylamide) in Water_ethanol Mixture at Low Alcohol Concentration.pdf:PDF},
  keywords     = {PNIPAM,Co-nonsolvency,cononsolvency,Molecular dynamics simulations,Microgels,preferential adsorption,self-diffusion,aqueous alcohol,ethanol},
  printed      = {printed},
  url          = {https://www.sciencedirect.com/science/article/pii/S0167732219349050},
}

@Article{Zhao2019,
  author       = {Chuanzhuang Zhao and Zhiyuan Ma and X.X. Zhu},
  journal      = {Progress in Polymer Science},
  title        = {Rational design of thermoresponsive polymers in aqueous solutions: A thermodynamics map},
  year         = {2019},
  issn         = {0079-6700},
  pages        = {269--291},
  volume       = {90},
  abstract     = {Temperature variations may induce changes in solution properties for thermoresponsive polymers, which have drawn much research attention due to their potential applications in different areas. To meet the practical requirements, rational design of the polymers is important and necessary. We reviewed literature in this field and proposed a thermodynamic map to guide the design of such polymers. The map is drawn up based on the enthalpic and entropic contributions (ΔHm and ΔSm) to the free energy change of mixing (ΔGm). The map is divided into four zones: soluble, insoluble, upper critical solution temperature (UCST), and lower critical solution temperature (LCST), with two lines representing the freezing and boiling points of the solvent (water) as two boundaries for the UCST and LCST zones. With the help of such a map, we attempt to illustrate how the UCST and LCST are affected by the various interactions in polymer-water mixtures, such as hydrophobic and ionic interactions, and hydrogen bonding, so that the thermoresponsive properties of a polymer can be predicted according to their molecular structures. The critical temperatures UCST and/or LCST of a polymer can be obtained from the slope of the straight line that passes through the original point and the location of the polymer on the map. Examples in the literature are shown to fit in different zones of this map, and we also demonstrate how the variations of the chemical composition or the molecular structure of the polymers can change the intra- and inter-molecular interactions involved, which in turn change the solution properties of the polymers and induce changes in the critical solution temperatures. This map may be used in the design and preparation of thermoresponsive polymers with UCST and LCST on demand.},
  creationdate = {2023-02-14T00:00:00},
  doi          = {https://doi.org/10.1016/j.progpolymsci.2019.01.001},
  keywords     = {Thermoresponsive polymers, LCST, UCST, Molecular design, Themodynamics, review, elsevier},
  printed      = {printed},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079670018302958},
}

@Article{Bharadwaj2020,
  author       = {Swaminath Bharadwaj and Divya Nayar and Cahit Dalgicdir and Nico F. A. van der Vegt},
  journal      = {Communications Chemistry},
  title        = {A cosolvent surfactant mechanism affects polymer collapse in miscible good solvents},
  year         = {2020},
  volume       = {3},
  abstract     = {The coil–globule transition of aqueous polymers is of profound significance in understanding the structure and function of responsive soft matter. In particular, the remarkable effect of amphiphilic cosolvents (e.g., alcohols) that leads to both swelling and collapse of stimuli-responsive polymers has been hotly debated in the literature, often with contradictory mechanisms proposed. Using molecular dynamics simulations, we herein demonstrate that alcohols reduce the free energy cost of creating a repulsive polymer–solvent interface via a surfactant-like mechanism which surprisingly drives polymer collapse at low alcohol concentrations. This hitherto neglected role of interfacial solvation thermodynamics is common to all coil–globule transitions, and rationalizes the experimentally observed effects of higher alcohols and polymer molecular weight on the coil-to-globule transition of thermoresponsive polymers. Polymer–(co)solvent attractive interactions reinforce or compensate this mechanism and it is this interplay which drives polymer swelling or collapse.},
  creationdate = {2023-02-14T00:00:00},
  doi          = {https://doi.org/10.1038/s42004-020-00405-x},
  file         = {:Bharadwaj2020 - A Cosolvent Surfactant Mechanism Affects Polymer Collapse in Miscible Good Solvents.pdf:PDF},
  keywords     = {cononsolvency,van der Vegt,surfactant,simulation,model,aqueous alcohol},
  priority     = {prio1},
  url          = {https://doi.org/10.1038/s42004-020-00405-x},
}

@Article{Tanaka1979,
  author       = {Tanaka,Toyoichi and Fillmore,David J.},
  journal      = {The Journal of Chemical Physics},
  title        = {Kinetics of swelling of gels},
  year         = {1979},
  number       = {3},
  pages        = {1214--1218},
  volume       = {70},
  comment      = {contradictions(?) in K. Nothdurft, D. H. Müller, S. D. Mürtz, A. A. Meyer,
L. P. B. Guerzoni, A. Jans, A. J. C. Kühne, L. De Laporte,
T. Brands, A. Bardow and W. Richtering, J. Phys. Chem. B,
2021, 125, 1503–1512.},
  creationdate = {2023-02-15T00:00:00},
  doi          = {10.1063/1.437602},
  eprint       = {https://doi.org/10.1063/1.437602},
  file         = {:Tanaka1979 - Kinetics of Swelling of Gels.pdf:PDF},
  keywords     = {kinetics, gel, polyacrylamide, laser light scattering},
  url          = {https://doi.org/10.1063/1.437602},
}

@Article{Wrede2018,
  author       = {Wrede, Oliver and Yvonne Reimann and Stefan Lülsdorf and Daniel Emmrich and Kristina Schneider and Andreas Josef Schmid and Diana Zauser and Yvonne Hannappel and André Beyer and Ralf Schweins and Armin Gölzhäuser and Thomas Hellweg and Thomas Sottmann},
  journal      = {scientific reports},
  title        = {Volume phase transition kinetics of smart N-n-propylacrylamide microgels studied by time-resolved pressure jump small angle neutron scattering},
  year         = {2018},
  volume       = {8},
  abstract     = {The use of smart colloidal microgels for advanced applications critically depends on their response kinetics. We use pressure jump small angle neutron scattering with supreme time resolution to study the rapid volume phase transition kinetics of such microgels. Utilizing the pressure induced microphase separation inside the microgels we were able to resolve their collapse and swelling kinetics. While the collapse occurs on a time scale of 10 ms, the particle swelling turned out to be much faster. Photon correlation spectroscopy and static small angle neutron scattering unambiguously show, that the much slower collapse can be associated with the complex particle architecture exhibiting a loosely-crosslinked outer region and a denser inner core region. These insights into the kinetics of stimuliresponsive materials are of high relevance for their applications as nano-actuators, sensors or drug carriers. Moreover, the used refined pressure jump small angle neutron scattering technique is of broad interest for soft matter studies.},
  creationdate = {2023-02-15T00:00:00},
  doi          = {https://doi.org/10.1038/s41598-018-31976-4},
  file         = {:Wrede2018 - Volume Phase Transition Kinetics of Smart N N Propylacrylamide Microgels Studied by Time Resolved Pressure Jump Small Angle Neutron Scattering.pdf:PDF},
  keywords     = {kinetics, microgel, neutron, SANS, pressure jump, photon correlation spectroscopy, PCS},
  url          = {https://doi.org/10.1038/s41598-018-31976-4},
}

@Article{Geiger2021,
  author       = {Geiger, Christina and Reitenbach, Julija and Kreuzer, Lucas P. and Widmann, Tobias and Wang, Peixi and Cubitt, Robert and Henschel, Cristiane and Laschewsky, André and Papadakis, Christine M. and Müller-Buschbaum, Peter},
  journal      = {Macromolecules},
  title        = {PMMA-b-PNIPAM Thin Films Display Cononsolvency-Driven Response in Mixed Water/Methanol Vapors},
  year         = {2021},
  number       = {7},
  pages        = {3517--3530},
  volume       = {54},
  abstract     = {The swelling and solvation of 100–200 nm thin films of a diblock copolymer consisting of a short poly(methyl methacrylate) (PMMA) block and a long poly(N-isopropylacrylamide) (PNIPAM) block are investigated in mixed water/methanol vapors. The processes are followed in real time using spectral reflectance (SR), time-of-flight neutron reflectometry (ToF-NR), and Fourier transform infrared (FT-IR) spectroscopy, applying two neutron scattering contrast variation sequences. After hydration in pure water vapor, the vapor composition (relative to a flow rate of 1 L/min ≙ 100\%) is changed to 70\% water (D2O/H2O) and 30\% methanol (CH3OH/CD3OH). Upon the mixed vapor stimulus, a two-step response is found, in which an initially enhanced swelling of the films is followed by a contraction. Differences in the solvent exchange kinetics found in ToF-NR experiments coincide with characteristic changes in the FT-IR spectra. While the initially enhanced swelling of the films is driven by the absorption of methanol, the film contraction is related to the release of both solvents, with almost no further change in solvent composition. In analogy to the coil-to-globule transition encountered in the polymer solution, these film response characteristics are attributed to the cononsolvency behavior of PNIPAM in water/methanol mixtures.},
  creationdate = {2023-02-20T00:00:00},
  doi          = {10.1021/acs.macromol.1c00021},
  eprint       = {https://doi.org/10.1021/acs.macromol.1c00021},
  file         = {:Geiger2021 - PMMA B PNIPAM Thin Films Display Cononsolvency Driven Response in Mixed Water_Methanol Vapors.pdf:PDF;:PMMAbPNIPAMThinFilmsDisplayCononsolvencyDrivenResponseInMixedWaterMethanolVapors-SI_GeigerEtAl_Macromol2021.pdf:PDF},
  keywords     = {cononsolvency, methanol, pNIPAM, copolymer, PMMA, thin film, vapor, time-resolved, kinetics, dynamics, spectral reflectance, time of flight neutron reflectometry, infrared, FTIR, PMMA, Polymethylmethacrylat},
  url          = {https://doi.org/10.1021/acs.macromol.1c00021},
}

@Article{Lai2013,
  author       = {Lai, Hengjie and Chen, Qianjin and Wu, Peiyi},
  journal      = {Soft Matter},
  title        = {The core–shell structure of PNIPAM collapsed chain conformation induces a bimodal transition on cooling},
  year         = {2013},
  pages        = {3985--3993},
  volume       = {9},
  abstract     = {The core–shell structure of a poly(N-isopropylacrylamide) (PNIPAM) collapsed chain conformation is an intermediate conformation formed in the heating process{,} which was found not only in single-chain solution but also in dilute aqueous solution. However{,} the relationship between the intermediate structures and thermodynamic properties is still not clear. Herein{,} the behavior of the bimodal transition{,} in which two exothermic peaks appear in the DSC cooling curves{,} has been investigated through different effects of polymer molecular weight{,} polymer concentration and thermal history. The results show that the higher-temperature peak (T2) is attributed to the hydration of the loose shell while the lower-temperature peak (T1) is ascribed to the further hydration of the compact core. However{,} the bimodal transition in cooling is observed clearly only when the PNIPAM concentration is less than its overlap concentration (C*). Moreover{,} it is found that the ratio of the T2 peak can be enhanced either with higher heating rate or less isothermal time at high temperature{,} since more structures of the loose periphery could be preserved in these cases. For measurements in the cooling–heating cycle{,} in addition{,} the result also reveals that the assembled behavior of the core–shell structure is reversible.},
  creationdate = {2023-02-24T00:00:00},
  doi          = {10.1039/C3SM27761E},
  file         = {:Lai2013 - The Core–shell Structure of PNIPAM Collapsed Chain Conformation Induces a Bimodal Transition on Cooling.pdf:PDF;:TheCoreShellStructureOfPNIPAMChainCollapsedConformationInducesABimodalTransitionInCooling-SI_LaiEtAl_SoftMatter2013.pdf:PDF},
  issue        = {15},
  keywords     = {pNIPAM,linear,two-step,dsc,hysteresis,aggregation,beta,ageing,equilibration,heating rate,kinetics},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C3SM27761E},
}

@Article{Tada2016,
  author       = {Tada, Takanori and Hirano, Tomohiro and Ute, Koichi and Katsumoto, Yukiteru and Asoh, Taka-Aki and Shoji, Tatsuya and Kitamura, Noboru and Tsuboi, Yasuyuki},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Effects of Syndiotacticity on the Dynamic and Static Phase Separation Properties of Poly(N-isopropylacrylamide) in Aqueous Solution},
  year         = {2016},
  note         = {PMID: 27414162},
  number       = {31},
  pages        = {7724--7730},
  volume       = {120},
  abstract     = {The dynamic and static phase separation behavior in aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions is highly sensitive to the tacticity of PNIPAM. We investigated the phase separation dynamics of aqueous solutions of PNIPAM with different tacticities (atactic and syndiotactic-rich types) and found that the phase separation dynamics of syndiotactic-rich PNIPAM was much different from that of atactic-type PNIPAM. First, phase separation in syndiotactic-rich PNIPAM was faster. Second, there was a critical point (Ccp) in the concentration dependence of the phase separation rate: the phase separation accelerated dramatically when the solution concentration was higher than 2.0 wt \% (= Ccp). Third, syndiotactic-rich PNIPAM required a higher thermal energy for phase separation compared to atactic PNIPAM. Such behavior can be explained on the basis of the high hydrophobicity of syndiotactic-rich PNIPAM in a dehydrated state and a diffusion-controlled aggregation model. The present study shows that precise control of the stereoregularity will open new channels toward the design and development of stimuli-responsive-polymer-based smart materials.},
  creationdate = {2023-02-24T00:00:00},
  doi          = {10.1021/acs.jpcb.6b03200},
  eprint       = {https://doi.org/10.1021/acs.jpcb.6b03200},
  file         = {:Tada2016 - Effects of Syndiotacticity on the Dynamic and Static Phase Separation Properties of Poly(N Isopropylacrylamide) in Aqueous Solution.pdf:PDF;:EffectsOfSyndiotacticityOnTheDynamicAndStaticPhaseSeparationPropertiesOfPolyNIsopropylacrylamideInAqueousSolution-SI_TadaEtAl_JPC2016.pdf:PDF},
  keywords     = {pNIPAM, LCST, kinetics, tacticity, concentration, optical transmittance, turbidity},
  relevance    = {relevant},
  url          = {https://doi.org/10.1021/acs.jpcb.6b03200},
}

@Article{Jora2017,
  author       = {Manazael Z. Jora and Marcus V.C. Cardoso and Edvaldo Sabadini},
  journal      = {Journal of Molecular Liquids},
  title        = {Correlation between viscosity, diffusion coefficient and spin-spin relaxation rate in 1H NMR of water-alcohols solutions},
  year         = {2017},
  issn         = {0167-7322},
  pages        = {341--346},
  volume       = {238},
  abstract     = {In this paper we investigate correlations between viscosity (ηs), 1H spin-spin relaxation times (T2) and diffusion coefficients (Ds) of protons obtained in a low field 1H NMR (20MHz) of solutions of methanol, ethanol, 1-propanol, 2-propanol and tert-butanol with water in all range of concentrations. As each of these three properties are associated with different dynamics of the molecules (ηs: transportation across planes of flow; Ds: translational diffusion; T2: rotational diffusion), we investigate their correlations with the micro-heterogeneity of the different alcohol-water mixtures.},
  creationdate = {2023-03-03T00:00:00},
  doi          = {https://doi.org/10.1016/j.molliq.2017.05.006},
  file         = {:Jora2017 - Correlation between Viscosity, Diffusion Coefficient and Spin Spin Relaxation Rate in 1H NMR of Water Alcohols Solutions.pdf:PDF},
  keywords     = {Intermolecular interactions, 1H NMR relaxation, Advective and diffusive transportation, Proton chemical exchange, Tetrahedral water arrangements, katharina, michael},
  readstatus   = {read},
  url          = {https://www.sciencedirect.com/science/article/pii/S0167732217303409},
}

@Article{Pethes2021,
  author       = {Ildikó Pethes and László Pusztai and Koji Ohara and László Temleitner},
  journal      = {Journal of Molecular Liquids},
  title        = {Temperature-dependent structure of 1-propanol/water mixtures: X-ray diffraction experiments and computer simulations at low and high alcohol contents},
  year         = {2021},
  issn         = {0167-7322},
  pages        = {117188},
  volume       = {340},
  abstract     = {Aqueous mixtures of 1-propanol have been investigated by high-energy synchrotron X-ray diffraction upon cooling. X-ray weighted total scattering structure factors of 6 mixtures, from 8 mol% to 89 mol% alcohol content, as well as that of pure 1-propanol are reported from room temperature down to the freezing points of the liquids. Molecular dynamics simulations have been performed, in order to interpret measured data. The all atom OPLS-AA potential model was used for 1-propanol, combined with both the SPC/E and the TIP4P/2005 water models: both combinations provide a semi-quantitative description of the measured total structure factors at low and high alcohol contents, while the agreement is qualitative for the mixture with 71 mol% of 1-propanol. From the simulated particle configurations, partial radial distribution functions were calculated. Furthermore, detailed description of the hydrogen bonded network is provided, in terms of hydrogen bond numbers, analysis of proton donor–acceptor ratios, size distributions of hydrogen bonded clusters and ring size statistics. Strong temperature dependence of the percolation threshold, as well as of the participation of the number of doubly hydrogen bonded molecules in cyclic entities, has been found for the mixture with 89 mol% of 1-propanol. Above an alcohol content of 20 mol%, 5-fold rings are the most frequent cyclic entities, with a strong temperature dependence in terms of the number of rings.},
  creationdate = {2023-03-03T00:00:00},
  doi          = {https://doi.org/10.1016/j.molliq.2021.117188},
  file         = {:Pethes2021 - Temperature Dependent Structure of 1 Propanol_water Mixtures_ X Ray Diffraction Experiments and Computer Simulations at Low and High Alcohol Contents.pdf:PDF},
  keywords     = {X-ray diffraction, Molecular dynamics simulation, 1-Propanol-water mixtures, Temperature dependence, Hydrogen bonded network, katharaina, michael, aqueous alcohol, cononsolvency, aqueous propanol phase diagram},
  priority     = {prio1},
  url          = {https://www.sciencedirect.com/science/article/pii/S0167732221019127},
}

@Article{Sevryugin2018,
  author       = {V. A. Sevryugin and N. M. Azancheev and G. N. Kosova},
  journal      = {Appl. Magn. Reson.},
  title        = {Translational Mobility of Components and Structure of Water-Ethanol Solutions},
  year         = {2018},
  pages        = {357--367},
  volume       = {49},
  abstract     = {The concentration dependences of self-diffusion coefficients of water and ethanol molecules in water–ethanol solutions are obtained by the method of nuclear magnetic resonance spectroscopy with the pulse magnetic field gradient. On the basis of the ideas of hydration of ethanol molecules, the obtained dependences are interpreted and assumptions are made about the structural organization of water–ethanol solutions in the region of diluted and concentrated solutions.},
  creationdate = {2023-03-03T00:00:00},
  doi          = {https://doi.org/10.1007/s00723-017-0974-x},
  file         = {:Sevryugin2018 - Translational Mobility of Components and Structure of Water Ethanol Solutions.pdf:PDF},
  keywords     = {katharina, michael, pfg, aqueous alcohol, cononsolvency, nmr, diffusion},
  url          = {https://doi.org/10.1007/s00723-017-0974-x},
}

@Article{Li2014,
  author       = {Li, Ruoyu and D’Agostino, Carmine and McGregor, James and Mantle, Michael D. and Zeitler, J. Axel and Gladden, Lynn F.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Mesoscopic Structuring and Dynamics of Alcohol/Water Solutions Probed by Terahertz Time-Domain Spectroscopy and Pulsed Field Gradient Nuclear Magnetic Resonance},
  year         = {2014},
  note         = {PMID: 25117060},
  number       = {34},
  pages        = {10156--10166},
  volume       = {118},
  abstract     = {Terahertz and PFG-NMR techniques are used to explore transitions in the structuring of binary alcohol/water mixtures. Three critical alcohol mole fractions (x1, x2, x3) are identified: methanol (10, 30, 70 mol \%), ethanol (7, 15, 60 mol \%), 1-propanol (2, 10, 50 mol \%), and 2-propanol (2, 10, 50 mol \%). Above compositions of x1 no isolated alcohol molecules exist, and below x1 the formation of large hydration shells around the hydrophobic moieties of the alcohol is favored. The maximum number of water molecules, N0, in the hydration shell surrounding a single alcohol molecule increases with the length of the carbon chain of the alcohol. At x2 the greatest nonideality of the liquid structure exists with the formation of extended hydrogen bonded networks between alcohol and water molecules. The terahertz data show the maximum absorption relative to that predicted for an ideal mixture at that composition, while the PFG-NMR data exhibit a minimum in the alkyl chain self-diffusivity at x2, showing that the alcohol has reached a minimum in diffusion when this extended alcohol–water network has reached the highest degree of structuring. At x3 an equivalence of the alkyl and alcohol hydroxyl diffusion coefficients is determined by PFG-NMR, suggesting that the molecular mobility of the alcohol molecules becomes independent of that of the water molecules.},
  creationdate = {2023-03-03T00:00:00},
  doi          = {10.1021/jp502799x},
  eprint       = {https://doi.org/10.1021/jp502799x},
  file         = {:Li2014 - Mesoscopic Structuring and Dynamics of Alcohol_Water Solutions Probed by Terahertz Time Domain Spectroscopy and Pulsed Field Gradient Nuclear Magnetic Resonance.pdf:PDF},
  keywords     = {katharina, michael, aqueous alcohol, pfg, nmr, terahertz time-domain spectroscopy, TTDS},
  url          = {https://doi.org/10.1021/jp502799x},
}

@Article{Choi2020,
  author       = {Choi, Seungeui and Parameswaran, Saravanan and Choi, Jun-Ho},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Understanding alcohol aggregates and the water hydrogen bond network towards miscibility in alcohol solutions: graph theoretical analysis},
  year         = {2020},
  pages        = {17181--17195},
  volume       = {22},
  abstract     = {Under ambient conditions{,} methanol and ethanol are miscible in water at all concentrations{,} while n-butanol is partially miscible. This is the first study to quantitatively examine the miscibility of butanol and compare with miscible alcohols by employing molecular dynamics simulations and graph theoretical analysis of three water-alcohol mixtures at various concentrations. We show how distinct alcohol aggregates are formed{,} thereby affecting the water structure{,} which established the relationship between the morphological structure of the aggregates and the miscibility of the alcohol in aqueous solution. The aggregates of methanol and ethanol in highly concentrated solutions form an extended H-bond network that intertwines well with the H-bond network of water. n-Butanol tends to self-associate and form large aggregates{,} while such aggregates are segregated from water. Graph theoretical analysis revealed that the alcohol aggregates of methanol and ethanol solutions have a morphological structure different from that of n-butanol{,} although there is no significant difference in morphology between the three pure alcohols. These two distinct alcohol aggregates are classified as water-compatible and water-incompatible depending upon their interaction with the water H-bond network{,} and their effect on the water structure was investigated. Our study reveals that the water-compatible network of alcohol aggregates in methanol and ethanol solutions disrupts the water H-bond networks{,} while the water-incompatible network of n-butanol aggregates does not considerably alter the water structure{,} which is consistent with the experimental results. Furthermore{,} we propose that miscible alcohols form water-compatible networks in binary aqueous systems while partially miscible alcohols form water-incompatible networks. The bifurcating hypothesis on the alcohol aggregation behavior in liquid water is of critical use to understand the fundamental issues such as solubility and phase separation in solution systems.},
  creationdate = {2023-03-03T00:00:00},
  doi          = {10.1039/D0CP01991G},
  file         = {:Choi2020 - Understanding Alcohol Aggregates and the Water Hydrogen Bond Network Towards Miscibility in Alcohol Solutions_ Graph Theoretical Analysis.pdf:PDF},
  issue        = {30},
  keywords     = {katharina, michael, aqueous alcohol, aqueous methanol, aqueous ethanol, n-butanol, molecular dynamics simulation, graph theoretical analysis, graph theory, hydrogen bond network},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D0CP01991G},
}

@Article{Pothoczki2018,
  author       = {Pothoczki, Szilvia and Pusztai, László and Bakó, Imre},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Variations of the Hydrogen Bonding and Hydrogen-Bonded Network in Ethanol–Water Mixtures on Cooling},
  year         = {2018},
  note         = {PMID: 29893130},
  number       = {26},
  pages        = {6790--6800},
  volume       = {122},
  abstract     = {Molecular dynamics computer simulations have been conducted for ethanol–water liquid mixtures in the water-rich side of the composition range, with 10, 20, and 30 mol \% of alcohol, at temperatures between room temperature and the experimental freezing point of the given mixture. All-atom-type (optimized potential for liquid simulations) interatomic potentials have been assumed for ethanol, in combination with two kinds of rigid water models (SPC/E and TIP4P/2005). Both combinations have provided excellent reproductions of the experimental X-ray total structure factors at each temperature; this yielded a strong basis for further structural analyses. Beyond partial radial distribution functions, various descriptors of hydrogen-bonded assemblies, as well as of the hydrogen-bonded network have been determined. A clear tendency was observed toward that an increasing proportion of water molecules participate in hydrogen bonding with exactly two donor and two acceptor sites as temperature decreases. Concerning larger assemblies held together by hydrogen bonding, the main focus was put on the properties of cyclic entities: it was found that, similarly to methanol–water mixtures, the number of hydrogen-bonded rings has increased with lowering temperature. However, for ethanol–water mixtures, the dominance of 5-fold rings, and not 6-fold rings, could be observed.},
  creationdate = {2023-03-03T00:00:00},
  doi          = {10.1021/acs.jpcb.8b02493},
  eprint       = {https://doi.org/10.1021/acs.jpcb.8b02493},
  file         = {:Pothoczki2018 - Variations of the Hydrogen Bonding and Hydrogen Bonded Network in Ethanol–Water Mixtures on Cooling.pdf:PDF},
  keywords     = {katharina, michael, hydrogen bond network, molecular dynamics simulation, aqueous ethanol, aqueous alcohol, x-ray},
  url          = {https://doi.org/10.1021/acs.jpcb.8b02493},
}

@Article{Lanzalaco2017,
  author         = {Lanzalaco, Sonia and Armelin, Elaine},
  journal        = {Gels},
  title          = {Poly(N-isopropylacrylamide) and Copolymers: A Review on Recent Progresses in Biomedical Applications},
  year           = {2017},
  issn           = {2310-2861},
  number         = {4},
  volume         = {3},
  abstract       = {The innate ability of poly(N-isopropylacrylamide) (PNIPAAm) thermo-responsive hydrogel to copolymerize and to graft synthetic polymers and biomolecules, in conjunction with the highly controlled methods of radical polymerization which are now available, have expedited the widespread number of papers published in the last decade—especially in the biomedical field. Therefore, PNIPAAm-based hydrogels are extensively investigated for applications on the controlled delivery of active molecules, in self-healing materials, tissue engineering, regenerative medicine, or in the smart encapsulation of cells. The most promising polymers for biodegradability enhancement of PNIPAAm hydrogels are probably poly(ethylene glycol) (PEG) and/or poly(ε-caprolactone) (PCL), whereas the biocompatibility is mostly achieved with biopolymers. Ultimately, advances in three-dimensional bioprinting technology would contribute to the design of new devices and medical tools with thermal stimuli response needs, fabricated with PNIPAAm hydrogels.},
  article-number = {36},
  creationdate   = {2023-03-08T00:00:00},
  doi            = {10.3390/gels3040036},
  file           = {:Lanzalaco2017 - Poly(N Isopropylacrylamide) and Copolymers_ a Review on Recent Progresses in Biomedical Applications.pdf:PDF},
  keywords       = {review, pNIPAM, biomedical, drug delivery, application-focused, application focused},
  pubmedid       = {30920531},
  url            = {https://www.mdpi.com/2310-2861/3/4/36},
}

@Article{Hughes1954,
  author       = {A. J. Hughes},
  journal      = {Nature},
  title        = {The Einstein Relation between Relative Viscosity and Volume Concentration of Suspensions of Spheres},
  year         = {1954},
  pages        = {1089--1090},
  volume       = {173},
  creationdate = {2023-03-11T00:00:00},
  doi          = {https://doi.org/10.1038/1731089a0},
  file         = {:Hughes1954 - The Einstein Relation between Relative Viscosity and Volume Concentration of Suspensions of Spheres.pdf:PDF},
  keywords     = {einstein relation, viscosity, suspension, concentration},
  url          = {https://doi.org/10.1038/1731089a0},
}

@Article{Mardles1940,
  author       = {Mardles, E. W. J.},
  journal      = {Nature},
  title        = {Viscosity of Suspensions and the Einstein Equation},
  year         = {1940},
  pages        = {970},
  volume       = {145},
  creationdate = {2023-03-11T00:00:00},
  doi          = {https://doi.org/10.1038/145970a0},
  file         = {:Mardles1940 - Viscosity of Suspensions and the Einstein Equation.pdf:PDF},
  keywords     = {einstein relation, viscosity, suspension, concentration},
  url          = {https://doi.org/10.1038/145970a0},
}

@Article{Einstein1906,
  author       = {Einstein, A.},
  journal      = {Ann. Phys.},
  title        = {A new determination of molecular dimensions},
  year         = {1906},
  pages        = {289--306},
  volume       = {19},
  creationdate = {2023-03-11T00:00:00},
  file         = {:EINSTEIN1906 - A New Determination of Molecular Dimensions.pdf:PDF},
  keywords     = {einstein relation, viscosity, concentration, suspension},
  url          = {https://cir.nii.ac.jp/crid/1570009750238339072},
}

@Article{Haruki2011,
  author       = {Shinichiro Haruki and Sohei Sukenaga and Noritaka Saito and Kunihiko Nakashima},
  journal      = {High Temp. Mater. Proc.},
  title        = {Viscosity Estimation of Spherical Particles Dispersed Suspension},
  year         = {2011},
  pages        = {405--409},
  volume       = {30},
  abstract     = {The viscosity measurement has been made forsuspensions consisting of polyethylene beads and siliconeoil matrix as a function of mean diameter of beads and shearrate.   The  relative  viscosity  is  found  to  increase  with  in-creasing the volume fraction of beads and decrease with themean diameter of beads and shear rate. We also tested sev-eral  viscosity  equations  to  reproduce  the  viscosity  valuesof  spherical  particle dispersed  suspension.   However,  anyequation could not reproduce well the experimental viscos-ity values of suspension measured under various conditions.Some modification is needed by considering some experi-mental conditions (volume fraction, mean diameter of beadsand shear rate).  Then, the modified Einstein–Roscoe equa-tion is recommended for reproducing the viscosity valuesof suspension under various conditions.},
  creationdate = {2023-03-11T00:00:00},
  doi          = {10.1515/HTMP.2011.062},
  file         = {:Haruki2011 - Viscosity Estimation of Spherical Particles Dispersed Suspension.pdf:PDF},
  keywords     = {einstein relation, viscosity, suspension, concentration},
}

@Article{Roscoe1952,
  author       = {R. Roscoe},
  journal      = {British Journal of Applied Physics},
  title        = {The viscosity of suspensions of rigid spheres},
  year         = {1952},
  month        = aug,
  number       = {8},
  pages        = {267},
  volume       = {3},
  abstract     = {An explanation is given of the dependence of the relative viscosity on the size distribution of the suspended spheres, an effect recently observed by Ward and Whitmore.(1) It is shown theoretically that if the spheres are of very diverse sizes, the relative viscosity is (1 - c)-2.5 for all values of the volume concentration c. For spheres of equal size, the validity of the Einstein expression for the relative viscosity (1 + 2.5c) is restricted to concentrations well below c = 0.05; while for medium and high concentrations the relative viscosity is given by the theoretical expression (1 - 1.35c)-2.5. The use of the latter formula in interpreting measurements on the viscosity of solutions is briefly indicated.},
  creationdate = {2023-03-11T00:00:00},
  doi          = {10.1088/0508-3443/3/8/306},
  file         = {:Roscoe1952 - The Viscosity of Suspensions of Rigid Spheres.pdf:PDF},
  keywords     = {einstein relation, viscosity, concentration, suspension},
  url          = {https://dx.doi.org/10.1088/0508-3443/3/8/306},
}

@Article{Kubota1990,
  author       = {Kubota, Kenji. and Fujishige, Shouei. and Ando, Isao.},
  journal      = {The Journal of Physical Chemistry},
  title        = {Single-chain transition of poly(N-isopropylacrylamide) in water},
  year         = {1990},
  number       = {12},
  pages        = {5154--5158},
  volume       = {94},
  abstract     = {The temperature dependence of the radius of gyration and the hydrodynamic radius of poly(N-isopropylacrylamides) with various molecular weights (1.63 X 101 23456—2.52 X 107 in water was obtained in the relatively good through poor regions by use of static and dynamic light scattering techniques. The dimensions of the polymer show sharp decreases in the poor solvent (collapsed) region. The observed transition in polymer dimensions is analyzed in terms of a coil-globule transition, which is one of the most important problems of polymer solution physics. Reasonable agreement with the theoretical predictions is obtained. This water-soluble polymer system shows a fairly narrow crossover region compared with the polystyrene systems.},
  creationdate = {2023-03-11T00:00:00},
  doi          = {10.1021/j100375a070},
  eprint       = {https://doi.org/10.1021/j100375a070},
  file         = {:Kubota1990 - Single Chain Transition of Poly(N Isopropylacrylamide) in Water.pdf:PDF},
  keywords     = {hydrodynamic radius, radius of gyration, pNIPAM, molecular weight, SLS, DLS, light scattering},
  url          = {https://doi.org/10.1021/j100375a070},
}

@InBook{Klemperer1983,
  author       = {Klemperer, Walter G.},
  editor       = {Lambert, Joseph B. and Riddell, Frank G.},
  pages        = {245--260},
  publisher    = {Springer Netherlands},
  title        = {Application of 17O NMR Spectroscopy to Structural Problems},
  year         = {1983},
  address      = {Dordrecht},
  isbn         = {978-94-009-7130-1},
  abstract     = {As a low-abundance, quadrupolar nucleus, 17O has often been overlooked as a viable NMR nucleus for structure determination. The 17O nucleus has, however, proved to be a surprisingly convenient nucleus for study by NMR techniques due to the availability of water and dioxygen enriched in 17O and the relatively small magnitude of the 17O quadrupole moment. This chapter focuses on two practical aspects of 17O NMR spectroscopy. First, methods for optimizing sensitivity and resolution are outlined. Correlations between chemical shift and structural environment are then presented in the context of examples selected from the organometallic, organic, inorganic, and biochemical literature.},
  booktitle    = {The Multinuclear Approach to NMR Spectroscopy},
  creationdate = {2023-03-15T00:00:00},
  doi          = {10.1007/978-94-009-7130-1_11},
  file         = {:Klemperer1983 - Application of 17O NMR Spectroscopy to Structural Problems.pdf:PDF},
  keywords     = {book, relaxation, 17O, chemistry, relaxation},
  url          = {https://doi.org/10.1007/978-94-009-7130-1_11},
}

@Misc{EckertTutorial,
  author       = {Hellmut Eckert},
  howpublished = {Tutorial, Uni Münster},
  title        = {Nuclear Electric Quadrupolar Interactions in NMR Spectroscopy - An Introduction},
  creationdate = {2023-03-15T00:00:00},
  file         = {:EckertTutorial - Nuclear Electric Quadrupolar Interactions in NMR Spectroscopy an Introduction.pdf:PDF},
  keywords     = {uncitable},
}

@InCollection{CuperlovicCulf2013,
  author       = {Miroslava Čuperlović-Culf},
  booktitle    = {NMR Metabolomics in Cancer Research},
  publisher    = {Woodhead Publishing},
  title        = {3 - Experimental methodology},
  year         = {2013},
  editor       = {Miroslava Čuperlović-Culf},
  isbn         = {978-1-907568-84-8},
  pages        = {139--213},
  series       = {Woodhead Publishing Series in Biomedicine},
  abstract     = {NMR spectroscopy is an information-rich, highly reliable and versatile method with superior performance in structure identification, analysis and mixture analysis. It is already established as a major method in chemistry for structural analysis of molecules of various sizes. Over the last decade NMR has also become one of the major analytical tools in metabolomics analysis. The analysis of mixtures as well as high throughput analysis of sensitive biological samples puts specific requirements on the experimentation. NMR is uniquely positioned for its speed, robustness and ability to measure variety of samples both in vitro and in vivo. This chapter provides an outline of NMR methodology and its applications in metabolomics. The physics of NMR is briefly outlined. More attention is focused on the experimental applications in metabolomics, with consideration of sample preparation and NMR experimentations. Details of the most often used 1D and 2D experiments as well as water suppressions routines are provided.},
  creationdate = {2023-03-15T00:00:00},
  doi          = {https://doi.org/10.1533/9781908818263.139},
  file         = {:CuperlovicCulf2013 - 3 Experimental Methodology.pdf:PDF},
  keywords     = {NMR metabolomics, NMR metabolomics sample preparation, NMR mixture analysis, water suppression for metabolomics, metabolic biomarkers for cancer diagnostics, application-focused, application focused},
  url          = {https://www.sciencedirect.com/science/article/pii/B9781907568848500032},
}

@Article{Zhang2017,
  author       = {Zhang, Qilu and Weber, Christine and Schubert, Ulrich S. and Hoogenboom, Richard},
  journal      = {Mater. Horiz.},
  title        = {Thermoresponsive polymers with lower critical solution temperature: from fundamental aspects and measuring techniques to recommended turbidimetry conditions},
  year         = {2017},
  pages        = {109--116},
  volume       = {4},
  abstract     = {Thermoresponsive polymers that undergo reversible phase transition by responding to an environmental temperature change{,} in particular polymers showing lower critical solution temperature (LCST){,} are frequently used as smart materials that have found increasing applications. Recently{,} there has been a rapid growth in interest on LCST polymers and many new research groups are entering the field from a wide range of application areas. While it is great to see more researchers working on LCST polymers{,} the downside of this rapid growth is that the fundamentals of the LCST phase transition behavior are not always clearly known and respected. Hence{,} this focus article provides a systematic discussion of the key aspects of the LCST behavior of polymers starting from fundamentals of LCST behavior to practical determination of cloud point temperature (Tcp). Finally{,} we offer a basic set of recommended measuring conditions for determination of Tcp (10 mg mL−1; 0.5 °C min−1; 600 nm) to facilitate the comparison of the LCST behavior and Tcp values of polymers developed and studied in different laboratories around the globe{,} which is nowadays nearly impossible since various techniques and parameters are being utilized for the measurements. It should be noted that these recommended conditions serve as a robust tool for turbidimetry{,} which is one out of the many characterization techniques one should utilize to fully understand LCST behavior of polymers.},
  creationdate = {2023-03-20T00:00:00},
  doi          = {10.1039/C7MH00016B},
  file         = {:Zhang2017 - Thermoresponsive Polymers with Lower Critical Solution Temperature_ from Fundamental Aspects and Measuring Techniques to Recommended Turbidimetry Conditions.pdf:PDF},
  issue        = {2},
  keywords     = {lcst, thermoresponsive, review, cloud point, turbidimetry},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C7MH00016B},
}

@Article{Cook2021,
  author       = {Cook, Michael T. and Haddow, Peter and Kirton, Stewart B. and McAuley, William J.},
  journal      = {Advanced Functional Materials},
  title        = {Polymers Exhibiting Lower Critical Solution Temperatures as a Route to Thermoreversible Gelators for Healthcare},
  year         = {2021},
  number       = {8},
  pages        = {2008123},
  volume       = {31},
  abstract     = {The ability to trigger changes to material properties with external stimuli, so-called “smart” behavior, has enabled novel technologies for a wide range of healthcare applications. Response to small changes in temperature is particularly attractive, where material transformations may be triggered by contact with the human body. Thermoreversible gelators are materials where warming triggers reversible phase change from low viscosity polymer solution to a gel state. These systems can be generated by the exploitation of macromolecules with lower critical solution temperatures included in their architectures. The resultant materials are attractive for topical and mucosal drug delivery, as well as for injectables. In addition, the materials are attractive for tissue engineering and 3D printing. The fundamental science underpinning these systems is described, along with progress in each class of material and their applications. Significant opportunities exist in the fundamental understanding of how polymer chemistry and nanoscience describe the performance of these systems and guide the rational design of novel systems. Furthermore, barriers to translating technologies must be addressed, for example, rigorous toxicological evaluation is rarely conducted. As such, applications remain tied to narrow fields, and advancements will be made where the existing knowledge in these areas may be applied to novel problems of science.},
  creationdate = {2023-03-20T00:00:00},
  doi          = {https://doi.org/10.1002/adfm.202008123},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/adfm.202008123},
  file         = {:Cook2021 - Polymers Exhibiting Lower Critical Solution Temperatures As a Route to Thermoreversible Gelators for Healthcare.pdf:PDF},
  keywords     = {bioprinting, drug delivery, hydrogels, stimuli-responsive polymers, temperature-responsive polymers, thermogelling materials, thermoresponsive, review, lcst, application-focused, application focused},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202008123},
}

@Article{VanDurme2004,
  author       = {Van Durme, Kurt and Van Assche, Guy and Van Mele, Bruno},
  journal      = {Macromolecules},
  title        = {Kinetics of Demixing and Remixing in Poly(N-isopropylacrylamide)/Water Studied by Modulated Temperature DSC},
  year         = {2004},
  number       = {25},
  pages        = {9596--9605},
  volume       = {37},
  abstract     = {The heat capacity signal from modulated temperature DSC can be used to measure the onset of phase separation in aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions, showing a type II LCST demixing behavior. Quasi-isothermal measurements through the phase transition show large excess contributions in the (apparent) heat capacity, caused by demixing and remixing heat effects on the time scale of the modulation. These excess contributions and their time-dependent evolution are useful to describe the kinetics of phase separation and to follow the related morphology development. Partial vitrification of the polymer-rich phase slows down the remixing kinetics.},
  creationdate = {2023-03-20T00:00:00},
  doi          = {10.1021/ma048472b},
  eprint       = {https://doi.org/10.1021/ma048472b},
  file         = {:VanDurme2004 - Kinetics of Demixing and Remixing in Poly(N Isopropylacrylamide)_Water Studied by Modulated Temperature DSC.pdf:PDF},
  keywords     = {kinetics, pNIPAM, thermoresponsive, dsc, lcst},
  url          = {https://doi.org/10.1021/ma048472b},
}

@Article{Wang1996,
  author       = {W. Wang and D.A. Tree and M.S. High},
  journal      = {Fluid Phase Equilibria},
  title        = {A comparison of lattice-fluid models for the calculation of the liquid-liquid equilibria of polymer solutions},
  year         = {1996},
  issn         = {0378-3812},
  number       = {1},
  pages        = {47--62},
  volume       = {114},
  abstract     = {The group contribution lattice-fluid equation of state (GCLF) has been compared to the Sanchez-Lacombe (S-L) equation of state and experimental data for liquid-liquid equilibrium in polymer-solvent systems. Both equations of state are shown to be capable of predicting upper critical solution temperatures, lower critical solution temperatures, simultaneous upper and lower critical temperatures and “hour glass” behavior in which there is no upper or lower critical temperature. The predictions of the GCLF model and S-L model are compared to systems which show a LCST and both a LCST and UCST. The specific systems studied include: acetic aciddodecane, polyisobutylenen-pentane, polyethylenen-hexane, polystyrenen-hexane, polyisobutylenen-pentane, and polystyreneacetone. The GCLF showed good agreement with the experimental data for systems with a LCST. In all cases the GCLF model performed better than the S-L model. The GCLF showed good sensitivity to the molecular weight of the polymer, but failed to show the needed sensitivity to pressure. The enhanced performance of the GCLF model was attributed to using saturated vapor and liquid properties simultaneously to regress the group parameters for the model.},
  creationdate = {2023-03-20T00:00:00},
  doi          = {https://doi.org/10.1016/0378-3812(95)02814-5},
  file         = {:Wang1996 - A Comparison of Lattice Fluid Models for the Calculation of the Liquid Liquid Equilibria of Polymer Solutions.pdf:PDF},
  keywords     = {Equation of state, Polymer solutions, lcst, theory, model},
  url          = {https://www.sciencedirect.com/science/article/pii/0378381295028145},
}

@Article{Sato1999,
  author       = {Sato,Takaaki and Chiba,Akio and Nozaki,Ryusuke},
  journal      = {The Journal of Chemical Physics},
  title        = {Dynamical aspects of mixing schemes in ethanol–water mixtures in terms of the excess partial molar activation free energy, enthalpy, and entropy of the dielectric relaxation process},
  year         = {1999},
  number       = {5},
  pages        = {2508--2521},
  volume       = {110},
  creationdate = {2023-03-21T00:00:00},
  doi          = {10.1063/1.477956},
  eprint       = {https://doi.org/10.1063/1.477956},
  file         = {:Sato1999 - Dynamical Aspects of Mixing Schemes in Ethanol–water Mixtures in Terms of the Excess Partial Molar Activation Free Energy, Enthalpy, and Entropy of the Dielectric Relaxation Process.pdf:PDF},
  keywords     = {aqueous ethanol, dielectrics, cononsolvency, thermodynamics, enthalpy, entropy, free energy, concentration dependence, spectral density},
  url          = {https://doi.org/10.1063/1.477956},
}

@Article{Kuppers1971,
  author       = {James R Kuppers},
  journal      = {Journal of Magnetic Resonance (1969)},
  title        = {Chemical shifts of the coalesced hydroxy proton magnetic resonance signal and departures from ideality in aqueous alcohol mixtures. I. The tert-butanol-water system},
  year         = {1971},
  issn         = {0022-2364},
  number       = {2},
  pages        = {220--225},
  volume       = {4},
  abstract     = {Maximum downfield chemical shifts of the coalesced hydroxy proton signal, relative to that predicted for an ideal solution, occurred at tert-butanol concentrations for which thermodynamic properties suggest the highest degree of water structuring. Shifts in the opposite direction reached extreme values near the azeotropic composition of the tert-butanol-water system.},
  creationdate = {2023-03-23T00:00:00},
  doi          = {10.1016/0022-2364(71)90106-5},
  file         = {:Kuppers1971 - Chemical Shifts of the Coalesced Hydroxy Proton Magnetic Resonance Signal and Departures from Ideality in Aqueous Alcohol Mixtures. I. the Tert Butanol Water System.pdf:PDF},
  keywords     = {aqueous alcohol, tert-butanol, TBA, nmr, chemical shift, thermodynamics, viscosity, entropy, excess volume, enthalpy},
  url          = {https://www.sciencedirect.com/science/article/pii/0022236471901065},
}

@Article{Spiess1969,
  author       = {Spiess,H. W. and Garrett,B. B. and Sheline,R. K. and Rabideau,S. W.},
  journal      = {The Journal of Chemical Physics},
  title        = {Oxygen‐17 Quadrupole Coupling Parameters for Water in Its Various Phases},
  year         = {1969},
  number       = {3},
  pages        = {1201--1205},
  volume       = {51},
  abstract     = {Analysis of 17 0 NMR data in D 217 0 ice yields a quadrupole coupling constant, e 2 qQ/h= 6.66±0.lOMHz, and an asymmetry parameter, '1=0.935±0.01. Comparison with the data for liquid and gas indicates a temperature dependence of the 17 0 quadrupole coupling constant in the liquid and explains the unusual linewidth behavior for liquid D2170. Charge distributions in the water molecule in both the solid and gaseous states have been obtained by a valence-shell atomic-orbital population analysis based on the experimental data for the 170 quadrupole coupling parameters and the molecular dipole moment. The results were used to calculate the quadrupole coupling constant for the deuterium nucleus. Good agreement with experimental data was obtained for both the solid and gaseous states. Comparison of the calculations for the two phases suggests that the intermolecular effects in ice are mostly electrostatic.},
  creationdate = {2023-03-23T00:00:00},
  doi          = {10.1063/1.1672122},
  eprint       = {https://doi.org/10.1063/1.1672122},
  file         = {:Spiess1969 - Oxygen‐17 Quadrupole Coupling Parameters for Water in Its Various Phases.pdf:PDF},
  keywords     = {17o, nmr, qcc},
  url          = {https://doi.org/10.1063/1.1672122},
}

@Article{Franks1966,
  author       = {Franks, F. and Ives, D. J. G.},
  journal      = {Q. Rev. Chem. Soc.},
  title        = {The structural properties of alcohol–water mixtures},
  year         = {1966},
  pages        = {1--44},
  volume       = {20},
  creationdate = {2023-03-23T00:00:00},
  doi          = {10.1039/QR9662000001},
  file         = {:Franks1966 - The Structural Properties of Alcohol–water Mixtures.pdf:PDF},
  keywords     = {aqueous alcohol, review},
  url          = {http://dx.doi.org/10.1039/QR9662000001},
}

@Article{Kudish1974,
  author       = {Kudish, Albert I. and Wolf, David and Steckel, Fritz},
  journal      = {J. Chem. Soc.{,} Faraday Trans. 1},
  title        = {Physical properties of oxygen-17 water. Absolute viscosity and density of H217O between 15 and 35°C},
  year         = {1974},
  pages        = {484--489},
  volume       = {70},
  abstract     = {The absolute viscosity of four oxygen-17 water samples is reported at 5°C intervals between 15 and 35°C. The absolute viscosity of 100 % HO is determined by extrapolation of the measured viscosity of a highly enriched oxygen-17 sample{,} i.e.{,} 86.53 %O. The values calculated{,} based upon Eyring{'}s theory of viscosity{,} for the other oxygen-17 samples are in excellent agreement with the experimental results. The isotope effect has been analyzed for HO relative to natural water. The viscosity ratio at 25°C for HO/HO is 1.0226{,} whereas that for HO/HO and DO/HO is 1.0536 and 1.2316{,} respectively.},
  creationdate = {2023-03-24T00:00:00},
  doi          = {10.1039/F19747000484},
  file         = {:Kudish1974 - Physical Properties of Oxygen 17 Water. Absolute Viscosity and Density of H217O between 15 and 35°C.pdf:PDF},
  issue        = {0},
  keywords     = {17o water, viscosity, h2o, density, d2o, isotope effect},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/F19747000484},
}

@Article{Schaefer1995,
  author       = {D. Schaefer and J. Leisen and H.W. Spiess},
  journal      = {Journal of Magnetic Resonance, Series A},
  title        = {Experimental Aspects of Multidimensional Exchange Solid-State NMR},
  year         = {1995},
  issn         = {1064-1858},
  number       = {1},
  pages        = {60--79},
  volume       = {115},
  abstract     = {A five-pulse sequence for two-dimensional exchange 2H NMR that results in improved processability of the obtained spectra is presented, together with the phase cycle necessary to eliminate unwanted signal contributions. The scheme of the three-dimensional Fourier transformation to yield pure-absorption-mode three-dimensional 2H NMR spectra is presented, and the off-resonance measurement of multidimensional 2H NMR experiments is discussed. Furthermore, the phase cycles of six- and eight-pulse sequences for the acquisition of undistorted three-dimensional 2H NMR spectra are derived from the phase cycles of the 2D pulse sequences. Differences in the phase cycles for spin-12 nuclei, such as 13C, and spin-1 nuclei, such as 2H, are explicitly addressed.},
  creationdate = {2023-04-05T00:00:00},
  doi          = {https://doi.org/10.1006/jmra.1995.1149},
  file         = {:Schaefer1995 - Experimental Aspects of Multidimensional Exchange Solid State NMR.pdf:PDF},
  keywords     = {2h-nmr, phase cycle, theory},
  printed      = {printed},
  url          = {https://www.sciencedirect.com/science/article/pii/S1064185885711497},
}

@Article{Kariyo2005,
  author       = {Sobiroh Kariyo and Markus Küppers and Manohan V. Badiger and Anabathula Prabhakar and Bharatam Jagadeesh and Siegfried Stapf and Bernhard Blümich},
  journal      = {Magnetic Resonance Imaging},
  title        = {Morphology and chain dynamics during collapse transition of PNIPAM gels studied by combined imaging, relaxometry and 129Xe spectroscopy techniques},
  year         = {2005},
  issn         = {0730-725X},
  note         = {Proceedings of the Seventh International Conference on Recent Advances in MR Applications to Porous Media},
  number       = {2},
  pages        = {249--253},
  volume       = {23},
  abstract     = {The temperature-induced shape transition of poly(N-isopropylacrylamide) gels of different cross-link densities was investigated by a combination of NMR techniques allowing the characterization of both the macroscopic collapse as well as the changes on a molecular scale related to the expulsion of water from the gel network. The proton-containing gel phase was visualized by swelling in heavy water, and the volume change was monitored by proton imaging for cross-link densities between 0.5% and 2.5%. Above the transition temperature of 35°C, gel collapse led to a volume change of up to a factor of 17 for the gel of smallest cross-link density. Two spectral lines of 129Xe are found in the gel state and are assigned to the hydrophobic and hydrophilic parts of the network. In the collapsed state, the hydrophobic peak shows a strong shift while the hydrophilic peak disappears. A considerable shortening of both T1 and T2 of the gel protons upon collapse was found at a field of 4.7 T. At lower fields, the effect becomes more pronounced and qualitatively different dispersion behaviors between the swollen and the collapsed states are observed.},
  creationdate = {2023-04-10T00:00:00},
  doi          = {https://doi.org/10.1016/j.mri.2004.11.019},
  file         = {:Kariyo2005 - Morphology and Chain Dynamics during Collapse Transition of PNIPAM Gels Studied by Combined Imaging, Relaxometry and 129Xe Spectroscopy Techniques.pdf:PDF},
  keywords     = {hydrogel, LCST, Relaxometry, Networks, 129Xe spectroscopy, pNIPAM, Fast Field Cycling, 1H nmr, exchange},
  url          = {https://www.sciencedirect.com/science/article/pii/S0730725X05000214},
}

@Article{Vogel2001,
  author       = {Vogel,M. and Rössler,E.},
  journal      = {The Journal of Chemical Physics},
  title        = {Slow $\beta$ process in simple organic glass formers studied by one- and two-dimensional 2H nuclear magnetic resonance. I},
  year         = {2001},
  number       = {13},
  pages        = {5802--5815},
  volume       = {114},
  creationdate = {2023-04-15T00:00:00},
  doi          = {10.1063/1.1351159},
  eprint       = {https://doi.org/10.1063/1.1351159},
  file         = {:Vogel2001 - Slow Β Process in Simple Organic Glass Formers Studied by One and Two Dimensional 2H Nuclear Magnetic Resonance. I.pdf:PDF},
  keywords     = {2h nmr},
  url          = {https://doi.org/10.1063/1.1351159},
}

@Article{Vogel2001a,
  author       = {Vogel,M. and Rössler,E.},
  journal      = {The Journal of Chemical Physics},
  title        = {Slow $\beta$ process in simple organic glass formers studied by one and two-dimensional 2H nuclear magnetic resonance. II. Discussion of motional models},
  year         = {2001},
  number       = {23},
  pages        = {10883--10891},
  volume       = {115},
  creationdate = {2023-04-15T00:00:00},
  doi          = {10.1063/1.1415495},
  eprint       = {https://doi.org/10.1063/1.1415495},
  file         = {:Vogel2001a - Slow Β Process in Simple Organic Glass Formers Studied by One and Two Dimensional 2H Nuclear Magnetic Resonance. II. Discussion of Motional Models.pdf:PDF},
  keywords     = {2h nmr},
  url          = {https://doi.org/10.1063/1.1415495},
}

@Article{Ananiadou2021,
  author       = {Ananiadou, Antonela and Papamokos, George and Steinhart, Martin and Floudas, George},
  journal      = {The Journal of Chemical Physics},
  title        = {{Effect of confinement on the dynamics of 1-propanol and other monohydroxy alcohols}},
  year         = {2021},
  issn         = {0021-9606},
  month        = nov,
  note         = {184504},
  number       = {18},
  volume       = {155},
  abstract     = {{We report the effect of confinement on the dynamics of three monohydroxy alcohols (1-propanol, 2-ethyl-1-hexanol, and 4-methyl-3-heptanol) differing in their chemical structure and, consequently, in the dielectric strength of the “Debye” process. Density functional theory calculations in bulk 1-propanol identified both linear and ring-like associations composed of up to five repeat units. The simulation results revealed that the ring structures, with a low dipole moment (∼2 D), are energetically preferred over the linear assemblies with a dipole moment of 2.18 D per repeat unit. Under confinement in nanoporous alumina (in templates with pore diameters ranging from 400 to 20 nm), all dynamic processes were found to speed up irrespective of the molecular architecture. The characteristic freezing temperatures of the α and the Debye-like processes followed the pore size dependence: Ta,D=Ta,Dbulk−A/d1/2, where d is the pore diameter. The characteristic “freezing” temperatures for the Debye-like (the slow process for confined 1-propanol is non-Debye) and the α-processes decrease, respectively, by 6.5 and 13 K in confined 1-propanol, by 9.5 and 19 K in confined 2-ethyl-1-hexanol, and by 9 and 23 K in confined 4-methyl-3-heptanol within the same 25 nm pores. In 2-ethyl-1-hexanol, confinement reduced the number of linearly associated repeats from approximately heptamers in the bulk to dimers within 25 pores. In addition, the slower process in bulk 2-ethyl-1-hexanol and 4-methyl-3-heptanol, where the signal is dominated by ring-like supramolecular assemblies, is clearly non-Debye. The results suggest that the effect of confinement is dominant in the latter assemblies.}},
  creationdate = {2023-06-02T00:00:00},
  doi          = {10.1063/5.0063967},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/5.0063967/13564357/184504\_1\_online.pdf},
  file         = {:Ananiadou2021 - Effect of Confinement on the Dynamics of 1 Propanol and Other Monohydroxy Alcohols.pdf:PDF},
  keywords     = {katharina, floudas, confinement, 1-propanol, PrOH, monohydroxy, alcohol, bds, dielectrics, dft, theory, calculation, simulation, spectral density},
  printed      = {printed},
  url          = {https://doi.org/10.1063/5.0063967},
}

@Article{Bierwirth2019,
  author       = {Bierwirth, S. Peter and Honorio, Gabriel and Gainaru, Catalin and B{\"o}hmer, Roland},
  journal      = {The Journal of Chemical Physics},
  title        = {{Linear and nonlinear shear studies reveal supramolecular responses in supercooled monohydroxy alcohols with faint dielectric signatures}},
  year         = {2019},
  issn         = {0021-9606},
  month        = mar,
  note         = {104501},
  number       = {10},
  volume       = {150},
  abstract     = {{Monohydroxy alcohols (MAs) with methyl and hydroxyl side groups attached to the same carbon atom in the alkyl backbone can display very weak structural and supramolecular dielectric relaxation processes when probed in the regime of small electrical fields. This can render their separation and assignment difficult in the pure liquids. When mixing with bromoalkanes, a faint Debye-like process can be resolved dielectrically for 4-methyl-4-heptanol. To achieve a separation of structural and supramolecular processes in pure 4-methyl-4-heptanol and 3-methyl-3-heptanol, mechanical experiments are carried out in the linear-response regime as well as using medium-angle oscillatory shear amplitudes. It is demonstrated that first-order and third-order nonlinear mechanical effects allow for a clear identification of supramolecular viscoelastic modes even for alcohols in which they leave only a weak signature in the linear-response shear modulus. Additionally, the nonlinear rheological behavior of 2-ethyl-1-hexanol is studied, revealing that its linearly detected terminal mode does not coincide with that revealed beyond the linear-response regime. This finding contrasts with those for the other MAs studied in this work.}},
  creationdate = {2023-06-02T00:00:00},
  doi          = {10.1063/1.5086529},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.5086529/13950593/104501\_1\_online.pdf},
  file         = {:Bierwirth2019 - Linear and Nonlinear Shear Studies Reveal Supramolecular Responses in Supercooled Monohydroxy Alcohols with Faint Dielectric Signatures.pdf:PDF},
  keywords     = {katharina, rheology, monohydroxy alcohols, dielectrics, bds, supramolecular, shear},
  url          = {https://doi.org/10.1063/1.5086529},
}

@Article{Hansen1997,
  author       = {Hansen, C. and Stickel, F. and Berger, T. and Richert, R. and Fischer, E. W.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Dynamics of glass-forming liquids. III. Comparing the dielectric $\alpha$- and $\beta$-relaxation of 1-propanol and o-terphenyl}},
  year         = {1997},
  issn         = {0021-9606},
  month        = jul,
  number       = {4},
  pages        = {1086--1093},
  volume       = {107},
  abstract     = {{We have measured the dielectric relaxation of the glass-former 1-propanol for temperatures between 65 and 350 K in the frequency range 10−2 to 2⋅1010 Hz and the photon correlation spectroscopy decays near Tg. Attributing the strong Debye-type process of 1-propanol to distinct -OH group effects leaves two faster processes related to the structural relaxation which can be identified as α-relaxation and Johari–Goldstein type β-relaxation characteristic of nonhydrogen-bonding supercooled liquids. From the temperature dependent relaxation times τ(T) regarding the three distinct loss peaks, we can specify an α-β-bifurcation temperature Tβ, which coincides with characteristic qualitative changes in the τ(T) behavior, as also observed for ortho-terphenyl and other glass-forming liquids. This assignment is confirmed by the correlation times derived from incoherent quasielastic light-scattering data obtained from the simultaneously measured photon-correlation spectroscopy.}},
  creationdate = {2023-06-02T00:00:00},
  doi          = {10.1063/1.474456},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/107/4/1086/10788302/1086\_1\_online.pdf},
  file         = {:Hansen1997 - Dynamics of Glass Forming Liquids. III. Comparing the Dielectric Α and Β Relaxation of 1 Propanol and O Terphenyl.pdf:PDF},
  keywords     = {katharina, dielectrics, bds, glass, 1-propanol, PrOH, PCS, Johari-Goldstein, hydrogen bond},
  printed      = {printed},
  url          = {https://doi.org/10.1063/1.474456},
}

@Article{Vasylkevych2019,
  author       = {O. A. Vasylkevych and V. I. Slisenko},
  journal      = {Reports of the National Academy of Sciences of Ukraine},
  title        = {Self-diffusion of molecules in water-ethanol solutions of low concentration. Neutron data},
  year         = {2019},
  note         = {"Issue 8". Unclear if volume or number is meant.},
  pages        = {46--51},
  volume       = {8},
  abstract     = {The work is devoted to the abnormal behavior of dilute wateralcohol solutions. The dynamics of molecules of the waterethanol system, depending on the concentration at 281 K, is researched by the method of quasielastic scattering of slow neutrons. The total selfdiffusion coefficient of molecules D, its singleparticle Ds-p and collective Dcoll components, and the time of settled molecule's life in the oscillating state t0 are determined. The region of small concentrations was studied in detail, and two minima in the coefficients D and Ds-p were detected in the vicinity of concentrations X = 0.04 mol.f. and X = 0.2 mol.f. Time t0 at these concentrations is increasing significantly. This indicates a significant decrease in the intensity of the activation mechanism of diffusion of molecules, which is quite possible due to the binding of water and ethanol molecules into complexes (clusters).},
  creationdate = {2023-06-30T00:00:00},
  doi          = {10.15407/dopovidi2019.08.046},
  file         = {:Vasylkevych2019 - Self Diffusion of Molecules in Water Ethanol Solutions of Low Concentration. Neutron Data.pdf:PDF},
  keywords     = {self-diffusion, aqueous ethanol, water, neutron, concentration-dependence, cononsolvency},
}

@Article{Arrighi1995,
  author       = {Arrighi, V. and Higgins, J. S. and Burgess, A. N. and Howells, W. S.},
  journal      = {Macromolecules},
  title        = {Rotation of Methyl Side Groups in Polymers: A Fourier Transform Approach to Quasielastic Neutron Scattering. 1. Homopolymers},
  year         = {1995},
  number       = {8},
  pages        = {2745--2753},
  volume       = {28},
  creationdate = {2023-07-04T00:00:00},
  doi          = {10.1021/ma00112a021},
  eprint       = {https://doi.org/10.1021/ma00112a021},
  file         = {:Arrighi1995 - Rotation of Methyl Side Groups in Polymers_ a Fourier Transform Approach to Quasielastic Neutron Scattering. 1. Homopolymers.pdf:PDF},
  keywords     = {methyl group rotation, quasielastic neutron scattering, QENS, polymer},
  url          = {https://doi.org/10.1021/ma00112a021},
}

@Article{Flaemig2020,
  author       = {Fl{\"a}mig, M. and Hofmann, M. and Fatkullin, N. and R{\"o}ssler, E. A.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {NMR Relaxometry: The Canonical Case Glycerol},
  year         = {2020},
  note         = {PMID: 31967826},
  number       = {8},
  pages        = {1557--1570},
  volume       = {124},
  abstract     = {We present a quantitative description of the proton spin–lattice relaxation rate R1(T,ω) of glycerol including temperatures from 191 to 360 K and a frequency range 10 kHz < ω/2π < 20 MHz covered by the field-cycling technique. The analysis encompasses the data compiled by Noack and co-workers in 1971, so far, the most complete data set (10 kHz > ω/2π < 117 MHz). Applying frequency–temperature superposition, master curves are constructed extending over 15 decades in frequency/time. They are described by contributions reflecting translational and rotational dynamics mediated by inter- and intramolecular relaxation pathways. The rotational part of the spectral density/susceptibility shows high similarity with those reported by dielectric spectroscopy or photon correlation spectroscopy (PCS). In addition to a Cole-Davidson-like peak, a high-frequency “excess wing” has to be accounted for. Quantitative agreement with the PCS susceptibility is found which probes the same order of the rotational correlation function. The translational contribution is reproduced by applying the force-free hard sphere model, describing diffusion of dipolarly coupled spin systems. Rotational and translational time constants are compared to those from other techniques. Our approach is paradigmatic for the analysis of spin relaxation in glass-forming liquids. It also solves long-standing deficiencies regarding the analyses of deuteron relaxation. Moreover, the case of glycerol is special as its large separation of translation and rotation dynamics, probably because of its hydrogen bond network, is not found in nonassociated liquids.},
  creationdate = {2023-07-05T00:00:00},
  doi          = {10.1021/acs.jpcb.9b11770},
  eprint       = {https://doi.org/10.1021/acs.jpcb.9b11770},
  file         = {:Flaemig2020 - NMR Relaxometry_ the Canonical Case Glycerol.pdf:PDF},
  keywords     = {1h nmr, glycerol, glycerin, field cycling, relaxation, t1, t2, spectral density, intra, inter},
  url          = {https://doi.org/10.1021/acs.jpcb.9b11770},
}

@Article{Kruk2012,
  author       = {D. Kruk and A. Herrmann and E.A. Rössler},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {Field-cycling NMR relaxometry of viscous liquids and polymers},
  year         = {2012},
  issn         = {0079-6565},
  pages        = {33--64},
  volume       = {63},
  creationdate = {2023-07-07T00:00:00},
  doi          = {https://doi.org/10.1016/j.pnmrs.2011.08.001},
  file         = {:Kruk2012 - Field Cycling NMR Relaxometry of Viscous Liquids and Polymers.pdf:PDF},
  keywords     = {Field cycling, NMR relaxometry, Molecular rotation, Diffusion, Viscous liquids, Glass transition, Polymer dynamics, review},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079656511000586},
}

@Article{Roos2015,
  author       = {Matthias Roos and Marius Hofmann and Susanne Link and Maria Ott and Jochen Balbach and Ernst Rössler and Kay Saalwächter and Alexey Krushelnitsky},
  journal      = {J Biomol NMR},
  title        = {The "long tail" of the protein tumbling correlation function: observation by 1H NMR relaxometry in a wide frequency and concentration range},
  year         = {2015},
  pages        = {403--415},
  volume       = {63},
  creationdate = {2023-07-07T00:00:00},
  doi          = {https://doi.org/10.1007/s10858-015-0001-1},
  file         = {:Roos2015 - The _long Tail_ of the Protein Tumbling Correlation Function_ Observation by 1H NMR Relaxometry in a Wide Frequency and Concentration Range.pdf:PDF;:TheLongTailOfTheProteinTumblingCorrelationFunction-ObservationBy1HNMRRelaxometryInAWideFrequencyAndConcentrationRange_RoosEtAl_JBiomolNMR2015_SI.pdf:PDF},
  keywords     = {1h nmr, relaxation, field cycling, polymer, spectral density},
  priority     = {prio1},
  url          = {https://doi.org/10.1007/s10858-015-0001-1},
}

@Article{Takaizumi1997,
  author       = {K. Takaizumi and T. Wakabayashi},
  journal      = {Journal of Solution Chemistry},
  title        = {The freezing process in methanol-, ethanol-, and propanol-water systems as revealed by differential scanning calorimetry},
  year         = {1997},
  pages        = {927--939},
  volume       = {26},
  abstract     = {Solid-liquid phase diagrams, including metastable phases, have been obtained by differential scanning calorimetry (DSC) for methanol-, ethanol-, and propanol-water systems. The metastable solid phases which are initially formed on cooling were detected for these three systems, in order to analyze the freezing processes and to correlate the formation of the metastable phases with solution structure.},
  creationdate = {2023-07-11T00:00:00},
  doi          = {10.1007/BF02768051},
  file         = {:Takaizumi1997 - The Freezing Process in Methanol , Ethanol , and Propanol Water Systems As Revealed by Differential Scanning Calorimetry.pdf:PDF},
  keywords     = {katharina, PrOH, aqueous propanol, DSC, low alcohols, aqueous methanol, MeOH, aqueous ethanol, EtOH, aqueous alcohol},
  url          = {https://doi.org/10.1007/BF02768051},
}

@Article{Bull1979,
  author       = {Bull, T. E. and Forsén, Sture and Turner, David L.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Nuclear magnetic relaxation of spin 5/2 and spin 7/2 nuclei including the effects of chemical exchange}},
  year         = {1979},
  issn         = {0021-9606},
  month        = jul,
  number       = {6},
  pages        = {3106--3111},
  volume       = {70},
  abstract     = {{An equation describing the multiexponential longitudinal and transverse relaxation of quadrupolar nuclei, including the effects of chemical exchange in the limit of fast exchange, is derived. It is difficult to produce analytical solutions for nuclei with spins greater than 3/2, but the equation is in a form convenient for numerical solution, and such solutions are presented for both the longitudinal and transverse relaxation of nuclei with spins 5/2 and 7/2 in the absence of chemical exchange, and for the case of two‐site exchange where one site is in the extreme narrowing limit. Longitudinal relaxation may be described approximately by a single exponential in all cases. However, the transverse relaxation generally must be described as the sum of three and four exponentials for the spin 5/2 and spin 7/2 cases, respectively, the amplitudes of which vary with the correlation time in the absence of exchange, and also with the ratio of the lifetimes of the nucleus in each state when two‐site exchange is considered.}},
  creationdate = {2023-07-12T00:00:00},
  doi          = {10.1063/1.437799},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/70/6/3106/11226108/3106\_1\_online.pdf},
  file         = {:Bull2008 - Nuclear Magnetic Relaxation of Spin 5_2 and Spin 7_2 Nuclei Including the Effects of Chemical Exchange.pdf:PDF},
  keywords     = {17o, nmr, theory, relaxation, t1, t2, chemical exchange},
  url          = {https://doi.org/10.1063/1.437799},
}

@InBook{Freude1993,
  author       = {Freude, D. and Haase, J.},
  editor       = {Pfeifer, Harry and Barker, Philip},
  pages        = {1--90},
  publisher    = {Springer Berlin Heidelberg},
  title        = {Quadrupole Effects in Solid-State Nuclear Magnetic Resonance},
  year         = {1993},
  address      = {Berlin, Heidelberg},
  isbn         = {978-3-642-50046-6},
  abstract     = {The applicability of nuclear magnetic resonance (NMR) spectroscopy continues to expand in physics, chemistry, material science, geology, biology, and medicine. An increasing range of NMR techniques is employed for either spectroscopic studies or imaging purposes, most becoming possible because of the high magnetic fields of superconducting magnets (almost an order of magnitude higher than ordinary iron magnets), and the availability of fast computers for controlling purposes and final data processing. These improvements together with the realization of fast mechanical sample spinning and new pulse techniques have led to high-resolution solid-state nuclear magnetic resonance. Because the perturbing effect of the electric quadrupole interaction becomes less important at higher magnetic fields, the investigation of powder samples with NMR techniques has become more feasible. As a result, the number of publications concerning NMR studies of quadrupole nuclei in powder samples rapidly increased in the eighties. However, since 1987 this number of publications is rather stable and amounts to about 100 per year.},
  booktitle    = {Special Applications},
  creationdate = {2023-07-12T00:00:00},
  doi          = {10.1007/978-3-642-50046-6_1},
  file         = {:Freude1993 - Quadrupole Effects in Solid State Nuclear Magnetic Resonance.pdf:PDF},
  keywords     = {17o, relaxation, nmr},
  url          = {https://doi.org/10.1007/978-3-642-50046-6_1},
}

@Article{Zhu2011,
  author       = {Zhu, Jianfeng and Wu, Gang},
  journal      = {Journal of the American Chemical Society},
  title        = {Quadrupole Central Transition 17O NMR Spectroscopy of Biological Macromolecules in Aqueous Solution},
  year         = {2011},
  note         = {PMID: 21175170},
  number       = {4},
  pages        = {920--932},
  volume       = {133},
  abstract     = {We demonstrate a general nuclear magnetic resonance (NMR) spectroscopic approach in obtaining high-resolution 17O (spin-5/2) NMR spectra for biological macromolecules in aqueous solution. This approach, termed quadrupole central transition (QCT) NMR, is based on the multiexponential relaxation properties of half-integer quadrupolar nuclei in molecules undergoing slow isotropic tumbling motion. Under such a circumstance, Redfield’s relaxation theory predicts that the central transition, mI = +1/2 ↔ −1/2, can exhibit relatively long transverse relaxation time constants, thus giving rise to relatively narrow spectral lines. Using three robust protein−ligand complexes of size ranging from 65 to 240 kDa, we have obtained 17O QCT NMR spectra with unprecedented resolution, allowing the chemical environment around the targeted oxygen atoms to be directly probed for the first time. The new QCT approach increases the size limit of molecular systems previously attainable by solution 17O NMR by nearly 3 orders of magnitude (1000-fold). We have also shown that, when both quadrupole and shielding anisotropy interactions are operative, 17O QCT NMR spectra display an analogous transverse relaxation optimized spectroscopy type behavior in that the condition for optimal resolution depends on the applied magnetic field. We conclude that, with the currently available moderate and ultrahigh magnetic fields (14 T and higher), this 17O QCT NMR approach is applicable to a wide variety of biological macromolecules. The new 17O NMR parameters so obtained for biological molecules are complementary to those obtained from 1H, 13C, and 15N NMR studies.},
  creationdate = {2023-07-12T00:00:00},
  doi          = {10.1021/ja1079207},
  eprint       = {https://doi.org/10.1021/ja1079207},
  file         = {:Zhu2011 - Quadrupole Central Transition 17O NMR Spectroscopy of Biological Macromolecules in Aqueous Solution.pdf:PDF},
  keywords     = {17o, central transition, nmr},
  url          = {https://doi.org/10.1021/ja1079207},
}

@Article{Kresse2011,
  author       = {B. Kresse and A.F. Privalov and F. Fujara},
  journal      = {Solid State Nuclear Magnetic Resonance},
  title        = {NMR field-cycling at ultralow magnetic fields},
  year         = {2011},
  issn         = {0926-2040},
  number       = {4},
  pages        = {134--137},
  volume       = {40},
  abstract     = {The paper describes some significant technical improvements of a home built NMR field cycling relaxometer [O. Lips, A. Privalov, S. Dvinskikh, F. Fujara, J. Magn. Reson. 149 (2001) 22–28] now allowing for fast switching of polarization fields (up to more than 1T) to evolution fields down to the sub-μT range. The most important instrumental details such as the description of an involved 3-dimensional resistive coil setup are given. Fields below about 5μT can only be stabilized by incorporation of an active field drift and fluctuation compensation tool. In this way, the smallest 1H Larmor frequency obtained and measured so far has been 12Hz.},
  creationdate = {2023-07-19T00:00:00},
  doi          = {https://doi.org/10.1016/j.ssnmr.2011.10.002},
  keywords     = {Field Cycling, FC NMR, Small Larmor frequencies},
  url          = {https://www.sciencedirect.com/science/article/pii/S0926204011001019},
}

@Article{Lin2021,
  author       = {Guoxing Lin},
  journal      = {Communications in Nonlinear Science and Numerical Simulation},
  title        = {Describing NMR relaxation by effective phase diffusion equation},
  year         = {2021},
  issn         = {1007-5704},
  pages        = {105825},
  volume       = {99},
  abstract     = {This paper proposes an effective diffusion equation method to analyze nuclear magnetic resonance (NMR) relaxation. NMR relaxation is a spin system recovery process, where the evolution of the spin system is affected by the random field due to Hamiltonians, such as dipolar couplings. The evolution of magnetization can be treated as a random walk in phase space described either by a normal or fractional phase diffusion equation. Based on these phase diffusion equations, the NMR relaxation rates and equations can be obtained, exemplified in the analysis of relaxations affected by an arbitrary random field, and by dipolar coupling for both like and unlike spins. The obtained theoretical results are consistent with the reported results in the literature. Additionally, the anomalous relaxation expression obtained from the Mittag-Leffler function based time correlation function can successfully fit the previously reported 13C T1 NMR experimental data of polyisobutylene (PIB) in the blend of PIB and head-to-head poly(propylene) (hhPP). Furthermore, the proposed phase diffusion approach provides an intuitive way to interpret NMR relaxation, particularly for the fractional NMR relaxation, which is still a challenge to explain by the available theoretical methods. The paper provides additional insights into NMR and magnetic resonance imaging (MRI) relaxation experiments.},
  creationdate = {2023-07-21T00:00:00},
  doi          = {https://doi.org/10.1016/j.cnsns.2021.105825},
  file         = {:Lin2021 - Describing NMR Relaxation by Effective Phase Diffusion Equation.pdf:PDF},
  keywords     = {NMR relaxation, Mittag-Leffler function, Kohlrausch-Williams-Watts function, Phase diffusion},
  url          = {https://www.sciencedirect.com/science/article/pii/S1007570421001362},
}

@Article{Schiller2023,
  author       = {Schiller, Verena and Knippen, Katharina and Loidl, Alois and Lunkenheimer, Peter and Volkmer, Dirk and Vogel, Michael},
  journal      = {The Journal of Chemical Physics},
  title        = {{2H NMR studies on the dynamics of supercooled water in a metal–organic framework}},
  year         = {2023},
  issn         = {0021-9606},
  month        = jul,
  number       = {3},
  pages        = {034501},
  volume       = {159},
  abstract     = {{We use 2H nuclear magnetic resonance (NMR) to study water (D2O) reorientation and diffusion in the metal–organic framework MFU-4l, which features a regular three-dimensional network of nearly spherical pores with diameters of 1.2 and 1.9 nm. We observe that the rotational correlation times follow Vogel–Fulcher–Tammann and Arrhenius (Ea = 0.48 eV) relations above ∼225 K and below ∼170 K, respectively, whereas the temperature dependence continuously evolves from one to the other behavior in the broad crossover zone in between. In the common temperature range, the present NMR results are fully consistent with previous broadband dielectric spectroscopy (BDS) data on water (H2O) in a very similar framework. Several of our observations, e.g., rotational–translational coupling, indicate that a bulk-like structural (α) relaxation is observed above the crossover region. When cooling through the crossover zone, a quasi-isotropic reorientation mechanism is retained, while 2H spin-lattice relaxation evolves from exponential to nonexponential, implying that the water dynamics probed at low temperatures does no longer fully restore ergodicity on the time scale of this experiment. We discuss that the latter effect may result from bulk-like and/or confinement-imposed spatially heterogeneous water properties. Comparison with previous NMR and BDS results for water in other confinements reveals that, for confinement sizes around 2 nm, water reorientation depends more on the pore diameter than on the pore chemistry, while water diffusion is strongly affected by the connectivity and topology of the pores.}},
  creationdate = {2023-08-02T00:00:00},
  doi          = {10.1063/5.0159256},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/5.0159256/18045482/034501\_1\_5.0159256.pdf},
  url          = {https://doi.org/10.1063/5.0159256},
}

@Article{Hawlicka1992,
  author       = {Hawlicka, Ewa and Grabowski, Roman},
  journal      = {The Journal of Physical Chemistry},
  title        = {Self-diffusion in water-alcohol systems. 3. 1-Propanol-water solutions of sodium iodide},
  year         = {1992},
  number       = {4},
  pages        = {1554--1557},
  volume       = {96},
  creationdate = {2023-08-31T00:00:00},
  doi          = {10.1021/j100183a013},
  eprint       = {https://doi.org/10.1021/j100183a013},
  file         = {:Hawlicka1992 - Self Diffusion in Water Alcohol Systems. 3. 1 Propanol Water Solutions of Sodium Iodide.pdf:PDF},
  keywords     = {cononsolvency, self-diffusion, propanol, aqueous alcohol, stokes-einstein-debye, sed},
  url          = {https://doi.org/10.1021/j100183a013},
}

@Article{Lodge1993,
  author       = {Lodge, Timothy P.},
  journal      = {The Journal of Physical Chemistry},
  title        = {Solvent dynamics, local friction, and the viscoelastic properties of polymer solutions},
  year         = {1993},
  number       = {8},
  pages        = {1480--1487},
  volume       = {97},
  creationdate = {2023-09-01T00:00:00},
  doi          = {10.1021/j100110a004},
  eprint       = {https://doi.org/10.1021/j100110a004},
  file         = {:Lodge1993 - Solvent Dynamics, Local Friction, and the Viscoelastic Properties of Polymer Solutions.pdf:PDF},
  keywords     = {polymer solution, solvent dynamics, oscillatory electric birefringence, OEB, depolarized Rayleigh scattering, DRS, light scattering, 13C-NMR},
  readstatus   = {read},
  url          = {https://doi.org/10.1021/j100110a004},
}

@PhdThesis{Demuth2019,
  author       = {Dominik Demuth},
  school       = {TU Darmstadt},
  title        = {Experimentelle Untersuchungen an Protein-\-Lösungsmittel-\-Mischungen},
  year         = {2019},
  month        = dec,
  type         = {phdthesis},
  creationdate = {2023-09-05T00:00:00},
  file         = {:Demuth2019 - Experimentelle Untersuchungen an Protein Lösungsmittel Mischungen.pdf:PDF},
}

@Article{Dueby2022,
  author       = {Dueby, Shivam and Dubey, Vikas and Indra, Sandipa and Daschakraborty, Snehasis},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Non-monotonic composition dependence of the breakdown of Stokes–Einstein relation for water in aqueous solutions of ethanol and 1-propanol: explanation using translational jump-diffusion approach},
  year         = {2022},
  pages        = {18738--18750},
  volume       = {24},
  abstract     = {A series of experimental and simulation studies examined the validity of the Stokes–Einstein relationship (SER) of water in binary water/alcohol mixtures of different mixture compositions. These studies revealed a strong non-monotonic composition dependence of the SER with maxima at the specific alcohol mole fraction where the non-idealities of the thermodynamic and transport properties are observed. The translational jump-diffusion (TJD) approach elucidated the breakdown of the SER in pure supercooled water as caused by the jump translation of molecules. The breakdown of SER in the supercooled water/methanol binary mixture was successfully explained using the same TJD approach. To further generalize the picture{,} here we focus on the non-monotonic composition dependence of SER breakdown of water in two water/alcohol mixtures (water/ethanol and water/propanol) for a broad temperature range. In agreement with previous studies{,} maximum breakdown of SER is observed for the mixture with alcohol mole fraction x = 0.2. Diffusion of the water molecules at the maximum SER breakdown point is largely contributed by jump-diffusion. The residual-diffusion{,} obtained by subtracting the jump-diffusion from the total diffusion{,} approximately follows the SER for different compositions and temperatures. We also performed hydrogen (H-)bond dynamics and observed that the contribution of jump-diffusion is proportional to the total free energy of activation of breaking all H-bonds that exist around a molecule. This study{,} therefore{,} suggests that the more a molecule is trapped by H-bonding{,} the more likely it is to diffuse through the jump-diffusion mechanism{,} eventually leading to an increasing degree of SER breakdown.},
  creationdate = {2023-09-05T00:00:00},
  doi          = {10.1039/D2CP02664C},
  file         = {:Dueby2022 - Non Monotonic Composition Dependence of the Breakdown of Stokes–Einstein Relation for Water in Aqueous Solutions of Ethanol and 1 Propanol_ Explanation Using Translational Jump Diffusion Approach.pdf:PDF;:NonMonotonicCompositionDependenceOfTheBreakdownOfStokesEinsteinRelationForWaterInAqueousSolutionsOfEthanolAnd1Propanol-ExplanationUsingTranslationalJumpDiffusionApproach_DuebyEtAl_PCCP2022_SI.pdf:PDF},
  issue        = {31},
  keywords     = {Stokes-Einstein,SED,aqueous alcohol,ethanol,1-propanol,simulation},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D2CP02664C},
}

@Article{Pratt1977,
  author       = {Pratt, Kerry C. and Wakeham, William A.},
  journal      = {J. Chem. Soc.{,} Faraday Trans. 2},
  title        = {Self-diffusion in water and monohydric alcohols},
  year         = {1977},
  pages        = {997--1002},
  volume       = {73},
  abstract     = {Self-diffusion coefficients for methanol{,} ethanol{,} n-propanol{,} i-propanol and water have been measured as a function of temperature in the range 25–65°C. A flow technique has been used for the first time in the determinations{,} and the diffusion process has been monitored with the aid of monodeuterated tracers. The self-diffusion coefficients reported for methanol and water are in good agreement with the best available data obtained using n.m.r. techniques. The results have been used to examine both the Eyring theory of liquid diffusion and the more recent correlation of Ertl and Dullien.},
  creationdate = {2023-09-05T00:00:00},
  doi          = {10.1039/F29777300997},
  file         = {:Pratt1977 - Self Diffusion in Water and Monohydric Alcohols.pdf:PDF},
  issue        = {7},
  keywords     = {self-diffusion, monohydric alcohols, methanol, ethanol, n-propanol, 1-propanol, i-propanol, 2-propanol, PrOH, aqueous alcohols},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/F29777300997},
}

@Article{Schrag1991,
  author       = {J.L. Schrag and T.M. Stokich and D.A. Strand and P.A. Merchak and C.J.T. Landry and D.R. Radtke and V.F. Man and T.P. Lodge and R.L. Morris and K.C. Hermann and S. Amelar and C.E. Eastman and M.A. Smeltzly},
  journal      = {Journal of Non-Crystalline Solids},
  title        = {Local modification of solvent dynamics by polymeric solutes},
  year         = {1991},
  issn         = {0022-3093},
  note         = {Proceedings of the International Discussion Meetings on Relaxations in Complex Systems},
  pages        = {537--543},
  volume       = {131-133},
  abstract     = {Extensive oscillatory flow birefringence and dynamic viscoelastic measurements on a variety of polymer-solvent systems indicate that the solvent contributions to the measured solution properties are not given by the neat solvent birefringence or viscosity, respectively, by contrast with the predictions of chain dynamics theory. Rather, the high frequency limiting plateaus observed in the loss components of both the dynamic birefringence and dynamic viscosity, designated S′∞ and η′∞, respectively, represent the appropriate solvent contributions. Measurements of solvent rotational and translational friction in some of the same polymer-solvent systems provide direct support for the postulate that the values of S′∞ and η′∞ reflect predominantly polymer-induced modifications to the dynamics of the solvent surrounding the chains.},
  creationdate = {2023-09-06T00:00:00},
  doi          = {https://doi.org/10.1016/0022-3093(91)90645-M},
  file         = {:Schrag1991 - Local Modification of Solvent Dynamics by Polymeric Solutes.pdf:PDF},
  keywords     = {Elsevier,Rheology,Time-Temperature Superposition,Frequency-Temperature Superposition,Viscosity,Oscillatory Flow Birefringence,Polystyrene,PS,Kerr coeffi,solvent reorientation},
  url          = {https://www.sciencedirect.com/science/article/pii/002230939190645M},
}

@Article{Blum1986,
  author       = {Frank D. Blum and Stephen Pickup and Kenneth R. Foster},
  journal      = {Journal of Colloid and Interface Science},
  title        = {Solvent self-diffusion in polymer solutions},
  year         = {1986},
  issn         = {0021-9797},
  number       = {2},
  pages        = {336--341},
  volume       = {113},
  abstract     = {We compare the solvent self-diffusion coefficients in a variety of aqueous and nonaqueous solutions, including polystyrene (PS) in toluene or cyclohexane, poly(ethylene oxide) (PEO) in water, and various biological materials. Remarkably similar changes are observed in the solvent self-diffusion properties relative to those of the neat solvent for all systems; no chemically specific effects can be resolved. Taken together, the transport data indicate substantial changes in the motional properties of the solvent due to interactions with the polymer. The reduction in transport might be determined by nonspecific kinetic effects associated with the presence of relatively immobile solute molecules.},
  creationdate = {2023-09-06T00:00:00},
  doi          = {https://doi.org/10.1016/0021-9797(86)90169-4},
  keywords     = {Elsevier},
  url          = {https://www.sciencedirect.com/science/article/pii/0021979786901694},
}

@Article{Becher2022,
  author         = {Becher, Manuel and Lichtinger, Anne and Minikejew, Rafael and Vogel, Michael and Rössler, Ernst A.},
  journal        = {International Journal of Molecular Sciences},
  title          = {NMR Relaxometry Accessing the Relaxation Spectrum in Molecular Glass Formers},
  year           = {2022},
  issn           = {1422-0067},
  number         = {9},
  volume         = {23},
  abstract       = {It is a longstanding question whether universality or specificity characterize the molecular dynamics underlying the glass transition of liquids. In particular, there is an ongoing debate to what degree the shape of dynamical susceptibilities is common to various molecular glass formers. Traditionally, results from dielectric spectroscopy and light scattering have dominated the discussion. Here, we show that nuclear magnetic resonance (NMR), primarily field-cycling relaxometry, has evolved into a valuable method, which provides access to both translational and rotational motions, depending on the probe nucleus. A comparison of 1H NMR results indicates that translation is more retarded with respect to rotation for liquids with fully established hydrogen-bond networks; however, the effect is not related to the slow Debye process of, for example, monohydroxy alcohols. As for the reorientation dynamics, the NMR susceptibilities of the structural (&alpha;) relaxation usually resemble those of light scattering, while the dielectric spectra of especially polar liquids have a different broadening, likely due to contributions from cross correlations between different molecules. Moreover, NMR relaxometry confirms that the excess wing on the high-frequency flank of the &alpha;-process is a generic relaxation feature of liquids approaching the glass transition. However, the relevance of this feature generally differs between various methods, possibly because of their different sensitivities to small-amplitude motions. As a major advantage, NMR is isotope specific; hence, it enables selective studies on a particular molecular entity or a particular component of a liquid mixture. Exploiting these possibilities, we show that the characteristic Cole&ndash;Davidson shape of the &alpha;-relaxation is retained in various ionic liquids and salt solutions, but the width parameter may differ for the components. In contrast, the low-frequency flank of the &alpha;-relaxation can be notably broadened for liquids in nanoscopic confinements. This effect also occurs in liquid mixtures with a prominent dynamical disparity in their components.},
  article-number = {5118},
  creationdate   = {2023-09-07T00:00:00},
  doi            = {10.3390/ijms23095118},
  file           = {:Becher2022 - NMR Relaxometry Accessing the Relaxation Spectrum in Molecular Glass Formers.pdf:PDF},
  pubmedid       = {35563506},
  url            = {https://www.mdpi.com/1422-0067/23/9/5118},
}

@Article{Yanase2018,
  author       = {Yanase, Keiichi and Buchner, Richard and Sato, Takaaki},
  journal      = {Phys. Rev. Mater.},
  title        = {Microglobule formation and a microscopic order parameter monitoring the phase transition of aqueous poly($N$-isopropylacrylamide) solution},
  year         = {2018},
  month        = aug,
  pages        = {085601},
  volume       = {2},
  abstract     = {The coil-to-globule transition of poly(N-isopropylacrylamide) (pNIPAm) in water is generally believed to be driven by hydrophobic interaction between the isopropyl groups of its side chains. However, it is still unclear how dehydration and critical fluctuations of the polymer chains are correlated. Here, we use small- and wide-angle x-ray scattering and dielectric relaxation spectroscopy to cover a wide range of the relevant length and time scales, enabling us to grasp an overall picture of this phase transition. We find that the hydration number of pNIPAm decreases only moderately with temperature up to about 6 K below its spinodal temperature T S , but then drops steeply on approaching T S . This rapid dehydration is coupled to a mean-field-like power-law divergence of the correlation length ξ , representing fluctuations of the density order parameter. Real-space decoding of an observed
interference peak reveals partial-globule formation even far below T S and demonstrates that the polymer-rich phase above T S can be understood as a high-density assembly of the microglobules. Strikingly, condensation of the microglobules and the divergence of ξ do not run parallel. Instead, the condensation occurs only above T S and is completed about 6 K above T S . The local number density of the microglobules, exhibiting a steplike increase just above T S , should be identified as an additional microscopic order parameter governing the phase transition of pNIPAm},
  creationdate = {2023-09-07T00:00:00},
  doi          = {10.1103/PhysRevMaterials.2.085601},
  file         = {:Yanase2018 - Microglobule Formation and a Microscopic Order Parameter Monitoring the Phase Transition of Aqueous Poly($N$ Isopropylacrylamide) Solution.pdf:PDF},
  issue        = {8},
  keywords     = {pNIPAM, dielectric relaxation, BDS, x-ray scattering, SAXS, WAXS, critical fluctuation, dehydration, denaturation},
  numpages     = {7},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevMaterials.2.085601},
}

@Article{Lee2006,
  author       = {Lee, Song Hi and Kapral, Raymond},
  journal      = {The Journal of Chemical Physics},
  title        = {{Mesoscopic description of solvent effects on polymer dynamics}},
  year         = {2006},
  issn         = {0021-9606},
  month        = jun,
  number       = {21},
  pages        = {214901},
  volume       = {124},
  abstract     = {{Solvent effects on polymer dynamics and structure are investigated using a mesoscopic solvent model that accounts for hydrodynamic interactions among the polymer beads. The simulation method combines molecular dynamics of the polymer chain, interacting with the solvent molecules through intermolecular forces, with mesoscopic multiparticle collision dynamics for the solvent molecules. Changes in the intermolecular forces between the polymer beads and mesoscopic solvent molecules are used to vary the solvent conditions from those for good to poor solvents. Polymer collapse and expansion dynamics following changes in solvent conditions are studied for homopolymer and block copolymer solutions. The frictional properties of polymers are also investigated.}},
  creationdate = {2023-09-07T00:00:00},
  doi          = {10.1063/1.2198201},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.2198201/15386856/214901\_1\_online.pdf},
  file         = {:Lee2006 - Mesoscopic Description of Solvent Effects on Polymer Dynamics.pdf:PDF},
  keywords     = {theory, models, polymer dynamics},
  url          = {https://doi.org/10.1063/1.2198201},
}

@Article{Arbe2016,
  author       = {Arbe, A. and Malo de Molina, P. and Alvarez, F. and Frick, B. and Colmenero, J.},
  journal      = {Phys. Rev. Lett.},
  title        = {Dielectric Susceptibility of Liquid Water: Microscopic Insights from Coherent and Incoherent Neutron Scattering},
  year         = {2016},
  month        = oct,
  pages        = {185501},
  volume       = {117},
  abstract     = {The analysis of neutron scattering results on H dynamics (H 2 O) and the dynamic structure factor (D 2 O) around the intermolecular peak and at intermediate length scales in terms of the susceptibilities reveals three processes (diffusive, local relaxational and vibrational) at frequencies below 3 THz, to which the contributions commonly invoked in dielectric studies can be directly mapped. We achieve a unified description of the results from both techniques, clarifying the nature of the molecular motions involved in the dielectric spectra and their impact on the structural relaxation.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {10.1103/PhysRevLett.117.185501},
  file         = {:Arbe2016 - Dielectric Susceptibility of Liquid Water_ Microscopic Insights from Coherent and Incoherent Neutron Scattering.pdf:PDF},
  issue        = {18},
  keywords     = {water, dielectric spectroscopy, bds, neutron scattering, coherent neutron, incoherent neutron, three debye model},
  numpages     = {5},
  publisher    = {American Physical Society},
  readstatus   = {skimmed},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.117.185501},
}

@Article{Vogel2008,
  author       = {Vogel, M.},
  journal      = {Phys. Rev. Lett.},
  title        = {Origins of Apparent Fragile-to-Strong Transitions of Protein Hydration Waters},
  year         = {2008},
  month        = nov,
  pages        = {225701},
  volume       = {101},
  abstract     = {2 H NMR is used to study the mechanisms for the reorientation of protein hydration water. In the past, crossovers in temperature-dependent correlation times were reported at T x1  225 K (X 1 ) and T x 2 200 K (X 2 ). We show that neither X 1 nor X 2 are related to a fragile-to-strong transition. Our results rule out an existence of X 1 . Also, they indicate that water performs thermally activated and distorted tetrahedral jumps at T < T x2 , implying that X 2 originates in an onset of this motion, which may be related to a universal defect diffusion in materials with defined hydrogen-bond networks.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {10.1103/PhysRevLett.101.225701},
  file         = {:Vogel2008 - Origins of Apparent Fragile to Strong Transitions of Protein Hydration Waters.pdf:PDF},
  issue        = {22},
  keywords     = {hydration water,nmr,fragile-to-strong transition,hydration shell,glass former,2h-nmr,protein},
  numpages     = {4},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.101.225701},
}

@Article{Lusceac2010,
  author       = {Sorin A. Lusceac and Michael R. Vogel and Claudia R. Herbers},
  journal      = {Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics},
  title        = {2H and 13C NMR studies on the temperature-dependent water and protein dynamics in hydrated elastin, myoglobin and collagen},
  year         = {2010},
  issn         = {1570-9639},
  note         = {Includes Special Section: Protein-Water Interactions},
  number       = {1},
  pages        = {41--48},
  volume       = {1804},
  abstract     = {2H NMR spin-lattice relaxation and line-shape analyses are performed to study the temperature-dependent dynamics of water in the hydration shells of myoglobin, elastin, and collagen. The results show that the dynamical behaviors of the hydration waters are similar for these proteins when using comparable hydration levels of h=0.25–0.43. Since water dynamics is characterized by strongly nonexponential correlation functions, we use a Cole–Cole spectral density for spin-lattice relaxation analysis, leading to correlation times, which are in nice agreement with results for the main dielectric relaxation process observed for various proteins in the literature. The temperature dependence can roughly be described by an Arrhenius law, with the possibility of a weak crossover in the vicinity of 220 K. Near ambient temperatures, the results substantially depend on the exact shape of the spectral density so that deviations from an Arrhenius behavior cannot be excluded in the high-temperature regime. However, for the studied proteins, the data give no evidence for the existence of a sharp fragile-to-strong transition reported for lysozyme at about 220 K. Line-shape analysis reveals that the mechanism for the rotational motion of hydration waters changes in the vicinity of 220 K. For myoglobin, we observe an isotropic motion at high temperatures and an anisotropic large-amplitude motion at low temperatures. Both mechanisms coexist in the vicinity of 220 K. 13C CP MAS spectra show that hydration results in enhanced elastin dynamics at ambient temperatures, where the enhancement varies among different amino acids. Upon cooling, the enhanced mobility decreases. Comparison of 2H and 13C NMR data reveals that the observed protein dynamics is slower than the water dynamics.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {https://doi.org/10.1016/j.bbapap.2009.06.009},
  file         = {:Lusceac2010 - 2H and 13C NMR Studies on the Temperature Dependent Water and Protein Dynamics in Hydrated Elastin, Myoglobin and Collagen.pdf:PDF},
  keywords     = {NMR,Water dynamics,Myoglobin,Elastin,Collagen,hydration water,hydration shell,spectral density,protein},
  url          = {https://www.sciencedirect.com/science/article/pii/S1570963909001459},
}

@Article{Daniel2004,
  author       = {Daniel, R. M. and Finney, J. L. and Stoneham, M. and Halle, Bertil},
  journal      = {Philosophical Transactions of the Royal Society of London. Series B: Biological Sciences},
  title        = {Protein hydration dynamics in solution: a critical survey},
  year         = {2004},
  number       = {1448},
  pages        = {1207--1224},
  volume       = {359},
  abstract     = {The properties of water in biological systems have been studied for well over a century by a wide range of physical techniques, but progress has been slow and erratic. Protein hydration—the perturbation of water structure and dynamics by the protein surface—has been a particularly rich source of controversy and confusion. Our aim here is to critically examine central concepts in the description of protein hydration, and to assess the experimental basis for the current view of protein hydration, with the focus on dynamic aspects. Recent oxygen–17 magnetic relaxation dispersion (MRD) experiments have shown that the vast majority of water molecules in the protein hydration layer suffer a mere twofold dynamic retardation compared with bulk water. The high mobility of hydration water ensures that all thermally activated processes at the protein–water interface, such as binding, recognition and catalysis, can proceed at high rates. The MRD–derived picture of a highly mobile hydration layer is consistent with recent molecular dynamics simulations, but is incompatible with results deduced from intermolecular nuclear Overhauser effect spectroscopy, dielectric relaxation and fluorescence spectroscopy. It is also inconsistent with the common view of hydration effects on protein hydrodynamics. Here, we show how these discrepancies can be resolved.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {10.1098/rstb.2004.1499},
  eprint       = {https://royalsocietypublishing.org/doi/pdf/10.1098/rstb.2004.1499},
  file         = {:Daniel2004 - Protein Hydration Dynamics in Solution_ a Critical Survey.pdf:PDF},
  keywords     = {hydration water, review, 17o-nmr, magnetic relaxation dispersion, hydration shell, protein hydration},
  priority     = {prio1},
  url          = {https://royalsocietypublishing.org/doi/abs/10.1098/rstb.2004.1499},
}

@Article{Denisov1997,
  author       = {Vladimir P. Denisov and Göran Carlström and Kandadai Venu and Bertil Halle},
  journal      = {Journal of Molecular Biology},
  title        = {Kinetics of DNA hydration11Edited by I. Tinoco},
  year         = {1997},
  issn         = {0022-2836},
  number       = {1},
  pages        = {118--136},
  volume       = {268},
  abstract     = {The hydration of the d(CGCGAATTCGCG) B-DNA duplex in solution was studied by nuclear magnetic relaxation dispersion (NMRD) of the water nuclei 1H, 2H, and 17O, and by nuclear Overhauser effects (NOEs) in high-resolution two-dimensional 1H NMR spectra. By comparing results from the free duplex with those from its complex with netropsin, water molecules in the “spine of hydration” in the AATT region of the minor groove could be distinguished from hydration water elsewhere in the duplex. The 2H and 17O relaxation dispersions yield a model-independent residence time of 0.9(±0.1) ns at 4°C for five highly ordered water molecules in the spine. When corrected for frequency offset effects, the NOE data yield the same residence time as the NMRD data, giving credence to both methods. At 27°C, the residence time is estimated to 0.2 ns, a factor of 40 shorter than the tumbling time of the duplex. The NMRD data show that all water molecules associated with the duplex, except the five molecules in the spine, have residence times significantly shorter than 1 ns at 4°C. There is thus no long-lived hydration structure associated with the phosphate backbone. In contrast to 2H and 17O, the 1H relaxation dispersion is dominated by labile DNA protons and therefore provides little information about DNA hydration.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {https://doi.org/10.1006/jmbi.1996.0862},
  file         = {:Denisov1997 - Kinetics of DNA Hydration11Edited by I. Tinoco.pdf:PDF},
  keywords     = {DNA hydration kinetics, water residence time, netropsin, oxygen-17 relaxation dispersion, 17o-NMR spectroscopy, 2h-nmr, 1h-nmr, nculear overhauser effect, NOE},
  priority     = {prio1},
  url          = {https://www.sciencedirect.com/science/article/pii/S0022283696908621},
}

@Article{Ortony2011,
  author       = {Julia H Ortony and Chi-Yuan Cheng and John M Franck and Ravinath Kausik and Anna Pavlova and Jasmine Hunt and Songi Han},
  journal      = {New Journal of Physics},
  title        = {Probing the hydration water diffusion of macromolecular surfaces and interfaces},
  year         = {2011},
  month        = jan,
  number       = {1},
  pages        = {015006},
  volume       = {13},
  abstract     = {We probe the translational dynamics of the hydration water surrounding the macromolecular surfaces of selected polyelectrolytes, lipid vesicles and intrinsically disordered proteins with site specificity in aqueous solutions. These measurements are made possible by the recent development of a new instrumental and methodological approach based on Overhauser dynamic nuclear polarization (DNP)-enhanced nuclear magnetic resonance (NMR) spectroscopy. This technique selectively amplifies 1H NMR signals of hydration water around a spin label that is attached to a molecular site of interest. The selective 1H NMR amplification within molecular length scales of a spin label is achieved by utilizing short-distance range (∼r−3) magnetic dipolar interactions between the 1H spin of water and the electron spin of a nitroxide radical-based label. Key features include the fact that only minute quantities (&lt;10 μl) and dilute (⩾100 μM) sample concentrations are needed. There is no size limit on the macromolecule or molecular assembly to be analyzed. Hydration water with translational correlation times between 10 and 800 ps is measured within ∼10 Å distance of the spin label, encompassing the typical thickness of a hydration layer with three water molecules across. The hydration water moving within this time scale has significant implications, as this is what is modulated whenever macromolecules or molecular assemblies undergo interactions, binding or conformational changes. We demonstrate, with the examples of polymer complexation, protein aggregation and lipid–polymer interaction, that the measurements of interfacial hydration dynamics can sensitively and site specifically probe macromolecular interactions.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {10.1088/1367-2630/13/1/015006},
  file         = {:Ortony2011 - Probing the Hydration Water Diffusion of Macromolecular Surfaces and Interfaces.pdf:PDF},
  keywords     = {hydration water, hydration shell, 1h-nmr, nuclear overhauser, NOE, dynamic nuclear polarization, DNP},
  url          = {https://dx.doi.org/10.1088/1367-2630/13/1/015006},
}

@Article{Zichi1986,
  author       = {Zichi, Dominic A. and Rossky, Peter J.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Solvent molecular dynamics in regions of hydrophobic hydration}},
  year         = {1986},
  issn         = {0021-9606},
  month        = mar,
  number       = {5},
  pages        = {2814--2822},
  volume       = {84},
  abstract     = {{We present a dynamical analysis of the solvent in an aqueous solution of two nonpolar atomic solutes which are constrained to an interatomic distance corresponding to a solvent‐separated free energy minimum. The results are obtained from a molecular dynamics simulation using ST2 model water. Molecular mobility for solvent near the solutes is seen to be retarded, as evidenced in translational diffusion and rotational reorientation. These slower net motions are analogous to pure solvent dynamics at a temperature reduced by 10–15 °C. An analysis of intermolecular hydrogen bonding reveals that solvation shell molecules have correspondingly longer bond half‐lives compared to bulk molecules, by a factor of 1.5–2.0. The spectral densities for intermolecular vibrations are computed from translational and rotational velocity autocorrelation functions for shell and bulk motions. These densities are seen to correlate well with the local binding energy distributions.}},
  creationdate = {2023-09-08T00:00:00},
  doi          = {10.1063/1.450307},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/84/5/2814/9724298/2814\_1\_online.pdf},
  file         = {:Zichi1986 - Solvent Molecular Dynamics in Regions of Hydrophobic Hydration.pdf:PDF},
  keywords     = {hydrophobic hydration, clathrate, molecular dynamics simulation, free energy, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://doi.org/10.1063/1.450307},
}

@Article{Pissis2013,
  author       = {Pissis, Polycarpos and Kyritsis, Apostolos},
  journal      = {Journal of Polymer Science Part B: Polymer Physics},
  title        = {Hydration studies in polymer hydrogels},
  year         = {2013},
  number       = {3},
  pages        = {159--175},
  volume       = {51},
  abstract     = {Polymer hydrogels have attracted much interest in recent years based on numerous applications mainly in biotechnology and medicine. For the knowledge-based design and development of new materials for these and similar applications, it is essential to understand better the hydration properties of hydrogels and of polymers in general. With this term, we mean the particular organization of water in the hydrogel, which determines the properties of the water component, typically different than those of bulk water, and the impact of water on the properties of the polymer matrix itself. In this review, we focus on recent work with hydrogels based on poly(hydroxyethyl acrylate), mostly copolymers with a second hydrophobic polymer and silica nanocomposites. The combination of water sorption/diffusion, thermal and dielectric studies, by fully exploiting the capabilities of each individual technique, proves essential in providing significant information on particular aspects of hydration, such as water uptake, water organization, and diffusion coefficients; glass transition and plasticization; water and polymer dynamics; protonic conductivity, and in revealing interesting correlations between these particular aspects. In the outlook similarities and differences to other related systems, such as protein-water and polymer solutions in non-polar solvents, are stressed in the perspective of a broader study. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013},
  creationdate = {2023-09-08T00:00:00},
  doi          = {https://doi.org/10.1002/polb.23220},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.23220},
  file         = {:Pissis2013 - Hydration Studies in Polymer Hydrogels.pdf:PDF},
  keywords     = {copolymers,nanocomposites,plasticization,polymer dynamics,polymer hydrogels,protonic conductivity,relaxation,uncrystallized water,water clusters,much-cited,review},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.23220},
}

@Article{Debta2022,
  author       = {Debta, Sanghamitra and Bhutia, Sonam Zangpo and Satapathy, Dillip K. and Ghosh, Pijush},
  journal      = {Soft Matter},
  title        = {Intrinsic-water desorption induced thermomechanical response of hydrogels},
  year         = {2022},
  pages        = {8285--8294},
  volume       = {18},
  abstract     = {We report an interplay between the desorption of intrinsic water and relaxation of polymer chains resulting in an unusual thermomechanical response of a hydrogel{,} wherein the elastic modulus increases in a certain temperature range followed by a sharp decrease with a further increase in temperature. We establish that{,} in a hydrogel{,} the desorption of disparate water types having distinct binding energy affects the consolidation and relaxation behaviour of the matrix{,} which in turn affects the mechanical properties at different temperature ranges. Using temperature-dependent dielectric relaxation spectroscopy and nanoindentation techniques{,} the chain dynamics and mechanical properties are investigated.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {10.1039/D2SM01054B},
  file         = {:Debta2022 - Intrinsic Water Desorption Induced Thermomechanical Response of Hydrogels.pdf:PDF},
  issue        = {43},
  keywords     = {hydrogel, thermoresponsive, dielectric spectroscopy, bds, indentation, elastic modulus},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D2SM01054B},
}

@Article{Yao2021,
  author       = {Yao, Helen and Olsen, Bradley D.},
  journal      = {Soft Matter},
  title        = {SANS quantification of bound water in water-soluble polymers across multiple concentration regimes},
  year         = {2021},
  pages        = {5303--5318},
  volume       = {17},
  abstract     = {Contrast-variation small-angle neutron scattering (CV-SANS) is a widely used technique for quantifying hydration water in soft matter systems{,} but it is predominantly applied in the dilute regime or for systems with a well-defined structure factor. Here{,} CV-SANS was used to quantify the number of hydration water molecules associating with three water-soluble polymers with different critical solution temperatures and types of water–solute interactions in dilute{,} semidilute{,} and concentrated solution through the exploration of novel methods of data fitting and analysis. Multiple SANS fitting workflows with varying levels of model assumptions were evaluated and compared to give insight into SANS model selection. These fitting pathways ranged from general{,} model-free algorithms to more standard form and structure factor fitting. In addition{,} Monte Carlo bootstrapping was evaluated as a method to estimate parameter uncertainty through simulation of technical replicates. The most robust fitting workflow for dilute solutions was found to be form factor fitting without CV-SANS (i.e. polymer in 100% D2O). For semidilute and concentrated solutions{,} while the model-free approach can be mathematically defined for CV-SANS data{,} the addition of a structure factor imposes physical constraints on the optimization problem{,} suggesting that the optimal fitting pathway should include appropriate form and structure factor models. The measured hydration numbers were consistent with the number of tightly bound water molecules associated with each monomer unit{,} and the concentration dependence of the hydration number was largely governed by the chemistry-specific interactions between water and polymer. Polymers with weaker water–polymer interactions (i.e. those with fewer hydration water molecules) were found to have more bound water at higher concentrations than those with stronger water–polymer interactions due to the increase in the number of forced water–polymer contacts in the concentrated system. This SANS-based method to count hydration water molecules can be applied to polymers in any concentration regime{,} which will lead to improved understanding of water–polymer interactions and their impact on materials design.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {10.1039/D0SM01962C},
  file         = {:Yao2021 - SANS Quantification of Bound Water in Water Soluble Polymers across Multiple Concentration Regimes.pdf:PDF;:SANSQuantificationOfBoundWaterInWaterSolublePolymersAcrossMultipleConcentrationRegimes_YaoEtAl_SoftMatter2021_SI.pdf:PDF},
  issue        = {21},
  keywords     = {pNIPAM, bound water, hydration shell, concentration dependence, CV-SANS, thermoresponsive, hydration number},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D0SM01962C},
}

@Article{Niebuur2019,
  author       = {Niebuur, Bart-Jan and Lohstroh, Wiebke and Appavou, Marie-Sousai and Schulte, Alfons and Papadakis, Christine M.},
  journal      = {Macromolecules},
  title        = {Water Dynamics in a Concentrated Poly(N-isopropyl\-acrylamide) Solution at Variable Pressure},
  year         = {2019},
  number       = {5},
  pages        = {1942--1954},
  volume       = {52},
  abstract     = {Using quasi-elastic neutron scattering (QENS), we study the dynamics of water in a concentrated poly(N-isopropylacrylamide) solution over a large temperature range across the demixing transition at pressures of 0.1 and 130 MPa. The QENS spectra extending in frequency from 1 to 3 × 103 GHz and in momentum transfer from 0.45 to 1.65 Å–1 reveal the relaxation of hydration water as well as multiple dynamic processes in bulk water. At the cloud point, the fraction of hydration water decreases abruptly at 0.1 MPa, whereas at 130 MPa, it decreases smoothly. The susceptibility spectra of hydration water occur at lower frequencies than those of pure water and the dependence of the relaxation times on momentum transfer can be described by a jump-diffusion model. At a pressure of 0.1 MPa, the hydration water remaining in the two-phase region is more constrained than at 130 MPa. We attribute these findings to the pressure-dependent hydration interactions.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {10.1021/acs.macromol.8b02708},
  eprint       = {https://doi.org/10.1021/acs.macromol.8b02708},
  file         = {:Niebuur2019 - Water Dynamics in a Concentrated Poly(N Isopropylacrylamide) Solution at Variable Pressure.pdf:PDF;:WaterDynamicsInAConcentratedPolyNIsopropylacrylamideSolutionAtVariablePressure_NiebuurEtAl_Macromol2019_SI.pdf:PDF},
  keywords     = {QUENS, neutron scattering, pNIPAM, pressure, concentration, hydration water},
  url          = {https://doi.org/10.1021/acs.macromol.8b02708},
}

@Article{Grossutti2016,
  author       = {Grossutti, Michael and Dutcher, John R.},
  journal      = {Biomacromolecules},
  title        = {Correlation Between Chain Architecture and Hydration Water Structure in Polysaccharides},
  year         = {2016},
  note         = {PMID: 26859153},
  number       = {3},
  pages        = {1198--1204},
  volume       = {17},
  abstract     = {The physical properties of confined water can differ dramatically from those of bulk water. Hydration water associated with polysaccharides provides a particularly interesting example of confined water, because differences in polysaccharide structure provide different spatially confined environments for water sorption. We have used attenuated total reflection infrared (ATR-IR) spectroscopy to investigate the structure of hydration water in films of three different polysaccharides under controlled relative humidity (RH) conditions. We compare the results obtained for films of highly branched, dendrimer-like phytoglycogen nanoparticles to those obtained for two unbranched polysaccharides, hyaluronic acid (HA), and chitosan. We find similarities between the water structuring in the two linear polysaccharides and significant differences for phytoglycogen. In particular, the results suggest that the high degree of branching in phytoglycogen leads to a much more well-ordered water structure (low density, high connectivity network water), indicating the strong influence of chain architecture on the structuring of water. These measurements provide unique insight into the relationship between the structure and hydration of polysaccharides, which is important for understanding and exploiting these sustainable nanomaterials in a wide range of applications.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {10.1021/acs.biomac.6b00026},
  eprint       = {https://doi.org/10.1021/acs.biomac.6b00026},
  file         = {:Grossutti2016 - Correlation between Chain Architecture and Hydration Water Structure in Polysaccharides.pdf:PDF;:CorrelationBetweenChainArchitectureAndHydrationWaterStructureInPolysaccharides_GrossuttiEtAl_BioMac2016_SI.pdf:PDF},
  keywords     = {hydration water, infrared, relative humidity, hydration shell, dendrimer, chitosan, polysaccharide},
  url          = {https://doi.org/10.1021/acs.biomac.6b00026},
}

@Article{Chi2017,
  author       = {Chi, Yongmei and Xu, Songjie and Xu, Xin and Cao, Yuting and Dong, Jian},
  journal      = {Journal of Polymer Science Part B: Polymer Physics},
  title        = {Studies of relationship between polymer structure and hydration environment in amphiphilic polytartaramides},
  year         = {2017},
  number       = {2},
  pages        = {138--145},
  volume       = {55},
  abstract     = {The relationships between the chemical structures and hydration environment of the polymers can provide significant insight into the water-amphiphilic polymer interactions. Here, the hydrophobicity of amphiphilic block copolymers poly(ethylene tartaramide-b-alkyl isocyanate) is gradually tuned by using of a series of pendant alkyl (isopropyl, n-butyl, cyclopentyl, and cyclohexyl) groups. Dynamics of hydration probed by low-field NMR relaxometry exhibits a heterogeneous environment of water molecules, corresponding to tightly bound water with slow re-orientational mobility and loosely bound water with fast re-orientational mobility. Progressively larger amounts of bound water are present in the copolymers, ongoing from pendant isopropyl, n-butyl, cyclopentyl, and finally to cyclohexyl group. Water in the copolymer bearing the cyclohexyl group has a significantly high partial specific heat capacity. Therefore, hydrophobic interaction between the polymer and water is enhanced when the hydrophobicity of the polymer is increased, resulting in considerable hydrophobic hydration with decreased mobility of the bound water.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {https://doi.org/10.1002/polb.24231},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.24231},
  file         = {:Chi2017 - Studies of Relationship between Polymer Structure and Hydration Environment in Amphiphilic Polytartaramides.pdf:PDF},
  keywords     = {amphiphiles, 1H-NMR, differential scanning calorimetry (DSC), heat capacity, relaxation time, hydration water, hydration shell, field-cycling},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.24231},
}

@Article{Spagnoli2015,
  author       = {Spagnoli, Sylvie and Morfin, Isabelle and Gonzalez, Miguel A. and C̨arc̨abal, Pierre and Plazanet, Marie},
  journal      = {Langmuir},
  title        = {Solvent Contribution to the Stability of a Physical Gel Characterized by Quasi-Elastic Neutron Scattering},
  year         = {2015},
  note         = {PMID: 25652143},
  number       = {8},
  pages        = {2554--2560},
  volume       = {31},
  abstract     = {The dynamics of a physical gel, namely, low-molecular-mass organic gelator methyl-4,6-O-benzylidene-α-d-mannopyranoside (α-manno) in water and toluene, are probed by neutron scattering. Using high gelator concentrations, we were able to determine, on a time scale from a few picoseconds to 1 nanosecond, the number of solvent molecules that are immobilized by the rigid network formed by the gelators. We found that only a few toluene molecules per gelator participate in the network which is formed by hydrogen bonding between the gelators’ sugar moieties. In water, however, the interactions leading to the gel formations are weaker, involving dipolar, hydrophobic, or π–π interactions, and hydrogen bonds are formed between the gelators and the surrounding water. Therefore, around 10 to 14 water molecules per gelator are immobilized by the presence of the network. This study shows that neutron scattering can give valuable information about the behavior of solvent confined in a molecular gel.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {10.1021/la5045656},
  eprint       = {https://doi.org/10.1021/la5045656},
  file         = {:Spagnoli2015 - Solvent Contribution to the Stability of a Physical Gel Characterized by Quasi Elastic Neutron Scattering.pdf:PDF},
  keywords     = {QENS, neutron scattering, hydration shell, hydration water, gel},
  url          = {https://doi.org/10.1021/la5045656},
}

@Article{Sekine2014,
  author       = {Yurina Sekine and Hajime Takagi and Sayoko Sudo and Yutaro Kajiwara and Hiroshi Fukazawa and Tomoko Ikeda-Fukazawa},
  journal      = {Polymer},
  title        = {Dependence of structure of polymer side chain on water structure in hydrogels},
  year         = {2014},
  issn         = {0032-3861},
  number       = {24},
  pages        = {6320--6324},
  volume       = {55},
  abstract     = {To investigate the effects of structure of polymer side chains on structure of water in hydrogels, Raman spectra of polyacrylamide (PAA) and poly-N,N,-dimethylacrylamide (PDMAA) hydrogels were measured. PAA and PDMAA have similar chemical structures, except for the side chain structure. The result shows that the frequency of the O–H stretching mode for the PAA hydrogel decreases as the water content decreases, while that for the PDMAA hydrogel increases. Furthermore, the analysis of the relative intensities of the O–H stretching modes shows that the number density of tetragonal water structures differs between the hydrogels. We conclude that most of the bound water molecules in the PAA hydrogel form four strong hydrogen bonds with the hydrophilic groups in the side chain of PAA, whereas those in the PDMAA hydrogel form weak hydrogen bonds with surrounding water molecules. The water structure is an important factor governing the physical and chemical properties of gel materials.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {https://doi.org/10.1016/j.polymer.2014.10.011},
  file         = {:Sekine2014 - Dependence of Structure of Polymer Side Chain on Water Structure in Hydrogels.pdf:PDF},
  keywords     = {Hydrogel, Water, Raman spectroscopy, hydration water, hydration shell, PAA, PDMA},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386114009070},
}

@Article{Panagopoulou2013,
  author       = {Anna Panagopoulou and Joan Vázquez Molina and Apostolos Kyritsis and Manuel Monleón Pradas and Anna Vallés Lluch and Gloria Gallego Ferrer and Polycarpos Pissis},
  journal      = {Food Biophysics},
  title        = {Glass Transition and Water Dynamics in Hyaluronic Acid Hydrogels},
  year         = {2013},
  pages        = {192--202},
  volume       = {8},
  creationdate = {2023-09-08T00:00:00},
  doi          = {https://doi.org/10.1007/s11483-013-9295-2},
  file         = {:Panagopoulou2013 - Glass Transition and Water Dynamics in Hyaluronic Acid Hydrogels.pdf:PDF},
  keywords     = {hydration shell, hydration water, dielectrics, bds},
  url          = {https://doi.org/10.1007/s11483-013-9295-2},
}

@Article{Ganapathy1995,
  author       = {Ganapathy, S. and Ray, Siddharth S. and Rajamohanan, P. R. and Mashelkar, R. A.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Hydration in polymer studied through magic angle spinning nuclear magnetic resonance and heteronuclear $^{13}$C\{$^{1}$H\} Overhauser enhancement spectroscopy: Cross‐relaxation and location of water in poly(acrylamide)}},
  year         = {1995},
  issn         = {0021-9606},
  month        = oct,
  number       = {15},
  pages        = {6783--6794},
  volume       = {103},
  abstract     = {{A combination of magic angle spinning (MAS) and heteronuclear 13C\\{1H\\} Overhauser enhancement spectroscopy (HOESY) is shown to be a powerful technique for studying hydration in polymers. This is demonstrated in poly(acrylamide)–water system. The increased spectral resolution due to MAS is shown to resolve polymer–polymer and polymer–water dipolar correlations in the two dimensional HOESY experiment. The 2D experiment is thus shown to lead to an indirect detection of water interacting with the polymer. The one dimensional transient Overhauser experiment involving selective inversion of water allows the study of cross‐relaxation between water protons and carbonyl carbon in the polymer side chain. The cross‐relaxation rate is rationalized in terms of a direct dipole–dipole interaction between the carbonyl carbon and the hydrated bound water. Based on temperature dependent 17O spin‐lattice relaxation time measurements and a two‐step motional model for water, we gather that water molecules close to the observed polymer site reorient anisotropically, typically an order of magnitude slower than in pure water. The correlation time for bound water mobility has been estimated to be 0.58×10−10 s at 298 K, and, in turn, has been used to locate hydrated water at a distance of 3.45 Å from amide carbonyl. This is the first time such an estimate has been made for hydrated water in a polymer using HOESY data.}},
  creationdate = {2023-09-08T00:00:00},
  doi          = {10.1063/1.470357},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/103/15/6783/10777318/6783\_1\_online.pdf},
  file         = {:Ganapathy1995 - Hydration in Polymer Studied through Magic Angle Spinning Nuclear Magnetic Resonance and Heteronuclear 13C_1H_ Overhauser Enhancement Spectroscopy_ Cross‐relaxation and Location of Water in Poly(acrylamide).pdf:PDF},
  keywords     = {hydration water, nuclear overhauser effect, NOE, 17O-NMR, MAS, 13C-NMR, 1H-NMR, HOESY, 2d-nmr, spin-lattice relaxation, SLR, hydration water, hydration shell, poly(acrylamide)},
  url          = {https://doi.org/10.1063/1.470357},
}

@Article{Vorobev2007,
  author       = {Vorob'ev, Mikhail and Churochkina, Natalia and Khokhlov, Alexei and Stepnova, Evgenia},
  journal      = {Macromolecular Bioscience},
  title        = {Hydration Characterization of Hydrophobically Modified Polymers by Dielectric Measurements in the Millimeter Range},
  year         = {2007},
  number       = {4},
  pages        = {475--481},
  volume       = {7},
  abstract     = {Bound water molecules, the fraction of water molecules that are present in the hydration shells of polymers, lose their rotational mobility in the time scale of 10–50 ps, leading to additional ordering compared with unperturbed water. The amount of bound water per number of carbons in the nonpolar groups as measured by the method of waveguide dielectric resonance increased in the following order: hydrophobically modified chitosan < globular protein < hydrophobically modified polyacrylamide. The hydrophobic modification of acrylamide and chitosan polymers gave smaller variation in hydration than did both the coil-to-globule transition of poly(N-isopropylacrylamide) and the masking of nonpolar groups within the protein globule.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {https://doi.org/10.1002/mabi.200600231},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/mabi.200600231},
  file         = {:Vorobev2007 - Hydration Characterization of Hydrophobically Modified Polymers by Dielectric Measurements in the Millimeter Range.pdf:PDF},
  keywords     = {chitosan, hydrophobicity, microwave, solution properties, water, pNIPAM, hydration shell, hydration water, dielectrics, chitosan},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/mabi.200600231},
}

@Article{Satokawa2008,
  author       = {Satokawa, Yuichi and Shikata, Toshiyuki},
  journal      = {Macromolecules},
  title        = {Hydration Structure and Dynamic Behavior of Poly(vinyl alcohol)s in Aqueous Solution},
  year         = {2008},
  number       = {8},
  pages        = {2908--2913},
  volume       = {41},
  abstract     = {High-frequency dielectric relaxation measurements up to 20 GHz were conducted in aqueous solutions of poly(vinyl alcohol)s (PVAs) to examine their hydration structures and dynamic behavior. Dielectric relaxation spectra of aqueous PVA solutions decomposed well into three sets of the Debye-type relaxation modes. This was attributed to the rotational relaxation mode of free water molecules, an exchange mode of water molecules hydrated to hydroxy (OH) groups for bulk water, and local motions of PVA main chains. OH groups of PVAs keep ca. 2−2.2 hydrated water molecules in aqueous solution, in contrast to the hydration behavior of 1,4-cyclohexanedimethanol and 1,4-cyclohexanediol model molecules possessing OH groups that lack intramolecular hydrogen bond formation, which keep ca. 5 water molecules per OH group in aqueous solution. In the case of PVAs, the formation of intramolecular hydrogen bonding between mainly adjacent OH groups effectively diminishes their hydration numbers.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {10.1021/ma702793t},
  eprint       = {https://doi.org/10.1021/ma702793t},
  file         = {:Satokawa2008 - Hydration Structure and Dynamic Behavior of Poly(vinyl Alcohol)s in Aqueous Solution.pdf:PDF},
  keywords     = {dielectrics, bds, PVA, poly(vinyl alcohol), hydration water, hydration shell, hydration number},
  url          = {https://doi.org/10.1021/ma702793t},
}

@Article{Hager1980,
  author       = {Hager, S. L. and Macrury, T. B.},
  journal      = {Journal of Applied Polymer Science},
  title        = {Investigation of phase behavior and water binding in poly(alkylene oxide) solutions},
  year         = {1980},
  number       = {8},
  pages        = {1559--1571},
  volume       = {25},
  abstract     = {The aqueous solution properties of alkylene oxide polymers and copolymers are related to their interaction with water. In an attempt to better understand this behavior, differential scanning calorimetry has been employed to measure phase changes and water binding in solutions of polyethylene glycol (PEG), polypropylene glycol (PPG), and a 50/50 random copolymer of ethylene oxide and propylene oxide. PEG (Mn = 3510) forms a crystalline eutectic with water at 0.48 weight fraction of polymer. The liquidus curve for water can be fit accurately using the Flory–Huggins expression for solute activity with an interaction parameter of 0.05. PPG and the random copolymer do not crystallize and thus do not form a crystalline eutectic. Based on decreases in the heat of fusion of free water with added polymer, PEG binds more water than the copolymer which binds more water than PPG. The estimated hydration numbers per polymer segment are 1.5 for PPG, 2.3 for the copolymer, and 2.7 for PEG.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {https://doi.org/10.1002/app.1980.070250805},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/app.1980.070250805},
  file         = {:Hager1980 - Investigation of Phase Behavior and Water Binding in Poly(alkylene Oxide) Solutions.pdf:PDF},
  keywords     = {hydration water, PEG, PPG, flory-huggins, hydration number, copolymer, DSC},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/app.1980.070250805},
}

@InProceedings{Aoki2018,
  author       = {Aoki, Katsuyoshi and Hata, Ryusuke and Kaneyasu, Junya F. and Schwaab, Gerhard and Shiraki, Kentaro and Hattori, Toshiaki},
  booktitle    = {2018 43rd International Conference on Infrared, Millimeter, and Terahertz Waves (IRMMW-THz)},
  title        = {Hydration of Aqueous Polymers Investigated by Terahertz Spectroscopy and Principal Component Analysis},
  year         = {2018},
  pages        = {1--2},
  abstract     = {Hydration in aqueous solutions of poly(ethyleneglycol) (PEG) and poly(propylene glycol) (PPG) was studied using terahertz spectroscopy and principal component analysis (PCA). An addition of a methyl group to a PEG repeat unit increases the number of hydration water per repeat unit. With the result of PCA, the fast relaxation process of hydration water is discussed, and the dielectric loss spectra of PEG and PPG hydration water were estimated.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {10.1109/IRMMW-THz.2018.8510049},
  file         = {:Aoki2018 - Hydration of Aqueous Polymers Investigated by Terahertz Spectroscopy and Principal Component Analysis.pdf:PDF},
  keywords     = {hydration water, hydration shell, PEG, PPG, principal component analysis, PCA, hydration number, dielectrics, BDS},
}

@Article{Kripotou2019,
  author       = {Sotiria Kripotou and Konstantinos Zafeiris and Maria Culebras-Martı́nez and Gloria Gallego Ferrer and Apostolos Kyritsis},
  journal      = {The European Physical Journal E},
  title        = {Dynamics of hydration water in gelatin and hyaluronic acid hydrogels},
  year         = {2019},
  pages        = {109},
  volume       = {42},
  abstract     = {We employed broadband dielectric spectroscopy (BDS), for the investigation of the water dynamics in partially hydrated hyaluronic acid (HA), and gelatin (Gel), enzymatically crosslinked hydrogels, in the water fraction ranges 0.14 ≤ h w ≤ 0.75. Our results indicate that at low hydrations (h w ≤ 0.25), where the dielectric response of the hydrogels is identical during cooling and heating, water plasticizes strongly the polymeric matrix and is organized in clusters giving rise to ν-process, secondary water relaxation and to an additional slower relaxation process. This later process has been found to be related with the dc charge conductivity and can be described in terms of the conduction current relaxation mechanism. At slightly higher hydrations, however, always below the hydration level where ice is formed during cooling, we have recorded in HA hydrogel a strong water dielectric relaxation process, I LDAm , which has Arrhenius-like temperature dependence and large time scale resembling relaxation processes recorded in bulk low density amorphous solid water structures. This relaxation process shows a strong-to-fragile transition at −90 ◦ C and our data suggest that the VTF-like process recorded at T > −90 ◦ C is controlled by the same molecular process like long range charge transport. In addition, our data imply that the crossover temperature is related with the onset of structural rearrangements (increase in configurational entropy) of the macromolecules. In partially crystallized hydrogels (h ≥ 0.60) HA exhibits at low temperatures the ice dielectric process consistent with the bulk hexagonal ice, whereas Gel hydrogel exhibits as main low temperature process a slow relaxation process that refers to open tetrahedral structures of water similar to low density amorphous ice structures and to bulk cubic ice. Regarding the water secondary relaxation processes, we have shown that the ν-process and the I LDAm process are activated in water hydrogen bond networks with different structures.},
  creationdate = {2023-09-08T00:00:00},
  doi          = {https://doi.org/10.1140/epje/i2019-11871-2},
  file         = {:Kripotou2019 - Dynamics of Hydration Water in Gelatin and Hyaluronic Acid Hydrogels.pdf:PDF},
  keywords     = {supercooled water, hydration water, nu-process},
}

@Article{Biswas2020,
  author       = {Sohag Biswas and Bhabani S. Mallik},
  journal      = {Journal of Molecular Liquids},
  title        = {Aqueous hydroxyl group as the vibrational probe to access the hydrophobicity of amide derivatives},
  year         = {2020},
  issn         = {0167-7322},
  pages        = {112395},
  volume       = {301},
  abstract     = {First principles molecular dynamics (FPMD) simulations of relatively dilute aqueous solutions of N-methylformamide (NMF), N, N-dimethylacetamide (DMA), N-methylacetamide (NMA) were carried out to elucidate the effects of variation of hydrophobicity of amide molecules on structure, dynamics and spectral properties of solvating water molecules. A quantitative analysis of dangling OH groups of water molecules, one of the consequences of hydrophobicity, around the amide molecules was performed to explore the structure of surrounding water molecules. We observe that DMA has the most hydrophobic character among the three amide molecules; the lifetime of dangling OH mode of water molecules and the number of such modes are found to be more inside the solvation shell of DMA as compared to NMA and NMF molecules. Overall this lifetime is more inside the solvation shell of amides compared to the bulk water molecules for all aqueous solutions of amides. Rotational dynamics calculation suggests significant retardation of OH bonds of water near the amide oxygen atom (O) due to the OwHw⋯O strong hydrogen bonds. A moderate slowdown of reorientational dynamics is also observed for OH modes that are close to the hydrophobic surface of DMA in its aqueous solution. Vibrational density of states (VDOS) and frequency distribution calculations point out the higher average stretching frequency (~3600–3850 cm−1) of free OH groups. Hydrogen bond lifetime calculations conceive that DMA, having three methyl groups, makes stronger hydrogen bonds through the CO moiety. Vibrational spectral diffusion of bulk water and solvation shell water molecules were also calculated in combination with wavelet transform and frequency-frequency autocorrelation functions. The CO group affected OH stretching frequency bands for aqueous solutions of NMF and NMA molecules are more pronounced than that of DMA. However, NH affected OH frequency bands are less pronounced for NMA and DMA due to the presence of more number of hydrophobic methyl groups. Going from NMF to DMA, the OH frequency bands inside the amide solvation shells shift towards the higher value due to the enhancement of hydrophobicity. The vibrational spectral diffusion of OH modes around CO and NH (N for DMA) groups, as well as for bulk water molecules, is also investigated. Three time scales were found for these calculations for all the cases. The fast time scales in the range ~50–100 fs are due to the amide-water intact hydrogen bonding, and two slower time scales in the range ~0.6–3.90 ps and ~10–20 ps were found. The time scales in the range of ~0.6 to 3.90 ps can be attributed to carbonyl-water and N-H-water hydrogen bonding, and the very long time scales are due to the escape dynamics water molecules from the solvation shell of CO and NH (N for DMA) groups.},
  comment      = {Elsevier Paper},
  creationdate = {2023-09-11T00:00:00},
  doi          = {https://doi.org/10.1016/j.molliq.2019.112395},
  keywords     = {methylformamide, dimethylacetamide, methylacetamide, First principles molecular dynamics, Hydrophobicity, Ultrafast spectroscopy, hydration water, hydration shell, hydrophobic hydration, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://www.sciencedirect.com/science/article/pii/S0167732219346501},
}

@Article{NusratMafy2016,
  author       = {Nusrat Mafy, Noushaba and Muhibur Rahman, M. and Mollah, M. Yousuf A. and Susan, Md. Abu Bin Hasan},
  journal      = {ChemistrySelect},
  title        = {Temperature Perturbation on Hydrogen Bonding in Aqueous Solutions at Different Amide Concentrations},
  year         = {2016},
  number       = {18},
  pages        = {5789--5800},
  volume       = {1},
  abstract     = {A series of amides with variation in the number of methyl and amine groups were used as additives of water. Perturbations of water structure by variation of temperature and concentration of urea, formamide, N-methylformamide, and N,N-dimethylformamide was systematically analyzed by vibrational spectroscopy. The water absorption band was critically analyzed by 2D-correlation spectroscopy, its deconvolution and derivative spectra. Degree of perturbation of the water structure was evaluated to provide strong evidence on molecular level interactions, self-aggregation, and modification of the network of water structure. Clusters of water-amides were energetically optimized and consequent theoretical vibrational frequencies of C−N and C=O groups of amide were found to be consistent with experimental frequencies. The water structure underwent disruption through formation of hydrogen bond with amide; while self-aggregated amide and hydrophobic alkyl group assisted formation of ice-like network around them.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {https://doi.org/10.1002/slct.201601136},
  eprint       = {https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/slct.201601136},
  file         = {:NusratMafy2016 - Temperature Perturbation on Hydrogen Bonding in Aqueous Solutions at Different Amide Concentrations.pdf:PDF},
  keywords     = {density functional calculations, hydrogen bond, ice-like water, self-aggregation, 2D correlation spectroscopy, ATR-FTIR, FT-NIR},
  url          = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/slct.201601136},
}

@Article{Kim2015,
  author       = {Kim, Jehoon and Tian, Yun and Wu, Jianzhong},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Thermodynamic and Structural Evidence for Reduced Hydrogen Bonding among Water Molecules near Small Hydrophobic Solutes},
  year         = {2015},
  note         = {PMID: 26264740},
  number       = {36},
  pages        = {12108--12116},
  volume       = {119},
  abstract     = {The structure of water molecules near a hydrophobic solute remains elusive despite a long history of scrutiny. Here, we re-examine the subtle issue by a combination of thermodynamic analysis for Henry’s constants of several nonpolar gases over a broad range of temperatures and molecular dynamic simulations for the water structure in the hydration shell using several popular semiempirical models of liquid water. Both the structural and thermodynamic data indicate that hydrophobic hydration reduces the degree of the hydrogen bonding among water molecules, and the effect becomes more prominent at high temperatures. Hydrogen-bond formation is slightly hindered near a hydrophobic solute due to the restriction of the degree of freedom for water molecules in the solvation shell, and the confinement effect becomes more significant as temperature increases. Reduction in the extent of hydrogen bonding is fully consistent with a positive contribution of a small hydrophobic solute to the solution heat capacity. As predicted by the scaled-particle theory, both Henry’s constants and simulation results suggest that the hydration entropy is determined primarily by cavity formation in liquid water, with its magnitude rising with the solute size but declining with temperature.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/acs.jpcb.5b05281},
  eprint       = {https://doi.org/10.1021/acs.jpcb.5b05281},
  file         = {:Kim2015 - Thermodynamic and Structural Evidence for Reduced Hydrogen Bonding among Water Molecules near Small Hydrophobic Solutes.pdf:PDF;:ThermodynamicAndStructuralEvidenceForReducedHydrogenBondingAmongwaterMoleculesNearSmallHydrophobicSolutes_KimEtAl_JPC2015_SI.pdf:PDF},
  keywords     = {hydration shell, hydration water, hydrophobic hydration, molecular dynamics simulation, theory, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://doi.org/10.1021/acs.jpcb.5b05281},
}

@Article{Galamba2014,
  author       = {Galamba, N.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Water Tetrahedrons, Hydrogen-Bond Dynamics, and the Orientational Mobility of Water around Hydrophobic Solutes},
  year         = {2014},
  note         = {PMID: 24660958},
  number       = {15},
  pages        = {4169--4176},
  volume       = {118},
  abstract     = {Despite being intensively studied, the magnitude of specific structural and dynamic perturbations of water next to hydrophobic surfaces remains a matter of debate. Here we show, from molecular dynamics, that the structure of a subset of water molecules in the first hydration layer, those preserving four nearest water neighbors, resembles that of water at ∼10 °C, and that the origin of the orientational slowdown is mainly a decrease of the hydrogen-bond (HB) acceptor switch frequency, while water structuring plays a minor role, slightly accelerating HB acceptor switches. By portraying the mean HB dynamics of water as a doubly periodic event, we demonstrate that the orientational retardation factor is effectively defined by the ratio of the HB acceptor switch period in the hydration layer and bulk. Excluded volume delays HB acceptor switches, accelerating the orientational relaxation of ∼1/3 of the water molecules on the hydration layer in this time scale, but this is largely exceeded by the decrease of the HB switch frequency, consistent with 2D IR spectroscopy experiments, and at the origin of longer HB lifetimes. The orientational mobility of water populations with long HB lifetimes is also probed, and although a relaxation plateau is observed at ∼10 ps consistent with fs IR spectroscopy experiments, no water molecule is rotationally frozen at any time scale. The proposed molecular picture is consistent with fs IR, 2D IR, and NMR experimental results on the orientational retardation of water and reveals the magnitude of “hidden” enhanced ordered water pentamers formed near hydrophobic solutes.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/jp500067a},
  eprint       = {https://doi.org/10.1021/jp500067a},
  file         = {:Galamba2014 - Water Tetrahedrons, Hydrogen Bond Dynamics, and the Orientational Mobility of Water around Hydrophobic Solutes.pdf:PDF;:WaterTetrahedronsHydrogenBondDynamicAndTheOrientationalMobilityOfWaterAroundHydrophobicSolutes_JPC2014_SI.pdf:PDF},
  keywords     = {hydrogen bond dynamics, hydrophobic hydration, hydration shell, molecular dynamics simulation, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://doi.org/10.1021/jp500067a},
}

@Article{DuboueDijon2014,
  author       = {Duboué-Dijon, Elise and Fogarty, Aoife C. and Laage, Damien},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Temperature Dependence of Hydrophobic Hydration Dynamics: From Retardation to Acceleration},
  year         = {2014},
  note         = {PMID: 24460522},
  number       = {6},
  pages        = {1574--1583},
  volume       = {118},
  abstract     = {The perturbation induced by a hydrophobic solute on water dynamics is essential in many biochemical processes, but its mechanism and magnitude are still debated. A stringent test of the different proposed pictures is provided by recent NMR measurements by Qvist and Halle (J. Am. Chem. Soc. 2008, 130, 10345–10353) which showed that, unexpectedly, the perturbation changes in a non-monotonic fashion when the solution is cooled below room temperature. Here we perform and analyze molecular dynamics simulations of a small paradigm amphiphilic solute, trimethylamine N-oxide (TMAO), in dilute aqueous solutions over the 218–350 K temperature range. We first show that our simulations properly reproduce the non-monotonic temperature dependence. We then develop a model which combines our previously suggested entropic excluded-volume effect with a perturbation factor arising from the difference between local structural fluctuations in the shell and the bulk. Our model provides a detailed molecular understanding of the hydrophobic perturbation over the full temperature range investigated. It shows that the excluded-volume factor brings a dominant temperature-independent contribution to the perturbation at all temperatures, and provides a very good approximation at room temperature. The non-monotonic temperature dependence of the perturbation is shown to arise from the structural factor and mostly from relative shifts between the shell and bulk distributions of local structures, whose amplitude remains very small compared to the widths of those distributions.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/jp408603n},
  eprint       = {https://doi.org/10.1021/jp408603n},
  file         = {:DuboueDijon2014 - Temperature Dependence of Hydrophobic Hydration Dynamics_ from Retardation to Acceleration.pdf:PDF},
  keywords     = {hydration shell, hydrophobic hydration, molecular dynamics simulation, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://doi.org/10.1021/jp408603n},
}

@Article{Galamba2013,
  author       = {Galamba, N.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Water’s Structure around Hydrophobic Solutes and the Iceberg Model},
  year         = {2013},
  note         = {PMID: 23360515},
  number       = {7},
  pages        = {2153--2159},
  volume       = {117},
  abstract     = {The structure of water in the hydration shells of small hydrophobic solutes was investigated through molecular dynamics. The results show that a subset of water molecules in the first hydration shell of a nonpolar solute have a significantly enhanced tetrahedrality and a slightly larger number of hydrogen bonds, relative to the molecules in water at room temperature, consistent with the experimentally observed negative excess entropy and increased heat capacity of hydrophobic solutions at room temperature. This ordering results from the rearrangement of a small number of water molecules near the nonpolar solutes that occupy one to two vertices of the enhanced water tetrahedra. Although this structuring is not nearly like that often associated with a literal interpretation of the term “iceberg” in the Frank and Evans iceberg model, it does support a moderate interpretation of this model. Thus, the tetrahedral orientational order of this ensemble of water molecules is comparable to that of liquid water at ∼10 °C, although not accompanied by the small contraction of the O–O distance observed in cold water. Further, we show that the structural changes of water in the vicinity of small nonpolar solutes cannot be inferred from the water radial distribution functions, explaining why this increased ordering is not observed through neutron diffraction experiments. The present results restore a molecular view where the slower translational and reorientational dynamics of water near hydrophobic groups has a structural equivalent resembling water at low temperatures.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/jp310649n},
  eprint       = {https://doi.org/10.1021/jp310649n},
  file         = {:Galamba2013 - Water’s Structure around Hydrophobic Solutes and the Iceberg Model.pdf:PDF},
  keywords     = {molecular dynamics simulation, hydrophobic hydration, hydration shell, iceberg model, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://doi.org/10.1021/jp310649n},
}

@Article{Grabowska2021,
  author       = {Grabowska, Joanna and Kuffel, Anna and Zielkiewicz, Jan},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Revealing the Frank–Evans “Iceberg” Structures within the Solvation Layer around Hydrophobic Solutes},
  year         = {2021},
  note         = {PMID: 33539702},
  number       = {6},
  pages        = {1611--1617},
  volume       = {125},
  abstract     = {Using computer simulations, the structural properties of solvation water of three model hydrophobic molecules, methane and two fullerenes (C60 and C80), were studied. Systems were simulated at temperatures in the range of 250–298 K. By analyzing both the local ordering of the molecules of water in the solvation layers and the structure of hydrogen bond network, it is shown that in the solvation layer of hydrophobic molecules, ordered aggregates consisting of water molecules are formed. Even though it is difficult to define the exact structure of these aggregates, their existence alone is clearly noticeable. Moreover, these aggregates become more pronounced with the decrease of temperature. The existence of the ordered aggregates around the hydrophobic solutes complies with the concept of “icebergs” proposed by Frank and Evans.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/acs.jpcb.0c09489},
  eprint       = {https://doi.org/10.1021/acs.jpcb.0c09489},
  file         = {:Grabowska2021 - Revealing the Frank–Evans “Iceberg” Structures within the Solvation Layer around Hydrophobic Solutes.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/HydrationShells/RevealingTheFrankEvansIcebergStructuresWithinTheSolvationLayerAroundHydrophobicSolutes_JPC2021_SI.pdf:PDF},
  keywords     = {iceberg, molecular dynamics simulation, hydration shell, hydrophobic hydration, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://doi.org/10.1021/acs.jpcb.0c09489},
}

@Article{Titantah2012,
  author       = {Titantah, John Tatini and Karttunen, Mikko},
  journal      = {Journal of the American Chemical Society},
  title        = {Long-Time Correlations and Hydrophobe-Modified Hydrogen-Bonding Dynamics in Hydrophobic Hydration},
  year         = {2012},
  note         = {PMID: 22582830},
  number       = {22},
  pages        = {9362--9368},
  volume       = {134},
  abstract     = {The physical mechanisms behind hydrophobic hydration have been debated for over 65 years. Spectroscopic techniques have the ability to probe the dynamics of water in increasing detail, but many fundamental issues remain controversial. We have performed systematic first-principles ab initio Car–Parrinello molecular dynamics simulations over a broad temperature range and provide a detailed microscopic view on the dynamics of hydration water around a hydrophobic molecule, tetramethylurea. Our simulations provide a unifying view and resolve some of the controversies concerning femtosecond-infrared, THz–GHz dielectric relaxation, and nuclear magnetic resonance experiments and classical molecular dynamics simulations. Our computational results are in good quantitative agreement with experiments, and we provide a physical picture of the long-debated “iceberg” model; we show that the slow, long-time component is present within the hydration shell and that molecular jumps and over-coordination play important roles. We show that the structure and dynamics of hydration water around an organic molecule are non-uniform.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/ja301908a},
  eprint       = {https://doi.org/10.1021/ja301908a},
  file         = {:Titantah2012 - Long Time Correlations and Hydrophobe Modified Hydrogen Bonding Dynamics in Hydrophobic Hydration.pdf:PDF;:LongTimeCorrelationsAndHydrophobeModifiedHydrogenBondingDynamicsInHydrophobicHydration_TitantahEtAl_ACS2012_SI.pdf:PDF},
  keywords     = {hydrophobic hydration, molecular dynamics simulation, ab initio, dielectric relaxation, nmr, iceberg, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://doi.org/10.1021/ja301908a},
}

@Article{Pham2011,
  author       = {Pham, Van-Thai and Penfold, Thomas J. and van der Veen, Renske M. and Lima, Frederico and El Nahhas, Amal and Johnson, Steve L. and Beaud, Paul and Abela, Rafael and Bressler, Christian and Tavernelli, Ivano and Milne, Christopher J. and Chergui, Majed},
  journal      = {Journal of the American Chemical Society},
  title        = {Probing the Transition from Hydrophilic to Hydrophobic Solvation with Atomic Scale Resolution},
  year         = {2011},
  note         = {PMID: 21740023},
  number       = {32},
  pages        = {12740--12748},
  volume       = {133},
  abstract     = {Picosecond and femtosecond X-ray absorption spectroscopy is used to probe the changes of the solvent shell structure upon electron abstraction of aqueous iodide using an ultrashort laser pulse. The transient L1,3 edge EXAFS at 50 ps time delay points to the formation of an expanded water cavity around the iodine atom, in good agreement with classical and quantum mechanical/molecular mechanics (QM/MM) molecular dynamics (MD) simulations. These also show that while the hydrogen atoms pointed toward iodide, they predominantly point toward the bulk solvent in the case of iodine, suggesting a hydrophobic behavior. This is further confirmed by quantum chemical (QC) calculations of I–/I0(H2O)n=1–4 clusters. The L1 edge sub-picosecond spectra point to the existence of a transient species that is not present at 50 ps. The QC calculations and the QM/MM MD simulations identify this transient species as an I0(OH2) complex inside the cavity. The simulations show that upon electron abstraction most of the water molecules move away from iodine, while one comes closer to form the complex that lives for 3–4 ps. This time is governed by the reorganization of the main solvation shell, basically the time it takes for the water molecules to reform an H-bond network. Only then is the interaction with the solvation shell strong enough to pull the water molecule of the complex toward the bulk solvent. Overall, much of the behavior at early times is determined by the reorientational dynamics of water molecules and the formation of a complete network of hydrogen bonded molecules in the first solvation shell.},
  comment      = {Video Available},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/ja203882y},
  eprint       = {https://doi.org/10.1021/ja203882y},
  file         = {:Pham2011 - Probing the Transition from Hydrophilic to Hydrophobic Solvation with Atomic Scale Resolution.pdf:PDF;:ProbingTheTransitionFromHydrophilicToHydrophobicSolvationWithAtomicScaleResolution_PhamEtAl_ACS2011_SI1.pdf:PDF;:ProbingTheTransitionFromHydrophilicToHydrophobicSolvationWithAtomicScaleResolution_PhamEtAl_ACS2011_SI2.mpg:mpg},
  keywords     = {hydration shell, hydophobic hydration, x-ray absorption spectroscopy, molecular dynamics simulation, hydrogen bond},
  url          = {https://doi.org/10.1021/ja203882y},
}

@Article{Laage2009,
  author       = {Laage, Damien and Stirnemann, Guillaume and Hynes, James T.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Why Water Reorientation Slows without Iceberg Formation around Hydrophobic Solutes},
  year         = {2009},
  note         = {PMID: 19193030},
  number       = {8},
  pages        = {2428--2435},
  volume       = {113},
  abstract     = {The dynamics of water molecules next to hydrophobic solutes is investigated, specifically addressing the recent controversy raised by the first time-resolved observations, which concluded that some water molecules are immobilized by hydrophobic groups, in strong contrast to previous NMR conclusions. Through molecular dynamics simulations and an analytic jump reorientation model, we identify the water reorientation mechanism next to a hydrophobic solute and provide evidence that no water molecules are immobilized by hydrophobic solutes. Their moderate rotational slowdown compared to bulk water (e.g., by a factor of less than 2 at low solute concentration) is mainly due to slower hydrogen-bond exchange. The slowdown is quantitatively described by a solute excluded volume effect at the transition state for the key hydrogen-bond exchange in the reorientation mechanism. We show that this picture is consistent with both ultrafast anisotropy and NMR experimental results and that the transition state excluded volume theory yields quantitative predictions of the rotational slowdown for diverse hydrophobic solutes of varying size over a wide concentration range. We also explain why hydrophobic groups slow water reorientation less than do some hydrophilic groups.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/jp809521t},
  eprint       = {https://doi.org/10.1021/jp809521t},
  file         = {:Laage2009 - Why Water Reorientation Slows without Iceberg Formation around Hydrophobic Solutes.pdf:PDF},
  keywords     = {iceberg, molecular dynamics simulation, nmr, hydration shell, hydrophobic hydration, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://doi.org/10.1021/jp809521t},
}

@Article{Qvist2008,
  author       = {Qvist, Johan and Halle, Bertil},
  journal      = {Journal of the American Chemical Society},
  title        = {Thermal Signature of Hydrophobic Hydration Dynamics},
  year         = {2008},
  note         = {PMID: 18624406},
  number       = {31},
  pages        = {10345--10353},
  volume       = {130},
  abstract     = {Hydrophobic hydration, the perturbation of the aqueous solvent near an apolar solute or interface, is a fundamental ingredient in many chemical and biological processes. Both bulk water and aqueous solutions of apolar solutes behave anomalously at low temperatures for reasons that are not fully understood. Here, we use 2H NMR relaxation to characterize the rotational dynamics in hydrophobic hydration shells over a wide temperature range, extending down to 243 K. We examine four partly hydrophobic solutes: the peptides N-acetyl-glycine-N′-methylamide and N-acetyl-leucine-N′-methylamide, and the osmolytes trimethylamine N-oxide and tetramethylurea. For all four solutes, we find that water rotates with lower activation energy in the hydration shell than in bulk water below 255 ± 2 K. At still lower temperatures, water rotation is predicted to be faster in the shell than in bulk. We rationalize this behavior in terms of the geometric constraints imposed by the solute. These findings reverse the classical “iceberg” view of hydrophobic hydration by indicating that hydrophobic hydration water is less ice-like than bulk water. Our results also challenge the “structural temperature” concept. The two investigated osmolytes have opposite effects on protein stability but have virtually the same effect on water dynamics, suggesting that they do not act indirectly via solvent perturbations. The NMR-derived picture of hydrophobic hydration dynamics differs substantially from views emerging from recent quasielastic neutron scattering and pump−probe infrared spectroscopy studies of the same solutes. We discuss the possible reasons for these discrepancies.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/ja802668w},
  eprint       = {https://doi.org/10.1021/ja802668w},
  file         = {:Qvist2008 - Thermal Signature of Hydrophobic Hydration Dynamics.pdf:PDF},
  keywords     = {hydration shell, hydrophobic hydration, 2h-nmr, iceberg, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  priority     = {prio1},
  url          = {https://doi.org/10.1021/ja802668w},
}

@Article{Rezus2007,
  author       = {Rezus, Y. L. A. and Bakker, H. J.},
  journal      = {Phys. Rev. Lett.},
  title        = {Observation of Immobilized Water Molecules around Hydrophobic Groups},
  year         = {2007},
  month        = oct,
  pages        = {148301},
  volume       = {99},
  abstract     = {We have used femtosecond midinfrared spectroscopy to study the orientational mobility of water molecules in the hydration shells of hydrophobic groups. Our results show that hydrophobic groups are surrounded by a number of water molecules that display much slower orientational dynamics than the bulk liquid and that are therefore effectively immobilized. It turns out that each methyl group is surrounded by four immobilized water OH groups.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1103/PhysRevLett.99.148301},
  file         = {:Rezus2007 - Observation of Immobilized Water Molecules around Hydrophobic Groups.pdf:PDF},
  issue        = {14},
  keywords     = {hydrophobic hydration, hydration shell, mid infrared, clathrate},
  numpages     = {4},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.99.148301},
}

@Article{Chanda2006,
  author       = {Chanda, Jnanojjal and Chakraborty, Sudip and Bandyopadhyay, Sanjoy},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Sensitivity of Hydrogen Bond Lifetime Dynamics to the Presence of Ethanol at the Interface of a Phospholipid Bilayer},
  year         = {2006},
  note         = {PMID: 16494438},
  number       = {8},
  pages        = {3791--3797},
  volume       = {110},
  abstract     = {Atomistic molecular dynamics simulations of a fully hydrated liquid crystalline lamellar phase of a dimyrystoylphosphatidylcholine lipid bilayer containing ethanol at 1:1 composition as well as of the pure lamellar phase of the bilayer have been performed. Detailed analyses have been carried out to investigate the effects of ethanol, if any, on the lifetime dynamics of lipid−water and water−water hydrogen bonds in the hydration layer of the lipid headgroups. The nonexponential hydrogen bond lifetime correlation functions have been analyzed by using the formalism of Luzar and Chandler, which allowed the identification of the bound states at the bilayer interface and the quantification of the dynamic equilibrium between the bound and the free water molecules, in terms of time-dependent relaxation rates. The calculations show that the overall relaxation of phosphate−water hydrogen bonds is faster in the presence of ethanol. Studies of the residence time and the number fluctuation of the hydration layer water molecules reveal that the presence of ethanol molecules decreases the rigidity of the lipid hydration layer.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/jp054275i},
  eprint       = {https://doi.org/10.1021/jp054275i},
  file         = {:Chanda2006 - Sensitivity of Hydrogen Bond Lifetime Dynamics to the Presence of Ethanol at the Interface of a Phospholipid Bilayer.pdf:PDF},
  keywords     = {aqueous alcohol, molecular dynamics simulation, hydration shell, dangling bond},
  url          = {https://doi.org/10.1021/jp054275i},
}

@Article{Choudhury2005,
  author       = {Choudhury, Niharendu and Pettitt, B. Montgomery},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Dynamics of Water Trapped between Hydrophobic Solutes},
  year         = {2005},
  note         = {PMID: 16851715},
  number       = {13},
  pages        = {6422--6429},
  volume       = {109},
  abstract     = {We describe the model dynamical behavior of the solvent between two nanoscopic hydrophobic solutes. The dynamics of the vicinal water in various sized traps is found to be significantly different from bulk behavior. We consider the dynamics at normal temperature and pressure at three intersolute distances corresponding to the three solvent separated minima in the free energy profile between the solutes with attractions. These three states correspond to one, two, and three intervening layers of water molecules. Results are obtained from a molecular dynamics simulation at constant temperature and pressure (NPT) ensemble. Translational diffusion of water molecules trapped between the two solutes has been analyzed from the velocity correlation function as well as from the mean square displacement of the water molecules. The rotational behavior has been analyzed through the reorientational dynamics of the dipole moment vector of the water molecule by calculating both first and second rank dipole−dipole correlation functions. Both the translational and reorientational mobilities of water are found to be much slower at the smaller separation and increases as the separation between solutes becomes larger. The occupation time distribution functions calculated from the trajectories also show that the relaxation is much slower for the smallest intersolute separation as compared to other wider separations. The sublinear trend in mean square displacement and the stretched exponential decay of the relaxation of dipolar correlation and occupation distribution function indicate that the dynamical behavior of water in the confined region between two large hydrophobic solutes departs from usual Brownian behavior. This behavior is reminiscent of the behavior of water in the vicinity of protein surface clefts or trapped between two domains of a protein.},
  comment      = {very thin layers -> diff coeff well-defined?},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/jp045439i},
  eprint       = {https://doi.org/10.1021/jp045439i},
  file         = {:Choudhury2005 - Dynamics of Water Trapped between Hydrophobic Solutes.pdf:PDF},
  keywords     = {hydrophobic hydration, hydration shell, molecular dynamics simulation, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://doi.org/10.1021/jp045439i},
}

@Article{Yamaguchi2004,
  author       = {Yamaguchi, T. and Matsuoka, T. and Koda, S.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Mode-coupling study on the dynamics of hydrophobic hydration}},
  year         = {2004},
  issn         = {0021-9606},
  month        = apr,
  number       = {16},
  pages        = {7590--7601},
  volume       = {120},
  abstract     = {{The molecular motion of water in water–hydrophobic solute mixtures was investigated by the mode-coupling theory for molecular liquids based on the interaction-site description. When the model Lennard-Jones solute was mixed with water, both the translational and reorientational motions of solvent water become slower, in harmony with various experiments and molecular dynamics simulations. We compared the mechanism of the slowing down with that of the pressure dependence of the molecular motion of neat water [T. Yamaguchi, S.-H. Chong, and F. Hirata, J. Chem. Phys. 119, 1021 (2003)]. We found that the decrease in the solvent mobility caused by the solute can essentially be elucidated by the same mechanism: That is, the fluctuation of the number density of solvent due to the cavity formation by the solute strengthens the friction on the collective polarization through the dielectric friction mechanism: We also employed the solute molecule that is the same as solvent water except for the amount of partial charges, in order to alter the strength of the solute–solvent interaction continuously. The mobility of the solvent water was reduced both by the hydrophobic and strongly hydrophilic solutes, but it was enhanced in the intermediate case. Such a behavior was discussed in connection with the concept of positive and negative hydrations.}},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1063/1.1687319},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/120/16/7590/10855243/7590\_1\_online.pdf},
  file         = {:Yamaguchi2004 - Mode Coupling Study on the Dynamics of Hydrophobic Hydration.pdf:PDF},
  keywords     = {mode coupling theory, hydrophobic hydration, hydration shell, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://doi.org/10.1063/1.1687319},
}

@Article{Bizzarri2002,
  author       = {Bizzarri, Anna Rita and Cannistraro, Salvatore},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Molecular Dynamics of Water at the Protein−Solvent Interface},
  year         = {2002},
  number       = {26},
  pages        = {6617--6633},
  volume       = {106},
  abstract     = {The use of molecular dynamics simulation to investigate the properties of hydration water around proteins is outlined. A variety of structural and dynamical properties of the protein hydration water are reviewed and compared with those of bulk and with the corresponding experimental results. In particular, the accessibility to the protein medium, the hydrogen bond networking capability, the residence times, the diffusive mobility, the relaxation behavior, and the inelastic vibrational features of hydration water are analyzed in framework of the peculiar interactions of water at the protein surface. All these features, which can be traced back to the complexity of the overall protein−solvent energy landscape, are discussed in connection with the role played by hydration water in the biological functionality.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/jp020100m},
  eprint       = {https://doi.org/10.1021/jp020100m},
  file         = {:Bizzarri2002 - Molecular Dynamics of Water at the Protein−Solvent Interface.pdf:PDF},
  keywords     = {hydration shell, molecular dynamics simulation, review},
  priority     = {prio1},
  readstatus   = {skimmed},
  url          = {https://doi.org/10.1021/jp020100m},
}

@Article{Pratt2002,
  author       = {Pratt, Lawrence R.},
  journal      = {Annual Review of Physical Chemistry},
  title        = {MOLECULAR THEORY OF HYDROPHOBIC EFFECTS: “She is too mean to have her name repeated.”},
  year         = {2002},
  note         = {PMID: 11972014},
  number       = {1},
  pages        = {409--436},
  volume       = {53},
  abstract     = {This paper reviews the molecular theory of hydrophobic effects relevant to biomolecular structure and assembly in aqueous solution. Recent progress has resulted in simple, validated molecular statistical thermodynamic theories and clarification of confusing theories of decades ago. Current work is resolving effects of wider variations of thermodynamic state, e.g., pressure denaturation of soluble proteins, and more exotic questions such as effects of surface chemistry in treating stability of macromolecular structures in aqueous solution.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1146/annurev.physchem.53.090401.093500},
  eprint       = {https://doi.org/10.1146/annurev.physchem.53.090401.093500},
  file         = {:Pratt2002 - MOLECULAR THEORY oF HYDROPHOBIC EFFECTS_ “She Is Too Mean to Have Her Name Repeated.”.pdf:PDF},
  keywords     = {review, theory, hydrophobic hydration, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://doi.org/10.1146/annurev.physchem.53.090401.093500},
}

@Article{Astley1999,
  author       = {Astley, Tim and Birch, Gordon G. and Drew, Michael G. B. and Rodger, P. Mark},
  journal      = {The Journal of Physical Chemistry A},
  title        = {Lifetime of a Hydrogen Bond in Aqueous Solutions of Carbohydrates},
  year         = {1999},
  number       = {26},
  pages        = {5080--5090},
  volume       = {103},
  abstract     = {In this paper we present a novel method of calculating hydrogen bond lifetimes that circumvents many of the problems encountered with existing methods. The method is based on a three-level model in which the pair of molecules are hydrogen bonded, not hydrogen bonded, or in an intermediate state; hydrogen bonds are identified within the intermediate state according to how the dimer enters and leaves the intermediate state. An effective dimer interaction energy is used to define these three states. The hysteresis introduced by this definition makes it possible to distinguish between large-amplitude vibrations in the hydrogen-bonding coordinates and real bond-breaking events. The method is applied to a dilute aqueous glucose solution and shown to generate hydrogen bond lifetimes that are in accord with both chemical intuition and experiment.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/jp9900279},
  eprint       = {https://doi.org/10.1021/jp9900279},
  file         = {:Astley1999 - Lifetime of a Hydrogen Bond in Aqueous Solutions of Carbohydrates.pdf:PDF},
  keywords     = {hydration shell, hydrogen bond dynamics, H-bond lifetime, molecular dynamics simulation, dangling bond},
  url          = {https://doi.org/10.1021/jp9900279},
}

@Article{Luzar1996,
  author       = {Alenka Luzar and David Chandler},
  journal      = {Nature},
  title        = {Hydrogen-bond kinetics in liquid water},
  year         = {1996},
  pages        = {55--57},
  volume       = {379},
  abstract     = {HYDROGEN bonds play a crucial role in the behaviour of water [1-4] their spatial patterns and fluctuations characterize the structure and dynamics of the liquid [5-7] The processes of breaking and making hydrogen bonds in the condensed phase can be probed indirectly by a variety of experimental techniques\ and more quantitative information can be obtained from computer simulations[9]. In particular, simulations have revealed that on long timescales the relaxation behaviour of hydrogen bonds in liquid water exhibit non-exponential kinetics [7,10-13], suggesting that bond making and breaking are not simple processes characterized by well defined rate constants. Here we show that these kinetics can be understood in terms of an interplay between diffusion and hydrogen-bond dynamics. In our model, which can be extended to other hydrogen-bonded liquids, diffusion governs whether a specific pair of water molecules are near neighbours, and hydro- gen bonds between such pairs form and persist at random with average lifetimes determined by rate constants for bond making and breaking.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {https://doi.org/10.1038/379055a0},
  file         = {:Luzar1996 - Hydrogen Bond Kinetics in Liquid Water.pdf:PDF},
  keywords     = {hydrogen bond kinetics, molecular dynamics simulation},
  url          = {https://doi.org/10.1038/379055a0},
}

@Article{Benigno1996,
  author       = {Benigno, Andrea J. and Ahmed, Ednan and Berg, Mark},
  journal      = {The Journal of Chemical Physics},
  title        = {{The influence of solvent dynamics on the lifetime of solute–solvent hydrogen bonds}},
  year         = {1996},
  issn         = {0021-9606},
  month        = may,
  number       = {19},
  pages        = {7382--7394},
  volume       = {104},
  abstract     = {{The lifetimes of the hydrogen bonds formed between resorufin and the solvents ethanol, ethylene glycol, and 1,3‐butanediol are measured as a function of temperature. The results show that the hydrogen‐bond breaking reaction is strongly influenced by the dynamics of the solvent, in violation of traditional transition‐state theory. The relevant solvent dynamics are not well described by the viscosity of the solvent, but do correlate with the dielectric relaxation time. We propose a model in which the hydrogen bond initially breaks to form a poorly solvated, ‘‘dangling’’ hydrogen bond, which has a high probability of geminate recombination. The product is not stabilized until the solvent hydrogen‐bond structure can reorganize to incorporate the ‘‘dangling’’ bond. The same reorganization determines the dielectric relaxation time.}},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1063/1.471454},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/104/19/7382/10779300/7382\_1\_online.pdf},
  file         = {:Benigno1996 - The Influence of Solvent Dynamics on the Lifetime of Solute–solvent Hydrogen Bonds.pdf:PDF},
  keywords     = {hydrogen bond kinetics, ethanol, dielectric relaxation, dangling bond},
  url          = {https://doi.org/10.1063/1.471454},
}

@Article{Ludwig1995a,
  author       = {R. Ludwig},
  journal      = {Chemical Physics},
  title        = {NMR relaxation studies in water-alcohol mixtures: the water-rich region},
  year         = {1995},
  issn         = {0301-0104},
  number       = {1},
  pages        = {329--337},
  volume       = {195},
  abstract     = {NMR proton relaxation time measurements in water-alcohol mixtures have been performed for an alcohol mole fraction X ranging from 0 to 0.1. By varying the 17O-content in water, different contributions to the proton relaxation rate could be separated and from the 17OH dipolee interacton contribution the correlation time of the OH bond in the water molecule was determined. This reorientational correlation time of water increases by addition of alcohol molecules and depends linearly on the number of proton donors and acceptors. These results are compared to recent computer simulation and dielectric relaxation data. Additional oxygen-17 relaxation measurements on water yielded the quadrupole coupling constant, which shows a significant dependence on the alcohol concentration. The decreased mobility and the increased structural order of water in these mixtures can be related to the hydrophobic hydration.},
  comment      = {Ludwig},
  creationdate = {2023-09-11T00:00:00},
  doi          = {https://doi.org/10.1016/0301-0104(95)00050-X},
  file         = {:Ludwig1995a - NMR Relaxation Studies in Water Alcohol Mixtures_ the Water Rich Region.pdf:PDF},
  keywords     = {1h-nmr, aqueous alcohol, 17o-nmr, simulation, dielectric relaxation, quadupole coupling constant},
  url          = {https://www.sciencedirect.com/science/article/pii/030101049500050X},
}

@Article{Onori1996,
  author       = {G. Onori and A. Santucci},
  journal      = {Journal of Molecular Liquids},
  title        = {Dynamical and structural properties of water/alcohol mixtures},
  year         = {1996},
  issn         = {0167-7322},
  note         = {Relaxation Phenomena in Molecular Systems},
  pages        = {161--181},
  volume       = {69},
  abstract     = {Our recent studies related to the properties of alcohol/water mixtures, show the occurrence of some kind of molecular aggregation in the water rich region of composition beyond a threshold alcohol concentration x2∗. The observed behaviour suggests that for x2 < x2∗ the alcohol molecules are essentially dispersed and surrounded by “water cages” where the short range order and microdynamic of water molecules are changed with respect to those of pure water. Alcohol molecules are in mutual contact at higher concentration, only, when almost all water is involved in hydration shells of alcohol molecules. In addition, these studies show that the stabilisation of micellar structure and nucleic acids conformation in water/alcohol mixtures is closely linked to the properties and anomalous behaviour of the solvent systems. Accordingly, these results support the hypothesis that the dominant mechanism by which an alcohol affects these processes is through its effect on the structure of water. The main results of these investigations are reviewed and discussed in this paper.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {https://doi.org/10.1016/S0167-7322(96)90012-4},
  file         = {:Onori1996 - Dynamical and Structural Properties of Water_alcohol Mixtures.pdf:PDF},
  keywords     = {aqueous alcohol, cononsolvency, clathrate, monohydric alcohol, infrared, compressibility, hydration shell, review, self-association},
  priority     = {prio1},
  url          = {https://www.sciencedirect.com/science/article/pii/S0167732296900124},
}

@Article{Laaksonen1991,
  author       = {Aatto Laaksonen and Peter Stilbs},
  journal      = {Molecular Physics},
  title        = {Molecular dynamics and NMR study of methane-water systems},
  year         = {1991},
  number       = {4},
  pages        = {747--764},
  volume       = {74},
  abstract     = {Molecular dynamics of methane-water systems have been studied through computer simulations (MD), nuclear spin relaxation and self diffusion methods (NMR). MD simulation results give support to the concept of hydrophobic hydration by enhancing the water structure around the methane to create a clathrate. Spontaneous contacts between methanes is observed only at high densities, while so-called solvent-separated configurations are present in all simulations. The dynamics of the solvent water molecules is slowed down. In particular, the reorientational motion is sensitive to the presence of methane in solution. The simulated translational diffusion of methanes as solutes is also slowed down, but is higher than observed experimentally. The rotational motion of methanes is very sensitive to variation of the density while, the translational motion of methane is more constant and follows that of water. Methane acts nearly as a free rotor. The simulated reorientational correlation times for methane in water solution are in good agreement with experiment.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1080/00268979100102551},
  eprint       = {https://doi.org/10.1080/00268979100102551},
  file         = {:Laaksonen1991 - Molecular Dynamics and NMR Study of Methane Water Systems.pdf:PDF},
  keywords     = {molecular dynamics simulation, nmr, self-diffusion, hydrophobic hydration, clathrate, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/00268979100102551},
}

@Article{Bulone1989,
  author       = {Bulone, D. and Spinnato, C. and Madonia, F. and Palma, M. U.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Viscosity of aqueous solutions of monohydric alcohols in the normal and supercooled states}},
  year         = {1989},
  issn         = {0021-9606},
  month        = jul,
  number       = {1},
  pages        = {408--415},
  volume       = {91},
  abstract     = {{Viscosities of solutions of Met−, Et−, and n‐PropOH were measured by quasielastic light scattering of polystyrene lattice spheres of 800 Å diameter, in the low‐concentration, low‐temperature ranges where effects of alcohols on the structure and properties of liquid water are most pronounced. Raw data already indicate that alcohols promote the formation of clathrate‐like structures of H bonds which add to those occurring naturally in the pure solvent. Evaluation of the number of water molecules taking part in longer‐lived structures further indicates that this promotion is most effective in the infinite‐dilution limit. Available thermodynamic data agree with this evaluation. Mismatches among solute‐promoted clathrate‐like cages are evidenced. The known disruptive effects of alcohols on the anomalous properties of cold and supercooled water are thus understood in terms of limitations to the correlation length of density fluctuations, set by mismatches. A contribution of OH groups to cage promotion is also evidenced at least at low temperature. Constraints or hindrances to the motion of water molecules, irrespective of their nature, appear to be effective in favoring structures of stabler, longer‐lived H bonds, corresponding to water molecules of lower mobility. This offers a unified view of hydrophobic and hydrophilic interactions which agrees with earlier work and with more recent computer experiments. The possibility here evidenced for structures of H bonds promoted in solvent water of being conflictual or synergistic, adds to the microscopic understanding of solvent‐mediated interactions, e.g., of biosolutes.}},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1063/1.457662},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/91/1/408/15357648/408\_1\_online.pdf},
  file         = {:Bulone1989 - Viscosity of Aqueous Solutions of Monohydric Alcohols in the Normal and Supercooled States.pdf:PDF},
  keywords     = {aqueous alcohol, cononsolvency, light scattering, viscosity, methanol, ethanol, n-propanol, polystyrene, PS},
  url          = {https://doi.org/10.1063/1.457662},
}

@Article{Tarek2000,
  author       = {Mounir Tarek and Douglas J. Tobias},
  journal      = {Biophysical Journal},
  title        = {The Dynamics of Protein Hydration Water: A Quantitative Comparison of Molecular Dynamics Simulations and Neutron-scattering Experiments},
  year         = {2000},
  issn         = {0006-3495},
  number       = {6},
  pages        = {3244--3257},
  volume       = {79},
  abstract     = {We present results from an extensive molecular dynamics simulation study of water hydrating the protein Ribonuclease A, at a series of temperatures in cluster, crystal, and powder environments. The dynamics of protein hydration water appear to be very similar in crystal and powder environments at moderate to high hydration levels. Thus, we contend that experiments performed on powder samples are appropriate for discussing hydration water dynamics in native protein environments. Our analysis reveals that simulations performed on cluster models consisting of proteins surrounded by a finite water shell with free boundaries are not appropriate for the study of the solvent dynamics. Detailed comparison to available x-ray diffraction and inelastic neutron-scattering data shows that current generation force fields are capable of accurately reproducing the structural and dynamical observables. On the time scale of tens of picoseconds, at room temperature and high hydration, significant water translational diffusion and rotational motion occur. At low hydration, the water molecules are translationally confined but display appreciable rotational motion. Below the protein dynamical transition temperature, both translational and rotational motions of the water molecules are essentially arrested. Taken together, these results suggest that water translational motion is necessary for the structural relaxation that permits anharmonic and diffusive motions in proteins. Furthermore, it appears that the exchange of protein–water hydrogen bonds by water rotational/librational motion is not sufficient to permit protein structural relaxation. Rather, the complete exchange of protein-bound water molecules by translational displacement seems to be required.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {https://doi.org/10.1016/S0006-3495(00)76557-X},
  file         = {:Tarek2000 - The Dynamics of Protein Hydration Water_ a Quantitative Comparison of Molecular Dynamics Simulations and Neutron Scattering Experiments.pdf:PDF},
  keywords     = {hydration water, molecular dynamics simulation, neutron scattering, hydration shell, x-ray},
  url          = {https://www.sciencedirect.com/science/article/pii/S000634950076557X},
}

@Article{Blokzijl1993,
  author       = {Blokzijl, Wilfried and Engberts, Jan B. F. N.},
  journal      = {Angewandte Chemie},
  title        = {Hydrophobe Effekte – Ansichten und Tatsachen},
  year         = {1993},
  number       = {11},
  pages        = {1610--1648},
  volume       = {105},
  abstract     = {Das Bestreben relativ unpolarer Verbindungen, sich in wäßriger Lösung aneinander zu lagern, wird mit dem Begriff hydrophobe Wechselwirkungen beschrieben. Diese Wechselwirkungen sind in vielen Gebieten der Chemie, einschließlich der Chemie in vivo, von entscheidender Bedeutung. Enzym-Substrat-Wechselwirkungen, die Anordnung von Lipiden in biologischen Membranen, die Aggregation oberflächenaktiver Stoffe und kinetische Solvenseffekte in wasserreichen Lösungsmittelsystemen – sie alle werden in erster Linie durch hydrophobe Wechselwirkungen bestimmt. Trotz enormer Anstrengungen weiß man noch wenig über die Hydratation unpolarer Moleküle und über die nichtkovalenten Wechselwirkungen zwischen diesen Molekülen in Wasser. Wenn man sich nun die Frage stellt, was denn die treibende Kraft hinter hydrophoben Wechselwirkungen ist, so führt dies zu der Forderung, die herausragenden Eigenschaften flüssigen Wassers genau zu verstehen. Diese übersicht beschreibt einige neue Erkenntnisse auf diesem Gebiet aus den letzten zehn Jahren. Schwerpunkte sind sowohl die hydrophobe Hydratation als auch hydrophobe Wechselwirkungen, denn beide Phänomene hängen ganz eng zusammen. Es hat sich gezeigt, daß viele der bisherigen Sichtweisen zutiefst unbefriedigend sind, und man hat mutige Versuche unternommen, die treibende Kraft für hydrophobe Wechselwirkungen zwischen zwei oder vielen Molekülen zu verstehen. Hier wird eine zugegebenerweise persönliche Auswahl experimenteller und theoretischer Entwicklungen der letzten Zeit vorgestellt und, wenn nötig, durch Hinweise auf relevante frühere Studien ergänzt.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {https://doi.org/10.1002/ange.19931051103},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/ange.19931051103},
  file         = {:Blokzijl1993 - Hydrophobe Effekte – Ansichten Und Tatsachen.pdf:PDF},
  keywords     = {hydration shell, hydrophobic hydration, review, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/ange.19931051103},
}

@Article{Sanchez1991,
  author       = {Sanchez, Isaac C.},
  journal      = {Macromolecules},
  title        = {Volume fluctuation thermodynamics of polymer solutions},
  year         = {1991},
  number       = {4},
  pages        = {908--916},
  volume       = {24},
  abstract     = {The idea of “volume fluctuation thermodynamics” is formally developed to show in general terms how solution properties are affected by finite compressibility and by the mismatch in pure-component equation of state properties. For a binary solution, the intensive Gibbs free energy (g) is a function of its three canonical intensive variables: temperature(T), pressure(P), and composition (phi). However, an equivalent thermodynamic formulation is to treat g as a function of four independent variables (T, P, phi and v) subject to a minimization condition that determines the equilibrium intensive volume, v. Alternatively, the formalism can be developed as a Legendre transform, which transforms g into itself with v replaced by a field variable that at equilibrium equals zero. This artifice allows the easy separation of constant volume (incompressible) and volume fluctuation (compressible) contributions to solution thermodynamic properties. It also provides convenient recipes for the calculation of thermodynamic properties for any statistical mechanical model. It is shown that the pressure composition coefficient, (dP /dphi )T,v, plays an important role in solution thermodynamics and reflects to a large degree the mismatch in pure-component equation of state properties. Contrary to popular belief, the magnitude of volume changes on mixing has little to do with equation of state effects on other thermodynamic properties. It is suggested that P-V-T measurements on solutions can be very effective in testing compressible molecular models. Multicomponent systems are also treated. A somewhat counterintuitive conclusion is that sometimes the more degrees of freedom a system has, the more difficult it is to achieve phase stability.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/ma00004a016},
  eprint       = {https://doi.org/10.1021/ma00004a016},
  file         = {:Sanchez1991 - Volume Fluctuation Thermodynamics of Polymer Solutions.pdf:PDF},
  keywords     = {critical fluctuation, thermodynamics, gibbs free energy, theory, polymer solution},
  url          = {https://doi.org/10.1021/ma00004a016},
}

@Article{Tanaka2002,
  author       = {Tanaka, Hajime and Nakanishi, Yohei and Takubo, Naoko},
  journal      = {Phys. Rev. E},
  title        = {Nonuniversal nature of dynamic critical anomaly in polymer solutions},
  year         = {2002},
  month        = jan,
  pages        = {021802},
  volume       = {65},
  abstract     = {Critical anomaly of viscosity has been studied for ideal polymer solutions, focusing on its dependence on the molecular weight of polymer Mw. According to the conventional understanding that polymer solutions should belong to the same dynamic universal class as classical fluids, the critical exponent of viscosity yc should be a universal constant (~0.04). Contrary to this, we find that yc significantly decreases with increasing Mw. This unusual behavior can be explained by the dynamic coupling of critical concentration fluctuations with an additional slow viscoelastic mode intrinsic to polymer solutions. Our dynamic light scattering measurements support this picture.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1103/PhysRevE.65.021802},
  file         = {:Tanaka2002 - Nonuniversal Nature of Dynamic Critical Anomaly in Polymer Solutions.pdf:PDF},
  issue        = {2},
  keywords     = {critical fluctuations, polymer solution, molecular weight, dynamic light scattering},
  numpages     = {5},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevE.65.021802},
}

@Article{Anisimov2005,
  author       = {Anisimov, M. A. and Kostko, A. F. and Sengers, J. V. and Yudin, I. K.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Competition of mesoscales and crossover to theta-point tricriticality in near-critical polymer solutions}},
  year         = {2005},
  issn         = {0021-9606},
  month        = oct,
  number       = {16},
  pages        = {164901},
  volume       = {123},
  abstract     = {{The approach to asymptotic critical behavior in polymer solutions is governed by a competition between the correlation length of critical fluctuations diverging at the critical point of phase separation and an additional mesoscopic length scale, the radius of gyration. In this paper we present a theory for crossover between two universal regimes: a regime with Ising (fluctuation-induced) asymptotic critical behavior, where the correlation length prevails, and a mean-field tricritical regime with theta-point behavior controlled by the mesoscopic polymer chain. The theory yields a universal scaled description of existing experimental phase-equilibria data and is in excellent agreement with our light-scattering experiments on polystyrene solutions in cyclohexane with polymer molecular weights ranging from 2×10e5 up to 11.4×10e6. The experiments demonstrate unambiguously that crossover to theta-point tricriticality is controlled by a competition of the two mesoscales. The critical amplitudes deduced from our experiments depend on the polymer molecular weight as predicted by de Gennes [Phys. Lett. 26A, 313 (1968)]. Experimental evidence for the presence of logarithmic corrections to mean-field tricritical theta-point behavior in the molecular-weight dependence of the critical parameters is also presented.}},
  comment      = {See also: Anisimov et al., Phys Rev E, 2002 and Kostko et al., Phys Rev E 2007},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1063/1.2056543},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.2056543/15373976/164901\_1\_online.pdf},
  file         = {:Anisimov2005 - Competition of Mesoscales and Crossover to Theta Point Tricriticality in near Critical Polymer Solutions.pdf:PDF},
  keywords     = {critical fluctuation, polymer solution, tricritical, theta-point, crossover, ising-model, mean field, light scattering, polystyrene},
  url          = {https://doi.org/10.1063/1.2056543},
}

@Article{Anisimov2002,
  author       = {Anisimov, M. A. and Kostko, A. F. and Sengers, J. V.},
  journal      = {Phys. Rev. E},
  title        = {Competition of mesoscales and crossover to tricriticality in polymer solutions},
  year         = {2002},
  month        = may,
  pages        = {051805},
  volume       = {65},
  abstract     = {We show that the approach to asymptotic fluctuation-induced critical behavior in polymer solutions is governed by a competition between a correlation length diverging at the critical point and an additional mesoscopic length-scale, the radius of gyration. Accurate light scattering experiments on polystyrene solutions in cyclohexane with polymer molecular weights ranging from 200 000 up to 11.4x10e6 clearly demonstrate a crossover between two universal regimes: a regime with Ising asymptotic critical behavior, where the correlation length prevails, and a regime with tricritical U-point behavior determined by a mesoscopic polymerchain length.},
  comment      = {See also: Anisimov et al., JCP 2005 and Kostko et al., Phys Rev E 2007},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1103/PhysRevE.65.051805},
  file         = {:Anisimov2002 - Competition of Mesoscales and Crossover to Tricriticality in Polymer Solutions.pdf:PDF},
  issue        = {5},
  keywords     = {critical fluctuation, polymer solution, tricritical, theta-point, crossover, ising-model, mean field, light scattering, polystyrene},
  numpages     = {4},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevE.65.051805},
}

@Article{Kostko2007,
  author       = {Kostko, A. F. and Anisimov, M. A. and Sengers, J. V.},
  journal      = {Phys. Rev. E},
  title        = {Dynamics of critical fluctuations in polymer solutions},
  year         = {2007},
  month        = aug,
  pages        = {021804},
  volume       = {76},
  abstract     = {Using dynamic light scattering we have investigated the time dependence of fluctuations near the critical point of phase separation in solutions of polystyrene in cyclohexane with polymer molecular weights ranging from 196 000 to 11.4x10e6 g mol^{−1}. At the lowest polymer molecular weight the dynamic correlation function follows a single-exponential decay with a decay rate that can be represented by the mode-coupling theory of critical dynamics but with a mesoscopic viscosity that characterizes the hydrodynamic environment of the polymers in the solution. At all higher polymer molecular weights two distinct dynamic modes are observed, a slow and a fast mode, that originate from a coupling of the critical concentration fluctuations with viscoelastic relaxation of the polymer chain in solutions. This coupling causes an additional slowing down of the fluctuations on top of the well-known critical slowing down expected in the absence of a coupling between the two modes. From an analysis of the time dependence of the experimental dynamic correlation functions in terms of a theory of coupling of dynamic modes we are able to determine the viscoelastic properties of the polymers in the solution. These viscoelastic properties diverge in the theta-point limit of infinite polymer molecular weight.},
  comment      = {See also: Anisimov et al., Phys Rev E, 2002 and Anisimov et al., JCP 2005},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1103/PhysRevE.76.021804},
  file         = {:Kostko2007 - Dynamics of Critical Fluctuations in Polymer Solutions.pdf:PDF},
  issue        = {2},
  keywords     = {dynamic light scattering, critical fluctuation, polymer solution, polystyrene, molecular weight, theta-point},
  numpages     = {14},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevE.76.021804},
}

@Misc{anisimov2022,
  author        = {Mikhail A. Anisimov and Thomas J. Longo and Jan V. Sengers},
  title         = {Critical Fluctuations in Polymer Solutions: Crossover from Criticality to Tricriticality},
  year          = {2022},
  abstract      = {Critical fluctuations in fluids and fluid mixtures yield a nonanalytic asymptotic Ising-like critical thermodynamic behavior in terms of power laws with universal exponents. In polymer solutions, the amplitudes of these power laws depend on the degree of polymerization. Nonasymptotic behavior (upon the departure from the critical point) is particularly interesting in the case of polymer solutions, where it is governed by a competition between the correlation length of the critical fluctuations and the radius of gyration of the polymer molecules. If the correlation length is the dominant length scale, Ising-like critical behavior is observed. If, however, the radius of gyration exceeds the correlation length, tricritical behavior with mean-field critical exponents is observed. The Ising-like critical region shrinks with the increase of the polymer molecular weight. In the limit of an infinite degree of polymerization, the Ising-like critical region vanishes, yielding to theta-point tricriticality.},
  archiveprefix = {arXiv},
  comment       = {Chapter intended for "50 years of the renormalization group/Dedicated to the memory of Michael E. Fisher", edited by A. Aharony, O. Entin-Wohlman, D. Huse, and L. Radzihovsky},
  creationdate  = {2023-09-11T00:00:00},
  eprint        = {2209.12965},
  file          = {:anisimov2022 - Critical Fluctuations in Polymer Solutions_ Crossover from Criticality to Tricriticality.pdf:PDF},
  keywords      = {polymer solutions, critical fluctuations, tricriticality, crossover, ising-model, mean-field},
  primaryclass  = {cond-mat.soft},
}

@Article{Benmouna1993,
  author       = {Benmouna, M. and Seils, J. and Meier, G. and Patkowski, A. and Fischer, E. W.},
  journal      = {Macromolecules},
  title        = {Critical fluctuations in ternary polymer solutions},
  year         = {1993},
  number       = {4},
  pages        = {668--678},
  volume       = {26},
  abstract     = {The dynamics of critical fluctuations and spinodal decomposition in trnary mixtures of two polymers and a solvent are studied. The special case of a symmetrical mixture where concentration and composition fluctuations are decoupled is considered. The dynamical structure factor S_I(q,t) which is directly measurable in the zero-average contrast condition is examined in detail. Its decay rate Gamma_I is calculated in the presence of hydrocynamic interaction, and various scaling properties with the wavevector q are identified. These are found to be sensitive to the approximation made for the chain form factor P(q), and a particular scaling not found in polymer blends is obtained in the intermediate q-range. The hydrodynamic interactions identified iwht mode coupling effects in critical mixtures are also discussed in detial. The kinetics of spinodal decomposition in the early stages is examined only in the linear approximations.},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1021/ma00056a018},
  eprint       = {https://doi.org/10.1021/ma00056a018},
  file         = {:Benmouna1993 - Critical Fluctuations in Ternary Polymer Solutions.pdf:PDF},
  keywords     = {critical fluctuations, ternary polymer solutions, mode coupling theory, spinodal decomposition},
  url          = {https://doi.org/10.1021/ma00056a018},
}

@Article{Wheeler1993,
  author       = {Wheeler, John C. and Pfeuty, Pierre M.},
  journal      = {Phys. Rev. Lett.},
  title        = {Critical concentration fluctuations in polymerizing solutions},
  year         = {1993},
  month        = sep,
  pages        = {1653--1656},
  volume       = {71},
  abstract     = {Equilibrium polymerization in a solvent exhibits critical concentration fluctuations governed by a nonclassical critical exponent. A dramatic enhancement of the concentration fluctuations above those given by mean field theory (Flory theory) is predicted that persists even far from the transition. The predicted behavior explains recent neutron scattering results on polymerization in living polymer solutions and suggests improvements in experimental conditions. It is also in accord with recent measurements of scattering from solutions of giant polymeric micelles},
  creationdate = {2023-09-11T00:00:00},
  doi          = {10.1103/PhysRevLett.71.1653},
  file         = {:Wheeler1993 - Critical Concentration Fluctuations in Polymerizing Solutions.pdf:PDF},
  issue        = {10},
  keywords     = {critical fluctuations, flory theory, mean field, neutron scattering, living polymer solution},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.71.1653},
}

@Article{Philipp2014,
  author       = {Philipp, Martine and Kyriakos, Konstantinos and Silvi, Luca and Lohstroh, Wiebke and Petry, Winfried and Krüger, Jan K. and Papadakis, Christine M. and Müller-Buschbaum, Peter},
  journal      = {The Journal of Physical Chemistry B},
  title        = {From Molecular Dehydration to Excess Volumes of Phase-Separating PNIPAM Solutions},
  year         = {2014},
  note         = {PMID: 24666206},
  number       = {15},
  pages        = {4253--4260},
  volume       = {118},
  abstract     = {For aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions, a structural instability leads to the collapse and aggregation of the macromolecules at the temperature-induced demixing transition. The accompanying cooperative dehydration of the PNIPAM chains is known to play a crucial role in this phase separation. We elucidate the impact of partial dehydration of PNIPAM on the volume changes related to the phase separation of dilute to concentrated PNIPAM solutions. Quasi-elastic neutron scattering enables us to directly follow the isotropic jump diffusion behavior of the hydration water and the almost freely diffusing water. As the hydration number decreases from 8 to 2 for the demixing 25 mass \% PNIPAM solution, only a partial dehydration of the PNIPAM chains occurs. Dilatation studies reveal that the transition-induced volume changes depend in a remarkable manner on the PNIPAM concentration of the solutions. The excess volume per mole of H2O molecules expelled from the solvation layers of PNIPAM during phase separation probably strongly increases from dilute to concentrated PNIPAM solutions. This finding is qualitatively related to the immense strain-softening previously observed for demixing PNIPAM solutions.},
  creationdate = {2023-09-13T00:00:00},
  doi          = {10.1021/jp501539z},
  eprint       = {https://doi.org/10.1021/jp501539z},
  file         = {:Philipp2014 - From Molecular Dehydration to Excess Volumes of Phase Separating PNIPAM Solutions.pdf:PDF;:FromMolecularDehydrationToExcessVolumesOfPhaseSeparatingPNIPAMSolutions_PhilippEtAl_JPC2014_SI.pdf:PDF},
  keywords     = {pNIPAM, cooperative dehydration, excess volume, thermoresponsive, QENS, neutron scattering, hydration water, isotropic jump diffusion, self-diffusion},
  url          = {https://doi.org/10.1021/jp501539z},
}

@Article{Cho2003,
  author       = {Cho, Eun Chul and Lee, Jaeyoung and Cho, Kilwon},
  journal      = {Macromolecules},
  title        = {Role of Bound Water and Hydrophobic Interaction in Phase Transition of Poly(N-isopropylacrylamide) Aqueous Solution},
  year         = {2003},
  number       = {26},
  pages        = {9929--9934},
  volume       = {36},
  abstract     = {It has been suggested that the phase transition of the poly(N-isopropylacrylamide) (PNiPAM) aqueous solution consists of at least two different processes:  (1) a rearrangement of bound water around either hydrophobic or hydrophobic and hydrophilic group of PNiPAM and (2) a hydrophobic association of the hydrophobic groups in the PNiPAM chains or a residual interaction between the PNiPAM side chain residues. However, a single endothermic peak does not provide direct evidence for this suggestion. This study shows that the phase transition in PNiPAM aqueous solution comprises at least two processes by using temperature modulated differential scanning calorimetry. The single endothermic peak is separated into an endothermic and exothermic peak, and the heats from these peaks depend on the applied frequency. Curve fitting to experimental data interprets the transition mechanism of the PNiPAM aqueous solution in more detail, and the results and the limitation of the curve fitting are discussed.},
  creationdate = {2023-09-13T00:00:00},
  doi          = {10.1021/ma034851d},
  eprint       = {https://doi.org/10.1021/ma034851d},
  file         = {:Cho2003 - Role of Bound Water and Hydrophobic Interaction in Phase Transition of Poly(N Isopropylacrylamide) Aqueous Solution.pdf:PDF},
  keywords     = {pNIPAM, hydration water, hydrophobic hydration, hydration shell, dsc},
  url          = {https://doi.org/10.1021/ma034851d},
}

@Article{Futscher2017,
  author       = {Moritz H. Futscher and Martine Philipp and Peter Müller-Buschbaum and Alfons Schulte},
  journal      = {Sci Rep},
  title        = {The Role of Backbone Hydration of Poly(N-isopropyl acrylamide) Across the Volume Phase Transition Compared to its Monomer},
  year         = {2017},
  pages        = {17012},
  volume       = {7},
  abstract     = {Thermo-responsive polymers undergo a reversible coil-to-globule transition in water after which the chains collapse and aggregate into bigger globules when passing to above its lower critical solution temperature (LCST). The hydrogen bonding with the amide groups in the side chains has to be contrasted with the hydration interaction of the hydrophobic main-chain hydrocarbons. In the present investigation we study molecular changes in the polymer poly(N-isopropyl acrylamide) (PNIPAM) and in its monomer N-isopropyl acrylamide (NIPAM) in solution across the LCST transition. Employing Fourier-transform infrared spectroscopy we probe changes in conformation and hydrogen bonding. We observe a nearly discontinuous shift of the peak frequencies and areas of vibrational bands across the LCST transition for PNIPAM whereas NIPAM exhibits a continuous linear change with temperature. This supports the crucial role of the polymer backbone with respect to hydration changes in the amide group in combination with cooperative interactions of bound water along the backbone chain.},
  creationdate = {2023-09-13T00:00:00},
  doi          = {https://doi.org/10.1038/s41598-017-17272-7},
  file         = {:Futscher2017 - The Role of Backbone Hydration of Poly(N Isopropyl Acrylamide) across the Volume Phase Transition Compared to Its Monomer.pdf:PDF;:TheRoleOfBackboneHydrationOfPolyNIsopropylAcrylamideAcrossTheVolumePhaseTransitionComparedToItsMonomer_FutscherEtAl_SciRep2017_SI.pdf:PDF},
  keywords     = {pNIPAM, hydration shell, hydration water, hydrophobic hydration, hydrogen bonds, infrared, cooperative dehydration, monomer},
  url          = {https://doi.org/10.1038/s41598-017-17272-7},
}

@Article{Rolston1984,
  author       = {Rolston, J. H. and Gale, K. L.},
  journal      = {The Journal of Physical Chemistry},
  title        = {Fractionation of deuterium and protium between water and methanol},
  year         = {1984},
  number       = {19},
  pages        = {4394--4397},
  volume       = {88},
  abstract     = {The overall deuterium - protium separation factor, a, between hydrogen gas and aqueous methanol mixtures has been measured over the full composition range at temperatures between 25 and 55°C. At each temperature a increases smoothly with increasing mole fraction of methanol but the values fall significantly below thes traight line joining the separation factors for the methanol - hydrogen and water - hydrogen systems. The equilibrium constant, Kj(l), for exchange of a deuterium atom tracer between the hydroxyl groups of methanol and liquid water, calculated from the values of a for each solution, is independent of composition within experimental error. The value of KjO) at 25°C is 0.54±0.02, so that deuterium favors the methanol environment rather than water. The dependence of ATj(1) on absolute temperature, T, is given by the expression InA"¡(1)=-0.776+52.6/, which corresponds to a reaction enthalpy of - 0.43kJ-mol-1},
  comment      = {deuterium favours methanol, at room temperature independent of concentration},
  creationdate = {2023-09-14T00:00:00},
  doi          = {10.1021/j150663a042},
  eprint       = {https://doi.org/10.1021/j150663a042},
  file         = {:Rolston1984 - Fractionation of Deuterium and Protium between Water and Methanol.pdf:PDF},
  keywords     = {o-d exchange, hydrogen bond, aqueous alcohol},
  url          = {https://doi.org/10.1021/j150663a042},
}

@Article{Balu2007,
  author       = {Balu, Caroline and Delsanti, Michel and Guenoun, Patrick and Monti, Fabrice and Cloitre, Michel},
  journal      = {Langmuir},
  title        = {Colloidal Phase Separation of Concentrated PNIPAm Solutions},
  year         = {2007},
  note         = {PMID: 17269807},
  number       = {5},
  pages        = {2404--2407},
  volume       = {23},
  abstract     = {In the concentration range of 1−6 wt \%, solutions of a thermosensitive polymer (poly-N-isopropylacrylamide (PNIPAm), Mw = 1.4 × 105 g·mol-1) are shown to phase separate in the form of dense stable colloids of nearly pure polymer. Diffuse wave spectroscopy and small-angle neutron scattering both provide consistent measurements of the colloidal size as a function of temperature. Results are in agreement with a Cahn regime of spinodal decomposition blocked at an early stage, prior to a growth that would lead to a macroscopic phase separation. [Early results of this work were presented at the 231st American Chemical Society National Meeting, Symposium on Amphiphilic Polymers, Atlanta, GA, 2006, March 26−30.]},
  creationdate = {2023-09-14T00:00:00},
  doi          = {10.1021/la0627821},
  eprint       = {https://doi.org/10.1021/la0627821},
  file         = {:Balu2007 - Colloidal Phase Separation of Concentrated PNIPAm Solutions.pdf:PDF},
  keywords     = {pNIPAM, concentration, thermoresponsive, diffusive wave spectroscopy, small-angle neutron scattering, SANS, isotope effect, hydrodynamic radius},
  url          = {https://doi.org/10.1021/la0627821},
}

@Article{Raftopoulos2020,
  author       = {Raftopoulos, Konstantinos N. and Kyriakos, Konstantinos and Nuber, Matthias and Niebuur, Bart-Jan and Holderer, Olaf and Ohl, Michael and Ivanova, Oxana and Pasini, Stefano and Papadakis, Christine M.},
  journal      = {Soft Matter},
  title        = {Co-nonsolvency in concentrated aqueous solutions of PNIPAM: effect of methanol on the collective and the chain dynamics},
  year         = {2020},
  pages        = {8462--8472},
  volume       = {16},
  abstract     = {The polymer dynamics in concentrated solutions of poly(N-isopropyl acrylamide) (PNIPAM) in D2O/CD3OD mixtures is investigated in the one-phase region. Two polymer concentrations (9 and 25 wt%) and CD3OD contents in the solvent mixture of 0{,} 10 and 15 vol% are chosen. Temperature-resolved dynamic light scattering (DLS) reveals the collective dynamics. Two modes are observed{,} namely the fast relaxation of polymer segments within the blobs and the slow collective relaxation of the blobs. As the cloud point is approached{,} the correlation length related to the fast mode increases with CD3OD content. It features critical scaling behavior{,} which is consistent with mean-field behavior for the 9 wt% PNIPAM solution in pure D2O and with 3D Ising behavior for all other solutions. While the slow mode is not very strong in the 9 wt% PNIPAM solution in pure D2O{,} it is significantly more prominent as CD3OD is added and at all CD3OD contents in the 25 wt% solution{,} which may be attributed to enhanced interaction between the polymers. Neutron spin-echo spectroscopy (NSE) reveals a decay in the intermediate structure factor which indicates a diffusive process. For the polymer concentration of 9 wt%{,} the diffusion coefficients from NSE are similar to the ones from the fast relaxation observed in DLS. In contrast{,} they are significantly lower for the solutions having a polymer concentration of 25 wt%{,} which is attributed to the influence of the dominant large-scale dynamic heterogeneities. To summarize{,} addition of cosolvent leads to enhanced large-scale heterogeneities{,} which are reflected in the dynamic behavior at small length scales.},
  creationdate = {2023-09-14T00:00:00},
  doi          = {10.1039/D0SM01007C},
  file         = {:Raftopoulos2020 - Co Nonsolvency in Concentrated Aqueous Solutions of PNIPAM_ Effect of Methanol on the Collective and the Chain Dynamics.pdf:PDF},
  issue        = {36},
  keywords     = {pNIPAM, cononsolvency, methanol, dls, light scattering, neutron spin echo, NSE},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D0SM01007C},
}

@Article{Hannappel2021,
  author       = {Hannappel, Yvonne and Wiehemeier, Lars and Dirksen, Maxim and Kottke, Tilman and Hellweg, Thomas},
  journal      = {Macromolecular Chemistry and Physics},
  title        = {Smart Microgels from Unconventional Acrylamides},
  year         = {2021},
  number       = {13},
  pages        = {2100067},
  volume       = {222},
  abstract     = {In the present study, smart responsive microgels are synthesized from a series of alternative monomers, which are less common in micro- and nanogel research. Their swelling behavior is studied by means of photon correlation spectroscopy and Fourier transform infrared spectroscopy. In addition, these monomers are used to make copolymer microgels. In line with previous results for such copolymer particles the present work observes linear changes of the volume phase transition temperatures of the microgels as a function of the microgel composition. The presented systems allow to realize a broad range of transition temperatures, which is potentially interesting for applications in sensing, actuation, and drug delivery.},
  creationdate = {2023-09-19T00:00:00},
  doi          = {https://doi.org/10.1002/macp.202100067},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/macp.202100067},
  file         = {:Hannappel2021 - Smart Microgels from Unconventional Acrylamides.pdf:PDF},
  keywords     = {pNIPAM, acrylamide, atomic force microscopy, nanogels, photon correlation spectroscopy, precipitation polymerization, microgel, pNIPAM-alternatives},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/macp.202100067},
}

@Article{Kamal2016,
  author       = {Muhammad Shahzad Kamal and Ibnelwaleed A. Hussein and Abdullah S. Sultan and Nicolas {von Solms}},
  journal      = {Renewable and Sustainable Energy Reviews},
  title        = {Application of various water soluble polymers in gas hydrate inhibition},
  year         = {2016},
  issn         = {1364-0321},
  pages        = {206--225},
  volume       = {60},
  abstract     = {Formation of hydrates in gas transmission lines due to high pressures and low temperatures is a serious problem in the oil and gas industry with potential hazards and/or economic losses. Kinetic hydrate inhibitors are water soluble polymeric compounds that prevent or delay hydrate formation. This review presents the various types of water soluble polymers used for hydrate inhibition, including conventional and novel polymeric inhibitors along with their limitations. The review covers the relevant properties of vinyl lactam, amide, dendrimeric, fluorinated, and natural biodegradable polymers. The factors affecting the performance of these polymers and the structure–property relationships are reviewed. A comprehensive review of the techniques used to evaluate the performance of the polymeric inhibitors is given. This review also addresses recent developments, current and future challenges, and field applications of a range of polymeric kinetic hydrate inhibitors.},
  creationdate = {2023-09-19T00:00:00},
  doi          = {https://doi.org/10.1016/j.rser.2016.01.092},
  file         = {:Kamal2016 - Application of Various Water Soluble Polymers in Gas Hydrate Inhibition.pdf:PDF},
  keywords     = {Water soluble polymers, Poly(vinyl caprolactam), Gas hydrates, Kinetic inhibitors, Induction time, pNIPAM-alternatives, application focused, application-focused},
  url          = {https://www.sciencedirect.com/science/article/pii/S1364032116001222},
}

@Article{Cerveny2019,
  author       = {Cerveny, Silvina and Swenson, Jan},
  journal      = {The Journal of Chemical Physics},
  title        = {{Water dynamics in the hydration shells of biological and non-biological polymers}},
  year         = {2019},
  issn         = {0021-9606},
  month        = jun,
  number       = {23},
  pages        = {234904},
  volume       = {150},
  abstract     = {{The dynamics of water at supercooled temperatures in aqueous solutions of different types of solutes has been deeply analyzed in the literature. In these previous works and in most of the cases, a single relaxation of water molecules is observed. In this work, we analyze the dynamics of water in solutions for which a dual relaxation of water molecules is experimentally measured. We discuss the criteria for observing these two water relaxations in these specific solutions and their most likely origins. We also discuss how these two water relaxations relate to the relaxation behavior of bulk water and how the slower one is coupled to the solute dynamics and is essential for the dynamics and functional properties of proteins.}},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1063/1.5096392},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.5096392/14124119/234904\_1\_online.pdf},
  file         = {:Cerveny2019 - Water Dynamics in the Hydration Shells of Biological and Non Biological Polymers.pdf:PDF},
  keywords     = {hydration water, hydration shell, dsc, e-PLL, PVP, dextran, bds, two-state model},
  readstatus   = {skimmed},
  url          = {https://doi.org/10.1063/1.5096392},
}

@Article{Zhang2007a,
  author       = {Luyuan Zhang and Lijuan Wang and Ya-Ting Kao and Weihong Qiu and Yi Yang and Oghaghare Okobiah and Dongping Zhong},
  journal      = {Proceedings of the National Academy of Sciences},
  title        = {Mapping hydration dynamics around a protein surface},
  year         = {2007},
  number       = {47},
  pages        = {18461--18466},
  volume       = {104},
  abstract     = {Protein surface hydration is fundamental to its structure and activity. We report here the direct mapping of global hydration dynamics around a protein in its native and molten globular states, using a tryptophan scan by site-specific mutations. With 16 tryptophan mutants and in 29 different positions and states, we observed two robust, distinct water dynamics in the hydration layer on a few (≈1–8 ps) and tens to hundreds of picoseconds (≈20–200 ps), representing the initial local relaxation and subsequent collective network restructuring, respectively. Both time scales are strongly correlated with protein's structural and chemical properties. These results reveal the intimate relationship between hydration dynamics and protein fluctuations and such biologically relevant water–protein interactions fluctuate on picosecond time scales.},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1073/pnas.0707647104},
  eprint       = {https://www.pnas.org/doi/pdf/10.1073/pnas.0707647104},
  file         = {:Zhang2007a - Mapping Hydration Dynamics around a Protein Surface.pdf:PDF},
  keywords     = {hydration shell, hydration water dynamics, two-state model, flourescence},
  url          = {https://www.pnas.org/doi/abs/10.1073/pnas.0707647104},
}

@Article{Nilsson2005,
  author       = {Lennart Nilsson and Bertil Halle},
  journal      = {Proceedings of the National Academy of Sciences},
  title        = {Molecular origin of time-dependent fluorescence shifts in proteins},
  year         = {2005},
  number       = {39},
  pages        = {13867--13872},
  volume       = {102},
  abstract     = {Time-resolved fluorescence spectroscopy is used increasingly to probe molecular motions at the aqueous interfaces of biological macromolecules and membranes. By recording the time variation of the fluorescence frequency, thermal atomic fluctuations in the vicinity of the chromophore can be probed. From such fluorescence Stokes shift (FSS) experiments, it has been inferred that water motions in the hydration layer are slowed down by 1–3 orders of magnitude. To provide a more secure foundation for the interpretation of FSS data, we use molecular dynamics simulations to examine the molecular origin of the FSS from a tryptophan residue in a protein. By using linear response theory to decompose the FSS into its water and protein components, we find that the water component dominates the static FSS but decays rapidly. Thus, after a few picoseconds, the FSS essentially reflects protein dynamics, including the self-motion of the chromophore. Because of its collective nature, the FSS response is insensitive to the motion of individual water molecules. Collective water displacement by slowly fluctuating protein groups introduces a long-time tail in the water autocorrelation function, but this dynamic coupling is hardly manifested in the observed FSS. Our analysis reconciles FSS data with the picture of a highly dynamic hydration layer, derived mainly from magnetic relaxation dispersion and simulation studies, and calls for a revision of previous interpretations of FSS decays in terms of slow hydration dynamics at biomolecular and other interfaces.},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1073/pnas.0504181102},
  eprint       = {https://www.pnas.org/doi/pdf/10.1073/pnas.0504181102},
  keywords     = {hydration shell, hydration water, two-state model, flourescence spectroscopy, flourescence stokes shift, fss},
  url          = {https://www.pnas.org/doi/abs/10.1073/pnas.0504181102},
}

@Article{Vinh2011,
  author       = {Vinh, N. Q. and Allen, S. James and Plaxco, Kevin W.},
  journal      = {Journal of the American Chemical Society},
  title        = {Dielectric Spectroscopy of Proteins as a Quantitative Experimental Test of Computational Models of Their Low-Frequency Harmonic Motions},
  year         = {2011},
  note         = {PMID: 21542634},
  number       = {23},
  pages        = {8942--8947},
  volume       = {133},
  abstract     = {Decades of molecular dynamics and normal mode calculations suggest that the largest-scale collective vibrational modes of proteins span the picosecond to nanosecond time scale. Experimental investigation of these harmonic, low-amplitude motions, however, has proven challenging. In response, we have developed a vector network analyzer-based spectrometer that supports the accurate measurement of both the absorbance and refractive index of solvated biomolecules over the corresponding gigahertz to terahertz frequency regime, thus providing experimental information regarding their largest-scale, lowest frequency harmonic motions. We have used this spectrometer to measure the complex dielectric response of lysozyme solutions over the range 65 to 700 GHz and an effective medium model to separate the dielectric response of the solvated protein from that of its buffer. In doing so, we find that each lysozyme is surrounded by a tightly bound layer of 165 ± 15 water molecules that, in terms of their picosecond dynamics, behave as if they are an integral part of the protein. We also find that existing computational descriptions of the protein’s dynamics compare poorly with the results of our experiment. Specifically, published normal mode and molecular dynamics simulations do not explain the measured dielectric response unless we introduce a cutoff frequency of 250 GHz below which the density of vibrational modes drops to zero. This cutoff is physically plausible, given the known size of the protein and the known speed of sound in proteins, raising questions as to why it is not apparent in computational models of the protein’s motions.},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1021/ja200566u},
  eprint       = {https://doi.org/10.1021/ja200566u},
  file         = {:Vinh2011 - Dielectric Spectroscopy of Proteins As a Quantitative Experimental Test of Computational Models of Their Low Frequency Harmonic Motions.pdf:PDF;:DielectricSpectroscopyOfProteinsAsAQuantitativeExperimentalTestOfComputationalModelsOfTheirLosFrequencyHarmonicMotions_VinhEtAl_JAmChemSoc2011_SI.pdf:PDF},
  keywords     = {hydration shell, dielectrics},
  url          = {https://doi.org/10.1021/ja200566u},
}

@Article{Camisasca2016,
  author       = {Camisasca, G. and De Marzio, M. and Corradini, D. and Gallo, P.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Two structural relaxations in protein hydration water and their dynamic crossovers}},
  year         = {2016},
  issn         = {0021-9606},
  month        = jul,
  number       = {4},
  pages        = {044503},
  volume       = {145},
  abstract     = {We study the translational single particle dynamics of hydration water of lysozyme upon cooling by means of molecular dynamics simulations. We find that water close to the protein exhibits two distinct relaxations. By characterizing their behavior upon cooling, we are able to assign the first relaxation to the structural α-relaxation also present in bulk water and in other glass-forming liquids. The second, slower, relaxation can be ascribed to a dynamic coupling of hydration water motions to the fluctuations of the protein structure. Both relaxation times exhibit crossovers in the behavior upon cooling. For the α-process, we find upon cooling a crossover from a fragile behavior to a strong behavior at a temperature which is about five degrees higher than that of bulk water. The long-relaxation time appears strictly connected to the protein motion as it shows upon cooling a temperature crossover from a strong behavior with a lower activation energy to a strong behavior with a higher activation energy. The crossover temperature coincides with the temperature of the protein dynamical transition. These findings can help experimentalists to disentangle the different information coming from total correlators and to better characterize hydration water relaxations in different biomolecules.},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1063/1.4959286},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4959286/15517221/044503\_1\_online.pdf},
  file         = {:Camisasca2016 - Two Structural Relaxations in Protein Hydration Water and Their Dynamic Crossovers.pdf:PDF},
  keywords     = {hydration water, hydration shell, molecular dynamics simulation, two-state model},
  url          = {https://doi.org/10.1063/1.4959286},
}

@Article{Laage2017,
  author       = {Laage, Damien and Elsaesser, Thomas and Hynes, James T.},
  journal      = {Chemical Reviews},
  title        = {Water Dynamics in the Hydration Shells of Biomolecules},
  year         = {2017},
  note         = {PMID: 28248491},
  number       = {16},
  pages        = {10694--10725},
  volume       = {117},
  abstract     = {The structure and function of biomolecules are strongly influenced by their hydration shells. Structural fluctuations and molecular excitations of hydrating water molecules cover a broad range in space and time, from individual water molecules to larger pools and from femtosecond to microsecond time scales. Recent progress in theory and molecular dynamics simulations as well as in ultrafast vibrational spectroscopy has led to new and detailed insight into fluctuations of water structure, elementary water motions, electric fields at hydrated biointerfaces, and processes of vibrational relaxation and energy dissipation. Here, we review recent advances in both theory and experiment, focusing on hydrated DNA, proteins, and phospholipids, and compare dynamics in the hydration shells to bulk water.},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1021/acs.chemrev.6b00765},
  eprint       = {https://doi.org/10.1021/acs.chemrev.6b00765},
  keywords     = {hydration shell, hydration water, two-state model, nmr, molecular dynamics simulation, magnetic relaxation dispersion, review},
  priority     = {prio1},
  ranking      = {rank5},
  url          = {https://doi.org/10.1021/acs.chemrev.6b00765},
}

@Article{Kaieda2013,
  author       = {Kaieda, Shuji and Halle, Bertil},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Internal Water and Microsecond Dynamics in Myoglobin},
  year         = {2013},
  note         = {PMID: 24195787},
  number       = {47},
  pages        = {14676--14687},
  volume       = {117},
  abstract     = {Myoglobin (Mb) binds diatomic ligands, like O2, CO, and NO, in a cavity that is only transiently accessible. Crystallography and molecular simulations show that the ligands can migrate through an extensive network of transiently connected cavities but disagree on the locations and occupancy of internal hydration sites. Here, we use water 2H and 17O magnetic relaxation dispersion (MRD) to characterize the internal water molecules in Mb under physiological conditions. We find that equine carbonmonoxy Mb contains 4.5 ± 1.0 ordered internal water molecules with a mean survival time of 5.6 ± 0.5 μs at 25 °C. The likely locations of these water molecules are the four polar hydration sites, including one of the xenon-binding cavities, that are fully occupied in all high-resolution crystal structures of equine Mb. The finding that water escapes from these sites, located 17–31 Å apart in the protein, on the same μs time scale suggests a global exchange mechanism. We propose that this mechanism involves transient penetration of the protein by H-bonded water chains. Such a mechanism could play a functional role by eliminating trapped ligands. In addition, the MRD results indicate that 2 or 3 of the 11 histidine residues of equine Mb undergo intramolecular hydrogen exchange on a μs time scale.},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1021/jp409234g},
  eprint       = {https://doi.org/10.1021/jp409234g},
  file         = {:Kaieda2013 - Internal Water and Microsecond Dynamics in Myoglobin.pdf:PDF;:InternalWaterAndMicrosecondDynamicsInMyoglobin_KaiedaEtAl_JPC2013_SI.pdf:PDF},
  keywords     = {nmr, field cycling, magnetic relaxation dispersion, hydration water, hydration shell, myoglobin, 2h-nmr, 17o-nmr},
  priority     = {prio1},
  url          = {https://doi.org/10.1021/jp409234g},
}

@Article{Johannesson1998,
  author       = {Jóhannesson, Haukur and Halle, Bertil},
  journal      = {Journal of the American Chemical Society},
  title        = {Minor Groove Hydration of DNA in Solution:  Dependence on Base Composition and Sequence},
  year         = {1998},
  number       = {28},
  pages        = {6859--6870},
  volume       = {120},
  abstract     = {The hydration of six B-DNA dodecamers with A-tracts of variable length and sequence has been investigated via the nuclear magnetic relaxation dispersion (NMRD) of the water 2H and 17O resonances. By subdividing the aqueous DNA solution into microscopic emulsion droplets, NMRD measurements could be performed at −20 °C, thereby greatly enhancing the sensitivity of the method. The NMRD profiles show that all six dodecamers contain long-lived water molecules. These water molecules are displaced by netropsin and must therefore be located in the minor groove. The number of long-lived water molecules is correlated with the width of the minor groove as seen in crystal structures. The NMRD data are consistent with a single file of 3−9 long-lived water molecules located at the base pair steps and extending 1−2 steps on either side of the A-tract. Dodecamers with central A-tracts of sequence A4T4, T4A4, and (AT)4 are found to contain seven or nine long-lived water molecules, challenging the common view that T−A steps widen the minor groove and disrupt the hydration structure. The long-lived water molecules observed here are highly ordered with an entropy comparable to that of water molecules in ice, but most of them undergo a symmetric flip motion while residing in the groove. The mean water residence time is essentially the same, 10−15 ns at −20 °C, for all investigated dodecamers, suggesting that water exchange occurs from an open state with a uniformly wide minor groove. From the temperature dependence of the water residence time, an activation enthalpy of 53 kJ mol-1 is obtained for this process.},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1021/ja974316r},
  eprint       = {https://doi.org/10.1021/ja974316r},
  file         = {:Johannesson1998 - Minor Groove Hydration of DNA in Solution_ Dependence on Base Composition and Sequence.pdf:PDF},
  keywords     = {nmr, magnetic relaxation dispersion, 2h-nmr, 17o-nmr, DNA},
  priority     = {prio1},
  url          = {https://doi.org/10.1021/ja974316r},
}

@Article{Mattea2008,
  author       = {Carlos Mattea and Johan Qvist and Bertil Halle},
  journal      = {Biophysical Journal},
  title        = {Dynamics at the Protein-Water interface from 17O Spin Relaxation in Deeply Supercooled Solutions},
  year         = {2008},
  month        = sep,
  pages        = {2951--2963},
  volume       = {95},
  abstract     = {Most of the decisive molecular events in biology take place at the protein-water interface. The dynamical properties of the hydration layer are therefore of fundamental importance. To characterize the dynamical heterogeneity and rotational activation energy in the hydration layer, we measured the 17O spin relaxation rate in dilute solutions of three proteins in a wide temperature range extending down to 238 K. We find that the rotational correlation time can be described by a power-law distribution with exponent 2.1–2.3. Except for a small fraction of secluded hydration sites, the dynamic perturbation in the hydration layer is the same for all proteins and does not differ in any essential way from the hydration shell of small organic solutes. In both cases, the dynamic perturbation factor is ,2 at room temperature and exhibits a maximum near 262 K. This maximum implies that, at low temperatures, the rate of water molecule rotation has a weaker temperature dependence in the hydration layer than in bulk water. We attribute this difference to the temperature-independent constraints that the protein surface imposes on the water H-bond network. The free hydration layer studied here differs qualitatively from confined water in solid protein powder samples.},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1529/biophysj.108.135194},
  file         = {:Mattea2008 - Dynamics at the Protein Water Interface from 17O Spin Relaxation in Deeply Supercooled Solutions.pdf:PDF},
  keywords     = {17o-nmr,hydration shell,bovine pancreatic trypsin inhibitor,ubiquitin,beta-lactoglobulin,spin relaxation,emulsion},
}

@Article{Denisov1995,
  author       = {Vladimir P. Denisov and Bertil Halle},
  journal      = {Journal of Molecular Biology},
  title        = {Hydrogen Exchange and Protein Hydration: The Deuteron Spin Relaxation Dispersions of Bovine Pancreatic Trypsin Inhibitor and Ubiquitin},
  year         = {1995},
  issn         = {0022-2836},
  number       = {5},
  pages        = {698--709},
  volume       = {245},
  abstract     = {Water deuteron (2H) spin relaxation was used to study hydrogen exchange hydration, and protein dynamics in aqueous soltuions of the globular proteins bovine pancreatic trypsin inhibitor (BPTI) and ubiquitin. The frequency dispersion of the longitudinal2H relaxation rate was measured in the pD range 2 to 11 at 27°C. In contrast to the previously reported water17O relaxation dispersion from the same samples, the2H dispersion depends strongly on pD. This pD dependence is due to labile protein deuterons in acidic side-chains and surface peptide groups, which exchange rapidly with water deuterons. The pD dependence of the2H relaxation in BPTI solutions could be quantitatively accounted for in terms of known pKvalues and hydrogen exchange rate constants. For ubiquitin, labile protein deuterons contribute importantly to the2H relaxation dispersion even in the neutral pD range. The2H relaxation data also provided information about the orientational order and internal motion of OD and ND bonds in side-chains and surface peptides. A comparison of the water contribution to the2H dispersion with the17O dispersion indicates that one of the four internal water molecules of BPTI, presumably the deeply buried water molecule W122, exchanges more slowly (10−6to 10−4second) than the other three (10−8to 10−6second).},
  creationdate = {2023-09-19T00:00:00},
  doi          = {https://doi.org/10.1006/jmbi.1994.0056},
  file         = {:Denisov1995 - Hydrogen Exchange and Protein Hydration_ the Deuteron Spin Relaxation Dispersions of Bovine Pancreatic Trypsin Inhibitor and Ubiquitin.pdf:PDF},
  keywords     = {hydrogen exchange, protein hydration, nuclear magnetic resonance, 2h-nmr, bovine pancreatic trypsin inhibitor, ubiquitin},
  priority     = {prio1},
  url          = {https://www.sciencedirect.com/science/article/pii/S0022283684700568},
}

@Article{Halle1986,
  author       = {Halle, Bertil and Piculell, Lennart},
  journal      = {J. Chem. Soc.{,} Faraday Trans. 1},
  title        = {Water spin relaxation in colloidal systems. Part 3.—Interpretation of the low-frequency dispersion},
  year         = {1986},
  pages        = {415--429},
  volume       = {82},
  abstract     = {The contribution to the water O spin relaxation from slow molecular processes in colloidal solutions has been interpreted in terms of a general theory of spin relaxation in locally ordered fluids{,} coupled with a dynamic model which describes the translational motion of water molecules by a diffusion equation with an anisotropic and position-dependent diffusivity tensor. This model can explain all the experimental observations provided that the lateral and radial diffusivities of water molecules within 1 nm of the colloid surface are reduced by 1–2 and 2–3 orders of magnitude{,} respectively{,} compared with bulk water. The dynamic coupling between water motion and rotational diffusion of colloidal particles does not affect water O spin relaxation for particle radii > 10 nm.},
  comment      = {There is a part 1 and 2 to this series of papers.},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1039/F19868200415},
  file         = {:Halle1986 - Water Spin Relaxation in Colloidal Systems. Part 3.—Interpretation of the Low Frequency Dispersion.pdf:PDF},
  issue        = {2},
  keywords     = {17o-nmr, magnetic relaxation dispersion},
  priority     = {prio1},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/F19868200415},
}

@Article{Piculell1986,
  author       = {Piculell, Lennart and Halle, Bertil},
  journal      = {J. Chem. Soc.{,} Faraday Trans. 1},
  title        = {Water spin relaxation in colloidal systems. Part 2.—17O and 2H relaxation in protein solutions},
  year         = {1986},
  pages        = {401--414},
  volume       = {82},
  abstract     = {Oxygen-17 and deuteron longitudinal and transverse spin relaxation rates from aqueous protein solutions (mainly lysozyme and haemocyanin) have been measured as a function of temperature{,} pH and resonance frequency. A detailed comparison of the O and H data demonstrates that H relaxation has a dominant contribution which is not seen by O. This contribution is{,} at least partly{,} due to deuteron exchange with ionizable groups on the protein. Furthermore{,} we refute two widespread beliefs about solvent spin relaxation in protein solutions{,} namely that the discrete-exchange model leads to interpretational inconsistencies and that the low-frequency dispersion always reflects protein reorientation.},
  comment      = {this is part 2 of a series of at least 3 papers},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1039/F19868200401},
  file         = {:Piculell1986 - Water Spin Relaxation in Colloidal Systems. Part 2.—17O and 2H Relaxation in Protein Solutions.pdf:PDF},
  issue        = {2},
  keywords     = {2h-nmr, 17o-nmr, magnetic relaxation dispersion},
  priority     = {prio1},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/F19868200401},
}

@Article{Halle1987,
  author       = {Bertil Halle},
  journal      = {Molecular Physics},
  title        = {Theory of intramolecular spin relaxation by translational diffusion in locally ordered fluids},
  year         = {1987},
  number       = {2},
  pages        = {319--370},
  volume       = {60},
  abstract     = {The theory of spin relaxation induced by translational diffusion of small molecules or ions in locally ordered fluids, developed in parts I and II of this series, is extended to cylindrical geometry as, for example, in polyelectrolyte solutions or in hexagonal lyotropic liquid crystals. The theory is based on the Smoluchowski diffusion equation with nonuniform potential of mean force and translational diffusivity and on the cylindrical cell model. Formally exact closed-form expressions are derived for the zero-frequency spectral density associated with radial diffusion, while a general numerical algorithm is described for computing the full frequency-dependent spectral density. Several useful approximations, such as the dynamic cell approximation, the steady state approximation and the surface diffusion approximation, are formulated and their accuracy quantitatively assessed. Calculations are reported for a mean-field interaction model based on the nonlinear Poisson-Boltzmann equation, with emphasis on applications of the theory to counterion spin relaxation in polyelectrolyte solutions.},
  comment      = {this is part 3 of a series of at leat three papers.},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1080/00268978700100241},
  eprint       = {https://doi.org/10.1080/00268978700100241},
  file         = {:Halle1987 - Theory of Intramolecular Spin Relaxation by Translational Diffusion in Locally Ordered Fluids.pdf:PDF},
  keywords     = {nmr, theory},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/00268978700100241},
}

@Article{Denisov1995a,
  author       = {Vladimir P. Denisov and Bertil Halle},
  journal      = {Journal of Molecular Biology},
  title        = {Protein Hydration Dynamics in Aqueous Solution: A Comparison of Bovine Pancreatic Trypsin Inhibitor and Ubiquitin by Oxygen-17 Spin Relaxation Dispersion},
  year         = {1995},
  issn         = {0022-2836},
  number       = {5},
  pages        = {682--697},
  volume       = {245},
  abstract     = {Water oxygen-17 spin relaxation was used to study hydration and dynamcs of the globular proteins bovine pancreatic trypsin inhibitor (BPTI) and ubiquitin in aqueous solution. The frequency dispersion of the longitudinal and transverse relaxation rates was measured over the Larmor frequency range 2.6 to 49|4ru|MHz in the pD range 2 to 11 at 27°C. While the protein-induced relaxation enhancement was similar for the two proteins at high frequencies, it was an order of magnitude smaller for ubiquitin than for BPTI at low frequencies. This difference was ascribed to the absence, in ubiquitin, of highly ordered internal water molecules, which are known to be present in BPTI and in most other globular proteins. These observations demonstrate that the water relaxation dispersion in protein solutions is essentially due to a few structural water molecules buried within the protein matrix, but exchanging rapidly with the external water. The relaxation data indicate that the internal water molecules of BPTI exchange with bulk water on the time-scale 10−8to 10−6second thus lowering the recently reported upper bound on the residence time of these internal water molecules by four orders of magnitude, and implying that local unfolding occurs on the submircosecond time-scale The water molecules residing at the surface of the two proteins were found to be highly mobile, with an average rotational correlation time of approximately 20 picoseconds. For both proteins, the oxygen-17 relaxation depend only very weakly on pD, showing that ionic residues do not perturb hydration water dynamics more than other surface residues. We believe that the present results resolve the long-standing controversy regarding the mechanism behind the spin relaxation dispersion of water nuclei in protein solutions, thus establishing oxygen-17 relaxation as a powerful tool for studies of structurally and functionally important water molecules in proteins and other biomolecules.},
  comment      = {pD value is the analogon to a pH value, but for deuterated water. Relaxation times at low frequencies were measured with an iron-core electro magnet (Drusch EAR-35N).},
  creationdate = {2023-09-19T00:00:00},
  doi          = {https://doi.org/10.1006/jmbi.1994.0055},
  file         = {:Denisov1995a - Protein Hydration Dynamics in Aqueous Solution_ a Comparison of Bovine Pancreatic Trypsin Inhibitor and Ubiquitin by Oxygen 17 Spin Relaxation Dispersion.pdf:PDF},
  keywords     = {protein hydration, internal water, nuclear magnetic resonance, bovine pancreatic trypsin inhibitor, ubiquitin},
  readstatus   = {read},
  url          = {https://www.sciencedirect.com/science/article/pii/S0022283684700556},
}

@Article{Miller1973,
  author       = {Miller, Michael S. and Klotz, Irving M.},
  journal      = {Journal of the American Chemical Society},
  title        = {Hydrogen-deuterium exchange in some polymer amides},
  year         = {1973},
  number       = {17},
  pages        = {5694--5700},
  volume       = {95},
  abstract     = {The kinetics of hydrogen-deuterium exchange was followed for two polymers, poly(N-ethylacrylamide) and poly(N-ethylmethacrylamide), which contain side chain amide groups. Conformational information for these polymers was obtained from viscometry and nuclear magnetic resonance. Infrared spectra showed the presence of hydrogen-bonded and of free amide groups in both polymers. Single first-order exchange processes were observed, and the rate constants, k, obtained from the appearance of OH absorption bands or the disappearance of NH bands, are the same. The polymers exchange more slowly than structurally similar small amides. This behaviour is interpretable in terms of steric effects, changes in local dielectric constant in the region of the amide group, and changes in the character of water in the vicinity of the polymers.},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1021/ja00798a041},
  eprint       = {https://doi.org/10.1021/ja00798a041},
  file         = {:Miller1973 - Hydrogen Deuterium Exchange in Some Polymer Amides.pdf:PDF},
  keywords     = {hydrogen exchange, exchange rate constant, infrared, PEAM},
  url          = {https://doi.org/10.1021/ja00798a041},
}

@Article{Scarpa1967,
  author       = {Scarpa, Joannis S. and Mueller, Delbert Dean. and Klotz, Irving M.},
  journal      = {Journal of the American Chemical Society},
  title        = {Slow hydrogen-deuterium exchange in a non-.alpha.-helical polyamide},
  year         = {1967},
  number       = {24},
  pages        = {6024--6030},
  volume       = {89},
  creationdate = {2023-09-19T00:00:00},
  doi          = {10.1021/ja01000a006},
  eprint       = {https://doi.org/10.1021/ja01000a006},
  file         = {:Scarpa1967 - Slow Hydrogen Deuterium Exchange in a Non .alpha. Helical Polyamide.pdf:PDF},
  keywords     = {hydrogen exchange, pNIPAM, hydrogen-deuterium exchange, exchange rate},
  url          = {https://doi.org/10.1021/ja01000a006},
}

@Article{Meiboom2004,
  author       = {Meiboom, S.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Nuclear Magnetic Resonance Study of the Proton Transfer in Water}},
  year         = {2004},
  issn         = {0021-9606},
  month        = aug,
  number       = {2},
  pages        = {375--388},
  volume       = {34},
  abstract     = {{Measurements of the nuclear relaxation in water are reported. The transverse relaxation rate (1/T2) of the proton resonance is pH dependent. The effect is shown to be due to a spin‐spin splitting of the proton resonance by O17 (spin 5/2), which is only partially averaged out by proton exchange. The increase of relaxation rate is observable in natural water (0.037\\% O17), and becomes very appreciable in water enriched in O17. Additional information can be obtained by measuring relaxation rates in the presence of an rf field H1, using a method due to Solomon. A study of the width of the O17 resonance as a function of pH is in quantitative agreement with the results of the proton resonance. The observations provide a direct determination of the rate constants of the exchange reactions: H2O+H3O+→ lim k1H3O++H2O and H2O+HO−→ lim k2HO−+H2O.It is found that k1=(10.6±4)×109 liter mole−1 sec−1 and k2=(3.8±1.5)×109 liter mole−1 sec−1. The spin‐spin interaction between H and O17 in water is determined as 92±15 cps. In the Appendices, theoretical equations for the exchange contribution to the relaxation rate are derived.}},
  creationdate = {2023-09-20T00:00:00},
  doi          = {10.1063/1.1700960},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/34/2/375/8123794/375\_1\_online.pdf},
  file         = {:Meiboom2004 - Nuclear Magnetic Resonance Study of the Proton Transfer in Water.pdf:PDF},
  keywords     = {hydrogen exchange, nmr, pH, 17O-nmr, t2 relaxation, spin-spin relaxation, t1 rho},
  url          = {https://doi.org/10.1063/1.1700960},
}

@Article{Halle1981a,
  author       = {Bertil Halle and H{\aa}kan Wennerström},
  journal      = {Journal of Magnetic Resonance (1969)},
  title        = {Nearly exponential quadrupolar relaxation. A perturbation treatment},
  year         = {1981},
  issn         = {0022-2364},
  number       = {1},
  pages        = {89--100},
  volume       = {44},
  abstract     = {Quadrupolar nuclear spin relaxation is treated by a perturbation method, which shows that the relaxation is nearly exponential provided that the effective spectral density is only weakly frequency dependent. Approximate analytical expressions for the relaxation rates are derived and tested against the experimentally accessible apparent relaxation rates, for a fast-exchange two-state model. The results for spin I = 5/2 and 7/2 indicate that the analytical expressions are accurate to within a few percent in most experimental situations.},
  creationdate = {2023-09-20T00:00:00},
  doi          = {https://doi.org/10.1016/0022-2364(81)90192-X},
  file         = {:Halle1981a - Nearly Exponential Quadrupolar Relaxation. a Perturbation Treatment.pdf:PDF},
  keywords     = {17o-nmr, spin 5/2},
  priority     = {prio1},
  url          = {https://www.sciencedirect.com/science/article/pii/002223648190192X},
}

@Article{Shimizu1997,
  author       = {Shimizu, S. and Kimura, M. and Maruyama, T. and Kurita, K.},
  journal      = {Journal of Applied Crystallography},
  title        = {{Studies on Interaction Parameters of Poly({\textit N}-isopropylacrylamide) in 1-Propanol{--}Water Mixtures by Small-Angle X-ray Scattering}},
  year         = {1997},
  month        = oct,
  number       = {5 Part 2},
  pages        = {712--716},
  volume       = {30},
  abstract     = {Small-angle X-ray scattering from semidilute solutions of poly({\textit N}-isopropylacrylamide) in 1-propanol{--}water mixtures has been measured in a poor-solvent regime. The binary and ternary cluster integrals of polymer segments were determined from the concentration dependence of the correlation length at several temperatures just below the lower critical-solution temperature. The contributions of the segment{--}segment interactions to the entropy $S_\mathrm{int}$ and enthalpy $H_\mathrm{int}$ have been calculated from the temperature dependence of interaction parameters (binary and ternary cluster integrals) and it has been found that both values are positive. The dependence of $S_\mathrm{int}$ on the concentration of propanol does not show a simple linear relationship.},
  creationdate = {2023-09-21T00:00:00},
  doi          = {10.1107/S0021889897001398},
  file         = {:Shimizu1997 - Studies on Interaction Parameters of Poly(N Isopropylacrylamide) in 1 Propanol Water Mixtures by Small Angle X Ray Scattering.pdf:PDF},
  keywords     = {pNIPAM, cononsolvency, 1-propanol, aqueous alcohol, x-ray},
  url          = {https://doi.org/10.1107/S0021889897001398},
}

@Article{Kita2004,
  author       = {Kita, Rio and Kircher, Gunnar and Wiegand, Simone},
  journal      = {The Journal of Chemical Physics},
  title        = {{Thermally induced sign change of Soret coefficient for dilute and semidilute solutions of poly(N-isopropylacrylamide) in ethanol}},
  year         = {2004},
  issn         = {0021-9606},
  month        = oct,
  number       = {18},
  pages        = {9140--9146},
  volume       = {121},
  abstract     = {{We studied the thermal diffusion behavior of poly(N-isopropylacrylamide) (PNiPAM) in ethanol in a temperature range from T=14.0 °C to T=40.0 °C by means of thermal diffusion forced Rayleigh scattering. The obtained Soret coefficient ST of PNiPAM was positive for lower temperatures (T\\&lt;34 °C), while ST showed a negative value for higher temperatures (T\\&gt;34 °C). This means PNiPAM molecules move to the cold side for temperatures T\\&lt;34 °C, whereas they move to the warm side for T\\&gt;34 °C. This is the first nonaqueous polymeric system for which a sign change with temperature has been observed. We performed static and dynamic light scattering experiments in the same temperature range. The second virial coefficient determined from dilute solutions by static light scattering (SLS) was positive in the comparable temperature range. The results of SLS for the semidilute solution showed a strong repulsion among PNiPAM chains which was enhanced by increasing temperature. These results imply that the observed thermally induced sign change of ST does not depend on the intermolecular interactions among PNiPAM chains.}},
  creationdate = {2023-09-21T00:00:00},
  doi          = {10.1063/1.1803535},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/121/18/9140/10860660/9140\_1\_online.pdf},
  file         = {:Kita2004 - Thermally Induced Sign Change of Soret Coefficient for Dilute and Semidilute Solutions of Poly(N Isopropylacrylamide) in Ethanol.pdf:PDF},
  keywords     = {soret coefficient, pNIPAM, theory, light scattering, DLS, SLS, Rayleigh scattering, second virial coefficient},
  url          = {https://doi.org/10.1063/1.1803535},
}

@Article{Lele1997,
  author       = {Lele, A. K. and Hirve, M. M. and Badiger, M. V. and Mashelkar, R. A.},
  journal      = {Macromolecules},
  title        = {Predictions of Bound Water Content in Poly(N-isopropylacrylamide) Gel},
  year         = {1997},
  number       = {1},
  pages        = {157--159},
  volume       = {30},
  abstract     = {Water exists in two distinctly different physical states in a cross-linked hydrophilic polymeric gel. In the swollen state of the gel, most of the water is in a {\textquotedblleft}free{\textquotedblright} state and can freeze at the usual freezing point. However, some water molecules which are associated with the polymeric chains of the gel network cannot freeze at the usual freezing point. This water is called {\textquotedblleft}bound water{\textquotedblright}. It is essential to know the extent of free and bound water content (BWC) since they give useful physical insight into the mechanism of water transport within the system. For example, in the purification of water using polymeric membranes by reverse osmosis, the permeability of the membrane depends on the relative population of bound and free water fractions.1 The activity of biological systems such as proteins and enzymes depends upon how the water associates with these biomolecules in bringing out specific conformations, which in turn is dictated by the bound water fraction.2 It is reported that although the bulk water is not crucial for enzymatic hydration, the tightly bound structural water plays an important role in enzymatic catalysis.3,4 Equally importantly, the knowledge of BWC is vital in applications involved with controlling drug delivery and also controlling enzyme activity in gels.5 Recently, we have developed an extended lattice-fluid hydrogen-bond (LFHB) theory7 to predict the thermoreversible discontinuous volume phase transitions of poly(N-isopropylacrylamide) gel (PNIPAm) in water. In the present work, we show that the theory can also quantitatively predict the BWC in the PNIPAm gel throughout the volume transition. Our predictions are compared with the experimental data of Dong and Hoffman.6 We also show that the onset of free water is clearly demonstrated from 1H static line width NMR measurement on PNIPAm gel.},
  creationdate = {2022-07-07T00:00:00},
  doi          = {10.1021/ma950894l},
  eprint       = {https://doi.org/10.1021/ma950894l},
  file         = {:Lele1997 - Predictions of Bound Water Content in Poly(N Isopropylacrylamide) Gel.pdf:PDF},
  keywords     = {theory, bound water content, hydration number, hydrogen bonding, pNIPAM, thermoresponsive, LCST, hydrogel},
  url          = {https://doi.org/10.1021/ma950894l},
}

@Article{Cors2019,
  author         = {Cors, Marian and Wiehemeier, Lars and Oberdisse, Julian and Hellweg, Thomas},
  journal        = {Polymers},
  title          = {Deuteration-Induced Volume Phase Transition Temperature Shift of PNIPMAM Microgels},
  year           = {2019},
  issn           = {2073-4360},
  number         = {4},
  volume         = {11},
  abstract       = {The effect of deuteration on the volume phase transition (VPT) temperature of poly (N-isopropylmethacrylamide) (pNIPMAM) microgels in aqueous suspension is determined via IR spectroscopy and size measurements by photon correlation spectroscopy (PCS). We study the effect of a hydrogenated and a deuterated solvent (H2O/D2O), and of the hydrogenated and (partially) deuterated monomer. Deuteration of the monomer or copolymerization with deuterated monomers shifts the volume phase transition temperature (VPTT) by up to 8.4 K to higher temperatures, in good agreement with known results for pNIPAM microgels. Moreover, the shape of the swelling curve is found to depend on deuteration, with the highest deuteration leading to the sharpest VPT. Finally, the quantitative agreement between FTIR spectroscopy and PCS evidences the spatial homogeneity of the microgel particles. Our results are rationalized in terms of the effect of deuteration on hydrogen bonding. They shall be of primary importance for any experimental measurements close to the VPT involving isotopic substitution, and in particular contrast variation small angle neutron scattering.},
  article-number = {620},
  creationdate   = {2023-09-19T00:00:00},
  doi            = {10.3390/polym11040620},
  file           = {:Cors2019 - Deuteration Induced Volume Phase Transition Temperature Shift of PNIPMAM Microgels.pdf:PDF},
  keywords       = {pNIPMAM, microgel, isotope effect, infrared, photon correlation spectroscopy, IR, PCS, neutron scattering, contrast variation},
  pubmedid       = {30960604},
  url            = {https://www.mdpi.com/2073-4360/11/4/620},
}

@Article{Eggenberger1993,
  author       = {Rolf Eggenberger and Stefan Gerber and Hanspeter Huber and Debra Searles and Marc Welker},
  journal      = {Molecular Physics},
  title        = {The use of molecular dynamics simulations with ab initio SCF calculations for the determination of the oxygen-17 quadrupole coupling constant in liquid water},
  year         = {1993},
  number       = {5},
  pages        = {1177--1182},
  volume       = {80},
  abstract     = {Molecular dynamics simulations for H2 17O were performed with two different potentials from the literature. After equilibration, snapshots were taken at intervals and the configurations thereby obtained used to randomly select clusters of molecules. For the central oxygen of these clusters the electric field gradient was then calculated with standard ab initio self-consistent field (SCF) calculations. The field gradients were converted to quadrupole couplings with a factor obtained previously in gas phase calculations and averaged to obtain the 17O coupling in liquid water. At 300 K a best estimate of 8·9 ± 0·3 MHz for the coupling constant and 0·72 ± 0·04 for η were found. The coupling constant at 360 K is about 0·1 MHz larger but the temperature dependence is not significant.},
  creationdate = {2022-02-21T00:00:00},
  doi          = {10.1080/00268979300102961},
  eprint       = {https://doi.org/10.1080/00268979300102961},
  file         = {:Eggenberger1993 - The Use of Molecular Dynamics Simulations with Ab Initio SCF Calculations for the Determination of the Oxygen 17 Quadrupole Coupling Constant in Liquid Water.pdf:PDF},
  keywords     = {simulation, 17o, coupling constant},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/00268979300102961},
}

@Article{Mizuno2000,
  author       = {Kazuko Mizuno and Yuki Kimura and Hitomi Morichika and Yukari Nishimura and Shinji Shimada and Shiro Maeda and Shingo Imafuji and Torayuki Ochi},
  journal      = {Journal of Molecular Liquids},
  title        = {Hydrophobic hydration of tert-butyl alcohol probed by NMR and IR},
  year         = {2000},
  issn         = {0167-7322},
  note         = {Physics of Liquids - Foundation, Highlights, Challenges},
  number       = {1},
  pages        = {139--152},
  volume       = {85},
  abstract     = {The hydrophobic hydration in aqueous tert-butyl alcohol(TBA) mixtures was studied by examining the concentration and the temperature dependences of 1H and 13C chemical shifts in NMR, together with the concentration dependence of the frequency for the CH stretching vibration band, νCH. The chemical shifts were measured with the external double reference method, with which the bulk volume magnetic susceptibility for every sample mixture was also obtained to be used for the correction of the chemical shifts in situ. The polarization of the water molecules in the mixture probed by the 1H chemical shift, ∗δH2O, varies with concentration; δH2O increases at 23.3°C from 3.5 ppm in the TBA-rich region to the value for pure water at the mole fraction of water χW=0.84 and reaches to the maximum at χW=0.95. In the region of 0.84<χW<1.0, δH2O is larger than that for pure water, indicating clearly the presence of highly polarized or strongly hydrogen-bonding water molecules compared with pure water. The νCH also continues to increase with increasing χW from 2973.6cm−1 for pure TBA gently up to χW=0.84 and then steeply up to χW=0.95 to reach 2980.3cm−1, then remains constant up to the measurable concentration limit, χW=0.99. The polarization of TBA molecule was also found to increase in the same way as νCH. These results not only indicate the formation of associated complexes of TBA with water molecules, but also confirm the formation of polyhedron or cluster so far presented for mixing state in water-rich region. In addition to this the results show that the hydration of CH groups occurs through a kind of dispersion interaction between CH group and water oxygen, in which contraction of the CH bond occurs as demonstrated by the blueshifts of the CH stretching vibration band. The new mechanism of CH hydration, termed “push ball” hydration, is proposed.},
  creationdate = {2022-05-19T00:00:00},
  doi          = {https://doi.org/10.1016/S0167-7322(99)00170-1},
  file         = {:Mizuno2000 - Hydrophobic Hydration of Tert Butyl Alcohol Probed by NMR and IR.pdf:PDF},
  keywords     = {NMR, susceptibility, chemical shift, aqueous alcohol, 1H-NMR, 13C-NMR, concentration dependence, hydrophobic hydration, hydrophobic hydration OR hydration shell, hydrophobic hydration OR hydration shell OR hydration water, hydrophobic hydration OR hydration shell OR hydration water OR clathrate, hydrophobic hydration OR hydration shell OR hydration water OR clathrate OR pNIPAM},
  url          = {https://www.sciencedirect.com/science/article/pii/S0167732299001701},
}

@Article{Nishizawa2021,
  author       = {Nishizawa, Yuichiro and Minato, Haruka and Inui, Takumi and Saito, Ikuma and Kureha, Takuma and Shibayama, Mitsuhiro and Uchihashi, Takayuki and Suzuki, Daisuke},
  journal      = {RSC Adv.},
  title        = {Nanostructure and thermoresponsiveness of poly(N-isopropyl methacrylamide)-based hydrogel microspheres prepared via aqueous free radical precipitation polymerization},
  year         = {2021},
  pages        = {13130--13137},
  volume       = {11},
  abstract     = {Thermoresponsive hydrogel microspheres (microgels) are smart materials that quickly respond to external stimuli{,} and their thermoresponsiveness can be tuned by varying the constituent chemical species. Although uniformly sized microgels can be prepared via aqueous free radical precipitation polymerization{,} the nanostructure of the obtained microgels is complex and remains unclear so far. In the present study{,} the nanostructure and thermoresponsiveness of poly(N-isopropyl methacrylamide) (pNIPMAm)-based microgels{,} which have a volume-transition temperature of ∼43 °C{,} were evaluated mainly using temperature-controllable high-speed atomic force microscopy. These observations{,} which are characterized by high spatio-temporal resolution{,} revealed that the pNIPMAm microgels have a peculiar heterogeneous structure{,} for example a core–shell and non-thermoresponsive nanostructure in the core region{,} that originates from the precipitation polymerization process. Furthermore{,} it was found that the adsorption concentration of the microgels on the substrate is one of the keys for controlling their thermoresponsiveness. These findings can be expected to advance the design of new materials such as thermoresponsive nanosheets and stimuli-responsive coatings.},
  creationdate = {2023-09-21T00:00:00},
  doi          = {10.1039/D1RA01650D},
  file         = {:Nishizawa2021 - Nanostructure and Thermoresponsiveness of Poly(N Isopropyl Methacrylamide) Based Hydrogel Microspheres Prepared Via Aqueous Free Radical Precipitation Polymerization.pdf:PDF},
  issue        = {22},
  keywords     = {pNIPAM-alternative, pNIPMAM, microgel, thermoresponsive, AFM},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D1RA01650D},
}

@Article{Henschel2023,
  author       = {Cristiane Henschel and Dirk Schanzenbach and André Laschewsky and Chia-Hsin Ko and Christine M. Papadakis and Peter Müller-Buschbaum},
  journal      = {Colloid and Polymer Science},
  title        = {Thermoresponsive and co‐nonsolvency behavior of poly(N‐vinylisobutyramide) and poly(N‐isopropyl methacrylamide)as poly(N‐isopropyl acrylamide) analogs in aqueous media},
  year         = {2023},
  pages        = {703--720},
  volume       = {301},
  creationdate = {2023-09-21T00:00:00},
  doi          = {https://doi.org/10.1007/s00396-023-05083-4},
  file         = {:Henschel2023 - Thermoresponsive and Co‐nonsolvency Behavior of Poly(N‐vinylisobutyramide) and Poly(N‐isopropyl Methacrylamide)as Poly(N‐isopropyl Acrylamide) Analogs in Aqueous Media.pdf:PDF},
  keywords     = {pNIPAM, pNIPAM-alternatives, PNVIBAm, PNIPMAM, LCST, thermoresponsive, cononsolvency, aqueous alcohol, methanol, ethanol, iso-propanol, n-propanol, cloud point, DMF, DMSO, acetone, dioxane, THF, hysteresis},
  url          = {https://doi.org/10.1007/s00396-023-05083-4},
}

@Article{Dybal2009,
  author       = {Jiří Dybal and Miroslava Trchová and Pavel Schmidt},
  journal      = {Vibrational Spectroscopy},
  title        = {The role of water in structural changes of poly(N-isopropylacrylamide) and poly(N-isopropylmethacrylamide) studied by FTIR, Raman spectroscopy and quantum chemical calculations},
  year         = {2009},
  issn         = {0924-2031},
  note         = {RECENT PROGRESS IN VIBRATIONAL SPECTROSCOPY},
  number       = {1},
  pages        = {44--51},
  volume       = {51},
  abstract     = {Temperature-induced phase transition in water solutions of poly(N-isopropylacrylamide) (PNIPAM) and poly(N-isopropylmethacrylamide) (PNIPMAM) have been studied by ATR FTIR and Raman spectroscopy in combination with quantum chemical calculations. The presence or absence of the α-methyl group has a strong effect on the physical structure of water solutions. Although the hydrophobic interactions for PNIPMAM and PNIPAM are very similar, PNIPMAM with additional methyl group exhibits significantly weaker intermolecular interactions between the amide groups. That effect is the cause of the higher transition temperature Tt by about 8°C for PNIPMAM compared to PNIPAM due to the formation of larger compact structures. The presence of the methyl group is significant for the reversibility of the temperature transition during the backward cooling as the dissolution of more stable compact PNIPMAM requires overcoming of a higher energy barrier and shows a strong hysteresis.},
  creationdate = {2023-09-21T00:00:00},
  doi          = {https://doi.org/10.1016/j.vibspec.2008.10.003},
  file         = {:Dybal2009 - The Role of Water in Structural Changes of Poly(N Isopropylacrylamide) and Poly(N Isopropylmethacrylamide) Studied by FTIR, Raman Spectroscopy and Quantum Chemical Calculations.pdf:PDF},
  keywords     = {Poly(N-isopropylacrylamide), PNIPAM, Poly(N-isopropylmethacrylamide), pNIPMAM, pNIPAM-alternative, FTIR, infrared, light scattering, Raman spectroscopy, Phase transition, DFT, theory, calculations, hysteresis},
  url          = {https://www.sciencedirect.com/science/article/pii/S0924203108001720},
}

@Article{Juurinen2014,
  author       = {Juurinen, Iina and Galambosi, Szabolcs and Anghelescu-Hakala, Adina G. and Koskelo, Jaakko and Honkimäki, Veijo and Hämäläinen, Keijo and Huotari, Simo and Hakala, Mikko},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Molecular-Level Changes of Aqueous Poly(N-isopropylacrylamide) in Phase Transition},
  year         = {2014},
  note         = {PMID: 24786724},
  number       = {20},
  pages        = {5518--5523},
  volume       = {118},
  abstract     = {We report a Compton scattering study on the molecular-level structural changes of aqueous poly(N-isopropylacrylamide) (PNIPAM) across the conformational phase transition. PNIPAM is a thermoresponsive polymer that changes its conformation in water from the hydrophilic coil state to the collapsed hydrophobic globule state at 32 °C. Combined with density functional theory calculations, the Compton scattering experiments detect two type of changes in the phase transition. The amount of hydrogen bonds is found to reduce, and an elongation of the internal covalent bond lengths is observed. The elongation of the bonds indicates that not only the hydrogen bonding changes but there are other processes, most likely related to hydrophobic interaction, that should be taken into account in the phase transition.},
  creationdate = {2023-09-21T00:00:00},
  doi          = {10.1021/jp501913p},
  eprint       = {https://doi.org/10.1021/jp501913p},
  file         = {:Juurinen2014 - Molecular Level Changes of Aqueous Poly(N Isopropylacrylamide) in Phase Transition.pdf:PDF},
  keywords     = {pNIPAM, LCST, thermoresponsive, density functional theory calculations, compton scattering, hydrogen bond, hydration number, hydrophobic hydration},
  url          = {https://doi.org/10.1021/jp501913p},
}

@Article{Pagonis2004,
  author       = {Konstantinos Pagonis and Georgios Bokias},
  journal      = {Polymer},
  title        = {Upper critical solution temperature—type cononsolvency of poly(N,N-dimethylacrylamide) in water—organic solvent mixtures},
  year         = {2004},
  issn         = {0032-3861},
  number       = {7},
  pages        = {2149--2153},
  volume       = {45},
  abstract     = {The behaviour of linear poly(N,N-dimethylacrylamide) (PDMAM) chains was studied by turbidimetry and viscometry in mixtures of water with the polar organic solvents methanol, dioxane and acetone. The swelling–deswelling behaviour of PDMAM gels in the same solvent mixtures was also investigated. Contrary to the behaviour in water–methanol mixtures, in water–dioxane and water–acetone mixtures a significant shrinkage of polymer chains and deswelling of polymer gels, followed by phase separation, was observed for high organic solvent fractions. Cononsolvency phenomena were found to be temperature-dependent, as demixing occurred upon decreasing temperature. This upper critical solution temperature (UCST) phase separation behaviour in mixed solvents was studied by turbidimetry and compared to the well-known lower critical solution temperature (LCST) behaviour of poly(N-isopropylacrylamide) (PNIPAM) in similar solvents mixtures.},
  creationdate = {2023-09-21T00:00:00},
  doi          = {https://doi.org/10.1016/j.polymer.2004.01.063},
  file         = {:Pagonis2004 - Upper Critical Solution Temperature—type Cononsolvency of Poly(N,N Dimethylacrylamide) in Water—organic Solvent Mixtures.pdf:PDF},
  keywords     = {Poly(,-dimethylacrylamide), PDMAM, Cononsolvency, Upper critical solution temperature, UCST, aqueous alcohol, methanol, dioxane, acetone},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386104001193},
}

@Article{Chee2001,
  author       = {C.K Chee and S Rimmer and I Soutar and L Swanson},
  journal      = {Polymer},
  title        = {Fluorescence investigations of the thermally induced conformational transition of poly(N-isopropylacrylamide)},
  year         = {2001},
  issn         = {0032-3861},
  number       = {12},
  pages        = {5079--5087},
  volume       = {42},
  abstract     = {Poly(N-isopropylacrylamide), PNIPAM, undergoes phase separation, upon heating under semi-dilute conditions, at 32°C, the lower critical solution temperature (LCST). Upon subsequent cooling, the dispersion rapidly clears again, at the LCST, to form a single, homogeneous phase. In this paper we report that fluorescence techniques, including quenching and time-resolved anisotropy measurements (TRAMS) on ultra-dilute (10−3wt%) aqueous solutions of an acenaphthylene labelled sample, provide conclusive evidence that a coil collapse mechanism is implicated in the thermoreversible behaviour: the polymer undergoes a conformational switch from an open coil below 32°C to a compact, globular structure above the LCST. TRAMS reveal that a marked reduction in the segmental mobility of the polymer occurs at the onset of the LCST. In addition, a dramatic change in the accessibility of the label to aqueous-borne quenchers is also apparent at temperatures in excess of 32°C. PNIPAM is capable of solubilising low molar mass species in its compact form: changes in the vibrational fine structure of the emission spectrum of pyrene have been used to monitor uptake and release of the probe. Excited state lifetime measurements have also proven to be sensitive monitors of the conformational switch of PNIPAM: at temperatures greater than 32°C, τ increases to ca. 160ns which is indicative of pyrene sequestered in a hydrophobic, protective environment. Release of the probe into the aqueous phase results in a dramatic reduction of τ to ca. 130ns which is characteristic of pyrene dispersed in water. These data highlight the potential of NIPAM based polymers to act as carriers in controlled release applications. Fluorescence techniques have proved capable of monitoring changes in chain mobility, the degree of coil compaction and solubilization capacity (for organic guests) of PNIPAM as it is raised through its LCST. Information of this type is not readily obtained through other techniques and fluorescence approaches should prove invaluable in future investigations of the effects of chemical modification in attempts to manipulate the LCST of NIPAM-based systems.},
  creationdate = {2023-09-21T00:00:00},
  doi          = {https://doi.org/10.1016/S0032-3861(00)00821-1},
  file         = {:Chee2001 - Fluorescence Investigations of the Thermally Induced Conformational Transition of Poly(N Isopropylacrylamide).pdf:PDF},
  keywords     = {Poly(N-isopropylacrylamide), pNIPAM, Fluorescence, Conformational transition, segmental relaxation, chain dynamics},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386100008211},
}

@Article{Oliveira2018,
  author       = {de Oliveira, Tiago E. and Marques, Carlos M. and Netz, Paulo A.},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Molecular dynamics study of the LCST transition in aqueous poly(N-n-propylacrylamide)},
  year         = {2018},
  pages        = {10100--10107},
  volume       = {20},
  abstract     = {The breadth of technological applications of smart polymers relies on the possibility of tuning their molecular structure to respond to external stimuli. In this context{,} N-substituted acrylamide-based polymers are widely studied thermoresponsive polymers. Poly(N-n-propylacrylamide) (PNnPAm){,} which is a structural isomer of the poly(N-isopropylacrylamide) (PNIPAm) exhibits however{,} a lower phase transition in aqueous solution. In this work{,} we use all-atom molecular dynamics simulations of PNnPAm in aqueous solutions to study{,} from a microscopic point-of-view{,} the influence of chain size and concentration on the LCST of PNnPAm. Our analysis shows that the collapse of a single oligomer of PNnPAm upon heating is dependent on the chain length and corresponds to a complex interplay between hydration and intermolecular interactions. Analysis of systems with multiple chains shows an aggregation of PNnPAm chains above the LCST.},
  creationdate = {2023-09-21T00:00:00},
  doi          = {10.1039/C8CP00481A},
  file         = {:Oliveira2018 - Molecular Dynamics Study of the LCST Transition in Aqueous Poly(N N Propylacrylamide).pdf:PDF},
  issue        = {15},
  keywords     = {pNIPAM-alternative, pNnPAM, LCST, molecular dynamics simulation},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C8CP00481A},
}

@Article{Graziano2000,
  author       = {Giuseppe Graziano},
  journal      = {International Journal of Biological Macromolecules},
  title        = {On the temperature-induced coil to globule transition of poly-N-isopropylacrylamide in dilute aqueous solutions},
  year         = {2000},
  issn         = {0141-8130},
  number       = {1},
  pages        = {89--97},
  volume       = {27},
  abstract     = {Poly-N-isopropylacrylamide (PNIPAM) is a chemical isomer of poly-leucine, having the polar peptide group in the side-chain rather than in the backbone. It has been demonstrated experimentally that PNIPAM dissolved in aqueous solution undergoes a collapse transition from coil to globule on increasing temperature above the θ-point. By a careful reviewing of existing experimental data, we emphasize that such coil to globule collapse has to be considered an intramolecular first-order transition, analogous to the cold renaturation of small globular proteins. The main theoretical approaches to the coil to globule collapse in homopolymers are discussed briefly, and a critical comparison between the existing models is performed. We point out that, as a general result, the coil to globule collapse is expected to be a first-order transition for rigid and semi-rigid macromolecules. Finally, taking advantage of the analogy between the coil to globule collapse of PNIPAM and the cold renaturation of small globular proteins, we try to clarify some important and intriguing aspects of protein thermodynamics. This leads to the conclusion that the amphiphilic nature of polypeptide chain plays the fundamental role for the existence of two temperature-induced conformational transitions.},
  creationdate = {2023-09-21T00:00:00},
  doi          = {https://doi.org/10.1016/S0141-8130(99)00122-1},
  file         = {:Graziano2000 - On the Temperature Induced Coil to Globule Transition of Poly N Isopropylacrylamide in Dilute Aqueous Solutions.pdf:PDF},
  keywords     = {Coil to globule collapse, Cold renaturation, Conformational stability, Amphiphilicity, protein, polypeptide, pNIPAM, thermoresponsive, review},
  url          = {https://www.sciencedirect.com/science/article/pii/S0141813099001221},
}

@Article{Biswas2011,
  author       = {Biswas, Chandra Sekhar and Patel, Vijay Kumar and Vishwakarma, Niraj Kumar and Tiwari, Vimal K. and Maiti, Biswajit and Maiti, Pralay and Kamigaito, Masami and Okamoto, Yoshio and Ray, Biswajit},
  journal      = {Macromolecules},
  title        = {Effects of Tacticity and Molecular Weight of Poly(N-isopropylacrylamide) on Its Glass Transition Temperature},
  year         = {2011},
  number       = {14},
  pages        = {5822--5824},
  volume       = {44},
  abstract     = {A series of high molecular weight poly(N-isopropylacrylamide) (PNIPAM)s with low polydispersity (Mn = 7.0 × 104 to 10.2× 104 g mol–1, PDI = 1.23–1.35) having different isotacticity [meso diad (m) = 47–88\%]] was successfully synthesized using the reversible addition–fragmentation chain transfer (RAFT) polymerization method in the presence of different concentrations of Y(OTf)3 Lewis acid. Measurement of the glass transition temperature (Tg) of this high molecular weight isotactic PNIPAM series and the low molecular weight PNIPAM series (Mn = 3.5 × 104 to 4.0 × 104 g mol–1, PDI = 1.2–1.3) having different isotacticity [meso diad (m) = 45–72\%)] reported earlier by us (Ray et al. Polym. J. 2005, 37, 234) showed that Tg of PNIPAM decreases with increase in its meso diad content (m \%) and decrease in its molecular weight.},
  creationdate = {2023-09-22T00:00:00},
  doi          = {10.1021/ma200735k},
  eprint       = {https://doi.org/10.1021/ma200735k},
  file         = {:Biswas2011 - Effects of Tacticity and Molecular Weight of Poly(N Isopropylacrylamide) on Its Glass Transition Temperature.pdf:PDF;:EffectsOfTacticityAndMolecularWeightOfPolyNIsopropylacrylamideOnItsGlassTransitionTemperature_BiswasEtAl_Macromol2011_SI.pdf:PDF},
  keywords     = {pNIPAM, glass transition, tacticity, chain length, molecular weight, dsc},
  url          = {https://doi.org/10.1021/ma200735k},
}

@PhdThesis{MichalskaWalkowiak2022,
  author       = {Michalska-Walkowiak, Joanna},
  school       = {Universit{\"a}tsbibliothek der RWTH Aachen},
  title        = {Swelling and Association Kinetics of Linear PNIPAM-based Polymers at the Phase Transition},
  year         = {2022},
  creationdate = {2023-09-22T00:00:00},
  file         = {:michalska2022swelling - Swelling and Association Kinetics of Linear PNIPAM Based Polymers at the Phase Transition.pdf:PDF},
}

@Article{Radecki2015,
  author       = {Marek Radecki and Jiří Spěváček and Alexander Zhigunov and Zdeňka Sedláková and Lenka Hanyková},
  journal      = {European Polymer Journal},
  title        = {Temperature-induced phase transition in hydrogels of interpenetrating networks of poly(N-isopropylacrylamide) and polyacrylamide},
  year         = {2015},
  issn         = {0014-3057},
  pages        = {68--79},
  volume       = {68},
  abstract     = {Collapse transition in hydrogels of interpenetrating polymer networks (IPNs) of thermoresponsive poly(N-isopropylacrylamide) (PNIPAm) and hydrophilic polyacrylamide (PAAm) was studied by a combination of NMR spectroscopy, small-angle neutron scattering (SANS) and DSC. The influence of IPNs composition and preparation on the phase transition was examined with respect to possible application of these responsive materials for drug delivery and molecular separation. Heterogeneous nature and an existence of compact globular structures with gyration radius ∼20nm was revealed in all investigated IPN hydrogels by SANS. The increasing content of PAAm component in IPNs shifts the transition toward higher temperatures and the fraction pmax of polymer units with significantly reduced mobility detected by NMR as well as the enthalpy change ΔH in DSC measurements are reduced. Reversed order of adding components during IPNs preparation also significantly affects parameters of the phase transition and collapsed structures. IPN PAAm/PNIPAm 42/58 shows substantially reduced ΔH values of the transition in comparison with IPNs PNIPAm/PAAm. A certain portion of water (HDO) bound in globular structures was established from measurements of 1H NMR spectra and spin–spin relaxation times T2 in all PNIPAm/PAAm collapsed hydrogels and in collapsed hydrogel of the neat PNIPAm, while bound water was not detected by NMR in PAAm/PNIPAm hydrogel. A slow exchange regime between bound and free water was revealed in most cases. T2 relaxation times of bound HDO are then up to one order of magnitude smaller in comparison with “free” HDO. Interestingly enough, the bound HDO appears already at temperatures when polymer segments just begin to form collapsed structures. The fraction of bound water slowly decreases with time.},
  creationdate = {2023-09-22T00:00:00},
  doi          = {10.1016/j.eurpolymj.2015.04.019},
  file         = {:Radecki2015 - Temperature Induced Phase Transition in Hydrogels of Interpenetrating Networks of Poly(N Isopropylacrylamide) and Polyacrylamide.pdf:PDF},
  keywords     = {Temperature induced volume phase transition,thermoresponsive,Interpenetrating polymer network,Poly(-isopropylacrylamide),PNIPAM,Polyacrylamide,PAM,Hydrogel,NMR,SANS,DSC,ageing},
  url          = {https://www.sciencedirect.com/science/article/pii/S0014305715002359},
}

@Article{Yu2004,
  author       = {T.Leon Yu and Wen-Chi Lu and Wen-Horng Liu and Hsiu-Li Lin and Chih-Hao Chiu},
  journal      = {Polymer},
  title        = {Solvents effect on the physical properties of semi-dilute poly(N-isopropyl acryl amide) solutions},
  year         = {2004},
  issn         = {0032-3861},
  number       = {16},
  pages        = {5579--5589},
  volume       = {45},
  abstract     = {The physical properties of 5wt% poly(NIPAM) (Mv=3.22×105) semi-dilute solutions in H2O, D2O, and THF (tetrahydrofuran) solvents were studied using dynamic light scattering (DLS) and dynamic shear viscosity (DSV) measurements. The DLS data showed that there were poly(NIPAM) slow mode inter-polymer chains associations in H2O and D2O solvents. However, no DLS slow mode was observed in poly(NIPAM)/THF solutions. The DSV data showed that there are shear thickening behavior in these three poly(NIPAM) solutions, resulting in a maximum shear viscosity ηpeak in the viscosity η′(ω) versus shear frequency ω curve. The slow mode hydrodynamic radius 〈Rhs〉 of DLS measurements and the zero shear rate viscosity η0 and maximum viscosity ηpeak data of DSV measurements from poly(NIPAM)/H2O and poly(NIPAM)/D2O solutions show two critical transition temperatures with Tcr1=30–32°C and Tcr2=32–34°C. Poly(NIPASM)/D2O has higher Tcr1 and Tcr2 than poly(NIPASM)/H2O. However, no transition temperatures of poly(NIPAM)/THF solution were observed. The different temperature dependencies of these three solutions were attributed to the ‘solubility’ and ‘hydrogen bonding’ effects between poly(NIPAM) with H2O, D2O, and THF solvents. Without considering the polymer-solvent hydrogen bonding, the solubility of poly(NIPAM) in solvents decreases in the following sequence: THF>H2O>D2O and the degree of polymer-solvent hydrogen bonding increases in the following sequence: THF<H2O<D2O. The effects of the degree of ‘hydrogen bonding’ and the ‘solubility’ of polymer in solvents on the physical properties of poly(NIPAM) solutions are discussed.},
  creationdate = {2023-09-22T00:00:00},
  doi          = {https://doi.org/10.1016/j.polymer.2004.05.074},
  file         = {:YU20045579 - Solvents Effect on the Physical Properties of Semi Dilute Poly(N Isopropyl Acryl Amide) Solutions.pdf:PDF},
  keywords     = {Poly(N-isopropylacrylamide) solution, pNIPAM, concentration, semi-dilute, Dynamic light scattering, DLS, Dynamic shear viscosity, rheology, h2o, d2o, isotope-effect, thf},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386104005725},
}

@Article{Roget2022,
  author       = {Roget, Sean A. and Carter-Fenk, Kimberly A. and Fayer, Michael D.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Water Dynamics in Aqueous Poly-N-Isopropylacrylamide Below and Through the Lower Critical Solution Temperature},
  year         = {2022},
  note         = {PMID: 36067498},
  number       = {36},
  pages        = {7066--7075},
  volume       = {126},
  abstract     = {Poly-N-isopropylacrylamide (PNIPAM) is a thermo-responsive polymer that exhibits a reversible structural change from extended chains to aggregates in aqueous solution above its lower critical solution temperature (LCST). Using polarization-selective IR pump–probe spectroscopy, the water orientational dynamics in PNIPAM from below to above the LCST were examined and compared to those of its monomer solution, N-isopropylacrylamide (NIPAM), polyacrylamide, and an acrylamide monomer solution, which are not thermo-responsive. The OD stretch of dilute HOD in H2O is used as a vibrational probe of water orientational dynamics. Below the LCST of the polymer, NIPAM and PNIPAM solutions exhibited identical water dynamics that were significantly different from those of bulk water, containing both faster and slower components due to solute–water interactions. Therefore, there is no difference in the nature of water interactions with a single NIPAM moiety and a long polymer chain. For all systems, including PNIPAM below and above the LCST, the orientational dynamics were modeled with a bulk water component and a polymer/monomer-associated component based on previous experimental and computational findings. Above the LCST, PNIPAM showed fast water orientational relaxation but much slower long-time dynamics compared to those of NIPAM. The slow component in PNIPAM, which was too slow to be accurately measured due to the limited OD vibrational lifetime, is ascribed to water confined in small voids (<2 nm in diameter) of PNIPAM globules. These results highlight important details about thermo-responsive polymers and the dynamics of their solvation water as they undergo a significant structural change.},
  creationdate = {2023-09-22T00:00:00},
  doi          = {10.1021/acs.jpcb.2c05506},
  eprint       = {https://doi.org/10.1021/acs.jpcb.2c05506},
  file         = {:Roget2022 - Water Dynamics in Aqueous Poly N Isopropylacrylamide below and through the Lower Critical Solution Temperature.pdf:PDF;:WaterDynamicsInAqueousPolyNIsopropylAcrylamideBelowAndThroughTheLowerCriticalSolutionTemperature_RogetEtAl_JPC2022_SI.pdf:PDF},
  keywords     = {pNIPAM,buried water,LCST,Infrared,Polyacrylamide,PAA,NIPAM,acrylamide,monomer},
  url          = {https://doi.org/10.1021/acs.jpcb.2c05506},
}

@Article{Tsuboi2009,
  author       = {Yasuyuki Tsuboi and Yasuhiro Yoshida and Noboru Kitamura and Kaoru Iwai},
  journal      = {Chemical Physics Letters},
  title        = {Phase transition dynamics of fluorescent-labeled poly(N-isopropylacrylamide) in aqueous solution as revealed by time-resolved spectroscopy combined with a laser T-jump technique},
  year         = {2009},
  issn         = {0009-2614},
  number       = {1},
  pages        = {42--45},
  volume       = {468},
  abstract     = {In order to clarify the dynamics of phase transition from coiled states to globular states in a thermo-responsive polymer, poly(N-isopropylacrylamide) (PNIPAM), we developed a method of dynamic (time-resolved) fluorescence spectroscopy combined with a laser T-jump technique. Using this, we revealed the phase transition dynamics of fluorescent-labeled PNIPAM in aqueous solutions. The phase transition dynamics was reflected in a dynamic Stokes shift of a TICT fluorescence of the probe. The time constant of the phase transition (τ) was determined to be 35μs, irrespective of the sample concentration studied (0.1–1.0wt.%), and this was longer than that predicted from the diffusion–collision model.},
  creationdate = {2023-09-22T00:00:00},
  doi          = {https://doi.org/10.1016/j.cplett.2008.12.003},
  file         = {:Tsuboi2009 - Phase Transition Dynamics of Fluorescent Labeled Poly(N Isopropylacrylamide) in Aqueous Solution As Revealed by Time Resolved Spectroscopy Combined with a Laser T Jump Technique.pdf:PDF},
  keywords     = {pNIPAM, LCST, temperature-jump, transition kinetics, fluorescence, dynamic stokes shift, concentration-dependence},
  url          = {https://www.sciencedirect.com/science/article/pii/S000926140801628X},
}

@Article{Binkert1991,
  author       = {Binkert, T. and Oberreich, J. and Meewes, M. and Nyffenegger, R. and Ricka, J.},
  journal      = {Macromolecules},
  title        = {Coil-globule transition of poly(N-isopropylacrylamide): a study of segment mobility by fluorescence depolarization},
  year         = {1991},
  number       = {21},
  pages        = {5806--5810},
  volume       = {24},
  abstract     = {Time-resolved measurements of fluorescence polarization anisotropy were used to monitor the "freezing" of local motions due to the temperature-induced conformational transition of poly(N-isopropyl-acrylamide) in aqueous solutions. The label dye dansyl was covalently bound to polymers containing aminostyrene which were synthesized by radical polymerization. The reorientational relaxation of the labels is anisotropic and can be resolved into two components. These two relaxation modes are interpreted in terms of a simple model as (i) rotations of the label around a free axis (this mode is sensitive to microviscosity) and (ii) polymer-coupled reorientations reflecting the chain flexibility. Both relaxation times diverge above a transition temperature of 31°C. Our findings confirm the pucture of a conformational transition from extended coils to a compact globular state of the polymer.},
  creationdate = {2023-09-22T00:00:00},
  doi          = {10.1021/ma00021a013},
  eprint       = {https://doi.org/10.1021/ma00021a013},
  file         = {:Binkert1991 - Coil Globule Transition of Poly(N Isopropylacrylamide)_ a Study of Segment Mobility by Fluorescence Depolarization.pdf:PDF},
  keywords     = {pNIPAM, fluorescence},
  url          = {https://doi.org/10.1021/ma00021a013},
}

@Article{Concilio2022,
  author       = {Concilio, Matilde and Beyer, Valentin P. and Becer, C. Remzi},
  journal      = {Polym. Chem.},
  title        = {Thermoresponsive polymers in non-aqueous solutions},
  year         = {2022},
  pages        = {6423--6474},
  volume       = {13},
  abstract     = {Thermoresponsive polymers are gaining increasing interest for numerous applications especially in the biomedical and nanotechnology fields. The thermoresponsive behaviour of polymers has been extensively studied in pure water or water/organic solvent systems{,} however{,} temperature-induced phase transitions in other organic solvents are less common. Polymers in organic solvents exhibit a broad range of temperature-driven solution behaviours{,} from LCST and UCST{,} to sol–gel transitions{,} to micellization processes{,} among others{,} with potential applications as smart materials in electronics{,} in the lubricant industry{,} and in the biomedical field. This review article will focus on the thermoresponsive behaviour of polymers in different classes of organic solvents and mixtures thereof to emphasize and demonstrate the versatility and potential of these polymers.},
  creationdate = {2023-09-22T00:00:00},
  doi          = {10.1039/D2PY01147F},
  file         = {:Concilio2022 - Thermoresponsive Polymers in Non Aqueous Solutions.pdf:PDF},
  issue        = {47},
  keywords     = {thermoresponsive, review, cononsolvency, LCST, pNIPAM, PDMAEMA, PiPOx, PVC},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D2PY01147F},
}

@Article{Yin2023,
  author       = {Yin, Fang and Laborie, Pascale and Lonetti, Barbara and Gineste, Stéphane and Coppel, Yannick and Lauth-de Viguerie, Nancy and Marty, Jean-Daniel},
  journal      = {Macromolecules},
  title        = {Dual Thermo- and pH-Responsive Block Copolymer of Poly(N-isopropylacrylamide)-block-Poly(N,N-diethylamino Ethyl Acrylamide): Synthesis, Characterization, Phase Transition, and Self-Assembly Behavior in Aqueous Solution},
  year         = {2023},
  number       = {10},
  pages        = {3703--3720},
  volume       = {56},
  abstract     = {Doubly thermo- and pH-responsive poly(N-isopropylacrylamide)-block-poly(N,N-diethylamino ethyl acrylamide) (PNIPAM-b-PDEAEAM) with different compositions were synthesized by reversible addition–fragmentation chain-transfer (RAFT) polymerization. The properties (solubility, self-assembly behavior) of these polymers and corresponding homopolymers in solution depend on the value of pH and the protonation degree of the diethylamino moiety. The effect of the nature of the polymer chain ends also appears to be critical to fully understand this behavior. At pH 10, both PNIPAM and PDEAEAM blocks are thermoresponsive and make a cooperative contribution to phase transition, and stable spherical nanoobjects are detected as temperature rises over transition point. At pH 4, PNIPAM-b-PDEAEAM with longer PDEAEAM length displays a two-step thermoresponsive behavior; upon heating, PNIPAM chains undergo shrinkage and subsequent reorganization causing the formation of large aggregates with a positively charged shell made of PDEAEAM block in its protonated state. The aggregation processes are also particularly sensitive to kinetic considerations, and therefore, measured size of aggregates depends strongly on the history of polymer solution.},
  creationdate = {2023-09-23T00:00:00},
  doi          = {10.1021/acs.macromol.3c00424},
  eprint       = {https://doi.org/10.1021/acs.macromol.3c00424},
  file         = {:Yin2023 - Dual Thermo and PH Responsive Block Copolymer of Poly(N Isopropylacrylamide) Block Poly(N,N Diethylamino Ethyl Acrylamide)_ Synthesis, Characterization, Phase Transition, and Self Assembly Behavior in Aqueous Solution.pdf:PDF;:DualThermoAndPHResponsiveBlockCopolymerOfPolyNIsopropylacrylamideBloackPolyNNDiethylaminoEthylAcrylamide-SynthesisCharacterizationPhaseTransitionAndSelfAssemblyBehaviorInAqueousSolution_YinEtAl_Macromol2023_SI.pdf:PDF},
  keywords     = {pNIPAM, pNIPAM-alternatives, PDMA, PDEAAM, PNNBAM, PDMAEMA, PDEAEMA, PEPyMA, PDPAEMA, PDEAEAM, PEPyAM, dual-responsive, thermoresponsive, pH-responsive, block-copolymer},
  url          = {https://doi.org/10.1021/acs.macromol.3c00424},
}

@Article{Kang2016,
  author       = {Kang, Yunwon and Joo, Heesun and Kim, Jun Soo},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Collapse–Swelling Transitions of a Thermoresponsive, Single Poly(N-isopropylacrylamide) Chain in Water},
  year         = {2016},
  note         = {PMID: 27976588},
  number       = {51},
  pages        = {13184--13192},
  volume       = {120},
  abstract     = {We present molecular dynamics (MD) simulations of a single poly(N-isopropylacrylamide) (PNIPAM) chain in explicit water at temperatures between 270 and 320 K near the lower critical solution temperature (LCST). The force-fields of OPLS-AA and TIP4P/2005 are used for a PNIPAM chain and water molecules, respectively. Three independent simulations with durations of 1 μs are performed at each temperature for a 30-mer PNIPAM chain starting with three distinct conformations: extended, loosely collapsed, and tightly collapsed states. The simulation trajectories exhibit reversible conformational transitions between swollen- and collapsed-chain conformations, which has rarely been reported in previous simulation studies, with the overall transition occurring at different temperatures depending on the initial conformation. The inconsistency of the transition temperatures depending on the initial conformation implies that, in spite of the simulation duration of 1 μs distinctly longer than that in previous simulation studies, the conformational sampling from the MD simulations is not enough to draw conclusions on equilibrium properties. Instead of evaluating average properties, therefore, the focus is on dynamic changes in the chain conformation during reversible collapse–swelling transitions at each temperature. The simulation trajectories are analyzed in terms of the radius of gyration, intrachain distances, hydrophobic contacts, and chain–water and intrachain hydrogen bonding. In particular, the formation of stable intrachain hydrogen bonds is a signature of the tightly collapsed-chain conformations that persist, once formed, for the entire simulation duration.},
  creationdate = {2023-09-23T00:00:00},
  doi          = {10.1021/acs.jpcb.6b09165},
  eprint       = {https://doi.org/10.1021/acs.jpcb.6b09165},
  file         = {:Kang2016 - Collapse–Swelling Transitions of a Thermoresponsive, Single Poly(N Isopropylacrylamide) Chain in Water.pdf:PDF;:CollapseSwellingTransitionsOfAThermoresponsiveSinglePolyNIsopropylacrylamideChainInWater_KangEtAl_JPC2016_SI.pdf:PDF},
  keywords     = {pNIPAM, molecular dynamics simulation, oligomer},
  url          = {https://doi.org/10.1021/acs.jpcb.6b09165},
}

@Article{Hammouda2015,
  author       = {Hammouda,Boualem and Jia,Di and He,Cheng},
  journal      = {Open Access Journal of Science and Technology},
  title        = {Single-Chain Conformation for Interacting Poly(N-isopropylacrylamide) in Aqueous Solution},
  year         = {2015},
  note         = {Copyright - © 2015. This work is published under https://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and conditions, you may use this content in accordance with the terms of the License; Last updated - 2018-08-03},
  volume       = {3},
  abstract     = {The demixing phase behavior of Poly(N-isopropylacrylamide) (PNIPAM) aqueous solution is investigated using small-angle neutron scattering. This polymer phase separates upon heating and demixes around 32 ∘C. The pre-transition temperature range is characterized by two scattering modes; a low-Q (large-scale) signal and a high-Q dissolved chains signal. In order to get insight into this pre-transition region, especially the origin of the low-Q (large-scale) structure, the zero average contrast method is used in order to isolate single-chain conformations even in the demixing polymers transition region. This method consists of measuring deuterated and non-deuterated polymers dissolved in mixtures of deuterated and non-deuterated water for which the polymer scattering length density matches the solvent scattering length density. A fixed 4% polymer mass fraction is used in a contrast variation series where the d-water/h-water fraction is varied in order to determine the match point. The zero average contrast (match point) sample displays pure single-chain scattering with no interchain contributions. Our measurements prove that the large scale structure in this polymer solution is due to a transient polymer network formed through hydrophobic segment-segment interactions. Scattering intensity increases when the temperature gets close to the phase boundary. While the apparent radius of gyration increases substantially at the Lower Critical Solution Temperature (LCST) transition due to strong interchain correlation, the single-chain true radius of gyration has been found to decrease slightly with temperature when approaching the transition.},
  creationdate = {2023-09-23T00:00:00},
  doi          = {10.11131/2015/101152},
  file         = {:Hammouda2015 - Single Chain Conformation for Interacting Poly(N Isopropylacrylamide) in Aqueous Solution.pdf:PDF},
  keywords     = {PNIPAM,SANS,zero average contrast,contrast variation,LCST,phase transition,Conformation,NMR,Hydrogenation,Density,Ethanol,Hydrophobicity,water,deuterated synthesis,pre-shrinking,radius of gyration},
  language     = {English},
  priority     = {prio1},
  url          = {https://www.proquest.com/scholarly-journals/single-chain-conformation-interacting-poly-n/docview/2082014373/se-2},
}

@Article{Balachandar2023,
  author       = {Balachandar, Vijayakumar and Takatsuka, Masanobu and Kita, Rio and Shinyashiki, Naoki and Yagihara, Shin and Rathinasabapathy, Sampathkumar},
  journal      = {IEEE Transactions on Dielectrics and Electrical Insulation},
  title        = {Dynamic Behavior of Heavy Water Inside and Outside of Poly (N-Isopropylacrylamide) (PNIPAM) Microgel Using Broadband Dielectric Spectroscopy},
  year         = {2023},
  number       = {4},
  pages        = {1657--1662},
  volume       = {30},
  creationdate = {2023-09-23T00:00:00},
  doi          = {10.1109/TDEI.2023.3261832},
  file         = {:Balachandar2023 - Dynamic Behavior of Heavy Water inside and Outside of Poly (N Isopropylacrylamide) (PNIPAM) Microgel Using Broadband Dielectric Spectroscopy.pdf:PDF},
  keywords     = {isotope effect, d2o, pNIPAM, microgel, bds, dielectrics, two-state water model, solvent dynamics},
  url          = {https://ieeexplore.ieee.org/document/10081094},
}

@Article{Walter2010,
  author       = {Jonathan Walter and Viktor Ermatchkov and Jadran Vrabec and Hans Hasse},
  journal      = {Fluid Phase Equilibria},
  title        = {Molecular dynamics and experimental study of conformation change of poly(N-isopropylacrylamide) hydrogels in water},
  year         = {2010},
  issn         = {0378-3812},
  number       = {2},
  pages        = {164--172},
  volume       = {296},
  abstract     = {The conformation change of poly(N-isopropylacrylamide) (PNIPAAm) hydrogel as a function of temperature is studied both experimentally and by molecular simulation. The experiments show a Θ-temperature of approximately 305K and a width of the transition region of approximately 20K, independent of the amount of cross-linker. The conformation change of the hydrogel is caused by a conformation change of the single polymer chains in its backbone. The latter was studied by massively parallel molecular dynamics simulations with GROMACS 4. Different force fields for describing the hydrogel backbone (GROMOS-87, GROMOS-96 53A6 and OPLS-AA) as well as the water molecule (SPC/E and TIP4P) were investigated. In the simulations the mean radius of gyration of the polymer chains was monitored. Two force field combinations (GROMOS-96   53A6+TIP4P and OPLS-AA+SPC/E) yield the conformation change upon variation of the temperature. The results for OPLS-AA+SPC/E are in fair agreement with the experimental results.},
  creationdate = {2023-09-23T00:00:00},
  doi          = {https://doi.org/10.1016/j.fluid.2010.03.025},
  file         = {:Walter2010 - Molecular Dynamics and Experimental Study of Conformation Change of Poly(N Isopropylacrylamide) Hydrogels in Water.pdf:PDF},
  keywords     = {PNIPAm, Hydrogel, Polymer, Swelling, Conformation change, Molecular dynamics, Force field, Temperature, theta temperature, weight},
  url          = {https://www.sciencedirect.com/science/article/pii/S0378381210001652},
}

@Article{Corti1991,
  author       = {Corti, M. and Pavesi, L. and Rigamonti, A. and Tabak, F.},
  journal      = {Phys. Rev. A},
  title        = {Deuterium-NMR study of microscopic effects in collapsing polyacrylamide gels},
  year         = {1991},
  month        = jun,
  pages        = {6887--6893},
  volume       = {43},
  creationdate = {2023-09-25T00:00:00},
  doi          = {10.1103/PhysRevA.43.6887},
  file         = {:Corti1991 - Deuterium NMR Study of Microscopic Effects in Collapsing Polyacrylamide Gels.pdf:PDF},
  issue        = {12},
  keywords     = {pNIPAM-alternative, PAM-d, 2H-NMR, hydrogel, thermoresponsive, chain dynamics, diffusion, spectral density},
  numpages     = {0},
  priority     = {prio1},
  publisher    = {American Physical Society},
  readstatus   = {read},
  url          = {https://link.aps.org/doi/10.1103/PhysRevA.43.6887},
}

@Book{Gennes1979,
  author       = {Pierre-Gilles de Gennes},
  publisher    = {Cornell University Press},
  title        = {Scaling concepts in polymer physics},
  year         = {1979},
  isbn         = {080141203x},
  comment      = {print version available in ULB},
  creationdate = {2023-09-25T00:00:00},
  file         = {:Gennes1979 - Scaling Concepts in Polymer Physics.pdf:PDF},
  keywords     = {polymer, theory, scaling laws, book, overlap concentration},
}

@Article{Blinc1989,
  author       = {R. Blinc and O. Jarh and A. Zidanšek and A. Blinc},
  journal      = {Zeitschrift für Naturforschung A},
  title        = {NMR Determination of the Fractal Geometry of Gels Around the Collapse Transition},
  year         = {1989},
  number       = {2},
  pages        = {163--164},
  volume       = {44},
  creationdate = {2023-09-25T00:00:00},
  doi          = {doi:10.1515/zna-1989-0212},
  file         = {:Blinc1989 - NM R Determination of the Fractal Geometry of Gels around the Collapse Transition.pdf:PDF},
  keywords     = {nmr, polymer gels, stimuli-responsive, fractal dimension, theory},
  lastchecked  = {2023-09-25},
  url          = {https://doi.org/10.1515/zna-1989-0212},
}

@Article{Janssen2018,
  author       = {Janssen, Liesbeth M. C.},
  journal      = {Frontiers in Physics},
  title        = {Mode-Coupling Theory of the Glass Transition: A Primer},
  year         = {2018},
  issn         = {2296-424X},
  volume       = {6},
  abstract     = {Understanding the physics of glass formation remains one of the major unsolved challenges of condensed matter science. As a material solidifies into a glass, it exhibits a spectacular slowdown of the dynamics upon cooling or compression, but at the same time undergoes only minute structural changes. Among the numerous theories put forward to rationalize this complex behavior, Mode-Coupling Theory (MCT) stands out as a unique framework that provides a fully first-principles-based description of glass phenomenology. This review outlines the key physical ingredients of MCT, its predictions, successes, and failures, as well as recent improvements of the theory. We also discuss the extension and application of MCT to the emerging field of non-equilibrium active soft matter.},
  creationdate = {2023-09-25T00:00:00},
  doi          = {10.3389/fphy.2018.00097},
  file         = {:Janssen2018 - Mode Coupling Theory of the Glass Transition_ a Primer.pdf:PDF},
  keywords     = {review, mode coupling theory, glass transition},
  url          = {https://www.frontiersin.org/articles/10.3389/fphy.2018.00097},
}

@Article{Yang2017c,
  author       = {Yang, Man and Zhao, Kongshuang},
  journal      = {Journal of Polymer Science Part B: Polymer Physics},
  title        = {Cononsolvency of poly(N-isopropylacrylamide) in methanol aqueous solution—insight by dielectric spectroscopy},
  year         = {2017},
  number       = {16},
  pages        = {1227--1234},
  volume       = {55},
  abstract     = {Both water and methanol are good solvents for poly(N-isopropylacrylamide) (PNIPAM), while PNIPAM does not dissolve in their mixed solvents, this phenomenon is called cononsolvency. Cononsolvency is closely related to many phenomena in life but so far, its mechanism is still controversial. In this work, the dielectric behavior of PNIPAM methanol aqueous solution was studied in the frequency of 40Hz–40GHz. From lower frequency to higher frequency, four relaxations were found. They are, respectively, from global chain motion, local motion of backbone, motion of side chain group, and the dipole orientation of the solvent molecule. The solvent dependence of dielectric parameters for the chain motion implied that the PNIPAM chain has undergone the coil-globule-coil transition. Dielectric analysis to microwave frequency showed that the volume of the bound solvent units on PNIPAM chain increases with the increasing methanol concentration, which suggested that the structure of solvation units bound on PNIPAM side chains undergo a changing process experience from water to water-methanol cluster to the ternary methanol cluster. This work reveals the structure and dynamics of the PNIPAM chain and the solvent unit that involved in the solvation of PNIPAM, and provides some new insight into the cononsolvency phenomenon. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1227–1234},
  creationdate = {2023-09-25T00:00:00},
  doi          = {10.1002/polb.24377},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.24377},
  file         = {:Yang2017c - Cononsolvency of Poly(N Isopropylacrylamide) in Methanol Aqueous Solution—insight by Dielectric Spectroscopy.pdf:PDF},
  keywords     = {cononsolvency, dielectric properties, dielectric spectroscopy, bds, methanol, PNIPAM, phase separation, relaxation, stimuli-sensitive polymers, water, chain dynamics},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.24377},
}

@Article{Dueramae2023,
  author       = {Dueramae, Isala and Ishiyama, Taisei and Torigaki, Ayumi and Nakano, Shinya and Sasaki, Kaito and Kita, Rio and Shinyashiki, Naoki and Yagihara, Shin and Katsumoto, Yukiteru and Yoneyama, Masaru},
  journal      = {Macromolecules},
  title        = {Separation of Micro-Brownian Motion and Side-Group Rotational Motion for Poly(N-isopropylacrylamide) in 1,4-Dioxane Studied by Dielectric Relaxation Spectroscopy},
  year         = {2023},
  number       = {11},
  pages        = {4041--4048},
  volume       = {56},
  abstract     = {Dielectric relaxation of poly(N-isopropylacrylamide) (PNiPAM) was investigated in 1,4-dioxane as a low-polarity solvent at a concentration between 0 and 20 wt \%, temperature between 40 and −35 °C, and a frequency range between 40 Hz and 1.8 GHz. Results suggest that relaxation due to the molecular motion of PNiPAM has two components: relaxation of side-group rotational motion at ∼100 MHz and micro-Brownian motion of PNiPAM chain at ∼1 MHz at room temperature. These processes are described by the sum of two Cole–Cole equations. Furthermore, the relaxation times of these processes showed distinct temperature dependences, as confirmed by activation energies obtained from the Arrhenius plot. In addition, asymmetric relaxation was observed in the MHz region of PNiPAM in various solvents comprising two individual relaxations. This could explain some fundamental aspects of PNiPAM solution properties and provide a deeper understanding of the molecular dynamics of PNiPAM.},
  creationdate = {2023-09-25T00:00:00},
  doi          = {10.1021/acs.macromol.3c00064},
  eprint       = {https://doi.org/10.1021/acs.macromol.3c00064},
  file         = {:Dueramae2023 - Separation of Micro Brownian Motion and Side Group Rotational Motion for Poly(N Isopropylacrylamide) in 1,4 Dioxane Studied by Dielectric Relaxation Spectroscopy.pdf:PDF;:SeparationOfMicroBrownianMotionAndSideGroupRotationalMotionForPolyNIsopropylacrylamideIn14DioxaneStudiedByDielectricRelaxationSpectroscopy_DueramaeEtAl_Macromol2023_SI.pdf:PDF},
  keywords     = {pNIPAM, dielectrics, chain dynamics},
  url          = {https://doi.org/10.1021/acs.macromol.3c00064},
}

@Article{Colmenero2013,
  author       = {Colmenero, Juan and Arbe, Arantxa},
  journal      = {Journal of Polymer Science Part B: Polymer Physics},
  title        = {Recent progress on polymer dynamics by neutron scattering: From simple polymers to complex materials},
  year         = {2013},
  number       = {2},
  pages        = {87--113},
  volume       = {51},
  abstract     = {The recent (from 2010 onward) contributions of quasielastic neutron scattering techniques (time of flight, backscattering, and neutron spin echo) to the characterization and understanding of dynamical processes in soft materials based on polymers are analyzed. The selectivity provided by the combination of neutron scattering and isotopic—in particular, proton/deuterium—labeling allows the isolated study of chosen molecular groups and/or components in a system. This opportunity, together with the capability of neutrons to provide space/time resolution at the relevant length scales in soft matter, allows unraveling the nature of the large variety of molecular motions taking place in materials of increasing complexity. As a result, recent relevant works can be found dealing with dynamical process which associated characteristic lengths and nature are as diverse as, for example, phenyl motions in a glassy linear homopolymer like polystyrene and the chain dynamics of a polymer adsorbed on dispersed clay platelets. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013},
  creationdate = {2023-09-28T00:00:00},
  doi          = {https://doi.org/10.1002/polb.23178},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.23178},
  file         = {:Colmenero2013 - Recent Progress on Polymer Dynamics by Neutron Scattering_ from Simple Polymers to Complex Materials.pdf:PDF},
  keywords     = {molecular dynamics, neutron scattering, relaxation, review, poylmer dynamics, chain dynamics, pNIPAM, pNIPAM-alternatives},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.23178},
}

@Article{RubioRetama2008a,
  author       = {J. Rubio-Retama and B. Frick and Tilo Seydel and B. López-Ruiz and A. Fernandez-Barbero and E. López-Cabarcos},
  journal      = {Colloids and Surfaces A: Physicochemical and Engineering Aspects},
  title        = {Molecular motions in low cross-linked poly(N-isopropylacrylamide) microgels},
  year         = {2008},
  issn         = {0927-7757},
  note         = {Colloids and Interfaces for Nanoscience and Nanotechnology Selected papers from the 20th European Colloid and Interface Society (ECIS) Conference jointly organized with 18th European Chemistry at Interfaces Conference (ECIC) held on 17-22 September, 2006 in Budapest, Hungary},
  number       = {1},
  pages        = {149--153},
  volume       = {319},
  abstract     = {Non-ionic N-isopropylacrylamide (PNIPAM) microgel is employed to investigate the molecular motion of polymer chains in the swollen and collapsed states. This study is performed using incoherent elastic (IES) and quasielastic neutron scattering (IQNS). IES measurements show an increase of both, the elastic intensity and the oscillations of the polymer network vibrational amplitude at the transition temperature. IQNS was measured at two different selected temperatures 290K and 327K corresponding to the swollen and collapsed states, respectively. The diffusion constant from IQNS experiments decreases nearly two orders of magnitude when the microgel de-swells and finally collapses.},
  creationdate = {2023-09-28T00:00:00},
  doi          = {https://doi.org/10.1016/j.colsurfa.2007.05.009},
  file         = {:RubioRetama2008a - Molecular Motions in Low Cross Linked Poly(N Isopropylacrylamide) Microgels.pdf:PDF},
  keywords     = {Microgels, Molecular dynamics, Neutron scattering, Volume phase transition, PNIPAM},
  url          = {https://www.sciencedirect.com/science/article/pii/S0927775707003883},
}

@Article{Nakagawa2023,
  author         = {Nakagawa, Hiroshi and Yamamoto, Naoki},
  journal        = {Life},
  title          = {Incoherent Neutron Scattering and Terahertz Time-Domain Spectroscopy on Protein and Hydration Water},
  year           = {2023},
  issn           = {2075-1729},
  number         = {2},
  volume         = {13},
  abstract       = {Incoherent inelastic and quasi-elastic neutron scattering (INS) and terahertz time-domain spectroscopy (THz-TDS) are spectroscopy methods that directly detect molecular dynamics, with an overlap in the measured energy regions of each method. Due to the different characteristics of their probes (i.e., neutron and light), the information obtained and the sample conditions suitable for each method differ. In this review, we introduce the differences in the quantum beam properties of the two methods and their associated advantages and disadvantages in molecular spectroscopy. Neutrons are scattered via interaction with nuclei; one characteristic of neutron scattering is a large incoherent scattering cross-section of a hydrogen atom. INS records the auto-correlation functions of atomic positions. By using the difference in neutron scattering cross-sections of isotopes in multi-component systems, some molecules can be selectively observed. In contrast, THz-TDS observes the cross-correlation function of dipole moments. In water-containing biomolecular samples, the absorption of water molecules is particularly large. While INS requires large-scale experimental facilities, such as accelerators and nuclear reactors, THz-TDS can be performed at the laboratory level. In the analysis of water molecule dynamics, INS is primarily sensitive to translational diffusion motion, while THz-TDS observes rotational motion in the spectrum. The two techniques are complementary in many respects, and a combination of the two is very useful in analyzing the dynamics of biomolecules and hydration water.},
  article-number = {318},
  creationdate   = {2023-09-29T00:00:00},
  doi            = {10.3390/life13020318},
  file           = {:Nakagawa2023 - Incoherent Neutron Scattering and Terahertz Time Domain Spectroscopy on Protein and Hydration Water.pdf:PDF},
  keywords       = {hydration shell,protein,QENS,neutrons,terahertz spectroscopy,review},
  pubmedid       = {36836676},
  url            = {https://www.mdpi.com/2075-1729/13/2/318},
}

@Article{Galbraith2017,
  author       = {Madeline L. Galbraith and Jeffry D. Madura},
  journal      = {Journal of Molecular Graphics and Modelling},
  title        = {Identifying trends in hydration behavior for modifications to the hydrophobicity of poly(n-isopropylacrylamide)},
  year         = {2017},
  issn         = {1093-3263},
  pages        = {168--175},
  volume       = {78},
  abstract     = {Poly(n-isopropylacrylamide), PNIPAM, is a thermo-responsive polymer that has been thoroughly studied for its many applications, such as drug delivery and actuators. Below the lower critical solution temperature (LCST), PNIPAM is well hydrated in the elongated conformation. The transition occuring at the LCST results in a less hydrated collapsed state above the LCST. This volume phase transition is dependent upon the hydration of the polymer and its hydrophobicity. Some research has been done on potential modifications of PNIPAM for applications, but until now there has not been a study of the hydration properties as a function of hydrophobicity. The work presented in this paper applies a Voronoi analysis of the hydration of PNIPAM, as well as PNIPAM with other alkyl substituents. We show from classical MD simulations that increasing hydrophobicity can increase the volume phase change, but there is a lower limit to this trend. Additionally, replica exchange molecular dynamics were conducted on PNIPAM showing a fluctuation between elongated and collapsed states near the LCST.},
  creationdate = {2023-09-29T00:00:00},
  doi          = {https://doi.org/10.1016/j.jmgm.2017.09.021},
  file         = {:Galbraith2017 - Identifying Trends in Hydration Behavior for Modifications to the Hydrophobicity of Poly(n Isopropylacrylamide).pdf:PDF},
  keywords     = {PNIPAM, Voronoi, Hydration, LCST, pNIPAM-alternatives, molecular dynamics simulation, critical fluctuations},
  url          = {https://www.sciencedirect.com/science/article/pii/S1093326317304187},
}

@Article{Nachaki2022,
  author       = {Nachaki, Ernest O. and Leonik, Fedra M. and Kuroda, Daniel G.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Effect of the N-Alkyl Side Chain on the Amide–Water Interactions},
  year         = {2022},
  note         = {PMID: 36219826},
  number       = {41},
  pages        = {8290--8299},
  volume       = {126},
  abstract     = {Amide–water interactions influence the structure and functions of amide-based systems, such as proteins and homopolymers. In particular, the N-alkylation of the amide unit appears to play a critical role in defining the interactions of the amide group. Previous studies have linked the thermal behavior of amide-based polymers to the nature of their N-alkyl side chain. However, the connection between the chemical structure of the N-alkyl and the hydration of the amide remains elusive. In this study, the solvation structure and dynamics of amides, having differing N-alkyl groups, are investigated using a combination of linear and nonlinear infrared spectroscopies and computational methods. Interestingly, the dynamics of the amide local environment do not slow down as the N-alkyl side chain becomes bulkier, but rather speeds up. Computational calculations confirm the hydration dynamics and assign the effect to smaller amplitude and faster rotations of the bulkier group. It is also observed experimentally that the hydrogen-bond making and breaking between water and the amide carbonyl do not directly relate to the size of the N-alkyl side chain. The bulkier N-isopropyl substituent presents significantly slower chemical exchange dynamics than smaller chains (ethyl and methyl), but the two small groups do not present a major difference. The hydrogen-bond making and breaking disparities and similarities among groups are well modeled by the theory demonstrating that the N-alkyl group affects the amide hydration structure and dynamics via a steric effect. In summary, the results presented here show that the size of the N-substituted alkyl group significantly influences the hydration dynamics of amides and stress the importance of considering this effect on much larger systems, such as polymers.},
  creationdate = {2023-09-29T00:00:00},
  doi          = {10.1021/acs.jpcb.2c04988},
  eprint       = {https://doi.org/10.1021/acs.jpcb.2c04988},
  file         = {:Nachaki2022 - Effect of the N Alkyl Side Chain on the Amide–Water Interactions.pdf:PDF;:EffectOfTheNAlkylSideChainOnTheAmideWaterInteractions_NachakiEtAl_JPC2022_SI.pdf:PDF},
  keywords     = {pNIPAM, pNIPAM-alternatives, infrared, TD-FTIR, molecular dynamics simulation, dft, hydration, chemical exchange},
  url          = {https://doi.org/10.1021/acs.jpcb.2c04988},
}

@Article{Ko2020,
  author       = {Ko, Chia-Hsin and Claude, Kora-Lee and Niebuur, Bart-Jan and Jung, Florian A. and Kang, Jia-Jhen and Schanzenbach, Dirk and Frielinghaus, Henrich and Barnsley, Lester C. and Wu, Baohu and Pipich, Vitaliy and Schulte, Alfons and Müller-Buschbaum, Peter and Laschewsky, André and Papadakis, Christine M.},
  journal      = {Macromolecules},
  title        = {Temperature-Dependent Phase Behavior of the Thermoresponsive Polymer Poly(N-isopropylmethacrylamide) in an Aqueous Solution},
  year         = {2020},
  number       = {16},
  pages        = {6816--6827},
  volume       = {53},
  abstract     = {Poly(N-isopropylmethacrylamide) (PNIPMAM) is a thermoresponsive polymer, exhibiting lower critical solution temperature (LCST) behavior in an aqueous solution. We investigate the temperature-dependent phase behavior of PNIPMAM solutions in D2O using turbidimetry, differential scanning calorimetry (DSC), small-angle and very small angle neutron scattering (SANS and VSANS), and Raman spectroscopy, covering a large concentration range, and compare the results from PNIPMAM with the findings from its analogue poly(N-isopropylacrylamide) (PNIPAM). We find that the PNIPMAM chains only dehydrate 2–3 °C above the macroscopic cloud point temperature, TCP. Even in the one-phase state, loosely packed, large-scale inhomogeneities and physical cross-links are observed, and the chain conformation of PNIPMAM is more compact than the one of PNIPAM. This is attributed to the attractive intermolecular interactions between the hydrophobic moieties. The phase transition of PNIPMAM is broader than the one of PNIPAM. Upon heating to the two-phase state, the PNIPMAM chains collapse and form mesoglobules. These are larger and more hydrated than those for PNIPAM. This is attributed to the steric hindrance caused by the additional methyl groups, which weaken the intrapolymer interactions in the two-phase state. Thus, the methyl groups in the backbone of the PNIPMAM chains have a significant impact on the hydration and the structural behavior around the phase transition.},
  creationdate = {2023-09-30T00:00:00},
  doi          = {10.1021/acs.macromol.0c01256},
  eprint       = {https://doi.org/10.1021/acs.macromol.0c01256},
  file         = {:Ko2020 - Temperature Dependent Phase Behavior of the Thermoresponsive Polymer Poly(N Isopropylmethacrylamide) in an Aqueous Solution.pdf:PDF;:TemperatureDependentPhaseBehaviorOfTheThermoresponsivePolymerPolyNIsopropylmethacrylamideInAnAqueousSolution_KoEtAl_Macromol2020_SI.pdf:PDF},
  keywords     = {pNIPAM, pNIPAM-alternatives, pNIPMAM, LCST, DSC, turbidimetry, cloud point, SANS, VSANS, raman, concentration-dependent},
  readstatus   = {skimmed},
  url          = {https://doi.org/10.1021/acs.macromol.0c01256},
}

@Article{Roy2013,
  author       = {Roy, Debashish and Brooks, William L. A. and Sumerlin, Brent S.},
  journal      = {Chem. Soc. Rev.},
  title        = {New directions in thermoresponsive polymers},
  year         = {2013},
  pages        = {7214--7243},
  volume       = {42},
  abstract     = {Interest in thermoresponsive polymers has steadily grown over many decades{,} and a great deal of work has been dedicated to developing temperature sensitive macromolecules that can be crafted into new smart materials. However{,} the overwhelming majority of previously reported temperature-responsive polymers are based on poly(N-isopropylacrylamide) (PNIPAM){,} despite the fact that a wide range of other thermoresponsive polymers have demonstrated similar promise for the preparation of adaptive materials. Herein{,} we aim to highlight recent results that involve thermoresponsive systems that have not yet been as fully considered. Many of these (co)polymers represent clear opportunities for advancements in emerging biomedical and materials fields due to their increased biocompatibility and tuneable response. By highlighting recent examples of newly developed thermoresponsive polymer systems{,} we hope to promote the development of new generations of smart materials.},
  creationdate = {2023-10-01T00:00:00},
  doi          = {10.1039/C3CS35499G},
  file         = {:Roy2013 - New Directions in Thermoresponsive Polymers.pdf:PDF},
  issue        = {17},
  keywords     = {pNIPAM-alternatives, review},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C3CS35499G},
}

@Article{Seuring2013,
  author       = {Seuring, Jan and Agarwal, Seema},
  journal      = {ACS Macro Letters},
  title        = {Polymers with Upper Critical Solution Temperature in Aqueous Solution: Unexpected Properties from Known Building Blocks},
  year         = {2013},
  note         = {PMID: 35581788},
  number       = {7},
  pages        = {597--600},
  volume       = {2},
  abstract     = {Polymers showing an upper critical solution temperature (UCST) in aqueous solution were not rare, but the UCST was rarely observed under practically relevant conditions. Recently, much progress has been made in the synthesis of polymer systems that display UCST behavior under mild and physiologic conditions. Current developments focus on polymers that rely on hydrogen bonding. This viewpoint explains the historical context, presents the major properties, and concludes with a discussion of the most recent examples.},
  creationdate = {2023-10-01T00:00:00},
  doi          = {10.1021/mz400227y},
  eprint       = {https://doi.org/10.1021/mz400227y},
  file         = {:Seuring2013 - Polymers with Upper Critical Solution Temperature in Aqueous Solution_ Unexpected Properties from Known Building Blocks.pdf:PDF},
  keywords     = {UCST, review},
  url          = {https://doi.org/10.1021/mz400227y},
}

@Article{Plamper2007,
  author       = {Plamper, Felix A. and Ruppel, Markus and Schmalz, Alexander and Borisov, Oleg and Ballauff, Matthias and Müller, Axel H. E.},
  journal      = {Macromolecules},
  title        = {Tuning the Thermoresponsive Properties of Weak Polyelectrolytes:  Aqueous Solutions of Star-Shaped and Linear Poly(N,N-dimethylaminoethyl Methacrylate)},
  year         = {2007},
  number       = {23},
  pages        = {8361--8366},
  volume       = {40},
  abstract     = {We investigated the thermoresponsive behavior of aqueous solutions of star-shaped and linear poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA). The observed cloud points strongly decrease with increasing pH of the solution. This is explained by a weak charging of the star polymers with decreasing pH. A significant decrease of the cloud points with increasing molecular weight for high pH, i.e., for the almost uncharged state, was found to be virtually independent of the arm number and arm length. These findings are explained by classical Flory−Huggins theory. The increase of cloud points upon charging is captured by introduction of an effective degree of polymerization. Polymers with shorter arms show slightly higher cloud points at low pH than polymers with longer arms. The intramolecular segment density also influences the observed apparent pKb values, leading to higher values for stars with higher arm numbers.},
  creationdate = {2023-10-01T00:00:00},
  doi          = {10.1021/ma071203b},
  eprint       = {https://doi.org/10.1021/ma071203b},
  file         = {:Plamper2007 - Tuning the Thermoresponsive Properties of Weak Polyelectrolytes_ Aqueous Solutions of Star Shaped and Linear Poly(N,N Dimethylaminoethyl Methacrylate).pdf:PDF;:TuningTheThermoresponsivePropertiesOfWeakPolyelectrolytes-AqueousSolutionsOfStarShapedLinearPolyNNDimethylaminoethylMethycrylate_PlamperEtAl_Macromol2007_SI.pdf:PDF},
  keywords     = {pDMAEMA, pNIPMA-alternative, star-shaped, linear, weak electrolyte, pH-dependence},
  url          = {https://doi.org/10.1021/ma071203b},
}

@Article{Umecky2014,
  author       = {T. Umecky and T. Takamuku and T. Aida and T. Makino and T. Aizawa and M. Kanakubo},
  journal      = {J. Solution Chem.},
  title        = {NMR Studies on Solution Structures of Methanol and Ethanol Saturated with CO2},
  year         = {2014},
  pages        = {1539--1549},
  volume       = {43},
  creationdate = {2023-10-04T00:00:00},
  doi          = {https://doi.org/10.1007/s10953-014-0222-z},
  file         = {:Umecky2014 - NMR Studies on Solution Structures of Methanol and Ethanol Saturated with CO2.pdf:PDF;:Umecky2014 - NMR Studies on Solution Structures of Methanol and Ethanol Saturated with CO2.docx:Word 2007+},
  keywords     = {ethanol, methanol, susceptibility corrected chemical shift, 2H-nmr, 17O-nmr},
  url          = {https://doi.org/10.1007/s10953-014-0222-z},
}

@Article{Afroze2000,
  author       = {F Afroze and E Nies and H Berghmans},
  journal      = {Journal of Molecular Structure},
  title        = {Phase transitions in the system poly(N-isopropylacrylamide)/water and swelling behaviour of the corresponding networks},
  year         = {2000},
  issn         = {0022-2860},
  number       = {1},
  pages        = {55--68},
  volume       = {554},
  abstract     = {The phase behaviour of linear poly(N-isopropylacrylamide) (PNIPA) and chemically cross-linked PNIPA in water has been determined by calorimetric and optical techniques. Experiments for the linear polymer were conducted for three different molar masses and encompassed the whole accessible concentration range. In addition the binodal of the ‘monomer’ N-(isopropyl)propionamide (NIPPA) was determined by cloud point measurements. The phase behaviour was analysed in terms of the Flory–Huggins–Staverman theory amended with a strong concentration dependent interaction function. The analysis established that PNIPA/water is exemplar of Type II phase behaviour, indicating that the system does not fit the classic Flory–Huggins scheme. Distinctive of Type II behaviour is the existence of an off-zero liquid–liquid critical composition for a hypothetical polymer of infinite molar mass and the absence of the classic FH Θ-critical state. The Type II phase behaviour of the linear polymer is also found in the network and is shown to be responsible for the discontinuous volume response of the PNIPA gel. The peculiar swelling behaviour is a direct consequence of the invariant interference of the swelling curve with the liquid–liquid miscibility gap. Finally, the dependence of the enthalpy of melting of water in the polymer solution is not related to the formation of a strong complex between the polymer and the water molecules. Instead, the crystallisation and melting of water are impeded by the vitrification of the aqueous polymer solution.},
  creationdate = {2023-10-06T00:00:00},
  doi          = {https://doi.org/10.1016/S0022-2860(00)00559-7},
  file         = {:Afroze2000 - Phase Transitions in the System Poly(N Isopropylacrylamide)_water and Swelling Behaviour of the Corresponding Networks.pdf:PDF},
  keywords     = {Poly(-isopropylacrylamide), linear pNIPAM, pNIPAM hydrogel, binodal, cloud point, Flory-Huggins, Flory-Huggins-Staverman, Solutions, Demixing, Networks, Swelling, N-isopropylpropionamide, NIPPA, monomer},
  url          = {https://www.sciencedirect.com/science/article/pii/S0022286000005597},
}

@Article{Carper1997,
  author       = {Carper, W. Robert and Keller, Charles E.},
  journal      = {The Journal of Physical Chemistry A},
  title        = {Direct Determination of NMR Correlation Times from Spin−Lattice and Spin−Spin Relaxation Times},
  year         = {1997},
  number       = {18},
  pages        = {3246--3250},
  volume       = {101},
  abstract     = {The NMR rotational correlation equations for dipolar relaxation between 1H and the nuclei, 1H, 13C, 31P, and 113Cd have been solved for viscous solutions using the R2/R1 dipolar ratio. The rotational correlation times have been determined over the dipolar R2/R1 range of 1.1−1200 at field strengths of 4.7, 6.35, 7.05, 9.4, 11.75, and 14.1 T. The calculated correlation times at each field strength have been fitted to pairs of polynomials which reproduce the correlation times from R2/R1 values at a given temperature. The 13C−1H and 1H−1H equations are used to determine the 27Al nuclear quadrupole coupling constants in 1:2 LiCl−ethylaluminum dichloride melts and neat ethylaluminum dichloride. The 113Cd−1H and 31P−1H polynomials are used to characterize Cd2+ and inorganic phosphate binding sites in the enzyme, yeast inorganic pyrophosphatase.},
  creationdate = {2023-10-09T00:00:00},
  doi          = {10.1021/jp963338h},
  eprint       = {https://doi.org/10.1021/jp963338h},
  file         = {:Carper1997 - Direct Determination of NMR Correlation Times from Spin−Lattice and Spin−Spin Relaxation Times.pdf:PDF},
  keywords     = {NMR, theory, spin-spin relaxation, spin-lattice relaxation, t1, t2},
  priority     = {prio2},
  url          = {https://doi.org/10.1021/jp963338h},
}

@Article{Maruyama2013,
  author       = {Maruyama ,K. and Ohno ,S. and Nakada ,M.},
  journal      = {Journal of the Physical Society of Japan},
  title        = {QENS Studies on the Dynamics in Aqueous One-Propanol Solutions with KCl},
  year         = {2013},
  number       = {Suppl.A},
  pages        = {SA012},
  volume       = {82},
  abstract     = {AMATERAS is a very suitable spectrometer for investigation of diffusion dynamics of solutions and also for obtaining the dynamic structure factor S(Q,E) over large Q region. The aim of this paper is to investigate the diffusion dynamics of water molecules in the 1-propanol aqueous solution with small amount of KCl. The S(Q,E) for 1-propanol solutions with and without KCl were obtained. The result shows that the diffusion constant D is slightly larger for KCl containing solution than that without KCl.},
  creationdate = {2023-10-09T00:00:00},
  doi          = {10.7566/JPSJS.82SA.SA012},
  eprint       = {https://doi.org/10.7566/JPSJS.82SA.SA012},
  file         = {:Maruyama2013 - QENS Studies on the Dynamics in Aqueous One Propanol Solutions with KCl.pdf:PDF},
  keywords     = {QENS, aqueous propanol, 1-propanol, neutron, ionic strength, hydrophobic hydration, diffusion coefficient},
  url          = {https://doi.org/10.7566/JPSJS.82SA.SA012},
}

@Article{Hayashi1990,
  author       = {Hayashi, Hisashi. and Nishikawa, Keiko. and Iijima, Takao.},
  journal      = {The Journal of Physical Chemistry},
  title        = {Small-angle x-ray scattering study of fluctuations in 1-propanol-water and 2-propanol-water systems},
  year         = {1990},
  number       = {21},
  pages        = {8334--8338},
  volume       = {94},
  creationdate = {2023-10-09T00:00:00},
  doi          = {10.1021/j100384a062},
  eprint       = {https://doi.org/10.1021/j100384a062},
  file         = {:Hayashi1990 - Small Angle X Ray Scattering Study of Fluctuations in 1 Propanol Water and 2 Propanol Water Systems.pdf:PDF},
  keywords     = {x-ray, aqueous alcohol, aqueous propanol, 1-propanol, 2-propanol, n-propanol, isopropanol, PrOH, cluster},
  url          = {https://doi.org/10.1021/j100384a062},
}

@Article{Mashimo1991,
  author       = {Mashimo, Satoru and Umehara, Toshihiro and Redlin, Harald},
  journal      = {The Journal of Chemical Physics},
  title        = {{Structures of water and primary alcohol studied by microwave dielectric analyses}},
  year         = {1991},
  issn         = {0021-9606},
  month        = nov,
  number       = {9},
  pages        = {6257--6260},
  volume       = {95},
  abstract     = {{By the use of the time domain reflectometry method dielectric measurements were carried out first on methanol mixtures with ethanol and 1‐propanol, and second, water mixtures with methanol, ethanol and 1‐propanol in the frequency range 10 MHz–20 GHz. The first mixtures show a Debye relaxation and logarithm of the relaxation time is given by a linear function of the mole fraction of methanol. These mixtures have the same chainlike cluster of pure alcohol. The second mixtures show the same trend of the relaxation time in a region 0≤xw\\&lt;0.83, where xw is the mole fraction of water. In a region 0.83\\&lt;xw≤1.0, we observe an entirely different behavior, which indicates that the cluster of pure water appears for xw\\&gt;0.83 and that the cluster must be cyclic, consisting of six molecules.}},
  creationdate = {2023-10-09T00:00:00},
  doi          = {10.1063/1.461546},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/95/9/6257/14110186/6257\_1\_online.pdf},
  file         = {:Mashimo1991 - Structures of Water and Primary Alcohol Studied by Microwave Dielectric Analyses.pdf:PDF},
  keywords     = {dielectrics, aqueous alcohol, methanol, MeOH, ethanol, EtOH, propanol, PrOH},
  url          = {https://doi.org/10.1063/1.461546},
}

@Article{Sudo2006,
  author       = {Sudo, S. and Tobinai, S. and Shinyashiki, N. and Yagihara, S.},
  journal      = {AIP Conference Proceedings},
  title        = {{Broadband Dielectric Study on Glass Transition of 1‐Propanol‐Water Mixture}},
  year         = {2006},
  issn         = {0094-243X},
  month        = may,
  number       = {1},
  pages        = {149--152},
  volume       = {832},
  abstract     = {{We performed broadband dielectric measurements for pure 1‐propanol (PrOH) and 80 wt\\% PrOH‐water mixture in the temperature range of 78 K and 300 K and frequency range of 1 μHz and 30 GHz. For pure PrOH, Debye‐type primary process and two small processes at higher frequency than the primary loss peak are observed in whole the temperature range. For 80 wt\\% PrOH‐water mixture, the KWW‐type primary process and two small processes similar to the pure PrOH are observed above crossover temperature, TC. Below TC, additional process is observed at lower frequency range than the primary loss peak frequency. The relaxation time of the primary process for the 80 wt\\% PrOH‐water mixture agrees with that for pure PrOH below TC, while it is smaller than that for the pure PrOH above TC. For 80 wt\\% PrOH‐water mixture, the cooperative motion of PrOH and water by hydrogen bonding and/or clathrate‐like structure occurs above TC, and it leads to the KWW‐type primary process. On the other hand, this cooperative motion does not occur below TC, and the motion of PrOH and water molecules leads to the primary and low‐frequency processes, respectively.}},
  creationdate = {2023-10-09T00:00:00},
  doi          = {10.1063/1.2204477},
  eprint       = {https://pubs.aip.org/aip/acp/article-pdf/832/1/149/11990524/149\_1\_online.pdf},
  file         = {:Sudo2006 - Broadband Dielectric Study on Glass Transition of 1‐Propanol‐Water Mixture.pdf:PDF},
  keywords     = {aqueous alcohol, 1-propanol, PrOH, propanol-water, dielectrics, BDS, glass},
  priority     = {prio1},
  url          = {https://doi.org/10.1063/1.2204477},
}

@InBook{Ngai2011,
  author       = {Ngai, K.L.},
  pages        = {49--638},
  publisher    = {Springer New York},
  title        = {Glass-Forming Substances and Systems},
  year         = {2011},
  address      = {New York, NY},
  isbn         = {978-1-4419-7649-9},
  abstract     = {The glass transition or vitrification, which refers to the dramatic slowing down of kinetic processes, such as diffusion, viscous flow, and molecular reorientations, is a general phenomenon found in organic, inorganic, metallic, polymeric, colloidal, and biomolecular materials, as well as synthetic materials and systems. On decreasing temperature T or increasing pressure P, the structural relaxation time $\tau$$\alpha$ of supercooled liquids becomes increasingly long. Eventually the molecules cannot attain their dynamic equilibrium configurations on the timescale of observation, and vitrification commences. The science and technology of glass formation has a long history, starting from the first recorded recipe for glass that appeared a few millennia ago in Babylon. Nowadays, glasses are formed from many different kinds of materials. The use of glass is widespread, and the glass-making industry alone contributes significantly to the world economy.},
  booktitle    = {Relaxation and Diffusion in Complex Systems},
  creationdate = {2023-10-09T00:00:00},
  doi          = {10.1007/978-1-4419-7649-9_2},
  file         = {:Ngai2011 - Glass Forming Substances and Systems.pdf:PDF},
  keywords     = {glass, 1-propanol, PrOH, cage, johari-goldstein, alpha, beta, nu},
  url          = {https://doi.org/10.1007/978-1-4419-7649-9_2},
}

@Article{Shinyashiki2007,
  author       = {N Shinyashiki and S Sudo and S Yagihara and A Spanoudaki and A Kyritsis and P Pissis},
  journal      = {Journal of Physics: Condensed Matter},
  title        = {Relaxation processes of water in the liquid to glassy states of water mixtures studied by broadband dielectric spectroscopy},
  year         = {2007},
  month        = apr,
  number       = {20},
  pages        = {205113},
  volume       = {19},
  abstract     = {The relaxation processes of water mixtures of glycerol, ethylene glycol, ethylene glycol oligomers with two to six repeat units, poly(ethylene glycol) 400 and 600, fructose, and propanol have been studied by broadband dielectric spectroscopy at different water contents in the frequency range 10 µHz–20 GHz  and in the temperature range 300–80 K without water crystallization. The results show that, in the vicinity of the glass transition temperature of the mixtures, two kinds of water exist. Part of the water behaves as excess water retaining its inherent mobility and appearing as a separate relaxation process (named here the ν-process) at frequencies higher than the structural α-process at subzero temperatures. Another part of the water moves cooperatively with solute molecules and contributes to the α-process.},
  comment      = {where does the data (Table 1) for 90 wt% PrOH come from?},
  creationdate = {2023-10-09T00:00:00},
  doi          = {10.1088/0953-8984/19/20/205113},
  file         = {:Shinyashiki2007 - Relaxation Processes of Water in the Liquid to Glassy States of Water Mixtures Studied by Broadband Dielectric Spectroscopy.pdf:PDF},
  keywords     = {1-propanol, glass, nu, aqueous alcohol, review},
  url          = {https://dx.doi.org/10.1088/0953-8984/19/20/205113},
}

@Article{Manakov2013,
  author       = {A. Yu. Manakov and L. S. Aladko and A. G. Ogienko and A. I. Ancharov},
  journal      = {J Therm Anal Calorim},
  title        = {Hydrate formation in the system n-propanol-water},
  year         = {2013},
  pages        = {885--890},
  volume       = {111},
  creationdate = {2023-10-09T00:00:00},
  doi          = {10.1007/s10973-012-2246-1},
  file         = {:Manakov2013 - Hydrate Formation in the System N Propanol Water.pdf:PDF},
  keywords     = {propanol, 1-propanol, phase diagram, x-ray},
  url          = {https://doi.org/10.1007/s10973-012-2246-1},
}

@Article{Chapoy2008,
  author       = {Chapoy, Antonin and Anderson, Ross and Haghighi, Hooman and Edwards, Terry and Tohidi, Bahman},
  journal      = {Industrial \& Engineering Chemistry Research},
  title        = {Can n-Propanol Form Hydrate?},
  year         = {2008},
  number       = {5},
  pages        = {1689--1694},
  volume       = {47},
  abstract     = {Alcohols are generally considered hydrate inhibitors. The fact that 2-propanol, in addition to tert-butanol can form hydrates, suggests further investigation of this issue is required. In light of this, it was decided to assess the potential for hydrate formation by n-propanol. However, there are at present no data concerning its effects on hydrate stability available in the open literature. Here, we present freezing point data of n-propanol solutions (up to 80 mass \%). These data suggest existence of a peritectic point at 263.05 K and formation of clathrate hydrate in the n-propanol−water system. To confirm whether n-propanol, like 2-propanol, forms mixed hydrates with structure I formers at elevated pressures, dissociation conditions were measured for aqueous solution of 10, 16.4, and 25 mass \% n-propanol in the presence of methane at pressures up to 40 MPa and natural gas at around 10 MPa. The results show that n-propanol does not display a hydrate inhibition effect, which would be expected from an alcohol and may, in fact, take part in clathrate formation. Consequently, n-propanol has been modeled as a hydrate-forming compound by use of a thermodynamic model. Comparisons between experimental hydrate dissociation data and model predictions suggest that n-propanol may take part in structure II hydrate formation, occupying the large cavity of the hydrate structure.},
  creationdate = {2023-10-09T00:00:00},
  doi          = {10.1021/ie071019e},
  eprint       = {https://doi.org/10.1021/ie071019e},
  file         = {:Chapoy2008 - Can N Propanol Form Hydrate_.pdf:PDF},
  keywords     = {1-propanol, phase diagram, clathrate, hydrate},
  url          = {https://doi.org/10.1021/ie071019e},
}

@Article{Tomza2015,
  author       = {Paweł Tomza and Mirosław Antoni Czarnecki},
  journal      = {Journal of Molecular Liquids},
  title        = {Microheterogeneity in binary mixtures of propyl alcohols with water: NIR spectroscopic, two-dimensional correlation and multivariate curve resolution study},
  year         = {2015},
  issn         = {0167-7322},
  pages        = {115--120},
  volume       = {209},
  abstract     = {Separation at a molecular level is responsible for macroscopic structure of liquids and leads to anomalous behavior of the physicochemical properties of mixtures. Here, we present the study of the microheterogeneity in binary mixtures of propyl alcohols with water. Both alcohols are fully miscible with water but due to different structures one may expect some differences in the interaction with water at a molecular level. Thus, a special attention was paid for the changes in the separation of alcohol and water molecules in going from 1-propanol to 2-propanol. Our results indicate that in spite of different molecular structures, the binary mixtures of both alcohols with water reveal similar properties. In the water-poor region the molecules of alcohols are in the same environment as those in the pure liquid alcohols, while the molecules of water do not form separate clusters but are dispersed in the organic phase. At higher water content the molecules of water form clusters interacting with the OH groups of the alcohol's clusters. The transition from the dispersed state to the formation of water clusters is a continuous process. The largest deviation from the ideal mixture appears at an alcohol:water molar ratio of 1:2. The mixtures of both propyl alcohols differ mainly in the degree of hydration of the clusters. The clusters of 1-propanol are less hydrated than those of 2-propanol, hence 1-propanol/water mixture is more heterogeneous. On the basis of the present results and available literature data one can conclude that the extent of the microheterogeneity in the alcohol/water binary mixtures is related to the degree of self-association of the alcohol.},
  creationdate = {2023-10-10T00:00:00},
  doi          = {https://doi.org/10.1016/j.molliq.2015.05.033},
  file         = {:Tomza2015 - Microheterogeneity in Binary Mixtures of Propyl Alcohols with Water_ NIR Spectroscopic, Two Dimensional Correlation and Multivariate Curve Resolution Study.pdf:PDF},
  keywords     = {Microheterogeneity, Binary mixtures, Excess absorbance, Propyl alcohols, Water, Near-infrared spectroscopy, NIR, Two-dimensional correlation analysis, Multivariate curve resolution, aqueous alcohol, 1-propanol, 2-propanol},
  url          = {https://www.sciencedirect.com/science/article/pii/S0167732215301045},
}

@Article{Takamuku2004,
  author       = {Toshiyuki Takamuku and Hirokazu Maruyama and Kenji Watanabe and Toshio Yamaguchi},
  journal      = {Journal of Solution Chemistry},
  title        = {Structure of 1-Propanol-Water Mixtures Investigated by Large-Angle X-ray Scattering Technique},
  year         = {2004},
  pages        = {641--660},
  volume       = {33},
  abstract     = {Large-angle X-ray Scattering (LAXS) experiments at 298 K have been made on 1-propanol–water mixtures over the whole 1-propanol mole fraction range. The radial distribution functions show that the predominant clusters in 1-propanol–water mixtures change at 1-propanol mole fraction x 1pr = 0.1; the tetrahedral-like structure of water is mainly formed in the mixtures with x 1pr ≤ 0.1, while hydrogen-bonded chain clusters of 1-propanol molecules predominate in the mixtures at x 1pr > 0.1. From the present results, together with the previous ones on methanol–water, ethanol–water, and 2-propanol–water mixtures, size and shape effects of the hydrophobic groups on the structure of aliphatic alcohol–water mixtures are discussed at the molecular level. The anomalies of the enthalpies of mixing for 1-propanol–water mixtures at 298 K are interpreted on the basis of the proposed change in structure of the mixtures with 1-propanol mole fraction.},
  comment      = {Structure at room temperature. Other alcohols were investigated in previous papers},
  creationdate = {2023-10-10T00:00:00},
  doi          = {https://doi.org/10.1023/B:JOSL.0000043631.21673.8b},
  file         = {:Takamuku2004 - Structure of 1 Propanol Water Mixtures Investigated by Large Angle X Ray Scattering Technique.pdf:PDF},
  keywords     = {aqueous alcohol, x-ray, 1-propanol, review},
  url          = {https://doi.org/10.1023/B:JOSL.0000043631.21673.8b},
}

@Article{Ishidao1994,
  author       = {T. Ishidao and Y. Hashimoto and Y. Iwai and Y. Arai},
  journal      = {Colloid \& Polymer Science},
  title        = {Solvent concentrations of dimethyl\-sulfoxide-water and 1-propanol-water solutions inside and outside poly (N-isopropyl\-acrylamide) gel},
  year         = {1994},
  pages        = {1313--1316},
  volume       = {272},
  creationdate = {2023-10-10T00:00:00},
  doi          = {https://doi.org/10.1007/BF00657787},
  file         = {:Ishidao1994 - Solvent Concentrations of Dimethylsulfoxide Water and 1 Propanol Water Solutions inside and Outside Poly (N Isopropylacrylamide) Gel.pdf:PDF},
  keywords     = {pNIPAM, hydrogel, cononsolvency, 1-propanol, dmso},
  url          = {https://doi.org/10.1007/BF00657787},
}

@Article{Takahara2013,
  author       = {Takahara, Shuichi and Mori, Kenji and Kittaka, Shigeharu},
  journal      = {AIP Advances},
  title        = {{Dielectric study on two dynamic phases of 1-propanol confined in mesopores of MCM-41}},
  year         = {2013},
  issn         = {2158-3226},
  month        = feb,
  number       = {2},
  pages        = {022117},
  volume       = {3},
  abstract     = {{Two dynamic phases were recognized on the 1-propanol molecules confined in MCM-41 with pore diameters d = 2.1, 2.4, 2.7 and 3.6 nm by dielectric measurements, in which two types of confined states of liquid were investigated: surface-adsorbed (sa) and pore-filled (pf) liquid. The dielectric measurements in the frequency range 103–107 Hz and temperature range 120–300 K showed that the molecular motions became slower in the following order: bulk, pf and sa liquid, which is the same order as for methanol and ethanol confined in MCM-41 reported previously. For pf samples, two relaxation components, which correspond to molecules near the pore surface and at the center of the pores, were observed separately. This is somewhat different from the behavior of methanol and ethanol confined as pf state in which two relaxation components were also detected but a clear separation between them was not observed. This implies that 1-propanol molecules near the pore wall interact weakly with those at the central part of the pores. For the MCM-41 sample with the smallest pore diameter (d = 2.1 nm), however, the dielectric spectra of the pf sample were very similar to those of the sa sample. That is, the dynamic motion of molecules in the pf sample was inhibited by narrow space surrounded by monolayer molecules similarly to that in the sa sample.}},
  creationdate = {2023-10-10T00:00:00},
  doi          = {10.1063/1.4792604},
  eprint       = {https://pubs.aip.org/aip/adv/article-pdf/doi/10.1063/1.4792604/13060799/022117\_1\_online.pdf},
  file         = {:Takahara2013 - Dielectric Study on Two Dynamic Phases of 1 Propanol Confined in Mesopores of MCM 41.pdf:PDF},
  keywords     = {1-propanol, confinement, dielectrics},
  url          = {https://doi.org/10.1063/1.4792604},
}

@Article{Ohkubo2001,
  author       = {T Ohkubo and K Kaneko},
  journal      = {Colloids and Surfaces A: Physicochemical and Engineering Aspects},
  title        = {Oriented structures of alcohol hidden in carbon micropores with ERDF analysis},
  year         = {2001},
  issn         = {0927-7757},
  pages        = {177--185},
  volume       = {187-188},
  abstract     = {The X-ray diffraction (XRD) of alcohol molecules such as methanol, ethanol, and 1-propanol confined in slit-shaped graphitic micropores of activated carbon fibers (ACFs) having different pore widths was measured at 303 K. The effect of the pore width on the molecular assembly structure of alcohol in the micropores was examined. The XRD patterns were analyzed by use of the electron radial distribution function (ERDF) analysis. The adsorbed density of alcohol in micropores of 1.1 nm in width was close to the solid density, while that in micropores of 0.7 nm in width was smaller than the liquid density. The ERDF of alcohol adsorbed in the 0.7 nm micropores showed a highly ordered structure compared with the 1.1 nm micropores, which is completely different from the adsorbed density results. It was presumed that alcohol molecules are hydrogen-bonded to form a layered structure, which is fit for the slit-shaped micropore.},
  creationdate = {2023-10-10T00:00:00},
  doi          = {https://doi.org/10.1016/S0927-7757(01)00627-6},
  file         = {:Ohkubo2001 - Oriented Structures of Alcohol Hidden in Carbon Micropores with ERDF Analysis.pdf:PDF},
  keywords     = {Carbon micropores, ERDF analysis, Alcohol, X-ray diffraction (XRD), 1-propanol, x-ray, confinement, propanol structure, cage, hydrate},
  url          = {https://www.sciencedirect.com/science/article/pii/S0927775701006276},
}

@Article{Udachin2011,
  author       = {Udachin, Konstantin and Alavi, Saman and Ripmeester, John A.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Communication: Single crystal x-ray diffraction observation of hydrogen bonding between 1-propanol and water in a structure II clathrate hydrate}},
  year         = {2011},
  issn         = {0021-9606},
  month        = mar,
  number       = {12},
  pages        = {121104},
  volume       = {134},
  abstract     = {{Single crystal x-ray crystallography is used to detect guest–host hydrogen bonding in structure II (sII) binary clathrate hydrate of 1-propanol and methane. X-ray structural analysis shows that the 1-propanol oxygen atom is at a distance of 2.749 and 2.788 Å from the closest clathrate hydrate water oxygen atoms from a hexagonal face of the large sII cage. The 1-propanol hydroxyl hydrogen atom is disordered and at distances of 1.956 and 2.035 Å from the closest cage water oxygen atoms. These distances are compatible with guest–water hydrogen bonding. The C–C–C–O torsional angle in 1-propanol in the cage is 91.47° which corresponds to a staggered conformation for the guest. Molecular dynamics studies of this system demonstrated guest–water hydrogen bonding in this hydrate. The molecular dynamics simulations predict most probable distances for the 1-propanol–water oxygen atoms to be 2.725 Å, and the average C–C–C–O torsional angle to be ∼59° consistent with a gauche conformation. The individual cage distortions resulting from guest–host hydrogen bonding from the simulations are rather large, but due to the random nature of the hydrogen bonding of the guest with the 24 water molecules making up the hexagonal faces of the large sII cages, these distortions are not observed in the x-ray structure.}},
  creationdate = {2023-10-10T00:00:00},
  doi          = {10.1063/1.3574393},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.3574393/15435968/121104\_1\_online.pdf},
  file         = {:Udachin2011 - Communication_ Single Crystal X Ray Diffraction Observation of Hydrogen Bonding between 1 Propanol and Water in a Structure II Clathrate Hydrate.pdf:PDF},
  keywords     = {1-propanol structure, cage, hydrate, clathrate, x-ray, molecular dynamics simulation},
  url          = {https://doi.org/10.1063/1.3574393},
}

@Article{Gabriel2017,
  author       = {Gabriel, Jan and Pabst, Florian and Blochowicz, Thomas},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Debye Process and β-Relaxation in 1-Propanol Probed by Dielectric Spectroscopy and Depolarized Dynamic Light Scattering},
  year         = {2017},
  note         = {PMID: 28872311},
  number       = {37},
  pages        = {8847--8853},
  volume       = {121},
  abstract     = {We revisit the reorientational dynamics of 1-propanol as a prototype of a monohydroxy alcohol and H-bonding system by dielectric spectroscopy (DS) and depolarized dynamic light scattering (DDLS). In particular, we address the question of whether the Debye relaxation, which is seen as a dominant process in DS, is visible in light scattering and discuss how the Johari–Goldstein (JG) β-process, which is also a prominent feature of the dielectric spectrum, appears in photon correlation spectroscopy. For that purpose we performed depolarized photon correlation experiments with an improved setup and performed additional time domain dielectric experiments which gives us the possibility to compare dielectric and light scattering data in a broad temperature range. It turns out that the improved setup allows to unambiguously identify the JG β-process, which shows almost identical properties in DDLS as in the dielectric spectra, but a Debye relaxation is not present in the DDLS data and can be excluded down to a level of 2.5\% of the α-process amplitude.},
  creationdate = {2023-10-10T00:00:00},
  doi          = {10.1021/acs.jpcb.7b06134},
  eprint       = {https://doi.org/10.1021/acs.jpcb.7b06134},
  file         = {:Gabriel2017 - Debye Process and Β Relaxation in 1 Propanol Probed by Dielectric Spectroscopy and Depolarized Dynamic Light Scattering.pdf:PDF},
  keywords     = {1-propanol, dielectrics, light scattering, pcs, bds, johari-goldstein, alpha, beta, debye},
  ranking      = {rank4},
  url          = {https://doi.org/10.1021/acs.jpcb.7b06134},
}

@Article{Davidson1951,
  author       = {Davidson, D. W. and Cole, R. H.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Dielectric Relaxation in Glycerol, Propylene Glycol, and n‐Propanol}},
  year         = {1951},
  issn         = {0021-9606},
  month        = dec,
  number       = {12},
  pages        = {1484--1490},
  volume       = {19},
  abstract     = {{Complex dielectric constants have been measured at frequencies from below 20 c/s to 5 mc/s over the temperature range −40° to −75°C in glycerol, −45° to −90° in propylene glycol, and −80° to −140° in n‐propanol. The results for n‐propanol are described by the Debye equation, but the values for the other two require a modified equation corresponding to a broader range of dispersion at higher frequencies. In all three liquids, evidence is found for a second dispersion region at still higher frequencies, which accounts for much of the difference between the radio frequency and optical dielectric constant. The relaxation times are quantitatively described over wide ranges by an empirical rate equation of a form which also fits viscosity data. The significance of the various results is discussed.}},
  comment      = {electronic article published in december 2004},
  creationdate = {2023-10-11T00:00:00},
  doi          = {10.1063/1.1748105},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/19/12/1484/8111531/1484\_1\_online.pdf},
  file         = {:Davidson2004 - Dielectric Relaxation in Glycerol, Propylene Glycol, and N‐Propanol.pdf:PDF},
  keywords     = {1-propanol, bds, glass, alpha, beta},
  url          = {https://doi.org/10.1063/1.1748105},
}

@Article{Jagannathan1987,
  author       = {Jagannathan, N. R. and Venkateswaran, K. and Herring, F. G. and Patey, G. N. and Walker, David C.},
  journal      = {The Journal of Physical Chemistry},
  title        = {Localization of methanol, ethanol, and 2-propanol at micelles in water: an NMR T1-relaxation study},
  year         = {1987},
  number       = {17},
  pages        = {4553--4555},
  volume       = {91},
  abstract     = {Small aliphatic alcohols have been found to localize at dilute micelles rather than remain dispersed in water when surfactants are added, even at low concentrations. Evidence for this was obtained from the effects of added micelles on proton NMR spin-lattice relaxations induced by the microenvironment with and without paramagnetic ions. Use was made of the double pulse inversion-recovery technique ($\pi$-t $\pi$/2 sequence). These alcohols are among the most water-soluble organic compounds known, so their localization indicates how strongly all nonionic molcules are forced from water’s structure. By comparison with benzene it is suggested that the alcohols locate at the micelle surface. It was not possible to evaluate the actual degree of localization but it must be very “substantial”. The most striking effect was that paramagnetic Mn2+-induced relaxations were greatly enhanced by negatively charged micelles and weakly reduced by positive micelles. This is consistent with Mn2+ being attracted into or repelled from the micelle’s double layer and is due to magnetic dipolar coupling of the localized proton with the electronic spin of the paramagnetic ion.},
  creationdate = {2023-10-12T00:00:00},
  doi          = {10.1021/j100301a026},
  eprint       = {https://doi.org/10.1021/j100301a026},
  file         = {:Jagannathan1987 - Localization of Methanol, Ethanol, and 2 Propanol at Micelles in Water_ an NMR T1 Relaxation Study.pdf:PDF},
  keywords     = {aqueous alcohol, micelles, ethanol, methanol, 2-propanol, i-propanol, iso-propanol, nmr, t1, spin-lattice relaxation},
  url          = {https://doi.org/10.1021/j100301a026},
}

@Article{Seto1996,
  author       = {Seto, Tomoyoshi and Mashimo, Takashi and Yoshiya, Ikuto and Shimizu, Akio and Fumino, Koichi and Taniguchi, Yoshihiro},
  journal      = {Journal of Molecular Liquids},
  title        = {NMR Studies on Dynamic Structure of Hydrated Water Molecules in Alcohol-D2O Solutions},
  year         = {1996},
  number       = {1},
  pages        = {1--9},
  volume       = {70},
  abstract     = {The spin-lattice relaxation times (T1) of D and 17O nuclei of coordinated D2O molecules in n-ROH (R= Me, Et, Pr and Bu) dilute aqueous solutions in the concentration range of 0.2 and 1.0 mol kg−1( 0.004 - 0.02 molar fraction ) at 25°C were measured by NMR spectroscopy. The relaxation rates (R1=1/T1) of D and 17O nuclei increased linearly with the concentration. B1(i=D or 17O) is defined by R1=R10(1 + B1m), where R1 and R10 are spin-lattice relaxation rates of the D2O molecule at concentration m (mol kg−1) and that of pure D2O. B1 increases with the size of the alkyl group of n-ROH. T1 in alcohol/water solutions were interpreted with bulk and coordinated water. Positive and molecular size dependent B1, values are caused by the hydrophobic hydration of the alkyl group. The dynamic hydration number of alcohol solution had good correlation with partial molar volume quantitatively through solute-solvent interactions.},
  creationdate = {2023-10-12T00:00:00},
  doi          = {https://doi.org/10.1016/0167-7322(96)00951-8},
  file         = {:Seto1996 - NMR Studies on Dynamic Structure of Hydrated Water Molecules in Alcohol D2O Solutions.pdf:PDF},
  keywords     = {aqueous alcohols,nmr,spin-lattice relaxation,17o-nmr,2h-nmr,methanol,ethanol,propanol,butanol,hydration number,clathrate,hydrophobic hydration},
  url          = {https://www.sciencedirect.com/science/article/pii/0167732296009518},
}

@Article{Masashi2003,
  author       = {Mizukami Masashi and Kurihara Kazue},
  journal      = {Australian Journal of Chemistry},
  title        = {Hydrogen-Bonded Macroculster Formation of 1-Propanol and 2-Propanol on Silica Surfaces},
  year         = {2003},
  pages        = {1071--1080},
  volume       = {56},
  comment      = {paywall},
  creationdate = {2023-10-12T00:00:00},
  doi          = {https://doi.org/10.1071/CH03127},
  keywords     = {self-assembly, 1-propanol, 2-propanol, silica surface},
  ranking      = {rank4},
  url          = {https://doi.org/10.1071/CH03127},
}

@Article{Nakada2011,
  author       = {Nakada ,Masaru and Maruyama ,Kenji and Yamamuro ,Osamu and Kikuchi ,Tatsuya and Misawa ,Masakatsu},
  journal      = {Journal of the Physical Society of Japan},
  title        = {Unified Effect of Hydrophobic Hydration on the Dynamics and the Structure of Water Molecules in Lower Alcohol Aqueous Solutions},
  year         = {2011},
  number       = {4},
  pages        = {044604},
  volume       = {80},
  abstract     = {After the analysis of the quasi-elastic neutron scattering (QENS) spectra of lower alcoholic aqueous solutions, we found that the parameter α, which is the number fraction of hydrophobic hydrating water molecules, has an important role in describing the dynamics and other properties of these solutions. The diffusion coefficient D was obtained from QENS spectra using the relaxing cage model, and D was found to have the same linear relation against α for ethyl alcohol, n -propyl alcohol, i -propyl alcohol, and t -butyl alcohol (with a small deviation) aqueous solutions. The excess molar volume and average hydration number of these solutions could also be expressed with common parameters, which are independent of the alcohol species.},
  creationdate = {2023-10-13T00:00:00},
  doi          = {10.1143/JPSJ.80.044604},
  eprint       = {https://doi.org/10.1143/JPSJ.80.044604},
  file         = {:Nakada2011 - Unified Effect of Hydrophobic Hydration on the Dynamics and the Structure of Water Molecules in Lower Alcohol Aqueous Solutions.pdf:PDF},
  keywords     = {1-propanol, 2-propanol, ethanol, t-butanol, QENS, neutron, self-diffusion, hydrophobic hydration, hydration number},
  url          = {https://doi.org/10.1143/JPSJ.80.044604},
}

@Article{ShakerGaafar1993,
  author       = {Shaker-Gaafar, N. and Karger, N. and Wappmann, S. and Lüdemann, H.-D.},
  journal      = {Berichte der Bunsengesellschaft für physikalische Chemie},
  title        = {p,T-Dependence of Self-diffusion in Liquid Ethanol and the Propanols},
  year         = {1993},
  number       = {6},
  pages        = {805--811},
  volume       = {97},
  abstract     = {The p,T-dependence of the self diffusion coefficients D for ethanol-OD, 1- and 2-propanol-OH and -OD have been studied in a wide temperature range at pressures up to 200 MPa. The experiments were performed in strengthened high pressure glass cells by the pulsed field gradient NMR-technique. The isobaric temperature dependence of D is given by the VTF-equation. The isotherms can be fitted to the rough hard sphere model with an A-parameter that decreases strongly with falling temperature.},
  comment      = {paywall},
  creationdate = {2023-10-13T00:00:00},
  doi          = {https://doi.org/10.1002/bbpc.19930970610},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/bbpc.19930970610},
  keywords     = {Diffusion, High Pressure, Isotope Effects, Liquids, Spectroscopy, Nuclear Magnetic Resonance},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/bbpc.19930970610},
}

@Article{DiezPena2002,
  author       = {Díez-Peña, Eva and Quijada-Garrido, Isabel and Barrales-Rienda, José Manuel and Wilhelm, Manfred and Spiess, Hans Wolfgang},
  journal      = {Macromolecular Chemistry and Physics},
  title        = {NMR Studies of the Structure and Dynamics of Polymer Gels Based on N-Isopropylacrylamide (NiPAAm) and Methacrylic Acid (MAA)},
  year         = {2002},
  number       = {3},
  pages        = {491--502},
  volume       = {203},
  abstract     = {A series of copolymer gels and interpenetrating networks (IPN) based on N-isopropylacrylamide (NiPAAm) and methacrylic acid (MAA) were synthesized and subsequently investigated by magic angle spinning 1H MAS, cross polarization 13C CP-MAS and pulse-saturation transfer 13C PST-MAS NMR. The structure of the interpenetrating networks is compared to that of the copolymer gels with the same composition. The study of the proton lines reveals low mobility of the chains in the copolymer gels and IPN with higher concentration of MAA, whereas those which are predominantly NiPAAm show higher mobility and therefore narrower proton lines. 13C CP-MAS revealed an interaction between the components of the IPNs. The PST-MAS technique was utilized to study the structure of the polymers in the gel phase. Copolymer gels exhibit some additional peaks in the carbonyl region due to the new chemical environment in the stereoregular sequences. In order to assure assignment, uncrosslinked copolymers with similar compositions as the copolymer gels were synthesized for comparative purposes and examined by conventional solution-state 13C NMR. A linear homopolymer of NiPAAm was synthesized inside of a P(MAA) gel. The polymer was extracted after the completion of the reaction and characterized by solution 13C NMR. About 24\% of this P(NiPAAm) homopolymer could not be extracted presumably because of a strong hydrogen bonding or partial topological constrains. In the 13C NMR spectrum a new signal appeared in the carbonyl region due to MAA monomeric units. It may correspond to the methacrylic carbonyls interacting by hydrogen bonds with the amide groups.},
  creationdate = {2023-10-17T00:00:00},
  doi          = {https://doi.org/10.1002/1521-3935(20020201)203:3<491::AID-MACP491>3.0.CO;2-1},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/1521-3935%2820020201%29203%3A3%3C491%3A%3AAID-MACP491%3E3.0.CO%3B2-1},
  file         = {:DiezPena2002 - NMR Studies of the Structure and Dynamics of Polymer Gels Based on N Isopropylacrylamide (NiPAAm) and Methacrylic Acid (MAA).pdf:PDF},
  keywords     = {gels, interpenetrating networks (IPN), methacrylic acid, N-isopropylacrylamide, NMR, pNIPAM, PMAA, 1h-nmr, MAS, 13C-NMR, CP-MAS},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/1521-3935%2820020201%29203%3A3%3C491%3A%3AAID-MACP491%3E3.0.CO%3B2-1},
}

@Book{,
  editor       = {Vitaliy V. Khutoryanskiy and Theoni K. Georgiou},
  publisher    = {John Wiley \& Sons Ltd.},
  title        = {Temperature-responsive Polymers - Chemistry, Properties and Applications},
  year         = {2018},
  isbn         = {9781119157830},
  creationdate = {2023-11-06T00:00:00},
  doi          = {10.1002/9781119157830},
  file         = {:- Temperature Responsive Polymers Chemistry, Properties and Applications.pdf:PDF},
  keywords     = {thermo-responsive, book},
}

@Article{Moschos2023,
  author       = {Moschos, Vasileios and Ananiadou, Antonela and Floudas, George},
  journal      = {The Journal of Chemical Physics},
  title        = {{Dynamically and structurally heterogeneous 1-propanol/water mixtures}},
  year         = {2023},
  issn         = {0021-9606},
  month        = oct,
  number       = {16},
  pages        = {164903},
  volume       = {159},
  abstract     = {{1-propanol/water mixtures over the whole composition range (0 \\&lt; XV ≤ 1; XV is the 1-propanol volume fraction) are shown to be structurally and dynamically heterogeneous. By combining structural (x-ray diffraction), thermodynamic (differential scanning calorimetry) and dynamical probes (dielectric spectroscopy) we construct the pertinent phase diagram. It consists of liquid 1-propanol, liquid water, hexagonal ice and different hydrates, the latter sharing the same lattice. The phase diagram can be discussed in terms of four regimes, all having in common a droplet arrangement of the minority component. When water droplets are strongly confined by 1-propanol (regime I, 0.92 \\&lt; XV ≤ 1; “soft” confinement), water is unable to crystallize. It has dynamics reminiscent to the ultra-viscous water phase known as high-density liquid (HDL). When water droplets are moderately confined (regime II, 0.75 \\&lt; XV ≤ 0.92) water can crystallize via homogeneous nucleation. Strikingly, the homogeneous nucleation temperature is at 205 K, well within “no-man’s land.” The result is in line with earlier reports that soft confinement is the key to enter into the “no-man’s land”. When 1-propanol is the minority component (regimes III and IV), the structure and the dynamics are dominated by the 1-propanol/water interface with the formation of hydrates. The corresponding dynamical features suggest a link between hydrate formation and the two metastable phases of ultra-viscous water, HDL and low-density liquid.}},
  creationdate = {2023-11-20T00:00:00},
  doi          = {10.1063/5.0170504},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/5.0170504/18183969/164903\_1\_5.0170504.pdf},
  file         = {:Moschos2023 - Dynamically and Structurally Heterogeneous 1 Propanol_water Mixtures.pdf:PDF;:Moschos2023 - Dynamically and Structurally Heterogeneous 1 Propanol_water Mixtures.docx:Word 2007+},
  keywords     = {floudas, katharina, aqueous propanol, dsc, x-ray, bds, phase diagram, cage, clathrate, hydrophobic hydration},
  readstatus   = {read},
  url          = {https://doi.org/10.1063/5.0170504},
}

@Article{Findeisen2007,
  author       = {Findeisen, M. and Brand, T. and Berger, S.},
  journal      = {Magnetic Resonance in Chemistry},
  title        = {A 1H-NMR thermometer suitable for cryoprobes},
  year         = {2007},
  number       = {2},
  pages        = {175--178},
  volume       = {45},
  abstract     = {Most established NMR thermometers rely on temperature-dependent chemical shift differences measured from samples that are either neat or concentrated solutions (e.g. ethylene glycol, methanol). These are unsuitable for modern cryoprobes on account of strong radiation damping resulting from the high Q of the probe. Using perdeuterated methanol, we established a relationship between the chemical shift difference and temperature, and we show that this relationship is well fitted by a quadratic equation. The actual temperature within a sample tube in the probe was verified using a Pt-100 resistor. Copyright © 2006 John Wiley \& Sons, Ltd.},
  creationdate = {2023-11-20T00:00:00},
  doi          = {https://doi.org/10.1002/mrc.1941},
  eprint       = {https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/pdf/10.1002/mrc.1941},
  file         = {:Findeisen2007 - A 1H NMR Thermometer Suitable for Cryoprobes.pdf:PDF},
  keywords     = {NMR, temperature, cryoprobe, shift thermometer, Pt-100 resistor, methanol-d4, 1GHz},
  url          = {https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/abs/10.1002/mrc.1941},
}

@Article{Smith1966,
  author       = {D.W.G. Smith and J.G. Powles},
  journal      = {Molecular Physics},
  title        = {Proton spin-lattice relaxation in liquid water and liquid ammonia},
  year         = {1966},
  number       = {5},
  pages        = {451--463},
  volume       = {10},
  abstract     = {The proton spin-lattice relaxation time has been measured at 20·8 Mc/s for a series of solutions of water in heavy water and solutions of ammonia in heavy ammonia for the temperature range from the melting point to the liquid-vapour critical temperature. Measurements have also been made for water over limited temperature ranges at several fixed densities. The contributions to the spin-lattice relaxation time from direct dipolar and spin-rotation interactions have been separated. The spin-rotation interaction contribution appears to be the same for H2O as for HDO and also as between NH3, NH2D and NHD2 and this result is justified. The correlation times for molecular re-orientation, τd, and for molecular angular velocity, τsr, are derived from the results and in so doing some support for the Hubbard [12] relation betweent τsr and τd is adduced. It is found that at the critical temperature τsr≪τd which contrasts with other liquids for which it is usually found that τsr≪⃒τd. The spin-rotation interaction constants in the water and ammonia molecules are found to be approximately 120 kc/s and 80 kc/s, respectively. An attempt to separate the inter- and intra-molecular contributions to the dipolar spin-lattice relaxation time is possible in principle, in spite of the rapid proton exchange, but is frustrated by the fact that the equilibrium constants are little different from their statistical values. Nevertheless there is evidence that the two interactions vary in much the same way with temperature. The correlation times deduced from the dipolar relaxation time show close relationship with dielectric, self diffusion and deuteron relaxation time data. It is suggested that the re-orientation of both water and ammonia molecules may be by a small angle Brownian diffusion even near the critical temperature.},
  creationdate = {2023-11-24T00:00:00},
  doi          = {10.1080/00268976600100571},
  eprint       = {https://doi.org/10.1080/00268976600100571},
  file         = {:Smith1966 - Proton Spin Lattice Relaxation in Liquid Water and Liquid Ammonia.pdf:PDF},
  keywords     = {1H-nmr, proton spin-lattice relaxation, T1, hdo, water, h2o, d2o, dipole dilution},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/00268976600100571},
}

@Article{SzantayJr.1999,
  author       = {Szántay Jr., Csaba and Demeter, Ádám},
  journal      = {Concepts in Magnetic Resonance},
  title        = {Radiation damping diagnostics},
  year         = {1999},
  number       = {3},
  pages        = {121--145},
  volume       = {11},
  abstract     = {With the trend of designing supersensitive probes and very-high-field magnets, the phenomenon of radiation damping is increasingly being perceived as starting to invade the realm of normal nuclear magnetic resonance. This article explores the scope and limitations of the various spectral tools available to diagnose the presence of radiation damping. It is shown that the recovery rate of the Mz magnetization is the most sensitive parameter to indicate weak damping. This effect can be measured by using suitable gradient techniques. ©1999 John Wiley \& Sons, Inc. Concepts Magn Reson 11: 121–145, 1999},
  creationdate = {2023-11-25T00:00:00},
  doi          = {https://doi.org/10.1002/(SICI)1099-0534(1999)11:3<121::AID-CMR2>3.0.CO;2-Z},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/%28SICI%291099-0534%281999%2911%3A3%3C121%3A%3AAID-CMR2%3E3.0.CO%3B2-Z},
  file         = {:SzantayJr.1999 - Radiation Damping Diagnostics.pdf:PDF},
  keywords     = {radiation damping, FID shape, line shape, radiation damping difference spectroscopy (RADDSY), transition-band signals},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/%28SICI%291099-0534%281999%2911%3A3%3C121%3A%3AAID-CMR2%3E3.0.CO%3B2-Z},
}

@Article{Gray1979,
  author       = {D.L. Gray and A.G. Robiette},
  journal      = {Molecular Physics},
  title        = {The anharmonic force field and equilibrium structure of methane},
  year         = {1979},
  number       = {6},
  pages        = {1901--1920},
  volume       = {37},
  abstract     = {The anharmonic force field of methane has been refined to fit spectroscopic data from the isotopic species 12CH4, 13CH4, 12CH4, 12CH3D, 12CHD3 and 12CH2D2. Six of the thirteen cubic force constants have been determined experimentally, the remaining cubic constants being fixed at values derived from ab initio calculations. The quartic force field is very crude, in that only frrrr
 has been refined. It is concluded however that the cubic and quartic force fields, even though they are subject to limitations, provide a considerable improvement in the experimental determination of the r
e structure and the quadratic force field. The equilibrium bond length is found to be r
e(CH) = 1·0858 ± 0·001 Å.},
  creationdate = {2023-11-27T00:00:00},
  doi          = {10.1080/00268977900101401},
  eprint       = {https://doi.org/10.1080/00268977900101401},
  file         = {:Gray1979 - The Anharmonic Force Field and Equilibrium Structure of Methane.pdf:PDF},
  keywords     = {methane, structure, simulation, force field},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/00268977900101401},
}

@Article{Khodadadi2015,
  author       = {Khodadadi, S. and Sokolov, A. P.},
  journal      = {Soft Matter},
  title        = {Protein dynamics: from rattling in a cage to structural relaxation},
  year         = {2015},
  pages        = {4984--4998},
  volume       = {11},
  abstract     = {We present an overview of protein dynamics based mostly on results of neutron scattering{,} dielectric relaxation spectroscopy and molecular dynamics simulations. We identify several major classes of protein motions on the time scale from faster than picoseconds to several microseconds{,} and discuss the coupling of these processes to solvent dynamics. Our analysis suggests that the microsecond backbone relaxation process might be the main structural relaxation of the protein that defines its glass transition temperature{,} while faster processes present some localized secondary relaxations. Based on the overview{,} we formulate a general picture of protein dynamics and discuss the challenges in this field.},
  creationdate = {2023-11-29T00:00:00},
  doi          = {10.1039/C5SM00636H},
  file         = {:Khodadadi2015 - Protein Dynamics_ from Rattling in a Cage to Structural Relaxation.pdf:PDF},
  issue        = {25},
  keywords     = {protein dynamics,neutron scattering,bds,dielectrics,molecular dynamics simulation,md simulation,protein},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C5SM00636H},
}

@Article{Yu2014,
  author       = {Yu, Qian and Ista, Linnea K. and López, Gabriel P.},
  journal      = {Nanoscale},
  title        = {Nanopatterned antimicrobial enzymatic surfaces combining biocidal and fouling release properties},
  year         = {2014},
  pages        = {4750--4757},
  volume       = {6},
  abstract     = {Surfaces incorporating the antimicrobial enzyme{,} lysozyme{,} have been previously demonstrated to effectively disrupt bacterial cellular envelopes. As with any surface active antimicrobial{,} however{,} lysozyme-expressing surfaces become limited in their utility by the accumulation of dead bacteria and debris. Surfaces modified with environmentally responsive polymers{,} on the other hand{,} have been shown to reversibly attach and release both live and dead bacterial cells. In this work{,} we combine the antimicrobial activity of lysozyme with the fouling release capability of the thermally responsive polymer{,} poly(N-isopropylacrylamide) (PNIPAAm){,} which has a lower critical solution temperature (LCST) in water at ∼32 °C. Nanopatterned PNIPAAm brushes were fabricated using interferometric lithography followed by surface-initiated polymerization. Lysozyme was then adsorbed into the polymer-free regions of the substrate between the brushes to achieve a hybrid surface with switchable antimicrobial activity and fouling-release ability in response to the change of temperature. The temperature triggered hydration and conformational change of the nanopatterned PNIPAAm brushes provide the ability to temporally regulate the spatial concealment and exposure of adsorbed lysozyme. The biocidal efficacy and release properties of the hybrid surface were tested against Escherichia coli K12 and Staphylococcus epidermidis. The hybrid surfaces facilitated the attachment of bacteria at 37 °C for E. coli and 25 °C for S. epidermidis and when the temperature is above the LCST{,} collapsed and dehydrated PNIPAAm chains expose lysozyme to kill attached bacteria. Changing temperature across the LCST of PNIPAAm (e.g. from 37 °C to 25 °C for E. coli or from 25 °C to 37 °C for S. epidermidis) to induce a hydration transition of PNIPAAm promoted the release of dead bacteria and debris from the surfaces upon mild shearing. These results suggest that nano-engineered surfaces can provide an effective way for actively mitigating short term bacterial biofouling.},
  creationdate = {2023-12-04T00:00:00},
  doi          = {10.1039/C3NR06497B},
  file         = {:Yu2014 - Nanopatterned Antimicrobial Enzymatic Surfaces Combining Biocidal and Fouling Release Properties.pdf:PDF},
  issue        = {9},
  keywords     = {pNIPAM, anti-fouling, biomedical, application-focused, application focused},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C3NR06497B},
}

@Article{Whittaker1995,
  author       = {Andrew K. Whittaker and Tim Bremner and Fernando O. Zelaya},
  journal      = {Polymer},
  title        = {The effect of field inhomogeneities and molecular diffusion on the NMR transverse relaxation behaviour of polymer melts},
  year         = {1995},
  issn         = {0032-3861},
  number       = {11},
  pages        = {2159--2164},
  volume       = {36},
  abstract     = {The formation of spin-echoes in the Carr-Purcell-Meiboom Gill (CPMG) NMR experiment on rubbery polybutadiene (PBD) has been studied as a function of temperature and CPMG inter-pulse spacing. The influence of internal field gradients, and of diffusional motion of the polymer segments during the inter-pulse periods is demonstrated. The CPMG decays are well described by diffusion equations for the case of diffusion of particles through connecting cylinders. Microscopic voids of diameter of ∼ 0.5 nm adjacent to the reptating chain segments are suggested to be responsible for the magnetic field gradients.},
  creationdate = {2023-12-05T00:00:00},
  doi          = {https://doi.org/10.1016/0032-3861(95)95291-8},
  file         = {:Whittaker1995 - The Effect of Field Inhomogeneities and Molecular Diffusion on the NMR Transverse Relaxation Behaviour of Polymer Melts.pdf:PDF},
  keywords     = {polymer melt, NMR relaxation, molecular diffusion, cpmg, field inhomogeneities, t2, spin-spin relaxation},
  url          = {https://www.sciencedirect.com/science/article/pii/0032386195952918},
}

@Book{SchmidtRohr1994,
  author       = {K. Schmidt-Rohr and H. W. Spiess},
  publisher    = {Academic Press},
  title        = {Multidimensional solid-state NMR and polymers},
  year         = {1994},
  isbn         = {0126266301},
  creationdate = {2023-12-07T00:00:00},
  file         = {:SchmidtRohr1994 - Multidimensional Solid State NMR and Polymers.pdf:PDF},
  keywords     = {book, nmr},
}

@Article{Geukens2008,
  author   = {Geukens, Barbara and Meersman, Filip and Nies, Erik},
  journal  = {The Journal of Physical Chemistry B},
  title    = {Phase Behavior of N-(Isopropyl)\-propionamide in Aqueous Solution and Changes in Hydration Observed by FTIR Spectroscopy},
  year     = {2008},
  note     = {PMID: 18355069},
  number   = {15},
  pages    = {4474--4477},
  volume   = {112},
  abstract = {The phase behavior of N-(isopropyl)propionamide (NiPPA), which is the repeat unit of poly(N-isopropyl-acrylamide) (PNiPA), in deuterated aqueous solution was investigated. Temperature induces a phase separation of NiPPA in aqueous solution above the lower critical solution temperature (LCST), as shown by optical microscopy. The phase behavior of NiPPA resembles that of PNiPA, but the demixing domain is much narrower. Monitoring the liquid−liquid phase separation by Fourier transform infrared (FTIR) spectroscopy reveals that a fraction of the NiPPA molecules becomes dehydrated above the LCST. Our findings therefore shed new light on the results of a recent dielectric relaxation experiment in which the behavior of NiPPA was found to be “completely contrary” to that of PNiPA. It is argued that the differences in the spectroscopic results of polymer and repeat unit solutions can be easily understood from the phase behavior of NiPPA and PNiPA.},
  doi      = {10.1021/jp801127e},
  eprint   = {https://doi.org/10.1021/jp801127e},
  file     = {:Geukens2008 - Phase Behavior of N (Isopropyl)propionamide in Aqueous Solution and Changes in Hydration Observed by FTIR Spectroscopy.pdf:PDF;:PhaseBehaviorOfNIsopropylpropionamideInAqueousSolutionAndChangesInHydrationObservedByFTIRSpectroscopy_SI.pdf:PDF},
  keywords = {NIPPA, pNIPAM monomer analogue, FTIR, d2o, heavy water, LCST, concentration-dependence},
  url      = {https://doi.org/10.1021/jp801127e},
}

@Article{Kimmich2004,
  author       = {Rainer Kimmich and Esteban Anoardo},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {Field-cycling NMR relaxometry},
  year         = {2004},
  issn         = {0079-6565},
  number       = {3},
  pages        = {257--320},
  volume       = {44},
  creationdate = {2024-01-04T00:00:00},
  doi          = {https://doi.org/10.1016/j.pnmrs.2004.03.002},
  file         = {:Kimmich2004 - Field Cycling NMR Relaxometry.pdf:PDF},
  keywords     = {nmr, field cycling, theory},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079656504000196},
}

@Article{Fujara2014,
  author       = {Franz Fujara and Danuta Kruk and Alexei F. Privalov},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {Solid state Field-Cycling NMR relaxometry: Instrumental improvements and new applications},
  year         = {2014},
  issn         = {0079-6565},
  pages        = {39--69},
  volume       = {82},
  abstract     = {The paper reviews recent progress in field cycling (FC) NMR instrumentation and its application to solid state physics. Special emphasis is put on our own work during the last 15years on instrumentation, theory and applications. As far as instrumentation is concerned we report on our development of two types of electronical FC relaxometers, a mechanical FC relaxometer and a combination of FC and one-dimensional microimaging. Progress has been achieved with respect to several parameters such as the accessible field and temperature range as well as the incorporation of sample spinning. Since an appropriate analysis of FC data requires a careful consideration of relaxation theory, we include a theory section discussing the most relevant aspects of relaxation in solids which are related to residual dipolar and quadrupolar interactions. The most important limitations of relaxation theory are also discussed. With improved instrumentation and with the help of relaxation theory we get access to interesting new applications such as ionic motion in solid electrolytes, structure determination in molecular crystals, ultraslow polymer dynamics and rotational resonance phenomena.},
  creationdate = {2024-01-04T00:00:00},
  doi          = {https://doi.org/10.1016/j.pnmrs.2014.08.002},
  file         = {:Fujara2014 - Solid State Field Cycling NMR Relaxometry_ Instrumental Improvements and New Applications.pdf:PDF},
  keywords     = {NMR, Relaxometry, Field cycling, Instrumentation, Dynamical processes, review},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079656514000594},
}

@Article{Lips2001,
  author       = {O. Lips and A.F. Privalov and S.V. Dvinskikh and F. Fujara},
  journal      = {Journal of Magnetic Resonance},
  title        = {Magnet Design with High B0 Homogeneity for Fast-Field-Cycling NMR Applications},
  year         = {2001},
  issn         = {1090-7807},
  number       = {1},
  pages        = {22--28},
  volume       = {149},
  abstract     = {The design, construction, and performance of a low-inductance solenoidal coil with high B0 homogeneity for fast-field-cycling NMR is presented. It consists of six concentric layers. The conductor width is varied to minimize the B0 inhomogeneity in the volume of the sample. This is done using an algorithm which takes the real shape of the conductor directly into account. The calculated coil geometry can be manufactured easily using standard computerized numeric control equipment, which keeps the costs low. The coil is liquid cooled and produces a B0 field of 0.95 T at 800 A . The field inhomogeneity in a cylindrical volume (diameter 5 mm, length 10 mm) is about 10 ppm, and the inductance is 190 μH. Switching times below 200 μs can be achieved. During 6 months of operation the coil has shown good stability and reliability.},
  creationdate = {2024-01-04T08:22:05},
  doi          = {https://doi.org/10.1006/jmre.2000.2279},
  file         = {:Lips2001 - Magnet Design with High B0 Homogeneity for Fast Field Cycling NMR Applications.pdf:PDF},
  keywords     = {field cycling, instrumental},
  url          = {https://www.sciencedirect.com/science/article/pii/S1090780700922791},
}

@Article{Dries1988,
  author       = {Dries, Th. and Fujara, F. and Kiebel, M. and Rössler, E. and Sillescu, H.},
  journal      = {The Journal of Chemical Physics},
  title        = {{2H‐NMR study of the glass transition in supercooled ortho‐terphenyl}},
  year         = {1988},
  issn         = {0021-9606},
  month        = feb,
  number       = {4},
  pages        = {2139--2147},
  volume       = {88},
  abstract     = {{The glass forming molecular liquid ortho‐terphenyl has been investigated by 2H‐NMR techniques providing spin‐relaxation times (T1, T2), and spin‐alignment data which yield information on the time scale and geometry of ultra‐slow molecular reorientation. The main results are as follows: The primary glass transition (α process) is characterized by rotational molecular jumps with a jump size distribution weighted in favor of large jump angles, and by a distribution of correlation times. In addition intramolecular flip–flop jumps of the lateral phenyl rings are found which do not take part in the α process. Apart from this (secondary) intramolecular dynamics no residual small angle reorientation persists below Tg on the time scale (10−4 to 102 s) of the spin‐alignment experiment.}},
  creationdate = {2024-01-04T08:52:05},
  doi          = {10.1063/1.454047},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/88/4/2139/9726433/2139\_1\_online.pdf},
  file         = {:Dries1988 - 2H‐NMR Study of the Glass Transition in Supercooled Ortho‐terphenyl.pdf:PDF},
  keywords     = {glass transition, 2h-nmr, t1, t2, spin-lattice relaxation, spin-spin relaxation, johari-goldstein, alpha, beta, spin alignment, orto-terphenyl, otp},
  url          = {https://doi.org/10.1063/1.454047},
}

@Article{Schmidt2010,
  author       = {Schmidt, Stephan and Zeiser, Michael and Hellweg, Thomas and Duschl, Claus and Fery, Andreas and Möhwald, Helmuth},
  journal      = {Advanced Functional Materials},
  title        = {Adhesion and Mechanical Properties of PNIPAM Microgel Films and Their Potential Use as Switchable Cell Culture Substrates},
  year         = {2010},
  number       = {19},
  pages        = {3235--3243},
  volume       = {20},
  abstract     = {Thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) microgel films are shown to allow controlled detachment of adsorbed cells via temperature stimuli. Cell response occurs on the timescale of several minutes, is reversible, and allows for harvesting of cells in a mild fashion. The fact that microgels are attached non-covalently allows using them on a broad variety of (charged) surfaces and is a major advantage as compared to approaches relying on covalent attachment of active films. In the following, the microgels’ physico-chemical parameters in the adsorbed state and their changes upon temperature variation are studied in order to gain a deeper understanding of the involved phenomena. By means of atomic force microscopy (AFM), the water content, mechanical properties, and adhesion forces of the microgel films are studied as a function of temperature. The analysis shows that these properties change drastically when crossing the critical temperature of the polymer film, which is the basis of the fast cell response upon temperature changes. Furthermore, nanoscale mechanical analysis shows that the films posses a nanoscopic gradient in mechanical properties.},
  creationdate = {2024-01-09T10:06:00},
  doi          = {https://doi.org/10.1002/adfm.201000730},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/adfm.201000730},
  file         = {:Schmidt2010 - Adhesion and Mechanical Properties of PNIPAM Microgel Films and Their Potential Use As Switchable Cell Culture Substrates.pdf:PDF},
  keywords     = {atomic force microscopy, cell adhesion, hydrogels, thermally responsive materials, volume phase transitions, PNIPAM, application-focused, application focused},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.201000730},
}

@Article{Flaemig2016,
  author       = {Fl{\"a}mig, M. and Becher, M. and Hofmann, M. and K{\"o}rber, T. and Kresse, B. and Privalov, A. F. and Willner, L. and Kruk, D. and Fujara, F. and R{\"o}ssler, E. A.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Perspectives of Deuteron Field-Cycling NMR Relaxometry for Probing Molecular Dynamics in Soft Matter},
  year         = {2016},
  note         = {PMID: 27420118},
  number       = {31},
  pages        = {7754--7766},
  volume       = {120},
  abstract     = {Due to the single-particle character of the quadrupolar interaction in molecular systems, 2H NMR poses a unique method for probing reorientational dynamics. Spin–lattice relaxation gives access to the spectral density, and its frequency dependency can be monitored by field-cycling (FC) techniques. However, most FC NMR studies employ 1H; the use of 2H is still rare. We report on the application of 2H FC NMR for investigating the dynamics in molecular liquids and polymers. Commercial as well as home-built relaxometers are employed accessing a frequency range from 30 Hz to 6 MHz. Due to low gyromagnetic ratio, high coupling constants, and finite FC switching times, current 2H FC NMR does not reach the dispersion region in liquids (toluene and glycerol), yet good agreement with the results from conventional high-field (HF) relaxation studies is demonstrated. The pronounced difference at low frequencies between 2H and 1H FC NMR data shows the relevance of intermolecular relaxation in the case of 1H NMR. In the case of the polymers polybutadiene and poly(ethylene-alt-propylene), very similar relaxation dispersion is observed and attributed to Rouse and entanglement dynamics. Combination with HF 2H relaxation data via applying frequency–temperature superposition allows the reconstruction of the full spectral density reflecting both polymer as well as glassy dynamics. Transformation into the time domain yields the reorientational correlation function C2(t) extending over nine decades in time with a long-time power law, C2(t) $\propto$ t–0.45$\pm$0.05, which does not conform to the prediction of the tube-reptation model, for which $\propto$ t–0.25 is expected. Entanglement sets in below C2(t = τe) $ \cong$ S2 = 0.001, where τe is the entanglement time and S the corresponding order parameter. Finally, we discuss the future prospects of the 2H FC NMR technique.},
  creationdate = {2024-01-10T19:16:44},
  doi          = {10.1021/acs.jpcb.6b05109},
  eprint       = {https://doi.org/10.1021/acs.jpcb.6b05109},
  file         = {:Flaemig2016 - Perspectives of Deuteron Field Cycling NMR Relaxometry for Probing Molecular Dynamics in Soft Matter.pdf:PDF},
  keywords     = {field cycling, 2h-nmr, t1, spectral density},
  url          = {https://doi.org/10.1021/acs.jpcb.6b05109},
}

@Article{Korb2001,
  author       = {Korb, Jean-Pierre and Bryant, Robert G.},
  journal      = {The Journal of Chemical Physics},
  title        = {{The physical basis for the magnetic field dependence of proton spin-lattice relaxation rates in proteins}},
  year         = {2001},
  issn         = {0021-9606},
  month        = dec,
  number       = {23},
  pages        = {10964--10974},
  volume       = {115},
  abstract     = {{The magnetic field dependence of the proton spin-lattice relaxation rate in polymeric materials and biological macromolecules may report important dynamical information. In the case where the system is dynamically heterogeneous as in plasticized polymeric systems or hydrated biopolymers, the spin-lattice relaxation of the liquid-proton population is generally coupled to the spin-relaxation behavior of the solid spins that often dominate the observable response of the liquid. In many of these systems the magnetic field dependence of the proton spin-lattice relaxation rate may be represented as a power law: 1/T1(ω)=Aω−b where a is a constant and b is usually found to be in the range of 0.5 to 0.8. We have shown that this power law may arise naturally from localized structural fluctuations along the backbone of chain molecules that modulate the proton dipole–dipole couplings, which form a network described by a fractal dimension that may be less than the Euclidean dimension. When the model for the solid spin-lattice relaxation rate constant is incorporated into the relaxation equations that couple the liquid and solid spin population responses, the composite model accounts quantitatively for proton spin-lattice relaxation rates measured in immobilized and hydrated protein systems and provides a fundamental basis for understanding the parametric dependence of proton spin-lattice relaxation rates in dynamically heterogeneous systems such as hydrated biopolymers, proteins, and biological tissues.}},
  creationdate = {2024-01-10T19:27:04},
  doi          = {10.1063/1.1417509},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/115/23/10964/10836491/10964\_1\_online.pdf},
  file         = {:Korb2001 - The Physical Basis for the Magnetic Field Dependence of Proton Spin Lattice Relaxation Rates in Proteins.pdf:PDF},
  keywords     = {nmr, field cycling, t1, spin-lattice, 1h-nmr, proteins, hydration shell},
  url          = {https://doi.org/10.1063/1.1417509},
}

@Article{Steele2016,
  author       = {Steele, Rebecca M. and Korb, Jean-Pierre and Ferrante, Gianni and Bubici, Salvatore},
  journal      = {Magnetic Resonance in Chemistry},
  title        = {New applications and perspectives of fast field cycling NMR relaxometry},
  year         = {2016},
  number       = {6},
  pages        = {502--509},
  volume       = {54},
  abstract     = {The field cycling NMR relaxometry method (also known as fast field cycling (FFC) when instruments employing fast electrical switching of the magnetic field are used) allows determination of the spin-lattice relaxation time (T1) continuously over five decades of Larmor frequency. The method can be exploited to observe the T1 frequency dependence of protons, as well as any other NMR-sensitive nuclei, such as 2H, 13C, 31P, and 19F in a wide range of substances and materials. The information obtained is directly correlated with the physical/chemical properties of the compound and can be represented as a ‘nuclear magnetic resonance dispersion’ curve. We present some recent academic and industrial applications showing the relevance of exploiting FFC NMR relaxometry in complex materials to study the molecular dynamics or, simply, for fingerprinting or quality control purposes. The basic nuclear magnetic resonance dispersion features are outlined in representative examples of magnetic resonance imaging (MRI) contrast agents, porous media, proteins, and food stuffs. We will focus on the new directions and perspectives for the FFC technique. For instance, the introduction of the latest Wide Bore FFC NMR relaxometers allows probing, for the first time, of the dynamics of confined surface water contained in the macro-pores of carbonate rock cores. We also evidence the use of the latest field cycling technology with a new cryogen-free variable-field electromagnet, which enhances the range of available frequencies in the 2D T1–T2 correlation spectrum for separating oil and water in crude oil. Copyright © 2015 John Wiley \& Sons, Ltd.},
  creationdate = {2024-01-10T19:30:27},
  doi          = {https://doi.org/10.1002/mrc.4220},
  eprint       = {https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/pdf/10.1002/mrc.4220},
  file         = {:Steele2016 - New Applications and Perspectives of Fast Field Cycling NMR Relaxometry.pdf:PDF},
  keywords     = {NMR, relaxometry, fast field cycling relaxometry, T1, spin-lattivce relaxation, NMRD, molecular dynamics, low-field NMR, TD NMR},
  url          = {https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/abs/10.1002/mrc.4220},
}

@Article{Vorob’ev2005,
  author       = {Mikhail M. Vorob’ev and Nikolai G. Faleev},
  journal      = {Mendeleev Communications},
  title        = {Water ordering measurements in the aqueous polymer systems by waveguide dielectric resonance method},
  year         = {2005},
  issn         = {0959-9436},
  number       = {6},
  pages        = {259--261},
  volume       = {15},
  abstract     = {The method of waveguide dielectric resonance, a variation of millimeter spectroscopic technique, was used for the monitoring of water ordering in the hydration shells of synthetic polymers.},
  creationdate = {2024-01-12T03:59:16},
  doi          = {https://doi.org/10.1070/MC2005v015n06ABEH002160},
  file         = {:Vorob’ev2005 - Water Ordering Measurements in the Aqueous Polymer Systems by Waveguide Dielectric Resonance Method.pdf:PDF},
  url          = {https://www.sciencedirect.com/science/article/pii/S0959943605702741},
}

@PhdThesis{Becher2020,
  author       = {Manuel Becher},
  school       = {Technische Universit{\"a}t},
  title        = {NMR-Studien der molekularen Dynamik in ionischen Fl{\"u}ssigkeiten und Polymerelektrolyten},
  year         = {2020},
  address      = {Darmstadt},
  abstract     = {Glasbildende ionische Mischsysteme sind relevante Materialien in modernen Anwendungen der Energietechnik. Sie weisen neben der typischen Glasdynamik oft strukturelle Inhomogenit{\"a}ten auf, welche sich direkt auf Eigenschaften wie die Ionenleitf{\"a}higkeit auswirken. Im Rahmen dieser Arbeit standen zwei Klassen dieser Systeme im Fokus: Polymerelektrolyte (PE) und Ionische Fl{\"u}ssigkeiten (IL). Im Falle der PE findet sich ein Leitf{\"a}higkeitsmaximum bei mittleren Salzkonzentrationen, solche Mischungen zeigen gleichzeitig Anzeichen von Mikrophasenseparation in salzreiche und salzarme Dom{\"a}nen. Die betrachteten IL zeigen eine ansteigende Heterogenit{\"a}t der molekularen Dynamik bei Vergr{\"o}{\ss}erung ihrer Kationen, bis hin zur Aggregatsbildung der Kationen. Durch die Variation ihrer Zusammensetzung wurden die strukturellen Inhomogenit{\"a}ten von PE und IL systematisch ver{\"a}ndert. Der Einfluss dieser Inhomogenit{\"a}ten auf die lokale und langreichweitige Bewegung wurde durch isotopensensitive Kernspinresonanzmessungen getrennt f{\"u}r die einzelnen Komponenten. F{\"u}r die PE konnte die lokale Dynamik der Polymersegmente und der Lithiumionen erstmals {\"u}ber FC-Messungen analysiert werden. Die Rousedynamik der Polymerkette blieb dabei unter Salzzugabe auf einer reduzierten Frequenzskala unver{\"a}ndert. Zudem wurde gezeigt, dass die Lithiumionen derart stark vom Polymer komplexiert sind, dass sie dessen inh{\"a}rente Rousedynamik imitieren. F{\"u}r die Mischungen mit mittlerer Salzkonzentration fanden sich bimodale Suszeptibilit{\"a}ten der Segmentrelaxation, die einer Separation in schnelle und langsame Polymerdynamik zugeordnet wurden. F{\"u}r alle Mischungen zeigten diffusive und lokale Dynamik sowohl f{\"u}r die Ionen als auch das Polymer die gleiche Temperaturabh{\"a}ngigkeit, Rotations- und Translationsdynamik sind gekoppelt. Insbesondere gilt diese Kopplung auch zwischen den Komponenten, die Lithiumionendiffusion und die Reorientierungsdynamik der Polymersegmente erf{\"u}llen die Stokes-Einstein-Debye-Relation (SED-Relation) im gesamten Temperaturbereich. Im zweiten Teil der Dissertation wurde die Dynamik von Imidazol-basierten IL mit zwei verschiedenen Anionen untersucht und dabei die Kationgr{\"o}- {\ss}e anhand einer Restgruppe variiert. Mittels FC-NMR konnte deren strukturelle Relaxation von internen Bewegungsfreiheitsgraden separiert werden, es ergaben sich moderate Unterschiede zwischen Kationen- und Anionendynamik. Ein Hinweis auf eine Aggregatsbildung der Kationen wurde in der lokalen Dynamik nicht beobachtet. Durch Teildeuterierung der Kationen einiger IL konnte mittels 2H-SGR- und 2H-STE-Experimente die mikroskopische Dynamik bis nahe dem Glas{\"u}bergang abgebildet werden. Die Kationen reorientieren sich dabei isotrop {\"u}ber kleinwinklige Rotationsspr{\"u}nge. Messungen der diffusiven Bewegung mit SFG-NMR erm{\"o}glichten die Bestimmung kleiner Diffusionskoeffizienten. In Kombination mit den Ergebnissen der lokalen Dynamik konnte gezeigt werden, dass die SED-Relation f{\"u}r die Anionen unabh{\"a}ngig von der Gr{\"o}{\ss}e der Kationen erf{\"u}llt ist. F{\"u}r die Kationen kommt es f{\"u}r lange Restgruppen zum breakdown der SED-Relation. Dieser {\"a}u{\ss}ert sich, anders als f{\"u}r einkomponentige Glasbildner, durch ein Absinken des SED-Produkts, also einer relativen Verlangsamung der Diffusion. Ein entsprechendes Verhalten wurde vor dem Hintergrund von Kationaggregaten motiviert, die eine Barriere f{\"u}r die diffusive Bewegung darstellen. Zusammenfassend werden unterschiedliche Kopplungsmechanismen in den zwei Modellsystemen vorgefunden. In PE f{\"u}hrt die Komplexierung der Lithiumionen durch das Polymer zu einer engen Korrelation der Dynamik beider Komponenten, in IL entkoppelt die Kationdiffusion von dessen Rotationsbewegung. Es wurde anhand dieser Systeme gezeigt, wie sich strukturelle Inhomogenit{\"a}ten und Kopplungsmechanismen der einzelnen Komponenten in einer komplexen molekularen Dynamik {\"a}u{\ss}ern. Diese zu verstehen ist essentiell f{\"u}r das Design und die Optimierung von Materialien mit spezifischen Anwendungen.},
  creationdate = {2024-01-12T13:23:12},
  doi          = {https://doi.org/10.25534/tuprints-00011316},
  keywords     = {nmr, phd thesis, field cycling, glas formers, ionic liquids, relaxation, rouse, sed, 2h-nmr, spin-lattice relaxation, stimulated echo},
  language     = {de},
  url          = {http://tuprints.ulb.tu-darmstadt.de/11316/},
}

@Misc{Sun2004,
  author        = {Yong Sun},
  title         = {Discussing the Relationship between the Static and Dynamic Light Scattering},
  year          = {2004},
  archiveprefix = {arXiv},
  creationdate  = {2024-01-23T08:35:19},
  eprint        = {physics/0410064},
  file          = {:Sun2004 - Discussing the Relationship between the Static and Dynamic Light Scattering.pdf:PDF},
  keywords      = {hydrodynamic radius, DLS, SLS, Light Scattering, microgel, pNIPAM},
  primaryclass  = {physics.chem-ph},
}

@Article{Sattig2014,
  author       = {Sattig, M. and Vogel, M.},
  journal      = {The Journal of Physical Chemistry Letters},
  title        = {Dynamic Crossovers and Stepwise Solidification of Confined Water: A 2H NMR Study},
  year         = {2014},
  note         = {PMID: 26276198},
  number       = {1},
  pages        = {174--178},
  volume       = {5},
  abstract     = {2H NMR reveals two dynamic crossovers of supercooled water in nanoscopic (∼2 nm) confinement. At ∼225 K, a dynamic crossover of liquid water is accompanied by formation of a fraction of solid water. Therefore, we do not attribute the effect to a liquid–liquid phase transition but rather to a change from bulk-like to interface-dominated dynamics. Moreover, we argue that the α process and β process are observed in experiments above and below this temperature, respectively. Upon cooling through a dynamic crossover at ∼175 K, the dynamics of the liquid fraction becomes anisotropic and localized, implying solidification of the corresponding water network, most probably, during a confinement-affected glass transition.},
  creationdate = {2024-01-23T09:00:20},
  doi          = {10.1021/jz402539r},
  eprint       = {https://doi.org/10.1021/jz402539r},
  file         = {:Sattig2014 - Dynamic Crossovers and Stepwise Solidification of Confined Water_ a 2H NMR Study.pdf:PDF;:DynamicCrossOversAndStepwiseSolidificationOfConfinedWater-A2HNMRStudy_SattigEtAl_JPCL2014_SI.pdf:PDF},
  keywords     = {2h-nmr, d2o, confined water, coupling constant},
  url          = {https://doi.org/10.1021/jz402539r},
}

@Article{Boehmer2001,
  author       = {R. B{\"o}hmer and G. Diezemann and G. Hinze and E. R{\"o}ssler},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {Dynamics of supercooled liquids and glassy solids},
  year         = {2001},
  issn         = {0079-6565},
  number       = {3},
  pages        = {191--267},
  volume       = {39},
  creationdate = {2024-01-23T09:36:55},
  doi          = {https://doi.org/10.1016/S0079-6565(01)00036-X},
  file         = {:Boehmer2001 - Dynamics of Supercooled Liquids and Glassy Solids.pdf:PDF},
  keywords     = {Glass transition, Supercooled liquids, Orientational glasses, Spin-lattice relaxation, Stimulated echoes, Line-shape analysis, Heterogeneous relaxation, Multidimensional NMR, Slow dynamics},
  url          = {https://www.sciencedirect.com/science/article/pii/S007965650100036X},
}

@Article{Schiller2024,
  author       = {Schiller, Verena and Vogel, Michael},
  journal      = {Phys. Rev. Lett.},
  title        = {Ice-Water Equilibrium in Nanoscale Confinement},
  year         = {2024},
  month        = jan,
  pages        = {016201},
  volume       = {132},
  abstract     = {We show that 2D 2H NMR spectra enable valuable insights into the nature of an ice-water equilibrium in nanoscale confinement, which extends over a broad temperature range. In particular, 2D 2H NMR lineshape analysis allows us to determine the timescale on which the coexisting ice and water phases exchange molecules. For D2 O in a silica nanopore with a diameter of 5.4 nm, we find that the residence time of a water molecule in either phase is characterized by an NMR exchange time of τX ¼ 5.7 ms at 220 K. Thus, the ice-water equilibrium is highly dynamic, which is an important aspect for an understanding of deeply cooled confined and, possibly, bulk waters.},
  creationdate = {2024-01-23T09:40:26},
  doi          = {10.1103/PhysRevLett.132.016201},
  file         = {:Schiller2024 - Ice Water Equilibrium in Nanoscale Confinement.pdf:PDF;:IceWaterEquilibriumInNanoscaleConfinement_SchillerEtAl_PhysRevLett2024_SI.pdf:PDF},
  issue        = {1},
  keywords     = {home-built setups, 2h-nmr, 2d spectra, confined water, line shape analysis, LSA, exchange, silica nanopore},
  numpages     = {6},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.132.016201},
}

@Article{Jansen‐Glaw1989,
  author       = {Jansen‐Glaw, B. and Rössler, E. and Taupitz, M. and Vieth, H. M.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Hexamethylbenzene as a sensitive nuclear magnetic resonance probe for studying organic crystals and glasses}},
  year         = {1989},
  issn         = {0021-9606},
  month        = jun,
  number       = {12},
  pages        = {6858--6866},
  volume       = {90},
  abstract     = {{Deuterated hexamethylbenzene (HMB) is used as a probe molecule for 2H NMR studies of the crystalline state of hexachlorobenzene and of several organic glasses. By measuring the spin–lattice relaxation and the line shape in the temperature range of 4–300 K the dynamical parameters of the molecular reorientation are investigated. For the system HMB/hexachlorobenzene, we find exponential relaxation and for the corresponding T1 an increase of its activation energy by a factor of 2 in comparison to the neat HMB. A homogeneous mixing of the guest and host molecules is found at least for guest concentrations up to 7\\%. In contrast, nonexponential spin–lattice relaxation is characteristic for all glass matrices, indicating motional heterogeneities. A log–Gauss distribution for the corresponding motional correlation times gives a good fit of the data. Its width parameter decreases linearly with temperature, while the mean correlation times are described by an Arrhenius law. The mean activation energy is reduced by a factor of about 3.5 as compared to neat HMB, demonstrating a loose packing of the molecules in the glass matrices.}},
  creationdate = {2024-01-23T11:56:06},
  doi          = {10.1063/1.456259},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/90/12/6858/11035580/6858\_1\_online.pdf},
  file         = {:Jansen‐Glaw1989 - Hexamethylbenzene As a Sensitive Nuclear Magnetic Resonance Probe for Studying Organic Crystals and Glasses.pdf:PDF},
  keywords     = {log-gaussian spectral density, polymer plasticizer, glass, 2h-nmr, spin-lattice relaxation},
  url          = {https://doi.org/10.1063/1.456259},
}

@Article{Haaks2017,
  author       = {Haaks, Michael and Martin, Steve W. and Vogel, Michael},
  journal      = {Phys. Rev. B},
  title        = {Relation of short-range and long-range lithium ion dynamics in glass-ceramics: Insights from $^{7}\mathrm{Li}$ NMR field-cycling and field-gradient studies},
  year         = {2017},
  month        = sep,
  pages        = {104301},
  volume       = {96},
  creationdate = {2024-01-23T12:14:31},
  doi          = {10.1103/PhysRevB.96.104301},
  file         = {:Haaks2017 - Relation of Short Range and Long Range Lithium Ion Dynamics in Glass Ceramics_ Insights from $^7Li$ NMR Field Cycling and Field Gradient Studies.pdf:PDF},
  issue        = {10},
  keywords     = {log-gaussian spectral density, 7li-nmr, glass ceramics, ion conductor},
  numpages     = {9},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevB.96.104301},
}

@Article{Winter2020,
  author       = {Winter, Edda and Seipel, Philipp and Miß, Vanessa and Spannenberger, Stefan and Roling, Bernhard and Vogel, Michael},
  journal      = {The Journal of Physical Chemistry C},
  title        = {7Li NMR Studies of Short-Range and Long-Range Lithium Ion Dynamics in a Heat-Treated Lithium Iodide-Doped Lithium Thiophosphate Glass Featuring High Ion Conductivity},
  year         = {2020},
  number       = {52},
  pages        = {28614--28622},
  volume       = {124},
  abstract     = {We combine 7Li field-cycling relaxometry with 7Li field-gradient diffusometry to study both short-range and long-range lithium ion dynamics in a heat-treated 0.33 LiI + 0.67 Li3PS4 glass, which exhibits a high ionic conductivity of 6.5 mS/cm. 7Li field-cycling relaxometry, which provides access to the spin–lattice relaxation time T1 over broad frequency and temperature ranges, allows us to determine the activation energy distribution g(Ea) of the local jumps in a model-free way. We find that g(Ea) has a Gaussian form and is characterized by the mean energy Em = 0.40 eV and the standard deviation σ = 0.08 eV. 7Li field-gradient studies indicate free diffusion and yield self-diffusion coefficients of D ∼ 10–12 m2/s at ambient temperatures. Comparing our results for the short-range and long-range ion dynamics and considering previous knowledge about ionic conductivity, we show that the local jumps characterized by the Gaussian distribution g(Ea) determine the macroscopic transport. We conclude that the high ionic conductivity of the heat-treated glass does not result from the formation of minor crystalline regions during the annealing process but rather from a modification of the predominant amorphous phase.},
  creationdate = {2024-01-23T12:20:02},
  doi          = {10.1021/acs.jpcc.0c08801},
  eprint       = {https://doi.org/10.1021/acs.jpcc.0c08801},
  file         = {:Winter2020 - 7Li NMR Studies of Short Range and Long Range Lithium Ion Dynamics in a Heat Treated Lithium Iodide Doped Lithium Thiophosphate Glass Featuring High Ion Conductivity.pdf:PDF},
  keywords     = {log-gaussian spectral density, 7li-nmr, field cycling, sfg, ion conductor, spin-lattice relaxation, t1, FTS},
  url          = {https://doi.org/10.1021/acs.jpcc.0c08801},
}

@Article{Lusceac2011,
  author       = {Sorin A. Lusceac and Markus Rosenstihl and Michael Vogel and Catalin Gainaru and Ariane Fillmer and Roland B{\"o}hmer},
  journal      = {Journal of Non-Crystalline Solids},
  title        = {NMR and dielectric studies of hydrated collagen and elastin: Evidence for a delocalized secondary relaxation},
  year         = {2011},
  issn         = {0022-3093},
  note         = {6th International Discussion Meeting on Relaxation in Complex Systems},
  number       = {2},
  pages        = {655--663},
  volume       = {357},
  abstract     = {Using a combination of dielectric spectroscopy and solid-state deuteron NMR, the hydration water dynamics of connective tissue proteins is studied at sub-ambient temperatures. In this range, the water dynamics follows an Arrhenius law. A scaling analysis of dielectric losses, ‘two-phase’ NMR spectra, and spin-lattice relaxation times consistently yield evidence for a Gaussian distribution of energy barriers. With the dielectric data as input, random-walk simulations of a large-angle, water reorientation provide an approximate description of stimulated-echo data on hydrated elastin. This secondary process is quasi-isotropic and delocalized. The delocalization is inferred from previous NMR diffusometry experiments. It is emphasized that the phenomenology of this process is shared by many non-aqueous binary glasses in which the constituent components exhibit a sufficient dynamical contrast.},
  creationdate = {2024-01-23T12:49:29},
  doi          = {https://doi.org/10.1016/j.jnoncrysol.2010.07.035},
  file         = {:Lusceac2011 - NMR and Dielectric Studies of Hydrated Collagen and Elastin_ Evidence for a Delocalized Secondary Relaxation.pdf:PDF},
  keywords     = {Deuteron NMR, Dielectric spectroscopy, Proteins, Water dynamics},
  url          = {https://www.sciencedirect.com/science/article/pii/S0022309310004400},
}

@Article{Cerveny2008,
  author       = {Cerveny, Silvina and Alegr\'{\i}a, \'Angel and Colmenero, Juan},
  journal      = {Phys. Rev. E},
  title        = {Universal features of water dynamics in solutions of hydrophilic polymers, biopolymers, and small glass-forming materials},
  year         = {2008},
  month        = mar,
  pages        = {031803},
  volume       = {77},
  abstract     = {A systematic investigation by dielectric spectroscopy of 18 different water-rich mixtures with very different hydrophilic substances shows universal features for the water dynamics. The temperature dependence of the relaxation times exhibits a crossover from non-Arrhenius to Arrhenius behavior at the Tg range of the mixtures. Furthermore, the temperature dependence of the relaxation times presents a universal behavior both above and below the crossover temperature. We also show that these features suggest that the observed crossover is associated with the emergence of confinement effects.},
  creationdate = {2024-01-23T12:55:18},
  doi          = {10.1103/PhysRevE.77.031803},
  file         = {:Cerveny2008 - Universal Features of Water Dynamics in Solutions of Hydrophilic Polymers, Biopolymers, and Small Glass Forming Materials.pdf:PDF},
  issue        = {3},
  keywords     = {glass former,BDS,VFT,Arrhenius},
  numpages     = {5},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevE.77.031803},
}

@Article{Cerveny2004,
  author       = {Cerveny, Silvina and Schwartz, Gustavo A. and Bergman, Rikard and Swenson, Jan},
  journal      = {Phys. Rev. Lett.},
  title        = {Glass Transition and Relaxation Processes in Supercooled Water},
  year         = {2004},
  month        = dec,
  pages        = {245702},
  volume       = {93},
  creationdate = {2024-01-23T12:56:50},
  doi          = {10.1103/PhysRevLett.93.245702},
  file         = {:Cerveny2004 - Glass Transition and Relaxation Processes in Supercooled Water.pdf:PDF},
  issue        = {24},
  keywords     = {superooled water, glass transition},
  numpages     = {4},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.93.245702},
}

@Article{Cerveny2008a,
  author       = {Cerveny, Silvina and Alegría, Ángel and Colmenero, Juan},
  journal      = {The Journal of Chemical Physics},
  title        = {{Broadband dielectric investigation on poly(vinyl pyrrolidone) and its water mixtures}},
  year         = {2008},
  issn         = {0021-9606},
  month        = jan,
  number       = {4},
  pages        = {044901},
  volume       = {128},
  abstract     = {{Broadband dielectric spectroscopy and differential scanning calorimetry measurements have been performed to study the molecular dynamics poly (vinyl pyrrolidone) and its water solutions in a wide range of concentrations (0wt\% < wc < 55wt\%) and in the temperature range from 140to500K. The dry material was completely characterized showing the presence of two relaxations in the supercooled state. The slow one has the characteristics of a Johari-Goldstein-type relaxation. On the other hand, the low temperature water dynamics in the mixtures evidences a prominent loss peak due to the reorientation of water molecules inside the polymer matrix for all the hydration levels. We show that the relaxation times are almost water concentration (wc) independent from wc > 20wt\% suggesting that this dynamical process is dominated by water-water interactions. In addition, the temperature dependence of the water relaxation times exhibits a crossover from non-Arrhenius to Arrhenius behavior during cooling throughout the glass transition range, which has been interpreted as due to the constrains imposed by the rigid polymer matrix on the water molecules dynamics.}},
  creationdate = {2024-01-23T13:00:52},
  doi          = {10.1063/1.2822332},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.2822332/13474951/044901\_1\_online.pdf},
  file         = {:Cerveny2008a - Broadband Dielectric Investigation on Poly(vinyl Pyrrolidone) and Its Water Mixtures.pdf:PDF},
  keywords     = {bds, pvp, aqueous polymer solution, johari-goldstein, hydration shell},
  url          = {https://doi.org/10.1063/1.2822332},
}

@Article{Stock2024,
  author       = {Sebastian Stock and Regine von Klitzing and Amin Rahimzadeh},
  journal      = {scientific reports},
  title        = {Dynamic light scattering for particle characterization subjected to ultrasound: a study on compact particles and acousto-responsive microgels},
  year         = {2024},
  month        = jan,
  volume       = {14},
  abstract     = {In this report, we investigate dynamic light scattering (DLS) from both randomly diffusing silica particles and acousto-responsive microgels in aqueous dispersions under ultrasonic vibration. Employing high-frequency ultrasound (US) with low amplitude ensures that the polymers remain intact without damage. We derive theoretical expressions for the homodyne autocorrelation function, incorporating the US term alongside the diffusion term. Subsequently, we successfully combined US with a conventional DLS system to experimentally characterize compact silica particles and microgels under the influence of US. Our model allows us to extract essential parameters, including particle size, frequency, and amplitude of particle vibration, based on the correlation function of the scattered light intensity. The studies involving non-responsive silica particles demonstrate that the US does not disrupt size determination, establishing them as suitable reference systems. In addition, we could be able to experimentally resolve the µs-order motion of particles for the first time. Microgels subjected to the US show the same swelling/shrinking behavior as that induced by temperature but with significantly faster kinetics. The findings of this study have potential applications in various industrial and biomedical fields such as smart coatings and drug delivery that benefit from the characterization of macromolecules subjected to the US. Furthermore, the current work may lead to characterizing the mechanical properties of soft particles based on their vibration amplitude extracted using this method.},
  creationdate = {2024-01-30T08:02:13},
  doi          = {10.1038/s41598-024-51404-0},
  file         = {:Stock2024 - Dynamic Light Scattering for Particle Characterization Subjected to Ultrasound_ a Study on Compact Particles and Acousto Responsive Microgels.pdf:PDF},
  keywords     = {regine von klitzing, light scattering, pNIPAM, microgel, ultrasound, acoustoresponsive, hydrogen bonds, thermoresponsive},
  url          = {https://doi.org/10.1038/s41598-024-51404-0},
}

@Article{Stock2023,
  author       = {Stock, Sebastian and Mirau, Luca and Rutsch, Matthias and Wismath, Sonja and Kupnik, Mario and von Klitzing, Regine and Rahimzadeh, Amin},
  journal      = {Advanced Science},
  title        = {Ultrasound-Induced Adsorption of Acousto-Responsive Microgels at Water–Oil Interface},
  year         = {2023},
  number       = {n/a},
  pages        = {2305395},
  volume       = {n/a},
  abstract     = {Ultrasonic mixing is a well-established method to disperse and mix substances. However, the effects of ultrasound on dispersed soft particles as well as on their adsorption kinetics at interfaces remain unexplored. Ultrasound not only accelerates the movement of particles via acoustic streaming, but recent research indicates that it can also manipulate the interaction of soft particles with the surrounding liquid. In this study, it evaluates the adsorption kinetics of microgel at the water-oil interface under the influence of ultrasound. It quantifies how acoustic streaming accelerates the reduction of interfacial tension. It uses high-frequency and low-amplitude ultrasound, which has no destructive effects. Furthermore, it discusses the ultrasound-induced shrinking and thus interfacial rearrangement of the microgels, which plays a secondary but non-negligible role on interfacial tension reduction. It shows that the decrease in interfacial tension due to the acoustic streaming is stronger for microgels with higher cross-linker density. Moreover, it shows that ultrasound can induce a reversible decrease in interfacial tension due to the shrinkage of microgels at the interface. The presented results may lead to a better understanding in any field where ultrasonic waves meet soft particles, e.g., controlled destabilization in foams and emulsions or systems for drug release.},
  creationdate = {2024-01-30T08:11:12},
  doi          = {https://doi.org/10.1002/advs.202305395},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/advs.202305395},
  file         = {:Stock2023 - Ultrasound Induced Adsorption of Acousto Responsive Microgels at Water–Oil Interface.pdf:PDF},
  keywords     = {interfacial tension, microgels, ultrasound, water–oil interface, pNIPAM, regine von klitzing},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/advs.202305395},
}

@Article{Rahimzadeh2021,
  author       = {Rahimzadeh, Amin and Rutsch, Matthias and Kupnik, Mario and Klitzing, Regine von},
  journal      = {Langmuir},
  title        = {Visualization of Acoustic Energy Absorption in Confined Aqueous Solutions by PNIPAM Microgels: Effects of Bulk Viscosity},
  year         = {2021},
  note         = {PMID: 33961436},
  number       = {19},
  pages        = {5854--5863},
  volume       = {37},
  abstract     = {Ultrasound propagation in liquids is highly influenced by its attenuation due to viscous damping. The dissipated energy will be partially absorbed by the liquid due to its dynamic viscosity as well as its bulk viscosity. The former results in the generation of a flow that is called acoustic streaming, and the latter is associated with the vibrational and rotational relaxation of liquid molecules. Measuring the ultrasonic wave attenuation due to the bulk viscosity is presented as a novel method in this article. Poly(N-isopropylacrylamide) (PNIPAM) microgels, which are soluble in several solvents such as water, were used as acousto-responsive markers in water, which upon absorption of ultrasonic energy undergo a volume phase transition due to the breakage of their hydrogen bonds. Thus, they become insoluble in water, and due to shrinking, their optical density increases. As a result, their agglomeration can be seen as a turbid medium. We managed to visualize the ultrasonic energy absorption due to the bulk viscosity using the turbidity since the excess acoustic energy on top of the absorbed energy for the translational motion of liquid is spent to break the hydrogen bonds between PNIPAM and water. In addition, to quantify the turbidity phenomenon, the total energy required for breaking hydrogen bonds in the solution is calculated, and its evolution, according to the input power intensity, is quantified by image processing. The effect of viscosity by changing the microgel concentration was investigated, and it is shown that an increasing microgel concentration increases the acoustic energy absorption rate much greater than its dynamic viscosity. Therefore, the bulk viscosity, as the responsible parameter for this increase, is measured directly from the energy of broken hydrogen bonds. The results show that at low solution concentration (0.2 wt \%) the bulk viscosity is in the same order of magnitude as its dynamic viscosity. Increasing the concentrations to 1 and 5 wt \% increases the bulk viscosity and consequently the structural relaxation time by 1 and 2 orders of magnitude, respectively.},
  creationdate = {2024-01-30T08:15:58},
  doi          = {10.1021/acs.langmuir.1c00235},
  eprint       = {https://doi.org/10.1021/acs.langmuir.1c00235},
  file         = {:Rahimzadeh2021 - Visualization of Acoustic Energy Absorption in Confined Aqueous Solutions by PNIPAM Microgels_ Effects of Bulk Viscosity.pdf:PDF;:VisualizationOfAcousticEnergyAbsorptionInConfinedAqueousSolutionsByPNIPAMMicrogels-EffectsOfBulkViscosity_RahmizadegEtAl_Langmuir2021_SI.pdf:PDF},
  keywords     = {pNIPAM, microgel, acoustoresponsive, regine von klitzing, viscosity, hydrogen bonds},
  url          = {https://doi.org/10.1021/acs.langmuir.1c00235},
}

@Article{Ohta1991a,
  author       = {Hideo Ohta and Isao Ando and Shouei Fujishige and Kenji Kubota},
  journal      = {Journal of Molecular Structure},
  title        = {A 13C PST/MAS NMR study of poly (N-isopropylacrylamide) in solution and in the gel phase},
  year         = {1991},
  issn         = {0022-2860},
  number       = {3},
  pages        = {391--397},
  volume       = {245},
  abstract     = {13C Nuclear magnetic resonance (NMR) spectra of poly (N-isopropylacrylamide) (PNiPAM) in aqueous solution and in the gel phase are measured at temperatures in the range 11.5–44°C using a ceramic rotor sealed with a rubber O-ring. In these experiments, a high resolution spectrum in the gel phase was obtained by means of the pulse saturation transfer/magic angle spinning (PST/MAS) technique and so 13C chemical shift values for all the carbons of PNiPAM were obtained. It was found that the carbonyl and methylene 13C chemical shifts change in a stepwise manner at about 32°C, the temperature at which gelation occurs. On the basis of these results, the structural change of PNiPAM in going from isotropic solution to the gel phase was discussed.},
  creationdate = {2024-01-31T13:32:22},
  doi          = {https://doi.org/10.1016/0022-2860(91)87113-V},
  file         = {:Ohta1991a - A 13C PST_MAS NMR Study of Poly (N Isopropylacrylamide) in Solution and in the Gel Phase.pdf:PDF},
  keywords     = {pNIPAM, 13c-nmr, MAS, lcst},
  url          = {https://www.sciencedirect.com/science/article/pii/002228609187113V},
}

@Article{Mizuno1995,
  author       = {Mizuno, Kazuko and Miyashita, Yasue and Shindo, Yohji and Ogawa, Hideo},
  journal      = {The Journal of Physical Chemistry},
  title        = {{NMR} and {FT-IR} Studies of Hydrogen Bonds in Ethanol-Water Mixtures},
  year         = {1995},
  number       = {10},
  pages        = {3225--3228},
  volume       = {99},
  creationdate = {2024-02-08T08:58:17},
  doi          = {10.1021/j100010a037},
  eprint       = {https://doi.org/10.1021/j100010a037},
  file         = {:Mizuno1995 - NMR and FT IR Studies of Hydrogen Bonds in Ethanol Water Mixtures.pdf:PDF},
  keywords     = {nmr, chemical shift, hydrogen bond, nmr, FT-IR, aqueous alcohol, water-ethanol, ethanol-water},
  url          = {https://doi.org/10.1021/j100010a037},
}

@Article{Gutowsky1953,
  author       = {Gutowsky, H. S. and McCall, D. W. and Slichter, C. P.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Nuclear Magnetic Resonance Multiplets in Liquids}},
  year         = {1953},
  issn         = {0021-9606},
  month        = feb,
  number       = {2},
  pages        = {279--292},
  volume       = {21},
  abstract     = {{Multiple magnetic resonance lines have been observed for H1, F19, and P31 nuclei in compounds such as PH3, PF3, F2PO(OH), and BrF5, in the liquid state. The multiplets consisted of two to seven equally spaced narrow components, symmetrically placed about a central frequency, and with splittings from 0.02 to 0.8 gauss. These multiplets arise from a new variety of interaction among the nuclear moments in a molecule. Resonance lines were found to be multiple either when a nucleus interacted with a different species of nucleus or when there was interaction between nuclei of the same species with resonance frequencies separated by a chemical shift. No compounds exhibited multiplets attributable to interactions among structurally equivalent nuclei. Nor were multiplets caused by nuclei whose electric quadrupole moments were coupled to a direction fixed in the molecule.The number and relative intensities of the components of a multiplet were determined by the number and statistical weights of the various nuclear spin orientations of the nuclei causing the splitting. In a given molecule, the ratio of the multiplet splittings of the two different resonance lines was inversely proportional to the ratio of the gyromagnetic ratios of the interacting nuclei. The splittings were independent of applied magnetic field at 4180 and 6365 gauss; they were independent of temperature over ranges from 55°C to −130°C. In PF5, the one gas examined, the splitting of the doublet fluorine resonance was the same in the gas and liquid phases; also, the doublet was demonstrated to arise from coupling with the phosphorus nucleus, rather than from a chemical shift between the resonances from the apex and meridian fluorines in the bipyramidal structure, as proposed earlier.All of the above characteristics are accounted for theoretically by assuming the magnetic nuclei interact via magnetic fields inside the molecule. The qualitative aspects are predicted by coupling of the form A12μ1·μ2 between the nuclear moments μ1 and μ2. The coupling constant A12 depends upon the detailed mechanism, which must involve the molecular electrons. Second‐order perturbation theory was used to calculate the relative magnitudes of coupling via the electron orbital and the electron spin magnetic moments. The electron spin mechanism was found to give splittings ten to twenty times the orbital. Approximate calculation of the electron spin mechanism in several simpler cases gave good agreement with experiment. The influence upon the splittings of electric quadrupole coupling and spin‐lattice relaxation was considered and is discussed briefly.}},
  creationdate = {2024-02-08T15:21:13},
  doi          = {10.1063/1.1698874},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/21/2/279/18802561/279\_1\_online.pdf},
  file         = {:Gutowsky1953 - Nuclear Magnetic Resonance Multiplets in Liquids.pdf:PDF},
  keywords     = {nmr theory, spectra, exchange, chemical shift},
  url          = {https://doi.org/10.1063/1.1698874},
}

@Article{Luz1959,
  author       = {Luz, Z. and Gill, D. and Meiboom, S.},
  journal      = {The Journal of Chemical Physics},
  title        = {{NMR Study of the Protolysis Kinetics in Methanol and Ethanol}},
  year         = {1959},
  issn         = {0021-9606},
  month        = jun,
  number       = {6},
  pages        = {1540--1545},
  volume       = {30},
  abstract     = {{Measurements by the nuclear magnetic resonance technique of the hydrogen exchange kinetics in methanol and ethanol are reported. The exchange reaction is both acid and base catalyzed. The observed kinetics can be interpreted as a simple proton transfer between a neutral alcohol molecule and an alcoxonium, or alcoxyde ion, respectively. In methanol a third mechanism, not involving ions, was also observed. In ethanol this reaction is presumably too slow for detection by the NMR technique. The hydrogen exchange was also studied in alcohol‐water mixtures. Possible exchange mechanisms are discussed and values for their respective rate constants are given.}},
  creationdate = {2024-02-08T15:46:43},
  doi          = {10.1063/1.1730234},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/30/6/1540/18816422/1540\_1\_online.pdf},
  file         = {:Luz1959 - NMR Study of the Protolysis Kinetics in Methanol and Ethanol.pdf:PDF},
  keywords     = {1h-nmr, spectra, aqueous alcohol, water-ethanol, hydrogen exchange, multiplet},
  url          = {https://doi.org/10.1063/1.1730234},
}

@Article{Arnold1956,
  author       = {Arnold, James T.},
  journal      = {Phys. Rev.},
  title        = {Magnetic Resonances of Protons in Ethyl Alcohol},
  year         = {1956},
  month        = apr,
  pages        = {136--150},
  volume       = {102},
  creationdate = {2024-02-11T13:49:01},
  doi          = {10.1103/PhysRev.102.136},
  file         = {:PhysRev.102.136 - Magnetic Resonances of Protons in Ethyl Alcohol.pdf:PDF},
  issue        = {1},
  keywords     = {1h-nmr, chemical shift, ethanol, exchange},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRev.102.136},
}

@Article{Vogel2002,
  author       = {M Vogel and C Tschirwitz and G Schneider and C Koplin and P Medick and E Rössler},
  journal      = {Journal of Non-Crystalline Solids},
  title        = {A 2H NMR and dielectric spectroscopy study of the slow $\beta$-process in organic glass formers},
  year         = {2002},
  issn         = {0022-3093},
  pages        = {326--335},
  volume       = {307-310},
  abstract     = {We study the slow β-process of several organic compounds by recording dielectric and 2H NMR spectra below the glass transition temperature Tg. For the neat systems toluene, polybutadiene, cis-decalin and ethanol as well as for the binary glasses chlorobenzene/cis-decalin and toluene/2-picoline, the β-process manifests itself in very similar changes of the 2H NMR spectrum when varying the spatial resolution by increasing the interpulse delay tp in the solid-echo pulse sequence. These findings indicate that for all considered glasses, in particular, for both components of the binary mixtures, molecular dynamics involved in the β-process are highly comparable. A line-shape analysis reveals that the secondary relaxation is mainly caused by a highly restricted, step-wise reorientation of essentially all molecules.For the neat glasses 2-picoline, glycerol and polystyrene (PS) which do not show a β-peak in dielectric spectroscopy, there is no evidence for molecular reorientation in the 2H NMR spectra at T<Tg.},
  creationdate = {2024-02-12T20:25:10},
  doi          = {https://doi.org/10.1016/S0022-3093(02)01492-8},
  file         = {:Vogel2002 - A 2H NMR and Dielelectric Spectroscopy Study of the Slow Β Process in Organic Glass Formers.pdf:PDF},
  keywords     = {2h-nmr, ethanol-d2, glass former, alpha process, beta process, johari-goldstein},
  url          = {https://www.sciencedirect.com/science/article/pii/S0022309302014928},
}

@Article{Schmid2023,
  author       = {Schmid, Friederike},
  journal      = {ACS Polymers Au},
  title        = {Understanding and Modeling Polymers: The Challenge of Multiple Scales},
  year         = {2023},
  number       = {1},
  pages        = {28--58},
  volume       = {3},
  abstract     = {Polymer materials are multiscale systems by definition. Already the description of a single macromolecule involves a multitude of scales, and cooperative processes in polymer assemblies are governed by their interplay. Polymers have been among the first materials for which systematic multiscale techniques were developed, yet they continue to present extraordinary challenges for modellers. In this Perspective, we review popular models that are used to describe polymers on different scales and discuss scale-bridging strategies such as static and dynamic coarse-graining methods and multiresolution approaches. We close with a list of hard problems which still need to be solved in order to gain a comprehensive quantitative understanding of polymer systems.},
  creationdate = {2024-03-03T16:02:37},
  doi          = {10.1021/acspolymersau.2c00049},
  eprint       = {https://doi.org/10.1021/acspolymersau.2c00049},
  file         = {:Schmid2023 - Understanding and Modeling Polymers_ the Challenge of Multiple Scales.pdf:PDF},
  keywords     = {polymer models, theory, review},
  url          = {https://doi.org/10.1021/acspolymersau.2c00049},
}

@Article{Badreldin2023,
  author       = {Mostafa Badreldin and Pedro Salas-Ambrosio and Elisabeth Garanger and Sébastien Lecommandoux and Simon Harrisson and Colin Bonduelle},
  journal      = {Progress in Polymer Science},
  title        = {Thermoresponsive polymers: From natural proteins to amino acid based polymer synthesis},
  year         = {2023},
  issn         = {0079-6700},
  pages        = {101752},
  volume       = {147},
  abstract     = {In polymer science, thermoresponsiveness refers to macromolecular systems that display a marked and discontinuous change in their physical properties with temperature. Such smart polymers are the focus of increasing attention as they provide new solutions to many applications (e.g., drug delivery, nanotechnology, tissue engineering and biotechnology). This review focuses on amino acid based polymers, mainly synthetic polypeptides that are obtained by ring-opening polymerization. These include polymers based on natural amino acids, synthetic or modified amino acids and N-alkylated glycine derivatives. Based on what is known about the behavior of natural proteins in response to temperature variations, this review provides a comprehensive overview of the state of the art of thermosensitive polypeptides through a detailed description i) of the structure/thermoresponsiveness relationship, ii) of the mechanisms involved at the molecular level, iii) of their possible applications both in materials science and in biomedical applications.},
  creationdate = {2024-03-04T07:38:26},
  doi          = {https://doi.org/10.1016/j.progpolymsci.2023.101752},
  file         = {:Badreldin2023 - Thermoresponsive Polymers_ from Natural Proteins to Amino Acid Based Polymer Synthesis.pdf:PDF},
  keywords     = {Protein-like polymers, Ring-opening polymerization, Polypeptide, Thermoresponsive, LCST, Phase transition, Aggregation, review},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079670023001065},
}

@Article{Clark2012,
  author       = {E.A. Clark and J.E.G. Lipson},
  journal      = {Polymer},
  title        = {LCST and UCST behavior in polymer solutions and blends},
  year         = {2012},
  issn         = {0032-3861},
  number       = {2},
  pages        = {536--545},
  volume       = {53},
  abstract     = {We introduce a model for polymer solutions and blends that display both an upper and a lower critical solution temperature (UCST, LCST). Using our simple analytic lattice theory along with a fixed parameter set independent of both composition and temperature, we study solutions and blends exhibiting complicated miscibility patterns, including cases in which a UCST is below an LCST, or above. With respect to the former, we examine the conditions under which a so-called hourglass phase diagram may evolve. Where possible we compare directly with experiment, however, we also explore the behaviour of a number of hypothetical solutions and blends. One experimental solution of particular interest comprises star polystyrene (PS) and cyclohexane; in this case we supply what we believe are the only measured pressure-volume-temperature data for a high molecular weight (5.2 × 105 g/mol) star PS.},
  creationdate = {2024-03-04T07:43:21},
  doi          = {https://doi.org/10.1016/j.polymer.2011.11.045},
  file         = {:Clark2012 - LCST and UCST Behavior in Polymer Solutions and Blends.pdf:PDF},
  keywords     = {Star PS, polystyrene, cyclohexane, UCST and LCST, Liquid–liquid phase separation, lattice model},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386111009694},
}

@InBook{Eckelt2011,
  author       = {Eckelt, Anja and Eckelt, John and Wolf, Bernhard},
  publisher    = {John Wiley \& Sons, Ltd},
  title        = {Solubility of Polymers},
  year         = {2011},
  isbn         = {9780471440260},
  abstract     = {Detailed knowledge concerning the phase state (homogeneous or coexistence of two or more condensed phases) of polymer containing mixtures is indispensible in virtually any area related to the production or application of macromolecules. In addition to this qualitative information it is for many purposes highly desirable to dispose of quantitative data regarding solvent quality or, more generally, with respect to the thermodynamic interaction between the components of the mixtures. This contribution starts with a brief presentation of the thermodynamic criteria deciding on the phase state and presents the experimental methods used in this area. The next section gives an overview on typical behaviors of polymer solutions and polymer blends; it is followed by a part recalling widely used theoretical approaches. Finally, a data section collects solvents and non-solvents for a large number of polymers and presents some examples for the quantitative thermodynamic description of polymer solutions.},
  booktitle    = {Encyclopedia of Polymer Science and Technology},
  creationdate = {2024-03-20T08:02:07},
  doi          = {https://doi.org/10.1002/0471440264.pst345},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/0471440264.pst345},
  file         = {:Eckelt2011 - Solubility of Polymers.pdf:PDF},
  keywords     = {solubility, thermodynamics},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/0471440264.pst345},
}

@Book{Gedde2019,
  author       = {Ulf W. Gedde and Mikael S. Hedenqvist},
  publisher    = {Springer Cham},
  title        = {Fundamental Polymer Science},
  year         = {2019},
  edition      = {2},
  isbn         = {978-3-030-29794-7},
  series       = {Graduate Texts in Physics},
  creationdate = {2024-03-21T11:45:49},
  doi          = {doi.org/10.1007/978-3-030-29794-7},
  file         = {:Gedde2019 - Fundamental Polymer Science.pdf:PDF},
  keywords     = {book, polymers},
}

@Article{Flory1942,
  author       = {Flory, Paul J.},
  journal      = {The Journal of Chemical Physics},
  title        = {Thermodynamics of High Polymer Solutions},
  year         = {1942},
  issn         = {0021-9606},
  month        = jan,
  number       = {1},
  pages        = {51--61},
  volume       = {10},
  abstract     = {{A statistical mechanical treatment of high polymer solutions has been carried out on the basis of an idealized model, originally proposed by Meyer, which is analogous to the one ordinarily assumed in the derivation of the ``ideal'' solution laws for molecules of equal size. There is obtained for the entropy of mixing of n solvent and N linear polymer molecules (originally disoriented), ΔS=−k[(n/β) ln v1+N ln v2] where v1 and v2 are volume fractions and β is the number of solvent molecules replaceable by a freely orienting segment of the polymer chain. This expression is similar in form to the classical expression for equal‐sized molecules, mole fractions having been replaced by volume fractions. When the disparity between the sizes of the two components is great, this expression gives entropies differing widely from the classical values, which accounts for the large deviations of high polymer solutions from ``ideal'' behavior. The entropy of disorientation of a perfectly arranged linear polymer is found to be of the order of R cal. per chain segment. After introducing a suitable heat of mixing term, partial molal free energies are computed, and the calculations are compared with experimental data for all concentrations. Phase equilibria have been calculated in the region of partial miscibility. The theory predicts, in agreement with experiment, that the critical composition for partial miscibility lies at a low concentration of polymer. Low intrinsic viscosities of polymers dissolved in poor solvents are attributed to the tendency for the molecule to assume a more compact configuration in such an environment.}},
  creationdate = {2024-03-21T11:59:18},
  doi          = {10.1063/1.1723621},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/10/1/51/18792484/51\_1\_online.pdf},
  keywords     = {flory-huggins},
  url          = {https://doi.org/10.1063/1.1723621},
}

@Article{Huggins1942,
  author       = {Huggins, Maurice L.},
  journal      = {Journal of the American Chemical Society},
  title        = {Theory of Solutions of High Polymers1},
  year         = {1942},
  number       = {7},
  pages        = {1712--1719},
  volume       = {64},
  creationdate = {2024-03-21T12:00:14},
  doi          = {10.1021/ja01259a068},
  eprint       = {https://doi.org/10.1021/ja01259a068},
  keywords     = {flory-huggins},
  url          = {https://doi.org/10.1021/ja01259a068},
}

@Article{Huggins1942a,
  author       = {Huggins, Maurice L.},
  journal      = {Annals of the New York Academy of Sciences},
  title        = {THERMODYNAMIC PROPERTIES OF SOLUTIONS OF LONG-CHAIN COMPOUNDS},
  year         = {1942},
  number       = {1},
  pages        = {1--32},
  volume       = {43},
  creationdate = {2024-03-21T12:01:01},
  doi          = {https://doi.org/10.1111/j.1749-6632.1942.tb47940.x},
  eprint       = {https://nyaspubs.onlinelibrary.wiley.com/doi/pdf/10.1111/j.1749-6632.1942.tb47940.x},
  keywords     = {flory-huggins},
  url          = {https://nyaspubs.onlinelibrary.wiley.com/doi/abs/10.1111/j.1749-6632.1942.tb47940.x},
}

@Article{Huggins1941,
  author       = {Huggins, Maurice L.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Solutions of Long Chain Compounds}},
  year         = {1941},
  issn         = {0021-9606},
  month        = may,
  number       = {5},
  pages        = {440--440},
  volume       = {9},
  creationdate = {2024-03-21T12:01:27},
  doi          = {10.1063/1.1750930},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/9/5/440/18792175/440\_1\_online.pdf},
  keywords     = {flory-huggins},
  url          = {https://doi.org/10.1063/1.1750930},
}

@Book{Tadros2013,
  editor       = {Tadros, Tharwat},
  title        = {Encyclopedia of Colloid and Interface Science},
  year         = {2013},
  address      = {Berlin, Heidelberg},
  edition      = {1st ed. 2013},
  isbn         = {9783642206658},
  creationdate = {2024-03-25T07:44:50},
  hdsurl       = {https://hds.hebis.de/ulbda/Record/HEB326897046},
  keywords     = {book, polymer, colloid, flory-huggins},
  uniqueid     = {HEB326897046},
  url          = {https://doi.org/10.1007/978-3-642-20665-8},
}

@Book{Sillescu1966,
  author       = {Hans Sillescu},
  publisher    = {Springer Berlin Heidelberg},
  title        = {Kernmagnetische Resonanz},
  year         = {1966},
  creationdate = {2024-04-04T08:36:11},
  file         = {:Sillescu1966 - Kernmagnetische Resonanz.pdf:PDF},
  keywords     = {nmr, book, theory},
}

@Book{Slichter1990,
  author       = {Charles P. Slichter},
  editor       = {Helmut K. V. Lotsch},
  publisher    = {Springer Berlin-Heidelberg},
  title        = {Principles of Magnetic Resonance},
  year         = {1990},
  edition      = {Third},
  isbn         = {978-3-662-09441-9},
  series       = {Springer series in solid-state sciences},
  comment      = {different versions exists (hardcover/ebook, different publishers)},
  creationdate = {2024-10-14},
  doi          = {10.1007/978-3-662-09441-9},
  file         = {:Slichter1963 - Principles of Magnetic Resonance_ with Examples from Solid State Physics.pdf:PDF},
  keywords     = {NMR,theory,book},
}

@Book{Keeler1990,
  author       = {J. H. Keeler},
  editor       = {Pierre Granger and Robin K. Harris},
  publisher    = {Kluwer Academic Publishers},
  title        = {Multinuclear Magnetic Resonance in Liquids and Solids - Chemical Applications},
  year         = {1990},
  series       = {NATO ASI Series C: Mathematical and Physical Sciences},
  volume       = {322},
  creationdate = {2024-04-05T09:11:30},
}

@Article{Winnik1990,
  author       = {Winnik, Francoise M. and Ringsdorf, H. and Venzmer, J.},
  journal      = {Macromolecules},
  title        = {Methanol-water as a co-nonsolvent system for poly(N-isopropylacrylamide)},
  year         = {1990},
  number       = {8},
  pages        = {2415--2416},
  volume       = {23},
  creationdate = {2024-04-07T14:32:57},
  doi          = {10.1021/ma00210a048},
  eprint       = {https://doi.org/10.1021/ma00210a048},
  file         = {:Winnik1990 - Methanol Water As a Co Nonsolvent System for Poly(N Isopropylacrylamide).pdf:PDF},
  keywords     = {pNIPAM, cononsolvency, aqueous alcohol, aqueous methanol},
  url          = {https://doi.org/10.1021/ma00210a048},
}

@Article{Zhang2023,
  author       = {Zhang, Pengfei and Wang, Zheng and Wang, Zhen-Gang},
  journal      = {Macromolecules},
  title        = {Conformation Transition of a Homopolymer Chain in Binary Mixed Solvents},
  year         = {2023},
  number       = {1},
  pages        = {153--165},
  volume       = {56},
  abstract     = {On the basis of a minimal lattice model, we apply the Wang–Landau Monte Carlo (MC) algorithm and a Flory-type mean-field theory to investigate the conformation of a homopolymer chain in a mixture of binary solvents A and B. This MC method enables us to accurately locate the conformation transitions and to determine their nature over a large parameter space. We find that in a good solvent A, adding a small amount of better solvent B causes a continuous collapse transition when the difference in the solvent quality is large. Increasing the fraction of solvent B results in a smooth reswelling of the chain. We explain these findings by the delicate interplay among the mixing entropy of binary solvents, the chain conformational entropy, and the competition in the interactions between the monomer and the two solvents.},
  creationdate = {2024-04-07T14:45:49},
  doi          = {10.1021/acs.macromol.2c01896},
  eprint       = {https://doi.org/10.1021/acs.macromol.2c01896},
  file         = {:Zhang2023 - Conformation Transition of a Homopolymer Chain in Binary Mixed Solvents.pdf:PDF;:ConformationTransitionofAHomopolymerChainInBinaryMixedSolvents_ZhangEtAl_Macromolecules2023_SI.pdf:PDF},
  keywords     = {cononsolvency, theory, flory-huggins},
  url          = {https://doi.org/10.1021/acs.macromol.2c01896},
}

@Article{Tanaka2008,
  author       = {Tanaka, Fumihiko and Koga, Tsuyoshi and Winnik, Fran{\c{c}}oise M.},
  journal      = {Phys. Rev. Lett.},
  title        = {Temperature-Responsive Polymers in Mixed Solvents: Competitive Hydrogen Bonds Cause Cononsolvency},
  year         = {2008},
  month        = jul,
  pages        = {028302},
  volume       = {101},
  creationdate = {2024-04-07T14:54:05},
  doi          = {10.1103/PhysRevLett.101.028302},
  file         = {:Tanaka2008 - Temperature Responsive Polymers in Mixed Solvents_ Competitive Hydrogen Bonds Cause Cononsolvency.pdf:PDF},
  issue        = {2},
  keywords     = {thermoresponsive, cononsolvency, theory},
  numpages     = {4},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.101.028302},
}

@Article{Jeong2007,
  author       = {Soon-Yong Jeong and Ok-Hui Han},
  journal      = {Bulletin of the Korean Chemical Society},
  title        = {A Solid-State NMR Study of Water in Poly(vinyl butyral) by Magic Angle Spinning},
  year         = {2007},
  pages        = {662--666},
  volume       = {28},
  creationdate = {2024-04-08T08:38:40},
  file         = {:Jeong2007 - A Solid State NMR Study of Water in Poly(vinyl Butyral) by Magic Angle Spinning.pdf:PDF},
  keywords     = {NMR, MAS, centrifugation, hydration shell, poly(vinyl butyral)},
  url          = {https://doi.org/10.5012/BKCS.2007.28.4.662},
}

@Article{Papadakis2024,
  author       = {Papadakis, Christine M. and Niebuur, Bart-Jan and Schulte, Alfons},
  journal      = {Langmuir},
  title        = {Thermoresponsive Polymers under Pressure with a Focus on Poly(N-isopropylacrylamide) (PNIPAM)},
  year         = {2024},
  note         = {PMID: 38149782},
  number       = {1},
  pages        = {1--20},
  volume       = {40},
  abstract     = {Pressure is a key variable in the phase behavior of responsive polymers, both for applications and from a fundamental point of view. In this feature article, we review recent developments, particularly applications of neutron techniques such as small-angle neutron scattering (SANS) and quasi-elastic neutron scattering (QENS), across the temperature–pressure phase diagram. These are complemented by kinetic SANS experiments following pressure jumps. In the prototype system poly(N-isopropylacrylamide) (PNIPAM), QENS revealed the pressure-dependent characteristics of hydration water around the lower critical solution temperature transition. The size, water content, and inner structure of the mesoglobules formed in the two-phase region depend strongly on pressure, as shown by SANS. Beside these changes at the phase transition, the mesoglobule formation at low pressure is determined by kinetic factors, namely the formation of a polymer-rich, rigid shell, which hampers further growth by coalescence. At high pressure, in contrast, the growth proceeds by diffusion-limited coalescence without any kinetic hindrance. The disintegration of the mesoglobules evolves either via chain release from their surface or via swelling, depending on the osmotic pressure of the water. Moreover, we report on the profound influence of pressure on the cononsolvency effect. In the temperature–pressure frame, the one-phase region is hugely expanded upon the addition of the cosolvent methanol. SANS experiments unveil the enthalpic and entropic contributions to the effective Flory–Huggins interaction parameter between the segments and the solvent mixture. QENS experiments demonstrate an increase in polymer associated water with pressure, whereas methanol is released. Correspondingly, the solvent phase becomes enriched in methanol, providing a mechanism for the breakdown of cononsolvency at a high pressure. Finally, we outline future opportunities for high-pressure studies of thermoresponsive polymers, with a focus on neutron methods.},
  creationdate = {2024-04-08T10:08:26},
  doi          = {10.1021/acs.langmuir.3c02398},
  eprint       = {https://doi.org/10.1021/acs.langmuir.3c02398},
  file         = {:Papadakis2024 - Thermoresponsive Polymers under Pressure with a Focus on Poly(N Isopropylacrylamide) (PNIPAM).pdf:PDF;:ThermoresponsivePolymersUnderPressureWithAFocusOnPolyNIsopropylacrylamide_PapadakisEtAl_Langmuir2024_SI.pdf:PDF},
  keywords     = {cononsolvency, SANS, QENS, neutron, pressure-dependence, pNIPAM, review},
  url          = {https://doi.org/10.1021/acs.langmuir.3c02398},
}

@Article{Kauzmann1987,
  author       = {Walter Kauzmann},
  journal      = {Nature},
  title        = {Thermodynamics of unfolding},
  year         = {1987},
  pages        = {763--764},
  volume       = {325},
  creationdate = {2024-04-08T10:26:42},
  keywords     = {protein, denaturation, pressure-dependence, thermodynamics},
  url          = {https://doi.org/10.1038/325763a0},
}

@Article{Moelbert2003,
  author       = {Moelbert, Susanne and De Los Rios, Paolo},
  journal      = {Macromolecules},
  title        = {Hydrophobic Interaction Model for Upper and Lower Critical Solution Temperatures},
  year         = {2003},
  number       = {15},
  pages        = {5845--5853},
  volume       = {36},
  abstract     = {Hydration of hydrophobic solutes in water is the cause of different phenomena, including the hydrophobic heat capacity anomaly, which are not yet fully understood. Because of its topicality, there has recently been growing interest in the mechanism of hydrophobic aggregation and in the physics on which it is based. In this study we use a simple yet powerful mixture model for water, an adapted two-state Muller−Lee−Graziano model, to describe the energy levels of water molecules as a function of their proximity to nonpolar solute molecules. The model is shown to provide an appropriate description of many-body interactions between the hydrophobic solute particles. The solubility and aggregation of hydrophobic substances are studied by evaluating detailed Monte Carlo simulations in the vicinity of the first-order aggregation phase transition. A closed-loop coexistence curve is found, which is consistent with a mean-field calculation carried out for the same system. In addition, the destabilizing effect of a chaotropic substance in the solution is studied by suitable modification of the MLG model. These findings suggest that a simple model for the hydrophobic interaction may contain the primary physical processes involved in hydrophobic aggregation and in the chaotropic effect.},
  creationdate = {2024-04-08T11:15:09},
  doi          = {10.1021/ma025890c},
  eprint       = {https://doi.org/10.1021/ma025890c},
  file         = {:Moelbert2003 - Hydrophobic Interaction Model for Upper and Lower Critical Solution Temperatures.pdf:PDF},
  keywords     = {LCST, UCST, theory, hydration shell, hydrophobic hydration, aggregation},
  url          = {https://doi.org/10.1021/ma025890c},
}

@Article{Halperin2000,
  author       = {Halperin, A. and Goldbart, Paul M.},
  journal      = {Phys. Rev. E},
  title        = {Early stages of homopolymer collapse},
  year         = {2000},
  month        = jan,
  pages        = {565--573},
  volume       = {61},
  creationdate = {2024-04-08T16:10:19},
  doi          = {10.1103/PhysRevE.61.565},
  file         = {:Halperin2000 - Early Stages of Homopolymer Collapse.pdf:PDF},
  issue        = {1},
  keywords     = {review, theory, LCST, UCST, polymer solubility},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevE.61.565},
}

@Article{DiMarzio1999,
  author       = {E.A. {Di Marzio}},
  journal      = {Progress in Polymer Science},
  title        = {The ten classes of polymeric phase transitions: their use as models for self-assembly},
  year         = {1999},
  issn         = {0079-6700},
  number       = {3},
  pages        = {329--377},
  volume       = {24},
  abstract     = {A brief overview of the ten classes of polymer phase transitions is given. In each case the basic physics underlying the transition is given. Special attention is devoted to the polymer threading a membrane transition (PTM) since it allows us to understand the reason for the occurrence of the five classes of transition unique to the isolated polymer molecule. They are the PTM transition; the helix to random coil transition; adsorption; equilibrium polymerization/one-dimensional crystallization; the collapse transition. The five classes of transitions of interacting polymers are liquid crystals/plastic crystals; glasses; crystals; liquid–liquid polymer transitions; soaps–block copolymers/membranes–micelles–vesicles. A classification is made of the coupling of these transitions to one another in pairs, triplets, etc. and it is observed that the number of kinds of such transitions is in the thousands. Because of the five transitions unique to polymers it is argued that the class of materials richest in the occurrence of phase transitions are polymers. Self-assembly is viewed essentially as materials undergoing phase transitions. It is evident that of all materials, polymers express self-assembly in fullest measure. A classification scheme is given for self-assembled structures both in biology and as a technology opportunity. The paradigm developed in this paper enriches polymer science by revealing the existence of a large number of problems awaiting solution. This paradigm also provides a route towards understanding biological self-assembly.},
  creationdate = {2024-04-08T16:19:21},
  doi          = {https://doi.org/10.1016/S0079-6700(99)00008-8},
  file         = {:DiMarzio1999 - The Ten Classes of Polymeric Phase Transitions_ Their Use As Models for Self Assembly.pdf:PDF},
  keywords     = {Polymer phase transitions, aggregation, The ten polymer phase transitions, Biological self-assembly, Biopolymers, Structure inducing phase transitions, review},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079670099000088},
}

@Article{Keller1998,
  author       = {Andrew Keller and Stephen Z.D. Cheng},
  journal      = {Polymer},
  title        = {The role of metastability in polymer phase transitions},
  year         = {1998},
  issn         = {0032-3861},
  number       = {19},
  pages        = {4461--4487},
  volume       = {39},
  abstract     = {Polymer phases can be described in the same way as phases in other condensed matter using a number density operator and its correlation functions. This description requires the understanding of both symmetry operations and order at different atomic and molecular levels. Statistical mechanics provides a link between the microscopic description of structure and motion and the macroscopic thermodynamic properties. Within the limits of the laws of thermodynamics, polymers exhibit a rich variety of phase transition behaviours. By definition, a first-order phase transition in a temperature–pressure ensemble describes a transformation which involves a discontinuous change of all the thermodynamic functions but the Gibbs free energy at the transition temperature. Higher-ordered phase transitions are classified as critical phenomena. Of special interest is the role of metastability in phase and phase transition behaviours. A classical metastable state possesses a local free energy minimum, but it is not at the global stable equilibrium. Further, the existence of circumstantial metastability need to be invoked based on the constraints of size, dimensionality, order and symmetry; examples include polymorphism, mesophase concepts, crystal size, and thin film effects. Metastable behaviour is also observed in phase transformations that are impeded by kinetic limitations along the pathway to thermodynamic equilibrium. This is illustrated in structural and morphological investigations of crystallization and mesophase transitions, liquid–liquid phase separation, vitrification and gel formation, as well as combinations of all such transformation processes. In these cases, the metastable state often becomes the dominant state for the entire system, and is observed over a range of time and size scales. This review will describe the general principles of metastability in polymer phases and phase transitions and will provide illustrations from current experimental works in selected areas together with raising so far unaddressed conceptual issues of wider applicability to phase transformations in general.},
  creationdate = {2024-04-08T16:21:37},
  doi          = {https://doi.org/10.1016/S0032-3861(97)10320-2},
  file         = {:Keller1998 - The Role of Metastability in Polymer Phase Transitions.pdf:PDF},
  keywords     = {metastable state, metastability, polymer, review, aggregation},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386197103202},
}

@Article{Nuopponen2004,
  author       = {Markus Nuopponen and Jussi Ojala and Heikki Tenhu},
  journal      = {Polymer},
  title        = {Aggregation behaviour of well defined amphiphilic diblock copolymers with poly(N-isopropylacrylamide) and hydrophobic blocks},
  year         = {2004},
  issn         = {0032-3861},
  number       = {11},
  pages        = {3643--3650},
  volume       = {45},
  abstract     = {Series of amphiphilic diblock copolymers with poly(N-isopropylacrylamide) as a hydrophilic block and a hydrophobic block consisting of either polystyrene or poly(tert-butyl methacrylate) were synthesised using RAFT polymerisations. Differential scanning calorimetry showed the chemically different blocks being phase separated in dry polymers. Light scattering and microcalorimetry studies were performed on aqueous solutions to investigate the phase behavior of the diblock copolymers. By carefully transferring the polymers from an organic solvent to water, either micellar particles or large aggregates were obtained depending on the relative lengths of the blocks. Large aggregates collapsed upon heating, whereas collapse occurred slowly within a broad temperature range in the case of micelle like structures. However, microcalorimetrically the collapse of the PNIPAM chains was observed to take place in all samples, suggesting that the shells of the micellar particles are crowded in a way which hinders the compression of the poly(N-isopropylacrylamide) chains.},
  comment      = {aseyev (inbook) says, the paper says, pNIPAM is stable up to higher temperatures even though the copolymer is hydrophobic},
  creationdate = {2024-04-08T18:35:27},
  doi          = {https://doi.org/10.1016/j.polymer.2004.03.083},
  file         = {:Nuopponen2004 - Aggregation Behaviour of Well Defined Amphiphilic Diblock Copolymers with Poly(N Isopropylacrylamide) and Hydrophobic Blocks.pdf:PDF},
  keywords     = {Diblock copolymers, Polymeric micelles, Controlled radical polymerization, pNIPAM},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386104003374},
}

@Book{Reading2006,
  editor       = {Reading, Mike and Hourston, Douglas J},
  title        = {Modulated Temperature Differential Scanning Calorimetry : Theoretical and Practical Applications in Polymer Characterisation},
  year         = {2006},
  address      = {Dordrecht},
  edition      = {1st ed. 2006},
  isbn         = {9781402037504},
  series       = {Hot Topics in Thermal Analysis and Calorimetry},
  volume       = {6},
  creationdate = {2024-04-09T11:07:07},
  file         = {:Reading2006 - Modulated Temperature Differential Scanning Calorimetry _ Theoretical and Practical Applications in Polymer Characterisation.pdf:PDF},
  hdsurl       = {https://hds.hebis.de/ulbda/Record/HEB192034049},
  keywords     = {temperature modulated DSC, theory, book},
  uniqueid     = {HEB192034049},
  url          = {https://doi.org/10.1007/1-4020-3750-3},
}

@Article{Wang1999,
  author       = {Wang, Xiaohui and Wu, Chi},
  journal      = {Macromolecules},
  title        = {Light-Scattering Study of Coil-to-Globule Transition of a Poly(N-isopropylacrylamide) Chain in Deuterated Water},
  year         = {1999},
  number       = {13},
  pages        = {4299--4301},
  volume       = {32},
  abstract     = {Using a nearly monodisperse (Mw/Mn < 1.1) high molar mass (1.3 × 107 g/mol) poly(N-isopropylacrylamide) (PNIPAM), we studied the conformation change of individual PNIPAM chains between an extended random coil and a fully collapsed thermodynamically stable single chain globule in an extremely dilute D2O solution (∼6.3 × 10-7 g/mL) by a combination of static and dynamic laser light scattering (LLS). In comparison with PNIPAM in H2O, the ϑ-temperature of PNIPAM in D2O is slightly higher, shifting from 30.6 to 32.1 °C. Moreover, the coil-to-globule transition in D2O showed no molten globular state, different from PNIPAM in H2O. However, the molten globular state exists in the globule-to-coil transition in D2O. The size of the PNIPAM chains near the ϑ-temperature in the globule-to-coil transition is smaller than that in the coil-to-globule transition; i.e., there exists a hysteresis, similar to PNIPAM in H2O. The hysteresis can be attributed to the intrachain interaction formed in the globular state. Our results indicate that the PNIPAM chains are stiffer in D2O than in H2O.},
  creationdate = {2024-04-09T11:23:09},
  doi          = {10.1021/ma9902450},
  eprint       = {https://doi.org/10.1021/ma9902450},
  file         = {:Wang1999 - Light Scattering Study of Coil to Globule Transition of a Poly(N Isopropylacrylamide) Chain in Deuterated Water.pdf:PDF},
  keywords     = {pNIPAM, hysteresis, isotope effect, light scattering, hydrodynamic radius, radius of gyration},
  url          = {https://doi.org/10.1021/ma9902450},
}

@Article{Chu1995,
  author       = {Chu, Benjamin and Ying, Qicong and Grosberg, Alexander Yu.},
  journal      = {Macromolecules},
  title        = {Two-Stage Kinetics of Single-Chain Collapse. Polystyrene in Cyclohexane},
  year         = {1995},
  number       = {1},
  pages        = {180--189},
  volume       = {28},
  creationdate = {2024-04-09T11:52:33},
  doi          = {10.1021/ma00105a024},
  eprint       = {https://doi.org/10.1021/ma00105a024},
  file         = {:Chu1995 - Two Stage Kinetics of Single Chain Collapse. Polystyrene in Cyclohexane.pdf:PDF},
  keywords     = {polymer collapse kinetics, polystyrene, PS, cyclohexane, light scattering},
  url          = {https://doi.org/10.1021/ma00105a024},
}

@Article{Yu1992,
  author       = {Yu, Jiqun and Wang, Zhulun and Chu, Benjamin},
  journal      = {Macromolecules},
  title        = {Kinetic study of coil-to-globule transition},
  year         = {1992},
  number       = {5},
  pages        = {1618--1620},
  volume       = {25},
  creationdate = {2024-04-09T11:54:48},
  doi          = {10.1021/ma00031a041},
  eprint       = {https://doi.org/10.1021/ma00031a041},
  file         = {:Yu1992 - Kinetic Study of Coil to Globule Transition.pdf:PDF},
  keywords     = {polystyrene, PS, cyclohexane, polymer collapse kinetics, light scattering},
  url          = {https://doi.org/10.1021/ma00031a041},
}

@Article{Wu1995,
  author       = {Wu, Chi and Zhou, Shuiqin},
  journal      = {Macromolecules},
  title        = {Laser Light Scattering Study of the Phase Transition of Poly(N-isopropylacrylamide) in Water. 1. Single Chain},
  year         = {1995},
  number       = {24},
  pages        = {8381--8387},
  volume       = {28},
  creationdate = {2024-04-09T12:00:11},
  doi          = {10.1021/ma00128a056},
  eprint       = {https://doi.org/10.1021/ma00128a056},
  file         = {:Wu1995 - Laser Light Scattering Study of the Phase Transition of Poly(N Isopropylacrylamide) in Water. 1. Single Chain.pdf:PDF},
  keywords     = {pNIPAM, light scattering, dilute, hydrodynamic radius, radius of gyration, kinetics},
  url          = {https://doi.org/10.1021/ma00128a056},
}

@Article{Wu1995a,
  author       = {Wu, Chi and Zhou, Shuiqing},
  journal      = {Macromolecules},
  title        = {Thermodynamically Stable Globule State of a Single Poly(N-isopropylacrylamide) Chain in Water},
  year         = {1995},
  number       = {15},
  pages        = {5388--5390},
  volume       = {28},
  creationdate = {2024-04-09T13:10:42},
  doi          = {10.1021/ma00119a036},
  eprint       = {https://doi.org/10.1021/ma00119a036},
  file         = {:Wu1995a - Thermodynamically Stable Globule State of a Single Poly(N Isopropylacrylamide) Chain in Water.pdf:PDF},
  keywords     = {pNIPAM, light scattering, radius of gyration, hydrodynamic radius},
  url          = {https://doi.org/10.1021/ma00119a036},
}

@Article{Dawson1997,
  author       = {K.A. Dawson and A.V. Gorelov and E.G. Timoshenko and Yu.A. Kuznetsov and A. {Du Chesne}},
  journal      = {Physica A: Statistical Mechanics and its Applications},
  title        = {Formation of mesoglobules from phase separation in dilute polymer solutions: a study in experiment, theory, and applications},
  year         = {1997},
  issn         = {0378-4371},
  number       = {1},
  pages        = {68--80},
  volume       = {244},
  abstract     = {The appearance of spherical particles resulting from heating beyond the phase separation temperature in dilute solutions of poly(N-isopropylacrylamide) has been observed by dynamic light scattering (DLS). They have a relatively narrow size distribution. The size of particles increases with increasing concentration of polymer, and decreasing heating speed. Electron microscopy confirms the existence of spherical particles with size and polydispersity in agreement with DLS. We develop a theory based on the Gaussian self-consistent method for study of the equilibrium and kinetics of conformational transitions in homopolymer solutions. The theory leads to a natural interpretation of the mesoglobules as a very long-lived metastable state. Finally, we mention the potential for these mesoglobules to find applications.},
  creationdate = {2024-04-09T13:53:51},
  doi          = {https://doi.org/10.1016/S0378-4371(97)00299-9},
  file         = {:Dawson1997 - Formation of Mesoglobules from Phase Separation in Dilute Polymer Solutions_ a Study in Experiment, Theory, and Applications.pdf:PDF},
  keywords     = {Polymer solution, Aggregate, Collapse, Phase coexistence, pNIPAM, kinetics},
  url          = {https://www.sciencedirect.com/science/article/pii/S0378437197002999},
}

@Article{Boutris1997,
  author       = {C. Boutris and E.G. Chatzi and C. Kiparissides},
  journal      = {Polymer},
  title        = {Characterization of the LCST behaviour of aqueous poly(N-isopropylacrylamide) solutions by thermal and cloud point techniques},
  year         = {1997},
  issn         = {0032-3861},
  number       = {10},
  pages        = {2567--2570},
  volume       = {38},
  abstract     = {A systematic investigation of the phase separation behaviour of aqueous low molecular weight PNIPA solutions was carried out in order to quantitatively investigate the effect of measurement conditions on the reported phase separation temperatures in relation to three techniques, namely, differential scanning calorimetry, optical cloud point and u.v. turbidimetry. The PNIPA concentration was varied in the range 0.5–22 wt%. All three techniques yielded comparable phase separation temperatures, independently of the transition kinetics, provided that the time scale of the experiments is large enough to ensure close to equilibrium conditions.},
  creationdate = {2024-04-10T14:37:30},
  doi          = {https://doi.org/10.1016/S0032-3861(97)01024-0},
  file         = {:Boutris1997 - Characterization of the LCST Behaviour of Aqueous Poly(N Isopropylacrylamide) Solutions by Thermal and Cloud Point Techniques.pdf:PDF},
  keywords     = {lower critical solution temperature, LCST, poly(N-isopropylacrylamide), pNIPAM, phase separation, cloud point, concentration-dependence, dsc, turbidimetry, heating rate},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386197010240},
}

@Article{Grosberg1988,
  author       = {Grosberg, A. Yu. and Nechaev, S.K. and Shakhnovich, E.I.},
  journal      = {{Journal de Physique}},
  title        = {{The role of topological constraints in the kinetics of collapse of macromolecules}},
  year         = {1988},
  number       = {12},
  pages        = {2095--2100},
  volume       = {49},
  creationdate = {2024-04-11T10:52:36},
  doi          = {10.1051/jphys:0198800490120209500},
  file         = {:Grosberg1988 - The Role of Topological Constraints in the Kinetics of Collapse of Macromolecules.pdf:PDF},
  hal_id       = {jpa-00210891},
  hal_version  = {v1},
  keywords     = {fractals, macromolecular dynamics, collapse, kinetics},
  pdf          = {https://hal.science/jpa-00210891/file/ajp-jphys_1988_49_12_2095_0.pdf},
  publisher    = {{EDP Sciences}},
  url          = {https://hal.science/jpa-00210891},
}

@Article{Grosberg1993,
  author       = {Grosberg, A. Yu. and Kuznetsov, D. V.},
  journal      = {Macromolecules},
  title        = {Single-chain collapse or precipitation? Kinetic diagram of the states of a polymer solution},
  year         = {1993},
  number       = {16},
  pages        = {4249--4251},
  volume       = {26},
  creationdate = {2024-04-11T10:55:07},
  doi          = {10.1021/ma00068a027},
  eprint       = {https://doi.org/10.1021/ma00068a027},
  file         = {:Grosberg1993 - Single Chain Collapse or Precipitation_ Kinetic Diagram of the States of a Polymer Solution.pdf:PDF},
  keywords     = {macromolecules, collapse, kinetics},
  url          = {https://doi.org/10.1021/ma00068a027},
}

@Article{Qiu2013,
  author       = {XingPing Qiu and Tsuyoshi Koga and Fumihiko Tanaka and Françoise M. Winnik},
  journal      = {Sci. China Chem.},
  title        = {New insights into the effects of molecular weight and end group on the temperature-induced phase transition of poly(N-isopropylacrylamide) in water},
  year         = {2013},
  pages        = {56--64},
  volume       = {56},
  abstract     = {In an attempt to clarify issues related to the molecular weight dependence of the phase transition of poly(N-isopropylacrylamide) (PNIPAM) in water, we prepared a library of PNIPAM samples of well-controlled molecular weight (7000 to 45000 g/mol) bearing identical groups on each chain end. The polymers were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropylacrylamide (NIPAM) with a bifunctional chain tranfer agent and further end group modification. The effects of the end group chemical structure, hydroxyethyl (HE), propargyl (Pr), chloroethyl (CE), n-butyl (nBu), n-hexyl (nHe), and isobutylsulfanylthiosulfanyl (IBS) on the phase transition temperature of aqueous PNIPAM solutions were investigated by high-sensitivity differential scanning calorimetry (HS-DSC), yielding the enthalpy ΔH and the endotherm maximum temperature (T M), and turbidimetry, providing the cloud point (T CP) of each solution. The T CP and T M of the PNIPAM sample of lowest molar mass (M n 7,000 g/mol, 0.5 g/L) ranged, respectively, from 38.8 to 22.5 °C and 42.2 to 26.0 °C, depending on the structure of the end-group, whereas ΔH showed no strong end-group dependence. The phase transition of all polymers, except α,ω-di(n-butyl-PNIPAM), exhibited a marked dependence on the polymer molar mass.},
  creationdate = {2024-04-11T13:15:26},
  file         = {:Qiu2013 - New Insights into the Effects of Molecular Weight and End Group on the Temperature Induced Phase Transition of Poly(N Isopropylacrylamide) in Water.pdf:PDF},
  keywords     = {pNIPAM, molecular weight, end groups, dsc, trubidimetry, cloud point},
  url          = {https://doi.org/10.1007/s11426-012-4781-9},
}

@Article{Tang2010,
  author       = {Yecang Tang and Xi Liu},
  journal      = {Polymer},
  title        = {Collapse kinetics for individual poly(N-isopropylmethacrylamide) chains},
  year         = {2010},
  issn         = {0032-3861},
  number       = {4},
  pages        = {897--901},
  volume       = {51},
  abstract     = {The kinetics for the coil-to-globule transition of linear poly(N-isopropylmethacrylamide) (PiPMA) chains has been studied by use of the fluorescence and Rayleigh scattering with a fast laser pulse infrared heating. We have observed the two-stage kinetics in the collapse transition with the characteristic relaxation times, τfast and τslow, which are attributed to the nucleation and growth of pearls on the chain and the merging and coarsening of pearls to a globule, respectively. The collapse kinetics of PiPMA is similar to that of poly(N-isopropylacrylamide) which has one less methyl in each monomeric unit, indicating that the additional methyl groups in PiPMA chains slightly influence the kinetics. In other words, the pearls are not completely coarsened to form compact globules within τslow.},
  creationdate = {2024-04-11T13:23:35},
  doi          = {https://doi.org/10.1016/j.polymer.2009.12.037},
  file         = {:Tang2010 - Collapse Kinetics for Individual Poly(N Isopropylmethacrylamide) Chains.pdf:PDF},
  keywords     = {Fast infrared laser heating, Kinetics, Poly(-isopropylmethacrylamide), PNIPMAM},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386110000054},
}

@Article{Ye2007,
  author       = {Ye, Xiaodong and Lu, Yijie and Shen, Lei and Ding, Yanwei and Liu, Shilin and Zhang, Guangzhao and Wu, Chi},
  journal      = {Macromolecules},
  title        = {How Many Stages in the Coil-to-Globule Transition of Linear Homopolymer Chains in a Dilute Solution?},
  year         = {2007},
  number       = {14},
  pages        = {4750--4752},
  volume       = {40},
  creationdate = {2024-04-11T13:27:05},
  doi          = {10.1021/ma070167d},
  eprint       = {https://doi.org/10.1021/ma070167d},
  file         = {:Ye2007 - How Many Stages in the Coil to Globule Transition of Linear Homopolymer Chains in a Dilute Solution_.pdf:PDF},
  keywords     = {pNIPAM, kinetics, fluorescence, rayleigh scattering},
  url          = {https://doi.org/10.1021/ma070167d},
}

@Article{Xu2006,
  author       = {Xu, Jian and Zhu, Zhiyuan and Luo, Shizhong and Wu, Chi and Liu, Shiyong},
  journal      = {Phys. Rev. Lett.},
  title        = {First Observation of Two-Stage Collapsing Kinetics of a Single Synthetic Polymer Chain},
  year         = {2006},
  month        = jan,
  pages        = {027802},
  volume       = {96},
  abstract     = {Using a narrowly distributed poly(N-isoporpylacrylamide) (PNIPAM) chain with a degree of polymerization (N) of 3100, randomly labeled with pyrene, we have, for the first time, observed the two-stage kinetics of the coil-to-globule transition. Two characteristic relaxation times, fast for the crumpling of a random coil (12 ms) and slow for the collapsing of the crumpled chain to a compact globule (270 ms), were measured. To our knowledge, this is the first experimental evidence supporting the two-stage collapsing kinetics of single synthetic polymer chain previously proposed by de Gennes, Dawson, and Grosberg},
  creationdate = {2024-04-11T13:40:11},
  doi          = {10.1103/PhysRevLett.96.027802},
  file         = {:Xu2006 - First Observation of Two Stage Collapsing Kinetics of a Single Synthetic Polymer Chain.pdf:PDF},
  issue        = {2},
  keywords     = {kinetics, pNIPAM, cononsolvency, aqueous methanol, aqueous alcohol,},
  numpages     = {4},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.96.027802},
}

@Article{Ito1997,
  author       = {Ito, Daisuke and Kubota, Kenji},
  journal      = {Macromolecules},
  title        = {Solution Properties and Thermal Behavior of Poly(N-n-propylacrylamide) in Water},
  year         = {1997},
  number       = {25},
  pages        = {7828--7834},
  volume       = {30},
  abstract     = {Various molecular parameters characterizing the solution properties of poly(N-n-propylacrylamide) (PNnPAM) in water were determined over the molecular weight range of (13.3 to 159) × 104 at 10 °C by use of light scattering and viscosity measurements. PNnPAM molecules behave as highly hydrated flexible coils. The Laplace inversion method of autocorrelation function of the scattered light intensity ascertained the molecular weight dependence of molecular parameters. Thermal response of PNnPAM molecules in water was studied concerning that the PNnPAM gel exhibits a unique and sharp volume phase transition in contrast to poly(N-isopropylacrylamide) gel. Drastic decrease of the second virial coefficient was observed in a very narrow temperature region near the theta temperature, which was determined to be 22.54 ± 0.01 °C. Thermal response of PNnPAM molecules was discussed relating to the excluded volume effect, the hydrophobic interaction, and the chain stiffness.},
  creationdate = {2024-04-11T19:12:48},
  doi          = {10.1021/ma971005s},
  eprint       = {https://doi.org/10.1021/ma971005s},
  file         = {:Ito1997 - Solution Properties and Thermal Behavior of Poly(N N Propylacrylamide) in Water.pdf:PDF},
  keywords     = {pNIPAM-alternative, light scattering, viscosity, rheology, vpt, gel},
  url          = {https://doi.org/10.1021/ma971005s},
}

@Article{Hansen2016,
  author       = {Hansen, Michael Ryan and Graf, Robert and Spiess, Hans Wolfgang},
  journal      = {Chemical Reviews},
  title        = {Interplay of Structure and Dynamics in Functional Macromolecular and Supramolecular Systems As Revealed by Magnetic Resonance Spectroscopy},
  year         = {2016},
  note         = {PMID: 26312964},
  number       = {3},
  pages        = {1272--1308},
  volume       = {116},
  creationdate = {2024-04-11T19:30:43},
  doi          = {10.1021/acs.chemrev.5b00258},
  eprint       = {https://doi.org/10.1021/acs.chemrev.5b00258},
  file         = {:Hansen2016 - Interplay of Structure and Dynamics in Functional Macromolecular and Supramolecular Systems As Revealed by Magnetic Resonance Spectroscopy.pdf:PDF},
  keywords     = {review, nmr, polymers},
  url          = {https://doi.org/10.1021/acs.chemrev.5b00258},
}

@Article{Lu2011a,
  author       = {Lu, Yijie and Ye, Xiaodong and Li, Junfang and Li, Chunliang and Liu, Shilin},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Kinetics of Laser-Heating-Induced Phase Transition of Poly(N-isopropylacrylamide) Chains in Dilute and Semidilute Solutions},
  year         = {2011},
  note         = {PMID: 21910427},
  number       = {42},
  pages        = {12001--12006},
  volume       = {115},
  abstract     = {The kinetics of the phase transition of poly(N-isopropylacrylamide) (PNIPAM) chains from the dilute regime to the semidilute regime was studied by using a homemade fluorescence spectrometer equipped with an ultrafast pulsed infrared laser (width ∼10 ns and λ = 1.54 μm). We used 8-anilino-1-naphthalensulfonic acid ammonium salt (ANS) free in water as a fluorescent probe to monitor the conformation changes of the PNIPAM chains. Our results have revealed that in the dilute regime there exists two characteristic transition times that are less than 1 ms, namely, τpearls (∼0.02 ms), which can be attributed to the nucleation and initial growth of some “pearls” (locally contracting segments) on the chain, and τcoarsening (∼0.2 ms), which is related to the merging and coarsening of the pearls. At semidilute regime, an extra (third) process (τ ∼ 1.5 ms) appeared, and the contribution from the third process increased with PNIPAM concentration, which can presumably be related to the process of disentanglement of the polymer. A new method to detect the inhomogeneities of the polymer chain segments has been proposed.},
  creationdate = {2024-04-11T19:43:55},
  doi          = {10.1021/jp204853p},
  eprint       = {https://doi.org/10.1021/jp204853p},
  file         = {:Lu2011a - Kinetics of Laser Heating Induced Phase Transition of Poly(N Isopropylacrylamide) Chains in Dilute and Semidilute Solutions.pdf:PDF},
  keywords     = {pNIPAM, LCST, kinetics, collapse, semi-dilute, fluorescence},
  url          = {https://doi.org/10.1021/jp204853p},
}

@Article{Maleki2011,
  author       = {Maleki, Atoosa and Kjøniksen, Anna-Lena and Zhu, Kaizheng and Nyström, Bo},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Temperature-Induced Aggregation Kinetics in Aqueous Solutions of a Temperature-Sensitive Amphiphilic Block Copolymer},
  year         = {2011},
  note         = {PMID: 21699234},
  number       = {29},
  pages        = {8975--8980},
  volume       = {115},
  abstract     = {Time effects for the temperature-induced association complexes in solutions of the thermoresponsive poly(N-isopropylacrylamide)-block-poly(ethylene glycol)-block-poly(N-isopropylacrylamide) (PNIPAAM69-b-PEG23-b-PNIPAAM69) copolymer that exhibit a lower critical solution temperature were studied by means of turbidimetry and dynamic light scattering (DLS). The DLS results clearly show that at temperatures below the cloud point (CP) unimers coexist with intermicellar structures, which contract as the CP is approached. At this stage, no time effect was detected. At temperatures above the CP, large association structures are formed, and these aggregates dominate the decay of the correlation functions. A novel time-dependent growth of the aggregates was observed over several hours. The growth of the clusters is strengthened as the temperature rises, and this feature is supported by the turbidity results and the reduced scattered intensity experiments. For a low polymer concentration, an initial growth of the clusters is observed, whereas at longer times the apparent hydrodynamic radius from DLS is virtually constant. The results from this work stress the importance to check possible time effects in solutions of thermosensitive copolymers as the cloud point is approached.},
  creationdate = {2024-04-11T19:48:18},
  doi          = {10.1021/jp202607p},
  eprint       = {https://doi.org/10.1021/jp202607p},
  file         = {:Maleki2011 - Temperature Induced Aggregation Kinetics in Aqueous Solutions of a Temperature Sensitive Amphiphilic Block Copolymer.pdf:PDF},
  keywords     = {pNIPAM, aggregation, kinetics, blockcopolymer, PEG, cloud point, DLS, hydrodynamic radius},
  url          = {https://doi.org/10.1021/jp202607p},
}

@Article{Junk2011,
  author       = {Junk, Matthias J. N. and Li, Wen and Schlüter, A. Dieter and Wegner, Gerhard and Spiess, Hans W. and Zhang, Afang and Hinderberger, Dariush},
  journal      = {Journal of the American Chemical Society},
  title        = {Formation of a Mesoscopic Skin Barrier in Mesoglobules of Thermoresponsive Polymers},
  year         = {2011},
  note         = {PMID: 21661750},
  number       = {28},
  pages        = {10832--10838},
  volume       = {133},
  abstract     = {With the combination of molecular scale information from electron paramagnetic resonance (EPR) spectroscopy and meso-/macroscopic information from various other characterization techniques, the formation of mesoglobules of thermoresponsive dendronized polymers is explained. Apparent differences in the EPR spectra in dependence of the heating rate, the chemical nature of the dendritic substructure of the polymer, and the concentration are interpreted to be caused by the formation of a dense polymeric layer at the periphery of the mesoglobule. This skin barrier is formed in a narrow temperature range of ∼4 K above TC and prohibits the release of molecules that are incorporated in the polymer aggregate. In large mesoglobules, formed at low heating rates and at high polymer concentrations, a considerable amount of water is entrapped that microphase-separates from the collapsed polymer chains at high temperatures. This results in the aggregates possessing an aqueous core and a corona consisting of collapsed polymer chains. A fast heating rate, a low polymer concentration, and hydrophobic subunits in the dendritic polymer side chains make the entrapment of water less favorable and lead to a higher degree of vitrification. This may bear consequences for the design and use of thermoresponsive polymeric systems in the fast growing field of drug delivery.},
  creationdate = {2024-04-11T19:51:16},
  doi          = {10.1021/ja201217d},
  eprint       = {https://doi.org/10.1021/ja201217d},
  file         = {:Junk2011 - Formation of a Mesoscopic Skin Barrier in Mesoglobules of Thermoresponsive Polymers.pdf:PDF;:FormationOfAMesoscopicSkinBarrierInMesoglobulesOfThermoresponsivePolymers_JunkEtAl_JAmChemSoc2011_SI.pdf:PDF},
  keywords     = {drug delivery, skin barrier, mesoglobule, aggregation, EPR},
  url          = {https://doi.org/10.1021/ja201217d},
}

@Article{Zhang2009,
  author       = {Zhang, Shao-hua and Chen, Yang and Li, Heng and Weng, Yu-xiang},
  journal      = {Chinese Journal of Chemical Physics},
  title        = {{Transitional Process of Ploy(N-isopropylacrylamide) in Deuterated Solution}},
  year         = {2009},
  issn         = {1674-0068},
  month        = oct,
  number       = {5},
  pages        = {447--452},
  volume       = {22},
  abstract     = {{The fast phase-transitional process of ploy(N-isopropylacrylamide) (PNIPAM) in deuterated solution was studied by laser induced temperature jump technique combined with time-resolved mid-infrared absorbance difference spectroscopy on nanosecond level. The multi-peaks of amide I' band of PNIPAM among the energy range of 15651700 cm-1 was experimentally resolved to three groups (i, ii, iii) for the first time, while the distinct three-stage procedure in the phase transitional process of long-chain PNIPAM was observed firstly too. Furthermore, proper assignments were also made for the three group peaks in amide I' band and the three steps in the kinetics process of long-chain PNIPAM.}},
  creationdate = {2024-04-11T19:59:45},
  doi          = {10.1088/1674-0068/22/05/447-452},
  eprint       = {https://pubs.aip.org/cps/cjcp/article-pdf/22/5/447/11779100/447\_1\_online.pdf},
  file         = {:Zhang2009 - Transitional Process of Ploy(N Isopropylacrylamide) in Deuterated Solution.pdf:PDF},
  keywords     = {pNIPAM, kinetics, infrared},
  url          = {https://doi.org/10.1088/1674-0068/22/05/447-452},
}

@Article{Ding2006,
  author       = {Ding, Yanwei and Zhang, Guangzhao},
  journal      = {Macromolecules},
  title        = {Microcalorimetric Investigation on Association and Dissolution of Poly(N-isopropylacrylamide) Chains in Semidilute Solutions},
  year         = {2006},
  number       = {26},
  pages        = {9654--9657},
  volume       = {39},
  abstract     = {The concentration (C) effect on association and dissolution of linear poly(N-isopropylacrylamide) (PNIPAM) chains in dilute and semidilute aqueous solutions was investigated by using ultrasensitive differential scanning calorimetry (US−DSC). When C is below the overlap concentration (C*), both the phase-transition temperature (Tp) and enthalpy change (ΔH) in the heating process decrease as the solution becomes more dilute, while Tp and ΔH become independent of C in the semidilute regime (C > C*). Such a difference can be attributed to different contributions of interchain association and intrachain contraction in dilute and semidilute solutions. In the cooling process, Tp nearly remains a constant, but ΔH decreases as C increases in dilute solutions, but both of them slightly vary in the range C > C*. A hysteresis was observed in one heating-and-cooling cycle. Such a hysteresis becomes more obvious as C increases. The effect of scanning rate on both Tp and ΔH further confirms that the hysteresis is due to incomplete disruption of additional hydrogen bonds formed when the chains are in the collapsed state.},
  creationdate = {2024-04-11T20:08:32},
  doi          = {10.1021/ma062269u},
  eprint       = {https://doi.org/10.1021/ma062269u},
  file         = {:Ding2006 - Microcalorimetric Investigation on Association and Dissolution of Poly(N Isopropylacrylamide) Chains in Semidilute Solutions.pdf:PDF},
  keywords     = {aggregation, kinetics, pNIPAM, dsc, hysteresis, heating rate},
  url          = {https://doi.org/10.1021/ma062269u},
}

@Article{Ding2008,
  author       = {Ding, Yanwei and Ye, Xiaodong and Zhang, Guangzhao},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Can Coil-to-Globule Transition of a Single Chain Be Treated as a Phase Transition?},
  year         = {2008},
  note         = {PMID: 18588331},
  number       = {29},
  pages        = {8496--8498},
  volume       = {112},
  abstract     = {The effects of the concentration (C) and heating rate on the collapse and association of poly(N-isopropylacrylamide) chains in water have been investigated by use of ultrasensitive differential scanning calorimetry. In the dilute solutions, both the phase transition temperature (Tp) and enthalpy change (ΔH) increase with the heating rate but decrease with concentration. By extrapolation to zero heating rate and zero concentration, Tp and ΔH for coil-to-globule transition of a single chain in thermodynamic equilibrium can be obtained. In semidilute solutions, both Tp and ΔH increase with the heating rate but slightly vary with the concentration. Tp and ΔH for pure interchain association in equilibrium are obtained by extrapolation to zero heating rate. Our experiments reveal that only intrachain contraction occurs when the concentration is infinitely close to zero. When the concentration is above the overlap concentration (C*), only interchain association exists. In the range 0 < C < C*, both intrachain contraction and interchain association coexist.},
  creationdate = {2024-04-11T20:10:59},
  doi          = {10.1021/jp801002t},
  eprint       = {https://doi.org/10.1021/jp801002t},
  file         = {:Ding2008 - Can Coil to Globule Transition of a Single Chain Be Treated As a Phase Transition_.pdf:PDF},
  keywords     = {pNIPAM, dsc, heating rate, concentration-dependence, overlap concentration},
  url          = {https://doi.org/10.1021/jp801002t},
}

@Article{Yuan2006,
  author       = {Yuan, Guangcui and Wang, Xiaohong and Han, Charles C. and Wu, Chi},
  journal      = {Macromolecules},
  title        = {Reexamination of Slow Dynamics in Semidilute Solutions:  Temperature and Salt Effects on Semidilute Poly(N-isopropylacrylamide) Aqueous Solutions},
  year         = {2006},
  number       = {18},
  pages        = {6207--6209},
  volume       = {39},
  abstract     = {One fast and one slow relaxation mode were observed in semidilute aqueous solution of poly(N-isopropylacrylamide) (PNIPAM) by dynamic light scattering (DLS). The length scale of the slow relaxation was found to be comparable with the observation length (1/q) in our DLS measurements. To elucidate its origin, we varied the solution temperature and used different salts to study their effects on such a slow mode because it is known that they can influence the strength of the water−amide hydrogen bonding as well as the icelike structure of liquid water. As the temperature increases, the slow mode was gradually suppressed. Using a strong salting-out salt (Na2SO4) and a strong salting-in salt (NaSCN) with the same cation as two model systems, we found that the salting-out salt suppresses the slow dynamics, while the salting-in salt amplifies it. Our results reveal that the slow mode is related to a long-range correlated density or concentration fluctuation, namely, the interaction among the segments in different blobs on chains.},
  creationdate = {2024-04-11T20:15:12},
  doi          = {10.1021/ma061059e},
  eprint       = {https://doi.org/10.1021/ma061059e},
  file         = {:Yuan2006 - Reexamination of Slow Dynamics in Semidilute Solutions_ Temperature and Salt Effects on Semidilute Poly(N Isopropylacrylamide) Aqueous Solutions.pdf:PDF},
  keywords     = {pNIPAM, relaxation, dls},
  url          = {https://doi.org/10.1021/ma061059e},
}

@Article{Xu2023,
  author       = {Xu, Xiaoyan and Shibata, Kentaro and Ouchi, Makoto},
  journal      = {Polym. Chem.},
  title        = {Precision syntheses of poly(NIPAM-alt-HEMA) and effects of the alternating sequence on thermoresponsive behaviors in water},
  year         = {2023},
  pages        = {55--61},
  volume       = {14},
  abstract     = {In this work{,} an alternating copolymer of 2-hydroxyethyl methacrylate (HEMA) and N-isopropylacrylamide (NIPAM) [poly(NIPAM-alt-HEMA)] was synthesized via ATRP-based cyclopolymerization of a divinyl monomer carrying a transformable linker and aminolysis transformation of the resulting cyclopolymer with isopropylamine. The selective propagation in the cyclopolymerization leading to the alternating sequence was supported by the reactivity ratios of the two model monomers cut out from the divinyl monomer. The quantitative transformation and the alternating sequence were confirmed by 1H NMR{,} FT-IR{,} and MALDI-TOF-MS. The thus-obtained poly(NIPAM-alt-HEMA) underwent an LCST-type temperature-induced phase transition in water{,} and the thermoresponsive behavior was different from that of the corresponding statistical copolymers [poly(NIPAM-sta-HEMA)] as well as the homopolymer of NIPAM. The thermoresponsiveness specific to the alternating sequence is likely derived from the structural character that can affect the dehydration behavior{,} such as no existence of the consecutive NIPAM sequence and the adjacent circumstance of NIPAM units and hydroxy pendants of HEMA.},
  creationdate = {2024-04-12T09:08:10},
  doi          = {10.1039/D2PY01196D},
  file         = {:Xu2023 - Precision Syntheses of Poly(NIPAM Alt HEMA) and Effects of the Alternating Sequence on Thermoresponsive Behaviors in Water.pdf:PDF},
  issue        = {1},
  keywords     = {pNIPAM, HEMA, copolymer, 1h-nmr, FTIR, aggregation},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D2PY01196D},
}

@Article{Hamamura2019,
  author       = {Kento Hamamura and Keisuke Watanabe and Yusuke Sanada and Fumihiko Tanaka and Yukiteru Katsumoto},
  journal      = {Polymer},
  title        = {Relationship between the phase diagram and hysteresis in demixing and remixing for atactic and meso-rich Poly(N-isopropylacrylamide)s in water},
  year         = {2019},
  issn         = {0032-3861},
  pages        = {92--100},
  volume       = {161},
  abstract     = {Effects of the stereoregularity on the hysteresis in demixing and remixing of the aqueous solution of poly(N-isopropylacrylamide) (PNiPAm) observed as the dissociation of transmittance curves in heating and cooling have been studied. For the liquid-liquid phase separation of the monomer model (N-isopropyl propionamide)/water binary mixture, no hysteresis occurs in demixing and remixing when the scanning rate (vT) is small enough. On the other hand, the aqueous solution of an atactic PNiPAm with 46% of the meso content (m) shows the hysteresis even under a very dilute condition (0.01 wt%) at a slow vT of 0.01 °C min−1. The difference between demixing and remixing temperatures at vT → 0 systematically increases as m increases. The effect of stereoregularity is more significant for the cooling (remixing) process of the aqueous PNiPAm solution compared with that for the heating (demixing) process. These results strongly suggest that hysteresis arises from the structure of phase diagrams of the aqueous PNiPAm solution in which the liquid-liquid phase separation and sol-gel transition coexist [F. Tanaka et al. React. Funct. Polym. 2013, 73 (7)]. Above the demixing temperature (Tdmx), a dilute and a concentrated PNiPAm solutions appear, and the concentrated one of which solution undergoes physical gelation. The physical gel formed at the polymer-rich region returns to a sol by cooling at the remixing temperature Trmx, which lies possibly at lower than Tdmx. Thus, the hysteresis in demixing and remixing is observed.},
  creationdate = {2024-04-12T09:57:06},
  doi          = {https://doi.org/10.1016/j.polymer.2018.12.001},
  file         = {:Hamamura2019 - Relationship between the Phase Diagram and Hysteresis in Demixing and Remixing for Atactic and Meso Rich Poly(N Isopropylacrylamide)s in Water.pdf:PDF},
  keywords     = {Poly(N-isopropylacylamide), pNIPAM, Phase diagram, Hysteresis, tactiticy},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386118311066},
}

@Article{Kawaguchi2009,
  author       = {Kawaguchi, Tomoaki and Kobayashi, Kunihiko and Osa, Masashi and Yoshizaki, Takenao},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Is a “Cloud-Point Curve” in Aqueous Poly(N-isopropylacrylamide) Solution Binodal?},
  year         = {2009},
  note         = {PMID: 19331327},
  number       = {16},
  pages        = {5440--5447},
  volume       = {113},
  abstract     = {Transmittance of light passing through an aqueous solution of a linear poly(N-isopropylacrylamide) (PNIPA) sample synthesized by living anionic polymerization was examined in detail in the vicinity of its cloud point. It is found that the transmittance approaches a constant value between 0 and 100\% even at a temperature slightly higher than the cloud point, indicating that macroscopic phase separation does not take place at the cloud point in the solution and therefore the cloud-point curve does not correspond to the binodal. Static and dynamic light scattering measurements were then carried out for aqueous solutions of the linear sample and also of another one synthesized by radical polymerization, which has random-branched structure, at some temperatures considerably lower than the cloud point. It was found that both the PNIPA samples in aqueous solutions form aggregates even at such temperatures, and the number, size, and density profile of the aggregates depend on the kind of chain end group and also on the primary structure.},
  creationdate = {2024-04-12T10:05:51},
  doi          = {10.1021/jp9005795},
  eprint       = {https://doi.org/10.1021/jp9005795},
  file         = {:Kawaguchi2009 - Is a “Cloud Point Curve” in Aqueous Poly(N Isopropylacrylamide) Solution Binodal_.pdf:PDF},
  keywords     = {pNIPAM, cloud point, transmittance, binodal, dls, sls, aggregate, end group},
  url          = {https://doi.org/10.1021/jp9005795},
}

@Article{Han2022,
  author       = {Han, Jiayun and Takahashi, Rintaro and Kuang, Chen and Sato, Takahiro},
  journal      = {Langmuir},
  title        = {Phase Separation Behavior of Aqueous Poly(N-isopropylacrylamide) Solutions Studied by Scattering Experiments},
  year         = {2022},
  note         = {PMID: 34554751},
  number       = {17},
  pages        = {5089--5097},
  volume       = {38},
  abstract     = {We have investigated the colloidal phase-separating dilute solution of aqueous poly(N-isopropylacrylamide) (PNIPAM) with a molecular weight of 1.24 × 105 by small-angle X-ray scattering (SAXS) as well as static and dynamic light scattering (SLS and DLS). Those scattering experiments provide us with the average size and size distribution of concentrated-phase droplets and the concentration cconc of the coexisting concentrated phase. While the average droplet size is almost constant above 35 °C in the temperature-scan experiments, it is a decreasing function of temperature above 35 °C in the temperature-jump experiments. This heating rate dependence of the average droplet size arises from the fact that concentrated-phase droplets in the aqueous PNIPAM solution grow only in a limited temperature range (31.5–35 °C). The scattering results on the temperature dependence of cconc are combined with previously reported results of turbidity and DSC, giving the phase diagram of the Type II phase behavior with the off-zero critical point at high molecular weight.},
  creationdate = {2024-04-12T10:10:09},
  doi          = {10.1021/acs.langmuir.1c01917},
  eprint       = {https://doi.org/10.1021/acs.langmuir.1c01917},
  file         = {:Han2022 - Phase Separation Behavior of Aqueous Poly(N Isopropylacrylamide) Solutions Studied by Scattering Experiments.pdf:PDF},
  keywords     = {pNIPAM, SAXS, X-ray, DLS, SLS},
  url          = {https://doi.org/10.1021/acs.langmuir.1c01917},
}

@Article{Wang2023,
  author       = {Wang, Chi and Hashimoto, Takeji},
  journal      = {Macromolecules},
  title        = {Spinodal Decomposition, Nucleation Growth, and Arrested Macrophase Separation of Physical Gels of Atactic Poly(N-isopropyl\-acrylamide) in Water},
  year         = {2023},
  number       = {16},
  pages        = {6354--6374},
  volume       = {56},
  abstract     = {Aqueous solutions of atactic poly(N-isopropylacrylamide) (a-PNIPAM) with 5–12 wt \% concentrations exhibit physical gelation at temperatures lower than the binodal temperature (Tb). This phenomenon is clearly demonstrated by the hysteresis of dynamic storage modulus G′(T) during repeated heating and subsequent cooling protocol at T < Tb because of the difference in the T-dependent rate of interchain association and dissociation. Herein, we performed a temperature-sweep test at a low heating rate and at a low frequency to obtain dynamic rheological curves of the loss modulus and storage modulus. From these curves, two transition temperatures are derived, namely, the macroscopic gel temperature (Tgel) and the temperature at which G′ starts to rise (T1) owing to the enhanced interchain associations developing the self-similarly branched structures of associated chains. On heating, the one-phase a-PNIPAM solution undergoes pronounced concentration fluctuations at a temperature above T1 to enter the pregel regime followed by the formation of a macroscopic gel network at Tgel. The temperature sequence for the phase transitions is T1 + 2 °C ≅ Tgel < Tb, independent of concentration (ϕw). The spinodal temperatures of the a-PNIPAM solution (Ts,sol) and a-PNIPAM gel (Ts,gel) are obtained from small-angle X-ray scattering based on a theoretical model derived for the associated chains to account for the presence of gel junctions. The derived Ts,gel is slightly higher than Ts,sol; the gap is ca. 0.9–1.6 °C depending on ϕw. The derived Ts,sol and Ts,gel marginally decrease with increased ϕw. Using time-resolved light scattering (TRLS), the nucleation and growth (NG) and spinodal decomposition (SD) of the gel are validated at temperatures above Tb. The growth of the SD structure is dramatically hindered (or pinned down) within a very short period (<5 s). We find that Cahn’s linear theory for SD phase separation is inapplicable to derive Ts,gel in the present dynamically asymmetric system. On the basis of phase transformation from the pinned SD structure into the pinned NG structure, Ts,gel could be alternatively determined from the steady-state light-scattering profiles as a function of T obtained from TRLS with a stepwise cooling protocol. The estimated Ts,gel in this manner agrees with that derived from rigorous analyses of static SAXS as a function of temperature. On the basis of the present results, a phase diagram of semidilute a-PNIPAM/water solutions is constructed. At temperatures above Tb, the arrest of the macroscopic phase separation through NG and SD is found to develop pinned NG and SD structure depending on T and is thermoreversible. We propose that this temperature-dependent pinned NG and SD underlie the basic principle for the arrested macrophase separation and the thermoreversible change in the phase-separated structures of the physical gel as discussed in the text.},
  creationdate = {2024-04-12T10:18:39},
  doi          = {10.1021/acs.macromol.3c00599},
  eprint       = {https://doi.org/10.1021/acs.macromol.3c00599},
  file         = {:Wang2023 - Spinodal Decomposition, Nucleation Growth, and Arrested Macrophase Separation of Physical Gels of Atactic Poly(N Isopropylacrylamide) in Water.pdf:PDF;:SpinodalDecompositionNucleationGrowthAndArrestedMacrophaseSeparationOfPhysicalGelsOfAtacticPolyNIsopropylacrylamideInWater_WangEtAl_Macromol2023_Si.pdf:PDF},
  keywords     = {pNIPAM, hysteresis, rheology},
  url          = {https://doi.org/10.1021/acs.macromol.3c00599},
}

@Article{Maresov2008,
  author       = {Maresov, E. A. and Semenov, A. N.},
  journal      = {Macromolecules},
  title        = {Mesoglobule Morphologies of Amphiphilic Polymers},
  year         = {2008},
  number       = {23},
  pages        = {9439--9457},
  volume       = {41},
  abstract     = {A statistical theory of finite-sized aggregates and domain structures in dilute solutions of amphiphilic macromolecules (homopolymers or copolymers) is developed. A minimalist model involving, essentially, two types of chemical groups (insoluble H and soluble P) is studied in the regime where polymer tends to phase separate, forming rather dense amorphous particles with low surface energy. The surface tension and the elastic bending moduli of the polymer/solvent interface are obtained and are related to the molecular parameters. The Gaussian modulus κG is predicted to be negative; typically |κG| is smaller than the mean bending modulus κ2. It is shown that the condensed polymer phase can remain dense, homogeneous, and stable with respect to microphase separation even as the surface tension decreases down to zero (or below it). Stable large aggregates of well-defined size are predicted in this regime. The size of aggregates and their shape depend on surface tension γ, the spontaneous bending modulus κ1, and the ratio κG/κ2. We show that bicontinuous morphologies (rather than colloidally stable polymer mesoglobules) are thermodynamically favorable for small |κG|. We present a quantitative argument showing that the gyroid structure is more favorable than other bicontinuous morphologies (primitive cubic and double diamond). The γ−κ1 phase diagrams showing the regions of stability of different morphologies are obtained. Two types of spherical mesoglobules are predicted, namely equilibrium and metastable globules whose sizes are shown to be essentially different: they depend on κ1 in qualitatively different ways. Recent experimental data on mesoglobule formation in solutions of thermosensitive amphiphilic polymers are discussed in the theoretical light.},
  creationdate = {2024-04-12T10:36:46},
  doi          = {10.1021/ma801260g},
  eprint       = {https://doi.org/10.1021/ma801260g},
  file         = {:Maresov2008 - Mesoglobule Morphologies of Amphiphilic Polymers.pdf:PDF},
  keywords     = {mesoglobule, theory, pNIPAM, PVCL, PVME, poly(1-vinylimidazole), poly(2-ethylacrylic acid)},
  url          = {https://doi.org/10.1021/ma801260g},
}

@Article{Kujawa2006,
  author       = {Kujawa, Piotr and Aseyev, Vladimir and Tenhu, Heikki and Winnik, Françoise M.},
  journal      = {Macromolecules},
  title        = {Tempera\-ture-Sensitive Properties of Poly(N-isopropyl\-acrylamide) Mesoglobules Formed in Dilute Aqueous Solutions Heated above Their Demixing Point},
  year         = {2006},
  number       = {22},
  pages        = {7686--7693},
  volume       = {39},
  abstract     = {The kinetics of merging and/or chain exchange between mesoglobules formed in dilute aqueous solutions of fluorescently labeled poly(N-isopropylacrylamides) (PNIPAM) heated above their demixing temperature (Tdem) were monitored at specific temperatures between 30 and 50 °C via nonradiative energy transfer (NRET) using polymers carrying ∼0.25 mol \% of either naphthyl (Np, energy donor) or pyrene (Py, energy acceptor). Dynamic and static light scattering measurements (DSL and SLS) indicated that PNIPAM-Py and PNIPAM-Np solutions form stable mesoglobules when heated above 30 °C and that the size and size distribution of the mesoglobules depend on solution concentration and, more importantly, on the sample thermal history. Fluorescence depolarization measurements performed on mesoglobular solutions of PNIPAM-Np gave the temperature dependence of the probe anisotropy, an indication of the microviscosity sensed by the probe. The results show that samples heated within the ∼31 °C < T < 36 °C range consist of fluidlike particles able to merge and grow in size. At higher temperatures the mesoglobules act as rigid spheres unable to merge upon collision. These observations are interpreted in terms of the various mechanisms invoked to account for the stability of the PNIPAM mesoglobular phase.},
  creationdate = {2024-04-12T10:38:50},
  doi          = {10.1021/ma061604b},
  eprint       = {https://doi.org/10.1021/ma061604b},
  file         = {:Kujawa2006 - Temperature Sensitive Properties of Poly(N Isopropylacrylamide) Mesoglobules Formed in Dilute Aqueous Solutions Heated above Their Demixing Point.pdf:PDF},
  keywords     = {pNIPAM, kinetics, aggregates, mesoglobules, fluorescence, DLS, SLS},
  ranking      = {rank5},
  url          = {https://doi.org/10.1021/ma061604b},
}

@Article{MeierKoll2012,
  author       = {Meier-Koll, Andreas and Pipich, Vitaliy and Busch, Peter and Papadakis, Christine M. and Müller-Buschbaum, Peter},
  journal      = {Langmuir},
  title        = {Phase Separation in Semidilute Aqueous Poly(N-isopropylacrylamide) Solutions},
  year         = {2012},
  note         = {PMID: 22607150},
  number       = {23},
  pages        = {8791--8798},
  volume       = {28},
  abstract     = {The phase separation mechanism in semidilute aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions is investigated with small-angle neutron scattering (SANS). The nature of the phase transition is probed in static SANS measurements and with time-dependent SANS measurements after a temperature jump. The observed critical exponents of the phase transition describing the temperature dependence of the Ornstein–Zernike amplitude and correlation length are smaller than values from mean-field theory. Time-dependent SANS measurements show that the specific surface decreases with increasing time after a temperature jump above the phase transition. Thus, the formation of additional hydrogen bonds in the collapsed state is a kinetic effect: A certain fraction of water remains as bound water in the system. Moreover, H–D exchange reactions observed in PNIPAM have to be taken into account.},
  creationdate = {2024-04-12T10:45:09},
  doi          = {10.1021/la3015332},
  eprint       = {https://doi.org/10.1021/la3015332},
  file         = {:MeierKoll2012 - Phase Separation in Semidilute Aqueous Poly(N Isopropylacrylamide) Solutions.pdf:PDF},
  keywords     = {pNIPAM, SANS, kinetics},
  url          = {https://doi.org/10.1021/la3015332},
}

@Article{Zaccone2011,
  author       = {Zaccone, Alessio and Crassous, Jerome J. and B\'eri, Benjamin and Ballauff, Matthias},
  journal      = {Phys. Rev. Lett.},
  title        = {Quantifying the Reversible Association of Thermosensitive Nanoparticles},
  year         = {2011},
  month        = oct,
  pages        = {168303},
  volume       = {107},
  creationdate = {2024-04-15T09:48:19},
  doi          = {10.1103/PhysRevLett.107.168303},
  file         = {:Zaccone2011 - Quantifying the Reversible Association of Thermosensitive Nanoparticles.pdf:PDF},
  issue        = {16},
  keywords     = {aggregation, thermoresponsive, theory, pNIPAM},
  numpages     = {4},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.107.168303},
}

@InBook{Zhang2006,
  author       = {Zhang, Guangzhao and Wu, Chi},
  editor       = {Khokhlov, Alexei R.},
  pages        = {101--176},
  publisher    = {Springer Berlin Heidelberg},
  title        = {Folding and Formation of Mesoglobules in Dilute Copolymer Solutions},
  year         = {2006},
  address      = {Berlin, Heidelberg},
  isbn         = {978-3-540-32946-6},
  abstract     = {It is known that linear homopolymer chains can undergo a coil-to-globule-to-precipitationtransition when the solvent quality gradually changes from good to poor. It is also known that the observation of the coil-to-globule transition without any interchain association is extremely difficult if not impossible. On the other hand, the folding of individual amphiphilic copolymer chains, such as protein chains, in an extremely dilute solution is much easier. As the copolymer concentration increases, inevitable interchain association accompanied by intrachain folding can result in a stable mesoglobular phase (the aggregation of a limited number of chains), existing between single-chain globules and macroscopic phase separation (precipitation). In this article, we mainly review what we have accomplished in the last ten years by starting with a brief discussion of the folding of linear poly(N -isopropylacrylamide) (PNIPAM) homopolymer chains in water. Our focus is the folding of different hydrophilically or hydrophobically modified PNIPAM copolymer chains in extremely dilute solutions as well as the formation of stable mesoglobules made of amphiphilic copolymer chains in dilute solutions. The discoveries of the molten globular state and the ``ordered-coil'' state between the random-coil and compacted globular states will be illustrated. The effects of both the comonomer composition and distribution on the folding of individual copolymer chains into some unique core-shell nanostructures as well as the formation of the mesoglobular phase are discussed. The double roles of hydrophobic interaction in the formation and stabilization of stable mesoglobules will be explained in terms of the viscoelastic effect.},
  booktitle    = {Conformation-Dependent Design of Sequences in Copolymers I},
  creationdate = {2024-04-15T10:15:19},
  doi          = {10.1007/12_050},
  file         = {:Zhang2006 - Folding and Formation of Mesoglobules in Dilute Copolymer Solutions.pdf:PDF},
  keywords     = {pNIPAM, homopolymer, copolymer, coil-to-globule transition, mesoglobules, aggregates},
  url          = {https://doi.org/10.1007/12_050},
}

@Article{Osvath2017,
  author       = {Osváth, Zsófia and Iván, Béla},
  journal      = {Macromolecular Chemistry and Physics},
  title        = {The Dependence of the Cloud Point, Clearing Point, and Hysteresis of Poly(N-isopropylacrylamide) on Experimental Conditions: The Need for Standardization of Thermoresponsive Transition Determinations},
  year         = {2017},
  number       = {4},
  pages        = {1600470},
  volume       = {218},
  abstract     = {Inappropriately, the critical solution temperature (CST) of lower CST(LCST)- or upper CST(UCST)-type thermoresponsive polymers, measured by one, individual set of conditions, is considered almost exclusively as the LCST or UCST, respectively. These are correctly the minimum or maximum, respectively, of the full phase diagrams. Because the dynamic phase transition depends on the conditions, and no standardized or widely accepted process exists for CST determination, systematic investigations are carried out with the most widely investigated poly(N-isopropylacrylamide) (PNIPAAm) to unveil the effect of data evaluation, measurement conditions on the transmittance–temperature curves, cloud point (TCP), clearing point (TCL), and heating–cooling hysteresis. The unusual dependence of the fundamental hysteresis parameters, i.e., width of hysteresis (XH) and extent of transmittance recovery (YH), on a broad range of conditions is revealed for the first time. On the basis of the findings, the inflection point of transmittance(absorbance)–temperature curves as TCP and TCL, 0.1 wt\% solution, 0.2 °C min-1 heating/cooling steps with 5 min equilibration between the gradual change of temperature, 488 nm wavelength to obtain data comparable to light scattering at this wavelength, and determination of XH and YH are proposed as standard set of conditions.},
  creationdate = {2024-04-15T11:30:44},
  doi          = {https://doi.org/10.1002/macp.201600470},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/macp.201600470},
  file         = {:Osvath2017 - The Dependence of the Cloud Point, Clearing Point, and Hysteresis of Poly(N Isopropylacrylamide) on Experimental Conditions_ the Need for Standardization of Thermoresponsive Transition Determinations.pdf:PDF},
  keywords     = {cloud point and clearing point, hysteresis, lower or upper critical solution temperature (LCST or UCST), poly(N-isopropylacrylamide), pNIPAM, thermal phase transition, thermoresponsive},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/macp.201600470},
}

@Article{Song2019,
  author       = {Song, Li and Lin, Jiaxiang and Liu, Panpan and Li, Jingqing and Jiang, Shichun and Huang, Dinghai},
  journal      = {RSC Adv.},
  title        = {Quantitative determination of the spring entropy effect and its indication of the conformational change of polymer coils with varying concentration in aqueous poly(N-isopropylamide) solutions},
  year         = {2019},
  pages        = {5540--5549},
  volume       = {9},
  abstract     = {The lower critical solution temperature (LCST) phase separation behaviors of thermosensitive poly(N-isopropylacrylamide) (PNIPAM) aqueous solutions were investigated by power-compensation differential scanning calorimetry (DSC). The entropic effect and hence the change of swelling state of PNIPAM polymer coils in homogeneous concentrated aqueous solutions with varied solution composition was elucidated by the isothermal enthalpy demixing recovery behaviors in distinct concentration regions.},
  creationdate = {2024-04-15T11:53:24},
  doi          = {10.1039/C9RA00117D},
  file         = {:Song2019 - Quantitative Determination of the Spring Entropy Effect and Its Indication of the Conformational Change of Polymer Coils with Varying Concentration in Aqueous Poly(N Isopropylamide) Solutions.pdf:PDF},
  issue        = {10},
  keywords     = {pNIPAM, DSC, theory, LCST},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C9RA00117D},
}

@Article{Kato2018,
  author       = {Kato, Daiki and Sohn, Woon Yong and Katayama, Kenji},
  journal      = {ACS Omega},
  title        = {Aggregation-Induced Expansion of Poly-(N-isopropyl acrylamide) Solutions Observed Directly by the Transient Grating Imaging Technique},
  year         = {2018},
  note         = {PMID: 31458976},
  number       = {8},
  pages        = {8484--8490},
  volume       = {3},
  abstract     = {The anomalous volume expansion of poly-(N-isopropyl acrylamide) (PNIPAM) solutions was observed during the thermally induced polymer phase transition of aqueous solutions having concentrations in the 3–7 wt \% range. The process occurred on a millisecond time scale, and a laser temperature-jump time-resolved technique was used to bring about the process. After heating a solution with a pulse laser exploiting light absorption by dyes added to the solution itself, a phase transition was observed to take place, and the temporal changes associated with it were visualized through the transient grating imaging technique, whereby the solution was heated with a stripe pattern. We found several processes occurring on a millisecond time scale, all of which clearly took place after each PNIPAM molecule had collapsed structurally from a coiled to a globular conformation. During the so-called demixing process, the globular polymers aggregated with each other within 10 ms, and suddenly the polymer phase expanded as aggregation progressed further. After this process, the individual globular polymers reverted to their coiled conformation via hydration during the remixing process. We proposed that solution expansion was caused by the mutual entangling of multiple globular PNIPAM molecules, instead each globule polymer was separated.},
  creationdate = {2024-04-15T11:55:57},
  doi          = {10.1021/acsomega.8b01241},
  eprint       = {https://doi.org/10.1021/acsomega.8b01241},
  file         = {:Kato2018 - Aggregation Induced Expansion of Poly (N Isopropyl Acrylamide) Solutions Observed Directly by the Transient Grating Imaging Technique.pdf:PDF;:AggregationInducedExpansionOfPolyNIsopropylacylamideSolutionsObservedDirectlyByTheTransientGratingImagingTechnique_KatoEtAl_ACSOmega2018_SI1.pdf:PDF},
  keywords     = {pNIPAM, aggregation, temperature-jump, concentration-dependent},
  url          = {https://doi.org/10.1021/acsomega.8b01241},
}

@Article{Kojima2010,
  author       = {Kojima, Hiroyuki and Tanaka, Fumihiko},
  journal      = {Macromolecules},
  title        = {Cooperative Hydration Induces Discontinuous Volume Phase Transition of Cross-Linked Poly(N-isopropylacrylamide) Gels in Water},
  year         = {2010},
  number       = {11},
  pages        = {5103--5113},
  volume       = {43},
  abstract     = {The concept of cooperative dehydration, defined as the simultaneous dissociation of the bound water molecules from the polymer chains in correlated sequences, is applied to study the collapse of cross-linked poly(N-isopropylacrylamide) (PNIPAM) gels in aqueous solutions upon heating above the critical temperature. We examined the applicability of this concept in two situations: (i) free swelling of PNIPAM gels in water (in the absence of applied force), (ii) swelling of PNIPAM gels in water subjected to a uniaxial tension. The transition becomes sharper as the cooperativity parameter σ of hydration decreases (increasing cooperativity), and there is a critical value σc ≃ 0.30 of the cooperativity parameter below which the volume transition is discontinuous. Hence, the real phase transition with thermodynamic discontinuity is shown to be possible for the nonionic polymer gels if the hydration is sufficiently cooperative. The calculations of the swelling ratio and the spinodal lines are compared with the experimental data of PNIPAM gels by Hirotsu for point i and by Suzuki for point ii.},
  creationdate = {2024-04-15T13:05:47},
  doi          = {10.1021/ma100588f},
  eprint       = {https://doi.org/10.1021/ma100588f},
  file         = {:Kojima2010 - Cooperative Hydration Induces Discontinuous Volume Phase Transition of Cross Linked Poly(N Isopropylacrylamide) Gels in Water.pdf:PDF},
  keywords     = {pNIPAM, cooperativity, gel, tension},
  url          = {https://doi.org/10.1021/ma100588f},
}

@Article{Tanaka1985,
  author       = {Tanaka, Toyoichi and Sato, Eriko and Hirokawa, Yoshitsugu and Hirotsu, Shunsuke and Peetermans, Joyce},
  journal      = {Phys. Rev. Lett.},
  title        = {Critical Kinetics of Volume Phase Transition of Gels},
  year         = {1985},
  month        = nov,
  pages        = {2455--2458},
  volume       = {55},
  creationdate = {2024-04-15T13:11:01},
  doi          = {10.1103/PhysRevLett.55.2455},
  file         = {:Tanaka1985 - Critical Kinetics of Volume Phase Transition of Gels.pdf:PDF},
  issue        = {22},
  keywords     = {pNIPAM, gel, kinetics, vpt},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.55.2455},
}

@Article{Adelsberger2012,
  author       = {Adelsberger, Joseph and Metwalli, Ezzeldin and Diethert, Alexander and Grillo, Isabelle and Bivigou-Koumba, Achille M. and Laschewsky, André and Müller-Buschbaum, Peter and Papadakis, Christine M.},
  journal      = {Macromolecular Rapid Communications},
  title        = {Kinetics of Collapse Transition and Cluster Formation in a Thermoresponsive Micellar Solution of P(S-b-NIPAM-b-S) Induced by a Temperature Jump},
  year         = {2012},
  number       = {3},
  pages        = {254--259},
  volume       = {33},
  abstract     = {Structural changes at the intra- as well as intermicellar level were induced by the LCST-type collapse transition of poly(N-isopropyl acrylamide) in ABA triblock copolymer micelles in water. The distinct process kinetics was followed in situ and in real-time using time-resolved small-angle neutron scattering (SANS), while a micellar solution of a triblock copolymer, consisting of two short deuterated polystyrene endblocks and a long thermoresponsive poly(N-isopropyl acrylamide) middle block, was heated rapidly above its cloud point. A very fast collapse together with a multistep aggregation behavior is observed. The findings of the transition occurring at several size and time levels may have implications for the design and application of such thermoresponsive self-assembled systems.},
  creationdate = {2024-04-15T13:21:34},
  doi          = {https://doi.org/10.1002/marc.201100631},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/marc.201100631},
  file         = {:Adelsberger2012 - Kinetics of Collapse Transition and Cluster Formation in a Thermoresponsive Micellar Solution of P(S B NIPAM B S) Induced by a Temperature Jump.pdf:PDF},
  keywords     = {polymer physics, thermoresponsive polymers, small-angle neutron scattering, time-resolved measurements, pNIPAM, blockcopolymer, SANS, kinetics, micelle, aggregation},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/marc.201100631},
}

@Article{Niebuur2019a,
  author       = {Niebuur, Bart-Jan and Chiappisi, Leonardo and Jung, Florian and Zhang, Xiaohan and Schulte, Alfons and Papadakis, Christine M.},
  journal      = {Macromolecules},
  title        = {Kinetics of Mesoglobule Formation and Growth in Aqueous Poly(N-isopropylacrylamide) Solutions: Pressure Jumps at Low and at High Pressure},
  year         = {2019},
  number       = {17},
  pages        = {6416--6427},
  volume       = {52},
  abstract     = {The mesoglobule formation and growth in an aqueous solution of poly(N-isopropylacrylamide) are investigated using time-resolved small-angle neutron scattering. Rapid pressure jumps initiate phase separation at both low (below 20 MPa) and high pressures (above 101 MPa). Measurements were carried out in a time range from 50 ms to ∼1650 s after the jump, covering a large range of momentum transfers. The dehydration of the polymer at the coexistence line is much stronger at low pressures than at high pressures, which significantly affects the mechanism of phase separation: At low pressures, the diffusion-limited coalescence of the mesoglobules is strongly slowed down by the viscoelastic effect due to their dense shell. Moreover, the target pressure has a strong influence on the relative importance of these kinetic effects. In the high-pressure regime, the viscoelastic effect does not play a role, and diffusion-limited coalescence proceeds without hindrance.},
  creationdate = {2024-04-15T14:01:04},
  doi          = {10.1021/acs.macromol.9b00937},
  eprint       = {https://doi.org/10.1021/acs.macromol.9b00937},
  file         = {:Niebuur2019a - Kinetics of Mesoglobule Formation and Growth in Aqueous Poly(N Isopropylacrylamide) Solutions_ Pressure Jumps at Low and at High Pressure.pdf:PDF},
  keywords     = {pNIPAM, aggregates, kinetics, mesoglobules, pressure-jump},
  url          = {https://doi.org/10.1021/acs.macromol.9b00937},
}

@Article{Pham2018,
  author       = {Quoc-Thai Pham and Zong-Han Yao and Ya-Ting Chang and Fu-Ming Wang and Chorng-Shyan Chern},
  journal      = {Journal of the Taiwan Institute of Chemical Engineers},
  title        = {LCST phase transition kinetics of aqueous poly(N-isopropylacrylamide) solution},
  year         = {2018},
  issn         = {1876-1070},
  pages        = {63--69},
  volume       = {93},
  abstract     = {LCST phase transition kinetics of aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions was studied by using non-isothermal differential scanning calorimeter (DSC) and isothermal dynamic light scattering (DLS) techniques. The DSC data obtained from 5 and 10 wt% PNIPAM solutions were used in isoconversional kinetics analysis. The resultant large activation energy (Eα) and pre-exponential factor indicated that the phase transition occurred by cooperatively breaking multiple hydrogen bonds. Eα decreased with increasing temperature approximately in a hyperbola form. Theoretical nucleation and growth models were used to adequately describe the temperature dependent Eα. Furthermore, the phase transition process obeyed Avrami–Erofeev nucleation and growth models. As to the 0.05 wt% PNIPAM solution using the isothermal DLS technique, the reaction rate constant was determined at different temperatures, and the Avrami–Arofeev nucleation and growth models adopted to predict the phase transition process.},
  creationdate = {2024-04-15T14:04:05},
  doi          = {https://doi.org/10.1016/j.jtice.2018.07.045},
  file         = {:Pham2018 - LCST Phase Transition Kinetics of Aqueous Poly(N Isopropylacrylamide) Solution.pdf:PDF;:Pham2018 - LCST Phase Transition Kinetics of Aqueous Poly(N Isopropylacrylamide) Solution.docx:Word 2007+},
  keywords     = {Poly(N-isopropylacrylamide), Temperature-responsive, LCST phase transition, Kinetics, Nucleation and growth models},
  url          = {https://www.sciencedirect.com/science/article/pii/S1876107018304498},
}

@Article{Aleksandrova2014,
  author       = {Aleksandrova, Ralitsa and Philipp, Martine and Müller, Ulrich and Riobóo, Rafael Jiménez and Ostermeyer, Martin and Sanctuary, Roland and Müller-Buschbaum, Peter and Krüger, Jan K.},
  journal      = {Langmuir},
  title        = {Phase Instability and Molecular Kinetics Provoked by Repeated Crossing of the Demixing Transition of PNIPAM Solutions},
  year         = {2014},
  note         = {PMID: 25215653},
  number       = {39},
  pages        = {11792--11801},
  volume       = {30},
  abstract     = {The demixing process of aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions can occur either via a nucleation and growth process or via spinodal decomposition. The ensuing self-assembly, leading to heterogeneous morphologies within the PNIPAM solution, is codetermined by kinetic processes caused by molecular transport. By subjecting PNIPAM solutions to cyclic changes in temperature leading to repeated crossing of the demixing transition, we are able to assess the importance of kinetics as well as of overheating and supercooling of the phase transition within the metastable range delimited by the binodal and spinodal lines. First indications about the location of these stability limits for the low- and high-temperature phases, separated by about 1.6 K, could be gained by detailed kinetic studies of the refractive index. These investigations are made possible due to the novel technique of temperature-modulated optical refractometry.},
  comment      = {Method only applicable to homogeneous solution, i.e. to low temps or temperatures above the LCST where aggregates have not yet grown too much},
  creationdate = {2024-04-15T14:07:02},
  doi          = {10.1021/la5026763},
  eprint       = {https://doi.org/10.1021/la5026763},
  file         = {:Aleksandrova2014 - Phase Instability and Molecular Kinetics Provoked by Repeated Crossing of the Demixing Transition of PNIPAM Solutions.pdf:PDF},
  keywords     = {pNIPAM, aggregation, kinetics, temperature-modulated optical refractometry, densitometry},
  url          = {https://doi.org/10.1021/la5026763},
}

@Article{Farasat2014,
  author       = {Farasat, Reza and Vyazovkin, Sergey},
  journal      = {Macromolecular Chemistry and Physics},
  title        = {Coil-to-Globule Transition of Poly(N-isopropylacrylamide) in Aqueous Solution: Kinetics in Bulk and Nanopores},
  year         = {2014},
  number       = {21},
  pages        = {2112--2118},
  volume       = {215},
  abstract     = {Differential scanning calorimetry (DSC) is used to study the kinetics of the coil-to-globule transition in aqueous solutions of poly(N-isopropoylacrylamide) (PNIPAM) prepared in the bulk (3 and 10 wt\%) and nanoconfined (10 wt\% inside 30 nm silica pores) forms. It is demonstrated that the kinetics can be described in terms of the classical nucleation model. The proposed treatment affords estimating the free-energy barrier and pre-exponential factor of the transition. The application of the nucleation model to the DSC data collected for the three systems studied provides physical insights into the effect of increasing the transition temperature due to dilution and nanoconfinement. Dilution appears to raise the free-energy barrier, whereas nanoconfinement causes a decrease in the pre-exponential factor.},
  creationdate = {2024-04-15T14:10:56},
  doi          = {https://doi.org/10.1002/macp.201400354},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/macp.201400354},
  file         = {:Farasat2014 - Coil to Globule Transition of Poly(N Isopropylacrylamide) in Aqueous Solution_ Kinetics in Bulk and Nanopores.pdf:PDF},
  keywords     = {differential scanning calorimetry, DSC, kinetics, nucleation, phase transitions, poly(N-isopropylacrylamide), pNIPAM, nanopores, confinement, heating rate},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/macp.201400354},
}

@Article{Philipp2013,
  author       = {Philipp, Martine and Müller, Ulrich and Jiménez Riobóo, Rafael J. and Sanctuary, Roland and Müller-Buschbaum, Peter and Krüger, Jan K.},
  journal      = {Soft Matter},
  title        = {Kinetic processes at the demixing transition of PNIPAM solutions},
  year         = {2013},
  pages        = {9887--9896},
  volume       = {9},
  abstract     = {Kinetic processes{,} which are joined with mass transport{,} are studied in the vicinity of the sharp LCST-type demixing transition of semi-dilute aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions. These processes are slow as compared to the highly cooperative collapse of individual polymer chains. Purely elastic properties{,} that are particularly sensitive to this phase transition{,} are addressed depending on the temperature{,} space and time by Brillouin spectroscopy. Above the demixing temperature Tc{,} we discriminate between kinetics related to the phase separation into PNIPAM-rich and PNIPAM-poor domains and kinetics connected to the impact of gravitation on the on-going phase separation. Using shallow temperature jumps of 0.3 °C{,} the growth of compact PNIPAM-rich agglomerates with identical gel-like mechanical consistency is provoked independently of temperature and position within the sample above Tc. Astonishingly{,} the transition temperature does not vary while heating or cooling the solutions across the phase transition{,} although the elastic properties depend strongly on space and time during the equilibration of PNIPAM concentration gradients following the re-entrance into the low-temperature phase.},
  creationdate = {2024-04-15T14:14:17},
  doi          = {10.1039/C3SM51333E},
  file         = {:Philipp2013 - Kinetic Processes at the Demixing Transition of PNIPAM Solutions.pdf:PDF},
  issue        = {41},
  keywords     = {pNIPAM, LCST, brillouin spectroscopy, aggregates, sedimentation, elasticity},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C3SM51333E},
}

@Article{Tanaka1992,
  author       = {Tanaka, Hajime},
  journal      = {Macromolecules},
  title        = {Appearance of a moving droplet phase and unusual networklike or spongelike patterns in a phase-separating polymer solution with a double-well-shaped phase diagram},
  year         = {1992},
  number       = {23},
  pages        = {6377--6380},
  volume       = {25},
  creationdate = {2024-04-15T15:43:27},
  doi          = {10.1021/ma00049a042},
  eprint       = {https://doi.org/10.1021/ma00049a042},
  file         = {:Tanaka1992 - Appearance of a Moving Droplet Phase and Unusual Networklike or Spongelike Patterns in a Phase Separating Polymer Solution with a Double Well Shaped Phase Diagram.pdf:PDF},
  keywords     = {poly(vinyl methyl ether), PVME, spinodal decomposition, LCST},
  url          = {https://doi.org/10.1021/ma00049a042},
}

@Article{Tanaka1993,
  author       = {Tanaka, Hajime},
  journal      = {Phys. Rev. Lett.},
  title        = {Unusual phase separation in a polymer solution caused by asymmetric molecular dynamics},
  year         = {1993},
  month        = nov,
  pages        = {3158--3161},
  volume       = {71},
  creationdate = {2024-04-15T15:47:12},
  doi          = {10.1103/PhysRevLett.71.3158},
  file         = {:Tanaka1993 - Unusual Phase Separation in a Polymer Solution Caused by Asymmetric Molecular Dynamics.pdf:PDF},
  issue        = {19},
  keywords     = {viscoelastic effect},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.71.3158},
}

@Article{Chuang2000,
  author       = {Chuang, Jeffrey and Grosberg, Alexander Yu. and Tanaka, Toyoichi},
  journal      = {The Journal of Chemical Physics},
  title        = {{Topological repulsion between polymer globules}},
  year         = {2000},
  issn         = {0021-9606},
  month        = apr,
  number       = {14},
  pages        = {6434--6442},
  volume       = {112},
  abstract     = {{The work is motivated by the experimental observation of B. Chu et al. [Macromolecules 28, 180 (1995)] which suggests that, while polymer globules in dilute solution in poor solvent are supposed to be very sticky, in actuality they collide many hundreds of times before merging and before aggregation starts. We argue that this slow-down is caused by an “entanglement force” which is operational on the prereptational time scale. This force arises from the fact that two touching globules cannot enjoy the mixing entropy gain expected in equilibrium until after they explore all conformations, including entangled ones. We report a molecular dynamics simulation in which we were able to measure the entanglement force as a function of distance. The important conclusion we can formulate so far is qualitative; the entanglement force exists and is sufficient to explain the observed slow-down of aggregation.}},
  creationdate = {2024-04-15T15:50:46},
  doi          = {10.1063/1.481275},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/112/14/6434/19138291/6434\_1\_online.pdf},
  file         = {:Chuang2000 - Topological Repulsion between Polymer Globules.pdf:PDF},
  keywords     = {aggregates, viscoelastic effect, globules},
  url          = {https://doi.org/10.1063/1.481275},
}

@Article{SchaeferSoenen1997,
  author       = {Schäfer-Soenen, H. and Moerkerke, R. and Berghmans, H. and Koningsveld, R. and Dušek, K. and Šolc, K.},
  journal      = {Macromolecules},
  title        = {Zero and Off-Zero Critical Concentrations in Systems Containing Polydisperse Polymers with Very High Molar Masses. 2. The System Water-Poly(vinyl methyl ether)},
  year         = {1997},
  number       = {3},
  pages        = {410--416},
  volume       = {30},
  abstract     = {Cloud-point curves by DSC measurements at different scanning rates on solutions of two samples of poly(vinyl methyl ether) in water show two minima in a temperature-composition plot. The significance of the data was confirmed by static measurements of the coexisting-phase compositions and phase-volume ratios. A thermodynamic analysis in terms of a strongly concentration-dependent interaction parameter leads to the conclusion that the system H2O/PVME exhibits so-called type III behavior. For polymers of infinite molar mass, such behavior is characterized by the occurrence of two off-zero critical concentrations, in addition to the usual zero critical concentration marking the ϑ state.},
  comment      = {the presumable actual original paper (https://doi.org/10.1135/cccc19951661) is behind a paywall},
  creationdate = {2024-04-15T17:11:31},
  doi          = {10.1021/ma960114o},
  eprint       = {https://doi.org/10.1021/ma960114o},
  file         = {:SchaeferSoenen1997 - Zero and off Zero Critical Concentrations in Systems Containing Polydisperse Polymers with Very High Molar Masses. 2. the System Water-Poly(vinyl Methyl Ether).pdf:PDF},
  keywords     = {polymer solution classification},
  url          = {https://doi.org/10.1021/ma960114o},
}

@Article{Vyazovkin2017,
  author       = {Vyazovkin, Sergey},
  journal      = {Macromolecular Rapid Communications},
  title        = {Isoconversional Kinetics of Polymers: The Decade Past},
  year         = {2017},
  number       = {3},
  pages        = {1600615},
  volume       = {38},
  abstract     = {This article surveys the decade of progress accomplished in the application of isoconversional methods to thermally stimulated processes in polymers. The processes of interest include: crystallization and melting of polymers, gelation of polymer solutions and gel melting, denaturation (unfolding) of proteins, glass transition, polymerization and crosslinking (curing), and thermal and thermo-oxidative degradation. Special attention is paid to the kinetics of polymeric nanomaterials. The article discusses basic principles for understanding the variations in the activation energy and emphasizes the possibility of using models for linking such variations to the parameters of individual kinetic steps. It is stressed that many kinetic effects are not linked to a change in the activation energy alone and may arise from changes in the preexponential factor and reaction model. Also noted is that some isoconversional methods are inapplicable to processes taking place on cooling and cannot be used to study such processes as the melt crystallization.},
  creationdate = {2024-04-16T10:03:48},
  doi          = {https://doi.org/10.1002/marc.201600615},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/marc.201600615},
  keywords     = {differential scanning calorimetry (DSC), epoxy, nanoparticles, organoclay, thermogravimetric analysis (TGA), review},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/marc.201600615},
}

@Article{Johansson1974,
  author       = {Johansson, Allan and Kollman, Peter and Rothenberg, Steve and McKelvey, John},
  journal      = {Journal of the American Chemical Society},
  title        = {Hydrogen bonding ability of the amide group},
  year         = {1974},
  number       = {12},
  pages        = {3794--3800},
  volume       = {96},
  comment      = {pham2018 cites this to say that breaking hydrogen bonds costs about 6-32 kJ per mole of amide group},
  creationdate = {2024-04-16T10:58:24},
  doi          = {10.1021/ja00819a013},
  eprint       = {https://doi.org/10.1021/ja00819a013},
  file         = {:Johansson1974 - Hydrogen Bonding Ability of the Amide Group.pdf:PDF},
  keywords     = {hydrogen bonds, amide, activation energy},
  url          = {https://doi.org/10.1021/ja00819a013},
}

@Article{Tiktopulo1995,
  author       = {Tiktopulo, Elizaveta I. and Uversky, Vladimir N. and Lushchik, Vanda B. and Klenin, Stanislav I. and Bychkova, Valentina E. and Ptitsyn, Oleg B.},
  journal      = {Macromolecules},
  title        = {"Domain" Coil-Globule Transition in Homopolymers},
  year         = {1995},
  number       = {22},
  pages        = {7519--7524},
  volume       = {28},
  abstract     = {The temperature-induced coil-globule transition has been studied in dilute aqueous solutions (with 200 mg/L SDS) for different fractions of polyW-isopropylacrylamide) (PNIPAM) and poly(N-isopropylmethacrylamide) (PNIPMAM) using scanning microcalorimetry, diffusion, and size-exclusion chromatography (FPLC). It has been shown that both these polymers undergo a coil-globule transition upon temperature increase. This transition is accompanied by cooperative heat absorption and a decrease of heat capacity, which makes it similar to the cold denaturation of globular proteins. The globule—coil transition is an “all-or-none” process only for the fractions with the lowest molecular weights (~10 x 10^2) while fractions of larger molecular weights behave as if they consist of quasi-independent cooperative units, the “domains”. The number of “domains” in a macromolecule is proportional to the molecular weight of the polymer. This suggests that the “domain” character of cooperative transitions in large proteins does not, in principle, need evolutionary-selected amino acid sequences but can occur even in homopolymers.},
  creationdate = {2024-04-16T11:07:36},
  doi          = {10.1021/ma00126a032},
  eprint       = {https://doi.org/10.1021/ma00126a032},
  file         = {:Tiktopulo1995 - _Domain_ Coil Globule Transition in Homopolymers.pdf:PDF},
  keywords     = {pNIPAM, PNIPMAM, calorimetry, dsc, diffusion, GPC, denaturation},
  url          = {https://doi.org/10.1021/ma00126a032},
}

@Article{Kogure2000,
  author       = {Kogure, Y. and Hiki, Y.},
  journal      = {Journal of Applied Physics},
  title        = {{Complex and simple relaxations observed in thermal-activation phenomena}},
  year         = {2000},
  issn         = {0021-8979},
  month        = jul,
  number       = {1},
  pages        = {582--587},
  volume       = {88},
  abstract     = {{Among the relaxations of thermal-activation type τ=τ0 exp(E/kBT), “complex” relaxations showing the following abnormal characteristics were noted: (1) a strong correlation between the activation energy E and the preexponential factor τ0; (2) unreasonably small values of τ0(≪10-14 s) and unusually large values of E. As examples, (a) the viscosity relaxation in amorphous materials near the glass transition, and (b) the anelastic relaxation in heavily cold-worked alloys are shown. These are compared with examples of relaxation with normal characteristics, or “simple” relaxation. In complex relaxation, the “compensation effect,” a linear decrease of log τ0 with increasing E, can be seen. Cooperative jumps of relaxing elements were taken into consideration, and a simple formalism for interpreting the complex relaxation was derived. The above examples of complex relaxation were analyzed by considering (a) the cooperative movement of several atoms over potential barriers existing in the amorphous materials, and (b) the cooperative movement of dislocation segments over a potential barrier resulting from impurity atoms.}},
  creationdate = {2024-04-16T11:20:54},
  doi          = {10.1063/1.373699},
  eprint       = {https://pubs.aip.org/aip/jap/article-pdf/88/1/582/19247760/582\_1\_online.pdf},
  file         = {:Kogure2000 - Complex and Simple Relaxations Observed in Thermal Activation Phenomena.pdf:PDF},
  keywords     = {cooperativity, activation energy, thermal activation},
  url          = {https://doi.org/10.1063/1.373699},
}

@Article{Tsuboi2008,
  author       = {Tsuboi, Yasuyuki and Yoshida, Yasuhiro and Okada, Kensaku and Kitamura, Noboru},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Phase Separation Dynamics of Aqueous Solutions of Thermoresponsive Polymers Studied by a Laser T-Jump Technique},
  year         = {2008},
  note         = {PMID: 18266358},
  number       = {9},
  pages        = {2562--2565},
  volume       = {112},
  abstract     = {Poly(N-isopropylacrylamide) and poly(vinyl methyl ether) are well-known thermoresponsive polymers. The aqueous solutions of these polymers exhibit a phase transition followed by phase separation with LCST ∼ 305−310 K. In the present study, the dynamic behavior of the phase separation was analyzed by a laser T-jump method. Two different T-jump methodologies were employed:  the first was a dye-photosensitized T-jump technique (indirect heating) using 532 nm laser pulses, while the other was a direct heating T-jump technique using 1.2 μm laser pulses. Both methods gave similar results. The time constants (τ) of the phase separation were systematically determined for 1−10 wt \% aqueous solutions of the polymers, and a hydrodynamic radius (R) dependence for τ was clearly observed. The values of τ increased linearly with increasing square of R. The present behavior is interpretable in the framework of Tanaka's model for the volume phase transition of a gel, since each of the polymer chains are entangled in the present sample solutions, which can be regarded as approximating to a gel in solution.},
  creationdate = {2024-04-18T08:46:17},
  doi          = {10.1021/jp711128s},
  eprint       = {https://doi.org/10.1021/jp711128s},
  file         = {:Tsuboi2008 - Phase Separation Dynamics of Aqueous Solutions of Thermoresponsive Polymers Studied by a Laser T Jump Technique.pdf:PDF},
  keywords     = {pNIPAM, PVME, kinetics},
  url          = {https://doi.org/10.1021/jp711128s},
}

@Article{Ushiro2020,
  author       = {Ushiro, Kenta and Shoji, Tatsuya and Matsumoto, Mitsuhiro and Asoh, Taka-Aki and Horibe, Hideo and Katsumoto, Yukiteru and Tsuboi, Yasuyuki},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Microanalysis of Single Poly(N-isopropyl\-acrylamide) Droplet Produced by an Optical Tweezer in Water: Isotacticity Dependence of Growth and Chemical Structure of the Droplet},
  year         = {2020},
  note         = {PMID: 32900197},
  number       = {38},
  pages        = {8454--8463},
  volume       = {124},
  abstract     = {Thermoresponsive phase separation mechanisms of aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions were investigated using an optical tweezer combined with a Raman microspectroscope. A near-infrared laser beam (λ = 1064 nm) was focused into the solution to produce and trap a single polymer microdroplet under an optical microscope. The laser beam played two important roles: The first role is to locally heat the solution to induce phase separation in which numerous polymer microdroplets are generated around the focus, while the second one is to collect these microdroplets. Eventually, a single polymer droplet was stably produced and trapped at the focus. Our method enabled us to perform two types of microanalysis for the droplet. Analysis I is real-time monitoring the growth of the polymer droplets by which we can determine the growth rate of droplets. Analysis II is Raman microspectroscopy to reveal chemical components of the droplets. By means of these two analyses, we revealed important phase separation mechanisms in terms of stereoregularity (isotacticity) dependence. From analysis I, we show that droplet growth is governed by the Ostwald ripening mechanism and the growth is accelerated by increasing the isotacticity. From analysis II, we show that the gelation is promoted in the droplet (physical gel formation) with increasing isotacticity. Our technique should be a versatile tool to explore liquid–liquid phase separation mechanisms for various binary solution systems.},
  creationdate = {2024-04-18T08:53:04},
  doi          = {10.1021/acs.jpcb.0c06932},
  eprint       = {https://doi.org/10.1021/acs.jpcb.0c06932},
  file         = {:Ushiro2020 - Microanalysis of Single Poly(N Isopropylacrylamide) Droplet Produced by an Optical Tweezer in Water_ Isotacticity Dependence of Growth and Chemical Structure of the Droplet.pdf:PDF;:MicroanalysisOfSinglePolyNIsopropylacrylamideDropletProducedByAnOpticalTweezerInWater-IsotacticitiyDependenceOfGrowthAndChemicalStructureOfTheDroplet_UshiroEtAl_JPC2020_SI.pdf:PDF},
  keywords     = {pNIPAM, tacticity, kinetics, optical tweezer, raman spectroscopy},
  url          = {https://doi.org/10.1021/acs.jpcb.0c06932},
}

@Article{Tada2013,
  author       = {Tada, Takanori and Katsumoto, Yukiteru and Goossens, Karel and Uji-i, Hiroshi and Hofkens, Johan and Shoji, Tatsuya and Kitamura, Noboru and Tsuboi, Yasuyuki},
  journal      = {The Journal of Physical Chemistry C},
  title        = {Accelerating the Phase Separation in Aqueous Poly(N-isopropylacrylamide) Solutions by Slight Modification of the Polymer Stereoregularity: A Single Molecule Fluorescence Study},
  year         = {2013},
  number       = {20},
  pages        = {10818--10824},
  volume       = {117},
  abstract     = {We discovered for aqueous thermoresponsive polymer solutions that only a slight change in stereoregularity of the polymer can drastically accelerate phase separation. Single molecule fluorescence tracking (SMT) for an isotactic-slight-rich (meso-diad-rich) polymer sample solution revealed an interpolymer nanonetwork even before phase separation, and also revealed a novel phase in which translational molecular motion was frozen after phase separation. For such systems, fluorescence correlation spectroscopy (FCS) provided quantitative information on molecular diffusion. The results on FCS well agreed with the interpolymer nanonetwork model that was proposed on the basis of SMT measurement. We demonstrate such a novel method to control phase separation dynamics and also the interpolymer nanonetwork model.},
  creationdate = {2024-04-18T08:57:56},
  doi          = {10.1021/jp4027173},
  eprint       = {https://doi.org/10.1021/jp4027173},
  file         = {:Tada2013 - Accelerating the Phase Separation in Aqueous Poly(N Isopropylacrylamide) Solutions by Slight Modification of the Polymer Stereoregularity_ a Single Molecule Fluorescence Study.pdf:PDF;:Tada2013 - Accelerating the Phase Separation in Aqueous Poly(N Isopropylacrylamide) Solutions by Slight Modification of the Polymer Stereoregularity_ a Single Molecule Fluorescence Study.avi:avi;:ata-1 5wt% 34degree.avi:avi;:iso-1 5wt% 24degree.avi.avi:avi;:iso-2 above clouding point.avi:avi;:jp4027173_si_005.pdf:PDF},
  keywords     = {pNIPAM, tacticity, kinetics},
  url          = {https://doi.org/10.1021/jp4027173},
}

@Article{Philipp2012,
  author       = {Philipp, Martine and Müller, Ulrich and Aleksandrova, Ralitsa and Sanctuary, Roland and Müller-Buschbaum, Peter and Krüger, Jan K.},
  journal      = {Soft Matter},
  title        = {On the elastic nature of the demixing transition of aqueous PNIPAM solutions},
  year         = {2012},
  pages        = {11387--11395},
  volume       = {8},
  abstract     = {Mechanical instabilities accompanying the demixing transition of semi-dilute aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions are probed for the first time with Brillouin spectroscopy{,} densitometry and refractometry. The particular role of the elastic moduli and the mass density at this coil-to-globule transition followed by molecular aggregation is investigated. Even though the demixing transition of PNIPAM solutions is denoted as a volume phase transition{,} it turns out that this transition is governed by the elastic properties{,} instead of the volume properties. This is consistent with earlier findings made for the demixing transition in chemically cross-linked PNIPAM hydrogels. Above the demixing temperature{,} Brillouin spectroscopy discriminates compact PNIPAM-rich agglomerates with sizes larger than 200 nm. Interestingly{,} these agglomerates possess a sharp distribution of elastic moduli{,} which can be attributed without any doubt to a material with gel-like mechanical consistency. Thus the phase-separated PNIPAM-rich agglomerates are not in the glassy state.},
  creationdate = {2024-04-18T09:42:00},
  doi          = {10.1039/C2SM26527C},
  file         = {:Philipp2012 - On the Elastic Nature of the Demixing Transition of Aqueous PNIPAM Solutions.pdf:PDF},
  issue        = {44},
  keywords     = {pNIPAM, brillouin spectroscopy, densitometry, refractometry, viscosity, aggregates, vitrification},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C2SM26527C},
}

@Article{Inoue2013,
  author       = {Inoue, Hayato and Kuwahara, Shota and Katayama, Kenji},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {The whole process of phase transition and relaxation of poly(N-isopropylacrylamide) aqueous solution},
  year         = {2013},
  pages        = {3814--3819},
  volume       = {15},
  abstract     = {We observed the whole dynamics from the phase transition to the molecular relaxation of a poly(N-isopropylacrylamide) (PNIPAM) aqueous solution using the heterodyne transient grating (HD-TG) method combined with the laser temperature-jump technique. The initial phase transition corresponding to coil to globule conformational transition occurred with a time constant of 96 ± 7 μs. Then{,} the globule molecules aggregated due to hydrophobic interaction{,} and the size of the aggregates increased sufficiently to scatter light (11 ± 1 ms) when the temperature achieved by heating was high enough to exceed the phase transition temperature. The aggregates loosened due to thermal diffusion with a time constant of 44 ± 5 ms. Even after that{,} the released globule molecules returned back to the coil state with a lifetime of 1.5–5 s{,} as we reported in a previous paper (H. Inoue et al.{,} Phys. Chem. Chem. Phys.{,} 2012{,} 14{,} 5620–5627).},
  creationdate = {2024-04-18T09:47:28},
  doi          = {10.1039/C3CP43309A},
  file         = {:Inoue2013 - The Whole Process of Phase Transition and Relaxation of Poly(N Isopropylacrylamide) Aqueous Solution.pdf:PDF},
  issue        = {11},
  keywords     = {pNIPAM, kinetics, laser T-jump},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C3CP43309A},
}

@Article{Inoue2012,
  author       = {Inoue, Hayato and Katayama, Kenji and Iwai, Kaoru and Miura, Atsushi and Masuhara, Hiroshi},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Conformational relaxation dynamics of a poly(N-isopropylacrylamide) aqueous solution measured using the laser temperature jump transient grating method},
  year         = {2012},
  pages        = {5620--5627},
  volume       = {14},
  abstract     = {We observed phase transition and phase relaxation processes of a poly(N-isopropylacrylamide) (PNIPAM) aqueous solution using the heterodyne transient grating (HD-TG) method combined with the laser temperature jump technique. The sample temperature was instantaneously raised by about 1.0 K after irradiation of a pump pulse to crystal violet (CV) molecules for heating{,} and the phase transition was induced for the sample with an initial temperature just below the lower critical solution temperature (LCST); the following phase relaxation dynamics was observed. Turbidity relaxation was observed in both the turbidity and HD-TG responses{,} while another relaxation process was observed only in the HD-TG response{,} namely via the refractive index change. It is suggested that this response is due to formation of globule molecules or their assemblies since they would have nothing to do with turbidity change but would affect the refractive index{,} which is dependent on the molar volume of a chemical species. Furthermore{,} the grating spacing dependence of the HD-TG responses suggests that the response was caused by the counter propagating diffusion of the coil molecules as a reactant species and the globule molecules as a product species and the lifetime of the globule molecules ranged from 1.5 to 5 seconds. Thus{,} we conclude that the turbidity reflects the dynamics of aggregate conditions{,} not molecular conditions. The coil and globule sizes were estimated from the obtained diffusion coefficient. The sizes of the coil molecules did not change at the initial temperatures below the LCST but increased sharply as it approaches LCST. We propose that the coil-state molecules associate due to hydrophobic interaction when the initial temperature was higher than LCST minus 0.5 K and that the globule-state molecules generated from the coil-state molecules showed a similar trend in temperature. The phase transition was also induced by heating under a microscope{,} and the relaxation process was followed using the fluorescence peak shift of a fluorescent molecule-labeled PNIPAM. The result also supports the existence of a globule molecule or its assembly remains for several seconds in the phase relaxation.},
  creationdate = {2024-04-18T09:51:27},
  doi          = {10.1039/C2CP40243B},
  file         = {:Inoue2012 - Conformational Relaxation Dynamics of a Poly(N Isopropylacrylamide) Aqueous Solution Measured Using the Laser Temperature Jump Transient Grating Method.pdf:PDF},
  issue        = {16},
  keywords     = {pNIPAM, kinetics, laser T-Jump, turbidity, mesoglobules},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C2CP40243B},
}

@Article{Kujawa2001,
  author       = {Kujawa, Piotr and Winnik, Françoise M.},
  journal      = {Macromolecules},
  title        = {Volumetric Studies of Aqueous Polymer Solutions Using Pressure Perturbation Calorimetry:  A New Look at the Temperature-Induced Phase Transition of Poly(N-isopropylacrylamide) in Water and D2O},
  year         = {2001},
  number       = {12},
  pages        = {4130--4135},
  volume       = {34},
  abstract     = {We report the first application of pressure perturbation calorimetry (PPC) to determine the hydration properties of poly(N-isopropylacrylamide) (PNIPAM) in H2O and in D2O as the solutions undergo a temperature-induced phase transition. The technique, which measures the heat change resulting from a pressure change above a solution of PNIPAM placed in a microcalorimeter cell, yields the temperature dependence of the coefficient of thermal expansion, αp, of the polymer in solution and the change in volume of the solvation layer around the polymer chain. In the temperature ranges below and above the phase transition, αp of PNIPAM in H2O increased linearly with temperature. It underwent a sharp increase at the transition temperature, Tmax, then rapidly decreased. The phase transition was accompanied by an increase in the partial specific volume of the hydrated polymer. This increase was significantly higher for solutions of PNIPAM in D2O, compared to H2O. A study by PPC of the phase transition of hydrophobically modified PNIPAM samples that undergo micellization in water demonstrated that the hydration of the polymeric micelles varies significantly as a function of the degree of hydrophobic substitution and length of the alkyl group linked to the polymer.},
  creationdate = {2024-04-18T10:25:37},
  doi          = {10.1021/ma002082h},
  eprint       = {https://doi.org/10.1021/ma002082h},
  file         = {:Kujawa2001 - Volumetric Studies of Aqueous Polymer Solutions Using Pressure Perturbation Calorimetry_ a New Look at the Temperature Induced Phase Transition of Poly(N Isopropylacrylamide) in Water and D2O.pdf:PDF},
  keywords     = {pressure perturbation calorimetry, pNIPAM, thermal expansion coefficient, hydrophobic modification, isotope effect},
  url          = {https://doi.org/10.1021/ma002082h},
}

@Article{Kubota1990a,
  author       = {Kenji Kubota and Shouei Fujishige and Isao Ando},
  journal      = {Polymer Journal},
  title        = {Solution Properties of Poly(N-isopropylacrylamide) in Water},
  year         = {1990},
  month        = jan,
  pages        = {15--20},
  volume       = {22},
  abstract     = {Various molecular parameters characterizing the solution properties of poly(N-isopropylacrylamide) (in the range of molecular weight from 13.8 to 910×104) in water at 20°C and the temperature dependence of them in the range of 20°C to 30.6°C were determined with static and dynamic light scattering technique. (Modified) Flory’s fifth power law of excluded volume effect predicts well the temperature dependence of the chain dimension. It is shown that this polymer molecule behaves as a flexible coil from the molecular weight dependence of these parameters and the relation between the interpenetration function and expansion coefficients. The unique thermal behavior of this solution, temperature of phase change being independent of molecular weights and concentrations at least in the range of 1 wt%, should be mainly attributed to the hydrated structure.},
  creationdate = {2024-04-18T11:29:48},
  file         = {:Kubota1990a - Solution Properties of Poly(N Isopropylacrylamide) in Water.pdf:PDF},
  keywords     = {pNIPAM, chain-length dependence, DLS, SLS, flory},
  url          = {https://doi.org/10.1295/polymj.22.15},
}

@Article{Tong1999,
  author       = {Tong, Zhen and Zeng, Fang and Zheng, Xu and Sato, Takahiro},
  journal      = {Macromolecules},
  title        = {Inverse Molecular Weight Dependence of Cloud Points for Aqueous Poly(N-isopropylacrylamide) Solutions},
  year         = {1999},
  number       = {13},
  pages        = {4488--4490},
  volume       = {32},
  creationdate = {2024-04-18T11:34:29},
  doi          = {10.1021/ma990062d},
  eprint       = {https://doi.org/10.1021/ma990062d},
  file         = {:Tong1999 - Inverse Molecular Weight Dependence of Cloud Points for Aqueous Poly(N Isopropylacrylamide) Solutions.pdf:PDF},
  keywords     = {pNIPAM, molecular-weight dependence},
  url          = {https://doi.org/10.1021/ma990062d},
}

@Article{Ray2005,
  author       = {Biswajit Ray and Yoshio Okamoto and Masami Kamigaito and Mitsuo Sawamoto and Ken-ichi Seno and Shokyoku Kanaoka and Sadahito Aoshima},
  journal      = {Polymer Journal},
  title        = {Effect of Tacticity of Poly(N-isopropylacrylamide) on the Phase Separation Temperature of Its Aqueous Solutions},
  year         = {2005},
  pages        = {234--237},
  volume       = {37},
  creationdate = {2024-04-18T13:10:28},
  doi          = {https://doi.org/10.1295/polymj.37.234},
  file         = {:Ray2005 - Effect of Tacticity of Poly(N Isopropylacrylamide) on the Phase Separation Temperature of Its Aqueous Solutions.pdf:PDF},
  keywords     = {pNIPAM, tacticity},
}

@Article{Katsumoto2008,
  author       = {Katsumoto, Yukiteru and Kubosaki, Noriyuki},
  journal      = {Macromolecules},
  title        = {Tacticity Effects on the Phase Diagram for Poly(N-isopropyl\-acrylamide) in Water},
  year         = {2008},
  number       = {15},
  pages        = {5955--5956},
  volume       = {41},
  creationdate = {2024-04-18T13:27:53},
  doi          = {10.1021/ma800881r},
  eprint       = {https://doi.org/10.1021/ma800881r},
  file         = {:Katsumoto2008 - Tacticity Effects on the Phase Diagram for Poly(N Isopropylacrylamide) in Water.pdf:PDF;:TacticityEffectsOnThePhaseDiagramForPolyNIsopropylacrylamideInWater_KatsumotoEtAl_Macromol2008_SI.pdf:PDF},
  keywords     = {pNIPAM, tacticity, transmittance, turbidity, cloud-point},
  url          = {https://doi.org/10.1021/ma800881r},
}

@Article{Katsumoto2010,
  author       = {Katsumoto, Yukiteru and Kubosaki, Noriyuki and Miyata, Tatsuhiko},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Molecular Approach To Understand the Tacticity Effects on the Hydrophilicity of Poly(N-isopropylacrylamide): Solubility of Dimer Model Compounds in Water},
  year         = {2010},
  note         = {PMID: 20919708},
  number       = {42},
  pages        = {13312--13318},
  volume       = {114},
  abstract     = {Although it has been suggested that the tacticity affects the hydrophilicity of poly(N-isopropylacrylamide) (PNiPA), little is known about the physical background of this phenomenon. In this study, we investigated the solubility of the dimer model compounds (DNiPA). The partition coefficient of DNiPA in the two phases of a water/chloroform mixture has indicated that DNiPA with the racemo configuration (r-DNiPA) is more soluble in water than DNiPA with the meso configuration (m-DNiPA). The difference of the hydration free energy between m- and r-DNiPA is estimated to be 1.2 kJ mol-1. The molecular mechanics (MM) calculations with the GB/SA model have revealed that r-DNiPA in water is more stable by ca. 1 kJ mol-1 than m-DNiPA, which is in excellent agreement with the experimental result. The MM calculations have also indicated that the intramolecular interaction of m-DNiPA is stronger than that of r-DNiPA, while r-DNiPA is advantageous in terms of the hydration free energy and conformational entropy.},
  creationdate = {2024-04-18T13:44:20},
  doi          = {10.1021/jp107442h},
  eprint       = {https://doi.org/10.1021/jp107442h},
  file         = {:Katsumoto2010 - Molecular Approach to Understand the Tacticity Effects on the Hydrophilicity of Poly(N Isopropylacrylamide)_ Solubility of Dimer Model Compounds in Water.pdf:PDF;:MolecularApproachToUnderstandTheTacticityEffectsOnTheHydrophlicityOfPolyNIsopropyacrylamide-SolubilityOfDimerModelCompoundsInWater_KatsumotoEtAl_JPC2010_SI.pdf:PDF},
  keywords     = {pNIPAM, tacticity, dimer, 1h-nmr, calculations},
  url          = {https://doi.org/10.1021/jp107442h},
}

@Article{Autieri2011,
  author       = {Autieri, Emmanuel and Chiessi, Ester and Lonardi, Alice and Paradossi, Gaio and Sega, Marcello},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Conformation and Dynamics of Poly(N-isopropyl acrylamide) Trimers in Water: A Molecular Dynamics and Metadynamics Simulation Study},
  year         = {2011},
  note         = {PMID: 21517084},
  number       = {19},
  pages        = {5827--5839},
  volume       = {115},
  abstract     = {Conformational features, structure, and dynamic properties of the trimer of poly(N-isopropyl acrylamide), (NIPAAm)3, in aqueous solution at 293 and 323 K were investigated by a double simulation approach. The free energy behavior as a function of backbone conformation was obtained by metadynamics-umbrella sampling simulations. The structural characteristics, the intramolecular and water hydrogen bonding, and the torsional dynamics were analyzed by molecular dynamics simulations. The four stereoisomers of (NIPAAm)3, representing syndiotactic, isotactic, and atactic sequences, were studied to highlight the tacticity effect on the system properties. The simulation results indicate that the experimentally observed lower hydrophilicity of isotactic poly(N-isopropyl acrylamide), in comparison with the syndiotactic one, is related to a lower conformational entropy. The atactic stereoisomers display the highest intramolecular hydrogen bond capability, at both studied temperatures, due to formation of hydrogen bonds between external amide groups. The mobility of the backbone in the syndiotactic trimer is more homogeneous than in other stereoisomers. The temperature increase was found mainly to affect the conformation of N-isopropyl amide side chains, and a structural rearrangement was observed for the atactic stereoisomers, in agreement with their experimental solution behavior. Simulation results are discussed in relation with available experimental data on solution properties and reactivity of poly(N-isopropyl acrylamide).},
  creationdate = {2024-04-18T13:48:20},
  doi          = {10.1021/jp2020929},
  eprint       = {https://doi.org/10.1021/jp2020929},
  file         = {:Autieri2011 - Conformation and Dynamics of Poly(N Isopropyl Acrylamide) Trimers in Water_ a Molecular Dynamics and Metadynamics Simulation Study.pdf:PDF;:ConformationAndDynamicsOfPolyNIsopropylacrylamideTrimersInWater-AMolecularDynamicsAndMetadynamicsSimulationStudy_AutieriEtAl_JPC2011_SI.pdf:PDF},
  keywords     = {pNIPAM, tacticity, trimer, molecular dynamics, simulation},
  url          = {https://doi.org/10.1021/jp2020929},
}

@Article{Tsuboi2012,
  author       = {Tsuboi, Yasuyuki and Tada, Takanori and Shoji, Tatsuya and Kitamura, Noboru},
  journal      = {Macromolecular Chemistry and Physics},
  title        = {Phase-Separation Dynamics of Aqueous Poly (N-isopropylacrylamide) Solutions: Characteristic Behavior of the Molecular Weight and Concentration Dependences},
  year         = {2012},
  number       = {18},
  pages        = {1879--1884},
  volume       = {213},
  abstract     = {The dynamics of thermoresponsive phase-separation processes in aqueous poly(N-isopropylacrylamide) (PNIPAM) was studied using a laser temperature-jump technique combined with photometry. The time constant for phase separation (τ) was determined with high accuracy for various molecular weights (Mw) and concentrations (C) of PNIPAM in solution. For the C-dependence, τ decreased with increasing concentration, and eventually converged to a constant value (≈ 50 ms) at high concentration. Such behavior can be interpreted in terms of inter-polymer-chain entanglement and diffusion prior to phase separation. On the other hand, there was an optimum value of Mw at which the phase separation was fastest. The origins of these experimental results are discussed within the framework of a diffusion-controlled model.},
  creationdate = {2024-04-18T13:58:19},
  doi          = {10.1002/macp.201200190},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/macp.201200190},
  file         = {:Tsuboi2012 - Phase Separation Dynamics of Aqueous Poly (N Isopropylacrylamide) Solutions_ Characteristic Behavior of the Molecular Weight and Concentration Dependences.pdf:PDF},
  keywords     = {hydrogels, kinetics, phase separation, stimuli-sensitive polymer},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/macp.201200190},
}

@Article{Tsuboi2005,
  author       = {Tsuboi, Yasuyuki and Nishino, Masayuki and Sasaki, Tetsuya and Kitamura, Noboru},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Poly(N-Isopropylacrylamide) Microparticles Produced by Radiation Pressure of a Focused Laser Beam:  A Structural Analysis by Confocal Raman Microspectroscopy Combined with a Laser-Trapping Technique},
  year         = {2005},
  note         = {PMID: 16851799},
  number       = {15},
  pages        = {7033--7039},
  volume       = {109},
  abstract     = {We developed a confocal Raman microspectroscopy system combined with a laser trapping technique and applied it to aqueous solutions (H2O and D2O) of poly(N-isopropylacrylamide) (PNIPA), which is well-known as a representative thermo-responsive polymer, i.e., phase transition/separation between coiled and globular states. By introducing a near-infrared (1064 nm) laser beam into a microscope, PNIPA microparticles were produced at the focused spot of the laser beam, both in H2O and D2O. By using the present system, we succeeded in obtaining the Raman spectra of PNIPA in the coiled and globular states over a wide wavenumber region (800-3500 cm-1) for the first time. For the D2O solutions (in which the photothermal effect is negligible and hence the microparticles should be produced purely by the effect of radiation pressure), some significant differences were observed in the Raman spectra for the coiled state, in the globular state, and for laser induced microparticles. By analyzing these spectra in detail, we revealed that the structure of the laser-induced microparticles was analogous to that in the globular state. We also discuss the fundamental mechanism underlying the transformation of the higher order structure of a polymer by radiation pressure.},
  creationdate = {2024-04-18T14:38:02},
  doi          = {10.1021/jp044894b},
  eprint       = {https://doi.org/10.1021/jp044894b},
  file         = {:Tsuboi2005 - Poly(N Isopropylacrylamide) Microparticles Produced by Radiation Pressure of a Focused Laser Beam_ a Structural Analysis by Confocal Raman Microspectroscopy Combined with a Laser Trapping Technique.pdf:PDF},
  keywords     = {pNIPAM, isotope effect, h2o, d2o, raman spectroscopy},
  url          = {https://doi.org/10.1021/jp044894b},
}

@Article{Shoji2015,
  author       = {Tatsuya Shoji and Riku Nohara and Noboru Kitamura and Yasuyuki Tsuboi},
  journal      = {Analytica Chimica Acta},
  title        = {A method for an approximate determination of a polymer-rich-domain concentration in phase-separated poly(N-isopropylacrylamide) aqueous solution by means of confocal Raman microspectroscopy combined with optical tweezers},
  year         = {2015},
  issn         = {0003-2670},
  pages        = {118--121},
  volume       = {854},
  abstract     = {The paper demonstrates that a confocal Raman microspectroscope combined with optical tweezers is a promising technique to estimate polymer concentration in polymer-rich domain in phase-separated-aqueous polymer solution. The sample polymer is poly-(N-isopropylacrylamide) (PNIPAM) that is well-known as a representative thermo-responsive polymer. Optical tweezers can selectively trap the polymer-rich domain at the focal point in non-contact and non-intrusive modes. Such situation allows us to determine polymer concentration in the domain, which has been unclear due to a lack of appropriate analytical technique. It is applicable for a variety of other thermo-responsive polymers.},
  creationdate = {2024-04-18T14:47:01},
  doi          = {https://doi.org/10.1016/j.aca.2014.11.001},
  file         = {:Shoji2015 - A Method for an Approximate Determination of a Polymer Rich Domain Concentration in Phase Separated Poly(N Isopropylacrylamide) Aqueous Solution by Means of Confocal Raman Microspectroscopy Combined with Optical Tweezers.pdf:PDF},
  keywords     = {Confocal Raman microspectroscopy, raman spectroscopy, Thermo-responsive polymer, thermoresponsive, Poly-(-isopropylacrylamide), pNIPAM, Optical tweezers, Optical trapping, Near-infrared laser beam, Radiation force, Photothermal effect},
  url          = {https://www.sciencedirect.com/science/article/pii/S0003267014013130},
}

@Article{LocatelliChampagne2013,
  author       = {Clémentine Locatelli-Champagne and Michel Cloitre},
  journal      = {Colloid Polym Sci},
  title        = {Monitoring mesoglobules formation in PNIPAm solutions using Nile Red solvatochomism},
  year         = {2013},
  pages        = {2911--2916},
  volume       = {291},
  abstract     = {Nile Red solvatochromism is used to monitor phase separation in concentrated poly(N-isopropyl acrylamide) (PNIPAm) aqueous solutions. Below the lower critical solution temperature (LCST), Nile Red molecules are in a polar environment and thus exhibit negligible fluorescence. Above the LCST, the aggregation of the PNIPAm chains into hydrophobic mesoglobules provides a nonpolar environment, causing a strong increase of fluorescence. The spectra show two emission bands, which can be related to the partitioning of Nile Red molecules between the core and the surface of the mesoglobules. More generally, the technique appears as a new and promising tool to probe microheterogeneities in polymer solutions or mixtures},
  creationdate = {2024-04-19T07:34:47},
  doi          = {10.1007/s00396-013-3035-5},
  file         = {:LocatelliChampagne2013 - Monitoring Mesoglobules Formation in PNIPAm Solutions Using Nile Red Solvatochomism.pdf:PDF},
  keywords     = {pNIPAM, mesoglobule, fluorescence, solvatochromism, Nile Red, thermoresponsive, LCST, aggregation},
}

@Article{Qiu2007,
  author       = {Qiu, Xing-Ping and Tanaka, Fumihiko and Winnik, Françoise M.},
  journal      = {Macromolecules},
  title        = {Temperature-Induced Phase Transition of Well-Defined Cyclic Poly(N-isopropylacrylamide)s in Aqueous Solution},
  year         = {2007},
  number       = {20},
  pages        = {7069--7071},
  volume       = {40},
  creationdate = {2024-04-19T07:49:23},
  doi          = {10.1021/ma071359b},
  eprint       = {https://doi.org/10.1021/ma071359b},
  file         = {:Qiu2007 - Temperature Induced Phase Transition of Well Defined Cyclic Poly(N Isopropylacrylamide)s in Aqueous Solution.pdf:PDF;:TemperatureInducedPhaseTransitionOfWellDefinedCyclicPolyNIsopropylacrylamidesInAqueousSolution_QiuEtAl_Macromol2007_SI2.pdf:PDF;:Qiu2007 - Temperature Induced Phase Transition of Well Defined Cyclic Poly(N Isopropylacrylamide)s in Aqueous Solution.doc:Word},
  keywords     = {cylic pNIPAM,},
  url          = {https://doi.org/10.1021/ma071359b},
}

@Article{Wu1997,
  author       = {Wu, Chi and Zhou, Shuiqin},
  journal      = {Macromolecules},
  title        = {Volume Phase Transition of Swollen Gels:  Discontinuous or Continuous?},
  year         = {1997},
  number       = {3},
  pages        = {574--576},
  volume       = {30},
  abstract     = {Poly(N-isopropylacrylamide) (PNIPAM) linear chains and spherical microgels were studied using laser light scattering. The volume change associated with the temperature dependence of the hydrodynamic radii of both the linear chains and the spherical microgels is continuous, in contrast to a discontinuous volume phase transition observed for a bulk PNIPAM gel with an identical composition. A reexamination of the volume phase transition theory shows that the phase transition temperature depends on the length of the subchain between two neighboring cross-linking points inside the gel. A comparison of the results of the linear chains and the spherical microgels suggests that the volume change of a polymer gel should be practically continuous because the inhomogeneity of the subchain length smears the volume phase transition. A possible explanation is also presented to rationalize the discontinuous volume phase transition observed in certain bulk PNIPAM gels, which is based on the bulk shear module of the gel and the microscopically inhomogeneous shrinking generated inside the gel in the volume phase transition.},
  creationdate = {2024-04-19T07:53:09},
  doi          = {10.1021/ma960499a},
  eprint       = {https://doi.org/10.1021/ma960499a},
  file         = {:Wu1997 - Volume Phase Transition of Swollen Gels_ Discontinuous or Continuous_.pdf:PDF},
  keywords     = {pNIPAM, linear, microgel, light scattering, hydrodynamic radius},
  url          = {https://doi.org/10.1021/ma960499a},
}

@Article{Tang2004,
  author       = {Tang, Shijun and Hu, Zhibing and Cheng, Zhengdong and Wu, Jianzhong},
  journal      = {Langmuir},
  title        = {Crystallization Kinetics of Thermosensitive Colloids Probed by Transmission Spectroscopy},
  year         = {2004},
  note         = {PMID: 15379518},
  number       = {20},
  pages        = {8858--8864},
  volume       = {20},
  abstract     = {The kinetics of crystallization of poly-N-isopropylacrylamide (PNIPAM) particles has been investigated using the UV-visible transmission spectroscopy. Since the particle size decreases with the increase in temperature, microgel dispersions of different volume fractions have been obtained by varying the temperature of a single sample. It is found that the rates of the change in crystallinity, the average crystallite size, and the number density of crystallites at the most rapid stage over a certain time interval at various temperatures can be described by the power-law relations. At 19 °C, the PNIPAM system behaves as a hard sphere system under microgravity. The hard sphere theory based on Monte Carlo simulation has been used as a reference point to compare with conventional hard spheres, soft spheres, and PNIPAM spheres.},
  creationdate = {2024-04-19T07:59:00},
  doi          = {10.1021/la049203h},
  eprint       = {https://doi.org/10.1021/la049203h},
  file         = {:Tang2004 - Crystallization Kinetics of Thermosensitive Colloids Probed by Transmission Spectroscopy.pdf:PDF},
  keywords     = {crystallizaiton, pNIPAM, kinetics, UV-vis, monte carlo simulation, DLS, microgel, turbidity},
  url          = {https://doi.org/10.1021/la049203h},
}

@Article{Kubelka2009,
  author       = {Jan Kubelka},
  journal      = {Photochemistry \& Photobiological Sciences},
  title        = {Time-resolved methods in biophysics. 9. Laser temperature-jump methods for investigating biomolecular dynamics},
  year         = {2009},
  pages        = {499--512},
  volume       = {8},
  creationdate = {2024-04-19T08:17:00},
  file         = {:Kubelka2009 - Time Resolved Methods in Biophysics. 9. Laser Temperature Jump Methods for Investigating Biomolecular Dynamics.pdf:PDF},
  keywords     = {review, laser temperature jump, kinetics, proteins, biomolecules, foling},
  url          = {https://doi.org/10.1039/b819929a},
}

@Article{Katsumoto2007,
  author       = {Katsumoto, Yukiteru and Tanaka, Takeyuki and Ihara, Katsunori and Koyama, Misao and Ozaki, Yukihiro},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Contribution of Intramolecular CO···H-N Hydrogen Bonding to the Solvent-Induced Reentrant Phase Separation of Poly(N-isopropylacrylamide)},
  year         = {2007},
  note         = {PMID: 17941665},
  number       = {44},
  pages        = {12730--12737},
  volume       = {111},
  abstract     = {Changes in the local environment around amide groups of poly(N-isopropylacrylamide) (PNiPA) during a solvent-induced reentrant phase separation have been investigated by infrared spectroscopy combined with quantum chemical calculations. The addition of methanol or tetrahydrofuran as a cosolvent to an aqueous solution of PNiPA causes spectral changes in the amide I regions. By preparing a dimer model compound for PNiPA, we can establish the assignment of the amide I bands for the polymer in solutions. Hydrogen-deuterium exchange experiments of the amide protons of PNiPA and its dimer models have revealed that the amide groups of PNiPA form an intramolecular CO···H-N hydrogen bond even in a good solvent. The result has suggested that the change in the amide I envelope of PNiPA observed during the solvent-induced phase transition reflects the modification of the intramolecular CO···H-N hydrogen bond of PNiPA as well as the variation in solvation state of the amide groups. On the basis of the assignment, we have discussed contributions of the intramolecular CO···H-N hydrogen bond to the phase behavior of PNiPA.},
  creationdate = {2024-04-19T11:11:17},
  doi          = {10.1021/jp0750452},
  eprint       = {https://doi.org/10.1021/jp0750452},
  file         = {:ContributionOfIntramolecularCOHNHydrogenBondingToTheSolventInducedReentrantPhaseSeparationOfPolyNIsopropylacrylamide_KatsumotoEtAl_JPC2007_SI.pdf:PDF},
  keywords     = {pNIPAM, hydrogen bonds, amide, hydratio shell, cononsolvency, hydrogen exchange, infrared, FTIR, quantum chemical calculations},
  url          = {https://doi.org/10.1021/jp0750452},
}

@Article{Osaka2009,
  author       = {Osaka, Noboru and Shibayama, Mitsuhiro and Kikuchi, Tatsuya and Yamamuro, Osamu},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Quasi-Elastic Neutron Scattering Study on Water and Polymer Dynamics in Thermo/Pressure Sensitive Polymer Solutions},
  year         = {2009},
  note         = {PMID: 19725571},
  number       = {39},
  pages        = {12870--12876},
  volume       = {113},
  abstract     = {Dynamics of water and poly(N-isopropylacrylamide) (PNIPA) in concentrated aqueous solutions, where the majority of water molecules are attached to polymer chains, has been investigated with use of incoherent quasi-elastic neutron scattering (QENS) and dynamic light scattering (DLS) measurements as functions of temperature, T, and hydrostatic pressure, P. It was observed by QENS that the self-diffusion coefficient, Dwater, of water in PNIPA/H2O solutions increased by P at temperatures below the lower critical solution temperature (LCST) of PNIPA aqueous solutions. However, above the LCST, Dwater decreased by P, as is often reported in non-hydrogen bonding solutions. In isobaric heating runs, therefore, the jump in Dwater at LCST decreased with increasing pressure. On the other hand, the mean-square displacement, ⟨u2⟩, of the local vibrational motion of PNIPA in PNIPA/D2O solutions, where the incoherent scattering signal of PNIPA was predominantly observed, was reduced due to the aggregation behavior of PNIPA by pressurizing, which was also confirmed by using DLS. The jump in ⟨u2⟩ at the LCST became gradual by pressurizing, which was consistent with the changes of the dynamics of water obtained in PNIPA/H2O solutions.},
  creationdate = {2024-04-19T11:36:18},
  doi          = {10.1021/jp902960b},
  eprint       = {https://doi.org/10.1021/jp902960b},
  file         = {:Osaka2009 - Quasi Elastic Neutron Scattering Study on Water and Polymer Dynamics in Thermo_Pressure Sensitive Polymer Solutions.pdf:PDF},
  keywords     = {pNIPAM, QENS, DLS, pressure-dependence, diffusion, aggregates},
  url          = {https://doi.org/10.1021/jp902960b},
}

@Article{Liu2005a,
  author       = {Liu, Guangming and Zhang, Guangzhao},
  journal      = {Langmuir},
  title        = {Reentrant Behavior of Poly(N-isopropyl\-acrylamide) Brushes in Water−Methanol Mixtures Investigated with a Quartz Crystal Microbalance},
  year         = {2005},
  note         = {PMID: 15723514},
  number       = {5},
  pages        = {2086--2090},
  volume       = {21},
  abstract     = {The solvent composition induced reentrant behavior of poly(N-isopropylacrylamide) (PNIPAM) chains grafted on a SiO2 surface in water−methanol mixtures was investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D) at 20 °C. The frequency and energy dissipation responses showed that the grafted PNIPAM chains sharply collapse when the methanol content (xm) reaches ∼17 mol \%. In the range 17−50 mol \%, the grafted chains remain in a collapsed state. Further increase of the methanol content leads to an abrupt reswelling of the collapsed chains at xm > ∼50 mol \%. The sharp reentrant swelling-to-collapse-to-swelling transition was attributed to the water−methanol complexation instead of the preferential adsorption effect. Our results also suggest that the water−methanol complexation is not induced by hydrophobic interaction but by hydrogen bonding.},
  creationdate = {2024-04-22T10:45:07},
  doi          = {10.1021/la047326w},
  eprint       = {https://doi.org/10.1021/la047326w},
  file         = {:Liu2005a - Reentrant Behavior of Poly(N Isopropylacrylamide) Brushes in Water−Methanol Mixtures Investigated with a Quartz Crystal Microbalance.pdf:PDF},
  keywords     = {pNIPAM, planar brush, cononsolvency, qcmb, aqueous methanol, reswelling},
  url          = {https://doi.org/10.1021/la047326w},
}

@Article{Garner2009,
  author       = {Brett W. Garner and Tong Cai and Santaneel Ghosh and Zhibing Hu and Arup Neogi},
  journal      = {Applied Physics Express},
  title        = {Refractive Index Change Due to Volume-Phase Transition in Polyacrylamide Gel Nanospheres for Optoelectronics and Bio-photonics},
  year         = {2009},
  month        = apr,
  number       = {5},
  pages        = {057001},
  volume       = {2},
  abstract     = {Poly(N-isopropylacrylamide) (PNIPAM) hydrogel nanospheres response to global temperature stimuli across the low critical solution temperature is studied as the water content in the polymer network is modified. The refractive index of gel nanoparticles was measured as a function of temperature using spectroscopic ellipsometry. The volume of the nanospheres reduces by 40% resulting in a modification of light scattering properties of the medium. A change in temperature from 33 to 34 °C results in a volume contraction of nanospheres which is accompanied by 8–10% enhancement in the refractive index of the gel network.},
  creationdate = {2024-04-22T11:04:14},
  doi          = {10.1143/APEX.2.057001},
  file         = {:Garner2009 - Refractive Index Change Due to Volume Phase Transition in Polyacrylamide Gel Nanospheres for Optoelectronics and Bio Photonics.pdf:PDF},
  keywords     = {pNIPAM, ellipsometry, DLS, microgel, refractive index},
  url          = {https://dx.doi.org/10.1143/APEX.2.057001},
}

@Article{Zhou2008a,
  author       = {Zhou, Xuechang and Li, Junfang and Wu, Chi and Zheng, Bo},
  journal      = {Macromolecular Rapid Communications},
  title        = {Constructing the Phase Diagram of an Aqueous Solution of Poly(N-isopropyl acrylamide) by Controlled Microevaporation in a Nanoliter Microchamber},
  year         = {2008},
  number       = {16},
  pages        = {1363--1367},
  volume       = {29},
  abstract     = {This paper describes a poly(dimethylsiloxane) (PDMS)-based microfluidic platform for constructing the phase diagram of poly(N-isopropyl acrylamide) (PNIPAM) in aqueous solution. The PNIPAM solution was delivered into a nanoliter chamber through the main microchannel. An osmotic pressure difference was established between the chamber and the control microchannel by flowing a high-concentration salt solution in the control microchannel. Controlled evaporation of water resulted in increasing concentration of PNIPAM. A phase diagram of PNIPAM was built by measuring the cloud points at different concentrations, with a minimum point at ≈40 wt.-\%. The microfluidic platform has the advantages of low sample consumption and rapid heat exchange rates, and allows studying viscous polymer solution.},
  comment      = {chamber size small enought to possibly impose confinement effects. Can salt diffuse from the control channel into the main chamber?},
  creationdate = {2024-04-22T11:14:51},
  doi          = {https://doi.org/10.1002/marc.200800229},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/marc.200800229},
  file         = {:Zhou2008a - Constructing the Phase Diagram of an Aqueous Solution of Poly(N Isopropyl Acrylamide) by Controlled Microevaporation in a Nanoliter Microchamber.pdf:PDF},
  keywords     = {microfluidics, osmotic pressure, phase diagram, polysiloxanes, water-soluble polymers},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/marc.200800229},
}

@Article{Gill1993,
  author       = {P. S. Gill and S. R. Sauerbrunn and M. Reading},
  journal      = {Journal of Thermal Analysis},
  title        = {Modulated differential scanning calorimetry},
  year         = {1993},
  month        = sep,
  pages        = {931--939},
  volume       = {40},
  creationdate = {2024-04-22T11:25:37},
  doi          = {https://doi.org/10.1007/BF02546852},
  file         = {:Gill1993 - Modulated Differential Scanning Calorimetry.pdf:PDF},
  keywords     = {temperature-modulated dsc},
  url          = {https://doi.org/10.1007/BF02546852},
}

@Article{Boller1995,
  author       = {Andreas Boller and Christoph Schick and Bernhard Wunderlich},
  journal      = {Thermochimica Acta},
  title        = {Modulated differential scanning calorimetry in the glass transition region},
  year         = {1995},
  issn         = {0040-6031},
  note         = {Transition Phenomena in Condensed Matter},
  pages        = {97--111},
  volume       = {266},
  abstract     = {Modulated differential scanning calorimetry (MDSC) presents two time scales to the measurement of the glass transition, a fast one, fixed by the modulation time period, and a slow one, fixed by the average, underlying heating or cooling rate. The same situation arises in dynamic mechanical and dielectric measurements. The various time effects on the glass transition are discussed and documented with experiments on the reference material polystyrene. It will be shown that MDSC can measure the glass transition temperature largely independent of the thermal history (and the heating or cooling rates), but dependent on the modulation frequency. This distinguishes MDSC from standard calorimetry that can measure accurate data on the glass transition only on cooling, a mode of operation often neither convenient nor very precise.},
  creationdate = {2024-04-22T11:28:01},
  doi          = {https://doi.org/10.1016/0040-6031(95)02552-9},
  file         = {:Boller1995 - Modulated Differential Scanning Calorimetry in the Glass Transition Region.pdf:PDF},
  keywords     = {Ageing, Dynamic mechanical analysis, Glass transition, Hysteresis, MDSC, Modulated calorimetry, temperature-modulated DSC, Polystyrene, PS, Quasi-isothermal measurement},
  url          = {https://www.sciencedirect.com/science/article/pii/0040603195025529},
}

@Article{Mueller2013,
  author       = {U. Müller and M. Philipp and M. Thomassey and R. Sanctuary and J.K. Krüger},
  journal      = {Thermochimica Acta},
  title        = {Temperature modulated optical refractometry: A quasi-isothermal method to determine the dynamic volume expansion coefficient},
  year         = {2013},
  issn         = {0040-6031},
  pages        = {17--22},
  volume       = {555},
  abstract     = {The volume expansion coefficient is a thermodynamic key parameter yielding insight into molecular cohesion and organization of condensed matter. We present here the novel experimental technique temperature modulated optical refractometry (TMOR) to determine not only the static but also the dynamic volume expansion coefficient of transparent condensed matter of cubic or isotropic symmetry. A specialty of TMOR is its capability to measure the volume expansion coefficient under quasi-isothermal conditions. In this experimental mode TMOR is able to differentiate between static, dynamic and kinetic contributions to the volume expansion coefficient. Due to these features TMOR especially qualifies for the investigation of structural changes provoked by structural phase transitions, glass transitions and other structure-related transformations in transparent condensed matter. The scientific potential of this novel experimental technique is demonstrated by evidencing anomalies of the complex volume expansion coefficient accompanying the chemically induced glass transition occurring during the formation of a covalently cross-linked epoxy network.},
  creationdate = {2024-04-22T11:33:48},
  doi          = {https://doi.org/10.1016/j.tca.2012.12.011},
  file         = {:Mueller2013 - Temperature Modulated Optical Refractometry_ a Quasi Isothermal Method to Determine the Dynamic Volume Expansion Coefficient.pdf:PDF},
  keywords     = {Refractive index, Thermal expansion, Temperature modulation, Epoxy, Heat capacity, temperature-modulated optical refractometry, TMOR},
  url          = {https://www.sciencedirect.com/science/article/pii/S004060311200593X},
}

@Article{Philipp2014a,
  author       = {Philipp, Martine and Aleksandrova, Ralitsa and Müller, Ulrich and Ostermeyer, Martin and Sanctuary, Roland and Müller-Buschbaum, Peter and Krüger, Jan K.},
  journal      = {Soft Matter},
  title        = {Molecular versus macroscopic perspective on the demixing transition of aqueous PNIPAM solutions by studying the dual character of the refractive index},
  year         = {2014},
  pages        = {7297--7305},
  volume       = {10},
  abstract     = {The phase separation of aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions is known to strongly affect their volume expansion behaviour and the elastic moduli{,} as the latter are strongly coupled to the macroscopic order parameter. On the molecular scale{,} considerable changes in H-bonding and hydrophobic interactions{,} as well as in the structure govern the demixing process. However{,} the relationship between the molecular and macroscopic order parameters is unclear for such complex phase-separating solutions. We contribute to the clarification of this problem by relating optical to volumetric properties across the demixing transition of dilute to concentrated aqueous PNIPAM solutions. Far from the demixing temperature{,} the temperature dependence of the refractive index is predominantly determined by thermal expansion. In the course of phase separation{,} the refractive index is dominated by the anomalous behaviour of the specific refractivity{,} which reflects the spatio-temporally averaged changes in molecular interactions and the structural reorganization of the demixing solutions. Moreover{,} the presence of relaxation processes is studied by the complex expansion coefficient using the novel technique of temperature modulated optical refractometry.},
  creationdate = {2024-04-22T11:35:35},
  doi          = {10.1039/C4SM01222D},
  file         = {:Philipp2014a - Molecular Versus Macroscopic Perspective on the Demixing Transition of Aqueous PNIPAM Solutions by Studying the Dual Character of the Refractive Index.pdf:PDF},
  issue        = {37},
  keywords     = {temperature-modulated optical refractometry, TMOR, pNIPAM},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C4SM01222D},
}

@Article{Nagase2009,
  author       = {Nagase, Kenichi and Kobayashi, Jun and Okano, Teruo},
  journal      = {Journal of The Royal Society Interface},
  title        = {Temperature-responsive intelligent interfaces for biomolecular separation and cell sheet engineering},
  year         = {2009},
  number       = {suppl\_3},
  pages        = {S293--S309},
  volume       = {6},
  abstract     = {Temperature-responsive intelligent surfaces, prepared by the modification of an interface with poly(N-isopropylacrylamide) and its derivatives, have been used for biomedical applications. Such surfaces exhibit temperature-responsive hydrophilic/hydrophobic alterations with external temperature changes, which, in turn, result in thermally modulated interactions with biomolecules and cells. In this review, we focus on the application of these intelligent surfaces to chromatographic separation and cell cultures. Chromatographic separations using several types of intelligent surfaces are mentioned briefly, and various effects related to the separation of bioactive compounds are discussed, including wettability, copolymer composition and graft polymer architecture. Similarly, we also summarize temperature-responsive cell culture substrates that allow the recovery of confluent cell monolayers as contiguous living cell sheets for tissue-engineering applications. The key factors in temperature-dependent cell adhesion/detachment control are discussed from the viewpoint of grafting temperature-responsive polymers, and new methodologies for effective cell sheet culturing and the construction of thick tissues are summarized.},
  creationdate = {2024-04-22T14:57:16},
  doi          = {10.1098/rsif.2008.0499.focus},
  eprint       = {https://royalsocietypublishing.org/doi/pdf/10.1098/rsif.2008.0499.focus},
  file         = {:Nagase2009 - Temperature Responsive Intelligent Interfaces for Biomolecular Separation and Cell Sheet Engineering.pdf:PDF},
  keywords     = {pNIPAM, review, pNIPAM-alternatives, application-focused, application focused},
  url          = {https://royalsocietypublishing.org/doi/abs/10.1098/rsif.2008.0499.focus},
}

@Article{Wei2009,
  author       = {Hua Wei and Si-Xue Cheng and Xian-Zheng Zhang and Ren-Xi Zhuo},
  journal      = {Progress in Polymer Science},
  title        = {Thermo-sensitive polymeric micelles based on poly(N-isopropylacrylamide) as drug carriers},
  year         = {2009},
  issn         = {0079-6700},
  number       = {9},
  pages        = {893--910},
  volume       = {34},
  abstract     = {Amphiphilic copolymers are well developed as precursors for the preparation of micellar drug carriers. Poly(N-isopropylacrylamide) (PNIPAAm) is one of the most extensively studied thermo-sensitive polymers that exhibits a lower critical solution temperature (LCST) at around 33°C in aqueous solution. Over the past decade, considerable efforts have been devoted to design and preparation of PNIPAAm-based thermo-sensitive polymeric micelles as delivery vehicles for controlled drug release. Present review highlights the recent developments in this field, and focuses on two categories of PNIPAAm-based copolymer micelles as smart drug delivery systems, i.e. micelles with PNIPAAm as hydrophilic shell-forming segments below the LCST and micelles with PNIPAAm as hydrophobic core-forming segments above the LCST.},
  creationdate = {2024-04-22T14:59:28},
  doi          = {https://doi.org/10.1016/j.progpolymsci.2009.05.002},
  file         = {:Wei2009 - Thermo Sensitive Polymeric Micelles Based on Poly(N Isopropylacrylamide) As Drug Carriers.pdf:PDF},
  keywords     = {Thermo-sensitive, thermoresponsive, Micelle, Poly(-isopropylacrylamide), pNIPAM, Self-assembly, Drug delivery, review, core-shell, application-focused, application focused},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079670009000525},
}

@Article{Dai2009,
  author       = {Dai, Sheng and Ravi, Palaniswamy and Tam, Kam Chiu},
  journal      = {Soft Matter},
  title        = {Thermo- and photo-responsive polymeric systems},
  year         = {2009},
  pages        = {2513--2533},
  volume       = {5},
  abstract     = {Since the first reported thermal phase transition of poly(N-isopropylacrylamide) by Heskin in 1968{,} this unique polymer has continued to gain popularity. Because of their potential applications in the field of biomedical science{,} various responsive polymeric systems{,} such as those induced by pH{,} salt{,} co-solvent{,} thermal{,} light{,} electric and magnetic field{,} have been synthesized and studied. This review reports on recent developments (over the last 10 years) of thermo- and photo-responsive homopolymers{,} copolymers{,} microgels{,} hydrogels and polymer brushes at interfaces{,} where the synthesis{,} physicochemical properties{,} and potential applications are highlighted. Although homopolymers and microgels undergo phase transitions upon the application of external stimuli{,} block copolymers{,} however{,} self-assemble into different nanostructures. Such reversible phase transitions and self-assembly behaviors have generated many robust structures that can be applied in coating industries{,} personal/home care{,} petroleum{,} drug/protein/DNA delivery and separation processes.},
  creationdate = {2024-04-22T15:02:20},
  doi          = {10.1039/B820044K},
  file         = {:Dai2009 - Thermo and Photo Responsive Polymeric Systems.pdf:PDF},
  issue        = {13},
  keywords     = {pNIPAM, pNIPAM-alternatives, review, stimuli-responsive, application-focused, application focused},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/B820044K},
}

@Article{Schwall2009,
  author       = {Schwall, Christine T. and Banerjee, Ipsita A.},
  journal      = {Materials},
  title        = {Micro- and Nanoscale Hydrogel Systems for Drug Delivery and Tissue Engineering},
  year         = {2009},
  issn         = {1996-1944},
  number       = {2},
  pages        = {577--612},
  volume       = {2},
  abstract     = {The pursuit for targeted drug delivery systems has led to the development of highly improved biomaterials with enhanced biocompatibility and biodegradability properties. Micro- and nanoscale components of hydrogels prepared from both natural and artificial components have been gaining significant importance due to their potential uses in cell based therapies, tissue engineering, liquid micro-lenses, cancer therapy, and drug delivery. In this review some of the recent methodologies used in the preparation of a number of synthetic hydrogels such as poly(N-isopropylacrylamide) (pNIPAm), poly(ethylene glycol) (PEG), poly(ethylene oxide) (PEO), polyvinyl alcohol methylacrylate co-polymers (PVA-MA) and polylactic acid (PLA), as well as some of the natural hydrogels and their applications have been discussed in detail.},
  creationdate = {2024-04-22T15:04:16},
  doi          = {10.3390/ma2020577},
  file         = {:Schwall2009 - Micro and Nanoscale Hydrogel Systems for Drug Delivery and Tissue Engineering.pdf:PDF},
  keywords     = {review, drug delivery, tissue engineering, pNIPAM, pNIPAM-alternatives, PEG, PEO, PVA, PMA, polylactic acid, PLA, hydrogel, application-focused, application focused, PEG|PEO},
  url          = {https://www.mdpi.com/1996-1944/2/2/577},
}

@InBook{Welsch2011,
  author       = {Welsch, Nicole and Ballauff, Matthias and Lu, Yan},
  editor       = {Pich, Andrij and Richtering, Walter},
  pages        = {129--163},
  publisher    = {Springer Berlin Heidelberg},
  title        = {Microgels as Nanoreactors: Applications in Catalysis},
  year         = {2011},
  address      = {Berlin, Heidelberg},
  isbn         = {978-3-642-16379-1},
  abstract     = {We review recent work on the use of ``smart'' microgel particles as ``nanoreactors'' for the immobilization of metal nanoparticles as well as enzymes. A general feature of the microgel systems under consideration is their ability to react to external stimuli such as the pH or temperature of the system. Special emphasis is given to our recent research work on thermosensitive core--shell microgel particles composed of a polystyrene core and a crosslinked poly(N-isopropylacrylamide) shell. Work done on these core--shell systems is compared to developments in the investigation of similar systems. Recently, it has been shown that these core--shell microgels can be used as ``nanoreactors'' for the immobilization of metal nanoparticles. The metal nanocomposite particles exhibit a ``smart'' catalytic behavior inasmuch as the catalytic activity of nanoparticles can be modulated through the volume transition that takes place within the thermosensitive shell of the carrier system. Moreover, microgel particles can work as efficient carrier systems for the immobilization of enzymes. The dependence of the enzymatic activity on temperature can also be manipulated by the temperature-dependent swelling behavior of the microgel. Thus, the microgel particles present an excellent ``active'' carrier system for applications in catalysis.},
  booktitle    = {Chemical Design of Responsive Microgels},
  comment      = {paywall},
  creationdate = {2024-04-22T15:07:29},
  doi          = {10.1007/12_2010_71},
  keywords     = {pNIPAM, microgel, catalysis, review, stimuli-responsive, application-focused, application focused},
  url          = {https://doi.org/10.1007/12_2010_71},
}

@Article{Guan2011,
  author       = {Guan, Ying and Zhang, Yongjun},
  journal      = {Soft Matter},
  title        = {PNIPAM microgels for biomedical applications: from dispersed particles to 3D assemblies},
  year         = {2011},
  pages        = {6375--6384},
  volume       = {7},
  abstract     = {Poly(N-isopropylacrylamide) (PNIPAM) microgel is perhaps the most well-known intelligent soft nanomaterial. Combining the strengths of hydrogel and nanoparticles{,} with unique stimuli-responsivity{,} PNIPAM microgels have found numerous biomedical applications{,} such as drug delivery{,} biosensing{,} and so on. Usually they were used as dispersed particles{,} however{,} they can also be used as building blocks to fabricate 2D films and 3D aggregates. These nanostructured assemblies exhibit new properties which the dispersed particles do not have{,} and new biomedical applications have been found for these assemblies. In this paper{,} the biomedical applications of PNIPAM microgels in the form of dispersed particles{,} 2D films and 3D aggregates were reviewed and some recent progress in this area was highlighted.},
  creationdate = {2024-04-22T15:09:20},
  doi          = {10.1039/C0SM01541E},
  file         = {:Guan2011 - PNIPAM Microgels for Biomedical Applications_ from Dispersed Particles to 3D Assemblies.pdf:PDF},
  issue        = {14},
  keywords     = {pNIPAM, review, application-focused, application focused},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C0SM01541E},
}

@Article{Talelli2011,
  author       = {Talelli, Marina and Hennink, Wim E},
  journal      = {Nanomedicine},
  title        = {Thermosensitive polymeric micelles for targeted drug delivery},
  year         = {2011},
  note         = {PMID: 21929459},
  number       = {7},
  pages        = {1245--1255},
  volume       = {6},
  abstract     = {Thermosensitive polymers are characterized by temperature-dependent aqueous solution properties. Below their lower critical solution temperature they are in an expanded state and fully dissolved, while above it they are dehydrated and insoluble. This has been exploited for the development of polymeric micelles that can be formed or destabilized depending on the solution temperature. Many micelle forming thermosensitive polymers have been described in literature, among which poly(N-isopropylacrylamide) (pNIPAAm), Pluronics (triblock copolymers of polypropylene oxide middle block flanked by two polyethylene oxide blocks) and poly(hydroxypropyl methacrylamide-lactate) (p(HPMAm-Lacn)) are the most frequently studied and some drug-loaded formulations based on thermosensitive polymers have reached clinical trials. The first generation of micelles composed of thermosensitive polymers was based on mere hydrophobic interactions between polymer blocks, while more recently shell or core crosslinking was introduced, in order to improve their stability in the circulation after intravenous administration and therefore, the accumulation of their depot in diseased areas. Various formulations of drug-loaded micelles based on thermosensitive polymers have shown promising results in vitro, as well as in vivo. This review gives an overview of the most important recent developments regarding the design and synthesis of various types of thermosensitve polymers for drug delivery.},
  comment      = {paywall},
  creationdate = {2024-04-22T15:11:37},
  doi          = {10.2217/nnm.11.91},
  eprint       = {https://doi.org/10.2217/nnm.11.91},
  keywords     = {pNIPAM, review, drug delivery, application-focused, application focused},
  url          = {https://doi.org/10.2217/nnm.11.91},
}

@Article{Ramos2012,
  author       = {Ramos, Jose and Imaz, Ainara and Forcada, Jacqueline},
  journal      = {Polym. Chem.},
  title        = {Temperature-sensitive nanogels: poly(N-vinylcaprolactam) versus poly(N-isopropylacrylamide)},
  year         = {2012},
  pages        = {852--856},
  volume       = {3},
  abstract     = {Poly(N-isopropylacrylamide) (PNIPAM) and poly(N-vinylcaprolactam) (PVCL) are temperature-responsive polymers which show a lower critical solution temperature (LCST) around 32 °C in aqueous solutions. Nanogels based on these temperature sensitive polymers swell at low temperatures and collapse at high ones{,} showing a volume phase transition temperature (VPTT) near physiological temperature. This unique behavior makes these nanogels attractive for biotechnological applications. PNIPAM is the building block of a huge amount of nanogels reported in the literature. However{,} PVCL is especially interesting due to the fact that it is very stable against hydrolysis and biocompatible. In this mini-review{,} various synthesis procedures together with the functionalization of different PNIPAM- and PVCL-based nanogels are revised and compared.},
  creationdate = {2024-04-22T15:13:39},
  doi          = {10.1039/C2PY00485B},
  file         = {:Ramos2012 - Temperature Sensitive Nanogels_ Poly(N Vinylcaprolactam) Versus Poly(N Isopropylacrylamide).pdf:PDF},
  issue        = {4},
  keywords     = {pNIPAM, pNIPAM-alternatives, PVCL, review, microgel},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C2PY00485B},
}

@Article{Gong2013,
  author       = {Gong, C. and Qi, T. and Wei, X. and Qu, Y. and Wu, Q. and Luo, F. and Qian, Z.},
  journal      = {Current Medicinal Chemistry},
  title        = {Thermosensitive Polymeric Hydrogels As Drug Delivery Systems},
  year         = {2013},
  issn         = {0929-8673},
  number       = {1},
  pages        = {79--94},
  volume       = {20},
  abstract     = {Thermosensitive hydrogels are very important biomaterials used in drug delivery systems (DDSs), which gained increasing attention of researchers. Thermosensitive hydrogels have great potential in various applications, such as drug delivery, cell encapsulation, tissue engineering, and etc. Especially, injectable thermosensitive hydrogels with lower sol-gel transition temperature around physiological temperature have been extensively studied. By in vivo injection, the hydrogels formed non-flowing gel at body temperature. Upon incorporation of pharmaceutical agents, the hydrogel systems could act as sustained drug release depot in situ. Injectable thermosensitive hydrogel systems have a number of advantages, including simplicity of drug formulation, protective environment for drugs, prolonged and localized drug delivery, and ease of application. The objective of this review is to summarize fundamentals, applications, and recent advances of injectable thermosensitive hydrogel as DDSs, including chitosan and related derivatives, poly(N-isopropylacrylamide)-based (PNIPAAM) copolymers, poly(ethylene oxide)/poly(propylene oxide) (PEO/PPO) copolymers and its derivatives, and poly(ethylene glycol)/ biodegradable polyester copolymers.},
  comment      = {paywall},
  creationdate = {2024-04-22T15:25:41},
  keywords     = {hydrogel, N-Isopropylacrylamide, pNIPAM, PLA, PHB, controlled release, phase transition, PCLA, PLGA, PEG, thermosensitive, drug delivery, PCL, chitosan, pluronic, Injectable, review, application-focused, application focused},
  url          = {https://www.ingentaconnect.com/content/ben/cmc/2013/00000020/00000001/art00009},
}

@Article{Hocine2013,
  author       = {Hocine, Sabrina and Li, Min-Hui},
  journal      = {Soft Matter},
  title        = {Thermoresponsive self-assembled polymer colloids in water},
  year         = {2013},
  pages        = {5839--5861},
  volume       = {9},
  abstract     = {Thermoresponsive polymer colloids made of amphiphilic block copolymers are reviewed in this paper. The main families of thermoresponsive polymers{,} including hydrophilic polymers with LCST (PEG{,} PNIPAM{,} poly(oxazoline)s and elastin-like polypeptides{,} etc.) and hydrophobic polymers with thermotropic phase transitions (liquid crystalline and crystalline polymers){,} are first described with the details of the underlying physical chemical principles. Polymer colloids with thermoresponsive polymers as the hydrophobic core{,} hydrophilic corona or both of them depending on temperature (schizophrenic systems) are discussed and their potential bio-related applications highlighted. We also take notice of the particular thermoresponsive properties of PEG in the polymer colloids. Hydrophilic PEG has its water solubility and degree of hydration decreased with increasing temperature in the range far below its LCST (∼100 °C). These properties can result in significant or even drastic morphological changes in colloids{,} which should be taken into account when designing thermoresponsive polymer colloids using the PEG corona.},
  creationdate = {2024-04-22T15:29:04},
  doi          = {10.1039/C3SM50428J},
  file         = {:Hocine2013 - Thermoresponsive Self Assembled Polymer Colloids in Water.pdf:PDF},
  issue        = {25},
  keywords     = {pNIPAM, pNIPAM-alternatives, PEG, review, application-focused, application focused},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C3SM50428J},
}

@Book{Papon2002,
  author       = {Pierre Papon and Jacques Leblond and Paul H. E. Meijer},
  publisher    = {Springer Berlin Heidelberg},
  title        = {The Physics of Phase Transitions, Concepts and Applications},
  year         = {2002},
  edition      = {1},
  series       = {Physics and Astronomy},
  comment      = {not about linear polymers in solution},
  creationdate = {2024-04-22T15:36:40},
  file         = {:Papon2002 - The Physics of Phase Transitions, Concepts and Applications.pdf:PDF},
  keywords     = {book, critical fluctuations, phase transitions, nucleation},
}

@Article{Debenedetti1997,
  author       = {Debenedetti, Pablo G},
  title        = {Metastable liquids: concepts and principles},
  year         = {1997},
  comment      = {paywall. looks more like glass transitions than polymer solutions},
  creationdate = {2024-04-22T15:44:05},
  publisher    = {Princeton university press},
}

@Article{Zhu1997,
  author       = {Zhu, Peng Wei and Napper, Donald H.},
  journal      = {The Journal of Chemical Physics},
  title        = {{The longer time collapse kinetics of interfacial poly(N-isopropylacrylamide) in water}},
  year         = {1997},
  issn         = {0021-9606},
  month        = apr,
  number       = {15},
  pages        = {6492--6498},
  volume       = {106},
  abstract     = {{The kinetics of the later stages of the temperature induced collapse transition of swollen poly(N-isopropylacrylamide) (PNIPAM) chains at interfaces in the presence of the surfactant sodium dodecyl sulfate were studied using dynamic light scattering (DLS). The longer time collapse processes were interpreted in terms of the “globule growth” model of Kuznetsov, Timoshenko, and Dawson (KTD) [J. Chem. Phys. 103, 4807 (1995)]. The relaxation times of the collapse transition were determined from the longer time kinetics and were found to decrease with increasing quench temperature above the θ temperature.}},
  creationdate = {2024-04-22T15:47:54},
  doi          = {10.1063/1.474098},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/106/15/6492/19166314/6492\_1\_online.pdf},
  file         = {:Zhu1997 - The Longer Time Collapse Kinetics of Interfacial Poly(N Isopropylacrylamide) in Water.pdf:PDF},
  keywords     = {pNIPAM, kinetics, SDS, interface, mesoglobule},
  url          = {https://doi.org/10.1063/1.474098},
}

@Article{Zhu1997a,
  author       = {Zhu, Peng Wei and Napper, Donald H.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Conformational Transitions of Poly(N-isopropylacrylamide) Chains Loopily Absorbed at the Surfaces of Poly(N-tert-butylacrylamide) Latex Particles in Water},
  year         = {1997},
  number       = {16},
  pages        = {3155--3160},
  volume       = {101},
  abstract     = {Results are presented for a light-scattering study of the conformational transitions and corresponding dynamics of poly(N-isopropylacrylamide) (PNIPAM) chains absorbed from water onto the surfaces of poly(N-tert-butylacrylamide) (PNTBA) latex particles. Similarities between the structures of PNIPAM and PNTBA meant that the PNIPAM chains were strongly adsorbed at the PNTBA surfaces. As the temperature was increased to the Î¸-temperature and above, the loopily adsorbed-to-globule conformational transition was observed. This was followed on cooling by the observation of an unexpected transition, the globule-to-extended chain conformation, that occurred under better than Î¸-solvency conditions. The latter transition was explained as resulting from a reduction in the number of contacts between the polymer chains and the latex particle surfaces as the globular conformation was adopted. An additional finding was that these extended conformations were unstable and subsequently relaxed toward the original loopily adsorbed conformation. The relaxation process for the extended-to-loopily adsorbed conformational transition was found to occur slowly and to depend on the temperature. It is proposed that kinetic constraints played an important role in this transition. The transition kinetics were analyzed with the aid of a stretched exponential function. The relaxation time thus calculated was found to increase with increasing temperature and obeyed an Arrhenius law over the temperature range studied. The apparent activation energy of the extended-to-loopily adsorbed conformational transition was estimated to be âˆ¼80 kJ mol-1.},
  creationdate = {2024-04-22T15:51:41},
  doi          = {10.1021/jp963424h},
  eprint       = {https://doi.org/10.1021/jp963424h},
  file         = {:Zhu1997a - Conformational Transitions of Poly(N Isopropylacrylamide) Chains Loopily Absorbed at the Surfaces of Poly(N Tert Butylacrylamide) Latex Particles in Water.pdf:PDF},
  keywords     = {pNIPAM, kinetics, pNTBA, latex particles},
  url          = {https://doi.org/10.1021/jp963424h},
}

@Article{Zhu2000,
  author       = {Zhu, Peng Wei and Napper, Donald H.},
  journal      = {Phys. Rev. E},
  title        = {Longer time kinetics of collapse transition of polymer-surfactant complexes at interfaces near to collapse temperatures},
  year         = {2000},
  month        = jun,
  pages        = {6866--6871},
  volume       = {61},
  abstract     = {The later stages of the collapse transition kinetics of fractionated poly(N-isopropylacrylamide) (PNIPAM) chains at interfaces in the presence of the surfactant sodium dodecyl sulfate (SDS) were studied for molecular weights ranging from $4.5\cdot10^{5}$ to $1.6\cdot10^{6}$. The interfacial PNIPAM-SDS complexes were quickly heated to the temperatures that were near to the collapse transition temperatures. The longer time collapse of the PNIPAM-SDS complexes at interfaces was found to proceed through two stages. The collapse kinetics at the later stages was interpreted in terms of a “globule growth” model. It was found that under the experimental conditions, the fast relaxation time was independent of the molecular weight, whereas the slow relaxation time was weakly dependent on the molecular weight.},
  creationdate = {2024-04-22T15:53:38},
  doi          = {10.1103/PhysRevE.61.6866},
  file         = {:Zhu2000 - Longer Time Kinetics of Collapse Transition of Polymer Surfactant Complexes at Interfaces near to Collapse Temperatures.pdf:PDF},
  issue        = {6},
  keywords     = {pNIPAM, kinetics, SDS, interface},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevE.61.6866},
}

@Article{Liu2005b,
  author       = {Liu, Guangming and Cheng, He and Yan, Lifeng and Zhang, Guangzhao},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Study of the Kinetics of the Pancake-to-Brush Transition of Poly(N-isopropylacrylamide) Chains},
  year         = {2005},
  note         = {PMID: 16853942},
  number       = {47},
  pages        = {22603--22607},
  volume       = {109},
  abstract     = {The chemical grafting of thiol-terminated poly(N-isopropylacrylamide) (HS-PNIPAM) chains to a gold surface from a solution was investigated with a quartz crystal microbalance (QCM) in real time. The frequency and energy dissipation responses revealed that short HS-PNIPAM chains exhibit three-regime kinetics of the grafting. In regimes I and II, the HS-PNIPAM chains form pancake and mushroom structures, respectively. In regime III, the chains form brushes. From regime II to regime III, the mushroom-to-brush transition occurs. For the longer HS-PNIPAM chains, because of the strong segment−surface interaction, the segments cannot desorb from the surface, and the chains do not undergo a pancake-to-brush transition.},
  creationdate = {2024-04-22T15:57:02},
  doi          = {10.1021/jp0538417},
  eprint       = {https://doi.org/10.1021/jp0538417},
  file         = {:Liu2005b - Study of the Kinetics of the Pancake to Brush Transition of Poly(N Isopropylacrylamide) Chains.pdf:PDF},
  keywords     = {pNIPAM, kinetics, brush, qcmb, pancake, mushroom},
  url          = {https://doi.org/10.1021/jp0538417},
}

@Article{Hu2010,
  author       = {Hu, Jinming and Wang, Di and Xu, Jian and Zhu, Zhiyuan and Liu, Shiyong},
  journal      = {Macromolecular Chemistry and Physics},
  title        = {Contraction and Collapsing Kinetics of Single Synthetic Polymer Chains at Small Quench Depths},
  year         = {2010},
  number       = {24},
  pages        = {2573--2584},
  volume       = {211},
  abstract     = {Chain contraction and collapsing kinetics of pyrene-labeled poly(N-isopropylacrylamide) (PNIPAM) single chains (\$\overline {M} \_{{\rm n}} \$ = 3.64 × 105 g · mol−1, \$\overline {M} \_{{\rm w}} /\overline {M} \_{{\rm n}} \$ = 1.17) were investigated by employing the stopped-flow technique coupled with fluorescence and light scattering detections, which can achieve millisecond jumping of solvent quality from good to above and below the θ-solvent condition at small quench depths. It was found that the coil-to-crumpled globule transition proceeds via an isotropic one stage process and the obtained characteristic relaxation times exhibit a monotonic decrease with increasing quench depths. The obtained experimental results were in qualitative agreement with previous theoretical considerations.},
  creationdate = {2024-04-22T16:06:41},
  doi          = {https://doi.org/10.1002/macp.201000476},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/macp.201000476},
  file         = {:Hu2010 - Contraction and Collapsing Kinetics of Single Synthetic Polymer Chains at Small Quench Depths.pdf:PDF},
  keywords     = {chain, fluorescence, light scattering, mixing, phase behavior, pNIPAM, pyrene, fluorescence, stopped-flow, microfluidics, light scattering, kinetics},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/macp.201000476},
}

@Article{Vyazovkin2006,
  author       = {Vyazovkin, Sergey and Sbirrazzuoli, Nicolas},
  journal      = {Macromolecular Rapid Communications},
  title        = {Isoconversional Kinetic Analysis of Thermally Stimulated Processes in Polymers},
  year         = {2006},
  number       = {18},
  pages        = {1515--1532},
  volume       = {27},
  abstract     = {Isoconversional kinetic analysis involves evaluating a dependence of the effective activation energy on conversion or temperature and using this dependence for making kinetic predictions and for exploring the mechanisms of thermally stimulated processes. The paper discusses major results obtained by the authors in the area of the isoconversional analysis of polymer kinetics over the past decade. It provides a brief introduction to isoconversional methods and surveys the impact made by isoconversional analysis in several application areas that include kinetic predictions, thermal degradation, crosslinking (curing), glass transition, and glass and melt crystallization. It is concluded that isoconversional analysis has been used broadly and fruitfully because it presents a fortunate compromise between the single-step Arrhenius kinetic treatments and the prevalent occurrence of processes whose kinetics are multi-step and/or non-Arrhenius. An isoconversional method applies the Arrhenius equation to a narrow temperature region, ΔT related to a given extent of conversion.},
  creationdate = {2024-04-22T16:11:30},
  doi          = {https://doi.org/10.1002/marc.200600404},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/marc.200600404},
  file         = {:Vyazovkin2006 - Isoconversional Kinetic Analysis of Thermally Stimulated Processes in Polymers.pdf:PDF},
  keywords     = {crystallization, curing of polymers, degradation, glass transition, kinetics, isoconversional kinetic analysis, kinetics, theory, activation energy, cross-links},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/marc.200600404},
}

@InCollection{Vyazovkin2018,
  author       = {Sergey Vyazovkin},
  booktitle    = {Recent Advances, Techniques and Applications},
  publisher    = {Elsevier Science B.V.},
  title        = {Chapter 4 - Modern Isoconversional Kinetics: From Misconceptions to Advances},
  year         = {2018},
  editor       = {Sergey Vyazovkin and Nobuyoshi Koga and Christoph Schick},
  pages        = {131--172},
  series       = {Handbook of Thermal Analysis and Calorimetry},
  volume       = {6},
  abstract     = {This chapter overviews the status of modern isoconversional kinetics, focusing on common misconceptions and recent advances in the field. The misconceptions discussed are associated with estimating the preexponential factor and reaction model, single-step approximation, meaning of isoconversional activation energy, and the application of isoconversional methods to the processes taking place on cooling. The advances covered include the development of the methodology as well as its expansion to new application areas such as polymer melting, solid-solid transition, solution crystallization, thermal decomposition during cooling, glass aging, gelation and gel melting, and denaturation of proteins. An essential advance in the methodology is related to the quantitative interpretation of variations in the isoconversional activation energy by linking its value to the kinetic parameters of individual single steps. This approach is advocated as a way of obtaining important insights into the kinetics of various thermally stimulated processes.},
  creationdate = {2024-04-22T16:19:40},
  doi          = {https://doi.org/10.1016/B978-0-444-64062-8.00008-5},
  file         = {:Vyazovkin2018 - Chapter 4 Modern Isoconversional Kinetics_ from Misconceptions to Advances.pdf:PDF},
  issn         = {1573-4374},
  keywords     = {book, Thermal analysis, isoconversional kinetics, Thermogravimetry (TGA), Calorimetry (DSC), Model-free kinetics, Nano- and biomaterials},
  url          = {https://www.sciencedirect.com/science/article/pii/B9780444640628000085},
}

@Article{Fussell2023,
  author       = {Fussell, S. L. and Royall, C. P. and van Duijneveldt, J. S.},
  journal      = {Langmuir},
  title        = {Controlling Kinetic Pathways in Demixing Microgel–Micelle Mixtures},
  year         = {2023},
  note         = {PMID: 36621908},
  number       = {3},
  pages        = {1010--1018},
  volume       = {39},
  abstract     = {We investigate the temperature-dependent phase behavior of mixtures of poly(N-isopropylacrylamide) (pNIPAM) microgel colloids and a triblock copolymer (PEO–PPO–PEO) surfactant. Usually, gelation in these systems results from an increase in temperature. Here we investigate the role of the heating rate, and surprisingly, we find that this causes the mechanism of aggregation to change from one which is driven by depletion of the microgels by the micelles at low temperatures to the association of the two species at high temperatures. We thus reveal two competing mechanisms for attractions between the microgel particles which can be controlled by changing the heating rate. We use this heating-rate-dependent response of the system to access multiple structures for the same system composition. Samples were found to demix into phases rich and poor in microgel particles at temperatures below 33 °C, under conditions where the microgels particles are partially swollen. Under rapid heating full demixing is bypassed, and gel networks are formed instead. The temperature history of the sample, therefore, allows for kinetic selection between different final structures, which may be metastable.},
  creationdate = {2024-04-23T16:06:40},
  doi          = {10.1021/acs.langmuir.2c02583},
  eprint       = {https://doi.org/10.1021/acs.langmuir.2c02583},
  file         = {:Fussell2023 - Controlling Kinetic Pathways in Demixing Microgel–Micelle Mixtures.pdf:PDF;:ControllingKineticPathwaysInDemixingMicrogelMicelleMixtures_FussellEtAl_Langmuir2023_SI4.mp4:mp4;:ControllingKineticPathwaysInDemixingMicrogelMicelleMixtures_FussellEtAl_Langmuir2023_SI3.mp4:mp4;:ControllingKineticPathwaysInDemixingMicrogelMicelleMixtures_FussellEtAl_Langmuir2023_SI2.mp4:mp4;:ControllingKineticPathwaysInDemixingMicrogelMicelleMixtures_FussellEtAl_Langmuir2023_SI5.pdf:PDF;:ControllingKineticPathwaysInDemixingMicrogelMicelleMixtures_FussellEtAl_Langmuir2023_SI1.mp4:mp4},
  keywords     = {pNIPAM, aggregation, kinetics, copolymer, micelles, heating rate, microgel, DLS, microscopy},
  url          = {https://doi.org/10.1021/acs.langmuir.2c02583},
}

@Article{Li2015,
  author       = {Li, Yuyan and Peng, Bo and Chen, Yongming},
  journal      = {Macromolecular Chemistry and Physics},
  title        = {Kinetically Trapped Block Copolymer Nano-Objects with Cylinder to Sphere Shape Transition Properties},
  year         = {2015},
  number       = {5},
  pages        = {495--503},
  volume       = {216},
  abstract     = {Here, the cylinder to sphere transition property is reported in kinetically trapped block copolymer (BCP) nano-objects made from polystyrene-block-poly(N-isopropylacrylamide) (PS-b-PNIPAM) in ethanol. The PS-b-PNIPAM BCPs are found to self-assemble into hexagonally packed cylindrical morphology in bulk. When dispersing the bulk microphase-separated BCP materials in selective solvent, nanocylinders stabilized by kinetically trapped PS cores were obtained. However, when the kinetic barrier is removed by external energy input, a morphology transition from cylinder to sphere occurred. The transition procedure could be accelerated by applying higher external energy, which could be realized by using higher temperatures as well as treating with ultrasonic. Additionally, lowering the kinetic barrier by using polymers with a shorter PS block also accelerates the morphology transition process.},
  creationdate = {2024-04-23T16:19:01},
  doi          = {https://doi.org/10.1002/macp.201400505},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/macp.201400505},
  file         = {:Li2015 - Kinetically Trapped Block Copolymer Nano Objects with Cylinder to Sphere Shape Transition Properties.pdf:PDF},
  keywords     = {block copolymers, kinetics, morphology, phase separation, self-assembly, pNIPAM, ethanol, synthesis, blockcopolymer, PS, TEM, DLS, transmittance, ultrasound},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/macp.201400505},
}

@Article{Vyazovkin2020a,
  author         = {Vyazovkin, Sergey},
  journal        = {Molecules},
  title          = {Kissinger Method in Kinetics of Materials: Things to Beware and Be Aware of},
  year           = {2020},
  issn           = {1420-3049},
  number         = {12},
  volume         = {25},
  abstract       = {The Kissinger method is an overwhelmingly popular way of estimating the activation energy of thermally stimulated processes studied by differential scanning calorimetry (DSC), differential thermal analysis (DTA), and derivative thermogravimetry (DTG). The simplicity of its use is offset considerably by the number of problems that result from underlying assumptions. The assumption of a first-order reaction introduces a certain evaluation error that may become very large when applying temperature programs other than linear heating. The assumption of heating is embedded in the final equation that makes the method inapplicable to any data obtained on cooling. The method yields a single activation energy in agreement with the assumption of single-step kinetics that creates a problem with the majority of applications. This is illustrated by applying the Kissinger method to some chemical reactions, crystallization, glass transition, and melting. In the cases when the isoconversional activation energy varies significantly, the Kissinger plots tend to be almost perfectly linear that means the method fails to detect the inherent complexity of the processes. It is stressed that the Kissinger method is never the best choice when one is looking for insights into the processes kinetics. Comparably simple isoconversional methods offer an insightful alternative.},
  article-number = {2813},
  creationdate   = {2024-04-24T07:41:47},
  doi            = {10.3390/molecules25122813},
  file           = {:Vyazovkin2020a - Kissinger Method in Kinetics of Materials_ Things to Beware and Be Aware of.pdf:PDF},
  keywords       = {DSC, review, kissinger plot, kinetics, activation energy, isoconversional analysis},
  pubmedid       = {32570880},
  url            = {https://www.mdpi.com/1420-3049/25/12/2813},
}

@Article{Wellen2014,
  author       = {Renate M.R. Wellen and Eduardo L. Canedo},
  journal      = {Polymer Testing},
  title        = {On the Kissinger equation and the estimate of activation energies for non-isothermal cold crystallization of PET},
  year         = {2014},
  issn         = {0142-9418},
  pages        = {33--38},
  volume       = {40},
  abstract     = {The activation energy for nonisothermal cold crystallization of polyethylene terephthalate (PET) and its blends with 1% polystyrene (PS) and 1% styrene-acrylonitrile copolymer (SAN) were measured based on differential scanning calorimetry (DSC). The Kissinger method was used to compute the activation energies in all cases, obtaining mean values of 120, 100, and 85 kJ/mole for neat PET, PET/1%PS and PET/1%SAN. A modified Kissinger procedure is proposed to estimate activation energies in polymer systems in which the relative crystallinity - measured at constant heating rates - can be correlated by the Ozawa model with a temperature-independent exponent. Values of the activation energy of 115 and 160 kJ/mole were obtained for cold crystallization of PET in the PET/1%PS and PET/1% SAN blends using the modified Kissinger procedure.},
  creationdate = {2024-04-24T07:44:43},
  doi          = {https://doi.org/10.1016/j.polymertesting.2014.08.008},
  file         = {:Wellen2014 - On the Kissinger Equation and the Estimate of Activation Energies for Non Isothermal Cold Crystallization of PET.pdf:PDF},
  keywords     = {Activation energy, Kissinger method, Nonisothermal cold crystallization, PET, isothermal analysis, dsc, ozawa model},
  url          = {https://www.sciencedirect.com/science/article/pii/S0142941814001822},
}

@Article{Illers1974,
  author       = {K.-H. Illers},
  journal      = {European Polymer Journal},
  title        = {Die ermittlung des schmelzpunktes von kristallinen polymeren mittels wärmeflusskalorimetrie (DSC)},
  year         = {1974},
  issn         = {0014-3057},
  number       = {10},
  pages        = {911--916},
  volume       = {10},
  abstract     = {Zusammenfassung
Kleine und imperfekte Kristalle in partiell-kristallinen Polymeren vergröβern und verbessern sich beim langsamen Erwärmen. Dadurch wird ihr Schmelzpunkt Tm zu höherer Temperatur verschoben. Um Tm der ursprünglich vorhandenen Kristalle zu messen, muβ mit hohen Aufheizgeschwindigkeiten gearbeitet werden. Dies ist bei den modernen, mit sehr kleinen Probemengen arbeitenden Wärmefluβkalorimetern möglich. Infolge der thermischen Trägheit der Meβzelle wird jedoch Tm um ΔT zu höherer Temperatur verfälscht. Aus der Theorie des Wärmefluβkalorimeters ergibt sich, daβkalorimeters ergibt sich, daβ der Fehler ΔT proportional der Quadratwurzel aus Aufheizgeschwindigkeit, Schmelzwärme und Probemasse ist Durch Messungen an scharf schmelzenden niedrigmolekularen Substanzen wurde dieses Quadratwurzelgesetz quantitativ bestätigt. Um den wahren Schmelzpunkt der in Polymeren vorhandenen Kristalle zu messen, muβ man die bei verschiedenen hohen Heizraten und konstanter Probenmasse ermittelten Schmelzpeaks gegen die Quadratwurzel der Heizraten auftragen und linear auf die Heizrate Null extrapolieren. Dieses Verfahren wird auf unterschiedlich kristallisierte Proben aus HDPE, LDPE und Polyamiden angewandt.
Small and imperfect crystals in polymers reorganize during slow heating. This leads to an increase of their melting point Tm. In order to measure the melting point of the original crystals, high heating rates are needed. This is possible with the modern heat-flow-calorimeters, which work with very small samples. The thermal lag of a DSC cell causes a shift of the melting peak by ΔT to higher temperature. From the theory of a heat-flow-calorimeter, it follows that the error ΔT is proportional to the square root of heating rate. heat of fusion and sample mass. Measurements with sharp melting low molecular weight compounds confirm that this square root relation is quantitatively followed. In order to measure the true melting point of the crystals present in a polymer sample, one has to use different high heating rates and constant sample mass. By plotting the melting peak temperatures as a function of the square root of heating rate and linear extrapolation to zero heating rate, the true melting point is found. This method is applied to HDPE, LDPE and some polyamides.
Résumé
Dans les polymères les cristaux petits et imparfaits se réorganisent au cours d'un échauffement lent. Ceci mène à un accroissement de leur température de fusion Tm. Afin de mesurer la température de fusion des cristaux originaux, des taux elevés d'échauffement sont nécessaires. Ceci est possible à l'aide des calorimètres à écoulement de chaleur modernes qui ne demandent que de très petits échantillons. Le délai thermique d'une cellule DSC cause une translation de la crête de fusion de ΔT à une température plus élevée. De la théorie du calorimètre à écoulement de chaleur il s'ensuit que l'erreur ΔT est proportionelle à la racine carrée du taux d'échauffement, de la chaleur de fusion et de la masse de l'échantillon. Des mesures sur des compounds de faible poids moléculaire et avec point de fusion soudain confirment quantitativement cette relation de la racine carrée. Afin de mesurer le véritable point de fusion des cristaux présents dans un échantillon de polymère, il faut utiliser des taux d'échauffement élevés différents et une masse constante d'échantillon. Un graphique des températures de fusion de crête en fonction de la racine carrée du taux d'échauffement et une extrapolation linéaire à zéro du taux d'échauffement mène au véritable point de fusion. Cette méthode est appliquée au polyéthylène haute et basse densité ainsi qu'à certains polyamides.
Resumen
Cristalli piccoli e imperfetti in polimeri si riorganizzano durante un riscaldamento lento. Ció conduce ad un aumento del loro punto di fusione Tm. Per poter misurare il punto di fusione dei cristalli originali. occorrono velocità di riscaldamento molto elevate. Ció è possibile con i moderni calorimetri heat-flow i quali funzionano con campioni molto piccoli. Il ritardo termico di una cella DSC causa uno spostamento del picco di fusione verso temperature più elevate di ΔT. Dalla teoria del calorimetro heat-flow deriva che l'errore ΔT è proporzionale alla radice quadrata della velocità di riscaldamento, del calore di fusione e della massa del campione. Delle misurazioni eseguite su composti a basso peso molecolare e a fusione acuta confermano che tale relazione secondo la radice quadrata viene seguita quantitativamente. Per misurare il vero punto di fusione dei cristalli presenti in un campione di polimero, si devono impiegare differenti elevate velocità di riscaldamento e masse di campione costante. Costruendo un diagramma a punti con le temperature di fusione di picco in funzione della radice quadrata della velocità di riscaldamento e quindi estrapolando linearmente alla velocità di riscaldamento nulla. si trova il vero punto di fusione. Tale metodo viene impiegato con l'HDPE, LDPE e alcuni poliamidi.},
  creationdate = {2024-04-24T08:01:24},
  doi          = {https://doi.org/10.1016/0014-3057(74)90027-5},
  file         = {:Illers1974 - Die Ermittlung Des Schmelzpunktes Von Kristallinen Polymeren Mittels Wärmeflusskalorimetrie (DSC).pdf:PDF},
  keywords     = {DSC, liquid crystalls, heating rate, melting point, annealing},
  url          = {https://www.sciencedirect.com/science/article/pii/0014305774900275},
}

@Book{Israelachvili2011,
  author       = {Israelachvili, Jacob N.},
  editor       = {Jacob N. Israelachvili},
  publisher    = {Academic Press},
  title        = {Intermolecular and surface forces},
  year         = {2011},
  address      = {Amsterdam},
  edition      = {Third edition},
  isbn         = {978-0-12-375182-9},
  creationdate = {2024-04-24T08:13:34},
  doi          = {https://doi.org/10.1016/B978-0-12-375182-9.10025-9},
  file         = {:Israelachvili2011 - Intermolecular and Surface Forces.pdf:PDF;:2---Thermodynamic-and-Statistical-Aspects-of-In_2011_Intermolecular-and-Surf.pdf:PDF;:3---Strong-Intermolecular-Forces--Covalent-and-_2011_Intermolecular-and-Surf.pdf:PDF;:4---Interactions-Involving-Polar-Molecul_2011_Intermolecular-and-Surface-For.pdf:PDF;:5---Interactions-Involving-the-Polarization-o_2011_Intermolecular-and-Surfac.pdf:PDF;:6---Van-der-Waals-Forces_2011_Intermolecular-and-Surface-Forces.pdf:PDF;:7---Repulsive-Steric-Forces--Total-Intermolecular-P_2011_Intermolecular-and-.pdf:PDF;:8---Special-Interactions--Hydrogen-Bonding-and-Hydr_2011_Intermolecular-and-.pdf:PDF;:9---Nonequilibrium-and-Time-Dependent-Inter_2011_Intermolecular-and-Surface-.pdf:PDF;:10---Unifying-Concepts-in-Intermolecular-and-In_2011_Intermolecular-and-Surf.pdf:PDF;:11---Contrasts-between-Intermolecular--Interparti_2011_Intermolecular-and-Su.pdf:PDF;:15---Solvation--Structural--and-Hydration-_2011_Intermolecular-and-Surface-F.pdf:PDF;:17---Adhesion-and-Wetting-Phenomena_2011_Intermolecular-and-Surface-Forces.pdf:PDF;:18---Friction-and-Lubrication-Forces_2011_Intermolecular-and-Surface-Forces.pdf:PDF;:19---Thermodynamic-Principles-of-Self-Ass_2011_Intermolecular-and-Surface-Fo.pdf:PDF;:20---Soft-and-Biological-Structures_2011_Intermolecular-and-Surface-Forces.pdf:PDF;:21---Interactions-of-Biological-Membranes-and_2011_Intermolecular-and-Surfac.pdf:PDF;:Chapter-12---Force-Measuring-Technique_2011_Intermolecular-and-Surface-Force.pdf:PDF;:Chapter-13---Van-der-Waals-Forces-between-Parti_2011_Intermolecular-and-Surf.pdf:PDF;:Chapter-14---Electrostatic-Forces-between-Surf_2011_Intermolecular-and-Surfa.pdf:PDF;:Chapter-16---Steric--Polymer-Mediated--and-Therm_2011_Intermolecular-and-Sur.pdf:PDF;:Chapter-22---Dynamic-Biointeractions_2011_Intermolecular-and-Surface-Forces.pdf:PDF;:Copyright_2011_Intermolecular-and-Surface-Forces.pdf:PDF;:Definitions-and-Glossary_2011_Intermolecular-and-Surface-Forces.pdf:PDF;:Front-Matter_2011_Intermolecular-and-Surface-Forces.pdf:PDF;:No-title-available_2011_Intermolecular-and-Surface-Forces.pdf:PDF;:No-title-available_2011_Intermolecular-and-Surface-Forces1.pdf:PDF;:Preface-to-Second-Edition_2011_Intermolecular-and-Surface-Forces.pdf:PDF;:Preface-to-the-First-Edition_2011_Intermolecular-and-Surface-Forces.pdf:PDF;:Preface-to-the-Third-Edition_2011_Intermolecular-and-Surface-Forces.pdf:PDF;:Units--Symbols--Useful-Quantities-and-Rela_2011_Intermolecular-and-Surface-F.pdf:PDF},
  keywords     = {book, hydrogen bonds},
  url          = {http://www.sciencedirect.com/science/book/9780123751829},
}

@Article{Ilmain1991,
  author       = {Franck Ilmain and Toyoichi Tanaka and Etsuo Kokufuta},
  journal      = {nature},
  title        = {Volume trannsition in a gel driven by hydrogen bonding},
  year         = {1991},
  pages        = {400--401},
  volume       = {349},
  abstract     = {interactions between macromolecules fall into four categories: ionic, hydrophobic, van der Waals and hydrogen bonding. Phase transitions in polymer gels provide a means of studying these interactions. Many gels will undergo reversible, discontinuous volume changes in response to changes in, for example, temperature, gel composition or light irradiation1–5. These transitions result from the competition between repulsive intermolecular forces, usually electrostatic in nature, that act to expand the polymer network, and an attractive force that acts to shrink it. Volume transitions in gels have been observed that are driven by all of the above-mentioned forces except hydrogen bonding (ref 6–10; T.T. et al, unpublished data; H. Inomata et al., personal communication). Here we report on a phase transition in an interpenetrating polymer network of poly(acrylamide) and poly(acrylic acid) that completes this picture—it is controlled by cooperative 'zipping' interactions between the molecules which result from hydrogen bonding. Cooperativity is an essential feature of the interactions, in that independent hydrogen bonds would not provide a sufficient driving force for the transition. A further novel characteristic of this phase transition is that the swelling (in water) is induced by an increase rather than a decrease in temperature.},
  creationdate = {2024-04-24T09:07:32},
  doi          = {https://doi.org/10.1038/349400a0},
  file         = {:Ilmain1991 - Volume Trannsition in a Gel Driven by Hydrogen Bonding.pdf:PDF},
  keywords     = {cooperativity, poly(acrylamide), poly(acrylic acid), PA, PAA},
  url          = {https://doi.org/10.1038/349400a0},
}

@Article{Philipp2013a,
  author       = {Philipp, Martine and Müller, Ulrich and Aleksandrova, Ralitsa and Sanctuary, Roland and Müller-Buschbaum, Peter and Krüger, Jan K.},
  journal      = {Soft Matter},
  title        = {Immense elastic nonlinearities at the demixing transition of aqueous PNIPAM solutions},
  year         = {2013},
  pages        = {5034--5041},
  volume       = {9},
  abstract     = {Elastic nonlinearities are particularly relevant for soft materials because of their inherently small linear elasticity. Nonlinear elastic properties may even take over the leading role for the transformation at mechanical instabilities accompanying many phase transitions in soft matter. Because of inherent experimental difficulties{,} only little is known about third order (nonlinear) elastic constants within liquids{,} gels and polymers. Here we show that a key concept to access third order elasticity in soft materials is the determination of mode Grüneisen parameters. We report the first direct observation of third order elastic constants across mechanical instabilities accompanying the liquid–liquid demixing transition of semi-dilute aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions. Immense elastic nonlinearities{,} leading to a strong strain-softening in the phase-separating PNIPAM solutions{,} are observed. Molecular mechanisms{,} which may be responsible for these immense elastic nonlinearities{,} are discussed. The importance of third order elastic constants in comparison to second order (linear) elastic constants in the demixing PNIPAM solutions evidences the need to focus more on the general role played by nonlinear elasticity at phase transitions within synthetic and biological liquids and gels.},
  creationdate = {2024-04-24T09:51:08},
  doi          = {10.1039/C3SM00034F},
  file         = {:Philipp2013a - Immense Elastic Nonlinearities at the Demixing Transition of Aqueous PNIPAM Solutions.pdf:PDF},
  issue        = {20},
  keywords     = {pNIPAM, nonlinear elasticity, grüneisen, brillouin spectroscopy, densitometry},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C3SM00034F},
}

@Article{SaidMohamed2011,
  author       = {Said-Mohamed, Cynthia and Niskanen, Jukka and Karesoja, Mikko and Pulkkinen, Petri and Tenhu, Heikki and Daoud, Mohamed and Lee, Lay-Theng},
  journal      = {Soft Matter},
  title        = {Interparticle distance in monolayers controlled by soft spacers},
  year         = {2011},
  pages        = {7112--7122},
  volume       = {7},
  abstract     = {This paper addresses the use of graft polymer layers as spacers to control interparticle distance in 2-dimensional monolayers. Gold nanoparticles grafted with thermosensitive PNIPAM-based polymers with a large range of molecular mass and different degrees of hydrophobicity have been studied. The hydrophobicity of the polymer is adjusted by incorporation of a comonomer n-propylamine. The resulting copolymer{,} PNIPAM-co-NPAM{,} exhibits lower collapse transition temperature and increased cooperativity in the collapse process with n ≈ 150 compared to n ≈ 100 for PNIPAM{,} n being the number of monomers per collapse domain. Langmuir isotherms of these polymers under moderate compression follow closely a π ≈ c3 behavior with corresponding critical exponent ν = 3/4 as predicted for 2-dimensional polymer conformation in good solvent. Nanoparticles grafted with these polymers form stable Langmuir monolayers where the graft polymer chains adopt a 2-D stretched conformation that tethers the nanoparticles to the interface. The nanoparticle cores are thus isolated by the polymer shells resulting in nanoparticle areas that increase with polymer chain length. Correspondingly{,} the interparticle distance is found to vary with chain length as Dp ≈ N0.8. For the Au-PNIPAM-NPAM{,} a moderate increase in temperature to near-θ conditions decreases the nanoparticle area by about 30% through lateral collapse of the polymer layer. This thermally induced molecular collapse in a 2-D monolayer is an unusual and novel observation that may be attributed to cooperative effects of the collapse transition of the new copolymer PNIPAM-co-NPAM.},
  creationdate = {2024-04-24T09:53:55},
  doi          = {10.1039/C1SM05397C},
  file         = {:SaidMohamed2011 - Interparticle Distance in Monolayers Controlled by Soft Spacers.pdf:PDF},
  issue        = {15},
  keywords     = {pNIPAM, cooperativity, brush, copolymer, microcalorimetry, dsc, compression irotherms, van't Hoff enthalpy},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C1SM05397C},
}

@Article{FernandezNieves2001,
  author       = {Fernández-Nieves, A. and Fernández-Barbero, A. and Vincent, B. and de las Nieves, F. J.},
  journal      = {Langmuir},
  title        = {Reversible Aggregation of Soft Particles},
  year         = {2001},
  number       = {6},
  pages        = {1841--1846},
  volume       = {17},
  abstract     = {In this work, the aggregation of microgel particles has been investigated, paying special attention to the structure of the clusters formed in the process. In particular, the aggregates' fractal dimension was determined by static light scattering. The results indicate that the aggregates are more compact than expected for diffusive aggregation. A reversible aggregation mechanism is proposed on the basis of the competition between osmotic and elastic contributions arising from the soft character of the particles. Aggregation proceeds in an energy minimum of restricted depth, giving rise to the formation of more compact clusters than expected. Finally, the process reversibility is tested, confirming the secondary minimum controlled aggregation.},
  creationdate = {2024-04-24T10:04:42},
  doi          = {10.1021/la001351u},
  eprint       = {https://doi.org/10.1021/la001351u},
  file         = {:FernandezNieves2001 - Reversible Aggregation of Soft Particles.pdf:PDF},
  keywords     = {PVP, poly(2-vinylpyridine), microgel, aggregates, SLS},
  url          = {https://doi.org/10.1021/la001351u},
}

@Article{Zaccone2013,
  author       = {Zaccone, Alessio and Crassous, Jérôme J. and Ballauff, Matthias},
  journal      = {The Journal of Chemical Physics},
  title        = {{Colloidal gelation with variable attraction energy}},
  year         = {2013},
  issn         = {0021-9606},
  month        = mar,
  number       = {10},
  pages        = {104908},
  volume       = {138},
  abstract     = {{We present an approximation scheme to the master kinetic equations for aggregation and gelation with thermal breakup in colloidal systems with variable attraction energy. With the cluster fractal dimension df as the only phenomenological parameter, rich physical behavior is predicted. The viscosity, the gelation time, and the cluster size are predicted in closed form analytically as a function of time, initial volume fraction, and attraction energy by combining the reversible clustering kinetics with an approximate hydrodynamic model. The fractal dimension df modulates the time evolution of cluster size, lag time and gelation time, and of the viscosity. The gelation transition is strongly nonequilibrium and time-dependent in the unstable region of the state diagram of colloids where the association rate is larger than the dissociation rate. Only upon approaching conditions where the initial association and the dissociation rates are comparable for all species (which is a condition for the detailed balance to be satisfied) aggregation can occur with df = 3. In this limit, homogeneous nucleation followed by Lifshitz-Slyozov coarsening is recovered. In this limited region of the state diagram the macroscopic gelation process is likely to be driven by large spontaneous fluctuations associated with spinodal decomposition.}},
  creationdate = {2024-04-24T10:08:46},
  doi          = {10.1063/1.4794695},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4794695/14083659/104908\_1\_online.pdf},
  file         = {:Zaccone2013 - Colloidal Gelation with Variable Attraction Energy.pdf:PDF},
  keywords     = {theory, aggregation, viscosity, gelation, clustering kinetics, fractal dimension, nucleation},
  url          = {https://doi.org/10.1063/1.4794695},
}

@Article{Wang2010,
  author       = {Wang, W. and Kaune, G. and Perlich, J. and Papadakis, C. M. and Bivigou Koumba, A. M. and Laschewsky, A. and Schlage, K. and Röhlsberger, R. and Roth, S. V. and Cubitt, R. and Müller-Buschbaum, P.},
  journal      = {Macromolecules},
  title        = {Swelling and switching kinetics of gold coated end-capped poly(N-isopropylacrylamide) thin films},
  year         = {2010},
  number       = {5},
  pages        = {2444--2452},
  volume       = {43},
  abstract     = {Thin thermoresponsive hydrogel films of poly(N-isopropylacrylamide) end-capped with n-butyltrithiocarbonate (nbc-PNIPAM) on silicon supports with a gold layer on top, causing an asymmetric confinement, are investigated. For two different gold layer thicknesses (nominally 0.4 and 5 nm), the swelling and switching kinetics are probed with in situ neutron reflectivity. With a temperature jump from 23 to 40 °C the film is switched from a swollen into a collapsed state. For the thin gold layer this switching is faster as compared to the thick gold layer. The switching is a two-step process of water release and a subsequent structural relaxation. In swelling and deswelling cycles, aging of the films is probed. After five cycles, the film exhibits enhanced water storage capacity. Grazing-incidence small-angle X-ray scattering (GISAXS) shows that these gold coated nbc-PNIPAM films do not age with respect to the inner structure but slightly roughen at the gold surface. As revealed by atomic force microscopy, the morphology of the gold layer is changed by the water uptake and release.},
  creationdate = {2024-04-24T10:14:41},
  doi          = {10.1021/ma902637a},
  eprint       = {https://doi.org/10.1021/ma902637a},
  file         = {:Wang2010 - Swelling and Switching Kinetics of Gold Coated End Capped Poly(N Isopropylacrylamide) Thin Films.pdf:PDF},
  keywords     = {pNIPAM, thin film, spin coating, gold sputter, kinetics, vapour, grazing-incidience x-ray, SAXS, AFM, neutron reflectivity, neutron scattering, time of flight, TOF, optical microscopy},
  url          = {https://doi.org/10.1021/ma902637a},
}

@Article{Rasmusson2004,
  author       = {Rasmusson, Mikael and Routh, Alex and Vincent, Brian},
  journal      = {Langmuir},
  title        = {Flocculation of Microgel Particles with Sodium Chloride and Sodium Polystyrene Sulfonate as a Function of Temperature},
  year         = {2004},
  note         = {PMID: 15875381},
  number       = {9},
  pages        = {3536--3542},
  volume       = {20},
  abstract     = {The flocculation behavior of poly(N-isopropylacrylamide) (PNIPAM) microgel particles, containing surface sulfate groups, has been studied as a function of sodium chloride [NaCl] concentration, between 0.1 and 800 mM NaCl and over the temperature range 25−60 °C. The critical flocculation temperature (CFT) of the particles was determined as a function of NaCl concentration. Three regions of NaCl concentration were established. First, at very low values of [NaCl] (<∼25 mM), no CFT value could be determined; this implies that the interparticle electrostatic repulsion is sufficient to prevent any flocculation occurring. This remains the case even at temperatures well in excess of the lower critical solution temperature for PNIPAM in solution, where the particles are essentially deswollen. Second, at intermediate [NaCl] (∼25−100 mM), the CFT decreased strongly with increasing [NaCl]. In this region, the electostatic forces are weakened sufficiently for the van der Waals forces to cause flocculation. Third, at higher [NaCl] (>∼100 mM), the electrostatic repulsion is screened out, and the CFT decreases linearly with [NaCl]. The reason for this decrease is the fact that aqueous solutions of NaCl become increasingly poorer solvent environments for PNIPAM with increasing [NaCl]. These trends are apparent also in the values determined for the hydrodynamic size of the stable PNIPAM particles as a function of [NaCl] and temperature. It is shown that the flocculation of the PNIPAM particles is consistent with a weak, reversible flocculation model. This is apparent, for example, from the fractal dimensions of the flocs (∼2.0), determined from the power law used to fit the time evolution of the hydrodynamic size of the flocs, and also from the estimated depth of the mimimum in the interparticle pair potential, based on the critical size of the primary particles where flocculation just begins to occur. The effect of adding sodium poly(styrene sulfonate) [PSS] to the PNIPAM dispersions, in the absence of NaCl, was also investigated. The minimum amount of PSS required to induce flocculation was found to decrease with increasing temperature.},
  creationdate = {2024-04-24T10:22:18},
  doi          = {10.1021/la049913n},
  eprint       = {https://doi.org/10.1021/la049913n},
  file         = {:Rasmusson2004 - Flocculation of Microgel Particles with Sodium Chloride and Sodium Polystyrene Sulfonate As a Function of Temperature.pdf:PDF},
  keywords     = {pNIPAM, microgel, aggregation, ionic strength, flocculation, fractal dimension, cluster, DLS, turbidity},
  url          = {https://doi.org/10.1021/la049913n},
}

@Article{Rioboo2021,
  author         = {Riobo{\'o}, Rafael J. Jiménez and Gontán, Nuria and Sanderson, Daniel and Desco, Manuel and G{\'o}mez-Gaviro, Maria Victoria},
  journal        = {International Journal of Molecular Sciences},
  title          = {Brillouin Spectroscopy: From Biomedical Research to New Generation Pathology Diagnosis},
  year           = {2021},
  issn           = {1422-0067},
  number         = {15},
  volume         = {22},
  abstract       = {Brillouin spectroscopy has recently gained considerable interest within the biomedical field as an innovative tool to study mechanical properties in biology. The Brillouin effect is based on the inelastic scattering of photons caused by their interaction with thermodynamically driven acoustic modes or phonons and it is highly dependent on the material’s elasticity. Therefore, Brillouin is a contactless, label-free optic approach to elastic and viscoelastic analysis that has enabled unprecedented analysis of ex vivo and in vivo mechanical behavior of several tissues with a micrometric resolution, paving the way to a promising future in clinical diagnosis. Here, we comprehensively review the different studies of this fast-moving field that have been performed up to date to provide a quick guide of the current literature. In addition, we offer a general view of Brillouin’s biomedical potential to encourage its further development to reach its implementation as a feasible, cost-effective pathology diagnostic tool.},
  article-number = {8055},
  creationdate   = {2024-04-24T10:32:20},
  doi            = {10.3390/ijms22158055},
  file           = {:Rioboo2021 - Brillouin Spectroscopy_ from Biomedical Research to New Generation Pathology Diagnosis.pdf:PDF},
  keywords       = {review, brillouin spectroscopy},
  pubmedid       = {34360822},
  url            = {https://www.mdpi.com/1422-0067/22/15/8055},
}

@Book{Zhu2005,
  editor       = {Yimei Zhu},
  publisher    = {Springer New York},
  title        = {Modern Techniques for Characterizing Magnetic Materials},
  year         = {2005},
  edition      = {first},
  isbn         = {978-0-387-23395-6},
  abstract     = {Characterization and Evaluation of Materials,
Magnetism,
Magnetic Materials,
Electronics and Microelectronics,
Instrumentation,
Surfaces and Interfaces,
Thin Films,
Condensed Matter Physics},
  creationdate = {2024-04-24T10:35:26},
  doi          = {https://doi.org/10.1007/b101202},
  file         = {:Zhu2005 - Modern Techniques for Characterizing Magnetic Materials.pdf:PDF},
  keywords     = {book, brillouin scattering},
}

@Article{Koizumi2004,
  author       = {Koizumi, Satoshi and Monkenbusch, Michael and Richter, Dieter and Schwahn, Dietmar and Farago, Bela},
  journal      = {The Journal of Chemical Physics},
  title        = {{Concentration fluctuations in polymer gel investigated by neutron scattering: Static inhomogeneity in swollen gel}},
  year         = {2004},
  issn         = {0021-9606},
  month        = dec,
  number       = {24},
  pages        = {12721--12731},
  volume       = {121},
  abstract     = {{By using small-angle neutron scattering (SANS) and neutron spin echo (NSE), we have quantitatively investigated the static inhomogeneity in poly (N-isopropyl acrylamide) gel (PNIPA) in microscopic length scales of 0.015\\&lt;q\\&lt;0.16 A−1, where q is a wave number of scattered neutrons. NSE revealed that at lower q(≅0.015 A−1), the concentration fluctuations in the PNIPA gel decays more slowly as compared to the PNIPA solution without crosslinks. According to our scenario that the slower decay found for the PNIPA gel is due to the static inhomogeneity coexisting in the swollen gel, small-angle scattering S(q) obtained by SANS has been quantitatively decomposed into thermal and static scattering components, respectively, Sth(q) and Sst(q). It was further revealed that (i) the q-region where Sst(q) becomes dominant is closely related to that for the abnormal butterfly scattering under stretching, and (ii) as the temperature increases toward the temperature for volume phase transition, Sst(q) of a squared Lorentzian shape increases more drastically than Sth(q) of a Lorentzian shape. These findings were quantitatively understood in the theoretical framework by Panyukov and Rabin [Macromolecules 29, 7960 (1996)] or by Onuki [J. Phys. II. France 2, 45 (1992)], taking into account stress-fluctuation coupling under coexistence of the inherent structural heterogeneity in the real gel. We further found that the static inhomogeneity showing Sst(q) seems to relate to the necklacelike microstructure, appearing after a shallow quench into the collapsed phase.}},
  creationdate = {2024-04-24T11:37:56},
  doi          = {10.1063/1.1823411},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/121/24/12721/19159823/12721\_1\_online.pdf},
  file         = {:Koizumi2004 - Concentration Fluctuations in Polymer Gel Investigated by Neutron Scattering_ Static Inhomogeneity in Swollen Gel.pdf:PDF},
  keywords     = {pNIPAM, SANS, NSE, heterogeneities, necklace, hydrogel, linear polymer},
  url          = {https://doi.org/10.1063/1.1823411},
}

@Article{Crassous2006,
  author       = {Crassous, J. J. and Siebenbürger, M. and Ballauff, M. and Drechsler, M. and Henrich, O. and Fuchs, M.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Thermosensitive core-shell particles as model systems for studying the flow behavior of concentrated colloidal dispersions}},
  year         = {2006},
  issn         = {0021-9606},
  month        = nov,
  number       = {20},
  pages        = {204906},
  volume       = {125},
  abstract     = {{We report on a comprehensive investigation of the flow behavior of colloidal thermosensitive core-shell particles at high densities. The particles consist of a solid core of poly(styrene) onto which a network of cross-linked poly(N-isopropylacrylamide) is affixed. Immersed in water the shell of these particles will swell if the temperature is low. Raising the temperature above 32°C leads to a volume transition within this shell which leads to a marked shrinking of the shell. The particles have well-defined core-shell structure and a narrow size distribution. The remaining electrostatic interactions due to a small number of charges affixed to the core particles can be screened by adding 0.05M KCl to the suspensions. Below the lower critical solution temperature at 32°C the particles are purely repulsive. Above this transition, a thermoreversible coagulation takes place. Lowering the temperature again leads to full dissociation of the aggregates formed by this process. The particles crystallize for effective volume fractions between 0.48 and 0.55. The crystallites can be molten by shear in order to reach a fluid sample again. The reduced shear stress measured in this metastable disordered state was found to be a unique function of the shear rate and the effective volume fraction. These reduced flow curves thus obtained can be described quantitatively by the theory of Fuchs and Cates [Phys. Rev. Lett. 89, 248304 (2002)] which is based on the mode-coupling theory of the glass transition.}},
  creationdate = {2024-04-26T11:14:49},
  doi          = {10.1063/1.2374886},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.2374886/15394140/204906\_1\_online.pdf},
  file         = {:Crassous2006 - Thermosensitive Core Shell Particles As Model Systems for Studying the Flow Behavior of Concentrated Colloidal Dispersions.pdf:PDF},
  keywords     = {pNIPAM, PS, gel, core-shell, nanoparticle, aggregation, crystal, ionic strength, shear rate, TEM, DLS, electrophoretic mobility, rheology},
  url          = {https://doi.org/10.1063/1.2374886},
}

@Article{FernandezBarbero2002,
  author       = {Fern\'andez-Barbero, A. and Fern\'andez-Nieves, A. and Grillo, I. and L\'opez-Cabarcos, E.},
  journal      = {Phys. Rev. E},
  title        = {Structural modifications in the swelling of inhomogeneous microgels by light and neutron scattering},
  year         = {2002},
  month        = nov,
  pages        = {051803},
  volume       = {66},
  creationdate = {2024-04-26T13:45:51},
  doi          = {10.1103/PhysRevE.66.051803},
  file         = {:FernandezBarbero2002 - Structural Modifications in the Swelling of Inhomogeneous Microgels by Light and Neutron Scattering.pdf:PDF},
  issue        = {5},
  keywords     = {pNIPAM, microgel, SANS, DLS, d2o, flory-rhener theory},
  numpages     = {10},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevE.66.051803},
}

@Article{Crassous2008,
  author       = {Jérôme J. Crassous and Alexander Wittemann and Miriam Siebenbürger and Marc Schrinner and Markus Drechsler and Matthias Ballauff},
  journal      = {Colloid Polym Sci},
  title        = {Direct imaging of temperature-sensitive core-shell latexes by cryogenic transmission electron microscopy},
  year         = {2008},
  pages        = {805--812},
  volume       = {286},
  creationdate = {2024-04-26T13:53:27},
  doi          = {https://doi.org/10.1007/s00396-008-1873-3},
  file         = {:Crassous2008 - Direct Imaging of Temperature Sensitive Core Shell Latexes by Cryogenic Transmission Electron Microscopy.pdf:PDF},
  keywords     = {pNIPAM, core-shell, TEM, crystallization},
  url          = {https://doi.org/10.1007/s00396-008-1873-3},
}

@Article{Kunugi2002,
  author       = {Shigeru Kunugi and Tomoko Tada and Naoki Tanaka and Kazuya Yamamoto and Mitsuru Akashi},
  journal      = {Polymer Journal},
  title        = {Microcalorimetric Study of Aqueous Solution Of A Thermoresponsive Polymer, poly(N-vinylisobutyramide) (PNVIBA)},
  year         = {2002},
  pages        = {383--388},
  volume       = {34},
  creationdate = {2024-04-26T14:25:16},
  doi          = {https://doi.org/10.1295/polymj.34.383},
  file         = {:Kunugi2002 - Microcalorimetric Study of Aqueous Solution of a Thermoresponsive Polymer, Poly(N Vinylisobutyramide) (PNVIBA).pdf:PDF},
  keywords     = {pNIPAM, PNVIBA, poly(N-vinylisobutyramide), dsc, microcalorimetry, thermodynamics, concentration-dependence, ionic strength, chain length dependence, molecular weight},
  url          = {https://doi.org/10.1295/polymj.34.383},
}

@Article{Zhang2001a,
  author       = {Zhang, Guangzhao and Wu, Chi},
  journal      = {Journal of the American Chemical Society},
  title        = {The Water/Methanol Complexation Induced Reentrant Coil-to-Globule-to-Coil Transition of Individual Homopolymer Chains in Extremely Dilute Solution},
  year         = {2001},
  number       = {7},
  pages        = {1376--1380},
  volume       = {123},
  abstract     = {Narrowly distributed ultralong linear poly(N-isopropylacrylamide) (PNIPAM) (Mw = 2.63 × 107 g/mol and Mw/Mn < 1.1) was successfully prepared by a combination of fractionation and filtration. Using this PNIPAM sample, we have studied the conformation change of individual PNIPAM chains in different methanol/water mixtures at 20 °C. Both water and methanol are good solvents for PNIPAM, but not a proper mixture of them. The PNIPAM chain collapsed sharply from a coil to a stable globule when the methanol content (xmethanol) reached ∼17 mol \%. In the range 17−40 mol \%, the PNIPAM chain remained in the globule state. Further addition of methanol finally led to a globule-to-coil transition at xmethanol ∼ 50 mol \%. The reentrant coil-to-globule-to-coil transition could be attributed to the formation of different water/methanol complexes, presumably, (H2O)m(CH3OH)n, which are poor solvents for PNIPAM. We have, for the first time, revealed that the conformation change of individual polymer chains can be used as an indicator to probe the complexation, similar to an indicator used in titration. Our results suggest that when xmethanol < ∼17 mol \%, the water/methanol molar ratio (m/n) is ∼5, while when xmethanol > 50 mol \%, m/n becomes 1. In the range of ∼17 mol \% < xmethanol < 50 mol \%, different intermediates with 1 ≤ m/n ≤ 5 coexist. The speculated structures of these complexes could be related to a water pentamer.},
  creationdate = {2024-04-26T15:28:21},
  doi          = {10.1021/ja003889s},
  eprint       = {https://doi.org/10.1021/ja003889s},
  file         = {:Zhang2001a - The Water_Methanol Complexation Induced Reentrant Coil to Globule to Coil Transition of Individual Homopolymer Chains in Extremely Dilute Solution.pdf:PDF},
  keywords     = {pNIPAM, cononsolvency, aqueous methanol, DLS, second virial coefficient, hydrodynamic radius},
  url          = {https://doi.org/10.1021/ja003889s},
}

@Article{Teertstra2009,
  author       = {Steven J. Teertstra and Wai Yau Lin and Mario Gauthier and Mark Ingratta and Jean Duhamel},
  journal      = {Polymer},
  title        = {Comparison of the long range polymer chain dynamics of polystyrene and cis-polyisoprene using polymers randomly labeled with pyrene},
  year         = {2009},
  issn         = {0032-3861},
  number       = {23},
  pages        = {5456--5466},
  volume       = {50},
  abstract     = {The ability of the Fluorescence Blob Model (FBM) to probe the chain dynamics of a polymer backbone was verified for the first time by investigating whether it responds to known differences in backbone flexibility for flexible cis-polyisoprene (PIP) and more sterically hindered polystyrene (PS), both randomly labeled with pyrene. For comparable pyrene contents, the steady-state fluorescence spectra indicated that Py-PIP formed considerably more excimer than the Py-PS samples. Analysis of the fluorescence decays with the FBM provided the rate constant for intramolecular excimer formation. This rate constant was much larger for Py-PIP than for Py-PS, in agreement with the enhanced excimer formation observed for Py-PIP. The enhanced ability of Py-PIP to form excimer is attributed to the PIP backbone being less sterically hindered than the PS backbone. This study is the first example of a comparison of the long range polymer chain dynamics for two different polymeric backbones randomly labeled with pyrene.},
  creationdate = {2024-04-26T16:44:57},
  doi          = {https://doi.org/10.1016/j.polymer.2009.09.036},
  file         = {:Teertstra2009 - Comparison of the Long Range Polymer Chain Dynamics of Polystyrene and Cis Polyisoprene Using Polymers Randomly Labeled with Pyrene.pdf:PDF},
  keywords     = {Fluorescence, Chain dynamics, Polyisoprene, PIP, pyrene, PS},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386109007939},
}

@Article{Winnik1990a,
  author       = {Winnik, Francoise M.},
  journal      = {Macromolecules},
  title        = {Fluorescence studies of aqueous solutions of poly(N-isopropylacrylamide) below and above their LCST},
  year         = {1990},
  number       = {1},
  pages        = {233--242},
  volume       = {23},
  creationdate = {2024-04-26T16:47:53},
  doi          = {10.1021/ma00203a040},
  eprint       = {https://doi.org/10.1021/ma00203a040},
  file         = {:Winnik1990a - Fluorescence Studies of Aqueous Solutions of Poly(N Isopropylacrylamide) below and above Their LCST.pdf:PDF},
  keywords     = {pNIPAM, fluorescence, pyrene, cononsolvency, aqueous methanol},
  url          = {https://doi.org/10.1021/ma00203a040},
}

@Article{Ramos2006,
  author       = {M.A. Ramos and I.M. Shmytko and E.A. Arnautova and R.J. Jiménez-Riobóo and V. Rodríguez-Mora and S. Vieira and M.J. Capitán},
  journal      = {Journal of Non-Crystalline Solids},
  title        = {On the phase diagram of polymorphic ethanol: Thermodynamic and structural studies},
  year         = {2006},
  issn         = {0022-3093},
  note         = {Proceedings of the 5th International Discussion Meeting on Relaxations in Complex Systems},
  number       = {42},
  pages        = {4769--4775},
  volume       = {352},
  abstract     = {It is well known that ethanol exhibits a very interesting polymorphism presenting different solid phases: a fully-ordered (monoclinic) crystal, a (bcc) plastic crystal, which by quenching becomes an orientationally-disordered crystal with glassy properties (hence sometimes named ‘glassy crystal’), and the ordinary amorphous glass. We have carried out calorimetric, X-ray diffraction, and Brillouin-scattering experiments above liquid-nitrogen temperatures and have found several new features that shed more light on the rich and interesting phase diagram of ethanol. Firstly, we have identified up to four different varieties of the monoclinic crystalline phase depending on the thermal history. We also present new specific-heat data of these glassy and crystalline phases below the glass transition temperature up to the melting temperature. Furthermore, we have unexpectedly found that the amorphous phase can also be obtained by the unusual route of a very slow cooling of the liquid in some particular experimental set-ups, evidencing the heterogeneous character of the crystallization kinetics of these molecular glass-formers.},
  creationdate = {2024-04-30T13:00:52},
  doi          = {https://doi.org/10.1016/j.jnoncrysol.2006.02.143},
  file         = {:Ramos2006 - On the Phase Diagram of Polymorphic Ethanol_ Thermodynamic and Structural Studies.pdf:PDF},
  keywords     = {Crystallization,Brillouin-scattering,X-ray diffraction,Glass transition,Liquid crystals and molecular liquids,Phases and equilibria,Structure,Thermal properties,Calorimetry,Thermodynamics,ethanol,plastic crystal,phase diagram},
  url          = {https://www.sciencedirect.com/science/article/pii/S0022309306008659},
}

@Article{Zhao2012,
  author       = {Li-Jun Zhao and Han-Shuang Xiao},
  journal      = {Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy},
  title        = {Aqueous solutions of lower alcohols investigated by pyrene fluorescence spectroscopy},
  year         = {2012},
  issn         = {1386-1425},
  pages        = {111--115},
  volume       = {88},
  abstract     = {The aqueous solutions of lower alcohols such as methanol, ethanol, 1-propanol and 2-propanol, were studied by fluorescence spectroscopy of pyrene, defining the Py scale for polarity. Sigmoidal curves were used to fit the Py values of aqueous alcohol solutions as a function of the logarithm of water–alcohol mole ratio, i.e., log(WAR). The results from curve fittings were discussed in terms of the structural transitions of aqueous alcohol solutions, as well as the dissociation constants for alcohol– and water–pyrene complexes. The microscopic alcohol and water phases were considered to be saturated with each other, and the structures of dilute aqueous alcohol solutions were found to be more complicated than those of concentrated ones.},
  creationdate = {2024-05-01T15:13:54},
  doi          = {https://doi.org/10.1016/j.saa.2011.12.009},
  file         = {:Zhao2012 - Aqueous Solutions of Lower Alcohols Investigated by Pyrene Fluorescence Spectroscopy.pdf:PDF},
  keywords     = {Aqueous alcohols, Pyrene, Fluorescence spectroscopy, cononsolvency, methanol, ethanol, 1-propanol, 2-propanol},
  url          = {https://www.sciencedirect.com/science/article/pii/S138614251101078X},
}

@Article{Zhang2015,
  author       = {Qilu Zhang and Richard Hoogenboom},
  journal      = {Progress in Polymer Science},
  title        = {Polymers with upper critical solution temperature behavior in alcohol/water solvent mixtures},
  year         = {2015},
  issn         = {0079-6700},
  note         = {Topical Volume on Polymer Chemistry},
  pages        = {122--142},
  volume       = {48},
  abstract     = {Thermoresponsive polymers are of great importance in numerous nanotechnological and biomedical applications. Compared to polymers that undergo a lower critical solution temperature (LCST) phase transition in aqueous solution, i.e., demixing occurs upon heating, polymers exhibiting the reversed upper critical solution temperature (UCST) behavior in aqueous solution have been much less documented as it is more challenging to achieve this behavior in aqueous solutions. Furthermore, the high sensitivity of UCST behavior to minor variation in polymer structure and solution composition hampered the development of applications based on these polymers [18]. However, polymers with UCST transition in alcohol/water solvent mixtures are more commonly reported and exhibit promising properties for the preparation of ‘smart’ materials. This review will focus on the theory and development of such polymers with UCST behavior in alcohol/water solvent mixtures. By highlighting reported examples of UCST polymers in alcohol/water solvent mixtures, we aim to demonstrate the versatility and potential that such UCST polymers possess as biomedical and ‘smart’ materials.},
  creationdate = {2024-05-01T16:25:11},
  doi          = {https://doi.org/10.1016/j.progpolymsci.2015.02.003},
  file         = {:Zhang2015 - Polymers with Upper Critical Solution Temperature Behavior in Alcohol_water Solvent Mixtures.pdf:PDF},
  keywords     = {Thermoresponsive polymer,UCST,Ethanol/water solvent mixture,Co-solvent,Co-nonsolvent,Self-assembly,pNIPAM,cononsolvency,review,aqueous ethanol},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079670015000295},
}

@Article{Nikolayev1996,
  author       = {Nikolayev, Vadim S. and Beysens, Daniel and Guenoun, Patrick},
  journal      = {Phys. Rev. Lett.},
  title        = {New Hydrodynamic Mechanism for Drop Coarsening},
  year         = {1996},
  month        = apr,
  pages        = {3144--3147},
  volume       = {76},
  creationdate = {2024-05-03T07:34:16},
  doi          = {10.1103/PhysRevLett.76.3144},
  file         = {:Nikolayev1996 - New Hydrodynamic Mechanism for Drop Coarsening.pdf:PDF},
  issue        = {17},
  keywords     = {aggregation, coalescence},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.76.3144},
}

@Article{Inomata1989,
  author       = {Inomata, Hiroshi and Yagi, Yasuhiko and Otake, Katsuto and Konno, Mikio and Saito, Shozaburo},
  journal      = {Macromolecules},
  title        = {Spinodal decomposition of an aqueous solution of poly(N-isopropylacrylamide)},
  year         = {1989},
  number       = {8},
  pages        = {3494--3495},
  volume       = {22},
  creationdate = {2024-05-03T07:40:58},
  doi          = {10.1021/ma00198a050},
  eprint       = {https://doi.org/10.1021/ma00198a050},
  file         = {:Inomata1989 - Spinodal Decomposition of an Aqueous Solution of Poly(N Isopropylacrylamide).pdf:PDF},
  keywords     = {pNIPAM, aggregation, cloud point, DSC, kinetics},
  url          = {https://doi.org/10.1021/ma00198a050},
}

@Article{Zhang2005,
  author       = {Zhang, Yanjie and Furyk, Steven and Bergbreiter, David E. and Cremer, Paul S.},
  journal      = {Journal of the American Chemical Society},
  title        = {Specific Ion Effects on the Water Solubility of Macromolecules:  PNIPAM and the Hofmeister Series},
  year         = {2005},
  note         = {PMID: 16218647},
  number       = {41},
  pages        = {14505--14510},
  volume       = {127},
  abstract     = {Aqueous processes ranging from protein folding and enzyme turnover to colloidal ordering and macromolecular precipitation are sensitive to the nature and concentration of the ions present in solution. Herein, the effect of a series of sodium salts on the lower critical solution temperature (LCST) of poly(N-isopropylacrylamide), PNIPAM, was investigated with a temperature gradient microfluidic device under a dark-field microscope. While the ability of a particular anion to lower the LCST generally followed the Hofmeister series, analysis of solvent isotope effects and of the changes in LCST with ion concentration and identity showed multiple mechanisms were at work. In solutions containing sufficient concentrations of strongly hydrated anions, the phase transition of PNIPAM was directly correlated with the hydration entropy of the anion. On the other hand, weakly hydrated anions were salted-out through surface tension effects and displayed improved hydration by direct ion binding.},
  creationdate = {2024-05-03T08:23:45},
  doi          = {10.1021/ja0546424},
  eprint       = {https://doi.org/10.1021/ja0546424},
  file         = {:Zhang2005 - Specific Ion Effects on the Water Solubility of Macromolecules_ PNIPAM and the Hofmeister Series.pdf:PDF;:SpecificIonEffectsOnTheWaterSolubilityOfMacromolecules-PNIPAMAndTheHofmeisterSeries_ZhangEtAl_JAmChemSoc2005_SI.pdf:PDF},
  keywords     = {pNIPAM, ionic strength, hofmeister series, isotope effect, stabilization, aggregation},
  url          = {https://doi.org/10.1021/ja0546424},
}

@Article{Freitag2002,
  author       = {Freitag, Ruth and Garret-Flaudy, Frédéric},
  journal      = {Langmuir},
  title        = {Salt Effects on the Thermoprecipitation of Poly-(N-isopropylacrylamide) Oligomers from Aqueous Solution},
  year         = {2002},
  number       = {9},
  pages        = {3434--3440},
  volume       = {18},
  abstract     = {Simple salts are known to influence the cloud point temperature of the aqueous solution of thermoresponsive compounds, such as poly-(N-isopropylacrylamide), PNIPAM. The effect of one series of anions (six potassium salts) and two series of cations (five alkali-metal hydroxides and chlorides, respectively) on the cloud point temperature of PNIPAM oligomers is investigated. All salts with the exception of low (<0.5 M) concentrations of KI are found to lower the cloud point temperature; the relationship between the temperature and the concentration of the added salt tends to be linear. The intensity of the effect of a given salt corresponds to its position in the Hoffmeister series. However, while the anions differ significantly in force, the cations−with the exception of Li+−show little difference in this regard. The observed effects are interpreted based on the structure making/structure breaking potential of the involved ions as evidenced by their viscosity B coefficients. While a relationship could be established for the anions this is less obvious for the cations. Moreover, while the structure breaking ability of the I-- anion to some extent explains its salting in ability at low concentrations, it does not account for the linear salting out effect observed at higher concentrations. The second attempt to interpret the results is based on the solvophobic theory, i.e., takes the contribution of both electrostatic and hydrophobic interactions into account. Thermodynamic data on the phase separation obtained through differential scanning calorimetry are used to calculate the unitary free Gibbs energy as a function of the molal salt concentration.},
  creationdate = {2024-05-03T08:37:10},
  doi          = {10.1021/la0106440},
  eprint       = {https://doi.org/10.1021/la0106440},
  file         = {:Freitag2002 - Salt Effects on the Thermoprecipitation of Poly (N Isopropylacrylamide) Oligomers from Aqueous Solution.pdf:PDF},
  keywords     = {pNIPAM, ionic strength, hofmeister series, DSC, cloud point},
  url          = {https://doi.org/10.1021/la0106440},
}

@Article{Cahn1961,
  author       = {John W Cahn},
  journal      = {Acta Metallurgica},
  title        = {On spinodal decomposition},
  year         = {1961},
  issn         = {0001-6160},
  number       = {9},
  pages        = {795--801},
  volume       = {9},
  abstract     = {The stability of a solid solution to all infinitesimal composition fluctuations is considered, taking surface tension and elastic energy into account. It is found that for infinite isotropic solids, free from imperfections the spinodal marks the limit of metastability to such fluctuations only if there is no change in molar volume with composition. Otherwise the elastic energy due to a fluctuation stabilizes the solution and alters the criterion for the limit of metastability. For an unstable solution the kinetics of decomposition are discussed and the expected mean particle size or wavelength of the most rapidly growing fluctuation is derived.
Résumé
L'auteur considère la stabilité d'une solution solide en relation avec des fluctuations infinitésimales de la composition. En tenant compte de la tension superficielle et de l'énergie élastique, on trouve que pour des solides isotropes infinis et exempts d'imperfections, la décomposition spinodale indique la limite de métastabilité aux fluctuations considérées seulement dans le cas où il n'intervient pas de modification du volume molaire avec la composition. Autrement, l'énergie élastique résultant d'une fluctuation stabilise la solution e tmodifie le critère de la limite de métastabilité. L'auteur discute de la cinétique de la décomposition dans le cas d'une solution instable et il en déduit la dimension moyenne de la particule ou de la longueur d'onde associée à la fluctuation la plus rapide.
Zusammenfassung
Die Stabilität einer festen Lösung gegenüber allen infinitesimalen Schwankungen der Zusammensetzung wird betrachtet, dabei werden Oberflächenspannung und elastische Energie mit berücksichtigt. Es wird gezeigt, daβ im unendlichen, isotropen und fehlerfreien Festkörper die Spinodale nur dann die Grenze der Metastabilität bezüglich solchen Schwankungen darstellt, wenn sich das molare Volumen mit der Zusammensetzung nicht ändert. Andernfalls stabilisiert die mit der Schwankung verknüpfte elastische Energie die Lösung und verändert die Bedingungen für die Grenze der Metastabilität. Für eine instabile Lösung wird die Kinetik der Umsetzung diskutiert und die zu erwartende mittlere Teilchengröβe oder die Wellenlänge der am schnellsten wachsenden Schwankung abgeleitet.},
  creationdate = {2024-05-03T08:54:59},
  doi          = {https://doi.org/10.1016/0001-6160(61)90182-1},
  file         = {:Cahn1961 - On Spinodal Decomposition.pdf:PDF},
  keywords     = {aggregation, spinodal, cahn, kinetics, volume contraction},
  url          = {https://www.sciencedirect.com/science/article/pii/0001616061901821},
}

@Article{vanAartsen1970,
  author       = {J.J. {van Aartsen}},
  journal      = {European Polymer Journal},
  title        = {Theoretical observations on spinodal decomposition of polymer solutions},
  year         = {1970},
  issn         = {0014-3057},
  number       = {7},
  pages        = {919--924},
  volume       = {6},
  abstract     = {In systems showing spinodal decomposition, it is to be expected that a certain dimension Dm will be realized most frequently. Although most concentration fluctuations present increase in amplitude with time, the rate of increase depends upon the wavelength of the fluctuation, so that some fluctuations will grow much more rapidly than others; as a result, there will be a fairly uniform dimension throughout the system. In order to obtain an estimate of the dimensions to be expected in the system PPO®-caprolactam, some theoretical observations have been combined to yield Dm values of the order of 1 μ, depending upon the temperature below the spinodal where the decomposition sets in.
Résumé
Dans le cas des systèmes qui présentent une décomposition spinodale, on doit s'attendre à ce qu'une certaine dimension Dm soit la plus fréquemment réalisée. Bien que la plupart des fluctuations de concentration ont une amplitude qui s'accroît avec le temps, la vitesse d'accroisement dépend de la longueur d'onde de la fluctuation, de telle sorte que certaines fluctuations s'accroissent beaucoup plus rapidement que d'autres; il en résulte l'existence d'une dimension pratiquement uniforme au sein du système. Dans le but de pouvoir estimer les dimensions auxquelles on doit s'attendre pour le système PPO®-caprolactame, on a réussi quelques observations théoriques pour obtenir des valeurs de Dm de l'ordre du micron, en tenant compte de la température inférieure à la température spinodale à laquelle la décomposition a lieu.
Resumen
Nei sistemi che presentano decomposizione spinodale, ci si dovrebbe aspettare che una certa dimensione Dm si realizzi più di frequente. Sebbene molte fluttuazioni di concentrazione aumentino in ampiezza con il tempo, la velocità dell'aumento dipende dalla lunghezza d'onda della fluttuazione, così che alcune fluttuazioni aumentano più rapidamente di altre; come risultato ci dovrebbe essere una dimensione quasi uniforme attraverso il sistema. Per ottenere un'idea delle dimensioni da aspettarsi nel sistema PPO®-caprolattame, sono state combinate alcune osservazioni teoriche per ottenere valori Dm dell'ordine di un micron, dipendenti dalla temperatura al di sotto della quale ha luogo la decomposizione spinodale.
Zusammenfassung
In Systemen, die spinodale Zersetzung zeigen, ist zu erwarten, daβ eine bestimmte Dimension Dm besonders häufig auftritt. Obwohl die meisten vorliegenden Konzentrationsschwankungen in ihrer Amplitude mit der Zeit zunehmen, hängt die Geschwindigkeit der Zunahme von der Wellenlänge der Schwankung ab, sodaβ einige Schwankungen sehr viel rascher zunehmen als andere. Daraus ergibt sich eine ziemlich gleichmäβige Dimension im ganzen System. Um eine Abschätzung der zu erwartenden Dimensionen im System PPO®-Caprolactam zu erhalten, wurden einige theoretische Beobachtungen Kombiniert und ergaben Dm Werte in der Gröβenordnung von 1 μ, in Abhängigkeit von der Temperatur unterhalb der Spinodalen bei der die Zersetzung beginnt.},
  creationdate = {2024-05-03T09:01:47},
  doi          = {https://doi.org/10.1016/0014-3057(70)90026-1},
  file         = {:vanAartsen1970 - Theoretical Observations on Spinodal Decomposition of Polymer Solutions.pdf:PDF},
  keywords     = {spinodal decomposition, theory, density fluctuations},
  url          = {https://www.sciencedirect.com/science/article/pii/0014305770900261},
}

@Article{Binder1983,
  author       = {Binder, K.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Collective diffusion, nucleation, and spinodal decomposition in polymer mixtures}},
  year         = {1983},
  issn         = {0021-9606},
  month        = dec,
  number       = {12},
  pages        = {6387--6409},
  volume       = {79},
  abstract     = {{The dynamics of concentration fluctuations in binary polymer mixtures AB, A and B being long and flexible chains, is studied near the critical point of unmixing. A ‘‘hydrodynamic’’ theory in close analogy to the treatments of Cahn–Hilliard and Cook for the dynamics of unmixing alloys is developed, and its validity is carefully analyzed. It is shown that homogeneous nucleation for long chains is negligible except in a narrow region of volume fraction φ0 near the spinodal curve φs0 of width (φs0−φ0)/φ0∝N−1, where N is the number of subunits of the chains. For N→∞ the spinodal curve hence is well defined, in contrast to mixtures with short‐range forces, and also the linearized theory of spinodal decomposition is predicted to have wider validity. The collective relaxation in the one‐phase region is described by a characteristic time involving the collective diffusion constant Dcoll τq=(Dcoll q2)−1, if the wave vector q is smaller than the inverse correlation length ξ−1coll, while in the range ξ−1coll≪q≪R−1 (R being the polymer coil radius) rates τ−1q∝q4 and in the range R−1≪q rates τ−1q∝q2 are predicted. Both the Rouse model and the reptation model for single‐chain relaxation are considered, and a comparison with previous treatments is made. One central result, namely that the wave vector qm of maximal growth in spinodal decomposition is typically of the order of qm∼R1, agrees with the results of Pincus. Experimental consequences are briefly discussed.}},
  creationdate = {2024-05-03T09:03:19},
  doi          = {10.1063/1.445747},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/79/12/6387/18946248/6387\_1\_online.pdf},
  file         = {:Binder1983 - Collective Diffusion, Nucleation, and Spinodal Decomposition in Polymer Mixtures.pdf:PDF},
  keywords     = {nucleation and growth, collective diffusion, spinodal decomposition, density fluctuations},
  url          = {https://doi.org/10.1063/1.445747},
}

@Article{Onuki1997,
  author       = {Onuki, Akira and Taniguchi, Takashi},
  journal      = {The Journal of Chemical Physics},
  title        = {{Viscoelastic effects in early stage phase separation in polymeric systems}},
  year         = {1997},
  issn         = {0021-9606},
  month        = apr,
  number       = {13},
  pages        = {5761--5770},
  volume       = {106},
  abstract     = {{We examine how viscoelasticity affects early stage spinodal decomposition in polymer solutions and blends when fluctuations of the stress and the composition are coupled in dynamics. The coupling is increased with increasing asymmetry between the two components. We introduce a long viscoelastic length ξve within which the stress relaxation governs the composition relaxation. It can be of the order of the tube length in the reptation theory in strongly asymmetric polymer blends. For shallow quenching phase separation proceeds on time scales slower than the stress relaxation time τ and the kinetic coefficient depends on the wave number q as q−2 for qξve\\&gt;1. On the other hand, for deep quenching phase separation takes place as in gels on time scales faster than τ. We describe the crossover between these two cases by assuming a single stress relaxation time.}},
  creationdate = {2024-05-03T09:09:48},
  doi          = {10.1063/1.473595},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/106/13/5761/19163892/5761\_1\_online.pdf},
  file         = {:Onuki1997 - Viscoelastic Effects in Early Stage Phase Separation in Polymeric Systems.pdf:PDF},
  keywords     = {aggregation, kinetics, viscoelastic effect, theory},
  url          = {https://doi.org/10.1063/1.473595},
}

@Article{Byrne1995,
  author       = {Byrne, Alan and Kiernan, Paul and Green, Daron and Dawson, Kenneth A.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Kinetics of homopolymer collapse}},
  year         = {1995},
  issn         = {0021-9606},
  month        = jan,
  number       = {1},
  pages        = {573--577},
  volume       = {102},
  abstract     = {{Langevin‐equation simulation is used to study the dynamics of a simple model of homopolymer collapse at infinite dilution for polymers of lengths N=100, 200, 300, 500, and 1024 units. Lennard‐Jones potentials are chosen to represent the bead–bead interactions and a harmonic potential bonds nearest‐neighbor beads. The Flory coil‐to‐collapsed globule transition is brought about by an adjustment of the Lennard‐Jones potential interactions. The average cluster size and distribution, along with the radius of gyration are used to characterize the collapse dynamics. Our results indicate that there are several kinetic mechanisms that lead to a collapsed polymer. At early times the dominant mechanisms involve cluster creation and growth by adsorption of slack polymer, whereas for later times the mechanism involves cluster coarsening. For this latter mechanism we find that the average cluster size 〈s〉 grows as 〈s〉=Atz, where z is dependent on u3, the third virial coefficient. Depending on the value of u3 we determine two values for z, first, z=0.60±0.02 for u3 not equal to zero and second z=0.66±0.03 for u3 equal to zero, both representing a departure from Lifshitz–Slyozov theory.}},
  creationdate = {2024-05-03T09:58:15},
  doi          = {10.1063/1.469437},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/102/1/573/19036276/573\_1\_online.pdf},
  file         = {:Byrne1995 - Kinetics of Homopolymer Collapse.pdf:PDF},
  keywords     = {simulation, langevin equation, aggregation kinetics},
  url          = {https://doi.org/10.1063/1.469437},
}

@Article{Kuznetsov1995,
  author       = {Kuznetsov, Yu. A. and Timoshenko, E. G. and Dawson, K. A.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Kinetics at the collapse transition of homopolymers and random copolymers}},
  year         = {1995},
  issn         = {0021-9606},
  month        = sep,
  number       = {11},
  pages        = {4807--4818},
  volume       = {103},
  abstract     = {{We describe the results of Monte Carlo simulations for kinetics at the collapse transition of a homopolymer in a lattice model. We find the kinetic laws corresponding to the three kinetic stages of the process: R2g(t)=R2g(0)−At7/11 at the early stage corresponding to formation and growth of locally collapsed clusters, the coarsening stage is characterized by growth of clusters according to the law S∝t1/2, where S is the average number of Kuhn units per cluster, and the final relaxation stage is described by the law R2g(t)=R2g(∞)+A1(1)e−t/τ1(1) with τ1(1)∝N2. We also present preliminary results on the equilibrium properties and ‘‘collapse’’ transition of a random copolymer. The transition curve is determined as a function of hydrophobic bead concentration na. We discuss the different collapsed copolymer states as a function of the composition. At low hydrophilicity we believe the critical value of the interaction parameter is governed by the law χc(na)∝na−2/3. In the kinetics we see unusual phenomena such as the appearance of a metastable long‐lived states with few clusters and nontrivial loop structure.}},
  creationdate = {2024-05-03T10:00:22},
  doi          = {10.1063/1.470615},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/103/11/4807/19044347/4807\_1\_online.pdf},
  file         = {:Kuznetsov1995 - Kinetics at the Collapse Transition of Homopolymers and Random Copolymers.pdf:PDF},
  keywords     = {aggregation kinetics, monte carlo simulation},
  url          = {https://doi.org/10.1063/1.470615},
}

@Article{Klushin1998,
  author       = {Klushin, L. I.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Kinetics of a homopolymer collapse: Beyond the Rouse–Zimm scaling}},
  year         = {1998},
  issn         = {0021-9606},
  month        = may,
  number       = {18},
  pages        = {7917--7920},
  volume       = {108},
  abstract     = {{We present a phenomenological theory describing the self-similar coarsening stage in the collapse of a long flexible homopolymer chain in a dilute solution upon a sudden quench. The approach is based on the “necklace” picture of the collapsing chain being composed of clusters separated by strands as demonstrated by computer simulations. The model represents a special class in the cluster growth problem where aggregation is driven by tension in the connecting strands. The mean cluster size in the free-draining limit is predicted to grow with time as s(t)∼t6/7(1+ν) where ν is the exponent characterizing the initial conformation of the coil. The characteristic collapse time scales as τc∼N1+ν∼N1.6 in agreement with the Langevin dynamics simulations. Incorporation of hydrodynamic effects leads to τc∼N1/3+ν∼N0.93. For a realistic experimental situation the theory presented thus predicts a much faster collapse than suggested by self-consistent field calculations.}},
  creationdate = {2024-05-03T10:02:22},
  doi          = {10.1063/1.476229},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/108/18/7917/19146319/7917\_1\_online.pdf},
  file         = {:Klushin1998 - Kinetics of a Homopolymer Collapse_ beyond the Rouse–Zimm Scaling.pdf:PDF},
  keywords     = {aggregation kinetics, theory, langevin simulations},
  url          = {https://doi.org/10.1063/1.476229},
}

@Article{Kikuchi2005,
  author       = {Kikuchi, N. and Ryder, J. F. and Pooley, C. M. and Yeomans, J. M.},
  journal      = {Phys. Rev. E},
  title        = {Kinetics of the polymer collapse transition: The role of hydrodynamics},
  year         = {2005},
  month        = jun,
  pages        = {061804},
  volume       = {71},
  creationdate = {2024-05-03T10:04:42},
  doi          = {10.1103/PhysRevE.71.061804},
  file         = {:Kikuchi2005 - Kinetics of the Polymer Collapse Transition_ the Role of Hydrodynamics.pdf:PDF},
  issue        = {6},
  keywords     = {aggregation kinetics, hydrodynamics},
  numpages     = {8},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevE.71.061804},
}

@Article{Laukkanen2004,
  author       = {Laukkanen, Antti and Valtola, Lauri and Winnik, Françoise M. and Tenhu, Heikki},
  journal      = {Macromolecules},
  title        = {Formation of Colloidally Stable Phase Separated Poly(N-vinylcaprolactam) in Water:  A Study by Dynamic Light Scattering, Microcalorimetry, and Pressure Perturbation Calorimetry},
  year         = {2004},
  number       = {6},
  pages        = {2268--2274},
  volume       = {37},
  abstract     = {The effect of temperature on aqueous solutions of poly(N-vinylcaprolactam) (PVCL) samples of molecular weights ranging from 21 000 to 1.5 × 106 g mol-1 was monitored by dynamic light scattering (DLS), high-sensitivity microcalorimetry (HS DSC), and pressure perturbation calorimetry (PPC) from 10 to 80 °C. The polymer was soluble in cold water and underwent phase separation at TCP ∼ 31−38 °C, depending on the molecular weight. The phase transition was endothermic, with an enthalpy change of 4.4 ± 0.4 kJ mol-1. Stable particles of average diameters 80 nm (high molecular weight PVCL) and ∼ 180 nm (low molecular weight PVCL) formed above the phase transition temperature. The coefficient of thermal expansion of PVCL in water (αpol), determined by PPC, underwent a sharp decrease at the temperature corresponding to the onset of phase transition, then it passed through a maximum, and decreased continuously with increasing temperature. The stability of the particles formed in PVCL solutions kept at temperatures exceeding TCP suggests that their surfaces possess a hydrophilic character. Results of microcalorimetric measurements carried out with solutions of PVCL in D2O add further strength to this conclusion. The thermodynamic and volumetric changes associated with the phase transition of aqueous PVCL solutions are compared to those of aqueous solutions of poly(N-isopropylacrylamide) (PNIPAM), a polymer that also undergoes a phase transition in water at ∼ 31 °C, and of poly(vinylpyrrolidone) (PVP), a polymer structurally related to PVCL, which is soluble in water at all the temperatures investigated here.},
  creationdate = {2024-05-03T10:51:04},
  doi          = {10.1021/ma035124l},
  eprint       = {https://doi.org/10.1021/ma035124l},
  file         = {:Laukkanen2004 - Formation of Colloidally Stable Phase Separated Poly(N Vinylcaprolactam) in Water_ a Study by Dynamic Light Scattering, Microcalorimetry, and Pressure Perturbation Calorimetry.pdf:PDF},
  keywords     = {PVCL, aggregation kinetics, DSC, DLS, pressure perturbation calorimetry, microcalorimetry, pNIPAM, isotope effect},
  url          = {https://doi.org/10.1021/ma035124l},
}

@Article{Vasilevskaya2003,
  author       = {Vasilevskaya, Valentina V. and Khalatur, Pavel G. and Khokhlov, Alexei R.},
  journal      = {Macromolecules},
  title        = {Conformational Polymorphism of Amphiphilic Polymers in a Poor Solvent},
  year         = {2003},
  number       = {26},
  pages        = {10103--10111},
  volume       = {36},
  abstract     = {To simulate amphiphilic polymers, we introduce an extended hydrophobic/hydrophilic (HP) model which, in contrast to the standard “beads-on-a-string” HP model, incorporates the dualistic nature of monomer units, each consisting of hydrophobic (H) and hydrophilic (P) interaction sites. For this coarse-grained model, the hydrophobically driven conformational transitions are studied using extensive molecular dynamics simulations. We find that, depending on the interaction between H and P sites, a variety of thermodynamically stable anisometric chain morphologies are possible in a solvent selectively poor for H sites, including disklike structures, stretched strings of intramolecular micelles, and cylindrical-shaped conformations. These microstructures are formed due to intramolecular segregation of chemically different H and P groups. Under certain conditions, the chain size Rg as a function of solvent quality can behave in a nonmonotonic manner, showing an increase when the solvent becomes poorer for hydrophobic sites. For the range of the chain lengths N simulated (N ≤ 1024), the formation of highly anisotropic conformations can lead to the Rg ∝ N0.9 scaling.},
  creationdate = {2024-05-03T11:04:29},
  doi          = {10.1021/ma0350563},
  eprint       = {https://doi.org/10.1021/ma0350563},
  file         = {:Vasilevskaya2003 - Conformational Polymorphism of Amphiphilic Polymers in a Poor Solvent.pdf:PDF},
  keywords     = {simulation, dangling chain, fuzzy globule, steric stabilization, buried groups},
  url          = {https://doi.org/10.1021/ma0350563},
}

@Article{Gil2004,
  author       = {Eun Seok Gil and Samuel M. Hudson},
  journal      = {Progress in Polymer Science},
  title        = {Stimuli-reponsive polymers and their bioconjugates},
  year         = {2004},
  issn         = {0079-6700},
  number       = {12},
  pages        = {1173--1222},
  volume       = {29},
  abstract     = {Stimuli responsive polymers can provide a variety of applications for the biomedical fields. The interest in these polymers has exponentially increased due to their promising potential. Among them, temperature and pH responsive mechanisms have been considerably investigated because they are relatively convenient and effective stimuli in many applications. In this review, our main purposes are focused on temperature and pH responsive polymer systems and additionally the other stimuli-based responsive polymers will be assessed. Dozens of reviews have been recently reported to introduce the field of stimuli responsive polymers. However, most of these reviews have been focused on one specific application such as drug delivery or one specific physical form such as hydrogels. In our point of view, the whole range of applications and physical forms of stimuli responsive polymers will be elucidated, which is more helpful to design new approaches because the basic concepts and mechanisms are systematically connected. This means that any new advanced concepts and mechanisms can be utilized in a variety of other applications as well as other physical forms. Also, we will describe the classification of stimuli responsive polymers by their mechanism of response to stimuli. Moreover, this review focuses on recent approaches of molecular designs which are extremely necessary to develop more desirable and functional stimuli responsive polymers.},
  creationdate = {2024-05-03T11:55:29},
  doi          = {https://doi.org/10.1016/j.progpolymsci.2004.08.003},
  file         = {:Gil2004 - Stimuli Reponsive Polymers and Their Bioconjugates.pdf:PDF},
  keywords     = {Stimuli responsive, Temperature responsive, pH responsive, Smart polymer, Intelligent polymer, Hydrogels, Micelles, Bioconjugates, Drug delivery, Poly(-isopropylacrylamide), PNIPAAm, pNIPAM, pNIPAM-alternatives, PEO, PPO, Block copolymer, LCST, Polyacids, Polybases, review, PEG},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079670004000826},
}

@Article{Ringsdorf1992,
  author       = {Ringsdorf, H. and Simon, J. and Winnik, F. M.},
  journal      = {Macromolecules},
  title        = {Hydrophobically-modified poly(N-isopropylacrylamides) in water: probing of the microdomain composition by nonradiative energy transfer},
  year         = {1992},
  number       = {20},
  pages        = {5353--5361},
  volume       = {25},
  creationdate = {2024-05-03T13:01:03},
  doi          = {10.1021/ma00046a038},
  eprint       = {https://doi.org/10.1021/ma00046a038},
  file         = {:Ringsdorf1992 - Hydrophobically Modified Poly(N Isopropylacrylamides) in Water_ Probing of the Microdomain Composition by Nonradiative Energy Transfer.pdf:PDF},
  keywords     = {fluorescence, NRET, pNIPAM},
  url          = {https://doi.org/10.1021/ma00046a038},
}

@Article{Ringsdorf1992a,
  author       = {Ringsdorf, H. and Simon, J. and Winnik, F. M.},
  journal      = {Macromolecules},
  title        = {Hydrophobically modified poly(N-isopropylacrylamides) in water: a look by fluorescence techniques at the heat-induced phase transition},
  year         = {1992},
  number       = {26},
  pages        = {7306--7312},
  volume       = {25},
  creationdate = {2024-05-03T13:02:42},
  doi          = {10.1021/ma00052a036},
  eprint       = {https://doi.org/10.1021/ma00052a036},
  file         = {:Ringsdorf1992a - Hydrophobically Modified Poly(N Isopropylacrylamides) in Water_ a Look by Fluorescence Techniques at the Heat Induced Phase Transition.pdf:PDF},
  keywords     = {pNIPAM, fluorescence},
  url          = {https://doi.org/10.1021/ma00052a036},
}

@Article{Ying1987,
  author       = {Ying, Qicong. and Chu, Benjamin.},
  journal      = {Macromolecules},
  title        = {Overlap concentration of macromolecules in solution},
  year         = {1987},
  number       = {2},
  pages        = {362--366},
  volume       = {20},
  creationdate = {2024-05-06T08:20:45},
  doi          = {10.1021/ma00168a023},
  eprint       = {https://doi.org/10.1021/ma00168a023},
  file         = {:Ying1987 - Overlap Concentration of Macromolecules in Solution.pdf:PDF},
  keywords     = {overlap concentration},
  url          = {https://doi.org/10.1021/ma00168a023},
}

@Article{Daoud1975,
  author       = {Daoud, M. and Cotton, J. P. and Farnoux, B. and Jannink, G. and Sarma, G. and Benoit, H. and Duplessix, C. and Picot, C. and de Gennes, P. G.},
  journal      = {Macromolecules},
  title        = {Solutions of Flexible Polymers. Neutron Experiments and Interpretation},
  year         = {1975},
  number       = {6},
  pages        = {804--818},
  volume       = {8},
  creationdate = {2024-05-06T08:43:20},
  doi          = {10.1021/ma60048a024},
  eprint       = {https://doi.org/10.1021/ma60048a024},
  file         = {:Daoud1975 - Solutions of Flexible Polymers. Neutron Experiments and Interpretation.pdf:PDF},
  keywords     = {overlap concentration, semi-dilute, dilute},
  url          = {https://doi.org/10.1021/ma60048a024},
}

@Article{Kremer1986,
  author       = {Kurt Kremer},
  journal      = {J. Phys. France},
  title        = {Glassy states of adsorbed flexible polymers and spread polymer "monolayers"},
  year         = {1986},
  number       = {8},
  pages        = {1269--1271},
  volume       = {47},
  creationdate = {2024-05-06T11:03:20},
  doi          = {10.1051/jphys:019860047080126900},
  file         = {:Kremer1986 - Glassy States of Adsorbed Flexible Polymers and Spread Polymer _monolayers_.pdf:PDF},
  keywords     = {adsorbed polymer, vitrification},
  url          = {https://doi.org/10.1051/jphys:019860047080126900},
}

@Article{Kuznetsov1996,
  author       = {Kuznetsov, Yu. A. and Timoshenko, E. G. and Dawson, K. A.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Kinetic laws at the collapse transition of a homopolymer}},
  year         = {1996},
  issn         = {0021-9606},
  month        = mar,
  number       = {9},
  pages        = {3338--3347},
  volume       = {104},
  abstract     = {{We present results from numerical analysis of the equations derived in the Gaussian self‐consistent method for kinetics at the collapse transition of a homopolymer in dilute solution. The kinetic laws are obtained with and without hydrodynamics for different quench depths and viscosities of the solvent. Some of our earlier analytical estimates are confirmed, and new ones generated. Thus the first kinetic stage for small quenches is described by a power law decrease in time of the squared radius of gyration with the universal exponent αi=9/11 (7/11) with (without) hydrodynamics. We find the scaling laws of the characteristic time of the coarsening stage, τm∼Nγm, and the final relaxation time, τf∼Nγf, as a function of the degree of polymerization N. These exponents are equal to γm=3/2, γf=1 in the regime of strong hydrodynamic interaction, and γm=2, γf=5/3 without hydrodynamics. We regard this paper as the completion of our work on the collapse kinetics of a bead and spring model of a homopolymer, but discuss the possibility of studying more complex systems.}},
  creationdate = {2024-05-06T11:16:32},
  doi          = {10.1063/1.471096},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/104/9/3338/19220086/3338\_1\_online.pdf},
  file         = {:Kuznetsov1996 - Kinetic Laws at the Collapse Transition of a Homopolymer.pdf:PDF},
  keywords     = {kinetics, aggregation, scaling, theory, calculation},
  url          = {https://doi.org/10.1063/1.471096},
}

@Article{Schoenhoff2002,
  author       = {Schönhoff, Monika and Larsson, Anders and Welzel, Petra B. and Kuckling, Dirk},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Thermoreversible Polymers Adsorbed to Colloidal Silica:  A 1H NMR and DSC Study of the Phase Transition in Confined Geometry},
  year         = {2002},
  number       = {32},
  pages        = {7800--7808},
  volume       = {106},
  abstract     = {The phase transition of the thermoreversible polymer PNIPAM, which shows a coil-to-globule transition due to the lower critical solution temperature (LCST) behavior in aqueous solution, is investigated in the restricted geometry of an adsorption layer. Furthermore, a charged copolymer is studied to investigate the influence of charges on the phase transition. Both polymers are adsorbed to colloidal silica and studied by 1H NMR and differential scanning calorimetric (DSC) experiments. In solid state 1H NMR relaxation experiments the signals of solid spins in trains and of liquid spins in tails and loops can be identified. 1H liquid state spectra detect the phase transition of the loops and tails into immobile segments with increasing temperature. The transition is broadened as compared to the polymer in solution, especially at low surface coverage. For the copolymer, the transition is incomplete, since mobile segments remain even at high temperature. They are attributed to electrostatic repulsion from the surface, leading to a mobile arrangement of the copolymer layer. Micro-DSC experiments confirm the finding of an increased width of the transition at the interface, which depends on the surface coverage. Furthermore, an increase of the transition temperature with decreasing polymer amount is observed, which is most pronounced for the copolymer, and is a further indication of an electrostatically hindered phase transition. In conclusion, despite a negligible influence of a low fraction of charges on the phase transition in solution, the phase transition in adsorption layers is very sensitive to charged segments. Combining NMR and DSC methods, local information on the transition behavior of different polymer segments at the interface, such as loops and tails, or charged monomers, can be obtained.},
  creationdate = {2024-05-06T11:32:49},
  doi          = {10.1021/jp015538l},
  eprint       = {https://doi.org/10.1021/jp015538l},
  file         = {:ThermoreversiblePolymersAdsorbedToColloidalSilica-A1HNMRAndDSCStudyOfThePhaseTransitionInConfinedGeometry_SchoenhoffEtAl_JPC2002.pdf:PDF},
  keywords     = {adsorbed layer, pNIPAM, thermoresponsive, 1H-NMR, DSC, copolymer, silica particles, high resolution, chemical shift},
  url          = {https://doi.org/10.1021/jp015538l},
}

@Article{Niebuur2018,
  author       = {Niebuur, Bart-Jan and Chiappisi, Leonardo and Zhang, Xiaohan and Jung, Florian and Schulte, Alfons and Papadakis, Christine M.},
  journal      = {ACS Macro Letters},
  title        = {Formation and Growth of Mesoglobules in Aqueous Poly(N-isopropylacrylamide) Solutions Revealed with Kinetic Small-Angle Neutron Scattering and Fast Pressure Jumps},
  year         = {2018},
  note         = {PMID: 35651267},
  number       = {10},
  pages        = {1155--1160},
  volume       = {7},
  abstract     = {The phase transition from swollen chains to polymer mesoglobules of an aqueous solution of poly(N-isopropylacrylamide) is investigated with kinetic small-angle neutron scattering with 50 ms time resolution in conjunction with millisecond pressure jumps across the coexistence line. The time-resolved study evidenced three distinct regimes: fractal clusters form during the first second and transform into compact mesoglobules. During the following ∼20 s, these grow by diffusion-limited coalescence. The final step consists of a slow growth characterized by an energy barrier of several kBT. The method opens opportunities for kinetic structural studies of multicomponent systems over wide length and time scales and gives a structural picture spanning from the chain collapse to mesoscopic phase separation.},
  creationdate = {2024-05-06T15:52:43},
  doi          = {10.1021/acsmacrolett.8b00605},
  eprint       = {https://doi.org/10.1021/acsmacrolett.8b00605},
  file         = {:Niebuur2018 - Formation and Growth of Mesoglobules in Aqueous Poly(N Isopropylacrylamide) Solutions Revealed with Kinetic Small Angle Neutron Scattering and Fast Pressure Jumps.pdf:PDF;:FormationAndGrowthOfMesoglobulesInAqueousPolyNIsopropylacrylamideSolutionsRevealedWithKineticSmallAngleNeutronScatteringAndFastPressureJumps_NiebuurEtAl_ACSMacroLett2018_SI.pdf:PDF},
  keywords     = {pNIPAM, SANS, pressure, aggregation, kinetics},
  url          = {https://doi.org/10.1021/acsmacrolett.8b00605},
}

@Article{Andersson1998,
  author       = {Matz Andersson and Anders Axelsson and Guido Zacchi},
  journal      = {Journal of Controlled Release},
  title        = {Swelling kinetics of poly(N-isopropylacrylamide) gel},
  year         = {1998},
  issn         = {0168-3659},
  number       = {1},
  pages        = {273--281},
  volume       = {50},
  abstract     = {In many gel applications the swelling and shrinking kinetics are very important, e.g. in controlled/slow release, where the kinetics determine the rate of out-diffusion of the active component, and in gel extraction where the gel is swollen and shrunk several times. In this study swelling kinetics of poly(N-isopropylacrylamide) gel (NiPAAm gel) was determined by monitoring the swelling process using a stereo microscope and a video camera. The swelling of spherical gel bodies could conveniently be studied after a temperature change. The results obtained were treated according to the approach of Tanaka and Fillmore, in which the swelling and shrinking of a gel is described as a motion of the gel network according to the diffusion equation. This was shown to be valid when the temperature changes are kept below the critical point of the gel. However, the model fails to describe the shrinking process when passing from below to above the critical temperature. The collective diffusion coefficient (D), defined as the osmotic bulk modulus divided by the friction factor, was determined by fitting to the experimental data. D was found to increase with temperature according to the Wilke–Chang relation D=2.0·10−11 +7.6·10−17 ·T/μ. The results were used to simulate the swelling/shrinking process. The simulations show the importance of having sufficiently small gel bodies to achieve a short swelling time.},
  creationdate = {2024-05-06T20:07:00},
  doi          = {https://doi.org/10.1016/S0168-3659(97)00151-X},
  file         = {:Andersson1998 - Swelling Kinetics of Poly(N Isopropylacrylamide) Gel.pdf:PDF},
  keywords     = {Gels,Kinetics of swelling,-isopropylacrylamide,Simulation,pNIPAM},
  url          = {https://www.sciencedirect.com/science/article/pii/S016836599700151X},
}

@Article{Wahl2020,
  author       = {Markus Solberg Wahl and Ailo Aasen and Dag Roar Hjelme and Øivind Wilhelmsen},
  journal      = {Fluid Phase Equilibria},
  title        = {Ice formation and growth in supercooled water–alcohol mixtures: Theory and experiments with dual fiber sensors},
  year         = {2020},
  issn         = {0378-3812},
  pages        = {112741},
  volume       = {522},
  abstract     = {Increased knowledge on fluid-solid phase transitions is needed, both when they are undesired and can impair process operations, and when strict control is required in fields such as food technology, the pharmaceutical industry and cryogenic CO2 capture. We present experimental results and theoretical predictions for the solid-formation and melting temperatures of ice in four binary water–alcohol mixtures containing methanol, ethanol, 1-propanol and 1-butanol. A dual fiber sensor set-up with a fiber Bragg grating sensor and a thin-core interferometer is used to detect the solid-formation. The predictions of melting temperatures with the cubic plus association equation of state combined with an ice model are in good agreement with experiments, but deviations are observed at higher alcohol concentrations. The measured degree of supercooling displays a highly non-linear dependence on the alcohol concentration. A heterogeneous nucleation model is developed to predict the solid-formation temperatures of the binary alcohol–water mixtures. The predictions from this model are in reasonable agreement with the measurements, but follow a qualitatively different trend that results in systematic deviations. In particular, the predicted degree of supercooling is found to be an essentially colligative property that increases smoothly with alcohol concentration. Experimental results are also presented for the growth rate of ice crystals in water–ethanol mixtures. For pure water, the measured crystal growth rate is 10.2 cm/s at 16 K supercooling. This is in excellent agreement with previous results from the literature. The crystal growth rate observed in ethanol–water mixtures however, can be orders of magnitude lower, where a mixture with 2% mole fraction ethanol has a growth rate of 2 mm/s. Further work is required to explain the large reduction in crystal growth rate with increasing alcohol concentration and to reproduce the behavior of the solid-formation temperatures with heterogeneous nucleation theory.},
  creationdate = {2024-05-07T11:09:46},
  doi          = {https://doi.org/10.1016/j.fluid.2020.112741},
  file         = {:Wahl2020 - Ice Formation and Growth in Supercooled Water–alcohol Mixtures_ Theory and Experiments with Dual Fiber Sensors.pdf:PDF},
  keywords     = {Heterogeneous nucleation, Phase transitions, Multimode interference, Fiber-optic sensors},
  url          = {https://www.sciencedirect.com/science/article/pii/S0378381220302880},
}

@Book{Flick1999,
  editor       = {Ernst W. Flick},
  publisher    = {Noyes Data Corporation},
  title        = {Industrial Solvents Handbook},
  year         = {1999},
  edition      = {Fifth},
  isbn         = {0-8155-1413-1},
  creationdate = {2024-05-07T11:36:15},
  file         = {:Flick1999 - Industrial Solvents Handbook.pdf:PDF},
  keywords     = {aqueous alcohol, monohydric alcohol, phase diagram},
}

@Article{Heatley2007,
  author       = {Heatley, Frank},
  title        = {Polymers: Relaxation and Dynamics of Synthetic Polymers in Solution},
  year         = {2007},
  booktitle    = {eMagRes},
  creationdate = {2024-05-10T10:31:19},
  doi          = {https://doi.org/10.1002/9780470034590.emrstm0408},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/9780470034590.emrstm0408},
  file         = {:Heatley2007 - Polymers_ Relaxation and Dynamics of Synthetic Polymers in Solution.pdf:PDF},
  isbn         = {9780470034590},
  keywords     = {NMR,review,polymer dynamics,high-resolution NMR},
  publisher    = {John Wiley & Sons, Ltd},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/9780470034590.emrstm0408},
}

@Article{Patterson1978,
  author       = {Patterson, G. D. and Lindsey, C. P. and Alms, G. R.},
  journal      = {Macromolecules},
  title        = {Rayleigh-Brillouin Spectroscopy and Molecular Motion in Toluene Solutions of Polystyrene},
  year         = {1978},
  number       = {6},
  pages        = {1242--1244},
  volume       = {11},
  creationdate = {2024-05-10T10:39:49},
  doi          = {10.1021/ma60066a034},
  eprint       = {https://doi.org/10.1021/ma60066a034},
  file         = {:Patterson1978 - Rayleigh Brillouin Spectroscopy and Molecular Motion in Toluene Solutions of Polystyrene.pdf:PDF},
  keywords     = {Brillouin Spectroscopy,Depolarized Light Scattering,Polystyrene,PS,Toluol,Toluene,Reorientation,Microviscosiy,local viscosity,viscosity},
  url          = {https://doi.org/10.1021/ma60066a034},
}

@Article{Rosenstihl2015,
  author       = {M. Rosenstihl and K. Kämpf and F. Klameth and M. Sattig and M. Vogel},
  journal      = {Journal of Non-Crystalline Solids},
  title        = {Dynamics of interfacial water},
  year         = {2015},
  issn         = {0022-3093},
  note         = {7th IDMRCS: Relaxation in Complex Systems},
  pages        = {449--458},
  volume       = {407},
  abstract     = {We use molecular dynamics computer simulations and nuclear magnetic resonance experiments to investigate the dynamics of water at interfaces of molecular roughness and low mobility. We find that, when approaching such interfaces, the structural relaxation of water, i.e., the α process, slows down even when specific attractive interactions are absent. This prominent effect is accompanied by a smooth transition from Vogel to Arrhenius temperature dependence and by a growing importance of jump events. Consistently, at protein surfaces, deviations from Arrhenius behavior are weak when free water does not exist. Furthermore, in nanoporous silica, a dynamic crossover of liquid water occurs when a fraction of solid water forms near 225K and, hence, the liquid dynamics changes from bulk-like to interface-dominated. At sufficiently low temperatures, water exhibits a quasi-universal β process, which is characterized by an activation energy of Ea=0.5eV and involves anisotropic reorientation about large angles. As a consequence of its large amplitude, the faster β process destroys essentially all orientational correlation, rendering observation of a possible slower α process difficult in standard experiments. Nevertheless, we find indications for the existence of structural relaxation down to a glass transition of interfacial water near 185K. Hydrated proteins show a highly restricted backbone motion with an amplitude, which decreases upon cooling and vanishes at comparable temperatures, providing evidence for a high relevance of water rearrangements in the hydration shell for secondary protein relaxations.},
  creationdate = {2024-05-10T10:50:29},
  doi          = {https://doi.org/10.1016/j.jnoncrysol.2014.08.040},
  file         = {:Rosenstihl2015 - Dynamics of Interfacial Water.pdf:PDF},
  keywords     = {Confined water,Mesoporous silica,Hydrated proteins,Nuclear magnetic resonance,Molecular dynamics simulations,protein,hydration shell,NMR,spectral density},
  url          = {https://www.sciencedirect.com/science/article/pii/S0022309314004256},
}

@Article{Vogel2010,
  author       = {Michael Vogel},
  journal      = {Eur. Phys. J. Spec. Top.},
  title        = {NMR studies on simple liquids in confinement},
  year         = {2010},
  pages        = {47--64},
  volume       = {189},
  creationdate = {2024-05-10T10:55:03},
  doi          = {10.1140/epjst/e2010-01309-9},
  file         = {:Vogel2010 - NMR Studies on Simple Liquids in Confinement.pdf:PDF},
  keywords     = {review,NMR,hydration shell},
}

@Article{Ma2021,
  author       = {Biao Ma and Li Wang and Li Han and Wensheng Cai and Xueguang Shao},
  journal      = {Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy},
  title        = {Understanding the effect of urea on the phase transition of poly(N-isopropylacrylamide) in aqueous solution by temperature-dependent near-infrared spectroscopy},
  year         = {2021},
  issn         = {1386-1425},
  pages        = {119573},
  volume       = {253},
  abstract     = {Regulating the folding state by denaturants is essential for the structure and function of proteins. Poly(N-isopropyl acrylamide) (PNIPAM) is usually regarded as a model for protein denaturation. The effects of urea, as a denaturant, on the aggregations of PNIPAM was studied by temperature-dependent near-infrared (NIR) spectroscopy, and particularly the variation of water structures was analyzed. The NIR spectra of the polymer-urea solutions containing different polymer concentrations were measured at different temperatures. N-way principal component analysis (NPCA) was performed to observe the spectral information. Three principal components (PCs) containing the spectral information of CH groups were obtained, showing three kinds of CH in the system. Obvious dehydration of the three CH groups occurs at 27.5 °C in solution, but the temperature turns to 27 °C for two kinds of the CH and 26.5 °C for the third one, respectively, in the urea-add solution. The effect of urea on the formation of the intramolecular hydrogen bonds that promotes polymer folding is suggested. The spectral information of NH in urea molecule indicates that the direct interaction of urea and polymer facilitates the stability of the polymer globule state. Furthermore, the spectral information of OH shows that the release of the water molecules with three hydrogen bonds (S3), which may connect the NH and CO groups in PNIPAM in solution, leads to the phase transition. When urea is added, urea may reduce the content of the S3 water to facilitate the release, making the phase transition at a low temperature.},
  creationdate = {2024-05-10T11:26:25},
  doi          = {https://doi.org/10.1016/j.saa.2021.119573},
  file         = {:Ma2021 - Understanding the Effect of Urea on the Phase Transition of Poly(N Isopropylacrylamide) in Aqueous Solution by Temperature Dependent near Infrared Spectroscopy.pdf:PDF},
  keywords     = {Near-infrared spectroscopy, Phase transition, Polymer, Protein denaturation, Water structure, N-way principal component analysis},
  url          = {https://www.sciencedirect.com/science/article/pii/S1386142521001499},
}

@Article{Lian2015,
  author       = {Lian, Cuixia and Zhang, Enzhong and Wang, Tao and Sun, Weixiang and Liu, Xinxing and Tong, Zhen},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Binding Interaction and Gelation in Aqueous Mixtures of Poly(N-isopropylacrylamide) and Hectorite Clay},
  year         = {2015},
  note         = {PMID: 25516283},
  number       = {2},
  pages        = {612--619},
  volume       = {119},
  abstract     = {The binding interaction between poly(N-isopropylacrylamide) (PNIPAm) chains and hectorite clay platelets was directly detected by quartz crystal microbalance with dissipation (QCM-D) to explore the cross-linking mechanism in the strong nanocomposite hydrogel (NC gel), which is in situ polymerized with NIPAm in the clay suspension. PNIPAm chains were allowed to be adsorbed on the gold surface of the QCM electrode. A large frequency shift Δf in the QCM as introducing the clay indicated that a large amount of clay platelets were adsorbed on the deposited PNIPAm layer. The relationship between the dissipation shift ΔD and Δf revealed that the adsorption included two steps of fast initial buildup and following densification of the clay platelets. In dilute aqueous mixtures, the PNIPAm chain and clay formed aggregates as observed from the hydrodynamic diameter. A gelation state diagram was established for concentrated aqueous PNIPAm–clay mixtures. The Raman spectrum pointed out the conformation change of the PNIPAm chains in aqueous solutions when the clay was added, which would be caused by the adsorption of PNIPAm chains to the clay platelets.},
  creationdate = {2024-05-10T11:53:39},
  doi          = {10.1021/jp510526j},
  eprint       = {https://doi.org/10.1021/jp510526j},
  file         = {:Lian2015 - Binding Interaction and Gelation in Aqueous Mixtures of Poly(N Isopropylacrylamide) and Hectorite Clay.pdf:PDF},
  keywords     = {pNIPAM,Hectorite,QCMB},
  url          = {https://doi.org/10.1021/jp510526j},
}

@Article{Hou2015,
  author       = {Hou, Lei and Wu, Peiyi},
  journal      = {Soft Matter},
  title        = {Understanding the UCST-type transition of P(AAm-co-AN) in H2O and D2O: dramatic effects of solvent isotopes},
  year         = {2015},
  pages        = {7059--7065},
  volume       = {11},
  abstract     = {The UCST-type transition of poly(acrylamide-co-acrylonitrile) (P(AAm-co-AN)) (molar fraction of AN: 13.3%; PDI = 3.2) in H2O and D2O is explored and compared by applying turbidity{,} DLS as well as FTIR measurements. The transition temperature of P(AAm-co-AN) in D2O is observed to be almost 10 °C higher than that in H2O at the same concentration{,} demonstrating a dramatic solvent isotope effect. Such a phenomenon could be rooted from a stronger interaction among polymer chains in D2O than in H2O{,} as indicated from DLS results. It is also observed in second-derivative analysis of FTIR spectra in the ν(CO) region{,} where all CO groups participate in the formation of inter-/intra-chain hydrogen bonds (CO⋯H–N) in D2O while there is still part of relatively “free” CO groups in H2O. Moreover{,} we find in the temperature-dependent FTIR spectra that CN groups exhibit hydrating behavior while CO groups present increased inter-/intra-molecular hydrogen bonding interaction (CO⋯H–N) upon cooling{,} revealing the later process to be the driving force of the UCST-type transition.},
  creationdate = {2024-05-10T12:54:04},
  doi          = {10.1039/C5SM01745A},
  file         = {:Hou2015 - Understanding the UCST Type Transition of P(AAm Co AN) in H2O and D2O_ Dramatic Effects of Solvent Isotopes.pdf:PDF},
  issue        = {35},
  keywords     = {isotope effect,h2o,d2o,turbidimetry,DLS,FTIR,LCST,UCST,hydrogen bond},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C5SM01745A},
}

@Article{Shirota1999a,
  author       = {Hideaki Shirota and Kazuyuki Horie},
  journal      = {Chemical Physics},
  title        = {Deuterium isotope effect on swelling process in aqueous polymer gels},
  year         = {1999},
  issn         = {0301-0104},
  number       = {1},
  pages        = {115--121},
  volume       = {242},
  abstract     = {The deuterium isotope effects on the swelling process of typical aqueous polymer gels (poly(N-isopropylacrylamide) gel and polyacrylamide gel) have been investigated in this study. The swelling times of both the poly(N-isopropylacrylamide) gel and the polyacrylamide gel in heavy water are longer than those in water. The deuterium isotope effect in the swelling process of gels is mainly arising from the higher viscosity in heavy water than in water. The additional deuterium isotope effect on the diffusion coefficient related to the swelling process should be due to the larger microscopic friction arising from the stronger polymer–solvent interaction in heavier water than in water. We also discuss in this paper the deuterium isotope effects on the size of the aqueous gels in the equilibrium state. Interestingly, the size in the equilibrium state of poly(N-isopropylacrylamide) gel in heavy water is larger than that in water. In contrast to poly(N-isopropylacrylamide) gel, the size in the equilibrium state of polyacrylamide gel in heavy water is smaller than that in water.},
  creationdate = {2024-05-10T13:14:31},
  doi          = {https://doi.org/10.1016/S0301-0104(99)00008-7},
  file         = {:Shirota1999a - Deuterium Isotope Effect on Swelling Process in Aqueous Polymer Gels.pdf:PDF},
  keywords     = {pNIPAM,pAA,poly(acrylamide),hydrogel,isotope effect,microscopy},
  url          = {https://www.sciencedirect.com/science/article/pii/S0301010499000087},
}

@Article{Shirota2000,
  author       = {Shirota, Hideaki and Ohkawa, Kazuya and Kuwabara, Nozomi and Endo, Noriko and Horie, Kazuyuki},
  journal      = {Macromolecular Chemistry and Physics},
  title        = {Deuterium isotope effects on swelling-shrinking states of polymer gels in aqueous solutions:Fluorescence study},
  year         = {2000},
  number       = {16},
  pages        = {2210--2219},
  volume       = {201},
  abstract     = {We have investigated the deuterium isotope effects on the microenvironment of the swelling-shrinking state of typical aqueous polymer gels (poly(N-isopropylacrylamide) gel and polyacrylamide gel) in aqueous binary solutions (methanol/water and acetone/water) by using a fluorescence probe. For comparison, we have also investigated the microenvironment of the linear polymers in the binary mixtures by using a fluorescence probe. Interestingly, the deuterium isotope effects in the bulk changes of poly(N-isopropylacrylamide) gel and polyacrylamide gel in the low organic-solvent composition region show opposite behaviour to each other, but the deuterium isotope effects in the microenvironment changes of (poly(N-isopropylacrylamide) gel and polyacrylamide gel display similar characteristics.},
  creationdate = {2024-05-10T13:18:50},
  doi          = {https://doi.org/10.1002/1521-3935(20001101)201:16<2210::AID-MACP2210>3.0.CO;2-A},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/1521-3935%2820001101%29201%3A16%3C2210%3A%3AAID-MACP2210%3E3.0.CO%3B2-A},
  file         = {:Shirota2000 - Deuterium Isotope Effects on Swelling Shrinking States of Polymer Gels in Aqueous Solutions_Fluorescence Study.pdf:PDF},
  keywords     = {pNIPAM,pAA,poly(acrylamide),isotope effect,fluorescence,cononsolc,aqueous methanol,aqueous alcohol,aqueous acetone},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/1521-3935%2820001101%29201%3A16%3C2210%3A%3AAID-MACP2210%3E3.0.CO%3B2-A},
}

@Article{Munk2013,
  author       = {Tommy Munk and Stefania Baldursdottir and Sami Hietala and Thomas Rades and Markus Nuopponen and Katriina Kalliomäki and Heikki Tenhu and Jukka Rantanen and Clare J. Strachan},
  journal      = {Polymer},
  title        = {Investigation of the phase separation of PNIPAM using infrared spectroscopy together with multivariate data analysis},
  year         = {2013},
  issn         = {0032-3861},
  number       = {26},
  pages        = {6947--6953},
  volume       = {54},
  abstract     = {The use of vibrational spectroscopy to investigate complex structural changes in polymers yields chemically rich data, but interpretation can be challenging and subtle but meaningful spectral changes may be missed through visual inspection alone. Multivariate analysis is an efficient approach to gain an oversight of small but systematic spectral differences anywhere within the spectra, providing further insight into structural changes and associated transformation mechanisms. In this study, the novel analytical approach of infrared spectroscopy combined with principal component analysis and Gaussian peak fitting was used to investigate the structural changes in aqueous solutions of a polymer, using poly(N-isopropyl acrylamide) (PNIPAM) in the atactic form and with controlled tacticity as a model system. Subtle spectral changes associated with the dehydration and phase separation upon heating included peak shifts, an area ratio change of the amide I band to the amide II band and formation of a new peak in the amide I band were efficiently detected. Dehydration and phase separation of PNIPAM occurred in two temperature ranges, one for the atactic and one for isotactic rich part, both involving a complex re-organization of the hydrogen bonds and change of the hydration layer. The changes agreed with existing results from other techniques, and new insights were gained into the effect of controlled tacticity on phase transformation behaviour. The study demonstrates that infrared spectroscopy combined with the multivariate analytical method principal component analysis and Gaussian peak fitting is an efficient approach to probing structural change in polymers during heating. The simplicity of the presented approach could find excellent use in analysing and understanding the molecular environment of a range of stimuli-responsive polymers, for instance block or grafted types of polymers, as well as those with controlled tacticity.},
  creationdate = {2024-05-10T13:27:25},
  doi          = {https://doi.org/10.1016/j.polymer.2013.10.033},
  file         = {:Munk2013 - Investigation of the Phase Separation of PNIPAM Using Infrared Spectroscopy Together with Multivariate Data Analysis.pdf:PDF},
  keywords     = {Phase separation,Infrared spectroscopy,Multivariate analysis,IR,pNIPAM,tacticity,hydrogen bonds,principal component analysis},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386113009877},
}

@Article{Chua2012,
  author       = {Chua, Pei Cheng and Kelland, Malcolm A. and Ishitake, Kenji and Satoh, Kotaro and Kamigaito, Masami and Okamoto, Yoshio},
  journal      = {Energy \& Fuels},
  title        = {Kinetic Hydrate Inhibition of Poly(N-isopropylmethacrylamide)s with Different Tacticities},
  year         = {2012},
  number       = {6},
  pages        = {3577--3585},
  volume       = {26},
  abstract     = {Poly(N-isopropylmethacrylamide)s (PNIPMAMs) have become commercially available as kinetic hydrate inhibitors (KHIs). PNIPMAMs are usually made by standard radical polymerization, which does not allow control over the polymer tacticity. We have now synthesized PNIPMAMs using stereospecific radical polymerization giving a fairly high degree of tacticity control. In this paper we present results on the performance of different tacticities in KHI tests with synthetic natural gas in stirred autoclaves and on tetrahydrofuran (THF) structure II hydrate crystal growth. The molecular weights of these polymers are almost the same. From the results, we can conclude the effect of polymer tacticity on the KHI performance of PNIPMAMs is noticeable but not very significant. PNIPMAMs with a higher syndiotactic percentage performed slightly better than PNIPMAMs with a lower syndiotactic percentage. Both polymers also gave a similar effect on the morphology of the THF hydrate crystals, indicating some kind of crystal surface adsorption. The PNIPMAMs investigated have a fairly high syndiotactic percentage. In fact, we found that it was difficult to make PNIPMAMs with less than 45\% syndiotactic percentage, even using standard radical polymerization methods. This suggests that any method to make commercial NIPMAM-based polymer KHIs via radical polymerization will necessarily give polymers with a fairly high percentage of syndiotacticity.},
  creationdate = {2024-05-10T13:32:53},
  doi          = {10.1021/ef3006355},
  eprint       = {https://doi.org/10.1021/ef3006355},
  file         = {:Chua2012 - Kinetic Hydrate Inhibition of Poly(N Isopropylmethacrylamide)s with Different Tacticities.pdf:PDF},
  keywords     = {PNIPMAM,poly(N-isopropyl methacrylamide),tacticity,kinetic hydrate inhibition,THF,stereospecific radical polymerization},
  url          = {https://doi.org/10.1021/ef3006355},
}

@Article{Deshmukh2012a,
  author       = {Deshmukh, Sanket A. and Sankaranarayanan, Subramanian K. R. S. and Mancini, Derrick C.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Vibrational Spectra of Proximal Water in a Thermo-Sensitive Polymer Undergoing Conformational Transition Across the Lower Critical Solution Temperature},
  year         = {2012},
  note         = {PMID: 22490002},
  number       = {18},
  pages        = {5501--5515},
  volume       = {116},
  abstract     = {The vibrational spectrum of water near a thermo-sensitive polymer poly(N-isopropylacrylamide) (PNIPAM) undergoing conformational transition through the lower critical solution temperature (LCST) is calculated using molecular dynamics simulations. The characteristic structural features observed at the atomic scale for these proximal water molecules in a solvated polymer chain while undergoing the conformational transition are strongly correlated to their vibrational densities of states. Comparison of the vibrational spectrum below LCST for the proximal water with the vibrational spectrum obtained for bulk water reveals a significant fraction of the hydrogen bonding between the proximal water molecules and the polymer side groups. Hydrogen-bonded bridges of water molecules are formed between two adjacent and alternate monomers. This network of hydrogen bonding results in formation of locally ordered water molecules at temperatures below the LCST. Analysis of the simulation trajectories confirms the presence of a quasi-stable solvation structure near the PNIPAM. The calculated vibrational spectra for proximal water above the LCST suggest significantly reduced hydrogen bonding with the polymer and indicate a reduction in the structural stability of proximal water around a collapsed polymer chain. Systematic trends in the observed peak intensities and frequency shifts at the low- and high-frequency ends of the spectrum can be correlated with the structural and dynamical changes of water molecules below and above the LCST transition, respectively, for various polymer chain lengths. The simulations reveal that, compared to bulk water, the libration bands are blue shifted and OH stretch bands red shifted for water in proximity to PNIPAM with 30 monomer units below the LCST. The simulations suggest that vibrational spectra can be used as a predictive tool for quantifying atomic-scale structural transitions in solvation of thermo-sensitive polymers such as PNIPAM.},
  creationdate = {2024-05-10T13:36:40},
  doi          = {10.1021/jp211831x},
  eprint       = {https://doi.org/10.1021/jp211831x},
  file         = {:Deshmukh2012a - Vibrational Spectra of Proximal Water in a Thermo Sensitive Polymer Undergoing Conformational Transition across the Lower Critical Solution Temperature.pdf:PDF},
  keywords     = {pNIPAM,hydration water,molecular dynamics simulation,solvation shell},
  url          = {https://doi.org/10.1021/jp211831x},
}

@Article{Tamai1996,
  author       = {Tamai, Yoshinori and Tanaka, Hideki and Nakanishi, Koichiro},
  journal      = {Macromolecules},
  title        = {Molecular Dynamics Study of Polymer−Water Interaction in Hydrogels. 1. Hydrogen-Bond Structure},
  year         = {1996},
  number       = {21},
  pages        = {6750--6760},
  volume       = {29},
  abstract     = {Molecular dynamics simulations have been performed for hydrogel models of poly(vinyl alcohol) (PVA), poly(vinyl methyl ether) (PVME), and poly(N-isopropylacrylamide) (PNiPAM). The spatial distributions and stability of hydrogen bonds in the vicinity of polymer segments are analyzed to investigate the properties of water which is highly cooperative with the surrounding polymer chains. Water−water hydrogen bonds are enhanced around hydrophobic groups especially for PVME and PNiPAM by the hydrophobic hydration. Hydrogen bonds are also stabilized around hydrophilic groups for PVME and PNiPAM. The stabilization is accounted for by a severe constraint of the mutual orientation between water and polar group.},
  creationdate = {2024-05-10T15:48:03},
  doi          = {10.1021/ma951635z},
  eprint       = {https://doi.org/10.1021/ma951635z},
  file         = {:Tamai1996a - Molecular Dynamics Study of Polymer−Water Interaction in Hydrogels. 1. Hydrogen Bond Structure.pdf:PDF},
  keywords     = {molecular dynamics simulation,PNIPAM,PVA,PVME,hydrogen bonds,hydration shell,hydrophobic hydration},
  url          = {https://doi.org/10.1021/ma951635z},
}

@Article{Peterson2001,
  author       = {Peterson, Steven C. and Echeverría, Isabel and Hahn, Stephen F. and Strand, Deidre A. and Schrag, John L.},
  journal      = {Journal of Polymer Science Part B: Polymer Physics},
  title        = {Apparent relaxation-time spectrum cutoff in dilute polymer solutions: An effect of solvent dynamics},
  year         = {2001},
  number       = {22},
  pages        = {2860--2873},
  volume       = {39},
  abstract     = {The apparent short time cutoff of the relaxation-time spectrum at surprisingly long times for polymers in solution is a well known but not yet understood observation. To elucidate its origins we revisit viscoelastic and oscillatory flow birefringence data for solutions and melts of two linear polymers (polystyrene and polyisoprene) and present new measurements of oscillatory flow birefringence of the latter. Previous measurements have suggested that the “flexibility” of both polymers in solution is smaller than in the melt on the basis of the breadth of the relaxation-time spectrum of the solution as compared with that of the melt. Our new measurements have explored a higher effective frequency range than was previously possible. This has allowed us to observe the effect of the rotational relaxation time of the solvent on the dynamics of the solution at high frequencies. To obtain the polymer global motion contribution, one now needs to subtract from the solution properties a frequency-dependent complex solvating environment contribution. We show that the decrease in apparent “flexibility” for solutions arises from the presence of a solvent that exhibits a rotational relaxation time and thus simple viscoelastic behavior somewhat near the frequency window of the experiment. Although recent predictions of a model for a chain in a solvent with a single relaxation time are in qualitative agreement with our results, our data suggest that the solution results may reflect the influence of solvent on the development of the “entropic spring” forces at short times. © 2001 John Wiley \& Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2860–2873, 2001},
  creationdate = {2024-05-10T16:40:06},
  doi          = {https://doi.org/10.1002/polb.10005},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.10005},
  file         = {:Peterson2001 - Apparent Relaxation Time Spectrum Cutoff in Dilute Polymer Solutions_ an Effect of Solvent Dynamics.pdf:PDF},
  keywords     = {polymer solutions,relaxation,bead-spring model,relaxation-time spectrum,solvent dynamics,rheology,solution properties,diffusion,oscillatory flow birefringene,polystyrene,PS,polyisoprene},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.10005},
}

@Article{Frezzato2006,
  author       = {Frezzato, Diego and Rastrelli, Federico and Bagno, Alessandro},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Nuclear Spin Relaxation Driven by Intermolecular Dipolar Interactions:  The Role of Solute−Solvent Pair Correlations in the Modeling of Spectral Density Functions},
  year         = {2006},
  note         = {PMID: 16539513},
  number       = {11},
  pages        = {5676--5689},
  volume       = {110},
  abstract     = {Nuclear spin relaxation provides useful information related to the dynamics of molecular systems. When relaxation is driven by intermolecular dipolar interactions, the relevant spectral density functions (SDFs) also have significant contributions, in principle, from distant spins all over the dynamic range typically probed by NMR experiments such as NOESY. In this work, we investigate the intermolecular dipolar spin relaxation as driven by the relative diffusion of solvent and solute molecules taking place under a central force field, and we examine the relevant implications for (preferential) solvation studies. For this purpose, we evaluate the SDFs by employing a numerical approach based on spatial discretization of the time-propagation equation, and we supply an analytical solution for the simplest case of a steplike mean-field potential. Several situations related to different solute−solvent pair correlation functions are examined in terms of static/dynamic effects and relaxation modes, and some conclusions are drawn about the interpretation of NOE measurements. While we confirm previous results concerning the spoiling effect of long-range spins (Halle, B. J. Chem. Phys. 2003, 119, 12372), we also show that SDFs are sufficiently sensitive to pair correlation functions that useful, yet rather complicated, inferences can be made on the nature of the solvation shell.},
  creationdate = {2024-05-13T10:20:49},
  doi          = {10.1021/jp0560157},
  eprint       = {https://doi.org/10.1021/jp0560157},
  file         = {:Frezzato2006 - Nuclear Spin Relaxation Driven by Intermolecular Dipolar Interactions_ the Role of Solute−Solvent Pair Correlations in the Modeling of Spectral Density Functions.pdf:PDF;:NuclearSpinRelaxationDrivenByIntermolecularDipolarInteractions-TheRoleOfSoluteSolventPairCorrelationsInTheModelingOfSpectralDensityFunctions_FrezzatoEtAl_JPC2006_SI.pdf:PDF},
  keywords     = {nmr,theory,calculations,spectral density,relaxation,dipolar interaction},
  url          = {https://doi.org/10.1021/jp0560157},
}

@Book{Vyazovkin2015,
  author       = {Vyazovkin, Sergey},
  publisher    = {Springer},
  title        = {Isoconversional Kinetics of Thermally Stimulated Processes},
  year         = {2015},
  address      = {Cham},
  edition      = {1st ed. 2015},
  isbn         = {9783319141756},
  creationdate = {2024-05-13T10:43:22},
  doi          = {10.1007/978-3-319-14175-6},
  file         = {:Vyazovkin2015 - Isoconversional Kinetics of Thermally Stimulated Processes.pdf:PDF},
  hdsurl       = {https://hds.hebis.de/ulbda/Record/HEB358010500},
  keywords     = {DSC,book,isoconversional kinetics,thermoresponsive},
  uniqueid     = {HEB358010500},
  url          = {https://doi.org/10.1007/978-3-319-14175-6},
}

@Article{Kim2020a,
  author       = {Kim, Young-Gon and Thérien-Aubin, Héloïse},
  journal      = {Macromolecules},
  title        = {Impact of the Solvent Quality on the Local Dynamics of Soft and Swollen Polymer Nanoparticles Functionalized with Polymer Chains},
  year         = {2020},
  note         = {PMID: 32921813},
  number       = {17},
  pages        = {7561--7569},
  volume       = {53},
  abstract     = {Grafting polymer chains on the surface of nanoparticles (NPs) is a strategy used to control the interaction between the NPs and their environment. The fate of the resulting particles in a given environment is strongly influenced by the solvent–polymer interaction. The solvent quality affects the behavior, conformation, and dynamics of the grafted polymer chains. However, when this polymer grafting strategy is used to functionalized polymer particles, the influence of solvent quality becomes even more complex; when the grafted polymer chains and the polymer nanoparticles are tethered together, the effect of the solvent quality on the behavior and dynamics of the system depends on the solvent interaction with both polymer components. To explore the relationship between the solvent quality and the dynamics of polymer-functionalized soft polymer NPs, we designed a system based on cross-linked polystyrene (PS) NPs grafted with a canopy of poly(methyl acrylate) (PMA). PS and PMA, two immiscible polymers, can be selectively solvated by using binary mixtures of solvents. NMR spectroscopy was used to address the effect of those selective solvents on the local mobility of the PS–PMA core-canopy NPs and revealed an interplay between the local mobility of the core and the local mobility of the canopy. A selective reduction of the solvent quality for the PMA canopy resulted in the expected reduction of the local mobility of the PMA chains, but also in the slower dynamics of the PS core. Similarly, a selective reduction of the solvent quality for the PS core resulted in a slower dynamics for both the PS core and the PMA canopy.},
  creationdate = {2024-05-13T10:53:44},
  doi          = {10.1021/acs.macromol.0c00346},
  eprint       = {https://doi.org/10.1021/acs.macromol.0c00346},
  file         = {:Kim2020a - Impact of the Solvent Quality on the Local Dynamics of Soft and Swollen Polymer Nanoparticles Functionalized with Polymer Chains.pdf:PDF;:ImpactOfTheSolventQualityOnTheLocalDynamicsOfSoftAndSwollenPolymerNanoparticlesFunctionalizedWithPolymerChains_KimEtAl_Macromol2020_SI.pdf:PDF},
  keywords     = {NMR,nanoparticle,brush,grafting,polystyrene,PS,poly(methyl acrylate),PMA,cosolvent,Hansen solubility,copolymer},
  url          = {https://doi.org/10.1021/acs.macromol.0c00346},
}

@Article{Milner1991,
  author       = {Milner, S. T.},
  journal      = {Phys. Rev. Lett.},
  title        = {Hydrodynamics of semidilute polymer solutions},
  year         = {1991},
  month        = mar,
  pages        = {1477--1480},
  volume       = {66},
  creationdate = {2024-05-13T11:15:09},
  doi          = {10.1103/PhysRevLett.66.1477},
  file         = {:Milner1991 - Hydrodynamics of Semidilute Polymer Solutions.pdf:PDF},
  issue        = {11},
  keywords     = {theory,hydrodynamics,entanglements,semidilute},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.66.1477},
}

@Article{Dachwitz1990,
  author       = {E. Dachwitz},
  journal      = {Zeitschrift für Naturforschung A},
  title        = {Studies of Polymer Solvation by Dielectric Relaxation Spectroscopy III: Polyvinyl Pyrrolidone in N-Methyl-2-Pyrrolidone, Ethanediol, Methanol, and Water},
  year         = {1990},
  number       = {2},
  pages        = {126--134},
  volume       = {45},
  abstract     = {The permittivity of the title solutions has been measured at frequencies between some MHz and 72 GHz at 20 °C. Polyvinyl pyrrolidone of relative molar mass ranging from 1200 to 360000 has been used. Referring to the concentration of monomeric repeat units (x = 0.65 maximum) there is no significant chain length effect. The permittivity data are described in terms of discrete Debye type spectral components. Special attention is paid to the contributions ascribable to the solvents, which are discussed with respect to their solvation behaviour. This can  be described by a three state solvent model as follows. Besides the "bulk" solvent a further contribution is found in any case which is due to loosely affected (slowed down) solvent. Moreover a part of the solvent appears to be tightly bound to the polymer at high concentrations. All the solvents considered show similar solvation properties, notwithstanding their different tendencies towards selfassociation.},
  creationdate = {2024-05-13T11:25:33},
  doi          = {doi:10.1515/zna-1990-0207},
  file         = {:Dachwitz1990 - Studies of Polymer Solvation by Dielectric Relaxation Spectroscopy III_ Polyvinyl Pyrrolidone in N Methyl 2 Pyrrolidone, Ethanediol, Methanol, and Water.pdf:PDF},
  keywords     = {BDS,solvent relaxation,polyvinyl pyrrolidone,concentration-dependent,ethanol,aqueous solution,methanol,PVP,poly(vinyl pyrrolidone)},
  lastchecked  = {2024-05-13},
  url          = {https://doi.org/10.1515/zna-1990-0207},
}

@Article{Nandi2000,
  author       = {Nandi, Nilashis and Bhattacharyya, Kankan and Bagchi, Biman},
  journal      = {Chemical Reviews},
  title        = {Dielectric Relaxation and Solvation Dynamics of Water in Complex Chemical and Biological Systems},
  year         = {2000},
  note         = {PMID: 11749282},
  number       = {6},
  pages        = {2013--2046},
  volume       = {100},
  creationdate = {2024-05-13T11:53:21},
  doi          = {10.1021/cr980127v},
  eprint       = {https://doi.org/10.1021/cr980127v},
  file         = {:Nandi2000 - Dielectric Relaxation and Solvation Dynamics of Water in Complex Chemical and Biological Systems.pdf:PDF},
  keywords     = {review,hydration shell,BDS,protein,hydrogel},
  url          = {https://doi.org/10.1021/cr980127v},
}

@Article{Cerveny2005,
  author       = {Cerveny, S. and Colmenero, J. and Alegría, A.},
  journal      = {Macromolecules},
  title        = {Dielectric Investigation of the Low-Temperature Water Dynamics in the Poly(vinyl methyl ether)/H2O System},
  year         = {2005},
  number       = {16},
  pages        = {7056--7063},
  volume       = {38},
  abstract     = {Broadband dielectric spectroscopy (10-1−106 Hz) and differential scanning calorimetry measurements have been performed to study the molecular dynamics of water solutions of poly(vinyl methyl ether) (PVME) in the concentration region up to 50 wt \% and in the temperature range from 150 to 250 K in order to investigate the low-temperature water dynamics in this system. A symmetric spectrum due to reorientation of water molecules inside the rigid polymer matrix was observed for all hydration levels. However, the dielectric relaxation results evidence that different “water types” can be distinguished depending on the hydration level. For moderate water content (ca. below 30 wt \%) the water molecules have both orientational and translational restrictions. For high water contents the excess water is able to fully reorientate at low temperatures and to crystallize above 230 K. Furthermore, our dielectric results support the idea that water molecules are not uniformly distributed among the monomeric units of PVME.},
  creationdate = {2024-05-13T13:14:25},
  doi          = {10.1021/ma050811t},
  eprint       = {https://doi.org/10.1021/ma050811t},
  file         = {:Cerveny2005 - Dielectric Investigation of the Low Temperature Water Dynamics in the Poly(vinyl Methyl Ether)_H2O System.pdf:PDF},
  keywords     = {PVME,DSC,BDS,hydration shell,spectral density},
  url          = {https://doi.org/10.1021/ma050811t},
}

@Article{Sasaki2020,
  author       = {Sasaki, Kaito and Bandai, Kenta and Takatsuka, Masanobu and Fujii, Mitsuki and Takagi, Minato and Kita, Rio and Yagihara, Shin and Kimura, Hiroshi and Shinyashiki, Naoki},
  journal      = {Frontiers in Physics},
  title        = {Heterogeneous Solvent Dielectric Relaxation in Polymer Solutions of Water and Alcohols},
  year         = {2020},
  issn         = {2296-424X},
  volume       = {8},
  abstract     = {The dynamics of polymer solutions are heterogeneous. The different molecule sizes and structures cause different mobilities of polymers and solvents. Recently, regarding the heterogeneity of water, two dielectric relaxation processes of water were argued in several supercooled polymer–water mixtures. To investigate whether this is unique to water, we performed broadband dielectric spectroscopy measurements of poly(vinylpyrrolidone)–water (PVP–water), PVP–propylene glycol, PVP–ethylene glycol, and PVP–propanol mixtures with 65 wt% PVP in a temperature range of 123–298 K. For the PVP–water mixture, α-relaxation of PVP and two distinct relaxation processes appeared simultaneously: one was the primary relaxation process of water (fast water process) and the other was the relatively small relaxation process (slow process), at a frequency between that of the α-process of PVP and the fast water process. The strength ratio of the large fast water and small slow processes remained nearly constant in all the temperatures measured. For the PVP–alcohol mixtures, in addition to the α-process of PVP, two or three relaxation processes of alcohol appeared. The primary relaxation process of alcohol above 240 K changed to the small fast secondary process. The small slow processes, which can be recognized below 240 K (the glass transition temperature of the α-process of PVP, T<sub>g,PVP</sub>) appears at intermediate frequency between that of the PVP α-process and the primary process of alcohol. The small slow process changed to the primary larger process. The properties of the multiple relaxation processes of solvents below T<sub>g,PVP</sub> in PVP–alcohol mixtures are completely different from those in PVP–water mixture.},
  creationdate = {2024-05-13T13:26:50},
  doi          = {10.3389/fphy.2020.00084},
  file         = {:Sasaki2020 - Heterogeneous Solvent Dielectric Relaxation in Polymer Solutions of Water and Alcohols.pdf:PDF},
  keywords     = {BDS,solvent relaxation,PVP,poly(vinyl pirrolidone),glycol,ehtylene glycol,propanol,propylene glycol},
  url          = {https://www.frontiersin.org/articles/10.3389/fphy.2020.00084},
}

@Article{Capaccioli2019,
  author       = {Capaccioli, S. and Ngai, K. L. and Ancherbak, S. and Bertoldo, M. and Ciampalini, G. and Thayyil, M. Shahin and Wang, Li-Min},
  journal      = {The Journal of Chemical Physics},
  title        = {{The JG $\beta$-relaxation in water and impact on the dynamics of aqueous mixtures and hydrated biomolecules}},
  year         = {2019},
  issn         = {0021-9606},
  month        = jul,
  number       = {3},
  pages        = {034504},
  volume       = {151},
  abstract     = {{Although by now the glass transition temperature of uncrystallized bulk water is generally accepted to manifest at temperature Tg near 136 K, not much known are the spectral dispersion of the structural α-relaxation and the temperature dependence of its relaxation time τα,bulk(T). Whether bulk water has the supposedly ubiquitous Johari-Goldstein (JG) β-relaxation is a question that has not been answered. By studying the structural α-relaxation over a wide range of temperatures in several aqueous mixtures without crystallization and with glass transition temperatures Tg close to 136 K, we deduce the properties of the α-relaxation and the temperature dependence of τα,bulk(T) of bulk water. The frequency dispersion of the α-relaxation is narrow, indicating that it is weakly cooperative. A single Vogel-Fulcher-Tammann (VFT) temperature dependence can describe the data of τα,bulk(T) at low temperatures as well as at high temperatures from neutron scattering and GHz–THz dielectric relaxation, and hence, there is no fragile to strong transition. The Tg-scaled VFT temperature dependence of τα,bulk(T) has a small fragility index m less than 44, indicating that water is a “strong” glass-former. The existence of the JG β-relaxation in bulk water is supported by its equivalent relaxation observed in water confined in spaces with lengths of nanometer scale and having Arrhenius T-dependence of its relaxation times τconf(T). The equivalence is justified by the drastic reduction of cooperativity of the α-relaxation in nanoconfinement and rendering it to become the JG β-relaxation. Thus, the τconf(T) from experiments can be taken as τβ,bulk(T), the JG β-relaxation time of bulk water. The ratio τα,bulk(Tg)/τβ,bulk(Tg) is smaller than most glass-formers, and it corresponds to the Kohlrausch α-correlation function, exp[−(t/τα,bulk)1−n], having (1−n) = 0.90. The dielectric data of many aqueous mixtures and hydrated biomolecules with Tg higher than that of water show the presence of a secondary ν-relaxation from the water component. The ν-relaxation is strongly connected to the α-relaxation in properties, and hence, it belongs to the special class of secondary relaxations in glass-forming systems. Typically, its relaxation time τν(T) is longer than τβ,bulk(T), but τν(T) becomes about the same as τβ,bulk(T) at sufficiently high water content. However, τν(T) does not become shorter than τβ,bulk(T). Thus, τβ,bulk(T) is the lower bound of τν(T) for all aqueous mixtures and hydrated biomolecules. Moreover, it is τβ,bulk(T) but not τα(T) that is responsible for the dynamic transition of hydrated globular proteins.}},
  creationdate = {2024-05-13T13:32:50},
  doi          = {10.1063/1.5100835},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.5100835/13941752/034504\_1\_online.pdf},
  file         = {:Capaccioli2019 - The JG Β Relaxation in Water and Impact on the Dynamics of Aqueous Mixtures and Hydrated Biomolecules.pdf:PDF},
  keywords     = {glass former,johari-goldstein,beta process,hydration shell},
  url          = {https://doi.org/10.1063/1.5100835},
}

@Article{Panagopoulou2012,
  author       = {Panagopoulou, A. and Kyritsis, A. and Shinyashiki, N. and Pissis, P.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Protein and Water Dynamics in Bovine Serum Albumin–Water Mixtures over Wide Ranges of Composition},
  year         = {2012},
  note         = {PMID: 22469064},
  number       = {15},
  pages        = {4593--4602},
  volume       = {116},
  abstract     = {Dielectric dynamic behavior of bovine serum albumin (BSA)–water mixtures over wide ranges of water fractions, from dry protein until 40 wt \% in water, was studied through dielectric relaxation spectroscopy (DRS). The α relaxation associated with the glass transition of the hydrated system was identified. The evolution of the low temperature dielectric relaxation of small polar groups of the protein surface with hydration level results in the enhancement of dielectric response and the decrease of relaxation times, until a critical water fraction, which corresponds to the percolation threshold for protonic conductivity. For water fractions higher than the critical one, the position of the secondary ν relaxation of water saturates in the Arrhenius diagram, while contributions originating from water molecules in excess (uncrystallized water or ice) follow separate relaxation modes slower than the ν relaxation.},
  creationdate = {2024-05-13T13:45:45},
  doi          = {10.1021/jp2105727},
  eprint       = {https://doi.org/10.1021/jp2105727},
  file         = {:Panagopoulou2012 - Protein and Water Dynamics in Bovine Serum Albumin–Water Mixtures Over Wide Ranges of Composition.pdf:PDF},
  keywords     = {BDS,BSA,hydration shell,DSC},
  url          = {https://doi.org/10.1021/jp2105727},
}

@Article{Levy2006,
  author       = {Levy, Yaakov and Onuchic, José N.},
  journal      = {Annual Review of Biophysics},
  title        = {WATER MEDIATION IN PROTEIN FOLDING AND MOLECULAR RECOGNITION},
  year         = {2006},
  issn         = {1936-1238},
  number       = {Volume 35, 2006},
  pages        = {389--415},
  volume       = {35},
  abstract     = {Water is essential for life in many ways, and without it biomolecules might no longer truly be biomolecules. In particular, water is important to the structure, stability, dynamics, and function of biological macromolecules. In protein folding, water mediates the collapse of the chain and the search for the native topology through a funneled energy landscape. Water actively participates in molecular recognition by mediating the interactions between binding partners and contributes to either enthalpic or entropic stabilization. Accordingly, water must be included in recognition and structure prediction codes to capture specificity. Thus water should not be treated as an inert environment, but rather as an integral and active component of biomolecular systems, where it has both dynamic and structural roles. Focusing on water sheds light on the physics and function of biological machinery and self-assembly and may advance our understanding of the natural design of proteins and nucleic acids.},
  creationdate = {2024-05-13T14:06:13},
  doi          = {https://doi.org/10.1146/annurev.biophys.35.040405.102134},
  file         = {:Levy2006 - WATER MEDIATION iN PROTEIN FOLDING aND MOLECULAR RECOGNITION.pdf:PDF},
  keywords     = {energy landscape, protein-DNA interactions, solvent effect, folding funnel, protein association},
  publisher    = {Annual Reviews},
  type         = {Journal Article},
  url          = {https://www.annualreviews.org/content/journals/10.1146/annurev.biophys.35.040405.102134},
}

@Article{Kyritsis2012,
  author       = {Kyritsis, A. and Panagopoulou, A. and Pissis, P. and I. Serra, R. S. and Gomez Ribelles, J. L. and Shinyashiki, N.},
  journal      = {IEEE Transactions on Dielectrics and Electrical Insulation},
  title        = {Water and protein dynamics in protein-water mixtures over wide range of composition},
  year         = {2012},
  number       = {4},
  pages        = {1239--1246},
  volume       = {19},
  creationdate = {2024-05-13T14:38:38},
  doi          = {10.1109/TDEI.2012.6259997},
  file         = {:Kyritsis2012 - Water and Protein Dynamics in Protein Water Mixtures Over Wide Range of Composition.pdf:PDF},
  keywords     = {Proteins, Temperature measurement, BDS, Crystallization, Frequency measurement, Hydrated protein, hydration shell, uncrystallized water, glass transition, solvent relaxation},
}

@Article{Kahlau2014,
  author       = {Kahlau, R. and Bock, D. and Schmidtke, B. and Rössler, E. A.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Dynamics of asymmetric binary glass formers. I. A dielectric and nuclear magnetic resonance spectroscopy study}},
  year         = {2014},
  issn         = {0021-9606},
  month        = jan,
  number       = {4},
  pages        = {044509},
  volume       = {140},
  abstract     = {{Dielectric spectroscopy as well as 2H and 31P nuclear magnetic resonance spectroscopy (NMR) are applied to probe the component dynamics of the binary glass former tripropyl phosphate (TPP)/polystyrene (PS/PS-d3) in the full concentration (cTPP) range. In addition, depolarized light scattering and differential scanning calorimetry experiments are performed. Two glass transition temperatures are found: Tg1(cTPP) reflects PS dynamics and shows a monotonic plasticizer effect, while the lower Tg2(cTPP) exhibits a maximum and is attributed to (faster) TPP dynamics, occurring in a slowly moving or immobilized PS matrix. Dielectric spectroscopy probing solely TPP identifies two different time scales, which are attributed to two sub-ensembles. One of them, again, shows fast TPP dynamics (α2-process), the other (α1-process) displays time constants identical with those of the slow PS matrix. Upon heating the α1-fraction of TPP decreases until above some temperature Tc only a single α2-population exists. Inversely, below Tc a fraction of the TPP molecules is trapped by the PS matrix. At low cTPP the α2-relaxation does not follow frequency-temperature superposition (FTS), instead it is governed by a temperature independent distribution of activation energies leading to correlation times which follow Arrhenius laws, i.e., the α2-relaxation resembles a secondary process. Yet, 31P NMR demonstrates that it involves isotropic reorientations of TPP molecules within a slowly moving or rigid matrix of PS. At high cTPP the super-Arrhenius temperature dependence of τ2(T), as well as FTS are recovered, known as typical of the glass transition in neat systems.}},
  creationdate = {2024-05-13T16:29:53},
  doi          = {10.1063/1.4861428},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4861428/15474135/044509\_1\_online.pdf},
  file         = {:Kahlau2014 - Dynamics of Asymmetric Binary Glass Formers. I. a Dielectric and Nuclear Magnetic Resonance Spectroscopy Study.pdf:PDF},
  keywords     = {glass former,NMR,BDS,PS,tripropyl phosphate,2H-NMR,31P-NMR,DSC,Light scattering,Frequency-temperature superposition,FTS,Time-temperature superposition,TTS,polystyrene},
  url          = {https://doi.org/10.1063/1.4861428},
}

@Article{Sasaki2017,
  author       = {Sasaki, Kaito and Panagopoulou, Anna and Kita, Rio and Shinyashiki, Naoki and Yagihara, Shin and Kyritsis, Apostolos and Pissis, Polycarpos},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Dynamics of Uncrystallized Water, Ice, and Hydrated Protein in Partially Crystallized Gelatin–Water Mixtures Studied by Broadband Dielectric Spectroscopy},
  year         = {2017},
  note         = {PMID: 27966346},
  number       = {1},
  pages        = {265--272},
  volume       = {121},
  abstract     = {The glass transition of partially crystallized gelatin–water mixtures was investigated using broadband dielectric spectroscopy (BDS) over a wide range of frequencies (10 mHz to 10 MHz), temperatures (113–298 K), and concentrations (10–45 wt \%). Three dielectric relaxation processes (processes I, II, and III) were clearly observed. Processes I, II, and III originate from uncrystallized water (UCW) in the hydration shells of gelatin, ice, and hydrated gelatin, respectively. A dynamic crossover, called the Arrhenius to non-Arrhenius transition of UCW, was observed at the glass transition temperature of the relaxation process of hydrated gelatin for all mixtures. The amount of UCW increases with increasing gelatin content. However, above 35 wt \% gelatin, the amount of UCW became more dependent on the gelatin concentration. This increase in UCW causes a decrease in the glass transition temperature of the cooperative motion of gelatin and UCW, which appears to result from a change in the aggregation structure of gelatin in the mixture at a gelatin concentration of approximately 35 wt \%. The temperature dependence of the relaxation time of process II has nearly the same activation energy as pure ice made by slow crystallization of ice Ih. This implies that process II originates from the dynamics of slowly crystallized ice Ih.},
  creationdate = {2024-05-13T16:46:14},
  doi          = {10.1021/acs.jpcb.6b04756},
  eprint       = {https://doi.org/10.1021/acs.jpcb.6b04756},
  file         = {:Sasaki2017 - Dynamics of Uncrystallized Water, Ice, and Hydrated Protein in Partially Crystallized Gelatin–Water Mixtures Studied by Broadband Dielectric Spectroscopy.pdf:PDF},
  keywords     = {glass former,hydration shell,BDS,gelatin,aqueous polymer solution,concentration-dependence},
  url          = {https://doi.org/10.1021/acs.jpcb.6b04756},
}

@Article{Einaga1994,
  author       = {Yoshiyuki Einaga},
  journal      = {Progress in Polymer Science},
  title        = {Thermodynamics of polymer solutions and mixtures},
  year         = {1994},
  issn         = {0079-6700},
  number       = {1},
  pages        = {1--28},
  volume       = {19},
  abstract     = {A review is provided for the present situation concerning theoretical predictions of phase equilibria in polymer solutions. Special attention is paid to ternary systems consisting of two polymers and one solvent or of one polymer and two solvents. A survey of the experimental data on various ternary systems has revealed that phase separation behavior is significantly and subtly affected by three interaction parameters for each pair of components, and that a quantitative description of the phase relations requires a very accurate expression of the interaction parameters as a function of temperature, composition of the system, molecular weight of the polymer, and so forth. One promising approach has recently been developed and is based on classical thermodynamic relations of general validity. This is described in some detail. It will be shown that this approach is useful for the characterization of thermodynamic properties of a given ternary system as a function of all relevant variables, and that it allows for the prediction of phase equilibrium behavior with sufficient accuracy.},
  creationdate = {2024-05-13T18:11:34},
  doi          = {https://doi.org/10.1016/0079-6700(94)90036-1},
  file         = {:Einaga1994 - Thermodynamics of Polymer Solutions and Mixtures.pdf:PDF},
  keywords     = {review,theory,thermodynamics,ternary mixture,cononsolvency},
  url          = {https://www.sciencedirect.com/science/article/pii/0079670094900361},
}

@Article{Braun2016,
  author       = {Braun, Daniel and Schmollngruber, Michael and Steinhauser, Othmar},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Rotational dynamics of water molecules near biological surfaces with implications for nuclear quadrupole relaxation},
  year         = {2016},
  pages        = {24620--24630},
  volume       = {18},
  abstract     = {Based on Molecular Dynamics simulations of two different systems{,} the protein ubiquitin dissolved in water and an AOT reverse micelle{,} we present a broad analysis of the single particle rotational dynamics of water. A comprehensive connection to NQR{,} which is a prominent experimental method in this field{,} is developed{,} based on a reformulation of its theoretical framework. Interpretation of experimental NQR results requires a model which usually assumes that the NQR experiences retardation only in the first hydration shell. Indeed{,} the present study shows that this first-shell model is correct. Moreover{,} previous experimental retardation factors are quantitatively reproduced. All of this is seemingly contradicted by results of other methods{,} e.g.{,} dielectric spectroscopy{,} responsible for a long-standing debate in this field. Our detailed analysis shows that NQR omits important information contained in overall water dynamics{,} most notably{,} the retardation of the water dipole axis in the electric field exerted by a biological surface.},
  creationdate = {2024-05-13T18:44:57},
  doi          = {10.1039/C6CP04000D},
  file         = {:Braun2016 - Rotational Dynamics of Water Molecules near Biological Surfaces with Implications for Nuclear Quadrupole Relaxation.pdf:PDF},
  issue        = {35},
  keywords     = {hydration shell,reorientational relaxation,molecular dynamics simulation,17O-NMR,BDS},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C6CP04000D},
}

@Article{Magazu2000,
  author       = {S. Magazù},
  journal      = {Journal of Molecular Structure},
  title        = {NMR, static and dynamic light and neutron scattering investigations on polymeric aqueous solutions},
  year         = {2000},
  issn         = {0022-2860},
  number       = {1},
  pages        = {47--59},
  volume       = {523},
  abstract     = {The topic dealt with in the present work is concerned with an overview of some experimental studies, performed by light scattering, QENS and NMR, on the structural and dynamical properties of aqueous solutions of PEO. The experimental findings show that PEO in water tends to assume, with respect to the melt case, a more ordered conformation closer to the crystalline one, and that the H2O/D2O substitution gives rise to different conformational arrangements. The reported evidence demonstrates that aggregation is not an inherent property of the PEO/water system. Finally, QENS shows that PEO affects the dynamics of water molecules in its neighbourhood.},
  creationdate = {2024-05-14T08:04:52},
  doi          = {https://doi.org/10.1016/S0022-2860(99)00411-1},
  file         = {:Magazu2000 - NMR, Static and Dynamic Light and Neutron Scattering Investigations on Polymeric Aqueous Solutions.pdf:PDF},
  keywords     = {Hydrogen bonded systems, Light scattering, Quasielastic neutron scattering, NMR, QENS, DLS, SLS, hydrodynamic radius, PEO, Poly(ethylene oxide), isotope effect, self-diffusion coefficient, hydration shell, PEG},
  url          = {https://www.sciencedirect.com/science/article/pii/S0022286099004111},
}

@Article{Kaatze1978,
  author       = {Kaatze, U. and Gottmann, O. and Podbielski, R. and Pottel, R. and Terveer, U.},
  journal      = {The Journal of Physical Chemistry},
  title        = {Dielectric relaxation in aqueous solutions of some oxygen-containing linear hydrocarbon polymers},
  year         = {1978},
  number       = {1},
  pages        = {112--120},
  volume       = {82},
  creationdate = {2024-05-14T08:25:30},
  doi          = {10.1021/j100490a025},
  eprint       = {https://doi.org/10.1021/j100490a025},
  file         = {:Kaatze1978 - Dielectric Relaxation in Aqueous Solutions of Some Oxygen Containing Linear Hydrocarbon Polymers.pdf:PDF},
  keywords     = {BDS, PEO, poly(ethylene oxide), PVA, poly(vinyl alcohol), PVME, poly(vinyl methyl ether), aqueous solution, dioxane, PVP, poly(vinyl pyrrolidone), PEG},
  url          = {https://doi.org/10.1021/j100490a025},
}

@Article{Shinyashiki1990,
  author       = {Shinyashiki, Naoki and Asaka, Nobuyuki and Mashimo, Satoru and Yagihara, Shin},
  journal      = {The Journal of Chemical Physics},
  title        = {{Dielectric study on dynamics of water in polymer matrix using a frequency range $10^6–10^{10}$ Hz}},
  year         = {1990},
  issn         = {0021-9606},
  month        = jul,
  number       = {1},
  pages        = {760--764},
  volume       = {93},
  abstract     = {{Dielectric measurements were made on polyethylene glycol (PEG) and polyvinyl pyrolidone (PVP)–water systems over a frequency range 106 –1010 Hz by a time domain reflectometry. Two relaxation peaks were observed in the PVP system. The high frequency process is caused by rotational diffusion of water clusters and concentration dependence of the relaxation time is well explained by the free volume theory. The low frequency process is attributed to water molecules bound to the polymer and its relaxation time is reasonably irrespective of the concentration. On the other hand, the PEG system shows a single relaxation process which is caused by the rotational diffusion of water clusters. A sign of the segmental motion was recognized barely for highly concentrated system of PEG.}},
  creationdate = {2024-05-14T08:31:37},
  doi          = {10.1063/1.459526},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/93/1/760/18987048/760\_1\_online.pdf},
  file         = {:Shinyashiki1990 - Dielectric Study on Dynamics of Water in Polymer Matrix Using a Frequency Range 106–1010 Hz.pdf:PDF},
  keywords     = {BDS,poly(vinyl pyrolidone),PVP,poly(ethylene glycol),PEG,aqueous solution,benzene,hydration shell},
  url          = {https://doi.org/10.1063/1.459526},
}

@Article{Zhong2011,
  author       = {Dongping Zhong and Samir Kumar Pal and Ahmed H. Zewail},
  journal      = {Chemical Physics Letters},
  title        = {Biological water: A critique},
  year         = {2011},
  issn         = {0009-2614},
  number       = {1},
  pages        = {1--11},
  volume       = {503},
  abstract     = {In this overview, we provide a critique of the hydration dynamics of macromolecules, particularly those of protein and DNA. Only in the past decade has femtosecond spectroscopy enabled direct access to the ultrafast dynamical motion of surface water. With the wealth of results from this spectroscopic technique, NMR, and neutron scattering, it is now established that hydration is indeed an ultrafast phenomenon, and in this sense the ‘iceberg model’ is invalid. Here, we overview the experimental and the theoretical studies, hoping to clarify the confusion resulting from some recent MD simulations. We maintain that there are two types of water hydration, those that reorient in the vicinity of the surface and those which are ordered, however in dynamic interaction with the protein.},
  creationdate = {2024-05-14T09:39:53},
  doi          = {https://doi.org/10.1016/j.cplett.2010.12.077},
  file         = {:Zhong2011 - Biological Water_ a Critique.pdf:PDF},
  keywords     = {review,protein,hydration water,NMR,light scattering,neutron scattering},
  url          = {https://www.sciencedirect.com/science/article/pii/S0009261410016647},
}

@Article{Ball2008,
  author       = {Ball, Philip},
  journal      = {Chemical Reviews},
  title        = {Water as an Active Constituent in Cell Biology},
  year         = {2008},
  note         = {PMID: 18095715},
  number       = {1},
  pages        = {74--108},
  volume       = {108},
  creationdate = {2024-05-14T09:44:08},
  doi          = {10.1021/cr068037a},
  eprint       = {https://doi.org/10.1021/cr068037a},
  file         = {:Ball2008 - Water As an Active Constituent in Cell Biology.pdf:PDF},
  keywords     = {review,hydration shell,protein},
  url          = {https://doi.org/10.1021/cr068037a},
}

@Article{Bhattacharyya2000,
  author       = {Bhattacharyya, Kankan and Bagchi, Biman},
  journal      = {The Journal of Physical Chemistry A},
  title        = {Slow Dynamics of Constrained Water in Complex Geometries},
  year         = {2000},
  number       = {46},
  pages        = {10603--10613},
  volume       = {104},
  abstract     = {Although water is often hailed as the lubricant of life, a detailed understanding of its role in many chemical and biological processes still eludes us. In many natural systems, water is confined in an environment where its free movement is restricted and its three-dimensional hydrogen-bonded network is disrupted. Very recently, several groups applied ultrafast laser spectroscopy to study the dynamics of the constrained water molecules. It is observed that the dynamic behavior of the confined water molecules is markedly different from that of the ordinary water molecules. The most striking result is the bimodal response of confined water, with one bulk water-like subpicosecond component and a much slower component in a time scale of hundreds or thousands of picoseconds. This slow second component constitutes 10−30\% of the total response and is crucial in the understanding of the role of water in complex chemical and biological processes. The origin of the slow component has been a subject of intense recent debate and has recently been attributed to a dynamic exchange between free and bound water. This interpretation seems to be in accord with the conclusion reached independently by intermolecular solute−water NOE and NMRD studies. In this article, a review of the recent experimental and theoretical work in this area is presented.},
  creationdate = {2024-05-14T09:53:29},
  doi          = {10.1021/jp001878f},
  eprint       = {https://doi.org/10.1021/jp001878f},
  file         = {:Bhattacharyya2000 - Slow Dynamics of Constrained Water in Complex Geometries.pdf:PDF},
  keywords     = {review,hydration shell,protein},
  url          = {https://doi.org/10.1021/jp001878f},
}

@Article{Melillo2021,
  author       = {Melillo, Jorge H. and Gabriel, Jan Philipp and Pabst, Florian and Blochowicz, Thomas and Cerveny, Silvina},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Dynamics of aqueous peptide solutions in folded and disordered states examined by dynamic light scattering and dielectric spectroscopy},
  year         = {2021},
  pages        = {15020--15029},
  volume       = {23},
  abstract     = {Characterizing the segmental dynamics of proteins{,} and intrinsically disordered proteins in particular{,} is a challenge in biophysics. In this study{,} by combining data from broadband dielectric spectroscopy (BDS) and both depolarized (DDLS) and polarized (PDLS) dynamic light scattering{,} we were able to determine the dynamics of a small peptide [ε-poly(lysine)] in water solutions in two different conformations (pure β-sheet at pH = 10 and a more disordered conformation at pH = 7). We found that the segmental (α-) relaxation{,} as probed by DDLS{,} is faster in the disordered state than in the folded conformation. The water dynamics{,} as detected by BDS{,} is also faster in the disordered state. In addition{,} the combination of BDS and DDLS results allows us to confirm the molecular origin of water-related processes observed by BDS. Finally{,} we discuss the origin of two slow processes (A and B processes) detected by DDLS and PDLS in both conformations and usually observed in other types of water solutions. For fully homogeneous ε-PLL solutions at pH = 10{,} the A-DLS process is assigned to the diffusion of individual β-sheets. The combination of both techniques opens a route for understanding the dynamics of peptides and other biological solutions.},
  creationdate = {2024-05-14T10:11:23},
  doi          = {10.1039/D1CP01893K},
  file         = {:Melillo2021 - Dynamics of Aqueous Peptide Solutions in Folded and Disordered States Examined by Dynamic Light Scattering and Dielectric Spectroscopy.pdf:PDF},
  issue        = {28},
  keywords     = {protein,hydration shell,e-lysine,DLS,BDS,DSC},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D1CP01893K},
}

@Article{Nasedkin2019,
  author       = {Nasedkin, Alexandr and Cerveny, Silvina and Swenson, Jan},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Molecular Insights into Dipole Relaxation Processes in Water–Lysine Mixtures},
  year         = {2019},
  note         = {PMID: 31268322},
  number       = {28},
  pages        = {6056--6064},
  volume       = {123},
  abstract     = {Dielectric spectroscopy is a robust method to investigate relaxations of molecular dipoles. It is particularly useful for studies of biological solutions because of the potential of this method to cover a broad range of dynamical time scales typical for such systems. However, this technique does not provide any information about the nature of the molecular motions, which leads to a certain underemployment of dielectric spectroscopy for gaining microscopic understanding of material properties. For such detailed understanding, computer simulations are valuable tools because they can provide information about the nature of molecular motions observed by, for example, dielectric spectroscopy and to further complement them with structural information. In this work, we acquire information about the nature of dipole relaxation, in n-lysine solutions by means of molecular dynamics simulations. Our results indicate that the experimentally observed main relaxation process of n-lysine has different origins for the single monomer and the polypeptide chains. The relaxation of 1-lysine is due to the motions of whole molecules, whereas the experimentally observed relaxation of 3-lysine and 4-lysine is due to the motions of the residues, which, in turn, are promoted by water relaxation. Furthermore, we propose a new structural model of the lysine amino acids, which can quantitatively account for the experimental dielectric relaxation data. Hydrogen bonding and the structure of water are also discussed in terms of their influence on relaxation processes.},
  creationdate = {2024-05-14T10:31:59},
  doi          = {10.1021/acs.jpcb.9b01928},
  eprint       = {https://doi.org/10.1021/acs.jpcb.9b01928},
  file         = {:Nasedkin2019 - Molecular Insights into Dipole Relaxation Processes in Water–Lysine Mixtures.pdf:PDF},
  keywords     = {aqueous lysine,BDS,molecular dynamics simulation},
  url          = {https://doi.org/10.1021/acs.jpcb.9b01928},
}

@Article{Cerveny2016,
  author       = {Cerveny, Silvina and Combarro-Palacios, Izaskun and Swenson, Jan},
  journal      = {The Journal of Physical Chemistry Letters},
  title        = {Evidence of Coupling between the Motions of Water and Peptides},
  year         = {2016},
  note         = {PMID: 27683955},
  number       = {20},
  pages        = {4093--4098},
  volume       = {7},
  abstract     = {Studies of protein dynamics at low temperatures are generally performed on hydrated powders and not in biologically realistic solutions of water because of water crystallization. However, here we avoid the problem of crystallization by reducing the size of the biomolecules. We have studied oligomers of the amino acid l-lysine, fully dissolved in water, and our dielectric relaxation data show that the glass transition-related dynamics of the oligomers is determined by the water dynamics, in a way similar to that previously observed for solvated proteins. This implies that the crucial role of water for protein dynamics can be extended to other types of macromolecular systems, where water is also able to determine their conformational fluctuations. Using the energy landscape picture of macromolecules, the thermodynamic criterion for such solvent-slaved macromolecular motions may be that the macromolecules need the entropy contribution from the solvent to overcome the enthalpy barriers between different conformational substates.},
  creationdate = {2024-05-14T10:40:14},
  doi          = {10.1021/acs.jpclett.6b01864},
  eprint       = {https://doi.org/10.1021/acs.jpclett.6b01864},
  file         = {:Cerveny2016 - Evidence of Coupling between the Motions of Water and Peptides.pdf:PDF;:EvidenceOfCouplingBetweenTheMotionsOfWaterAndPeptides_CervenyEtAl_JPCLett2016_SI1.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Proteins/EvidenceOfCouplingBetweenTheMotionsOfWaterAndPeptides_CervenyEtAl_JPCLett2016_SI2/jz6b01864_high_quality.mp4:mp4},
  keywords     = {lysine,BDS,peptide,glass former,l-lysine,e-lysine,n-lysine,beta-sheet,alpha-helix,protein},
  url          = {https://doi.org/10.1021/acs.jpclett.6b01864},
}

@Article{Singh2011,
  author       = {Singh, Lokendra P. and Cerveny, Silvina and Alegría, Angel and Colmenero, Juan},
  journal      = {ChemPhysChem},
  title        = {Broadband Dielectric Spectroscopic, Calorimetric, and FTIR-ATR Investigations of D-Arabinose Aqueous Solutions},
  year         = {2011},
  number       = {18},
  pages        = {3624--3633},
  volume       = {12},
  abstract     = {ract The dielectric relaxation behavior of D-arabinose aqueous solutions at different water concentrations is examined by broadband dielectric spectroscopy in the frequency range of 10−2–107 Hz and in the temperature range of 120–300 K. Differential scanning calorimetry is also performed to find the glass transition temperatures (Tg). In addition, the same solutions are analyzed by Fourier transform infrared (FTIR) spectroscopy using the attenuated total reflectance (ATR) method at the same temperature interval and in the frequency range of 3800–2800 cm−1. The temperature dependence of the relaxation times is examined for the different weight fractions (xw) of water along with the temperature dependence of dielectric strength. Two relaxation processes are observed in the aqueous solutions for all concentrations of water. The slower process, the so-called primary relaxation process (process-I), is responsible for the Tg whereas the faster one (designated as process-II) is due to the reorientational motion of the water molecules. As for other hydrophilic water solutions, dielectric data for process-II indicate the existence of a critical water concentration above which water mobility is less restricted. Accordingly, FTIR-ATR measurements on aqueous solutions show an increment in the intensity (area) of the OH stretching sub-band close to 3200 cm−1 as the water concentration increases.},
  creationdate = {2024-05-14T11:12:37},
  doi          = {https://doi.org/10.1002/cphc.201100469},
  eprint       = {https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/cphc.201100469},
  file         = {:Singh2011 - Broadband Dielectric Spectroscopic, Calorimetric, and FTIR ATR Investigations of D Arabinose Aqueous Solutions.pdf:PDF},
  keywords     = {aqueous solutions,calorimetry,carbohydrates,dielectric relaxation,IR spectroscopy,DSC,BDS,proteins,FTIR,infrared,glass former},
  url          = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/cphc.201100469},
}

@Article{Bagchi2005,
  author       = {Bagchi, Biman},
  journal      = {Chemical Reviews},
  title        = {Water Dynamics in the Hydration Layer around Proteins and Micelles},
  year         = {2005},
  note         = {PMID: 16159150},
  number       = {9},
  pages        = {3197--3219},
  volume       = {105},
  creationdate = {2024-05-14T11:35:41},
  doi          = {10.1021/cr020661+},
  eprint       = {https://doi.org/10.1021/cr020661+},
  file         = {:Bagchi2005 - Water Dynamics in the Hydration Layer around Proteins and Micelles.pdf:PDF},
  keywords     = {review,hydration shell},
  url          = {https://doi.org/10.1021/cr020661+},
}

@Article{Nordstierna2006,
  author       = {Nordstierna, Lars and Yushmanov, Pavel V. and Furó, István},
  journal      = {The Journal of Chemical Physics},
  title        = {{Solute-solvent contact by intermolecular cross relaxation. I. The nature of the water-hydrophobic interface}},
  year         = {2006},
  issn         = {0021-9606},
  month        = aug,
  number       = {7},
  pages        = {074704},
  volume       = {125},
  abstract     = {{Intermolecular cross-relaxation rates between solute and solvent were measured by \\{H1\\} F19 nuclear magnetic resonance experiments in aqueous molecular solutions of ammonium perfluoro-octanoate and sodium trifluoroacetate. The experiments performed at three different magnetic fields provide frequency-dependent cross-relaxation rates which demonstrate clearly the lack of extreme narrowing for nuclear spin relaxation by diffusionally modulated intermolecular interactions. Supplemented by suitable intramolecular cross-relaxation, longitudinal relaxation, and self-diffusion data, the obtained cross-relaxation rates are evaluated within the framework of recent relaxation models and provide information about the hydrophobic hydration. In particular, water dynamics around the trifluoromethyl group in ammonium perfluoro-octanoate are more retarded than that in the smaller trifluoroacetate.}},
  creationdate = {2024-05-14T11:46:40},
  doi          = {10.1063/1.2336199},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.2336199/16750322/074704\_1\_online.pdf},
  file         = {:Nordstierna2006 - Solute Solvent Contact by Intermolecular Cross Relaxation. I. the Nature of the Water Hydrophobic Interface.pdf:PDF},
  keywords     = {NMR,1h-nmr,19F-NMR,cross-relaxation,ammonium perfluoro-octanoate,sodium trifluoroacetate,magnetic relaxation dispersion,solvent dynamics,hydrophobic hydration},
  url          = {https://doi.org/10.1063/1.2336199},
}

@Article{Halle2003,
  author       = {Halle, Bertil},
  journal      = {The Journal of Chemical Physics},
  title        = {{Cross-relaxation between macromolecular and solvent spins: The role of long-range dipole couplings}},
  year         = {2003},
  issn         = {0021-9606},
  month        = dec,
  number       = {23},
  pages        = {12372--12385},
  volume       = {119},
  abstract     = {{Nuclear spin relaxation by intermolecular dipole–dipole interactions between macromolecular and solvent nuclear moments forms the basis of a widely used method for investigating macromolecular solvation. In particular, intermolecular cross-relaxation [or nuclear Overhauser effect (NOE)] between protein and water protons has been used to probe the mobility of water molecules interacting with the protein surface. The method rests on the assumption that the intermolecular NOE is of short (4–5 Å) range and thus provides information about the mobility of individual water molecules in hydration sites near the monitored protein protons. Here, we present a theoretical analysis of the spectral density function (SDF) that governs the cross-relaxation rates in the laboratory-fixed and rotating frames. In contrast to the r−6 dependence of the intramolecular NOEs used for structure determination, the intermolecular NOE is shown to be long-ranged with important contributions from thousands of water molecules. For a consistent interpretation of such NOEs, it is necessary to use a model that explictly incorporates motionally retarded hydration water molecules as well as unperturbed bulk water molecules. We formulate a diffusion model with a nonuniform solvent mobility and solve it to obtain an analytical expression for the SDF. Calculations with this nonuniform diffusion model demonstrate that intermolecular NOEs with surface protons are dominated by long-range dipole couplings to bulk water and therefore provide little or no information about hydration dynamics. The physical basis of this unexpected phenomenon is that the characteristic time scale for relaxation-inducing fluctuations is longer for the more numerous remote water molecules, despite their higher mobility. The analytical results presented here are generally applicable to intermolecular dipolar relaxation of like or unlike (nuclear or electron) spins in a variety of experimental situations.}},
  creationdate = {2024-05-14T11:57:04},
  doi          = {10.1063/1.1625632},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/119/23/12372/19267896/12372\_1\_online.pdf},
  file         = {:Halle2003 - Cross Relaxation between Macromolecular and Solvent Spins_ the Role of Long Range Dipole Couplings.pdf:PDF},
  keywords     = {nuclear overhauser effect,NOE,NMR,spin relaxation,protein,hydration shell,dipole interaction,spectral density},
  url          = {https://doi.org/10.1063/1.1625632},
}

@Article{Braun2017,
  author       = {Braun, Daniel and Schmollngruber, Michael and Steinhauser, Othmar},
  journal      = {The Journal of Physical Chemistry Letters},
  title        = {Revival of the Intermolecular Nuclear Overhauser Effect for Mapping Local Protein Hydration Dynamics},
  year         = {2017},
  note         = {PMID: 28686451},
  number       = {14},
  pages        = {3421--3426},
  volume       = {8},
  abstract     = {The highly heterogeneous hydration dynamics of protein–water interfaces is considered important for protein stability and dynamics, protein folding, enzymatic activity, and even drug design. The nuclear Overhauser effect (NOE) between protein and water protons is the only experimental observable which, in principle, can provide a map of locally resolved hydration dynamics. However, its utility was questioned in various theoretical studies that emphasized the contributions of long-range NOE interactions. We show by a detailed analysis based on molecular dynamics simulations that, contrary to recent claims, the protein–water NOE is an excellent observable to map local hydration dynamics at the protein surface.},
  creationdate = {2024-05-14T12:49:45},
  doi          = {10.1021/acs.jpclett.7b01013},
  eprint       = {https://doi.org/10.1021/acs.jpclett.7b01013},
  file         = {:Braun2017 - Revival of the Intermolecular Nuclear Overhauser Effect for Mapping Local Protein Hydration Dynamics.pdf:PDF;:RevivalOfTheIntermolecularNuclearOverhauserEffectForMappingLocalProteinHydrationDynamics_BraunEtAl_JPCLett2017_SI.pdf:PDF},
  keywords     = {nuclear overhauser effect,NOE,NMR,protein,hydration shell,molecular dynamics simulation},
  url          = {https://doi.org/10.1021/acs.jpclett.7b01013},
}

@Article{Okuno2020,
  author       = {Okuno, Yusuke and Szabo, Attila and Clore, G. Marius},
  journal      = {Journal of the American Chemical Society},
  title        = {Quantitative Interpretation of Solvent Paramagnetic Relaxation for Probing Protein–Cosolute Interactions},
  year         = {2020},
  note         = {PMID: 32286812},
  number       = {18},
  pages        = {8281--8290},
  volume       = {142},
  abstract     = {Protein–small cosolute molecule interactions are ubiquitous and known to modulate the solubility, stability, and function of many proteins. Characterization of such transient weak interactions at atomic resolution remains challenging. In this work, we develop a simple and practical NMR method for extracting both energetic and dynamic information on protein–cosolute interactions from solvent paramagnetic relaxation enhancement (sPRE) measurements. Our procedure is based on an approximate (non-Lorentzian) spectral density that behaves exactly at both high and low frequencies. This spectral density contains two parameters, one global related to the translational diffusion coefficient of the paramagnetic cosolute, and the other residue specific. These parameters can be readily determined from sPRE data, and then used to calculate analytically a concentration normalized equilibrium average of the interspin distance, ⟨r–6⟩norm, and an effective correlation time, τC, that provide measures of the energetics and dynamics of the interaction at atomic resolution. We compare our approach with existing ones, and demonstrate the utility of our method using experimental 1H longitudinal and transverse sPRE data recorded on the protein ubiquitin in the presence of two different nitroxide radical cosolutes, at multiple static magnetic fields. The approach for analyzing sPRE data outlined here provides a powerful tool for deepening our understanding of extremely weak protein–cosolute interactions.},
  creationdate = {2024-05-14T12:54:49},
  doi          = {10.1021/jacs.0c00747},
  eprint       = {https://doi.org/10.1021/jacs.0c00747},
  file         = {:Okuno2020 - Quantitative Interpretation of Solvent Paramagnetic Relaxation for Probing Protein–Cosolute Interactions.pdf:PDF;:QuantitativeInterpretationOfSolventParamagneticRelaxationForProbingProteinCosoluteInteractions_OkunoEtAl_JAmChemSoc2020_SI.pdf:PDF},
  keywords     = {NMR,spin relaxation,paramagnetic relaxation enhancement,spectral density,protein,1h-nmr,T1,T2,hydrodynamic radius,ubiquitin},
  url          = {https://doi.org/10.1021/jacs.0c00747},
}

@Article{Honegger2021,
  author       = {Honegger, Philipp and Di Pietro, Maria Enrica and Castiglione, Franca and Vaccarini, Chiara and Quant, Alea and Steinhauser, Othmar and Schröder, Christian and Mele, Andrea},
  journal      = {The Journal of Physical Chemistry Letters},
  title        = {The Intermolecular NOE Depends on Isotope Selection: Short Range vs Long Range Behavior},
  year         = {2021},
  note         = {PMID: 34472860},
  number       = {35},
  pages        = {8658--8663},
  volume       = {12},
  abstract     = {The nuclear Overhauser effect (NOE) is a powerful tool in molecular structure elucidation, combining the subtle chemical shift of NMR and three-dimensional information independent of chemical connectivity. Its usage for intermolecular studies, however, is fundamentally limited by an unspecific long-ranged interaction behavior. This joint experimental and computational work shows that proper selection of interacting isotopes can overcome these limitations: Isotopes with strongly differing gyromagnetic ratios give rise to short-ranged intermolecular NOEs. In this light, existing NOE experiments need to be re-evaluated and future ones can be designed accordingly. Thus, a new chapter on intermolecular structure elucidation is opened.},
  creationdate = {2024-05-14T13:01:18},
  doi          = {10.1021/acs.jpclett.1c02253},
  eprint       = {https://doi.org/10.1021/acs.jpclett.1c02253},
  file         = {:Honegger2021 - The Intermolecular NOE Depends on Isotope Selection_ Short Range Vs Long Range Behavior.pdf:PDF;:TheIntermolecularNOEDependsOnIsotopeSelection-ShortRangeVsLongRangeBehavior_HoneggerEtAl_JPhysChemLett2021_SI.pdf:PDF},
  keywords     = {NMR,nuclear overhauser effect,NOE},
  url          = {https://doi.org/10.1021/acs.jpclett.1c02253},
}

@Article{Okuno2023,
  author       = {Okuno, Yusuke and Clore, G. Marius},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Extending the Experimentally Accessible Range of Spin Dipole–Dipole Spectral Densities for Protein–Cosolute Interactions by Temperature-Dependent Solvent Paramagnetic Relaxation Enhancement Measurements},
  year         = {2023},
  note         = {PMID: 37681752},
  number       = {37},
  pages        = {7887--7898},
  volume       = {127},
  abstract     = {Longitudinal (Γ1) and transverse (Γ2) solvent paramagnetic relaxation enhancement (sPRE) yields field-dependent information in the form of spectral densities that provides unique information related to cosolute–protein interactions and electrostatics. A typical protein sPRE data set can only sample a few points on the spectral density curve, J(ω), within a narrow frequency window (500 MHz to ∼1 GHz). However, complex interactions and dynamics of paramagnetic cosolutes around a protein make it difficult to directly interpret the few experimentally accessible points of J(ω). In this paper, we show that it is possible to significantly extend the experimentally accessible frequency range (corresponding to a range from ∼270 MHz to 1.8 GHz) by acquiring a series of sPRE experiments at different temperatures. This approach is based on the scaling property of J(ω) originally proposed by Melchior and Fries for small molecules. Here, we demonstrate that the same scaling property also holds for geometrically far more complex systems such as proteins. Using the extended spectral densities derived from the scaling property as the reference dataset, we demonstrate that our previous approach that makes use of a non-Lorentzian Ansatz spectral density function to fit only J(0) and one to two J(ω) points allows one to obtain accurate values for the concentration-normalized equilibrium average of the electron–proton interspin separation ⟨r–6⟩norm and the correlation time τC, which provide quantitative information on the energetics and timescale, respectively, of local cosolute–protein interactions. We also show that effective near-surface potentials, ϕENS, obtained from ⟨r–6⟩norm provide a reliable and quantitative measure of intermolecular interactions including electrostatics, while ϕENS values obtained from only Γ1 or Γ2 sPRE rates can have significant artifacts as a consequence of potential variations and changes in the diffusive properties of the cosolute around the protein surface. Finally, we discuss the experimental feasibility and limitations of extracting the high-frequency limit of J(ω) that is related to ⟨r–8⟩norm and report on the extremely local intermolecular potential.},
  creationdate = {2024-05-14T13:03:37},
  doi          = {10.1021/acs.jpcb.3c05301},
  eprint       = {https://doi.org/10.1021/acs.jpcb.3c05301},
  file         = {:Okuno2023 - Extending the Experimentally Accessible Range of Spin Dipole–Dipole Spectral Densities for Protein–Cosolute Interactions by Temperature Dependent Solvent Paramagnetic Relaxation Enhancement Measurements.pdf:PDF;:ExtendingTheExperimentallyAccessibleRangeOfSpinDipoleDipoleSpectralDensitiesForProteinCosoluteInteractionsByTemperatureDependentSolventParamagneticRelaxationEnhancementMeasurements_OkunoEtAl_JPC2023_SI.pdf:PDF},
  keywords     = {NMR,paramagnetic relaxation enhancement,T1,T2,spectral density,protein},
  url          = {https://doi.org/10.1021/acs.jpcb.3c05301},
}

@Article{Wu2018,
  author       = {Wu, Tsung-Yu and Zrimsek, Alyssa B. and Bykov, Sergei V. and Jakubek, Ryan S. and Asher, Sanford A.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Hydrophobic Collapse Initiates the Poly(N-isopropylacrylamide) Volume Phase Transition Reaction Coordinate},
  year         = {2018},
  note         = {PMID: 29481081},
  number       = {11},
  pages        = {3008--3014},
  volume       = {122},
  abstract     = {The best-known examples of smart, responsive hydrogels derive from poly(N-isopropylacrylamide) (PNIPAM) cross-linked polymer networks. These hydrogels undergo volume phase transitions (VPTs) triggered by temperature, chemical, and/or environmental changes. PNIPAM hydrogels can undergo more than 50-fold volume changes within ∼1 μs intervals. Studies have tried to elucidate the molecular mechanism of these extraordinarily large responses. Nevertheless, the molecular reaction coordinates that drive the VPT remain unclear. Using visible nonresonance Raman temperature-jump spectroscopy, we determined the molecular ordering of this VPT. The PNIPAM hydrophobic isopropyl and methylene groups dehydrate with time constants of 109 ± 64 and 104 ± 44 ns, initiating the volume collapse of PNIPAM. The subsequent dehydration of the PNIPAM amide groups is significantly slower, as our group previously discovered (360 ± 85 ns). This determination of the ordering of the molecular reaction coordinate of the PNIPAM VPT enables the development of the next generation of super-responsive materials.},
  creationdate = {2024-05-14T13:14:51},
  doi          = {10.1021/acs.jpcb.8b00740},
  eprint       = {https://doi.org/10.1021/acs.jpcb.8b00740},
  file         = {:Wu2018 - Hydrophobic Collapse Initiates the Poly(N Isopropylacrylamide) Volume Phase Transition Reaction Coordinate.pdf:PDF;:HydrophobicCollapseInitiatesThePolyNIsopropylacrylamideVolumePhaseTransitionReactionCoordinate_WuEtAl_JPC2018_SI.pdf:PDF},
  keywords     = {pNIPAM,hydrogel,microgel,raman spectroscopy,hydrophobic hydration,kinetics,temperature jump,DLS},
  url          = {https://doi.org/10.1021/acs.jpcb.8b00740},
}

@Article{OrtizdeSolorzano2020,
  author       = {Ortiz de Solorzano, Isabel and Bejagam, Karteek K. and An, Yaxin and Singh, Samrendra K. and Deshmukh, Sanket A.},
  journal      = {Soft Matter},
  title        = {Solvation dynamics of N-substituted acrylamide polymers and the importance for phase transition behavior},
  year         = {2020},
  pages        = {1582--1593},
  volume       = {16},
  abstract     = {Functional groups present in thermo-responsive polymers are known to play an important role in aqueous solutions by manifesting their coil-to-globule conformational transition in a specific temperature range. Understanding the role of these functional groups and their interactions with water is of great interest as it may allow us to control both the nature and temperature of this coil-to-globule transition. In this work{,} polyacrylamide (PAAm){,} poly(N-isopropylacrylamide) (PNIPAm){,} and poly(N-isopropylmethacrylamide) (PNIPMAm) solvated in water are studied with the goal of discovering the structure of the solvent and its interaction with these polymers in determining the polymer conformations. Specifically{,} all-atom molecular dynamics (MD) simulations were performed on polymer chains with 30 monomer units (30-mers) at 295 K{,} 310 K and 320 K{,} which is below and above the lower critical solution temperature (LCST) of PNIPAm (LCST = 305 K) and PNIPMAm (LCST = 315 K){,} respectively. The MD simulation trajectories suggest that changes in the functional groups in the backbone and side-chains alter the water solvation shell around the polymer. This results in a change in the residence time probability and hydrogen bond characteristics of water at simulated temperatures. Specifically{,} water molecules reside for longer times near PAAm (no LCST) and PNIPMAm (LCST = 315 K) chains as compared to PNIPAm. This might be one of the possible causes for the higher LCST of PNIPMAm as compared to that of PNIPAm. These results can guide experimentalists and theoreticians to design new polymer structures with tailor-made LCST transitions while controlling the water solvation shell around the functional group.},
  creationdate = {2024-05-14T13:26:42},
  doi          = {10.1039/C9SM01798D},
  file         = {:OrtizdeSolorzano2020 - Solvation Dynamics of N Substituted Acrylamide Polymers and the Importance for Phase Transition Behavior.pdf:PDF;:SolvationDynamicsOfNSubstitutedAcrylamidePolymersAndTheImportanceForPhaseTransitionBehavior_OrtizDeSolorzanoEtAl_SoftMatter2020_SI.pdf:PDF},
  issue        = {6},
  keywords     = {pNIPAM,pNIPAM-Alternatives,pNIPMAM,PAA,molecular dynamics simulation,hydration shell},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C9SM01798D},
}

@Article{Zhu1997b,
  author       = {Zhu, Wei and Ediger, M. D.},
  journal      = {Macromolecules},
  title        = {Viscosity Dependence of Polystyrene Local Dynamics in Dilute Solution},
  year         = {1997},
  number       = {4},
  pages        = {1205--1210},
  volume       = {30},
  abstract     = {Variable-temperature 2H NMR T1 measurements have been performed on backbone-deuterated atactic polystyrene at two Larmor frequencies in four solvents:  toluene, cis-decalin, dibutyl phthalate, and dioctyl phthalate. The time integral 〈σ〉 of the C−D vector orientation correlation function is extracted from the T1 data without assuming a specific model for C−D vector reorientation. The hydrodynamic Kramers' theory in the high-friction limit cannot describe the viscosity and temperature dependence of 〈σ〉. In contrast, 〈σ〉 is found to have a power law dependence on solvent viscosity with an exponent of 0.76 ± 0.05, whether the viscosity is varied by changing solvent or temperature. The internal energy barrier for polystyrene C−D vector orientation is determined to be 14 ± 3 kJ/mol using the power law viscosity dependence. The inapplicability of Kramers' theory is attributed to the lack of a clear separation between the time scales of polymer and solvent motions. As expected on the basis of this explanation, the viscosity exponents for polystyrene and five other polymers are found to correlate with the molecular weight of the side groups.},
  creationdate = {2024-05-14T13:39:07},
  doi          = {10.1021/ma961426u},
  eprint       = {https://doi.org/10.1021/ma961426u},
  file         = {:Zhu1997b - Viscosity Dependence of Polystyrene Local Dynamics in Dilute Solution.pdf:PDF;:ViscosityDependenceOfPolystyreneLocalDynamicsInDiluteSolution_ZhuEtAl_Macromol1997_SI.pdf:PDF},
  keywords     = {NMR,Polystyrene,PS,2H-NMR,T1,Kramer,viscosity},
  url          = {https://doi.org/10.1021/ma961426u},
}

@Article{Swenson2006,
  author       = {Swenson, Jan and Jansson, Hel\'en and Bergman, Rikard},
  journal      = {Phys. Rev. Lett.},
  title        = {Relaxation Processes in Supercooled Confined Water and Implications for Protein Dynamics},
  year         = {2006},
  month        = jun,
  pages        = {247802},
  volume       = {96},
  creationdate = {2024-05-14T14:02:09},
  doi          = {10.1103/PhysRevLett.96.247802},
  file         = {:Swenson2006 - Relaxation Processes in Supercooled Confined Water and Implications for Protein Dynamics.pdf:PDF},
  issue        = {24},
  keywords     = {glass former,alpha-relaxation,confinement,fragility,BDS,QENS,propylene glycol,PG,clay,ethylene glycol,EG},
  numpages     = {4},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.96.247802},
}

@Article{Khodadadi2008,
  author       = {Khodadadi, S. and Pawlus, S. and Sokolov, A. P.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Influence of Hydration on Protein Dynamics: Combining Dielectric and Neutron Scattering Spectroscopy Data},
  year         = {2008},
  note         = {PMID: 18942780},
  number       = {45},
  pages        = {14273--14280},
  volume       = {112},
  abstract     = {Combining dielectric spectroscopy and neutron scattering data for hydrated lysozyme powders, we were able to identify several relaxation processes and follow protein dynamics at different hydration levels over a broad frequency and temperature range. We ascribe the main dielectric process to protein’s structural relaxation coupled to hydration water and the slowest dielectric process to a larger scale protein’s motions. Both relaxations exhibit a smooth, slightly super-Arrhenius temperature dependence between 300 and 180 K. The temperature dependence of the slowest process follows the main dielectric relaxation, emphasizing that the same friction mechanism might control both processes. No signs of a proposed sharp fragile-to-strong crossover at T ∼ 220 K are observed in temperature dependences of these processes. Both processes show strong dependence on hydration: the main dielectric process slows down by six orders with a decrease in hydration from h ∼ 0.37 (grams of water per grams of protein) to h ∼ 0.05. The slowest process shows even stronger dependence on hydration. The third (fastest) dielectric relaxation process has been detected only in samples with high hydration (h ∼ 0.3 and higher). We ascribe it to a secondary relaxation of hydration water. The mechanism of the protein dynamic transition and a general picture of the protein dynamics are discussed.},
  creationdate = {2024-05-14T14:21:10},
  doi          = {10.1021/jp8059807},
  eprint       = {https://doi.org/10.1021/jp8059807},
  file         = {:Khodadadi2008 - Influence of Hydration on Protein Dynamics_ Combining Dielectric and Neutron Scattering Spectroscopy Data.pdf:PDF},
  keywords     = {BDS,neutron scattering,protein,lysozyme,hydration shell,fragility,glass former},
  url          = {https://doi.org/10.1021/jp8059807},
}

@Article{Jansson2011,
  author       = {Jansson, Helén and Bergman, Rikard and Swenson, Jan},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Role of Solvent for the Dynamics and the Glass Transition of Proteins},
  year         = {2011},
  note         = {PMID: 21425816},
  number       = {14},
  pages        = {4099--4109},
  volume       = {115},
  abstract     = {For the first time, a systematic investigation of the glass transition and its related dynamics of myoglobin in water−glycerol solvent mixtures of different water contents is presented. By a combination of broadband dielectric spectroscopy and differential scanning calorimetry (DSC), we have studied the relation between the protein and solvent dynamics with the aim to better understand the calorimetric glass transition, Tg, of proteins and the role of solvent for protein dynamics. The results show that both the viscosity related α-relaxation in the solvent as well as several different protein relaxations are involved in the calorimetric glass transition, and that the broadness (ΔTg) of the transition depends strongly on the total amount of solvent. The main reason for this seems to be that the protein relaxation processes become more separated in time with decreasing solvent level. The results are compared to that of hydrated myoglobin where the hydration water does not give any direct contribution to the calorimetric Tg. However, the large-scale α-like relaxation in the hydration water is still responsible for the protein dynamics that freeze-in at Tg. Finally, the dielectric data show clearly that the protein relaxation processes exhibit similar temperature dependences as the α-relaxation in the solvent, as suggested for solvent-slaved protein motions.},
  creationdate = {2024-05-14T14:27:40},
  doi          = {10.1021/jp1089867},
  eprint       = {https://doi.org/10.1021/jp1089867},
  file         = {:Jansson2011 - Role of Solvent for the Dynamics and the Glass Transition of Proteins.pdf:PDF},
  keywords     = {myoglobin,protein,BDS,DSC,solvent dynamics,alpha-relaxation,glass former,aqueous glycerol},
  url          = {https://doi.org/10.1021/jp1089867},
}

@Article{Miura1996,
  author       = {Miura, Nobuhiro and Hayashi, Yoshihito and Mashimo, Satoru},
  journal      = {Biopolymers},
  title        = {Hinge-bending deformation of enzyme observed by microwave dielectric measurement},
  year         = {1996},
  number       = {2},
  pages        = {183--187},
  volume       = {39},
  abstract     = {A dielectric relaxation peak due to an intramolecular motion in the active site of trypsin was first observed in aqueous solution below the freezing temperature of bulk water by a time domain reflectometry method. If trypsin inhibitor is added to the solution, it vanishes. It is suggested that the motion observed is a hinge-bending deformation giving rise to the enzymatic activity of trypsin, which is prohibited by linkage of the trypsin inhibitor. Relaxation time of the motion is 3 × 102 ns at − 10°C. © 1996 John Wiley \& Sons, Inc.},
  creationdate = {2024-05-15T13:59:51},
  doi          = {https://doi.org/10.1002/(SICI)1097-0282(199608)39:2<183::AID-BIP6>3.0.CO;2-L},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/%28SICI%291097-0282%28199608%2939%3A2%3C183%3A%3AAID-BIP6%3E3.0.CO%3B2-L},
  file         = {:Miura1996 - Hinge Bending Deformation of Enzyme Observed by Microwave Dielectric Measurement.pdf:PDF},
  keywords     = {protein,BDS,hydration shell},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/%28SICI%291097-0282%28199608%2939%3A2%3C183%3A%3AAID-BIP6%3E3.0.CO%3B2-L},
}

@Article{Hayashi2007,
  author       = {Yoshihito Hayashi and Ikuya Oshige and Yoichi Katsumoto and Shinji Omori and Akio Yasuda},
  journal      = {Journal of Non-Crystalline Solids},
  title        = {Protein–solvent interaction in urea–water systems studied by dielectric spectroscopy},
  year         = {2007},
  issn         = {0022-3093},
  note         = {Dielectric Relaxation and Related Phenomena},
  number       = {47},
  pages        = {4492--4496},
  volume       = {353},
  abstract     = {Dielectric spectroscopy measurements were performed at 298K for bovine serum albumin (BSA) dissolved in aqueous solutions of urea (0–9 M with steps of 1M). It was shown that unfolding of BSA molecules by urea influenced the dynamic structures of water and urea molecules, and consequently changed their dielectric responses. At low urea concentrations (0–5M), unfolding of BSA molecules is not very significant and mainly the globular surface of the BSA interacts with the solvent molecules. In comparison with urea solutions without BSA, the high frequency dielectric spectrum (γ-dispersion) was significantly broadened with addition of the BSA, although the characteristic frequency was not affected much. Such behavior is similar to that reported for aqueous solutions of synthetic polyelectrolytes. At high urea concentrations (6–9M), significant unfolding of the BSA molecules occurred, exposing the hydrophobic side chains to the solvent and likely increasing the effects of hydrophobic hydration. As a result, the dielectric response of the solvent molecules was found to be more complicated.},
  creationdate = {2024-05-15T14:06:31},
  doi          = {https://doi.org/10.1016/j.jnoncrysol.2007.02.079},
  file         = {:Hayashi2007 - Protein–solvent Interaction in Urea–water Systems Studied by Dielectric Spectroscopy.pdf:PDF},
  keywords     = {Dielectric properties,relaxation,electric modulus,protein,BDS,ternary mixture,urea,cononsolvency},
  url          = {https://www.sciencedirect.com/science/article/pii/S0022309307009210},
}

@Article{Hayashi2002,
  author            = {Yoshihito Hayashi and Naoki Shinyashiki and Shin Yagihara},
  journal           = {Journal of Non-Crystalline Solids},
  title             = {Dynamical structure of water around biopolymers investigated by microwave dielectric measurements using time domain reflectometry method},
  year              = {2002},
  issn              = {0022-3093},
  number            = {1},
  pages             = {328--332},
  volume            = {305},
  abstract          = {The dynamical structure of free water around biopolymers, such as gelatin, collagen, and globular proteins, has been characterized based on relaxation time, τ, and Cole–Cole parameter, β, obtained from microwave dielectric measurements using a time domain reflectometry method. As reported previously, the plots of β against τ for free water in seven types of synthetic polymers in aqueous solutions against τ are classified into two groups based on polymer hydrophilicity. It is indicated that the dynamical structure of water around low-hydrophilic polymers is more uniform than those around high-hydrophilic polymers. In the present work, the plots for the aqueous gels of gelatin and globular protein in aqueous solutions indicate the same feature as those for high-hydrophilic polymers. It can be expected that the dynamical structure of free water around biopolymers is uneven. However, the water structure around collagen appears to be uniform, although collagen consists almost of the same peptide chains as those of gelatin. These results suggested that the water structure around highly ordered polymers, e.g., collagen, is also uniform.},
  comment-christoph = {water process largely outside the accessible frequency range},
  creationdate      = {2024-05-15T14:10:08},
  doi               = {https://doi.org/10.1016/S0022-3093(02)01113-4},
  file              = {:Hayashi2002 - Dynamical Structure of Water around Biopolymers Investigated by Microwave Dielectric Measurements Using Time Domain Reflectometry Method.pdf:PDF},
  keywords          = {BDS,protein,hydration shell,solvent dynamics,PVME,PAA,PVP,PEG,PVA},
  url               = {https://www.sciencedirect.com/science/article/pii/S0022309302011134},
}

@Book{Ngai2011a,
  author       = {Ngai, K.L},
  publisher    = {Springer},
  title        = {Relaxation and Diffusion in Complex Systems},
  year         = {2011},
  address      = {New York, NY},
  edition      = {First},
  isbn         = {9781441976499},
  series       = {Partially Ordered Systems},
  creationdate = {2024-05-15T14:18:07},
  doi          = {10.1007/978-1-4419-7649-9},
  file         = {:Ngai2011a - Relaxation and Diffusion in Complex Systems.pdf:PDF},
  hdsurl       = {https://hds.hebis.de/ulbda/Record/HEB234252200},
  keywords     = {book,relaxation,review,glass formers},
  uniqueid     = {HEB234252200},
  url          = {https://doi.org/10.1007/978-1-4419-7649-9},
}

@Article{Parker1992,
  author       = {Parker, A. A. and Hedrick, D. P. and Ritchey, W. M.},
  journal      = {Macromolecules},
  title        = {NMR studies of plasticizer motions in a polymer matrix},
  year         = {1992},
  number       = {13},
  pages        = {3365--3368},
  volume       = {25},
  creationdate = {2024-05-16T07:40:43},
  doi          = {10.1021/ma00039a008},
  eprint       = {https://doi.org/10.1021/ma00039a008},
  file         = {:Parker1992 - NMR Studies of Plasticizer Motions in a Polymer Matrix.pdf:PDF},
  keywords     = {NMR,plasitcizer},
  url          = {https://doi.org/10.1021/ma00039a008},
}

@Article{Bingemann2007,
  author       = {Bingemann, Dieter and Wirth, Nadine and Gmeiner, Jürgen and Rössler, Ernst A.},
  journal      = {Macromolecules},
  title        = {Decoupled Dynamics and Quasi-Logarithmic Relaxation in the Polymer−Plasticizer System Poly(methyl methacrylate)/Tri-m-cresyl Phosphate Studied with 2D NMR},
  year         = {2007},
  number       = {15},
  pages        = {5379--5388},
  volume       = {40},
  abstract     = {Studying the dynamics of the polymer−plasticizer system poly(methyl methacrylate) (PMMA)/tri-m-cresyl phosphate (TCP), we find pronounced dynamic heterogeneities for the additive TCP with one- and two-dimensional 31P NMR spectroscopy, whereas the dispersion of the dynamics of the polymer PMMA, studied simultaneously with 2H NMR, remains essentially unchanged upon addition of the plasticizer TCP, despite a large decrease in the correlation time. TCP molecules reorient isotropically even in a rigid polymer matrix at temperatures well below the glass transition of the plasticized PMMA. Taking advantage of the very large time window accessible with the stimulated echo technique for the 31P nucleus, we show that the orientational correlation functions of TCP change from Kohlrausch decays for pure TCP to quasi-logarithmic decays in the mixture, which resemble those from recent simulations with a bead-and-spring model [Moreno, A. J.; Colmenero, J. J. Chem. Phys. 2006, 124, 184906]. Two-dimensional spectra for TCP show that the dynamic heterogeneities of the plasticizer are transient in nature.},
  creationdate = {2024-05-16T08:22:45},
  doi          = {10.1021/ma070519g},
  eprint       = {https://doi.org/10.1021/ma070519g},
  file         = {:Bingemann2007 - Decoupled Dynamics and Quasi Logarithmic Relaxation in the Polymer−Plasticizer System Poly(methyl Methacrylate)_Tri M Cresyl Phosphate Studied with 2D NMR.pdf:PDF},
  keywords     = {NMR,plasticizer,31P-NMR,2H-NMR,glass former,2d-exchange},
  url          = {https://doi.org/10.1021/ma070519g},
}

@Article{Boehmer2021,
  author       = {B{\"o}hmer, Till and Horstmann, Robin and Gabriel, Jan Philipp and Pabst, Florian and Vogel, Michael and Blochowicz, Thomas},
  journal      = {Macromolecules},
  title        = {Origin of Apparent Slow Solvent Dynamics in Concentrated Polymer Solutions},
  year         = {2021},
  number       = {22},
  pages        = {10340--10349},
  volume       = {54},
  abstract     = {Due to their size disparity, the dynamics of solvent molecules in concentrated polymer solutions can be faster by several orders of magnitude compared to the polymer matrix. Despite these observations, past research suggests that a fraction of the solvent contributes to the slow dynamics on the timescale of the macromolecules. By combining depolarized dynamic light scattering and molecular dynamics simulations, we show that long-lived solvent–solvent cross-correlations cause these slow solvent contributions. They originate from the energy landscape that the solute imprints onto the neighboring solvent, leading to enhanced correlations between the positions and orientations of different solvent molecules until the solute relaxes. This mechanism explains the discrepancies found between the results of techniques probing collective and single-particle dynamics, such as dielectric and nuclear magnetic resonance spectroscopy. Our findings shed new light on how solvents behave in the vicinity of macromolecules and are of relevance for materials ranging from polymer-plasticizer systems to hydrated proteins.},
  creationdate = {2024-05-16T08:29:42},
  doi          = {10.1021/acs.macromol.1c01414},
  eprint       = {https://doi.org/10.1021/acs.macromol.1c01414},
  file         = {:Boehmer2021 - Origin of Apparent Slow Solvent Dynamics in Concentrated Polymer Solutions.pdf:PDF},
  keywords     = {plasticizer,molecular dynamics simulation,depolarized dynamic light scattering,cross-correlation},
  url          = {https://doi.org/10.1021/acs.macromol.1c01414},
}

@Article{Poetzschner2017,
  author       = {Pötzschner, B. and Mohamed, F. and Bächer, C. and Wagner, E. and Lichtinger, A. and Minikejew, R. and Kreger, K. and Schmidt, H.-W. and Rössler, E. A.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Non-polymeric asymmetric binary glass-formers. I. Main relaxations studied by dielectric, 2H NMR, and 31P NMR spectroscopy}},
  year         = {2017},
  issn         = {0021-9606},
  month        = apr,
  number       = {16},
  pages        = {164503},
  volume       = {146},
  abstract     = {{In Paper I of this series of two papers we study the main relaxations of a binary glass former made of the low-Tg component tripropyl phosphate (TPP, Tg = 134 K) and of a specially synthesized (deuterated) spirobichroman derivative (SBC, Tg = 356 K) as the non-polymeric high-Tg component for the full concentration range. A large Tg contrast of the neat components is put into effect. Dielectric spectroscopy and different techniques of 2H nuclear magnetic resonance (NMR) as well as of 31P NMR spectroscopy allow to selectively probe the dynamics of the components. For all concentrations, two well separated liquid-like processes are identified. The faster α2-process associated with the low-Tg component TPP shows pronounced dynamic heterogeneities reflected by quasi-logarithmic correlation functions at low TPP concentrations. The slower α1-process involves the reorientation of the high-Tg component SBC. Its correlation function is Kohlrausch-like as in neat glass formers. The corresponding time constants and consequently their glass transition temperatures Tg1 and Tg2 differ more the lower the TPP concentration is. Plasticizer and anti-plasticizer effect, respectively, is observed. At low temperatures a situation arises that the TPP molecules isotropically reorient in an arrested SBC matrix (Tg2 \\&lt; T \\&lt; Tg1). At T \\&lt; Tg2 the liquid-like reorientation of TPP gets arrested too. We find indications that a fraction of the TPP molecule takes part in the slower α1-process of the high-Tg component. All the features known from polymer-plasticizer systems are rediscovered in this non-polymeric highly asymmetric binary mixture. In Paper II [B. Pötzschner et al., J. Chem. Phys. 146, 164504 (2017)] we study the secondary (β-) relaxations of the mixtures.}},
  creationdate = {2024-05-16T08:34:40},
  doi          = {10.1063/1.4980084},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4980084/13578157/164503\_1\_online.pdf},
  file         = {:Poetzschner2017 - Non Polymeric Asymmetric Binary Glass Formers. I. Main Relaxations Studied by Dielectric, 2H NMR, and 31P NMR Spectroscopy.pdf:PDF},
  keywords     = {plasticizer,glass former,2H-NMR,31P-NMR,BDS},
  url          = {https://doi.org/10.1063/1.4980084},
}

@Article{Nakazawa2000,
  author       = {Nakazawa, Masaharu and Urakawa, Osamu and Adachi, Keiichiro},
  journal      = {Macromolecules},
  title        = {Effect of Local Heterogeneity on Dielectric Relaxation Spectra in Concentrated Solutions of Poly(vinyl acetate) and Poly(vinyl octanoate)},
  year         = {2000},
  number       = {21},
  pages        = {7898--7904},
  volume       = {33},
  abstract     = {The effect of local heterogeneity on the distribution of dielectric relaxation times was studied for concentrated solutions of poly(vinyl acetate) (PVAc) in 1-methylnaphthalene (MN) and those of poly(vinyl octanoate) (PVOc) in toluene (Tol). The half-widths Λ of the dielectric loss curves for the primary processes of those systems are compared with those of the PVAc/Tol system reported previously. The data indicate that Λ decreases in order of PVAc/Tol, PVAc/MN, and PVOc/Tol systems if compared at the same temperature T/Tg where Tg denotes the glass transition temperature of solutions. The half-width of each solution increases with decreasing temperature. The loss curve is calculated by assuming a Gaussian distribution of the local concentration φ which results in the distribution of relaxation times g(τ). The calculated loss curves agree fairly well with the observed ones. The broadening behavior is also explained by assuming that Λ is proportional to the amplitude of the local concentration fluctuation Δφ times the slope of the φ dependence curve of the average relaxation time τ. This assumption leads to a linear relationship between Λ and Δφ/(T − T0)2 where T0 is the Vogel critical temperature. Using this relation, we have attempted to estimate Δφ. Small-angle X-ray scattering was also measured on PVAc/MN solutions and found that the scattering intensity was lower than that for PVAc/Tol. This is consistent with the fact that Λ of PVAc/MN solutions is narrower than PVAc/Tol solutions.},
  creationdate = {2024-05-16T08:48:04},
  doi          = {10.1021/ma000102+},
  eprint       = {https://doi.org/10.1021/ma000102+},
  file         = {:Nakazawa2000 - Effect of Local Heterogeneity on Dielectric Relaxation Spectra in Concentrated Solutions of Poly(vinyl Acetate) and Poly(vinyl Octanoate).pdf:PDF},
  keywords     = {BDS,PVAc,poly(vinyl acetate),poly(vinyl octanoate),toluene,toluol,glass former,plasticizer, concentration fluctuation},
  url          = {https://doi.org/10.1021/ma000102+},
}

@Article{Sammler1990,
  author       = {Sammler, R. L. and Landry, C. J. T. and Woltman, G. R. and Schrag, John L.},
  journal      = {Macromolecules},
  title        = {Polydispersity effects on dilute-solution dynamic properties of linear homopolymers},
  year         = {1990},
  number       = {8},
  pages        = {2388--2396},
  volume       = {23},
  creationdate = {2024-05-16T09:01:33},
  doi          = {10.1021/ma00210a042},
  eprint       = {https://doi.org/10.1021/ma00210a042},
  file         = {:Sammler1990 - Polydispersity Effects on Dilute Solution Dynamic Properties of Linear Homopolymers.pdf:PDF},
  keywords     = {polydispersity,linear polymer,homopolymer,Zimm model,polystyrene,PS,aroclor,birefringence},
  url          = {https://doi.org/10.1021/ma00210a042},
}

@Article{Sasaki2016,
  author       = {Sasaki, Kaito and Matsui, Yurika and Miyara, Masahiko and Kita, Rio and Shinyashiki, Naoki and Yagihara, Shin},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Glass Transition and Dynamics of the Polymer and Water in the Poly(vinylpyrrolidone)–Water Mixtures Studied by Dielectric Relaxation Spectroscopy},
  year         = {2016},
  note         = {PMID: 27320337},
  number       = {27},
  pages        = {6882--6889},
  volume       = {120},
  abstract     = {In this study, broadband dielectric spectroscopy and differential scanning calorimetry (DSC) measurements are performed to study the dynamics of water and polymers in an aqueous solution of poly(vinylpyrrolidone) (PVP) with concentrations of 60, 65, and 70 wt \% PVP in a temperature range of 123–298 K. Two distinct relaxation processes, l- and h-processes, which originate from the segmental chain motion of PVP and the primary relaxation process of water, respectively, are observed simultaneously. The relationship between l- and h-processes and their temperature dependences mimic those of the α-process and Johari–Goldstein β-process, which are observed in ordinal glass formers. The relaxation time of the l-process, τl, obeys the Vogel–Fulcher (VF)-type temperature dependence, and the glass-transition temperature of the l-process, Tg,l, which is defined by the temperature that is reached in a τl of 100–1000 s, shows good agreement with the calorimetric Tg obtained by DSC. The temperature dependence of the relaxation time of the h-process, τh, exhibits a crossover from VF to Arrhenius behavior at the so-called fragile-to-strong transition (FST) of water at Tg,l. The temperature dependence of the relaxation strength of the h-process, Δεh, increases with a decrease in temperature from 298 K to Tg,l. Below Tg,l, Δεh is nearly constant or slightly decreases with decreasing temperature. According to previous studies on aqueous solutions of sugars and alcohols, the Δε of the ν-process, which originates from local motion of water, decreases with decreasing temperature above the Tg of the α-process, which originates from the cooperative motion of the solute and water. Therefore, the l-process in the PVP–water mixture is not a result of the cooperative motion of PVP and water but rather a result of the polymer–polymer cooperative motion of PVP. In addition, agreement among Tg,l, the temperature of the FST of water, and calorimetric Tg suggests that the FST of water occurs at Tg.},
  creationdate = {2024-05-16T09:41:27},
  doi          = {10.1021/acs.jpcb.6b05347},
  eprint       = {https://doi.org/10.1021/acs.jpcb.6b05347},
  file         = {:Sasaki2016 - Glass Transition and Dynamics of the Polymer and Water in the Poly(vinylpyrrolidone)–Water Mixtures Studied by Dielectric Relaxation Spectroscopy.pdf:PDF},
  keywords     = {BDS,PVP,aqueous solution,DSC,johari-goldstein,glass former},
  url          = {https://doi.org/10.1021/acs.jpcb.6b05347},
}

@Article{Bock2014,
  author       = {Bock, D. and Kahlau, R. and Pötzschner, B. and Körber, T. and Wagner, E. and Rössler, E. A.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Dynamics of asymmetric binary glass formers. II. Results from nuclear magnetic resonance spectroscopy}},
  year         = {2014},
  issn         = {0021-9606},
  month        = mar,
  number       = {9},
  pages        = {094505},
  volume       = {140},
  abstract     = {{Various 2H and 31P nuclear magnetic resonance (NMR) spectroscopy techniques are applied to probe the component dynamics of the binary glass former tripropyl phosphate (TPP)/polystyrene-d3 (PS) over the full concentration range. The results are quantitatively compared to those of a dielectric spectroscopy (DS) study on the same system previously published [R. Kahlau, D. Bock, B. Schmidtke, and E. A. Rössler, J. Chem. Phys. 140, 044509 (2014)]. While the PS dynamics does not significantly change in the mixtures compared to that of neat PS, two fractions of TPP molecules are identified, one joining the glass transition of PS in the mixture (α1-process), the second reorienting isotropically (α2-process) even in the rigid matrix of PS, although at low concentration resembling a secondary process regarding its manifestation in the DS spectra. Pronounced dynamical heterogeneities are found for the TPP α2-process, showing up in extremely stretched, quasi-logarithmic stimulated echo decays. While the time window of NMR is insufficient for recording the full correlation functions, DS results, covering a larger dynamical range, provide a satisfactory interpolation of the NMR data. Two-dimensional 31P NMR spectra prove exchange within the broadly distributed α2-process. As demonstrated by 2H NMR, the PS matrix reflects the faster α2-process of TPP by performing a spatially highly hindered motion on the same timescale.}},
  creationdate = {2024-05-16T10:29:26},
  doi          = {10.1063/1.4865945},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4865945/14923886/094505\_1\_online.pdf},
  file         = {:Bock2014 - Dynamics of Asymmetric Binary Glass Formers. II. Results from Nuclear Magnetic Resonance Spectroscopy.pdf:PDF},
  keywords     = {glass former,NMR,2H-NMR,polystyrene,PS,31P-NMR,tripropyl phosphate,BDS},
  url          = {https://doi.org/10.1063/1.4865945},
}








@Article{Shinyashiki1998,
  author            = {Shinyashiki, Naoki and Yagihara, Shin and Arita, Izumi and Mashimo, Satoru},
  journal           = {The Journal of Physical Chemistry B},
  title             = {Dynamics of Water in a Polymer Matrix Studied by a Microwave Dielectric Measurement},
  year              = {1998},
  number            = {17},
  pages             = {3249--3251},
  volume            = {102},
  abstract          = {Dielectric measurements on water mixtures of polymers such as poly(vinylpyrrolidone) (PVP), poly(ethylene glycol) (PEG), poly(vinyl methyl ether) (PVME), poly(vinyl alcohol) (PVA), poly(acrylic acid) (PAA), poly(ethylenimine) (PEI), and poly(allylamine) (PAlA) were performed over a frequency range from 300 MHz to 15 GHz at 25 °C. Dielectric dispersion and absorption curves related to the orientational motion of water can be described well by the Cole−Cole equation. The distribution of the relaxation time is interpreted by the variation of the water structure. The logarithmic plot of the relaxation time against the parameter for the distribution of the relaxation time suggests two groups of polymers. One group contains nonelectrolyte polymers and another contains electrolyte polymers and PVA. This result implies that water structures in the mixtures of the former group are more uniform and stable than that in the mixtures of the latter group.},
  comment-christoph = {water process largely outside the accessible frequency range. Maybe usefull for cited-by list},
  doi               = {10.1021/jp9729627},
  eprint            = {https://doi.org/10.1021/jp9729627},
  file              = {:Shinyashiki1998 - Dynamics of Water in a Polymer Matrix Studied by a Microwave Dielectric Measurement.pdf:PDF},
  keywords          = {BDS,PVP,PEG,PVME,PVA,PAA,poly(ethylenimine),PEI,poly(allylamine),PAIA,spectral density,hydration shell,solvent dynamics},
  url               = {https://doi.org/10.1021/jp9729627},
}

@Article{Hayashi2000,
  author            = {Hayashi, Yoshihito and Miura, Nobuhiro and Shinyashiki, Naoki and Yagihara, Shin and Mashimo, Satoru},
  journal           = {Biopolymers},
  title             = {Globule–coil transition of denatured globular protein investigated by a microwave dielectric technique},
  year              = {2000},
  number            = {6},
  pages             = {388--397},
  volume            = {54},
  abstract          = {A mechanism for the gel–glass transition of denatured globular protein has been explained from the viewpoint of the globule–coil transition with microwave dielectric measurements using a time domain reflectometry (TDR) method. Boiled egg white, which is an aqueous gel of egg white prepared by heat treatment at 100°C, becomes a glass on drying. In the gel state, the relaxation processes corresponding to the orientation of bulk water and the micro-Brownian motion of peptide chains of denatured protein were observed around 10 GHz and 10 MHz, respectively. When the gel–glass transition occurred, the relaxation strength for bulk water decreased rapidly as evaporation and breaking of water structure occurred. Simultaneously, the relaxation strength for micro-Brownian motion increased abruptly, as the structure of globular protein varied from globule state to coiled state. It is considered that the protein molecule spreads out and takes up a coiled state by reductions of hydrophobic and hydrophilic interactions of the globular protein. These reductions occur through a decrease in the amount of water. © 2000 John Wiley \& Sons, Inc. Biopoly 54: 388–397, 2000},
  comment-christoph = {water process largely outside the accessible frequency range},
  creationdate      = {2024-05-18},
  doi               = {https://doi.org/10.1002/1097-0282(200011)54:6<388::AID-BIP30>3.0.CO;2-K},
  eprint            = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/1097-0282%28200011%2954%3A6%3C388%3A%3AAID-BIP30%3E3.0.CO%3B2-K},
  file              = {:Hayashi2000 - Globule–coil Transition of Denatured Globular Protein Investigated by a Microwave Dielectric Technique.pdf:PDF},
  keywords          = {time domain reflectometry, gel–glass transition, unfolding of globular protein, peptide chain motion, water structure},
  url               = {https://onlinelibrary.wiley.com/doi/abs/10.1002/1097-0282%28200011%2954%3A6%3C388%3A%3AAID-BIP30%3E3.0.CO%3B2-K},
}

@Article{Dhara2000,
  author       = {Dibakar Dhara and Prabha R. Chatterji},
  journal      = {Journal of Macromolecular Science, Part C},
  title        = {Phase Transition in Linear and Cross-Linked Poly(N-Isopropylacrylamide) in Water: Effect of Various Types of Additives},
  year         = {2000},
  number       = {1},
  pages        = {51--68},
  volume       = {40},
  creationdate = {2024-05-22T08:18:05},
  doi          = {10.1081/MC-100100578},
  eprint       = {https://doi.org/10.1081/MC-100100578},
  file         = {:Dhara2000 - Phase Transition in Linear and Cross Linked Poly(N Isopropylacrylamide) in Water_ Effect of Various Types of Additives.pdf:PDF},
  keywords     = {pNIPAM,linear,gel,salt,cononsolvency,ionic strength,review},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1081/MC-100100578},
}

@Article{SihyunKim2024,
  author       = {Sihyun Kim, Seonyoung Jo and Taek Seung Lee},
  journal      = {Molecular Crystals and Liquid Crystals},
  title        = {Poly(N-isopropylacrylamide)-based hydrogel carrier containing Prussian blue for thermally controlled release},
  year         = {2024},
  number       = {0},
  pages        = {1--13},
  volume       = {0},
  abstract     = {A hydrogel consisted of poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAAm-co-AA) and Prussian blue (PB) was synthesized for a cargo carrier by controlling the release of organic dye under near infrared (NIR) light. The AA moiety of the hydrogel provided chemical bonding with Fe (III) ions for further PB formation. Biocompatible, NIR-responsive PB generated heat and the heat was transferred to the hydrogel. The NIPAAm moiety in the hydrogel was shrunken because of the low critical solution temperature behavior of the hydrogel, and the hydrogel released the loaded dye with 62\%. These results suggest dye-loaded hydrogel as a prospective platform for light-triggered carriers.},
  comment      = {paywall},
  creationdate = {2024-05-22T08:32:12},
  doi          = {10.1080/15421406.2024.2353949},
  eprint       = {https://doi.org/10.1080/15421406.2024.2353949},
  keywords     = {drug delivery, pNIPAM, copolymer, hydrogel, photoresponsive, application-focused, application focused},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/15421406.2024.2353949},
}

@InBook{Saito1993,
  author       = {Saito, S. and Konno, M. and Inomata, H.},
  editor       = {Du{\v{s}}ek, K.},
  pages        = {207--232},
  publisher    = {Springer Berlin Heidelberg},
  title        = {Volume phase transition of N-alkylacrylamide gels},
  year         = {1993},
  address      = {Berlin, Heidelberg},
  isbn         = {978-3-540-47737-2},
  abstract     = {Experimental and theoretical studies performed on thermoshrinking N-alkylacrylamide gels are described. Equilibrium swelling ratios are presented for the gels in the presence of no additives, a surfactant (SDS), inorganic salts, polar organic components and tetraalkylammonium bromides. The gel studies are carefully matched to polymer cloud point studies and it is shown that the hydrophobicity of the monomer unit of the polymer greatly controls the phase behavior. A new model which can describe not only thermoswelling but also thermoshrinking types of volume phase transitions is presented. Dynamical studies performed with light scattering during spinodal decomposition provide new information on diffusion coefficients and mass transfer in the gels. Our studies provide new data on the use of a gel in membrane applications. We report permeation characteristics of a composite membrane of thermosensitive gel and porous glass. These include volume flux and rejection properties. It is pointed out that the change in the permeation characteristics results from that in micropore structures of the gel.},
  booktitle    = {Responsive Gels: Volume Transitions I},
  comment      = {paywall},
  creationdate = {2024-05-22T08:35:29},
  doi          = {10.1007/3-540-56791-7_5},
  keywords     = {pNIPAM,book,gel},
  url          = {https://doi.org/10.1007/3-540-56791-7_5},
}

@Article{Mochizuki2017,
  author       = {Mochizuki, Kenji and Ben-Amotz, Dor},
  journal      = {The Journal of Physical Chemistry Letters},
  title        = {Hydration-Shell Transformation of Thermosensitive Aqueous Polymers},
  year         = {2017},
  note         = {PMID: 28277683},
  number       = {7},
  pages        = {1360--1364},
  volume       = {8},
  abstract     = {Although water plays a key role in the coil–globule transition of polymers and biomolecules, it is not clear whether a change in water structure drives or follows polymer collapse. Here, we address this question by using Raman multivariate curve resolution (Raman-MCR) spectroscopy to investigate the hydration shell structure around poly(N-isopropylacrylamide) (PNIPAM) and poly(propylene oxide) (PPO), both below and above the cloud point temperature at which the polymers collapse and form mesoscopic polymer-rich aggregates. We find that, upon clouding, the water surrounding long PNIPAM chains transforms to a less ordered and more weakly hydrogen bonded structure, while the water surrounding short PNIPAM and PPO chains remains similar above and below the cloud point. Furthermore, microfluidic temperature jump studies demonstrate that the onset of clouding precedes the hydration-shell structural transformation, and thus the observed water structural transformation is associated with ripening of aggregates composed of long-chain polymers, on a time scale that is long compared to the onset of clouding.},
  creationdate = {2024-05-22T11:44:03},
  doi          = {10.1021/acs.jpclett.7b00363},
  eprint       = {https://doi.org/10.1021/acs.jpclett.7b00363},
  file         = {:Mochizuki2017 - Hydration Shell Transformation of Thermosensitive Aqueous Polymers.pdf:PDF;:HydrationShellTransformationOfThermosensitiveAqueousPolymers_MochizukiEtAl_JPCLett2017_SI.pdf:PDF},
  keywords     = {pNIPAM,poly(ethylene oxide),PPO,hydration shell,raman spectroscopy,multivarate curve resolution,microfluidic,cloud point,kinetics},
  url          = {https://doi.org/10.1021/acs.jpclett.7b00363},
}

@Article{Wang2022,
  author       = {Wang, Dong and Li, Dongfang and Kelland, Malcolm A. and Cai, Haokun and Wang, Jie and Xu, Ying and Lu, Ping and Dong, Jian},
  journal      = {Langmuir},
  title        = {Unraveling Amphiphilic Poly(N-vinylcaprolactam)/Water Interface by Nuclear Magnetic Resonance Relaxometry: Control of Clathrate Hydrate Formation Kinetics},
  year         = {2022},
  note         = {PMID: 35380846},
  number       = {15},
  pages        = {4774--4784},
  volume       = {38},
  abstract     = {Water-soluble amphiphilic polymers are vital chemicals in the oil and gas industry to retard crystal growth of hydrocarbon hydrate via surface adsorption and suppress nucleation of a pristine hydrate nucleus, thereby preventing formation of hydrate blockages in flow lines during oil and natural gas production. Apart from a few theoretical modeling studies, an experimental method to study the polymer/water interface in the crystal growth is critically needed. Here, water motions in the hydration shells of an exemplary kinetic inhibitor, poly(N-vinylcaprolactam), during hydrate formation from the tetrahydrofuran/water system are revealed via nuclear magnetic resonance relaxometry. Unequivocal experiments show that the pivotal interfacial water in the tightly bound state gradually freezes at rates depending on the polymer molecular weight (MW). This is supported by nonfreezable water analysis, which is correlated to the inhibition time. The polymers tune the kinetics of the hydration process via interaction with and perturbation of the water molecules. The free water component in the polymer solution crystallizes at a very slow rate when in partially restricted mobility, whereas the bound water component increases in the reaction, with the polymer/water interface serving as the reaction sites. The appropriate MW (including average MW and polydispersity values) of the inhibitive polymers can give rise to maximal retardation of the hydrate crystal growth. This work will help control other multiphase crystallization kinetic processes through the design of inhibitors or promoters functioning in the interface.},
  creationdate = {2024-05-22T11:53:36},
  doi          = {10.1021/acs.langmuir.2c00472},
  eprint       = {https://doi.org/10.1021/acs.langmuir.2c00472},
  file         = {:Wang2022 - Unraveling Amphiphilic Poly(N Vinylcaprolactam)_Water Interface by Nuclear Magnetic Resonance Relaxometry_ Control of Clathrate Hydrate Formation Kinetics.pdf:PDF;:UnravelingAmphiphilicPolyNVinylcaprolactamWaterInteraceByNuclearMagneticResonanceRelaxometry-ControlOfClathrateHydrateFormationKinetics_WantEtAl_Langmuir2022_SI.pdf:PDF},
  keywords     = {NMR,relaxation,PVCL,thermoresponsive,aqueous polymer,T2,spin-spin relaxation time,magnetic relaxation dispersion,1H-NMR,Kinetics,Clathrate,hydration shell,THF,cononsolvency},
  url          = {https://doi.org/10.1021/acs.langmuir.2c00472},
}

@Article{Wang2024,
  author       = {Wang, Dong and Kelland, Malcolm A. and Xu, Ying and Wang, Xin and Lu, Ping and Dong, Jian},
  journal      = {Energy \& Fuels},
  title        = {Kinetic Hydrate Inhibition of Poly(N-isopropyl\-acrylamide) and Poly(N-isopropyl\-methacrylamide): A Comprehensive Analysis of Amphiphilicity and Hydrogen Bonding Effect},
  year         = {2024},
  number       = {4},
  pages        = {2790--2802},
  volume       = {38},
  abstract     = {Rapid formation of natural gas clathrate hydrates has been a significant hazard in off-shore natural gas drilling and gas transport. During operation, polymer inhibitors can serve as low-dosage kinetic inhibitors to prevent the formation of gas hydrates. A comprehensive consideration of the multiple factors involved in the actions of kinetic hydrate inhibitors (KHIs) can elucidate the inhibiting behavior of polymers. Here, amphiphilic poly(N-isopropylmethacrylamide) (PNIPMAm) (or poly(N-isopropylacrylamide)) are found to achieve weak to strong inhibition by the variable superimposed effect of the polymer’s amide group and hydrophobic effect of the polymer’s alkyl groups on the aqueous phase. The interfacial and bulk water mobility and hydrogen bonding energy in the polymer solutions are compared by low-temperature nuclear magnetic resonance (NMR) relaxometry. The mobility of the water is found to be sensitive to the hydrophobic α-methyl side group in PNIPMAm and its molecular weight when a guest molecule tetrahydrofuran is present. The water hydrogen bonding energies measured from NMR are also associated with the nonfreezable bound water amount revealed by differential scanning calorimetry. The α-methyl side group leads to a significant reduction of the water mobility, an increase in the hydrogen bonding energies of the interfacial water, and a decrease of the hydrate growth rate constants by 2 to 3 orders of magnitude. The retarded reaction kinetics of heterogeneous hydrate growth can be related to the hydrophobic effect of the polymer’s α-methyl side group and bound water properties (mobility and amount) in the interface.},
  creationdate = {2024-05-22T12:01:19},
  doi          = {10.1021/acs.energyfuels.3c03865},
  eprint       = {https://doi.org/10.1021/acs.energyfuels.3c03865},
  file         = {:Wang2024 - Kinetic Hydrate Inhibition of Poly(N Isopropylacrylamide) and Poly(N Isopropylmethacrylamide)_ a Comprehensive Analysis of Amphiphilicity and Hydrogen Bonding Effect.pdf:PDF;:KineticHydrateInhibitionOfPolyNIsopropylacrylamideAndPolyNIsopropylmethacrylamide-AComprehensiveAnalysisOfAmphiphilicityAndHydrogenBondingEffect_WantEtAl_EnergyAndFuels2024_SI.pdf:PDF},
  keywords     = {NMR,pNIPAM,PNIPMAM,magnetic relaxation dispersion,DSC,cononsolvency,THF,kinetics,hydration shel},
  url          = {https://doi.org/10.1021/acs.energyfuels.3c03865},
}

@Article{Bruce2019,
  author       = {Bruce, Ellen E. and van der Vegt, Nico F. A.},
  journal      = {Journal of the American Chemical Society},
  title        = {Molecular Scale Solvation in Complex Solutions},
  year         = {2019},
  note         = {PMID: 31318544},
  number       = {33},
  pages        = {12948--12956},
  volume       = {141},
  abstract     = {Complex solution environments are ubiquitous in nature. Most life science systems contain hydrated macromolecules whose solubility, function and stability are modulated by several small organic molecules or salts (cosolutes) present simultaneously. This Perspective discusses solvation of mixed cosolutes in water. Recent computer simulations and experiments have shown that nonadditive cosolute effects on the water solubility of thermoresponsive polymers and on protein stability have a common physical origin, rooted in solvent-excluded volume effects determined by mutually enhanced cosolute hydration in bulk. We discuss mixtures of weakly and strongly hydrated salts in the anionic Hofmeister series and mixtures of urea and trimethylamine N-oxide. Nonadditive phenomena in these mixtures lead to intriguing effects including consecutive polymer collapse and swelling transitions and counteraction of denaturant-induced protein unfolding. The combination of today’s advanced simulation methods and spectroscopy techniques should be used to improve further the understanding of these complex aqueous solubility problems.},
  creationdate = {2024-05-22T12:26:12},
  doi          = {10.1021/jacs.9b03469},
  eprint       = {https://doi.org/10.1021/jacs.9b03469},
  file         = {:Bruce2019 - Molecular Scale Solvation in Complex Solutions.pdf:PDF},
  keywords     = {hydration shell,simulation,ionic strength,hofmeister series,pNIPAM,cononsolvency,excluded volume,solubility,vibrational sum frequency spectroscopy},
  url          = {https://doi.org/10.1021/jacs.9b03469},
}

@Article{RodriguezRopero2015,
  author       = {Rodríguez-Ropero, Francisco and Hajari, Timir and van der Vegt, Nico F. A.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Mechanism of Polymer Collapse in Miscible Good Solvents},
  year         = {2015},
  note         = {PMID: 26619003},
  number       = {51},
  pages        = {15780--15788},
  volume       = {119},
  abstract     = {We propose a physical mechanism for co-nonsolvency of a stimulus-responsive polymer in water/methanol mixed solution based on results obtained with molecular simulations. Even though the phenomenon is well known, the mechanism behind co-nonsolvency is still under debate. Herein, we study co-nonsolvency of poly(N-isopropylacrylamide) (PNiPAM) in methanol aqueous solutions, the most widely studied and experimentally well-characterized system. Our results show that at low alcohol content of the solution methanol preferentially binds to the PNiPAM globule and drives polymer collapse. The energetics of electrostatic, hydrogen bonding, or bridging-type interactions with the globule is found to play no role. Instead, preferential methanol binding results in a significant increase in the globule’s configurational entropy, stabilizing methanol-enriched globular structures over wet globular structures in neat water. This mechanism drives the reduction of the lower critical solution temperature with increasing methanol content in the co-nonsolvency regime and eventually leads to polymer collapse. The globule-to-coil re-entrance at high methanol concentrations is instead driven by changes in solvent-excluded volume of the coil and globular states imparted by a decrease in solvent density with increasing methanol content of the solution: with increasing proportion of larger solvent particles (methanol), the entropic (cavity formation) cost of redistributing solvent molecules upon polymer re-entrance becomes smaller. This effect provides a natural explanation for the experimentally observed dependence of the re-entrance transition on chain molecular weight.},
  creationdate = {2024-05-22T13:25:08},
  doi          = {10.1021/acs.jpcb.5b10684},
  eprint       = {https://doi.org/10.1021/acs.jpcb.5b10684},
  file         = {:RodriguezRopero2015 - Mechanism of Polymer Collapse in Miscible Good Solvents.pdf:PDF},
  keywords     = {cononsolvency,aqueous methanol,pNIPAM,simulation,entropy,UCST,re-entrant transition,preferential adsorption},
  url          = {https://doi.org/10.1021/acs.jpcb.5b10684},
}








@Article{Roget2021,
  author       = {Roget, Sean A. and Piskulich, Zeke A. and Thompson, Ward H. and Fayer, Michael D.},
  journal      = {Journal of the American Chemical Society},
  title        = {Identical Water Dynamics in Acrylamide Hydrogels, Polymers, and Monomers in Solution: Ultrafast IR Spectroscopy and Molecular Dynamics Simulations},
  year         = {2021},
  note         = {PMID: 34491037},
  number       = {36},
  pages        = {14855--14868},
  volume       = {143},
  abstract     = {The dynamics and structure of water in polyacrylamide hydrogels (PAAm-HG), polyacrylamide, and acrylamide solutions are investigated using ultrafast infrared experiments on the OD stretch of dilute HOD/H2O and molecular dynamics simulations. The amide moiety of the monomer/polymers interacts strongly with water through hydrogen bonding (H-bonding). The FT-IR spectra of the three systems indicate that the range of H-bond strengths is relatively unchanged from bulk water. Vibrational population relaxation measurements show that the amide/water H-bonds are somewhat weaker but fall within the range of water/water H-bond strengths. A previous study of water dynamics in PAAm-HG suggested that the slowing observed was due to increasing confinement with concentration. Here, for the same concentrations of the amide moiety, the experimental results demonstrate that the reorientational dynamics (infrared pump–probe experiments) and structural dynamics (two-dimensional infrared spectroscopy) are identical in the three acrylamide systems studied. Molecular dynamics simulations of the water orientational relaxation in aqueous solutions of the acrylamide monomer, trimer, and pentamer are in good agreement with the experimental results and are essentially chain length independent. The simulations show that there is a slower, low-amplitude (<7\%) decay component not accessible by the experiments. The simulations examine the dynamics and structure of water H-bonded to acrylamide, in the first solvent shell, and beyond for acrylamide monomers and short chains. The experiments and simulations show that the slowing of water dynamics in PAAm-HG is not caused by confinement in the polymer network but rather by interactions with individual acrylamide moieties.},
  creationdate = {2024-05-22T14:27:59},
  doi          = {10.1021/jacs.1c07151},
  eprint       = {https://doi.org/10.1021/jacs.1c07151},
  file         = {:Roget2021 - Identical Water Dynamics in Acrylamide Hydrogels, Polymers, and Monomers in Solution_ Ultrafast IR Spectroscopy and Molecular Dynamics Simulations.pdf:PDF;:IdenticalWaterDynamicsInAcrylamideHydrogelsPolymersAndMonomersInSolution-UltrafastIRSpectroscopyAndMolecularDynamicsSimulations_RogetEtAl_JAmChemSoc2021_SI.pdf:PDF},
  keywords     = {infrared,IR,molecular dynamics simulation,PAA,poly(acrylamide),hydration shell,hydrogel,linear,monomer,hydrogen bond,reorientational dynamics,structural relaxation,D2O},
  url          = {https://doi.org/10.1021/jacs.1c07151},
}








@Article{Yan2018,
  author       = {Yan, Chang and Kramer, Patrick L. and Yuan, Rongfeng and Fayer, Michael D.},
  journal      = {Journal of the American Chemical Society},
  title        = {Water Dynamics in Polyacrylamide Hydrogels},
  year         = {2018},
  note         = {PMID: 29985609},
  number       = {30},
  pages        = {9466--9477},
  volume       = {140},
  abstract     = {Polymeric hydrogels have wide applications including electrophoresis, biocompatible materials, water superadsorbents, and contact lenses. The properties of hydrogels involve the poorly characterized molecular dynamics of water and solutes trapped within the three-dimensional cross-linked polymer networks. Here we apply ultrafast two-dimensional infrared (2D IR) vibrational echo and polarization-selective pump–probe (PSPP) spectroscopies to investigate the ultrafast molecular dynamics of water and a small molecular anion solute, selenocyanate (SeCN–), in polyacrylamide hydrogels. For all mass concentrations of polymer studied (5\% and above), the hydrogen-bonding network reorganization (spectral diffusion) dynamics and reorientation dynamics reported by both water and SeCN– solvated by water are significantly slower than in bulk water. As the polymer mass concentration increases, molecular dynamics in the hydrogels slow further. The magnitudes of the slowing, measured with both water and SeCN–, are similar. However, the entire hydrogen-bonding network of water molecules appears to slow down as a single ensemble, without a difference between the core water population and the interface water population at the polymer–water surface. In contrast, the dissolved SeCN– do exhibit two-component dynamics, where the major component is assigned to the anions fully solvated in the confined water nanopools. The slower component has a small amplitude which is correlated with the polymer mass concentration and is assigned to adsorbed anions strongly interacting with the polymer fiber networks.},
  creationdate = {2024-05-22T14:35:04},
  doi          = {10.1021/jacs.8b03547},
  eprint       = {https://doi.org/10.1021/jacs.8b03547},
  file         = {:Yan2018 - Water Dynamics in Polyacrylamide Hydrogels.pdf:PDF;:WaterDynamicsInPolyacrylamideHydrogels_YanEtAl_JAmChemSoc2018_SI.pdf:PDF},
  keywords     = {hydrogel,PAA,poly(acrylamide),infrared,IR,reorientational dynamics},
  url          = {https://doi.org/10.1021/jacs.8b03547},
}








@Article{Niebuur2021,
  author       = {Niebuur, Bart-Jan and Lohstroh, Wiebke and Ko, Chia-Hsin and Appavou, Marie-Sousai and Schulte, Alfons and Papadakis, Christine M.},
  journal      = {Macromolecules},
  title        = {Pressure Dependence of Water Dynamics in Concentrated Aqueous Poly(N-isopropylacrylamide) Solutions with a Methanol Cosolvent},
  year         = {2021},
  number       = {9},
  pages        = {4387--4400},
  volume       = {54},
  abstract     = {The water dynamics of a concentrated poly(N-isopropylacrylamide) (PNIPAM) solution in an 80:20 v/v water/methanol mixture are investigated across the cloud point Tcp at atmospheric and high pressure (200 MPa). Quasi-elastic neutron scattering (QENS) reveals the relaxation spectra of bulk and hydration water over a frequency range of 4 decades (GHz to THz) and their changes upon the reversal of co-non-solvency at high pressures. At atmospheric pressure, the susceptibility spectra in the one-phase region provide evidence of polymer-bound water, which is released in part nearly discontinuously at Tcp. Simultaneously, the elastic line strength increases abruptly, which is consistent with a coil-to-globule transition. At high pressures, the fraction of bound water decreases gradually with increasing temperature, while the elastic line strength increases at Tcp. Comparing the bulk diffusion time τd of water in the one-phase region with its values from the neat solvent mixture, dominant methanol adsorption is found at atmospheric pressure, whereas water adsorbs preferentially on the chains at high pressures. At 0.1 MPa, the relaxation time of bound water in the one-phase region near Tcp is smaller than that at 200 MPa, i.e., the binding strength between water and PNIPAM is weakened by the presence of adsorbed methanol. Raman spectroscopy, probing the interaction between the solvent molecules and the methyl groups of PNIPAM, indicates that methanol adsorbs to the hydrophobic groups at atmospheric pressure, while it is diminished at high pressures.},
  creationdate = {2024-05-22T15:19:07},
  doi          = {10.1021/acs.macromol.1c00111},
  eprint       = {https://doi.org/10.1021/acs.macromol.1c00111},
  file         = {:Niebuur2021 - Pressure Dependence of Water Dynamics in Concentrated Aqueous Poly(N Isopropylacrylamide) Solutions with a Methanol Cosolvent.pdf:PDF;:PressureDependenceOfWaterDynamicsInConcentratedAqueousPolyNIsopropylacrylamideSolutionsWithAMethanolCosolvent_NiebuurEtAl_Macromol2021_SI-corrected.pdf:PDF},
  keywords     = {pNIPAM,pressure,cononsolvency,aqueous alcohol,methanol,QENS,neutrons},
  url          = {https://doi.org/10.1021/acs.macromol.1c00111},
}

@Article{Niebuur2021a,
  author       = {Niebuur, Bart-Jan and Chiappisi, Leonardo and Jung, Florian A. and Zhang, Xiaohan and Schulte, Alfons and Papadakis, Christine M.},
  journal      = {Nanoscale},
  title        = {Nanoscale disintegration kinetics of mesoglobules in aqueous poly(N-isopropylacrylamide) solutions revealed by small-angle neutron scattering and pressure jumps},
  year         = {2021},
  pages        = {13421--13426},
  volume       = {13},
  abstract     = {Identification and control of the disintegration mechanism of polymer nanoparticles are essential for applications in transport and release including polymer delivery systems. Structural changes during the disintegration of poly(N-isopropylacrylamide) (PNIPAM) mesoglobules in aqueous solution are studied in situ and in real time using kinetic small-angle neutron scattering with a time resolution of 50 ms. Simultaneously length scales between 1 and 100 nm are resolved. By initiating phase separation through fast pressure jumps across the coexistence line{,} 3 wt% PNIPAM solutions are rapidly brought into the one-phase state. Starting at the same temperature (35.1 °C) and pressure (17 MPa) the target pressure is varied over the range 25–48 MPa{,} allowing to systematically alter the osmotic pressure of the solvent within the mesoglobules. Initially{,} the mesoglobules have a radius of gyration of about 80 nm and contain a small amount of water. Two disintegration mechanisms are identified: (i) for target pressures close to the coexistence line{,} single polymers are released from the surface of the mesoglobules{,} and the mesoglobules decrease in size{,} which takes ∼30 s. (ii) For target pressures more distant from the coexistence line{,} the mesoglobules are swollen by water{,} and subsequently the chains become more and more loosely associated. In this case{,} disintegration proceeds within less than 10 s{,} controlled by the osmotic pressure of the solvent.},
  creationdate = {2024-05-22T15:24:15},
  doi          = {10.1039/D1NR02859F},
  file         = {:Niebuur2021a - Nanoscale Disintegration Kinetics of Mesoglobules in Aqueous Poly(N Isopropylacrylamide) Solutions Revealed by Small Angle Neutron Scattering and Pressure Jumps.pdf:PDF},
  issue        = {31},
  keywords     = {SANS,pNIPAM,reentrant,kinetics,aggregation},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D1NR02859F},
}

@Article{Chang2024,
  author       = {Chang, Chun-Wei and Dargaville, Bronwin L. and Momot, Konstantin I. and Hutmacher, Dietmar W.},
  journal      = {J. Mater. Chem. B},
  title        = {An investigation of water status in gelatin methacrylate hydrogels by means of water relaxometry and differential scanning calorimetry},
  year         = {2024},
  pages        = {--},
  abstract     = {The relationship between molecular structure and water dynamics is a fundamental yet often neglected subject in the field of hydrogels for drug delivery{,} bioprinting{,} as well as biomaterial science and tissue engineering & regenerative medicine (TE&RM). Water is a fundamental constituent of hydrogel systems and engages via hydrogen bonding with the macromolecular network. The methods and techniques to measure and reveal the phenomena and dynamics of water within hydrogels are still limited. In this work{,} differential scanning calorimetry (DSC) was used as a quantitative method to analyze freezable (including free and freezable bound) and non-freezable bound water within gelatin methacrylate (GelMA) hydrogels. Nuclear magnetic resonance (NMR) is a complementary method for the study of water behavior and can be used to measure the spin-relaxation of water hydrogen nuclei{,} which is related to water dynamics. In this research{,} nuclear magnetic resonance relaxometry was employed to investigate the molecular state of water in GelMA hydrogels using spin–lattice (T1) and spin–spin (T2) spin-relaxation time constants. The data displays a trend of increasing bound water content with increasing GelMA concentration. In addition{,} T2 values were further applied to calculate microviscosity and translational diffusion coefficients. Water relaxation under various chemical environments{,} including different media{,} temperatures{,} gelatin sources{,} as well as crosslinking effects{,} were also examined. These comprehensive physical data sets offer fundamental insight into biomolecule transport within the GelMA hydrogel system{,} which ultimately are important for drug delivery{,} bioprinting{,} as well as biomaterial science and TE&RM communities.},
  creationdate = {2024-05-22T15:46:08},
  doi          = {10.1039/D4TB00053F},
  file         = {:Chang2024 - An Investigation of Water Status in Gelatin Methacrylate Hydrogels by Means of Water Relaxometry and Differential Scanning Calorimetry.pdf:PDF;:AnInvestigationOfWaterStatusInGelatinMethacryaletHydrogelsByMeansOfWatreRelaxometryAndDifferentialScanningCalorimetry_ChangEtAl_JMaterChem2024_SI.pdf:PDF},
  keywords     = {nmr,DSC,1H-NMR,spin-spin relaxation,spin-lattice relaxation,SLR,CPMG,saturation recovery,hydrogel,T1,T2,gelatin methycrylate,bound water,linear,gel,cross-linking},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D4TB00053F},
}

﻿
@Article{Blinc1995,
  author                     = {Blinc, R. and Rutar, V. and Zupancic, I. and Zidansek, A. and Lahajnar, G. and Slak, J.},
  journal                    = {APPLIED MAGNETIC RESONANCE},
  title                      = {PROTON NMR RELAXATION OF ADSORBED WATER IN GELATIN AND COLLAGEN},
  year                       = {1995},
  issn                       = {0937-9347},
  number                     = {2},
  pages                      = {193--216},
  volume                     = {9},
  abstract                   = {The dependence of the water self-diffusion coefficients as well as of
   the proton spin-lattice and spin-spin relaxation rates on the
   concentration have been studied in the gelatin-water system and in
   hydrated native collagen. The bound and free water fractions and the
   corresponding spin-spin and spin-lattice relaxation rates have been
   determined within the multi-phase water proton exchange model. Various
   theoretical models for the water proton cross-relaxation to the
   biopolymer have been studied and the results compared with the observed
   Larmor frequency dependence of the water proton spin-lattice relaxation
   rate.},
  address                    = {175 FIFTH AVE, NEW YORK, NY 10010},
  affiliation                = {BLINC, R (Corresponding Author), UNIV LJUBLJANA,JOZEF STEFAN INST,JAMOVA 39,LJUBLJANA 61111,SLOVENIA.},
  creationdate               = {2024-05-22T16:00:02},
  da                         = {2024-05-22},
  doc-delivery-number        = {TH964},
  doi                        = {10.1007/BF03162042},
  file                       = {:Blinc1995 - PROTON NMR RELAXATION oF ADSORBED WATER iN GELATIN aND COLLAGEN.pdf:PDF},
  journal-iso                = {Appl. Magn. Reson.},
  keywords                   = {1H-NMR,NMR,spin-lattice relaxation,T1,spin-spin relaxation,T2,bound water,spectral density,cross-relaxation,magnetic relaxation dispersion},
  keywords-plus              = {NONRADIATIVE DECAY; DISORDERED-SYSTEMS; DYNAMICS; FRACTONS; SCATTERING; PROTEINS; STATE; GELS},
  language                   = {English},
  number-of-cited-references = {25},
  orcid-numbers              = {Zidansek, Aleksander/0000-0002-7287-0158},
  publisher                  = {SPRINGER VERLAG},
  research-areas             = {Physics; Spectroscopy},
  researcherid-numbers       = {Zidansek, Aleksander/I-8569-2018},
  times-cited                = {24},
  type                       = {Article},
  unique-id                  = {WOS:A1995TH96400004},
  usage-count-last-180-days  = {1},
  usage-count-since-2013     = {7},
  web-of-science-categories  = {Physics, Atomic, Molecular \& Chemical; Spectroscopy},
  web-of-science-index       = {Science Citation Index Expanded (SCI-EXPANDED)},
}

@Article{Halle2006,
  author       = {Halle, Bertil},
  journal      = {Magnetic Resonance in Medicine},
  title        = {Molecular theory of field-dependent proton spin-lattice relaxation in tissue},
  year         = {2006},
  number       = {1},
  pages        = {60--72},
  volume       = {56},
  abstract     = {A molecular theory is presented for the field-dependent spin-lattice relaxation time of water in tissue. The theory attributes the large relaxation enhancement observed at low frequencies to intermediary protons in labile groups or internal water molecules that act as relaxation sinks for the bulk water protons. Exchange of intermediary protons not only transfers magnetization to bulk water protons, it also drives relaxation by a mechanism of exchange-mediated orientational randomization (EMOR). An analytical expression for T1 is derived that remains valid outside the motional-narrowing regime. Cross-relaxation between intermediary protons and polymer protons plays an important role, whereas spin diffusion among polymer protons can be neglected. For sufficiently slow exchange, the dispersion midpoint is determined by the local dipolar field rather than by molecular motions, which makes the dispersion frequency insensitive to temperature and system composition. The EMOR model differs fundamentally from previous models that identify collective polymer vibrations or hydration water dynamics as the molecular motion responsible for spin relaxation. Unlike previous models, the EMOR model accounts quantitatively for 1H magnetic relaxation dispersion (MRD) profiles from tissue model systems without invoking unrealistic parameter values.},
  creationdate = {2024-05-23T07:11:09},
  doi          = {https://doi.org/10.1002/mrm.20919},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/mrm.20919},
  file         = {:Halle2006 - Molecular Theory of Field Dependent Proton Spin Lattice Relaxation in Tissue.pdf:PDF},
  keywords     = {magnetic relaxation dispersion,proton exchange,cross-relaxation,spin diffusion,internal water,theory,hydrogel,exchange,NMR,1H-NMR,solvent dynamics,reorientational dynamics},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/mrm.20919},
}

@Article{VacaChavez2006a,
  author       = {Vaca Chávez, Fabian and Halle, Bertil},
  journal      = {Magnetic Resonance in Medicine},
  title        = {Molecular basis of water proton relaxation in gels and tissue},
  year         = {2006},
  number       = {1},
  pages        = {73--81},
  volume       = {56},
  abstract     = {An extensive set of water-1H magnetic relaxation dispersion (MRD) data are presented for aqueous agarose and gelatin gels. It is demonstrated that the EMOR model, which was developed in a companion paper to this study (see Halle, this issue), accounts for the dependence of the water-1H spin-lattice relaxation rate on resonance frequency over more than four decades and on pH. The parameter values deduced from analysis of the 1H MRD data are consistent with values derived from 2H MRD profiles from the same gels and with small-molecule reference data. This agreement indicates that the water-1H relaxation dispersion in aqueous biopolymer gels is produced directly by exchange-mediated orientational randomization of internal water molecules or labile biopolymer protons, with little or no role played by collective biopolymer vibrations or coherent spin diffusion. This ubiquitous mechanism is proposed to be the principal source of water-1H spin-lattice relaxation at low magnetic fields in all aqueous systems with rotationally immobile biopolymers, including biological tissue. The same mechanism also contributes to transverse and rotating-frame relaxation and magnetization transfer at high fields.},
  creationdate = {2024-05-23T07:24:35},
  doi          = {https://doi.org/10.1002/mrm.20912},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/mrm.20912},
  file         = {:VacaChavez2006 - Molecular Basis of Water Proton Relaxation in Gels and Tissue.pdf:PDF},
  keywords     = {agarose,gelatin,proton exchange,internal water,magnetic relaxation dispersion,1H-NMR,2H-NMR,MRD,NMR,spin-lattice relaxation,T1,aqueous polymer,protein,isotope effect},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/mrm.20912},
}

@Article{Halle1996,
  author       = {Bertil Halle},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {Spin dynamics of exchanging quadrupolar nuclei in locally anisotropic systems},
  year         = {1996},
  issn         = {0079-6565},
  number       = {2},
  pages        = {137--159},
  volume       = {28},
  creationdate = {2024-05-23T07:30:02},
  doi          = {https://doi.org/10.1016/0079-6565(95)01022-X},
  file         = {:Halle1996 - Spin Dynamics of Exchanging Quadrupolar Nuclei in Locally Anisotropic Systems.pdf:PDF},
  keywords     = {NMR,aqueous polymers,theory,Exchange-mediated orientational relaxation model,EMOR,2H-NMR},
  url          = {https://www.sciencedirect.com/science/article/pii/007965659501022X},
}








@Article{VacaChavez2006,
  author       = {Vaca Chávez, Fabian and Persson, Erik and Halle, Bertil},
  journal      = {Journal of the American Chemical Society},
  title        = {Internal Water Molecules and Magnetic Relaxation in Agarose Gels},
  year         = {2006},
  note         = {PMID: 16594727},
  number       = {14},
  pages        = {4902--4910},
  volume       = {128},
  abstract     = {Agarose gels have long been known to produce exceptionally large enhancements of the water 1H and 2H magnetic relaxation rates. The molecular basis for this effect has not been clearly established, despite its potential importance for a wide range of applications of agarose gels, including their use as biological tissue models in magnetic resonance imaging. To resolve this issue, we have measured the 2H magnetic relaxation dispersion profile from agarose gels over more than 4 frequency decades. We find a very large dispersion, which, at neutral pH, is produced entirely by internal water molecules, exchanging with bulk water on the time scale 10-8−10-6 s. The most long-lived of these dominate the dispersion and give rise to a temperature maximum in the low-frequency relaxation rate. At acidic pH, there is also a low-frequency contribution from hydroxyl deuterons exchanging on a time scale of 10-4 s. Our analysis of the dispersion profiles is based on a nonperturbative relaxation theory that remains valid outside the conventional motional-narrowing regime. The results of this analysis suggest that the internal water molecules responsible for the dispersion are located in the central cavity of the agarose double helix, as previously proposed on the basis of fiber diffraction data. The magnetic relaxation mechanism invoked here, where spin relaxation is induced directly by molecular exchange, also provides a molecular basis for understanding the water 1H relaxation behavior that governs the intrinsic magnetic resonance image contrast in biological tissue.},
  creationdate = {2024-05-23T07:42:08},
  doi          = {10.1021/ja058837n},
  eprint       = {https://doi.org/10.1021/ja058837n},
  file         = {:VacaChavez2006 - Internal Water Molecules and Magnetic Relaxation in Agarose Gels.pdf:PDF},
  keywords     = {1H-NMR,2H-NMR,NMR,magnetic relaxation dispersion,proteins,MRD,pH-dependence,exchange,exchange-mediated orientational relaxation,EMOR,agarose},
  url          = {https://doi.org/10.1021/ja058837n},
}








@Article{Wu2012,
  author       = {Wu, Jiang and Chen, Shengfu},
  journal      = {Langmuir},
  title        = {Investigation of the Hydration of Nonfouling Material Poly(ethylene glycol) by Low-Field Nuclear Magnetic Resonance},
  year         = {2012},
  note         = {PMID: 22220597},
  number       = {4},
  pages        = {2137--2144},
  volume       = {28},
  abstract     = {The strong surface hydration layer of nonfouling materials plays a key role in their resistance to nonspecific protein adsorption. Poly(ethylene glycol) (PEG) is an effective example of materials that can resist nonspecific protein adsorption and cell adhesion. Thus, the strong interaction between water molecules and PEG was investigated through each T2 component in water/PEG mixtures using multiexponential inversion of T2 relaxation time measured by the Carr–Purcell–Meiboom–Gill (CPMG) sequence of low-field nuclear magnetic resonance (LF-NMR). Results show that about one water molecule is tightly bound with one ethylene glycol (EG) unit, and additional water molecules over 1:1 ratio mainly swell the PEG matrix and are not tightly bound with PEG. This result was also supported by the endothermic behavior of water/PEG mixtures measured by differential scanning calorimetry (DSC). It is believed that the method developed could be also applied to investigate various interactions between macromolecules and other small molecules without using deuterium samples, which might open a novel route to quantitatively measure guest–host interactions in the future.},
  creationdate = {2024-05-23T08:20:52},
  doi          = {10.1021/la203827h},
  eprint       = {https://doi.org/10.1021/la203827h},
  file         = {:Wu2012 - Investigation of the Hydration of Nonfouling Material Poly(ethylene Glycol) by Low Field Nuclear Magnetic Resonance.pdf:PDF},
  keywords     = {low-field NMR,1H-NMR,NMR,CPMG,Spin-spin relaxation,T2,poly(ethylene glycol),PEG,aqueous polymer,anti-fouling,DSC},
  url          = {https://doi.org/10.1021/la203827h},
}

@Article{Mantsch1977,
  author       = {Henry H. Mantsch and Hazime Saitô and Ian C.P. Smith},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {Deuterium magnetic resonance, applications in chemistry, physics and biology},
  year         = {1977},
  issn         = {0079-6565},
  number       = {4},
  pages        = {211--272},
  volume       = {11},
  creationdate = {2024-05-24T08:28:10},
  doi          = {https://doi.org/10.1016/0079-6565(77)80010-1},
  file         = {:Mantsch1977 - Deuterium Magnetic Resonance, Applications in Chemistry, Physics and Biology.pdf:PDF},
  keywords     = {2H-NMR,isotope effect,hydrogen bond,review},
  url          = {https://www.sciencedirect.com/science/article/pii/0079656577800101},
}

@Article{Woessner1972,
  author       = {D.E. Woessner and B.S. Snowden},
  journal      = {Advances in Molecular Relaxation Processes},
  title        = {Magnetic relaxation under hindered rotation in fluids},
  year         = {1972},
  issn         = {0001-8716},
  number       = {1},
  pages        = {181--197},
  volume       = {3},
  creationdate = {2024-05-24T08:54:08},
  doi          = {https://doi.org/10.1016/0001-8716(72)80033-6},
  file         = {:Woessner1972 - Magnetic Relaxation under Hindered Rotation in Fluids.pdf:PDF},
  keywords     = {NMR,theory,anisotropic rotation,correlation function,symmetric top},
  url          = {https://www.sciencedirect.com/science/article/pii/0001871672800336},
}

@Article{Shimada1996,
  author       = {Shimada, Shigetaka and Kashima, Keiichi},
  journal      = {Polymer Journal},
  title        = {Spin Label Study of the Factors Affecting Molecular Motion of Poly(methyl methacrylate)},
  year         = {1996},
  issn         = {1349-0540},
  month        = aug,
  number       = {8},
  pages        = {690--695},
  volume       = {28},
  creationdate = {2024-05-24T10:37:53},
  doi          = {10.1295/polymj.28.690},
  file         = {:Shimada1996 - Spin Label Study of the Factors Affecting Molecular Motion of Poly(methyl Methacrylate).pdf:PDF},
  keywords     = {ESR,tacticity,molecular weight,chain length,PMMA,poly(methyl methacrylate)},
}

@Article{Veksli2000,
  author       = {Z Veksli and M Andreis and B Rakvin},
  journal      = {Progress in Polymer Science},
  title        = {ESR spectroscopy for the study of polymer heterogeneity},
  year         = {2000},
  issn         = {0079-6700},
  number       = {7},
  pages        = {949--986},
  volume       = {25},
  abstract     = {In recent years the motional and structural heterogeneity of polymers and their phase separation on a nanoscale length have been approached by many experimental techniques. This review compiles the literature on the application of electron spin resonance (ESR) spectroscopy — spin label/probe methods in heterogeneous polymer systems over the past decade. The achievements and limitations of the ESR method in the study of homopolymer heterogeneity, crosslinked polymer networks, polymer blends, interpenetrating networks, copolymers and block copolymers are overviewed and compared with some other allied methods. Recent analyses of complex ESR spectra and their corresponding motions are presented in the article. Information on molecular dynamics in a wide range of spin label/probe motion, free volume and free-volume distribution, phase separation, phase morphology and small molecule penetration are the main issues of the remaining sections. The last section covers some other ESR techniques such as continuous wave, linear and nonlinear methods and pulse ESR supported by their possible features or those already achieved in the field of polymer research. ESR advanced methods offer new possibilities to expand the limits as well as sensitivities of molecular dynamics detection in gaining information on realistic molecular behavior in complex polymer materials.},
  creationdate = {2024-05-24T10:42:55},
  doi          = {https://doi.org/10.1016/S0079-6700(00)00025-3},
  file         = {:Veksli2000 - ESR Spectroscopy for the Study of Polymer Heterogeneity.pdf:PDF},
  keywords     = {Electron spin resonance, ESR, Spin probe/spin label, Heterogeneity, Polymers, Copolymers, Polymer blends, Interpenetrating networks, review},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079670000000253},
}

@Article{Xu2021,
  author       = {Xu, Sihao and Trujillo, Francisco J. and Xu, Jiangtao and Boyer, Cyrille and Corrigan, Nathaniel},
  journal      = {Macromolecular Rapid Communications},
  title        = {Influence of Molecular Weight Distribution on the Thermoresponsive Transition of Poly(N-isopropylacrylamide)},
  year         = {2021},
  number       = {18},
  pages        = {2100212},
  volume       = {42},
  abstract     = {A series of poly(N-isopropylacrylamide) (PNIPAm) homopolymers with narrow molecular weight distributions (MWDs) is prepared via photoinduced electron/energy transfer–reversible addition-fragmentation chain transfer (PET–RAFT) polymerization. The thermal transition temperature of these polymer samples is analyzed via turbidity measurements in water/N,N'-dimethylformamide mixtures, which show that the cloud point temperatures are inversely proportional to the weight average molecular weight (Mw). Binary mixtures of the narrowly distributed PNIPAm samples are also prepared and the statistical parameters for the MWDs of these blends are determined. Very interestingly, for binary blends of the PNIPAm samples, the thermoresponsive transition is not only dependent on the Mw, which has been shown previously, but also on higher order statistical parameters of the MWDs. Specifically, at very high values of skewness and kurtosis, the polymer blends deviate from a single sharp thermoresponsive transition toward a broader thermal response, and eventually to a regime of two more distinct transitions. This work highlights the importance of in-depth characterization of polymer MWDs for thermoresponsive polymers.},
  creationdate = {2024-05-24T13:38:51},
  doi          = {https://doi.org/10.1002/marc.202100212},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/marc.202100212},
  file         = {:Xu2021 - Influence of Molecular Weight Distribution on the Thermoresponsive Transition of Poly(N Isopropylacrylamide).pdf:PDF},
  keywords     = {molecular weight distribution,PET–RAFT polymerization,poly(N-isopropylacrylamide),thermoresponsive polymers,pNIPAM,cloud point,turbidimetry,chain length},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/marc.202100212},
}

@Article{Ieong2012,
  author       = {Ieong, Nga Sze and Hasan, Muhammad and Phillips, Daniel J. and Saaka, Yussif and O{'}Reilly, Rachel K. and Gibson, Matthew I.},
  journal      = {Polym. Chem.},
  title        = {Polymers with molecular weight dependent LCSTs are essential for cooperative behaviour},
  year         = {2012},
  pages        = {794--799},
  volume       = {3},
  abstract     = {The potential to fine-tune the transition temperatures of polymers displaying lower-critical solution temperatures (LCST) by a simple mixing strategy is investigated. Using a panel of four distinct polymer classes (poly[oligo(ethyleneglycol)methacrylate]{,} poly(N-vinylpiperidone){,} poly(N-vinylcaprolactam) poly(N-isopropylacrylamide)) it was shown that only those with strong molecular weight dependent LCSTs produced a single{,} cooperative{,} transition when blended together. Furthermore{,} the actual transition temperature was linked to the weight average not the number average molecular weight. The only polymer which did not show strong molecular-weight-LCST correlation was poly(oligo(ethyleneglycol)methacrylate){,} which showed two independent transitions{,} one for each polymer.},
  creationdate = {2024-05-24T14:00:53},
  doi          = {10.1039/C2PY00604A},
  file         = {:Ieong2012 - Polymers with Molecular Weight Dependent LCSTs Are Essential for Cooperative Behaviour.pdf:PDF},
  issue        = {3},
  keywords     = {molecular weight distribution,LCST,pNIPAM},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C2PY00604A},
}

@Article{Cummins1985,
  author       = {Cummins, Peter L. and Bacskay, George B. and Hush, Noel S. and Halle, Bertil and Engström, Sven},
  journal      = {The Journal of Chemical Physics},
  title        = {{The effect of intermolecular interactions on the 2H and 17O quadrupole coupling constants in ice and liquid water}},
  year         = {1985},
  issn         = {0021-9606},
  month        = feb,
  number       = {4},
  pages        = {2002--2013},
  volume       = {82},
  abstract     = {{Using ab initio SCF molecular orbital techniques, the electric field gradients (efg’s) at the oxygen and hydrogen nuclei were calculated for water clusters ranging from dimer to pentamer in an attempt to reproduce the shift in 17O and 2H nuclear quadrupole coupling constants (qcc’s) that is observed on going from ice to vapor. For 2H, where the qcc shift is due mostly to the change in O–H bond length, excellent agreement with the experimental vapor → ice shift was obtained. For 17O, the change in the qcc is found to be mainly electronic in origin, effectively due to the polarization of the charge associated with the oxygen atom, and approximately 75\\% of the observed qcc shift was reproduced. On the basis of the calculations, estimates of the 17O and 2H qcc’s in liquid water were made that are consistent with the values obtained from an analysis of the available NMR relaxation data, provided that librational motions are properly taken into account. We also present results of SCF calculations on water interacting with a Li+, Na+, or Cl− ion, indicating that the effect of a nearby ion on the 2H and 17O qcc’s is similar to that produced by H bonding.}},
  creationdate = {2024-05-27T09:21:55},
  doi          = {10.1063/1.448384},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/82/4/2002/18951506/2002\_1\_online.pdf},
  file         = {:Cummins1985 - The Effect of Intermolecular Interactions on the 2H and 17O Quadrupole Coupling Constants in Ice and Liquid Water.pdf:PDF},
  keywords     = {NMR,17O-NMR,Quadrupole Coupling Constant,QCC,2H-NMR},
  url          = {https://doi.org/10.1063/1.448384},
}

@Article{Edmonds1972,
  author       = {D.T. Edmonds and A. Zussman},
  journal      = {Physics Letters A},
  title        = {Pure quadrupole resonance of 17O in ice},
  year         = {1972},
  issn         = {0375-9601},
  number       = {2},
  pages        = {167--169},
  volume       = {41},
  abstract     = {The pure quadrupole resonance of 17O has been detected in enriched ice at 77°K. The quadrupole coupling constants obtained, e2qzzQ/h = 6.525 ± 0.015 MHz and η = 0.925 ± 0.020, are very different from those of the isolated molecule indicating the powerful role played by hydrogen bonding in the solid.},
  creationdate = {2024-05-27T10:43:43},
  doi          = {https://doi.org/10.1016/0375-9601(72)91097-3},
  file         = {:Edmonds1972 - Pure Quadrupole Resonance of 17O in Ice.pdf:PDF},
  keywords     = {17O-NMR,NMR,Quadrupole Coupling Constant},
  url          = {https://www.sciencedirect.com/science/article/pii/0375960172910973},
}








@Article{Glasel1967,
  author       = {J A Glasel},
  journal      = {Proceedings of the National Academy of Sciences},
  title        = {A study of water in biological systems by O-17 magnetic resonance spectroscopy. II. Relaxation phenomena in pure water.},
  year         = {1967},
  number       = {1},
  pages        = {27--33},
  volume       = {58},
  creationdate = {2024-05-27T11:13:43},
  doi          = {10.1073/pnas.58.1.27},
  eprint       = {https://www.pnas.org/doi/pdf/10.1073/pnas.58.1.27},
  file         = {:Glasel1967 - A Study of Water in Biological Systems by O 17 Magnetic Resonance Spectroscopy. II. Relaxation Phenomena in Pure Water..pdf:PDF},
  keywords     = {17O-NMR,Quadrupole Coupling Constant},
  url          = {https://www.pnas.org/doi/abs/10.1073/pnas.58.1.27},
}








@Article{Garrett1967,
  author       = {Garrett, Barry B. and Denison, Arthur B. and Rabideau, Sherman W.},
  journal      = {The Journal of Physical Chemistry},
  title        = {Oxygen-17 relaxation in water},
  year         = {1967},
  number       = {8},
  pages        = {2606--2611},
  volume       = {71},
  creationdate = {2024-05-27T11:20:49},
  doi          = {10.1021/j100867a033},
  eprint       = {https://doi.org/10.1021/j100867a033},
  file         = {:Garrett1967 - Oxygen 17 Relaxation in Water.pdf:PDF},
  keywords     = {17O-NMR,quadrupole coupling constant},
  url          = {https://doi.org/10.1021/j100867a033},
}

@Article{Smith1999,
  author       = {M.E. Smith and E.R.H. {van Eck}},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {Recent advances in experimental solid state NMR methodology for half-integer spin quadrupolar nuclei},
  year         = {1999},
  issn         = {0079-6565},
  number       = {2},
  pages        = {159--201},
  volume       = {34},
  creationdate = {2024-05-27T13:48:46},
  doi          = {https://doi.org/10.1016/S0079-6565(98)00028-4},
  file         = {:Smith1999 - Recent Advances in Experimental Solid State NMR Methodology for Half Integer Spin Quadrupolar Nuclei.pdf:PDF},
  keywords     = {Materials characterisation,Solid-state,Quadrupole nuclei,NMR,theory,17O-NMR},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079656598000284},
}

@Article{Kentgens1997,
  author       = {A.P.M. Kentgens},
  journal      = {Geoderma},
  title        = {A practical guide to solid-state NMR of half-integer quadrupolar nuclei with some applications to disordered systems},
  year         = {1997},
  issn         = {0016-7061},
  note         = {NMR in Soil Science},
  number       = {3},
  pages        = {271--306},
  volume       = {80},
  abstract     = {The practical aspects for obtaining useful NMR spectra of half-integer quadrupolar nuclei in diamagnetic solids are discussed in some detail. The general appearance of the Magic-Angle Spinning (MAS) line shape is described. The effects of a distribution in isotropic chemical shift and quadrupole interaction on the MAS line shape is shown. The necessity of fast MAS and short excitation pulses is demonstrated. The possibilities of 27Al MAS NMR at high fields is shown for some clay minerals. Techniques to obtain spectra free of quadrupolar broadening, such as DOuble Rotation (DOR), Dynamic Angle Spinning WAS) and Multiple-Quantum Magic-Angle Spinning (MQMAS), are discussed with some emphasis on the newly developed MQMAS method. The latter is used to describe structural details of phosphorus-impregnated alumina and aluminosilicate sol-gel materials. These examples give a good indication of the capabilities of this new technique.},
  creationdate = {2024-05-27T13:58:58},
  doi          = {https://doi.org/10.1016/S0016-7061(97)00056-6},
  file         = {:Kentgens1997 - A Practical Guide to Solid State NMR of Half Integer Quadrupolar Nuclei with Some Applications to Disordered Systems.pdf:PDF},
  keywords     = {quadrupolar nuclei,MAS NMR,MQMAS,clays,alumina,aluminosilicate,NMR,17O-NMR},
  url          = {https://www.sciencedirect.com/science/article/pii/S0016706197000566},
}

@Article{Man2000,
  author           = {Pascal P. Man},
  journal          = {Encyclopedia of Analytical Chemistry},
  title            = {Quadrupole Couplings in Nuclear Magnetic Resonance, General},
  year             = {2000},
  pages            = {12224--12265},
  comment-saeckech = {paywall before https://onlinelibrary.wiley.com/doi/10.1002/9780470027318.a6111},
  creationdate     = {2024-05-27T14:33:55},
  file             = {:Man2000 - Quadrupole Couplings in Nuclear Magnetic Resonance, General.pdf:PDF},
  keywords         = {NMR,17O-NMR,Quadrupole Coupling Constant},
}

@Book{Mueller2021,
  author       = {Klaus Müller and Marco Geppi},
  publisher    = {Wiley-VCH},
  title        = {Solid State NMR: Principles, Methods, and Applications},
  year         = {2021},
  edition      = {First},
  isbn         = {978-3-527-31816-2},
  creationdate = {2024-05-27T18:47:02},
  keywords     = {NMR,theory,book},
  url          = {http://www.wiley-vch.de/publish/dt/books/ISBN978-3-527-31816-2/},
}

@Article{Hirokawa1984,
  author       = {Hirokawa, Yoshitsugu and Tanaka, Toyoichi},
  journal      = {The Journal of Chemical Physics},
  title        = {{Volume phase transition in a nonionic gel}},
  year         = {1984},
  issn         = {0021-9606},
  month        = dec,
  number       = {12},
  pages        = {6379--6380},
  volume       = {81},
  abstract     = {{Nonionic N‐isopropylacrylamide gel was found to undergo a discontinuous phase transition by changing a solvent composition or temperature. The observation that polymer gel with and without charge can undergo a first order volume phase transition is an evidence for the universality of the phase transition of polymer gels.}},
  creationdate = {2024-05-28T13:02:53},
  doi          = {10.1063/1.447548},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/81/12/6379/18951512/6379\_1\_online.pdf},
  file         = {:Hirokawa1984 - Volume Phase Transition in a Nonionic Gel.pdf:PDF},
  keywords     = {pNIPAM,hydrogel,cononsolvency,DMSO,hysteresis},
  url          = {https://doi.org/10.1063/1.447548},
}

@Article{Mukherji2023,
  author         = {Mukherji, Debashish and Kremer, Kurt},
  journal        = {Polymers},
  title          = {Smart Polymers for Soft Materials: From Solution Processing to Organic Solids},
  year           = {2023},
  issn           = {2073-4360},
  number         = {15},
  volume         = {15},
  abstract       = {Polymeric materials are ubiquitous in our everyday life, where they find a broad range of uses—spanning across common household items to advanced materials for modern technologies. In the context of the latter, so called “smart polymers” have received a lot of attention. These systems are soluble in water below their lower critical solution temperature Tℓ and often exhibit counterintuitive solvation behavior in mixed solvents. A polymer is known as smart-responsive when a slight change in external stimuli can significantly change its structure, functionm and stability. The interplay of different interactions, especially hydrogen bonds, can also be used for the design of lightweight high-performance organic solids with tunable properties. Here, a general scheme for establishing a structure–property relationship is a challenge using the conventional simulation techniques and also in standard experiments. From the theoretical side, a broad range of all-atom, multiscale, generic, and analytical techniques have been developed linking monomer level interaction details with macroscopic material properties. In this review, we briefly summarize the recent developments in the field of smart polymers, together with complementary experiments. For this purpose, we will specifically discuss the following: (1) the solution processing of responsive polymers and (2) their use in organic solids, with a goal to provide a microscopic understanding that may be used as a guiding tool for future experiments and/or simulations regarding designing advanced functional materials.},
  article-number = {3229},
  creationdate   = {2024-05-28T13:28:21},
  doi            = {10.3390/polym15153229},
  file           = {:Mukherji2023 - Smart Polymers for Soft Materials_ from Solution Processing to Organic Solids.pdf:PDF},
  keywords       = {review,stimuli-responsive,pNIPAM,cononsolvency},
  pubmedid       = {37571124},
  url            = {https://www.mdpi.com/2073-4360/15/15/3229},
}








@Article{Yong2022,
  author       = {Yong, Huaisong and Sommer, Jens-Uwe},
  journal      = {Macromolecules},
  title        = {Cononsolvency Effect: When the Hydrogen Bonding between a Polymer and a Cosolvent Matters},
  year         = {2022},
  number       = {24},
  pages        = {11034--11050},
  volume       = {55},
  abstract     = {Despite the fact that the observation of cononsolvency was reported as early as four decades ago, its phase-transition mechanism is still under debate. In this work, we provided a comprehensive study of the phase behaviors of poly(N-isopropylacrylamide) (PNiPAAm) in sulfoxide or sulfone aqueous solutions. We observed a sharp collapse transition of PNiPAAm brushes in sulfoxide but not in sulfone aqueous solutions by equilibrium measurements of in situ spectroscopic ellipsometry. We found that the hydrogen-bond formation between sulfoxide oxygens and amide hydrogens of the polymer chains plays a critical role in regulating the cononsolvency of PNiPAAm. We have extended the concept of preferential adsorption by taking into account hydrophobic interactions between cosolvent molecules, which are adsorbed on the polymer by hydrogen bonds. This can explain the experimental observations of PNiPAAm brushes in these solvent mixtures and sheds light on understanding the phase behaviors of polymer solutions where hydrogen bonds and hydrophobic interaction play a critical role. Our results can also be of interest for the liquid–liquid phase separation in the living cell where the condensation of proteins bound to large biomacromolecules plays an essential role.},
  creationdate = {2024-05-28T13:41:02},
  doi          = {10.1021/acs.macromol.2c01428},
  eprint       = {https://doi.org/10.1021/acs.macromol.2c01428},
  file         = {:Yong2022 - Cononsolvency Effect_ When the Hydrogen Bonding between a Polymer and a Cosolvent Matters.pdf:PDF;:CononsolvencyEffect-WhenTheHydrogenBondingBetweenAPolymerAndACosolventMatters_YongEtAl_Macromol2022_SI.pdf:PDF},
  keywords     = {pNIPAM,cononsolvency,ellipsometry,hydrogen bond,preferential adsorption,DMSO,isotope effect,brush},
  url          = {https://doi.org/10.1021/acs.macromol.2c01428},
}

@Article{Shibayama1992,
  author       = {Shibayama, Mitsuhiro and Tanaka, Toyoichi and Han, Charles C.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Small angle neutron scattering study on poly(N‐isopropyl acrylamide) gels near their volume‐phase transition temperature}},
  year         = {1992},
  issn         = {0021-9606},
  month        = nov,
  number       = {9},
  pages        = {6829--6841},
  volume       = {97},
  abstract     = {{The small angle neutron scattering experiments were conducted on N‐isopropyl acrylamide (NIPA) gels in D2O and on the corresponding NIPA solutions. The NIPA gels underwent a sharp, but a continuous volume phase transition at 34.6 °C from a swollen state to a shrunken state with increasing temperature. In the case of the gels, an excess scattering due to the presence of crosslinks was observed at low q region (q≤0.02 Å−1), where q is the magnitude of the scattering vector. The scattered intensity function for the gel was well described with a combination of Gauss and Lorentz‐type functions, i.e., I(q)=IG(0)exp[−Ξ2q2]+[IL(0)/(1+ξ2q2)] as proposed by Geissler et al. IG(0) and IL(0) are the intensities at q=0 for the contributions of Gaussian and Lorentzian functions, respectively. The Gaussian part results from solidlike inhomogeneity, having a characteristic size of Ξ, which is due to the introduction of crosslinks into the system. The Lorentzian part is originated from the liquid nature of the local concentration fluctuations of the gel characterized with a thermal blob of dimension ξ. Ξ decreases systematically with polymer volume fraction, φ, indicating the nature of Ξ being the solidlike inhomogeneity. On the other hand, the intensity function for solutions was well fitted with the so‐called Ornstein–Zernike (OZ) equation (a Lorentzian function), i.e., I(q)=[IL(0)/(1+ξ2q2)].It was found that both ξ and IL(0) diverged at the spinodal temperature, Ts. The critical exponents, ν and γ, for the temperature dependence of ξ and IL(0), were estimated to be ∼0.60 and 1.2 for the gel, respectively, which were larger than the values for the solution of the same polymers (ν=0.45 and γ=0.8). These critical exponents for the gels support that the volume‐phase transition of gels is classified to the three dimensional Ising model reported by Li and Tanaka. The concentration dependence of ξ and IL(0) was also well described with a power law relationship, i.e., ξ∼φνφ and IL(0)∼φγ;φ. The values of νφ and γφ at 23 °C are −3/4 and ∼−1/4, respectively, for the NIPA solutions, which are in good agreement with the theoretical prediction for polymer solutions in a good solvent. In the case of the NIPA gels, however, both νφ and γφ are ∼−1. These exponents were interpreted by taking account of the effects of crosslinking on the Flory’s interaction parameter.}},
  creationdate = {2024-05-28T14:40:54},
  doi          = {10.1063/1.463636},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/97/9/6829/19305499/6829\_1\_online.pdf},
  file         = {:Shibayama1992 - Small Angle Neutron Scattering Study on Poly(N‐isopropyl Acrylamide) Gels near Their Volume‐phase Transition Temperature.pdf:PDF},
  keywords     = {pNIPAM,hydrogel,monomer,SANS,isotope effect,D2O},
  url          = {https://doi.org/10.1063/1.463636},
}

@Article{Crowther1999,
  author       = {Helen M Crowther and Brian R Saunders and Sarah J Mears and Terence Cosgrove and Brian Vincent and Stephen M King and Ga-Er Yu},
  journal      = {Colloids and Surfaces A: Physicochemical and Engineering Aspects},
  title        = {Poly(NIPAM) microgel particle de-swelling: a light scattering and small-angle neutron scattering study},
  year         = {1999},
  issn         = {0927-7757},
  number       = {3},
  pages        = {327--333},
  volume       = {152},
  abstract     = {Small-angle neutron scattering (SANS) has been used to investigate structural changes during the de-swelling of poly(N-isopropylacrylamide) [poly(NIPAM)] microgel particles induced by temperature variation and the addition of free polymer [poly(ethylene oxide)]. The extent of particle de-swelling was characterized by photon correlation spectroscopy (PCS). Thermally-induced de-swelling of poly(NIPAM)/deuterated water dispersions occurred on increasing the temperature in the region of the lower critical solution temperature (LCST). The latter was found to be 34°C, which is 2°C higher than the value reported for poly(NIPAM) particles dispersed in water. The SANS data exhibit a Porod form (Q−4) of scattering in regard to the size of the colloidal particles. However, in the swollen state, the scattering measured at temperatures less than the LCST, also has a contribution from poly(NIPAM) chains in a solution-like environment (Ornstein–Zernike scattering). The trends observed in the SANS data as a function of temperature were simulated using a model comprised of Porod and Ornstein–Zernike scattering terms. The SANS data confirm earlier PCS measurements showing that addition of free polymer induces particle de-swelling. The SANS data obtained using added free polymer are the first examples of their type to be reported.},
  creationdate = {2024-05-28T14:42:24},
  doi          = {https://doi.org/10.1016/S0927-7757(98)00875-9},
  file         = {:Crowther1999 - Poly(NIPAM) Microgel Particle De Swelling_ a Light Scattering and Small Angle Neutron Scattering Study.pdf:PDF},
  keywords     = {SANS, Poly(NIPAM), Swelling, Microgel, Thermosensitive, pNIPAM, isotope effect, D2O, light scattering, PCS, PEO, PEG},
  url          = {https://www.sciencedirect.com/science/article/pii/S0927775798008759},
}








@Article{Hoepfner2014,
  author       = {Höpfner, Johannes and Guthausen, Gisela and Saalwächter, Kay and Wilhelm, Manfred},
  journal      = {Macromolecules},
  title        = {Network Structure and Inhomogeneities of Model and Commercial Polyelectrolyte Hydrogels as Investigated by Low-Field Proton NMR Techniques},
  year         = {2014},
  number       = {13},
  pages        = {4251--4265},
  volume       = {47},
  abstract     = {This work presents an experimental study of the network structure of swollen, charged hydrogels. We provide an in-depth comparison of two proton low-field NMR methods, i.e., transverse relaxation and double-quantum spectroscopy, that are both sensitive to residual orientation correlations of the network chain segments. The results are in both cases analyzed by help of integral inversion techniques, and both methods are demonstrated to provide comparable results despite the more qualitative nature of the transverse relaxation. We investigate model samples that are similar to commercial superabsorber materials based on partly neutralized and chemically cross-linked poly(acrylic acid) as prepared by free radical polymerization. The degree of cross-linking and the monomer concentration are varied during synthesis. Both parameters are found to affect the network structure and the amount of elastically inactive defects in a systematic way, and a comparison with commercial samples with homogeneous or purposely inhomogeneous core–shell structures proves that the cross-linking bimodality of the latter is readily revealed despite the rather large intrinsic inhomogeneity of the swollen gels.},
  creationdate = {2024-05-29T08:16:14},
  doi          = {10.1021/ma500558v},
  eprint       = {https://doi.org/10.1021/ma500558v},
  file         = {:Hoepfner2014 - Network Structure and Inhomogeneities of Model and Commercial Polyelectrolyte Hydrogels As Investigated by Low Field Proton NMR Techniques.pdf:PDF;:NetworkStructureAndInhomogeneitiesOfModelAndCommercialPolyelectrolyteHydrogelsAsInvestigatedByLowFieldProtonNMRTechniques_HoepfnerEtAl_Macromol2014_SI.pdf:PDF},
  keywords     = {NMR,inverse laplace transform,low-field NMR,1H-NMR,T2,hydrogel,double quantum resonance,DQ,residual dipolar coupling,CPMG vs HahnEcho},
  url          = {https://doi.org/10.1021/ma500558v},
}

@Article{Li2016a,
  author       = {Yaqiong Li and Xiunan Li and Chao Chen and Dawei Zhao and Zhiguo Su and Guanghui Ma and Rong Yu},
  journal      = {Carbohydrate Polymers},
  title        = {A rapid, non-invasive and non-destructive method for studying swelling behavior and microstructure variations of hydrogels},
  year         = {2016},
  issn         = {0144-8617},
  pages        = {1251--1260},
  volume       = {151},
  abstract     = {A new method for studying swelling behavior of hydrogels was developed based on low field NMR (LF-NMR). This method is established on these facts: firstly, internal water (water trapped in hydrogel) and external water (water outside of hydrogel) correspond to different components of transverse relaxation time (T2); secondly, T2 component amplitude is proportional to relative water content; and finally, T2 value is closely related to mesh size of hydrogel network, the main effect being due to the overall concentration (degree of swelling). This method was successfully applied to swelling ratio determination of chitosan/glutaraldehyde (CS/GA) hydrogels in situ, and the results had better accuracy and repeatability compared with that of weighing method. Furthermore, swelling kinetics at different pH and microstructure of CS/GA hydrogels was well elucidated based on T2. It is clearly showed that LF-NMR provides a powerful tool for probing processes related to water transport and microstructure variation of hydrogels.},
  creationdate = {2024-05-29T08:27:46},
  doi          = {https://doi.org/10.1016/j.carbpol.2016.06.054},
  file         = {:Li2016a - A Rapid, Non Invasive and Non Destructive Method for Studying Swelling Behavior and Microstructure Variations of Hydrogels.pdf:PDF},
  keywords     = {Hydrogels,Swelling,LF-NMR,,Microstructure,low-field NMR,NMR,1H-NMR,T2,CPMG},
  url          = {https://www.sciencedirect.com/science/article/pii/S0144861716307299},
}








@Article{Umut2023,
  author       = {Umut, Evrim and Beira, Maria Jardim and Oztop, Mecit Halil and Sahiner, Nurettin and Sebastião, Pedro José and Kruk, Danuta},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Water Dynamics in Dextran-Based Hydrogel Micro/Nanoparticles Studied by NMR Diffusometry and Relaxometry},
  year         = {2023},
  note         = {PMID: 37812396},
  number       = {41},
  pages        = {8950--8960},
  volume       = {127},
  abstract     = {Water dynamics in mesoporous dextran hydrogel micro/nanoparticles was investigated by means of nuclear magnetic resonance (NMR) techniques. High-resolution 1H NMR spectra and pulsed field gradient (PFG) NMR diffusometry measurements obtained on swollen state dextran micro/nanogel revealed the existence of different fractions of water molecules based on their interaction with the gel matrix. In addition to the translational diffusion of bulk water, two more diffusion processes characterized with self-diffusion coefficients 1 and 2 orders of magnitude smaller than that of bulk water were identified. 1H spin–lattice relaxation dispersion profiles obtained for a broad range of Larmor frequencies using fast field cycling (FFC) and conventional NMR relaxometry techniques allowed us to further clarify the mechanisms of molecular motion. According to the water proton pool fractions and associated self-diffusion coefficients, it is shown that the relaxation contribution associated with reorientation-mediated translational motions (RMTDs) dominates the relaxation dispersion observed at intermediate frequencies. At very low frequencies, the spin–lattice relaxation rate is dominated by the slow solid-gel dynamics probed by the water molecules interacting with the pores' surface hydroxyl groups due to the rapid chemical exchange between surface hydroxyl groups and free water. The correlation time for the thumbling-like motion of the dextran gel was found to be in the submillisecond range. The values of the self-diffusion and coherence lengths associated with motion of water molecules interacting with the solid-gel particles are consistent with the particle size and pore size distributions obtained for the studied dextran gels.},
  creationdate = {2024-05-29T09:46:08},
  doi          = {10.1021/acs.jpcb.3c04452},
  eprint       = {https://doi.org/10.1021/acs.jpcb.3c04452},
  file         = {:Umut2023 - Water Dynamics in Dextran Based Hydrogel Micro_Nanoparticles Studied by NMR Diffusometry and Relaxometry.pdf:PDF},
  keywords     = {1H-NMR,NMR,microgel,PFG,diffusion,dextran,field cycling,spin-lattice relaxation,T1},
  url          = {https://doi.org/10.1021/acs.jpcb.3c04452},
}

@Article{Stapf1995,
  author       = {Stapf, S. and Kimmich, R. and Seitter, R.-O.},
  journal      = {Phys. Rev. Lett.},
  title        = {Proton and Deuteron Field-Cycling NMR Relaxometry of Liquids in Porous Glasses: Evidence for L\'evy-Walk Statistics},
  year         = {1995},
  month        = oct,
  pages        = {2855--2858},
  volume       = {75},
  creationdate = {2024-05-29T10:04:11},
  doi          = {10.1103/PhysRevLett.75.2855},
  file         = {:Stapf1995 - Proton and Deuteron Field Cycling NMR Relaxometry of Liquids in Porous Glasses_ Evidence for Levy Walk Statistics.pdf:PDF},
  issue        = {15},
  keywords     = {NMR,1H-NMR,2H-NMR,Field Cycling,confinement},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.75.2855},
}

@Article{Calucci2009,
  author       = {Lucia Calucci and Claudia Forte},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {Proton longitudinal relaxation coupling in dynamically heterogeneous soft systems},
  year         = {2009},
  issn         = {0079-6565},
  number       = {4},
  pages        = {296--323},
  volume       = {55},
  creationdate = {2024-05-29T10:11:48},
  doi          = {https://doi.org/10.1016/j.pnmrs.2009.06.003},
  file         = {:Calucci2009 - Proton Longitudinal Relaxation Coupling in Dynamically Heterogeneous Soft Systems.pdf:PDF},
  keywords     = {Cross relaxation,Magnetization transfer,Water,NMRD,MRI contrast,chemical exchange,NMR,1H-NMR,spin-lattice relaxation,T1,review,confinement,soft confinement},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079656509000582},
}

@Article{Fung1976,
  author       = {Fung, B. M. and McGaughy, Tim W.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Molecular motions in liquid. I. Rotation of water and small alcohols studied by deuteron relaxation}},
  year         = {1976},
  issn         = {0021-9606},
  month        = oct,
  number       = {8},
  pages        = {2970--2976},
  volume       = {65},
  abstract     = {{The deuteron spin lattice relaxation time T1 of CH3OD, C2H5OD, (CH3)2CHOD, and (CH3)3CHOD is reported as a function of temperature and frequency. The deuteron T1 of the alcohols in dilute benzene solutions was also measured at 25°C. A detailed analysis of the experimental results and other magnetic and dielectric relaxation data from the literature was made. Based upon the analysis, it is suggested that the success of the Debye model in explaining the dielectric and magnetic relation behavior of water and small alcohols may be purely coincidental. It seems that the error in applying Stokes law for the rotation of a macroscopic sphere to small molecules in liquid and the error in assuming that water and alcohols rotate as monomers largely cancel each other, yielding much better apparent agreement between calculated and experimental data than those for nonassociating liquids. The deuteron T1’s for the alcohols are further analyzed in terms of anisotropic rotation.}},
  comment      = {OD groups of alcohols deuterated},
  creationdate = {2024-05-31T08:25:32},
  doi          = {10.1063/1.433533},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/65/8/2970/18903705/2970\_1\_online.pdf},
  file         = {:Fung1976 - Molecular Motions in Liquid. I. Rotation of Water and Small Alcohols Studied by Deuteron Relaxation.pdf:PDF},
  keywords     = {NMR,2H-NMR,spin-lattice relaxation,T1,methanol,ethanol,2-propanol,t-butanol},
  url          = {https://doi.org/10.1063/1.433533},
}






















@Article{Ferris2002,
  author       = {Thomas D. Ferris and Thomas C. Farrar},
  journal      = {Molecular Physics},
  title        = {The temperature dependence of the hydroxyl deuterium quadrupole coupling parameter and the rotational correlation time of the OD internuclear vector in neat ethanol-d 1},
  year         = {2002},
  number       = {2},
  pages        = {303--309},
  volume       = {100},
  abstract     = {The temperature dependence of the hydroxyl proton chemical shift and deuterium quadrupolar relaxation time of neat ethanol were measured over the temperature range 190–350 K. The proton isotropic chemical shift varies from 6.2 ppm at 190K to 4.7 ppm at 350 K. The deuterium NMR relaxation time in ethanol-d1 varies from 6.2 ms to 309 ms over the same range. Ab initio calculations performed on various ethanol clusters ranging in size from monomer to hexamer show a linear correlation (R2 = 0.99) between XD, the deuterium quadrupole coupling parameter, and δH, the isotropic proton chemical shift in ppm relative to TMS: XD(kHz) = 297.60 − 15.28δH. The temperature dependence of XD ranges from 199.5kHz at 190K to 221.4 kHz at 350 K. Using the values for XD and the relaxation time data, the temperature dependence of the OD rotational correlation time was found to vary from 282 ps at 190 K to 4.5 ps near the boiling point (350 K). Using these correlation times and bulk viscosity data, the Gierer-Wirtz model predicts a supramolecular cluster volume of about 317 Å3, the approximate volume of a cyclic pentamer cluter of ethanol molecules. The cluster volume was nearly constant from 340 K to about 290 K.},
  comment      = {paywall},
  creationdate = {2024-05-31T08:38:11},
  doi          = {10.1080/00268970110072377},
  eprint       = {https://doi.org/10.1080/00268970110072377},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/00268970110072377},
}

@Article{Saeckel2024,
  author       = {Säckel, Christoph and von Klitzing, Regine and Siegel, Renée and Senker, Jürgen and Vogel, Michael},
  journal      = {Frontiers in Soft Matter},
  title        = {Water dynamics in solutions of linear poly (N-isopropyl acrylamide) studied by 2H NMR field-cycling relaxometry},
  year         = {2024},
  issn         = {2813-0499},
  volume       = {4},
  abstract     = {We use <sup>2</sup>H nuclear magnetic resonance to study the dynamics of deuterated water in a solution of linear poly (N-isopropyl acrylamide) (pNIPAM, 4 wt%) across its coil-to-globule transition at a lower critical solubility temperature (LCST) around 32°C. In agreement with previous studies, we find that the <sup>2</sup>H spin-lattice (T<sub>1</sub>) and, in particular, spin-spin (T<sub>2</sub>) relaxation times abruptly decrease when heating through the LCST, indicating that the polymer collapse causes an emergence of a water fraction with strongly reduced mobility. To quantify the dynamics of this slow water fraction, we exploit the fact that <sup>2</sup>H field-cycling relaxometry allows us to measure the spectral density of the water reorientation in a broad frequency range. We find that the slow water fraction is characterised by a broad logarithmic Gaussian distribution of correlation times (σ<sub>LG</sub> = 2.3), which is centred about τ<sub>LG</sub> ≈ 10<sup>–9</sup> s near the LCST. Hence, the common assumption of a Debye spectral density does not apply. We argue that a minor water fraction, which is located inside the pNIPAM globules and shows dynamics governed by the disordered polymer matrix, accompanies a major water fraction with bulk-like dynamics above the LCST. The former fraction amounts to about 0.4 water molecules per NIPAM monomer. Several findings indicate fast exchange between these bound and free water fractions on the T<sub>1</sub> and T<sub>2</sub> time scales.},
  creationdate = {2024-05-31T13:36:26},
  doi          = {10.3389/frsfm.2024.1379816},
  file         = {:Saeckel2024 - Water Dynamics in Solutions of Linear Poly (N Isopropyl Acrylamide) Studied by 2H NMR Field Cycling Relaxometry.pdf:PDF;:Frontiers_2024_Jan_Published-2024-03-21-SI.PDF:PDF},
  keywords     = {NMR,pNIPAM,2H-NMR,spin-lattice relaxation,T1,spin-spin relaxation,D2O,spectral density,field cycling,confinement,lcst},
  priority     = {prio1},
  ranking      = {rank5},
  url          = {https://www.frontiersin.org/articles/10.3389/frsfm.2024.1379816},
}

@PhdThesis{Lusceac2006,
  author       = {Lusceac, Sorin A.},
  title        = {Study of relaxation processes in simple glass formers by means of 2H NMR spectroscopy},
  year         = {2006},
  address      = {Bayreuth},
  creationdate = {2024-05-31T15:10:24},
  file         = {:Lusceac2006 - Study of Relaxation Processes in Simple Glass Formers by Means of 2H NMR Spectroscopy.pdf:PDF},
  keywords     = {2H-NMR, Glass, Polybutadiene, beta process, Random Walk Simulation, polybutadiene, NMR, spectral density, relaxation, T1, lineshape},
  url          = {https://epub.uni-bayreuth.de/id/eprint/788/},
}

@Article{Benkhof1998,
  author       = {S. Benkhof and A. Kudlik and T. Blochowicz and E. R{\"{o}}ssler},
  journal      = {Journal of Physics: Condensed Matter},
  title        = {Two glass transitions in ethanol: a comparative dielectric relaxation study of the supercooled liquid and the plastic crystal},
  year         = {1998},
  month        = sep,
  number       = {37},
  pages        = {8155},
  volume       = {10},
  abstract     = {Ethanol is known to form two different kinds of glassy state, namely a structural glass and a glassy crystal, both showing the same glass transition temperature . The molecular dynamics in the different phases (supercooled liquid/plastic crystal) and during the corresponding phase transition is studied by dielectric spectroscopy in the frequency range  (30 K-250 K). Extracting the time constant, width parameter and relaxation strength of the main relaxation (the -process), very similar dielectric loss is found in both phases, including also the high-frequency wing. Comparing the temperature dependence of the time constants , the plastic crystal exhibits a less fragile behaviour. Additionally, a secondary relaxation is detected, again essentially the same in the two glassy states. We conclude that the motional mechanisms probed in the plastic crystal and in the supercooled liquid state are very similar.},
  creationdate = {2024-05-31T15:40:36},
  doi          = {10.1088/0953-8984/10/37/005},
  keywords     = {ethanol,michael vogel,dielectric relaxation,spectral density,phase diagram,johari-goldstein},
  url          = {https://dx.doi.org/10.1088/0953-8984/10/37/005},
}

@Article{Sanz2011,
  author       = {Sanz, Alejandro and Nogales, Aurora and Puente-Orench, In\'es and Jim\'enez-Ruiz, M\'onica and Ezquerra, Tiberio A.},
  journal      = {Phys. Rev. Lett.},
  title        = {Detection of Early Stage Precursor during Formation of Plastic Crystal Ethanol from the Supercooled Liquid State: A Simultaneous Dielectric Spectroscopy with Neutron Diffraction Study},
  year         = {2011},
  month        = jul,
  pages        = {025502},
  volume       = {107},
  creationdate = {2024-06-02T12:27:29},
  doi          = {10.1103/PhysRevLett.107.025502},
  file         = {:Sanz2011 - Detection of Early Stage Precursor during Formation of Plastic Crystal Ethanol from the Supercooled Liquid State_ a Simultaneous Dielectric Spectroscopy with Neutron Diffraction Study.pdf:PDF},
  issue        = {2},
  keywords     = {ethanol,plastic crystal,BDS,neutron diffraction,kinetics},
  numpages     = {4},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.107.025502},
}

@Article{Criado2000,
  author       = {Criado, A. and Jim\'enez-Ruiz, M. and Cabrillo, C. and Bermejo, F. J. and Fern\'andez-Perea, R. and Fischer, H. E. and Trouw, F. R.},
  journal      = {Phys. Rev. B},
  title        = {Rotational dynamics in the plastic-crystal phase of ethanol: Relevance for understanding the dynamics during the structural glass transition},
  year         = {2000},
  month        = may,
  pages        = {12082--12093},
  volume       = {61},
  creationdate = {2024-06-02T12:32:08},
  doi          = {10.1103/PhysRevB.61.12082},
  file         = {:Criado2000 - Rotational Dynamics in the Plastic Crystal Phase of Ethanol_ Relevance for Understanding the Dynamics during the Structural Glass Transition.pdf:PDF},
  issue        = {18},
  keywords     = {ethanol,plastic crystal,neutron scattering,glass former,molecular dynamics simulation},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevB.61.12082},
}

@Article{Srinivasan1996,
  author       = {Srinivasan, A. and Bermejo, F. J. and de Andr\'es, A. and Dawidowski, J. and Z\'u\~niga, J. and Criado, A.},
  journal      = {Phys. Rev. B},
  title        = {Evidence for a supercooled plastic-crystal phase in solid ethanol},
  year         = {1996},
  month        = apr,
  pages        = {8172--8175},
  volume       = {53},
  creationdate = {2024-06-02T12:36:02},
  doi          = {10.1103/PhysRevB.53.8172},
  file         = {:Srinivasan1996 - Evidence for a Supercooled Plastic Crystal Phase in Solid Ethanol.pdf:PDF},
  issue        = {13},
  keywords     = {ethanol,plastic crystal,X-Ray,Raman spectroscopy,glass former},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevB.53.8172},
}

@Article{Sanz2014,
  author       = {Sanz, Alejandro and Nogales, Aurora and Puente-Orench, Inés and Jiménez-Ruiz, Mónica and Ezquerra, Tiberio A.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Changes in mobility of plastic crystal ethanol during its transformation into the monoclinic crystal state}},
  year         = {2014},
  issn         = {0021-9606},
  month        = feb,
  number       = {5},
  pages        = {054510},
  volume       = {140},
  abstract     = {{Transformation of deuterated ethanol from the plastic crystal phase into the monoclinic one is investigated by means of a singular setup combining simultaneously dielectric spectroscopy with neutron diffraction. We postulate that a dynamic transition from plastic crystal to supercooled liquid-like configuration through a deep reorganization of the hydrogen-bonding network must take place as a previous step of the crystallization process. Once these precursor regions are formed, subsequent crystalline nucleation and growth develop with time.}},
  creationdate = {2024-06-02T12:38:44},
  doi          = {10.1063/1.4863694},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4863694/15475052/054510\_1\_online.pdf},
  file         = {:Sanz2014 - Changes in Mobility of Plastic Crystal Ethanol during Its Transformation into the Monoclinic Crystal State.pdf:PDF},
  keywords     = {ethanol,plastic crystal,glas former,BDS,neutron diffraction},
  url          = {https://doi.org/10.1063/1.4863694},
}

@Article{Drobyshev2013,
  author       = {Drobyshev, A. and Aldiyarov, A. and Katpaeva, K. and Korshikov, E. and Kurnosov, V. and Sokolov, D.},
  journal      = {Low Temperature Physics},
  title        = {Transformation of cryovacuum condensates of ethanol near the glass transition temperature},
  year         = {2013},
  issn         = {1063-777X},
  month        = aug,
  number       = {8},
  pages        = {714--718},
  volume       = {39},
  abstract     = {{Thin films of cryovacuum condensates of ethanol formed by condensation of the gas on a cooled metal substrate are studied by infrared spectrometry and thermal desorption techniques. The main purpose was to examine dynamic relaxation processes near the glass transition temperature and the transition from orientationally disordered to orders states in thin ethanol cryocondensate films. It was found that ethanol cryocondensate films formed by condensation at T = 16 K are in an amorphous state (ASE). Increasing the sample temperature to T = 80 K leads to the transformation of the ASE into a structural glass. With further heating to T = 97 K, the structural glass is converted into a supercooled liquid and at T = 105 K, a plastic crystal is formed.}},
  creationdate = {2024-06-02T12:47:04},
  doi          = {10.1063/1.4818634},
  eprint       = {https://pubs.aip.org/aip/ltp/article-pdf/39/8/714/13714141/714\_1\_online.pdf},
  file         = {:Drobyshev2013 - Transformation of Cryovacuum Condensates of Ethanol near the Glass Transition Temperature.pdf:PDF},
  keywords     = {ethanol,plastic crystal,glas former,infrared spectroscopy,thermal desorption,thin film},
  url          = {https://doi.org/10.1063/1.4818634},
}

@Article{Ramos2003,
  author       = {M. A. Ramos and C. Talón and R. J. Jiménez-Riobóo and S. Vieira},
  journal      = {Journal of Physics: Condensed Matter},
  title        = {Low-temperature specific heat of structural and orientational glasses of simple alcohols},
  year         = {2003},
  month        = mar,
  number       = {11},
  pages        = {S1007},
  volume       = {15},
  abstract     = {In this work, we review, extend and discuss low-temperature specific-heat experiments, that we have conducted on different molecular (hydrogen-bonded) solids both in crystalline and glassy (either amorphous or orientationally disordered) phases. In particular, we have measured the low-temperature specific heat Cp for a set of simple, well known alcohols: glycerol, propanol and ethanol. For glycerol, we have prepared and measured Cp of both glass and crystal phases down to 0.5 K. The same has been done for propanol, in this case comparing the strikingly different values observed for the two chemical isomers, 1-propanol and 2-propanol. Moreover, ethanol exhibits a very interesting polymorphism presenting three different solid phases at low temperature: a fully ordered (monoclinic) crystal, an orientationally disordered (cubic) crystal or ‘orientational glass’ and the ordinary structural (amorphous) glass. By measuring and comparing the low-temperature specific heat of the three phases, in the boson peak range 2–10 K as well as in the tunnelling-state range below 1 K, we provide a quantitative confirmation that ‘glassy behaviour’, either concerning low-temperature properties or the glass-transition phenomenon itself, is not directly related to the lack of long-range crystalline order occurring in amorphous solids.},
  creationdate = {2024-06-12T17:39:18},
  doi          = {10.1088/0953-8984/15/11/323},
  file         = {:Ramos2003 - Low Temperature Specific Heat of Structural and Orientational Glasses of Simple Alcohols.pdf:PDF},
  keywords     = {ethanol,glass former,DSC,propanol,glycerol,isotope effect,1-propanol,2-propanol},
  url          = {https://dx.doi.org/10.1088/0953-8984/15/11/323},
}

@Article{Efimov2015,
  author       = {Efimov, V. and Izotov, A. and Mezhov-Deglin, L. and Nesvizhevskii, V. and Rybchenko, O. and Zimin, A.},
  journal      = {Low Temperature Physics},
  title        = {{Structural and phase transitions in nanocluster ethanol samples at low temperatures}},
  year         = {2015},
  issn         = {1063-777X},
  month        = jun,
  number       = {6},
  pages        = {473--477},
  volume       = {41},
  abstract     = {{Results of neutron (SANS study) and x-ray diffraction experiments with nanocluster samples of deuteroethanol (C2D5OD) or ordinary pure ethanol (C2H5OH) are presented. A deuterated ethanol sample, formed via quick cooling of ethanol–helium mixture down to 1.6 K, had clusters with the size of d ∼ 20–30 nm at liquid helium temperatures. After warming up to liquid nitrogen temperatures the gel decays into an amorphous white powder. It was observed that these powder samples remained in the amorphous state even after keeping at T ≤ 90 K for a long time (a few months). The neutron studies were supported by further x-ray investigations of the structure and the phase transitions in the highly dispersed powder samples, which were created via the decay of the gel samples of ordinary ethanol at temperatures above liquid nitrogen up to 150 K at saturated nitrogen gas pressure. Annealing of the “gel” sample during half an hour at a temperature of T ∼ 110 K resulted in a phase transition to a monoclinic phase with the crystallite sizes ∼30–40 nm. For comparison we studied the structure and phase transitions in “bulk” samples, prepared via quick freezing of liquid ethanol down to liquid nitrogen temperature. The “bulk” sample had a similar transition at T ∼ 125 K, which is by 15 K higher than the temperature of the intensive phase transition in the “gel” sample. The mean grain size in the bulk material was d ≥ 60 nm.}},
  creationdate = {2024-06-13T10:21:50},
  doi          = {10.1063/1.4922102},
  eprint       = {https://pubs.aip.org/aip/ltp/article-pdf/41/6/473/13656477/473\_1\_online.pdf},
  file         = {:Efimov2015 - Structural and Phase Transitions in Nanocluster Ethanol Samples at Low Temperatures.pdf:PDF},
  keywords     = {ethanol,glass former,cluster,microphaseseparation,SANS,X-Ray,neutrons},
  url          = {https://doi.org/10.1063/1.4922102},
}

@Article{JimenezRuiz1999,
  author       = {Jim\'enez-Ruiz, M. and Gonz\'alez, M. A. and Bermejo, F. J. and Miller, M. A. and Birge, Norman O. and Cendoya, I. and Alegr\'{\i}a, A.},
  journal      = {Phys. Rev. B},
  title        = {Relaxational dynamics in the glassy, supercooled liquid, and orientationally disordered crystal phases of a polymorphic molecular material},
  year         = {1999},
  month        = apr,
  pages        = {9155--9166},
  volume       = {59},
  creationdate = {2024-06-13T13:11:30},
  doi          = {10.1103/PhysRevB.59.9155},
  file         = {:JimenezRuiz1999 - Relaxational Dynamics in the Glassy, Supercooled Liquid, and Orientationally Disordered Crystal Phases of a Polymorphic Molecular Material.pdf:PDF},
  issue        = {14},
  keywords     = {ethanol,glass former,BDS},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevB.59.9155},
}

@Article{Patil2023,
  author       = {Patil, Shalin and Sun, Ruikun and Cheng, Shinian and Cheng, Shiwang},
  journal      = {Phys. Rev. Lett.},
  title        = {Molecular Mechanism of the Debye Relaxation in Monohydroxy Alcohols Revealed from Rheo-Dielectric Spectroscopy},
  year         = {2023},
  month        = feb,
  pages        = {098201},
  volume       = {130},
  abstract     = {Rheo-dielectric spectroscopy is employed to investigate the effect of external shear on Debye-like relaxation of a model monohydroxy alcohol, i.e., the 2-ethyl-1-hexanol (2E1H). Shear deformation leads to strong acceleration in the structural relaxation, the Debye relaxation, and the terminal relaxation of 2E1H. Moreover, the shear-induced reduction in structural relaxation time, τα, scales quadratically with that of Debye time, τD, and the terminal flow time, τf, suggesting a relationship of τ2 D ∼ τα. Further analyses reveal τ2 D=τα of 2E1H follows Arrhenius temperature dependence that applies remarkably well to many other monohydroxy alcohols with different molecular sizes, architectures, and alcohol types. These results cannot be understood by the prevailing transient chain model, and suggest a H-bonding breakage facilitated sub-supramolecular reorientation as the origin of Debye relaxation of monohydroxy alcohols, akin to the molecular mechanism for the terminal relaxation of unentangled “living” polymers.},
  creationdate = {2024-06-13T13:25:48},
  doi          = {10.1103/PhysRevLett.130.098201},
  file         = {:Patil2023 - Molecular Mechanism of the Debye Relaxation in Monohydroxy Alcohols Revealed from Rheo Dielectric Spectroscopy.pdf:PDF},
  issue        = {9},
  keywords     = {BDS,transient chain,2-ethyl-1-hexanol,terminal mode},
  numpages     = {7},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.130.098201},
}

@Article{Gainaru2010,
  author       = {Gainaru, C. and Meier, R. and Schildmann, S. and Lederle, C. and Hiller, W. and R\"ossler, E. A. and B{\"o}hmer, R.},
  journal      = {Phys. Rev. Lett.},
  title        = {Nuclear-Magnetic-Resonance Measurements Reveal the Origin of the Debye Process in Monohydroxy Alcohols},
  year         = {2010},
  month        = dec,
  pages        = {258303},
  volume       = {105},
  creationdate = {2024-06-13T13:42:08},
  doi          = {10.1103/PhysRevLett.105.258303},
  file         = {:Gainaru2010 - Nuclear Magnetic Resonance Measurements Reveal the Origin of the Debye Process in Monohydroxy Alcohols.pdf:PDF},
  issue        = {25},
  keywords     = {2H-NMR,1H-NMR,NMR,BDS,n-butanol,transient chain},
  numpages     = {4},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevLett.105.258303},
}

@Article{Brand2002,
  author       = {Brand, R. and Lunkenheimer, P. and Loidl, A.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Relaxation dynamics in plastic crystals}},
  year         = {2002},
  issn         = {0021-9606},
  month        = jun,
  number       = {23},
  pages        = {10386--10401},
  volume       = {116},
  abstract     = {{We report dielectric data on six different plastic crystalline materials, namely 1-cyanoadamantane, adamantanone, pentachloronitrobenzene, cyclo-hexanol, ethanol, and meta-carborane, covering a frequency range of up to 14 decades and up to 20 GHz. Information on phase transitions, the α-relaxation, and relaxation processes beyond the α-relaxation are provided. The α-relaxation shows clear non-Debye behavior and varying degrees of deviation from thermally activated behavior. Our results reveal a generally rather low fragility of plastic crystals. In some of the investigated materials evidence for Johari–Goldstein type β-relaxations is obtained. In addition, the question of the so-called excess wing of the α-relaxation peak is addressed in detail. In all cases, it is either absent or can be ascribed to a β-relaxation submerged under the α-peak. Overall, the present work provides a broad database on the dielectric behavior of plastic crystals, and may be taken as a review of the dynamic phenomena occurring in these materials, many of them being observed also in structural glass formers.}},
  creationdate = {2024-06-13T13:46:22},
  doi          = {10.1063/1.1477186},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/116/23/10386/19105643/10386\_1\_online.pdf},
  file         = {:Brand2002 - Relaxation Dynamics in Plastic Crystals.pdf:PDF},
  keywords     = {plastic crystal,ethanol,1-cyanoadamantane,adamantanone,pentachloronitrobenzene,cyclo-hexanol,meta-carborane,BDS,johari-goldstein},
  url          = {https://doi.org/10.1063/1.1477186},
}

@Article{Chua2017,
  author       = {Chua, Y. Z. and Young-Gonzales, A. R. and Richert, R. and Ediger, M. D. and Schick, C.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Dynamics of supercooled liquid and plastic crystalline ethanol: Dielectric relaxation and AC nanocalorimetry distinguish structural α- and Debye relaxation processes}},
  year         = {2017},
  issn         = {0021-9606},
  month        = jul,
  number       = {1},
  pages        = {014502},
  volume       = {147},
  abstract     = {{Physical vapor deposition has been used to prepare glasses of ethanol. Upon heating, the glasses transformed into the supercooled liquid phase and then crystallized into the plastic crystal phase. The dynamic glass transition of the supercooled liquid is successfully measured by AC nanocalorimetry, and preliminary results for the plastic crystal are obtained. The frequency dependences of these dynamic glass transitions observed by AC nanocalorimetry are in disagreement with conclusions from previously published dielectric spectra of ethanol. Existing dielectric loss spectra have been carefully re-evaluated considering a Debye peak, which is a typical feature in the dielectric loss spectra of monohydroxy alcohols. The re-evaluated dielectric fits reveal a prominent dielectric Debye peak, a smaller and asymmetrically broadened peak, which is identified as the signature of the structural α-relaxation and a Johari-Goldstein secondary relaxation process. This new assignment of the dielectric processes is supported by the observation that the AC nanocalorimetry dynamic glass transition temperature, Tα, coincides with the dielectric structural α-relaxation process rather than the Debye process. The combined results from dielectric spectroscopy and AC nanocalorimetry on the plastic crystal of ethanol suggest the occurrence of a Debye process also in the plastic crystal phase.}},
  creationdate = {2024-06-13T13:59:53},
  doi          = {10.1063/1.4991006},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4991006/15533182/014502\_1\_online.pdf},
  file         = {:Chua2017 - Dynamics of Supercooled Liquid and Plastic Crystalline Ethanol_ Dielectric Relaxation and AC Nanocalorimetry Distinguish Structural Α and Debye Relaxation Processes.pdf:PDF},
  keywords     = {ethanol,plastic crystal,BDS,DSC,AC nanocalorimetry,transient chain,johari-goldstein},
  url          = {https://doi.org/10.1063/1.4991006},
}








@Article{Gallo2016,
  author       = {Gallo, Paola and Amann-Winkel, Katrin and Angell, Charles Austen and Anisimov, Mikhail Alexeevich and Caupin, Frédéric and Chakravarty, Charusita and Lascaris, Erik and Loerting, Thomas and Panagiotopoulos, Athanassios Zois and Russo, John and Sellberg, Jonas Alexander and Stanley, Harry Eugene and Tanaka, Hajime and Vega, Carlos and Xu, Limei and Pettersson, Lars Gunnar Moody},
  journal      = {Chemical Reviews},
  title        = {Water: A Tale of Two Liquids},
  year         = {2016},
  note         = {PMID: 27380438},
  number       = {13},
  pages        = {7463--7500},
  volume       = {116},
  abstract     = {Water is the most abundant liquid on earth and also the substance with the largest number of anomalies in its properties. It is a prerequisite for life and as such a most important subject of current research in chemical physics and physical chemistry. In spite of its simplicity as a liquid, it has an enormously rich phase diagram where different types of ices, amorphous phases, and anomalies disclose a path that points to unique thermodynamics of its supercooled liquid state that still hides many unraveled secrets. In this review we describe the behavior of water in the regime from ambient conditions to the deeply supercooled region. The review describes simulations and experiments on this anomalous liquid. Several scenarios have been proposed to explain the anomalous properties that become strongly enhanced in the supercooled region. Among those, the second critical-point scenario has been investigated extensively, and at present most experimental evidence point to this scenario. Starting from very low temperatures, a coexistence line between a high-density amorphous phase and a low-density amorphous phase would continue in a coexistence line between a high-density and a low-density liquid phase terminating in a liquid–liquid critical point, LLCP. On approaching this LLCP from the one-phase region, a crossover in thermodynamics and dynamics can be found. This is discussed based on a picture of a temperature-dependent balance between a high-density liquid and a low-density liquid favored by, respectively, entropy and enthalpy, leading to a consistent picture of the thermodynamics of bulk water. Ice nucleation is also discussed, since this is what severely impedes experimental investigation of the vicinity of the proposed LLCP. Experimental investigation of stretched water, i.e., water at negative pressure, gives access to a different regime of the complex water diagram. Different ways to inhibit crystallization through confinement and aqueous solutions are discussed through results from experiments and simulations using the most sophisticated and advanced techniques. These findings represent tiles of a global picture that still needs to be completed. Some of the possible experimental lines of research that are essential to complete this picture are explored.},
  creationdate = {2024-06-13T17:44:20},
  doi          = {10.1021/acs.chemrev.5b00750},
  eprint       = {https://doi.org/10.1021/acs.chemrev.5b00750},
  file         = {:Gallo2016 - Water_ a Tale of Two Liquids.pdf:PDF},
  keywords     = {water,review},
  url          = {https://doi.org/10.1021/acs.chemrev.5b00750},
}

@Article{Koga1977,
  author       = {Koga, Kunimasa and Yoshizumi, Hajime},
  journal      = {Journal of Food Science},
  title        = {Differential scanning calorimetry ({DSC}) studies on the structures of water-ethanol mixtures and aged whiskey},
  year         = {1977},
  number       = {5},
  pages        = {1213--1217},
  volume       = {42},
  abstract     = {DSC measurements of water-ethanol mixture in various ethanol concentrations were made in the temperature range from -160°C to +10°C. In the entire concentration range, eight peaks (peaks 1–8) were observed. The heat of every peak (J/g) remarkably changed at 40(V/V)\% and 60\% ethanol concentrations. At 40\% ethanol concentration, the heat of peak 3 (endotherm at -58°C) was at its maximum, while the heat of peak 6 (exotherm at -100°C) was at its minimum. The melting point of ethanol in the mixture was -74°C when the concentration was below 40\%, and -62°C when the concentration was above 40\%. At 60\%, the heats of peak 2 (exotherm at -52°C) and peak 6 were at their maxima. It is, therefore, considered that structural alterations of the mixture occur at 40\% and 60\%. Peak 3 was ascribed to the melting of strongly-interacted water and ethanol. Similar thermogram patterns were obtamed by the DSC measurements of barley malt whiskey aged for 7 yr in a new oak barrel which was burnt brown and had previously been treated with sherry. However, by comparing the heat of peak 3 of whiskey with that of the mixture, it was known that the interaction between water and ethanol in the aged whiskey was more stronger than that in the water-ethanol mixture.},
  creationdate = {2024-06-18T09:55:56},
  doi          = {https://doi.org/10.1111/j.1365-2621.1977.tb14462.x},
  eprint       = {https://ift.onlinelibrary.wiley.com/doi/pdf/10.1111/j.1365-2621.1977.tb14462.x},
  file         = {:KUNIMASA1977 - Differential Scanning Calorimetry (DSC) Studies on the Structures of Water Ethanol Mixtures and Aged Whiskey.pdf:PDF},
  keywords     = {ethanol,DSC,aqueous alcohol,aqueous ethanol,ethanol-water},
  url          = {https://ift.onlinelibrary.wiley.com/doi/abs/10.1111/j.1365-2621.1977.tb14462.x},
}

@Article{Koga1979,
  author       = {Koga, Kunimasa and Yoshizumi Hajime},
  journal      = {Journal of Food Science},
  title        = {Differential scanning calorimetry ({DSC}) studies on the freezing process of water-ethanol mixtures and distilled spirits},
  year         = {1979},
  number       = {5},
  pages        = {1386--1389},
  volume       = {44},
  abstract     = {DSC measurements of the freezing of water-ethanol mixtures in various ethanol concentrations were made in a temperature range from +20° C to -160°C. One exotherm was observed in the freezing process of each mixture. The freezing point, heat associated with the freezing process and kinetic constant of freezing (kf) were determined over the entire range of the ethanol concentration from the DSC thermogram. Log kf was plotted as a function of the reciprocal of the absolute temperature (T-1) of the mixtures. The freezing process of the mixtures in an ethanol concentration of 0˜75 (V/V)\% obeyed first order kinetics but at a concentration above 75\%, the freezing process did not do so. The slope of log kf versus 1/T plots (d log kf/dT-1) of the mixture at the concentration below 75\% was determined. The concentration below 75\% was divided into four ranges (0˜18.5\%, 18.5˜40\%, 40˜60\%, 60˜75\%) from a variation in the slope of the linear plots. The results of the, DSC measurements of freshly distilled spirits (raw whiskey from barley malt and grain spirits) coincided with those of simple water-ethanol mixtures. It is considered that the freezing reaction of distilled spirits proceeded by the same mechanism as that of the simple mixture of the corresponding ethanol concentration. Structures of distilled spirits as a function of ethanol concentration were discussed in terms of the interaction of water and ethanol molecules.},
  creationdate = {2024-06-18T09:58:37},
  doi          = {https://doi.org/10.1111/j.1365-2621.1979.tb06444.x},
  eprint       = {https://ift.onlinelibrary.wiley.com/doi/pdf/10.1111/j.1365-2621.1979.tb06444.x},
  file         = {:Koga1979 - Differential Scanning Calorimetry (DSC) Studies on the Freezing Process of Water Ethanol Mixtures and Distilled Spirits.pdf:PDF},
  keywords     = {ethanol,DSC,aqueous ethanol,aqueous alcohol,ethanol-water},
  url          = {https://ift.onlinelibrary.wiley.com/doi/abs/10.1111/j.1365-2621.1979.tb06444.x},
}

@Article{Tan2015,
  author       = {Tan, Ming-Liang and Miller, Benjamin T. and Te, Jerez and Cendagorta, Joseph R. and Brooks, Bernard R. and Ichiye, Toshiko},
  journal      = {The Journal of Chemical Physics},
  title        = {Hydrophobic hydration and the anomalous partial molar volumes in ethanol-water mixtures},
  year         = {2015},
  issn         = {0021-9606},
  month        = feb,
  number       = {6},
  pages        = {064501},
  volume       = {142},
  abstract     = {{The anomalous behavior in the partial molar volumes of ethanol-water mixtures at low concentrations of ethanol is studied using molecular dynamics simulations. Previous work indicates that the striking minimum in the partial molar volume of ethanol VE as a function of ethanol mole fraction XE is determined mainly by water-water interactions. These results were based on simulations that used one water model for the solute-water interactions but two different water models for the water-water interactions. This is confirmed here by using two more water models for the water-water interactions. Furthermore, the previous work indicates that the initial decrease is caused by association of the hydration shells of the hydrocarbon tails, and the minimum occurs at the concentration where all of the hydration shells are touching each other. Thus, the characteristics of the hydration of the tail that cause the decrease and the features of the water models that reproduce this type of hydration are also examined here. The results show that a single-site multipole water model with a charge distribution that mimics the large quadrupole and the p-orbital type electron density out of the molecular plane has “brittle” hydration with hydrogen bonds that break as the tails touch, which reproduces the deep minimum. However, water models with more typical site representations with partial charges lead to flexible hydration that tends to stay intact, which produces a shallow minimum. Thus, brittle hydration may play an essential role in hydrophobic association in water. }},
  creationdate = {2024-07-01T07:55:11},
  doi          = {10.1063/1.4906750},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4906750/14035146/064501\_1\_online.pdf},
  file         = {:Tan2015 - Hydrophobic Hydration and the Anomalous Partial Molar Volumes in Ethanol Water Mixtures.pdf:PDF},
  keywords     = {simulation,volume contraction,aqueous ethanol,aqueous alcohol,hydrophobic hydration,ethanol cluster},
  url          = {https://doi.org/10.1063/1.4906750},
}

@Article{Wakisaka2005,
  author       = {Wakisaka, Akihiro and Ohki, Takahiro},
  journal      = {Faraday Discuss.},
  title        = {Phase separation of water–alcohol binary mixtures induced by the microheterogeneity},
  year         = {2005},
  pages        = {231--245},
  volume       = {129},
  abstract     = {The relationship between liquid–liquid phase separation and microheterogeneity in water–primary alcohol mixtures was examined by analysing the mass spectra of clusters generated through the fragmentation of liquid droplets. By comparing the cluster structures of water–ethanol{,} –1-propanol{,} and –1-butanol binary mixtures at various alcohol concentrations{,} we discovered differences in the molecular clusters that control phase separation. We also studied the role of water in alcohol self-association. Alcohol self-association is promoted in the presence of a small amount of water (ca. 10 ∼ 20 wt%){,} in which the water–water hydrogen-bonding network is weak and does not contribute to alcohol self-association. We have demonstrated that alcohol self-association is also promoted by non-ideal mixing with other alcohols. The self-association of alcohol molecules complements the loss of stabilization energy caused by the relatively weak coexisting interactions. This complementary relationship among intermolecular interactions is an inherent property of solutions{,} and plays a key role in the phase separation process.},
  creationdate = {2024-07-01T08:01:05},
  doi          = {10.1039/B405391E},
  file         = {:Wakisaka2005 - Phase Separation of Water–alcohol Binary Mixtures Induced by the Microheterogeneity.pdf:PDF},
  issue        = {0},
  keywords     = {aqueous alcohol,aqueous ethanol,aqueous propanol,1-propanol,aqueous butanol,1-butanol,cluster,microheterogeneity,viscosity},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/B405391E},
}








@Article{Modig2004,
  author       = {Modig, Kristofer and Liepinsh, Edvards and Otting, Gottfried and Halle, Bertil},
  journal      = {Journal of the American Chemical Society},
  title        = {Dynamics of Protein and Peptide Hydration},
  year         = {2004},
  note         = {PMID: 14709075},
  number       = {1},
  pages        = {102--114},
  volume       = {126},
  abstract     = {Biological processes often involve the surfaces of proteins, where the structural and dynamic properties of the aqueous solvent are modified. Information about the dynamics of protein hydration can be obtained by measuring the magnetic relaxation dispersion (MRD) of the water 2H and 17O nuclei or by recording the nuclear Overhauser effect (NOE) between water and protein protons. Here, we use the MRD method to study the hydration of the cyclic peptide oxytocin and the globular protein BPTI in deeply supercooled solutions. The results provide a detailed characterization of water dynamics in the hydration layer at the surface of these biomolecules. More than 95\% of the water molecules in contact with the biomolecular surface are found to be no more than two-fold motionally retarded as compared to bulk water. In contrast to small nonpolar molecules, the retardation factor for BPTI showed little or no temperature dependence, suggesting that the exposed nonpolar residues do not induce clathrate-like hydrophobic hydration structures. New NOE data for oxytocin and published NOE data for BPTI were analyzed, and a mutually consistent interpretation of MRD and NOE results was achieved with the aid of a new theory of intermolecular dipolar relaxation that accounts explicitly for the dynamic perturbation at the biomolecular surface. The analysis indicates that water−protein NOEs are dominated by long-range dipolar couplings to bulk water, unless the monitored protein proton is near a partly or fully buried hydration site where the water molecule has a long residence time.},
  creationdate = {2024-07-02T14:41:51},
  doi          = {10.1021/ja038325d},
  eprint       = {https://doi.org/10.1021/ja038325d},
  file         = {:Modig2004 - Dynamics of Protein and Peptide Hydration.pdf:PDF;:DynamicsOfProteinAndPeptideHydration_ModigEtAl_JAmChemSoc2004_SI.pdf:PDF},
  keywords     = {protein,hydration shell,peptide,NMR,2H-NMR,17O-NMR,nuclear overhauser effect,NOE,magnetic relaxation dispersion,MRD,BPTI,oxytocin},
  url          = {https://doi.org/10.1021/ja038325d},
}

@Article{Calderara1997,
  author       = {Calderara, I. and Gougeon, R. and Delmotte, L. and Lemee, V. and Lougnot, D. J.},
  journal      = {Journal of Polymer Science Part A: Polymer Chemistry},
  title        = {NMR study of the structure and properties of poly(MMA-co-VP) crosslinked hydrogels},
  year         = {1997},
  number       = {17},
  pages        = {3619--3625},
  volume       = {35},
  abstract     = {1H- and 13C-NMR techniques were used to study the microscopic structure of NMA/VP copolymer hydrogels. Evidence was obtained for a plasticization effect of MMA chains by VP. An original 1H-NMR approach revealed the existence of several types of water with various degree of bounding to the polymer network, a conclusion that is corroborated by a complementary 13C-NMR study.},
  creationdate = {2024-07-08T12:50:57},
  doi          = {https://doi.org/10.1002/(SICI)1099-0518(199712)35:17<3619::AID-POLA1>3.0.CO;2-N},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/%28SICI%291099-0518%28199712%2935%3A17%3C3619%3A%3AAID-POLA1%3E3.0.CO%3B2-N},
  file         = {:Calderara1997 - NMR Study of the Structure and Properties of Poly(MMA Co VP) Crosslinked Hydrogels.pdf:PDF},
  keywords     = {NMR,structure,porperties,poly(MMA-co-VP),hydrogels,1H-NMR,13C-NMR,plasticizer},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/%28SICI%291099-0518%28199712%2935%3A17%3C3619%3A%3AAID-POLA1%3E3.0.CO%3B2-N},
}








@Article{McBrierty1992,
  author       = {McBrierty, V. J. and Quinn, F. X. and Keely, C. and Wilson, A. C. and Friends, G. D.},
  journal      = {Macromolecules},
  title        = {Water in hydrogels. 4. Poly(N-vinyl-2-pyrrolidinone-methyl methacrylate)/saline systems},
  year         = {1992},
  number       = {17},
  pages        = {4281--4284},
  volume       = {25},
  abstract     = {This paper examines the DSC and 23Na NMR response of poly(AT-vinyl-2-pyrrolidinone/meth-yl methacrylate) copolymer, P(NVP/MMA) hydrated with 2 % NaCl solution. The freezing point depression,the enthalpy of fusion, and the amount of nonfreezable water increase with the introduction of sodium ions.Devitrification observed over the DSC heating cycle in an earlier study on hydrated poly(hydroxyethyl meth-acrylate), P(HEMA), is absent in hydrated P(NVP/MMA). The observed isothermal crystallization behaviorwas monotonic. 23Na NMR line shapes recorded as a function of solution content revealed a sensitivity ofthe Na+ ion to its local environment. The line width and chemical shift increased abruptly as the degreeof hydration fell below the nonfreezable water content as determined by DSC in a way that is consistent with current views on the behavior of water in hydrogels.},
  creationdate = {2024-07-08T12:52:19},
  doi          = {10.1021/ma00043a006},
  eprint       = {https://doi.org/10.1021/ma00043a006},
  file         = {:McBrierty1992 - Water in Hydrogels. 4. Poly(N Vinyl 2 Pyrrolidinone Methyl Methacrylate)_saline Systems.pdf:PDF},
  keywords     = {DSC,NMR,23Na-NMR},
  url          = {https://doi.org/10.1021/ma00043a006},
}

@Article{Zhang2019,
  author       = {Binglong Zhang and He Liu and Jinzhong Dong and Shuiming Liu},
  journal      = {IOP Conference Series: Earth and Environmental Science},
  title        = {Effect of temperature and mole fraction on viscosity and thermal conductivity of water and ethanol mixture},
  year         = {2019},
  month        = feb,
  number       = {4},
  pages        = {042048},
  volume       = {227},
  abstract     = {The viscosity and thermal conductivity of the mixture as a heat exchange medium are the main factors affecting the heat transfer performance. In this paper, the mixture of water and ethanol is used as the research object. The viscosity and thermal conductivity of gas and liquid are calculated by various methods. Combined with the experimental data, the variation law with temperature and mole fraction is analysed, and the difference of different calculation methods is compared. When calculating the viscosity of water and ethanol mixture, the Teja and Rice method and the Jouyban and Acree method are suitable for different temperature ranges. The Jamieson method is more practical than the Baroncini method, when calculating the thermal conductivity. Finally, the calculation results are applied to an ejector refrigeration system calculation program, and it is found that the viscosity and thermal conductivity of the heat exchange medium have an important influence on the accuracy of the system performance calculation.},
  creationdate = {2024-07-26T17:31:50},
  doi          = {10.1088/1755-1315/227/4/042048},
  file         = {:Zhang2019 - Effect of Temperature and Mole Fraction on Viscosity and Thermal Conductivity of Water and Ethanol Mixture.pdf:PDF},
  keywords     = {aqueous ethanol,viscosity,aqueous alcohol},
  publisher    = {IOP Publishing},
  url          = {https://dx.doi.org/10.1088/1755-1315/227/4/042048},
}






















@Article{MarijanaMijakovic2015,
  author       = {Marijana Mijaković, Kamil Dawid Polok, Bernarda Kežić, Franjo Sokolić, Aurélien Perera and Larisa Zoranić},
  journal      = {Molecular Simulation},
  title        = {A comparison of force fields for ethanol–water mixtures},
  year         = {2015},
  number       = {9},
  pages        = {699--712},
  volume       = {41},
  abstract     = {Aqueous ethanol mixtures are studied through molecular dynamics simulations with the focus on exploring how various force field models reproduce the association and its influence on selected thermo-physical properties of these mixtures. The most important conclusion seems to be the inadequacy of all classical force fields to reproduce the very peculiar shape of the excess enthalpy of these mixtures, as a function of the ethanol concentration, neither quantitatively nor qualitatively. The Kirkwood–Buff (KB) integrals calculated using the simulation data follow the same trends as the experimental ones. This suggests complicated correlation of the excess enthalpy with the concentration fluctuation and clustering in these mixtures. The KB force field shows better overall agreement with experimental results than the other studied models.},
  comment      = {paywall},
  creationdate = {2024-08-01T12:58:27},
  doi          = {10.1080/08927022.2014.923567},
  eprint       = {https://doi.org/10.1080/08927022.2014.923567},
  keywords     = {aqueous alcohol,ethanol,simulation,force fields,review},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/08927022.2014.923567},
}

@Article{Kumar2020,
  author       = {Kumar, Shubham and Sarkar, Sarmistha and Bagchi, Biman},
  journal      = {The Journal of Chemical Physics},
  title        = {{Microscopic origin of breakdown of Stokes–Einstein relation in binary mixtures: Inherent structure analysis}},
  year         = {2020},
  issn         = {0021-9606},
  month        = apr,
  number       = {16},
  pages        = {164507},
  volume       = {152},
  abstract     = {{Aqueous binary mixtures often exhibit dramatic departure from the predicted hydrodynamic behavior when transport properties are plotted against composition. We show by inherent structure (IS) analysis that this sharp composition dependent breakdown of the Stokes–Einstein relation can be attributed to the non-monotonic variation in the average inherent structure energy of these mixtures. Further IS analysis reveals the existence of a unique ground state, stabilized by both the formation of an optimum number of H-bonds and a favorable hydrophobic interaction at this composition. The surprisingly sharp turnaround behavior observed in the effective hydrodynamic radius also owes its origin to the same combination of these two factors. Interestingly, the temperature dependence of isothermal compressibility shows a minimum at the particular composition. Extensive studies on water–dimethyl sulfoxide and water–ethanol mixtures using two different force-fields of water reveal many features that are nearly universal. A justification of this quasi-universal behavior is provided in terms of a mode-coupling theory (MCT) of viscosity, which can serve as the starting point of a remarkable correlation observed with the nearest neighbor structure, as captured by the first peaks of the radial distribution function, and the slowdown in the intermediate scattering function at intermediate wavenumbers. Therefore, the formation of the local structure captured through IS analysis can be correlated with the MCT.}},
  creationdate = {2024-08-02T09:10:50},
  doi          = {10.1063/5.0004725},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/5.0004725/13420762/164507\_1\_online.pdf},
  file         = {:Kumar2020 - Microscopic Origin of Breakdown of Stokes–Einstein Relation in Binary Mixtures_ Inherent Structure Analysis.pdf:PDF;:MicroscopicOriginOfBreakfownOfStokesEinsteinRelationInBinaryMixtures-InherentStructureAnalysis_KumarEtAl_JCP2020_SI.pdf:PDF},
  keywords     = {stokes-einstein,SED,simulation,aqueous alcohol,ethanol,DMSO,mode coupling theory},
  url          = {https://doi.org/10.1063/5.0004725},
}

@Article{Pothoczki2018a,
  author       = {Szilvia Pothoczki and László Pusztai and Imre Bakó},
  journal      = {Journal of Molecular Liquids},
  title        = {Temperature dependent dynamics in water-ethanol liquid mixtures},
  year         = {2018},
  issn         = {0167-7322},
  pages        = {571--579},
  volume       = {271},
  abstract     = {Temperature dependent hydrogen bond energetics and dynamical features, such as the diffusion coefficient and re-orientational times, have been determined for ethanol-water mixtures with 10, 20 and 30 mol% of ethanol. Concerning pairwise interaction energies between molecules, it is found that water-water interactions become stronger, while ethanol-ethanol ones become significantly weaker in the mixtures, than the corresponding values characteristic to the pure substances. Concerning the diffusion processes, for all concentrations the activation barrier of water and ethanol molecule become very similar to each other. Re-orientational motions of water and ethanol become slower as ethanol concentration is increasing. Characteristic re-orientational times of water in the mixtures are substantially longer than these values in the pure substance. On the other hand, this change for ethanol is only moderate. Re-orientational motions of water (especially the ones related to the H-bonded interaction) become very similar for those of ethanol in the mixtures.},
  creationdate = {2024-08-04T08:35:02},
  doi          = {https://doi.org/10.1016/j.molliq.2018.09.027},
  file         = {:Pothoczki2018a - Temperature Dependent Dynamics in Water Ethanol Liquid Mixtures.pdf:PDF},
  keywords     = {simulation,hydrogen bonds,aqueous alcohol,ethanol},
  url          = {https://www.sciencedirect.com/science/article/pii/S0167732218313357},
}

@Article{Yushmanov2006,
  author     = {Yushmanov, Pavel V. and Fur{\'{o}}, Istv{\'{a}}n and Iliopoulos, Ilias},
  journal    = {Macromolecular Chemistry and Physics},
  title      = {Kinetics of Demixing and Remixing Transitions in Aqueous Solutions of Poly(N-isopropylacrylamide): A Temperature-Jump 1H NMR Study},
  year       = {2006},
  number     = {21},
  pages      = {1972--1979},
  volume     = {207},
  abstract   = {The time course of the coil-to-globule collapse and intermolecular aggregation of poly(N-isopropylacrylamide) in aqueous solution upon exceeding the lower critical solution temperature (LCST) are investigated by temperature-jump 1H NMR spectroscopy. After the temperature jump, we record the time dependences of (i) the mobile fraction of the polymer chain as revealed by the intensity of the liquid-like NMR signal, (ii) the local mobility of those chains as revealed by the transverse relaxation time T2, and (iii) their self-diffusion coefficient D. The same data are also reported at their temperature-dependent long-time limits. The results suggest a sudden, faster than one second, collapse and intermolecular aggregation into globules and a slower reorganization/redistribution of the individual chains among and within the globular and mobile states. We found that all molecular changes are reversible if the temperature remains less than ca. 6--8 K above the LCST for less than a few minutes; under those conditions, experiments upon sudden temperature quench below the LCST show that the aggregates disintegrate and swell into coils in less than a few seconds. 1H NMR signal intensity of the methyl groups of 1 wt.-\% PNIPAM dissolved in 0.1 M NaCl solution in D2O in a temperature-jump experiment from 300 to 312 K. The data were recorded by the 90{$^{\circ}$}$-\tau$--(180{$^{\circ}$}$-$2$\tau$-)n-detection of the CPMG pulse sequence.},
  doi        = {10.1002/macp.200600394},
  eprint     = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/macp.200600394},
  keywords   = {PFG, self-diffusion coefficient, spin-lattice, spin-spin, T1, aggregation, miscibility, NMR, temperature jump, turbidity, PNIPAM, T2 relaxation, diffusion, CPMG},
  ranking    = {rank5},
  readstatus = {read},
  url        = {https://onlinelibrary.wiley.com/doi/abs/10.1002/macp.200600394},
}

@Article{Alam2014,
  author       = {Alam, Todd M. and Childress, Kimberly K. and Pastoor, Kevin and Rice, Charles V.},
  journal      = {Journal of Polymer Science Part B: Polymer Physics},
  title        = {Characterization of free, restricted, and entrapped water environments in poly(N-isopropyl acrylamide) hydrogels via 1H HRMAS PFG NMR spectroscopy},
  year         = {2014},
  number       = {23},
  pages        = {1521--1527},
  volume       = {52},
  abstract     = {Different water environments in poly(N-isopropyl acrylamide) (PNIPAAm) hydrogels are identified and characterized using 1H high resolution magic angle spinning (HRMAS) nuclear magnetic resonance (NMR). Local water environments corresponding to a “free” highly mobile species, along with waters showing restricted dynamics are resolved in these swollen hydro-gels. For photo-initiated polymerized PNIPAAm gels, an additional entrapped water species is observed. Spin–spin R2 relaxation experiments support the argument of reduced mobility in the restricted and entrapped water species. By combining pulse field gradient techniques with HRMAS NMR it is possible to directly measure the self-diffusion rate for these different water environments. The behavior of the heterogeneous water environments through the lower critical solution temperature transition is described. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 1521–1527},
  creationdate = {2024-05-22T14:05:27},
  doi          = {10.1002/polb.23591},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.23591},
  file         = {:Alam2014 - Characterization of Free, Restricted, and Entrapped Water Environments in Poly(N Isopropyl Acrylamide) Hydrogels Via 1H HRMAS PFG NMR Spectroscopy.pdf:PDF},
  keywords     = {diffusion,HRMAS,hydrogels,NMR,PFG,stimuli-sensitive polymers,thermoresponsive polymer,water,solvent dynamics,pNIPAM,1H-NMR,T2,spin-spin relaxation,exchange},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.23591},
}

@Article{Powles1963,
  author       = {J. G. Powles and J. H. Strange},
  journal      = {Proceedings of the Physical Society},
  title        = {Zero Time Resolution Nuclear Magnetic Resonance Transient in Solids},
  year         = {1963},
  month        = jul,
  number       = {1},
  pages        = {6},
  volume       = {82},
  abstract     = {A method is described for the experimental determination of the complete Bloch decay signal after a pulse for broad line nuclear magnetic resonances, as in solids. This method removes the necessity for constructing transient equipment of very short time resolution which would be extremely difficult. By means of apparatus with a time resolution of 3 μsec effectively zero time resolution has been attained. The method is tested by comparing the Fourier transform of the steady state absorption line with the Bloch decay. Agreement to 3% is obtained for many materials having lines up to 15 gauss broad. A theoretical analysis is given which supports the experimental results and which gives an explicit expression for the `echo Bloch decay' up to and including terms of fourth power in the time. Explicit expressions are given for static dipolar interaction for identical spins. It is shown that the second and fourth moments of the absorption lines can be obtained from the echo Bloch decay with an accuracy comparable with that from conventional steady-state methods and these are obtained very rapidly and with little labour.},
  creationdate = {2024-09-23T16:33:23},
  doi          = {10.1088/0370-1328/82/1/303},
  file         = {:Powles1963 - Zero Time Resolution Nuclear Magnetic Resonance Transient in Solids.pdf:PDF},
  keywords     = {nmr,solid echo,theory,quadrupolar interaction},
  url          = {https://dx.doi.org/10.1088/0370-1328/82/1/303},
}

@InCollection{Cohen1957,
  author       = {M.H. Cohen and F. Reif},
  publisher    = {Academic Press},
  title        = {Quadrupole Effects in Nuclear Magnetic Resonance Studies of Solids},
  year         = {1957},
  editor       = {FREDERICK SEITZ and DAVID TURNBULL},
  pages        = {321--438},
  series       = {Solid State Physics},
  volume       = {5},
  abstract     = {Publisher Summary
This chapter discusses quadrupole effects in nuclear magnetic resonance studies of solids. The first evidence that many nuclei possess magnetic moments came from the study of the hyperfine structure of atomic spectra in the visible region. The interaction of the nuclear magnetic moment with the magnetic field produced by the atomic electrons gives rise to a hyperfine spectrum that is relatively simple, being characterized by the well known “interval rule.” Marked departures from this interval rule do occur in a few cases, however, and some of the departures can definitely be attributed to the presence of a nuclear electric quadrupole interaction. The methods of radio-frequency spectroscopy are very well adapted for the investigation of the very small interaction energies to which nuclear moments give rise. They have led not only to much more precise determinations of nuclear magnetic moments, but also to a vastly increased knowledge of nuclear electric quadrupole effects. The first outstanding success along this line was the discovery, by the molecular beam resonance method, of the quadrupole moment of the deuteron. The field of electric quadrupole interactions in nuclear magnetic resonance can be divided roughly into two areas according to the relative magnitude of the nuclear quadrupole interactions.},
  comment      = {paywall},
  creationdate = {2024-10-04T13:41:04},
  doi          = {https://doi.org/10.1016/S0081-1947(08)60105-8},
  issn         = {0081-1947},
  keywords     = {NMR,theory,quadrupolar interaction},
  url          = {https://www.sciencedirect.com/science/article/pii/S0081194708601058},
}

@Article{Eden2003,
  author       = {Ed{\'e}n, Mattias},
  journal      = {Concepts in Magnetic Resonance Part A},
  title        = {Computer simulations in solid-state NMR. I. Spin dynamics theory},
  year         = {2003},
  number       = {1},
  pages        = {117--154},
  volume       = {17A},
  abstract     = {This article is the first in a series of publications that discuss the basics of the writing of computer programs for simulating solid-state NMR experiments with static and rotating samples. The present article gives an account of the relevant NMR theory needed for writing NMR simulation computer codes. The concept of irreducible spherical tensors is reviewed, as is how it may be used to construct Hamiltonians that represent the various NMR interactions. The spin dynamics that links the Hamiltonian to the time evolution of the nuclear spins and the detection of the NMR time-domain signal is discussed for static and rotating solids, as well as the relationship between the form of the Hamiltonian and the resulting NMR spectrum. © 2003 Wiley Periodicals, Inc. Concepts Magn Reson Part A 17A: 117–154, 2003.},
  creationdate = {2024-10-14T10:23:12},
  doi          = {https://doi.org/10.1002/cmr.a.10061},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.a.10061},
  file         = {:Eden2003 - Computer Simulations in Solid State NMR. I. Spin Dynamics Theory.pdf:PDF},
  keywords     = {solid-state NMR,numerical simulation,static solids,magic-angle spinning,dynamically inhomogeneous Hamiltonian,spherical tensor,NMR,theory,calculation,quadrupole},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.a.10061},
}

@Article{Eden2003a,
  author       = {Ed{\'e}n, Mattias},
  journal      = {Concepts in Magnetic Resonance Part A},
  title        = {Computer simulations in solid-state NMR. II. Implementations for static and rotating samples},
  year         = {2003},
  number       = {1},
  pages        = {1--23},
  volume       = {18A},
  abstract     = {In the first article in this series (Concepts Magn Reson Part A 17A:117–154, 2003), we outlined a theoretical framework for calculating solid-state NMR time-domain signals and frequency-domain spectra. This article explains how the theory may be implemented on a computer for simulating NMR signals from a single crystal in a static and rotating sample. The general building blocks of a computer program for numerically calculating NMR signals are discussed. Computer algorithms for carrying out the simulations are presented as flowcharts and implemented in C/C++ code. © 2003 Wiley Periodicals, Inc. Concepts Magn Reson Part A 18A: 1–23, 2003},
  creationdate = {2024-10-14T10:25:13},
  doi          = {https://doi.org/10.1002/cmr.a.10064},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.a.10064},
  file         = {:Eden2003a - Computer Simulations in Solid State NMR. II. Implementations for Static and Rotating Samples.pdf:PDF},
  keywords     = {solid-state NMR,numerical simulation,computer algorithm,static solids,magic-angle-spinning,dynamically inhomogeneous Hamiltonian,spherical tensor,NMR,calculation,theory,quadrupole},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.a.10064},
}

@Article{Eden2003b,
  author       = {Ed{\'e}n, Mattias},
  journal      = {Concepts in Magnetic Resonance Part A},
  title        = {Computer simulations in solid-state NMR. III. Powder averaging},
  year         = {2003},
  number       = {1},
  pages        = {24--55},
  volume       = {18A},
  abstract     = {As the final part in a series of articles on numerical simulations in solid-state NMR (Concepts Magn Reson 17A: 117–154, 2003 and Concepts Magn Reson Part A 18A: 1–23, 2003), aspects of simulations of NMR responses from powders are discussed. The underlying equations for powder averaging are derived, and it is demonstrated how powder averages may be estimated numerically. Orientational symmetry in solid-state NMR is summarized and exploited to achieve more efficient calculations. Explicit computer code in C/C++ is given for simulation of NMR spectra from powders containing (1) two homonuclear spins-1/2 in a static sample and (2) a heteronuclear two spin-1/2 system under magic-angle-spinning conditions. © 2003 Wiley Periodicals, Inc. Concepts Magn Reson Part A 18A: 24–55, 2003},
  creationdate = {2024-10-14T10:27:05},
  doi          = {https://doi.org/10.1002/cmr.a.10065},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.a.10065},
  file         = {:Eden2003b - Computer Simulations in Solid State NMR. III. Powder Averaging.pdf:PDF},
  keywords     = {solid-state NMR,numerical simulation,computer algorithm,powder average,orientational average,orientational symmetry,static solid,magic-angle-spinning,dynamically inhomogeneous Hamiltonian,NMR,quadrupole,calculation,theory},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.a.10065},
}

@Book{Slichter1963_old,
  author       = {Charles P. Slichter},
  editor       = {Frederick Seitz},
  publisher    = {Harper \& Row},
  title        = {Principles of Magnetic Resonance: with examples from solid state physics},
  year         = {1963},
  series       = {Harper's physics series},
  comment      = {different versions exists (hardcover/ebook, different publishers)},
  creationdate = {2024-10-14T16:09:42},
  keywords     = {NMR,theory,book},
}

@Article{Jeffrey1981,
  author       = {K. R. Jeffrey},
  journal      = {Bulletin of Magnetic Resoance},
  title        = {Nuclear Magnetic Relaxation In A Spin 1 System},
  year         = {1981},
  number       = {2-4},
  pages        = {69--82},
  volume       = {3},
  creationdate = {2024-10-14T17:09:22},
  file         = {:Jeffrey1981 - Nuclear Magnetic Relaxation in a Spin 1 System.pdf:PDF},
  keywords     = {NMR,theory,quadrupole,relaxation},
}

@Book{Hodgkinson2021a,
  author       = {Hodgkinson, Paul},
  publisher    = {The Royal Society of Chemistry},
  title        = {{Nuclear Magnetic Resonance: Volume 47}},
  year         = {2021},
  isbn         = {978-1-83916-391-3},
  month        = nov,
  abstract     = {{Nuclear magnetic resonance has proved a uniquely versatile and powerful spectroscopic technique, with applications across chemistry, physics and medicine. The success of NMR and its constant redevelopment means that the literature is vast and wide-ranging. Each chapter in this volume is a distillation of the key recent literature in different areas covering the spectrum of NMR theory and practice, and including solution-state, solid-state and in-vivo NMR. These reports will be invaluable both for new researchers wishing to engage with literature for the first time, and for seasoned practitioners, particularly service managers, wishing to keep in touch with the ever-expanding ways in which NMR is used.}},
  creationdate = {2024-10-15T08:17:04},
  doi          = {10.1039/9781839164965},
  file         = {:Hodgkinson2021a - Nuclear Magnetic Resonance_ Volume 47.pdf:PDF;:AuthorBiographies.pdf:PDF;:EditorBiography.pdf:PDF;:FrontMatter.pdf:PDF;:HyperpolarisationTechinques.pdf:PDF;:NMRInLivingSystems.pdf:PDF;:NMROfProteinsAndNucleicAcids.pdf:PDF;:NMROfSoftMatterSystems.pdf:PDF;:NuclearSpinRelaxation.pdf:PDF;:Preface.pdf:PDF;:SolidStateNMRSpectroscopy.pdf:PDF;:TheoreticalAndPracticalAspectsOfIndirectSpinSpinCouplings.pdf:PDF;:TheoryAndComputationOfNuclearShielding.pdf:PDF},
  keywords     = {book,NMR,theory,polymer},
  url          = {https://doi.org/10.1039/9781839164965},
}

@Article{Hahn1950,
  author       = {Hahn, Erwin L.},
  journal      = {Phys. Rev.},
  title        = {Spin Echoes},
  year         = {1950},
  month        = nov,
  pages        = {580--594},
  volume       = {80},
  creationdate = {2024-10-16T08:15:31},
  doi          = {10.1103/PhysRev.80.580},
  file         = {:Hahn1950 - Spin Echoes.pdf:PDF},
  issue        = {4},
  keywords     = {NMR,theory,hahn echo},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRev.80.580},
}

@Article{Man1993,
  author       = {Pascal P. Man},
  journal      = {Solid State Nuclear Magnetic Resonance},
  title        = {Determination of spin-52 quadrupolar coupling with two-pulse sequences},
  year         = {1993},
  issn         = {0926-2040},
  number       = {4},
  pages        = {165--180},
  volume       = {2},
  abstract     = {The density matrix of a spin-52 system excited by two in-phase pulses separated by a delay τ2 is calculated from the equilibrium state to the end of the second pulse. The interaction involved throughout the computation is the first-order quadrupolar interaction. Consequently, the results are valid for any ratio of the quadrupolar coupling to the amplitude of the radio-frequency pulse. It is shown that single- and multi-quantum coherences developed during the first pulse are detected at the end of the second pulse through single-quantum coherences. Other two-pulse sequences with various phase cyclings as well as the rotary echo sequence are also discussed and illustrated with the nuclei 27Al in a single crystal of corundum Al2O3.},
  creationdate = {2024-10-17T10:53:49},
  doi          = {https://doi.org/10.1016/0926-2040(93)90022-F},
  file         = {:Man1993 - Determination of Spin 52 Quadrupolar Coupling with Two Pulse Sequences.pdf:PDF},
  keywords     = {Al NMR, quadrupolar interaction, , two-pulse excitation},
  url          = {https://www.sciencedirect.com/science/article/pii/092620409390022F},
}

@Article{Powles1962,
  author       = {J.G. Powles and P. Mansfield},
  journal      = {Physics Letters},
  title        = {Double-pulse nuclear-resonance transients in solids},
  year         = {1962},
  issn         = {0031-9163},
  number       = {2},
  pages        = {58--59},
  volume       = {2},
  creationdate = {2024-10-17T11:02:18},
  doi          = {https://doi.org/10.1016/0031-9163(62)90147-6},
  file         = {:Powles1962 - Double Pulse Nuclear Resonance Transients in Solids.pdf:PDF},
  keywords     = {NMR,theory,solid echo},
  url          = {https://www.sciencedirect.com/science/article/pii/0031916362901476},
}

@Article{Mansfield1971,
  author       = {P. Mansfield},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {Pulsed NMR in solids},
  year         = {1971},
  issn         = {0079-6565},
  number       = {1},
  pages        = {41--101},
  volume       = {8},
  creationdate = {2024-10-17T11:04:09},
  doi          = {https://doi.org/10.1016/0079-6565(71)80002-X},
  file         = {:Mansfield1971 - Pulsed NMR in Solids.pdf:PDF},
  keywords     = {NMR,theory},
  url          = {https://www.sciencedirect.com/science/article/pii/007965657180002X},
}

@Article{Solomon1958,
  author       = {Solomon, I.},
  journal      = {Phys. Rev.},
  title        = {Multiple Echoes in Solids},
  year         = {1958},
  month        = apr,
  pages        = {61--65},
  volume       = {110},
  creationdate = {2024-10-17T11:22:25},
  doi          = {10.1103/PhysRev.110.61},
  file         = {:Solomon1958 - Multiple Echoes in Solids.pdf:PDF},
  issue        = {1},
  keywords     = {NMR,theory,solid echo},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRev.110.61},
}

@Article{Bloom1955,
  author       = {Bloom, M. and Hahn, E. L. and Herzog, B.},
  journal      = {Phys. Rev.},
  title        = {Free Magnetic Induction in Nuclear Quadrupole Resonance},
  year         = {1955},
  month        = mar,
  pages        = {1699--1709},
  volume       = {97},
  creationdate = {2024-10-17T11:49:24},
  doi          = {10.1103/PhysRev.97.1699},
  file         = {:Bloom1955 - Free Magnetic Induction in Nuclear Quadrupole Resonance.pdf:PDF},
  issue        = {6},
  keywords     = {NMR,theory,quadrupole},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRev.97.1699},
}

@Book{Dubbers2013,
  author       = {Dubbers, Dirk and Stöckmann, Hans-Jürgen},
  publisher    = {Springer Berlin Heidelberg},
  title        = {Quantum Physics: The Bottom-Up Approach : From the Simple Two-Level System to Irreducible Representations},
  year         = {2013},
  edition      = {First},
  isbn         = {9783642310607},
  series       = {Graduate Texts in Physics},
  creationdate = {2024-10-18T08:12:16},
  file         = {:Dubbers2013 - Quantum Physics_ the Bottom up Approach _ from the Simple Two Level System to Irreducible Representations.pdf:PDF},
  keywords     = {NMR,theory,book,wigner-eckart theo},
  url          = {https://doi.org/10.1007/978-3-642-31060-7},
}

@Article{Hoffmann2023,
  author       = {Hoffmann, Lars and Beerwerth, Joachim and Moch, Kevin and B{\"o}hmer, Roland},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Phenol, the simplest aromatic monohydroxy alcohol, displays a faint Debye-like process when mixed with a nonassociating liquid},
  year         = {2023},
  pages        = {24042--24059},
  volume       = {25},
  abstract     = {Solvated in propylene carbonate, viscous phenol is studied using dielectric spectroscopy and shear rheology. In addition, several oxygen-17 and deuteron nuclear magnetic resonance (NMR) techniques are applied to specifically isotope labeled equimolar mixtures. Quantum chemical calculations are used to check the electrical field gradient at phenol's oxygen site. The chosen combination of NMR methods facilitates the selective examination of potentially hydrogen-bond related contributions as well as those dominated by the structural relaxation. Taken together the present results for phenol in equimolar mixtures with the van der Waals liquid propylene carbonate provide evidence for the existence of a very weak Debye-like process that originates from ringlike supramolecular associates.},
  creationdate = {2024-10-19T11:54:06},
  doi          = {10.1039/D3CP02774K},
  file         = {:Hoffmann2023 - Phenol, the Simplest Aromatic Monohydroxy Alcohol, Displays a Faint Debye like Process When Mixed with a Nonassociating Liquid.pdf:PDF},
  issue        = {35},
  keywords     = {17o,bds,nmr,2h,debye-process},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D3CP02774K},
}

@InCollection{Redfield1965,
  author       = {A. G. Redfield},
  booktitle    = {Advances in Magnetic Resonance},
  publisher    = {Academic Press},
  title        = {The Theory of Relaxation Processes},
  year         = {1965},
  editor       = {John S. Waugh},
  pages        = {1-32},
  series       = {Advances in Magnetic and Optical Resonance},
  volume       = {1},
  comment      = {This work was started while the author was at Harvard University, and was then partially supported by Joint Services Contract N5ori-76, Project Order I.},
  creationdate = {2024-10-19T13:07:14},
  doi          = {https://doi.org/10.1016/B978-1-4832-3114-3.50007-6},
  issn         = {1057-2732},
  keywords     = {nmr,theory,relaxation,redfield},
  url          = {https://www.sciencedirect.com/science/article/pii/B9781483231143500076},
}

@Article{Wu2019,
  author       = {Gang Wu},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {17O NMR studies of organic and biological molecules in aqueous solution and in the solid state},
  year         = {2019},
  issn         = {0079-6565},
  pages        = {135-191},
  volume       = {114-115},
  abstract     = {This review describes the latest developments in the field of 17O NMR spectroscopy of organic and biological molecules both in aqueous solution and in the solid state. In the first part of the review, a general theoretical description of the nuclear quadrupole relaxation process in isotropic liquids is presented at a mathematical level suitable for non-specialists. In addition to the first-order quadrupole interaction, the theory also includes additional relaxation mechanisms such as the second-order quadrupole interaction and its cross correlation with shielding anisotropy. This complete theoretical treatment allows one to assess the transverse relaxation rate (thus the line width) of NMR signals from half-integer quadrupolar nuclei in solution over the entire range of motion. On the basis of this theoretical framework, we discuss general features of quadrupole-central-transition (QCT) NMR, which is a particularly powerful method of studying biomolecules in the slow motion regime. Then we review recent advances in 17O QCT NMR studies of biological macromolecules in aqueous solution. The second part of the review is concerned with solid-state 17O NMR studies of organic and biological molecules. As a sequel to the previous review on the same subject [G. Wu, Prog. Nucl. Magn. Reson. Spectrosc. 52 (2008) 118–169], the current review provides a complete coverage of the literature published since 2008 in this area.},
  creationdate = {2024-10-21T18:02:47},
  doi          = {https://doi.org/10.1016/j.pnmrs.2019.06.002},
  file         = {:Wu2019 - 17O NMR Studies of Organic and Biological Molecules in Aqueous Solution and in the Solid State.pdf:PDF},
  keywords     = {review,NMR,17o,relaxation,quadrupole,theory},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079656519300226},
}

@Article{Wu2016,
  author       = {Gang Wu},
  journal      = {Journal of Magnetic Resonance},
  title        = {An approximate analytical expression for the nuclear quadrupole transverse relaxation rate of half-integer spins in liquids},
  year         = {2016},
  issn         = {1090-7807},
  pages        = {176-178},
  volume       = {269},
  abstract     = {The nuclear quadrupole transverse relaxation process of half-integer spins in liquid samples is known to exhibit multi-exponential behaviors. Within the framework of Redfield’s relaxation theory, exact analytical expressions for describing such a process exist only for spin-3/2 nuclei. As a result, analyses of nuclear quadrupole transverse relaxation data for half-integer quadrupolar nuclei with spin >3/2 must rely on numerical diagonalization of the Redfield relaxation matrix over the entire motional range. In this work we propose an approximate analytical expression that can be used to analyze nuclear quadrupole transverse relaxation data of any half-integer spin in liquids over the entire motional range. The proposed equation yields results that are in excellent agreement with the exact numerical calculations.},
  creationdate = {2024-10-22T07:23:47},
  doi          = {https://doi.org/10.1016/j.jmr.2016.06.012},
  file         = {:Wu2016 - An Approximate Analytical Expression for the Nuclear Quadrupole Transverse Relaxation Rate of Half Integer Spins in Liquids.pdf:PDF},
  keywords     = {Half-integer spin,Quadrupolar interaction,Transverse relaxation,Molecular motion,Liquids,17o,nmr,theory,quadrupole,t2,spin-spin relaxation},
  url          = {https://www.sciencedirect.com/science/article/pii/S109078071630088X},
}

@Article{Baram1973,
  author       = {Baram, A. and Luz, Z. and Alexander, S.},
  journal      = {The Journal of Chemical Physics},
  title        = {{Resonance line shapes for semi‐integer spins in liquids}},
  year         = {1973},
  issn         = {0021-9606},
  month        = {05},
  number       = {10},
  pages        = {4558-4564},
  volume       = {58},
  abstract     = {{An effective Liouville equation which describes resonance line shapes and is accurate to first order in the nonsecular term is derived. The equation has a quasisecular form but includes T1 contributions and the effect of the modulation of second order shifts by the molecular rotation. Simple explicit expressions for the linewidth and shift of the −1/2 → 1/2 transition are derived which are valid when the rotation is fast compared to the static second order shifts. The width has a maximum near the the T1 minimum and a minimum. The line shape for slow motion is also discussed and results of numerical calculation are presented. It is shown that the equations can be interpreted as a modulation of the second order shifts.}},
  creationdate = {2024-10-22T07:59:19},
  doi          = {10.1063/1.1679019},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/58/10/4558/18885429/4558\_1\_online.pdf},
  file         = {:Baram1973 - Resonance Line Shapes for Semi‐integer Spins in Liquids.pdf:PDF},
  keywords     = {NMR,17o,quadrupole,lineshape,theory},
  url          = {https://doi.org/10.1063/1.1679019},
}

@Book{Hess2015,
  author       = {Hess, Siegfried},
  publisher    = {Springer Cham},
  title        = {Tensors for Physics},
  year         = {2015},
  edition      = {Frist},
  isbn         = {978-3-319-12787-3},
  month        = apr,
  series       = {Undergraduate Lecture Notes in Physics},
  creationdate = {2024-10-23T08:30:30},
  doi          = {10.1007/978-3-319-12787-3},
  file         = {:Hess2015 - Tensors for Physics.pdf:PDF},
  keywords     = {theory,quantum mechanics,book},
  url          = {https://doi.org/10.1007/978-3-319-12787-3},
}

@Article{McConnell1980,
  author       = {James McConnell},
  journal      = {Physica A: Statistical Mechanics and its Applications},
  title        = {Spectral densities of spherical harmonics for rotational Brownian motion},
  year         = {1980},
  issn         = {0378-4371},
  number       = {3},
  pages        = {539-546},
  volume       = {102},
  abstract     = {Spectral densities of spherical harmonics arising from the rotational Brownian motion of molecules are calculated. The molecules are supposed to be spherical or linear, and account is taken of the influence of their inertia. When the results for a spherical molecule are applied to nuclear magnetic resonance, an expression for spin-lattice relaxation time is deduced and this is shown to provide a small correction to one calculated by Bloembergen, Purcell and Pound8). It is pointed out that the theory may be extended to nuclear magnetic processes when the thermal molecular motion is anisotropic.},
  creationdate = {2024-10-24T16:19:59},
  doi          = {https://doi.org/10.1016/0378-4371(90)90183-S},
  file         = {:McConnell1980 - Spectral Densities of Spherical Harmonics for Rotational Brownian Motion.pdf:PDF},
  keywords     = {NMR,theory,relaxation,spectral density,spherical harmonics,bpp},
  url          = {https://www.sciencedirect.com/science/article/pii/037843719090183S},
}

@Book{Rose1957,
  author       = {M. E. Rose},
  publisher    = {John Wiley \& Sons},
  title        = {Elementary theory of angular momentum},
  year         = {1957},
  creationdate = {2024-10-24T16:45:33},
  file         = {:Rose1957 - Elementary Theory of Angular Momentum.pdf:PDF},
  keywords     = {book,theory,spherical harmonics,spectral density,anuglar moment},
}

@Article{Morrison1993,
  author       = {C. Morrison and M. Bloom},
  journal      = {Journal of Magnetic Resonance, Series A},
  title        = {General Orientation Dependence of NMR Spin-Lattice Relaxation for Spin 1},
  year         = {1993},
  issn         = {1064-1858},
  number       = {1},
  pages        = {1-7},
  volume       = {103},
  abstract     = {The theory of NMR spin-lattice relaxation of spin-1 nuclei relaxing via fluctuating quadrupolar interactions is considered within the Redfield approximation. The NMR spectrum is characterized in terms of the principal-axis coordinate system of the time-averaged electric-field gradient tensor. The most general form of the relaxation rates may be written in terms of the polar coordinates (β, α) of the magnetic field in the principal-axis coordinate system. It involves a sum of spherical harmonics up to order four, 1/Ti, = ∑4p=0 ∑pq=−pa(i)pqYpq(β, α), p even, where Ti represents T1z, T1q, and T2 and the a(i)pq values depend on reduced spectral densities and spherical order parameters which are independent of the orientation of the magnetic field. The number and types of order parameters required to characterize the orientation dependence of the relaxation rates depend on the symmetry of the motions as well as on the symmetry of the average electric-field gradient. Some examples of the use of the general theory are discussed.},
  creationdate = {2024-10-25T10:02:17},
  doi          = {https://doi.org/10.1006/jmra.1993.1123},
  file         = {:Morrison1993 - General Orientation Dependence of NMR Spin Lattice Relaxation for Spin 1.pdf:PDF},
  keywords     = {nmr,theory,spectral density,spin-lattice relaxation,T1,spherical harmonics,motional averaging},
  url          = {https://www.sciencedirect.com/science/article/pii/S106418588371123X},
}

@Article{Seelig1977,
  author       = {Seelig, Joachim},
  journal      = {Quarterly Reviews of Biophysics},
  title        = {Deuterium magnetic resonance: theory and application to lipid membranes},
  year         = {1977},
  number       = {3},
  pages        = {353–418},
  volume       = {10},
  creationdate = {2024-10-25T10:11:12},
  doi          = {10.1017/S0033583500002948},
  file         = {:Seelig1977 - Deuterium Magnetic Resonance_ Theory and Application to Lipid Membranes.pdf:PDF},
  keywords     = {NMR,theory,quadrupole,spherical harmonics},
}

@Book{Brink1994,
  author       = {Brink, D M and Satchler, G R},
  publisher    = {Oxford University Press},
  title        = {{Angular Momentum}},
  year         = {1994},
  isbn         = {9780198517597},
  month        = {02},
  abstract     = {{This book introduces the quantum theory of angular momentum to students who are unfamiliar with it and develops it to a stage useful for research. The first part contains the basic theory of rotations and angular momentum. As the book aims to emphasize applications, mathematical details are avoided and difficult theorems stated without proof. The second part contains examples of applications to a wide range of physical phenomena and presents a collection of results helpful in solving problems.}},
  creationdate = {2024-10-25T10:39:46},
  doi          = {10.1093/oso/9780198517597.001.0001},
  file         = {:Brink1994 - Angular Momentum.pdf:PDF},
  keywords     = {theory,spherical harmonics,book},
  url          = {https://doi.org/10.1093/oso/9780198517597.001.0001},
}






@Article{Gray1976,
  author       = {Gray, C. G. and Stiles, P. J.},
  journal      = {Canadian Journal of Physics},
  title        = {Spherical tensor approach to multipole expansions. II. Magnetostatic interactions},
  year         = {1976},
  number       = {5},
  pages        = {513-518},
  volume       = {54},
  abstract     = {The magnetic field due to a given current distribution, the interaction energy of a current distribution with an arbitrary external magnetic field, and the magnetostatic interaction energy between two current distributions are decomposed into multipolar components using spherical harmonic expansions. Diamagnetic interactions and the spin contributions to the multipole expansions are also discussed.},
  creationdate = {2024-10-28T17:56:16},
  doi          = {10.1139/p76-058},
  eprint       = {https://doi.org/10.1139/p76-058},
  file         = {:Gray1976 - Spherical Tensor Approach to Multipole Expansions. II. Magnetostatic Interactions.pdf:PDF},
  keywords     = {NMR,theory,multipole,dipole,quadrupole,spherical harmonics,spherical tensor operator},
  url          = {https://doi.org/10.1139/p76-058},
}

@Article{Bowden1986,
  author       = {G. J. Bowden and W. D. Hutchison},
  journal      = {Journal of Magnetic Resonance (1969)},
  title        = {Tensor operator formalism for multiple-quantum NMR. 1. Spin-1 nuclei},
  year         = {1986},
  issn         = {0022-2364},
  number       = {3},
  pages        = {403-414},
  volume       = {67},
  abstract     = {A mathematical treatment of multiple-quantum nuclear magnetic resonance (MQ NMR) for I = 1, based on irreducible tensor operators, is presented and discussed. In particular, stress is laid on the multipolar form of the density matrix during every stage of the MQ NMR experiment. It is argued that in the description of such experiments, tensor operators confer significant advantages over fictitious spin-12 matrices, and simple matrix transformations.},
  creationdate = {2024-10-25T11:42:19},
  doi          = {https://doi.org/10.1016/0022-2364(86)90378-1},
  file         = {:Bowden1986 - Tensor Operator Formalism for Multiple Quantum NMR. 1. Spin 1 Nuclei.pdf:PDF},
  keywords     = {nmr,theory,tensor operators,quadrupole,multipole,irreducible tensor operator,spherical tensor operator,spherical harmonics},
  url          = {https://www.sciencedirect.com/science/article/pii/0022236486903781},
}

@Article{Bowden1986a,
  author       = {G. J. Bowden and W. D. Hutchison and J. Khachan},
  journal      = {Journal of Magnetic Resonance (1969)},
  title        = {Tensor operator formalism for multiple-quantum NMR. 2. Spins 32, 2, and 52 and general I},
  year         = {1986},
  issn         = {0022-2364},
  number       = {3},
  pages        = {415-437},
  volume       = {67},
  abstract     = {Multiple-quantum nuclear magnetic (MQ NMR) experiments for I = 32, 2, and 52 nuclear assemblies are discussed within the framework of irreducible tensor operators. In general, it is shown that it is difficult to produce pure multipolar Tnn(s, a) states, where n = 2I, using simple nonselective rf pulses. However this problem can sometimes be remedied by adding NMR signals from two or more pulse sequences. In particular, signals originating from the pure T44(s) state, for I = 2 nuclei, can be easily obtained using signals from two simple MQ NMR pulse sequences. On the basis of the I = 1, 32, 2, and 52 results, some general comments are also made concerning (i) optimal MQ NMR pulse sequences, and (ii) “constants of the motion,” formed after the second rf pulse. In addition, general expressions are given for the evolution of the density matrix under (i) hard rf pulses, and (ii) the action of an axially symmetric quadrupole interaction, which hold for all I.},
  creationdate = {2024-10-25T11:43:09},
  doi          = {https://doi.org/10.1016/0022-2364(86)90379-3},
  file         = {:Bowden1986a - Tensor Operator Formalism for Multiple Quantum NMR. 2. Spins 32, 2, and 52 and General I.pdf:PDF},
  keywords     = {nmr,theory,tensor operators,quadrupole,multipole,irreducible tensor operator,spherical tensor operator,spherical harmonics},
  url          = {https://www.sciencedirect.com/science/article/pii/0022236486903793},
}

@InCollection{Huntress1970,
  author       = {Wesley T. Huntress},
  publisher    = {Academic Press},
  title        = {The Study of Anisotropic Rotation of Molecules in Liquids by NMR Quadrupolar Relaxation},
  year         = {1970},
  editor       = {John S. Waugh},
  pages        = {1--37},
  series       = {Advances in Magnetic and Optical Resonance},
  volume       = {4},
  comment      = {paywall},
  creationdate = {2024-10-25T14:00:28},
  doi          = {https://doi.org/10.1016/B978-0-12-025504-7.50007-6},
  issn         = {1057-2732},
  keywords     = {NMR,theory,spectral density,spherical harmonics,quadrupole,relaxation},
  url          = {https://www.sciencedirect.com/science/article/pii/B9780120255047500076},
}

@Article{Eden2014,
  author       = {Ed{\'e}n, Mattias},
  journal      = {Concepts in Magnetic Resonance Part A},
  title        = {Zeeman truncation in NMR. I. The role of operator commutation},
  year         = {2014},
  number       = {4},
  pages        = {91-108},
  volume       = {43},
  abstract     = {Hamiltonians are of pivotal importance for describing and analyzing NMR experiments. However, the “exact” spin Hamiltonian operators are in practice not utilized, but merely a simplified form referred to either as the “secular,” “Zeeman-truncated,” or “high-field” Hamiltonian. It results after accounting for the dominating role of the Zeeman interaction relative to all other, much smaller NMR interactions, such as chemical shifts, through-bond, or through-space spin–spin couplings. In this article and the following one, we introduce the Zeeman truncation process to newcomers to NMR by thoroughly reviewing the options available for reducing the full Hamiltonian of a spin interaction to its Zeeman-truncated counterpart. The present paper considers time-independent Hamiltonians, where we discuss the criteria for performing truncation, highlighting the role of operator commutation by a simple formalism that is equivalent to application of lowest-order static perturbation theory. The validity of the approximations are illustrated by examining the explicit matrix representations of the “exact” and “Zeeman truncated” Hamiltonians, considering the NMR interactions relevant for systems of interacting spin-1/2 nuclei. © 2015 Wiley Periodicals, Inc. Concepts Magn Reson Part A 43A: 91–108, 2015.},
  creationdate = {2024-10-29T12:52:17},
  doi          = {https://doi.org/10.1002/cmr.a.21319},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.a.21319},
  file         = {:Eden2014 - Zeeman Truncation in NMR. I. the Role of Operator Commutation.pdf:PDF},
  keywords     = {NMR Hamiltonians,operator truncation,secular approximation,high-field Hamiltonian,spherical tensors,NMR,theory},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.a.21319},
}

@Article{Eden2014a,
  author       = {Ed{\'e}n, Mattias},
  journal      = {Concepts in Magnetic Resonance Part A},
  title        = {Zeeman truncation in NMR. II. Time averaging in the rotating frame},
  year         = {2014},
  number       = {4},
  pages        = {109-126},
  volume       = {43},
  abstract     = {The truncation of NMR interactions by the Zeeman Hamiltonian is here examined from a different perspective than that of our previous article [Concepts Magn. Reson., vol. 43A, pages 91–108 (2015)]: a Zeeman-truncated Hamiltonian is arranged by transforming the initially stationary operator of the NMR interaction into the rotating frame, followed by a time-averaging procedure over one Larmor period ( ). We review the concept of an interaction frame, with focus on the rotating frame relevant for the Zeeman interaction, as well as the time-averaging procedure and the criteria for application of the resulting stationary Hamiltonian. A decisive advantage of this approach is its suitability for truncating time-dependent Hamiltonians, such as that of a radio-frequency (RF) field. Various options for reducing the time-dependent RF Hamiltonian into its stationary form are contrasted and thoroughly discussed. The role of Zeeman truncation is illustrated by examining the rotating-frame RF Hamiltonian associated with both on-resonance and off-resonance irradiation, where the time-independent operator character allows for applying the approximation strategies reviewed in our previous article. © 2015 Wiley Periodicals, Inc. Concepts Magn Reson Part A 43A: 109–126, 2015.},
  creationdate = {2024-10-29T12:53:30},
  doi          = {https://doi.org/10.1002/cmr.a.21301},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.a.21301},
  file         = {:Eden2014a - Zeeman Truncation in NMR. II. Time Averaging in the Rotating Frame.pdf:PDF},
  keywords     = {NMR Hamiltonians,RF Hamiltonian,interaction frame,time-averaging,average Hamiltonian theory,NMR,theory},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.a.21301},
}

@Book{Steigel1978,
  author       = {Steigel, Alois and Spiess, Hans Wolfgang},
  editor       = {P. Diehl and E. Fluck and R. Kosfeld},
  publisher    = {Springer},
  title        = {Dynamic NMR Spectroscopy},
  year         = {1978},
  address      = {Berlin, Heidelberg, New York},
  isbn         = {3540087842},
  series       = {NMR Basic principles and progress},
  volume       = {15},
  abstract     = {Steigel, A. Mechanistic studies of rearrangements and exchange reactions by dynamic NMR spectroscopy.--Spiess, H. W. Rotation of molecules and nuclear spin relaxation.},
  comment      = {sftp://element.fkp.physik.tu-darmstadt.de/share/e-Books_Papers/spiess%201978%20NMR%20principles%20and%20progress},
  creationdate = {2024-10-30T11:41:08},
  file         = {:Steigel1978 - Dynamic NMR Spectroscopy.jpg:JPG image;:2.jpg:JPG image;:3.jpg:JPG image;:4.jpg:JPG image;:5.jpg:JPG image;:6.jpg:JPG image;:7.jpg:JPG image;:8.jpg:JPG image;:9.jpg:JPG image;:10.jpg:JPG image;:11.jpg:JPG image;:12.jpg:JPG image;:13.jpg:JPG image;:14.jpg:JPG image;:15.jpg:JPG image;:16.jpg:JPG image;:17.jpg:JPG image;:18.jpg:JPG image;:19.jpg:JPG image;:20.jpg:JPG image;:21.jpg:JPG image;:22.jpg:JPG image;:23.jpg:JPG image;:24.jpg:JPG image;:25.jpg:JPG image;:26.jpg:JPG image;:27.jpg:JPG image;:28.jpg:JPG image;:29.jpg:JPG image;:30.jpg:JPG image;:31.jpg:JPG image;:32.jpg:JPG image;:33.jpg:JPG image;:34.jpg:JPG image;:35.jpg:JPG image;:36.jpg:JPG image;:37.jpg:JPG image;:38.jpg:JPG image;:39.jpg:JPG image;:40.jpg:JPG image;:41.jpg:JPG image;:42.jpg:JPG image;:43.jpg:JPG image;:44.jpg:JPG image;:45.jpg:JPG image;:46.jpg:JPG image;:47.jpg:JPG image;:48.jpg:JPG image;:49.jpg:JPG image;:50.jpg:JPG image;:51.jpg:JPG image;:52.jpg:JPG image;:53.jpg:JPG image;:54.jpg:JPG image;:55.jpg:JPG image;:56.jpg:JPG image;:57.jpg:JPG image;:58.jpg:JPG image;:59.jpg:JPG image;:60.jpg:JPG image;:61.jpg:JPG image;:62.jpg:JPG image;:63.jpg:JPG image;:64.jpg:JPG image;:65.jpg:JPG image;:66.jpg:JPG image;:67.jpg:JPG image;:68.jpg:JPG image;:69.jpg:JPG image;:70.jpg:JPG image;:71.jpg:JPG image;:72.jpg:JPG image;:73.jpg:JPG image;:74.jpg:JPG image;:75.jpg:JPG image;:76.jpg:JPG image;:78.jpg:JPG image;:79.jpg:JPG image;:80.jpg:JPG image;:81.jpg:JPG image;:82.jpg:JPG image},
  keywords     = {Nuclear magnetic resonance spectroscopy,DNMR-Spektroskopie,NMR,theory,book},
}

@Book{Muus2012,
  editor       = {L. T. Muus and P. W. Atkins},
  publisher    = {Springer},
  title        = {Electron Spin Relaxation in Liquids},
  year         = {2012},
  address      = {New York},
  edition      = {First},
  isbn         = {978-1-4615-8678-4},
  month        = dec,
  comment      = {original print version published by Plenum Press, New York, 1972},
  creationdate = {2024-10-30T16:28:28},
  file         = {:Muus2012 - Electron Spin Relaxation in Liquids.pdf:PDF},
  keywords     = {density matrix,NMR,theory,ESR,book},
}

@PhdThesis{Lips2004,
  author       = {Oliver Lips},
  school       = {Technische Universität Darmstadt},
  title        = {NMR-Untersuchungen an schnellen Ionenleitern vom LaF$_{3}$-Typ},
  year         = {2004},
  type         = {phdthesis},
  creationdate = {2024-11-01T15:23:41},
  file         = {:Lips2004 - NMR Untersuchungen an Schnellen Ionenleitern Vom LaF$_3$ Typ.pdf:PDF},
  keywords     = {PhD,field cycling,NMR},
}

@PhdThesis{Kresse2016,
  author       = {Holger Benjamin Kresse},
  school       = {Technische Universität Darmstadt},
  title        = {Field-Cycling NMR bei extrem kleinen Larmor-Frequenzen - Entwicklung und Anwendung},
  year         = {2016},
  type         = {phdthesis},
  creationdate = {2024-11-01T15:25:40},
  file         = {:Kresse2016 - Field Cycling NMR Bei Extrem Kleinen Larmor Frequenzen Entwicklung Und Anwendung.pdf:PDF},
  keywords     = {PhD,NMR,field cycling},
}

@Article{Noack1986,
  author       = {F. Noack},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {NMR field-cycling spectroscopy: principles and applications},
  year         = {1986},
  issn         = {0079-6565},
  number       = {3},
  pages        = {171-276},
  volume       = {18},
  creationdate = {2024-11-01T15:34:19},
  doi          = {https://doi.org/10.1016/0079-6565(86)80004-8},
  file         = {:Noack1986 - NMR Field Cycling Spectroscopy_ Principles and Applications.pdf:PDF},
  keywords     = {NMR,review,field cycling},
  url          = {https://www.sciencedirect.com/science/article/pii/0079656586800048},
}

@Article{Gaedke2007,
  author       = {A. Gädke and C. Schmitt and H. Stork and N. Nestle},
  journal      = {Magnetic Resonance Imaging},
  title        = {DAMARIS — a flexible and open software platform for NMR spectrometer control},
  year         = {2007},
  issn         = {0730-725X},
  note         = {Proceedings of the Eighth International Bologna Conference on Magnetic Resonance in Porous Media},
  number       = {4},
  pages        = {576},
  volume       = {25},
  creationdate = {2024-11-04T07:48:14},
  doi          = {https://doi.org/10.1016/j.mri.2007.01.081},
  file         = {:Gaedke2007 - DAMARIS — a Flexible and Open Software Platform for NMR Spectrometer Control.pdf:PDF},
  keywords     = {NMR,DAMARIS},
  url          = {https://www.sciencedirect.com/science/article/pii/S0730725X07001014},
}

@Misc{Demuth2023,
  author       = {Dominik Demuth},
  title        = {nmreval},
  year         = {2023},
  abstract     = {BSD 3-Clause License

Copyright (c) 2023 Dominik Demuth. 

Redistribution and use in source and binary forms, with or without modification, are permitted provided that the following conditions are met:

1. Redistributions of source code must retain the above copyright notice, this list of conditions and the following disclaimer.

2. Redistributions in binary form must reproduce the above copyright notice, this list of conditions and the following disclaimer in the documentation and/or other materials provided with the distribution.

3. Neither the name of the copyright holder nor the names of its contributors may be used to endorse or promote products derived from this software without specific prior written permission.

THIS SOFTWARE IS PROVIDED BY THE COPYRIGHT HOLDERS AND CONTRIBUTORS "AS IS" AND ANY EXPRESS OR IMPLIED WARRANTIES, INCLUDING, BUT NOT LIMITED TO, THE IMPLIED WARRANTIES OF MERCHANTABILITY AND FITNESS FOR A PARTICULAR PURPOSE ARE DISCLAIMED. IN NO EVENT SHALL THE COPYRIGHT HOLDER OR CONTRIBUTORS BE LIABLE FOR ANY DIRECT, INDIRECT, INCIDENTAL, SPECIAL, EXEMPLARY, OR CONSEQUENTIAL DAMAGES (INCLUDING, BUT NOT LIMITED TO, PROCUREMENT OF SUBSTITUTE GOODS OR SERVICES; LOSS OF USE, DATA, OR PROFITS; OR BUSINESS INTERRUPTION) HOWEVER CAUSED AND ON ANY THEORY OF LIABILITY, WHETHER IN CONTRACT, STRICT LIABILITY, OR TORT (INCLUDING NEGLIGENCE OR OTHERWISE) ARISING IN ANY WAY OUT OF THE USE OF THIS SOFTWARE, EVEN IF ADVISED OF THE POSSIBILITY OF SUCH DAMAGE.},
  comment      = {uncitable},
  creationdate = {2024-11-04T07:56:05},
  keywords     = {NMR,nmreval},
  url          = {https://gitea.pkm.physik.tu-darmstadt.de/IPKM/nmreval.git},
  urldate      = {2024-11-04},
}

@Misc{grace1991,
  abstract     = {GNU GENERAL PUBLIC LICENSE
		       Version 2, June 1991

 Copyright (C) 1989, 1991 Free Software Foundation, Inc.
                          675 Mass Ave, Cambridge, MA 02139, USA
 Everyone is permitted to copy and distribute verbatim copies
 of this license document, but changing it is not allowed.

			    Preamble

  The licenses for most software are designed to take away your
freedom to share and change it.  By contrast, the GNU General Public
License is intended to guarantee your freedom to share and change free
software--to make sure the software is free for all its users.  This
General Public License applies to most of the Free Software
Foundation's software and to any other program whose authors commit to
using it.  (Some other Free Software Foundation software is covered by
the GNU Library General Public License instead.)  You can apply it to
your programs, too.

  When we speak of free software, we are referring to freedom, not
price.  Our General Public Licenses are designed to make sure that you
have the freedom to distribute copies of free software (and charge for
this service if you wish), that you receive source code or can get it
if you want it, that you can change the software or use pieces of it
in new free programs; and that you know you can do these things.

  To protect your rights, we need to make restrictions that forbid
anyone to deny you these rights or to ask you to surrender the rights.
These restrictions translate to certain responsibilities for you if you
distribute copies of the software, or if you modify it.

  For example, if you distribute copies of such a program, whether
gratis or for a fee, you must give the recipients all the rights that
you have.  You must make sure that they, too, receive or can get the
source code.  And you must show them these terms so they know their
rights.

  We protect your rights with two steps: (1) copyright the software, and
(2) offer you this license which gives you legal permission to copy,
distribute and/or modify the software.

  Also, for each author's protection and ours, we want to make certain
that everyone understands that there is no warranty for this free
software.  If the software is modified by someone else and passed on, we
want its recipients to know that what they have is not the original, so
that any problems introduced by others will not reflect on the original
authors' reputations.

  Finally, any free program is threatened constantly by software
patents.  We wish to avoid the danger that redistributors of a free
program will individually obtain patent licenses, in effect making the
program proprietary.  To prevent this, we have made it clear that any
patent must be licensed for everyone's free use or not licensed at all.

  The precise terms and conditions for copying, distribution and
modification follow.

		    GNU GENERAL PUBLIC LICENSE
   TERMS AND CONDITIONS FOR COPYING, DISTRIBUTION AND MODIFICATION

  0. This License applies to any program or other work which contains
a notice placed by the copyright holder saying it may be distributed
under the terms of this General Public License.  The "Program", below,
refers to any such program or work, and a "work based on the Program"
means either the Program or any derivative work under copyright law:
that is to say, a work containing the Program or a portion of it,
either verbatim or with modifications and/or translated into another
language.  (Hereinafter, translation is included without limitation in
the term "modification".)  Each licensee is addressed as "you".

Activities other than copying, distribution and modification are not
covered by this License; they are outside its scope.  The act of
running the Program is not restricted, and the output from the Program
is covered only if its contents constitute a work based on the
Program (independent of having been made by running the Program).
Whether that is true depends on what the Program does.

  1. You may copy and distribute verbatim copies of the Program's
source code as you receive it, in any medium, provided that you
conspicuously and appropriately publish on each copy an appropriate
copyright notice and disclaimer of warranty; keep intact all the
notices that refer to this License and to the absence of any warranty;
and give any other recipients of the Program a copy of this License
along with the Program.

You may charge a fee for the physical act of transferring a copy, and
you may at your option offer warranty protection in exchange for a fee.

  2. You may modify your copy or copies of the Program or any portion
of it, thus forming a work based on the Program, and copy and
distribute such modifications or work under the terms of Section 1
above, provided that you also meet all of these conditions:

    a) You must cause the modified files to carry prominent notices
    stating that you changed the files and the date of any change.

    b) You must cause any work that you distribute or publish, that in
    whole or in part contains or is derived from the Program or any
    part thereof, to be licensed as a whole at no charge to all third
    parties under the terms of this License.

    c) If the modified program normally reads commands interactively
    when run, you must cause it, when started running for such
    interactive use in the most ordinary way, to print or display an
    announcement including an appropriate copyright notice and a
    notice that there is no warranty (or else, saying that you provide
    a warranty) and that users may redistribute the program under
    these conditions, and telling the user how to view a copy of this
    License.  (Exception: if the Program itself is interactive but
    does not normally print such an announcement, your work based on
    the Program is not required to print an announcement.)

These requirements apply to the modified work as a whole.  If
identifiable sections of that work are not derived from the Program,
and can be reasonably considered independent and separate works in
themselves, then this License, and its terms, do not apply to those
sections when you distribute them as separate works.  But when you
distribute the same sections as part of a whole which is a work based
on the Program, the distribution of the whole must be on the terms of
this License, whose permissions for other licensees extend to the
entire whole, and thus to each and every part regardless of who wrote it.

Thus, it is not the intent of this section to claim rights or contest
your rights to work written entirely by you; rather, the intent is to
exercise the right to control the distribution of derivative or
collective works based on the Program.

In addition, mere aggregation of another work not based on the Program
with the Program (or with a work based on the Program) on a volume of
a storage or distribution medium does not bring the other work under
the scope of this License.

  3. You may copy and distribute the Program (or a work based on it,
under Section 2) in object code or executable form under the terms of
Sections 1 and 2 above provided that you also do one of the following:

    a) Accompany it with the complete corresponding machine-readable
    source code, which must be distributed under the terms of Sections
    1 and 2 above on a medium customarily used for software interchange; or,

    b) Accompany it with a written offer, valid for at least three
    years, to give any third party, for a charge no more than your
    cost of physically performing source distribution, a complete
    machine-readable copy of the corresponding source code, to be
    distributed under the terms of Sections 1 and 2 above on a medium
    customarily used for software interchange; or,

    c) Accompany it with the information you received as to the offer
    to distribute corresponding source code.  (This alternative is
    allowed only for noncommercial distribution and only if you
    received the program in object code or executable form with such
    an offer, in accord with Subsection b above.)

The source code for a work means the preferred form of the work for
making modifications to it.  For an executable work, complete source
code means all the source code for all modules it contains, plus any
associated interface definition files, plus the scripts used to
control compilation and installation of the executable.  However, as a
special exception, the source code distributed need not include
anything that is normally distributed (in either source or binary
form) with the major components (compiler, kernel, and so on) of the
operating system on which the executable runs, unless that component
itself accompanies the executable.

If distribution of executable or object code is made by offering
access to copy from a designated place, then offering equivalent
access to copy the source code from the same place counts as
distribution of the source code, even though third parties are not
compelled to copy the source along with the object code.

  4. You may not copy, modify, sublicense, or distribute the Program
except as expressly provided under this License.  Any attempt
otherwise to copy, modify, sublicense or distribute the Program is
void, and will automatically terminate your rights under this License.
However, parties who have received copies, or rights, from you under
this License will not have their licenses terminated so long as such
parties remain in full compliance.

  5. You are not required to accept this License, since you have not
signed it.  However, nothing else grants you permission to modify or
distribute the Program or its derivative works.  These actions are
prohibited by law if you do not accept this License.  Therefore, by
modifying or distributing the Program (or any work based on the
Program), you indicate your acceptance of this License to do so, and
all its terms and conditions for copying, distributing or modifying
the Program or works based on it.

  6. Each time you redistribute the Program (or any work based on the
Program), the recipient automatically receives a license from the
original licensor to copy, distribute or modify the Program subject to
these terms and conditions.  You may not impose any further
restrictions on the recipients' exercise of the rights granted herein.
You are not responsible for enforcing compliance by third parties to
this License.

  7. If, as a consequence of a court judgment or allegation of patent
infringement or for any other reason (not limited to patent issues),
conditions are imposed on you (whether by court order, agreement or
otherwise) that contradict the conditions of this License, they do not
excuse you from the conditions of this License.  If you cannot
distribute so as to satisfy simultaneously your obligations under this
License and any other pertinent obligations, then as a consequence you
may not distribute the Program at all.  For example, if a patent
license would not permit royalty-free redistribution of the Program by
all those who receive copies directly or indirectly through you, then
the only way you could satisfy both it and this License would be to
refrain entirely from distribution of the Program.

If any portion of this section is held invalid or unenforceable under
any particular circumstance, the balance of the section is intended to
apply and the section as a whole is intended to apply in other
circumstances.

It is not the purpose of this section to induce you to infringe any
patents or other property right claims or to contest validity of any
such claims; this section has the sole purpose of protecting the
integrity of the free software distribution system, which is
implemented by public license practices.  Many people have made
generous contributions to the wide range of software distributed
through that system in reliance on consistent application of that
system; it is up to the author/donor to decide if he or she is willing
to distribute software through any other system and a licensee cannot
impose that choice.

This section is intended to make thoroughly clear what is believed to
be a consequence of the rest of this License.

  8. If the distribution and/or use of the Program is restricted in
certain countries either by patents or by copyrighted interfaces, the
original copyright holder who places the Program under this License
may add an explicit geographical distribution limitation excluding
those countries, so that distribution is permitted only in or among
countries not thus excluded.  In such case, this License incorporates
the limitation as if written in the body of this License.

  9. The Free Software Foundation may publish revised and/or new versions
of the General Public License from time to time.  Such new versions will
be similar in spirit to the present version, but may differ in detail to
address new problems or concerns.

Each version is given a distinguishing version number.  If the Program
specifies a version number of this License which applies to it and "any
later version", you have the option of following the terms and conditions
either of that version or of any later version published by the Free
Software Foundation.  If the Program does not specify a version number of
this License, you may choose any version ever published by the Free Software
Foundation.

  10. If you wish to incorporate parts of the Program into other free
programs whose distribution conditions are different, write to the author
to ask for permission.  For software which is copyrighted by the Free
Software Foundation, write to the Free Software Foundation; we sometimes
make exceptions for this.  Our decision will be guided by the two goals
of preserving the free status of all derivatives of our free software and
of promoting the sharing and reuse of software generally.

			    NO WARRANTY

  11. BECAUSE THE PROGRAM IS LICENSED FREE OF CHARGE, THERE IS NO WARRANTY
FOR THE PROGRAM, TO THE EXTENT PERMITTED BY APPLICABLE LAW.  EXCEPT WHEN
OTHERWISE STATED IN WRITING THE COPYRIGHT HOLDERS AND/OR OTHER PARTIES
PROVIDE THE PROGRAM "AS IS" WITHOUT WARRANTY OF ANY KIND, EITHER EXPRESSED
OR IMPLIED, INCLUDING, BUT NOT LIMITED TO, THE IMPLIED WARRANTIES OF
MERCHANTABILITY AND FITNESS FOR A PARTICULAR PURPOSE.  THE ENTIRE RISK AS
TO THE QUALITY AND PERFORMANCE OF THE PROGRAM IS WITH YOU.  SHOULD THE
PROGRAM PROVE DEFECTIVE, YOU ASSUME THE COST OF ALL NECESSARY SERVICING,
REPAIR OR CORRECTION.

  12. IN NO EVENT UNLESS REQUIRED BY APPLICABLE LAW OR AGREED TO IN WRITING
WILL ANY COPYRIGHT HOLDER, OR ANY OTHER PARTY WHO MAY MODIFY AND/OR
REDISTRIBUTE THE PROGRAM AS PERMITTED ABOVE, BE LIABLE TO YOU FOR DAMAGES,
INCLUDING ANY GENERAL, SPECIAL, INCIDENTAL OR CONSEQUENTIAL DAMAGES ARISING
OUT OF THE USE OR INABILITY TO USE THE PROGRAM (INCLUDING BUT NOT LIMITED
TO LOSS OF DATA OR DATA BEING RENDERED INACCURATE OR LOSSES SUSTAINED BY
YOU OR THIRD PARTIES OR A FAILURE OF THE PROGRAM TO OPERATE WITH ANY OTHER
PROGRAMS), EVEN IF SUCH HOLDER OR OTHER PARTY HAS BEEN ADVISED OF THE
POSSIBILITY OF SUCH DAMAGES.

		     END OF TERMS AND CONDITIONS

	Appendix: How to Apply These Terms to Your New Programs

  If you develop a new program, and you want it to be of the greatest
possible use to the public, the best way to achieve this is to make it
free software which everyone can redistribute and change under these terms.

  To do so, attach the following notices to the program.  It is safest
to attach them to the start of each source file to most effectively
convey the exclusion of warranty; and each file should have at least
the "copyright" line and a pointer to where the full notice is found.

    <one line to give the program's name and a brief idea of what it does.>
    Copyright (C) 19yy  <name of author>

    This program is free software; you can redistribute it and/or modify
    it under the terms of the GNU General Public License as published by
    the Free Software Foundation; either version 2 of the License, or
    (at your option) any later version.

    This program is distributed in the hope that it will be useful,
    but WITHOUT ANY WARRANTY; without even the implied warranty of
    MERCHANTABILITY or FITNESS FOR A PARTICULAR PURPOSE.  See the
    GNU General Public License for more details.

    You should have received a copy of the GNU General Public License
    along with this program; if not, write to the Free Software
    Foundation, Inc., 675 Mass Ave, Cambridge, MA 02139, USA.

Also add information on how to contact you by electronic and paper mail.

If the program is interactive, make it output a short notice like this
when it starts in an interactive mode:

    Gnomovision version 69, Copyright (C) 19yy name of author
    Gnomovision comes with ABSOLUTELY NO WARRANTY; for details type `show w'.
    This is free software, and you are welcome to redistribute it
    under certain conditions; type `show c' for details.

The hypothetical commands `show w' and `show c' should show the appropriate
parts of the General Public License.  Of course, the commands you use may
be called something other than `show w' and `show c'; they could even be
mouse-clicks or menu items--whatever suits your program.

You should also get your employer (if you work as a programmer) or your
school, if any, to sign a "copyright disclaimer" for the program, if
necessary.  Here is a sample; alter the names:

  Yoyodyne, Inc., hereby disclaims all copyright interest in the program
  `Gnomovision' (which makes passes at compilers) written by James Hacker.

  <signature of Ty Coon>, 1 April 1989
  Ty Coon, President of Vice

This General Public License does not permit incorporating your program into
proprietary programs.  If your program is a subroutine library, you may
consider it more useful to permit linking proprietary applications with the
library.  If this is what you want to do, use the GNU Library General
Public License instead of this License.},
  creationdate = {2024-11-04T08:12:56},
  file         = {:/autohome/saeckech/Promotion/Probenherstellung/BIS_Datenblatt_SigmaAldrich.pdf:PDF},
  keywords     = {uncitable},
  url          = {https://plasma-gate.weizmann.ac.il/Grace/},
  urldate      = {2024-11-04},
}

@Misc{COABerndKraftEtOH,
  author       = {{Bernd Kraft GmbH}},
  month        = oct,
  title        = {Ethanol HPLC gradient grade mind. 99,9 \%},
  year         = {2022},
  comment      = {Artikelnr. 20222, Chargennr. 22033726},
  creationdate = {2024-11-04T08:48:37},
  file         = {:BerndKraft2022 - Ethanol.pdf:PDF},
  keywords     = {Certificate of Analysis,EtOH,Sample Preparation,uncitable},
}

@Misc{COACortecnetH217O,
  author       = {{Cortecnet, France}},
  month        = mar,
  title        = {H2O},
  year         = {2023},
  creationdate = {2024-11-04T08:52:07},
  file         = {:Cortecnet2023 - H2O.pdf:PDF},
  keywords     = {Certificate of Analysis,Sample Preparation,17o,uncitable},
  url          = {certificate id: 8174B-PJ68},
}

@Misc{COAsigmaaldrichEtOH,
  author       = {{Merck KGaA, Germany}},
  month        = jun,
  title        = {Ethanol-d$_{2}$},
  year         = {2020},
  comment      = {Product Number: 347434, Batch Number MBBC9562},
  creationdate = {2024-11-04T08:53:45},
  file         = {:sigmaaldrich2020 - Ethanol D$_2$.pdf:PDF},
  keywords     = {Certificate of Analysis,Sample preparation,EtOH,uncitable},
}

@Misc{COAsigmaaldrichD2O,
  author       = {{Merck KGaA, Germany}},
  month        = oct,
  title        = {D$_{2}$O},
  year         = {2020},
  comment      = {Product Number: 151882, Batch Number: MKCN0543},
  creationdate = {2024-11-04T08:55:07},
  file         = {:sigmaaldrich2020a - D$_2$O.pdf:PDF},
  keywords     = {Certificate of Analysis,Sample preparation,D2O,uncitable},
}

@Misc{COAsigmaaldrichpNIPAM,
  author       = {{Merck KGaA, Germany}},
  month        = sep,
  title        = {p{NIPAM}},
  year         = {2019},
  comment      = {Product Number: 535311, Batch Number: MKCK7669},
  creationdate = {2024-11-04T09:01:56},
  file         = {:sigmaaldrich2019 - PNIPAM.pdf:PDF},
  keywords     = {Certificate of Analysis,Sample preparation,uncitable,pNIPAM},
}

@Article{Saeckel2025,
  author       = {Christoph Säckel and Regine von Klitzing and Michael Vogel},
  journal      = {Soft Matter},
  title        = {$^2$H and$^{17}$O NMR studies of solvent dynamics related to the cononsolvency of poly(N-isopropyl acrylamide) in ethanol-water mixtures},
  year         = {2025},
  creationdate = {2024-11-04T14:47:28},
  doi          = {10.1039/d5sm00055f},
  file         = {:/autohome/saeckech/Promotion/Papers/2024_Cononsolvency/Published/2HAnd17ONMRStudiesOfSolventDynamicsRelatedToTheCononsolvencyOfPolyNIsopropylacrylamideInEthanolWaterMixtures_SaeckelEtAl_SoftMatter2025.pdf:PDF;:/autohome/saeckech/Promotion/Papers/2024_Cononsolvency/Published/2HAnd17ONMRStudiesOfSolventDynamicsRelatedToTheCononsolvencyOfPolyNIsopropylacrylamideInEthanolWaterMixtures_SaeckelEtAl_SoftMatter2025_SI.pdf:PDF},
  keywords     = {NMR,pNIPAM,2H-NMR,spin-lattice relaxation,T1,spin-spin relaxation,D2O,cononsolvency,field cycling,confinement,aqueous alcohol,ethanol,h217o,T2,lcst,ucst},
  priority     = {prio1},
  publisher    = {The Royal Society of Chemistry},
  ranking      = {rank5},
  url          = {http://dx.doi.org/10.1039/D5SM00055F},
}

@Article{Sun2003,
  author       = {Pingchuan Sun and Baohui Li and Yinong Wang and Jianbiao Ma and Datong Ding and Binglin He},
  journal      = {European Polymer Journal},
  title        = {1H NMR studies of poly(N-isopropylacrylamide) gels near the phase transition},
  year         = {2003},
  issn         = {0014-3057},
  number       = {5},
  pages        = {1045--1050},
  volume       = {39},
  abstract     = {The phase transition and critical phenomenon of equilibrium swollen poly(N-isopropylacrylamide) (NIPA) hydrogels were studied by 1H NMR spectroscopy in liquid solution mode. The quantitative NMR observation shows that the peak height and line width of polymer proton and of the HOD proton, and relaxation times of HOD proton all transitionally change as the temperature approaches the transition temperature. The relaxation times of water protons are also measured quantitatively, which shows that the temperature dependence of relaxation times of HOD on temperature before the transition is not consistent with relaxation theory based on the assumption of dominated dipolar interaction between like-spin nuclei and isotropic rotational motion. To explain the surprising relaxation behavior of HOD, we suggest that the amount of bound water in gels increases gradually with temperature at the approach of the phase transition. The pulsed-gradient spin-echo NMR experiments of NIPA gel confirm this suggestion. We believe that these results have important implications concerning the mechanism of the phase transition of NIPA hydrogels.},
  creationdate = {2024-01-23T14:06:19},
  doi          = {https://doi.org/10.1016/S0014-3057(02)00326-9},
  file         = {:Sun2003 - 1H NMR Studies of Poly(N Isopropylacrylamide) Gels near the Phase Transition.pdf:PDF},
  keywords     = {pNIPAM, gels, 1h-nmr, relaxation, t1, t2, spin-lattice relaxation, spin-spin relaxation},
  url          = {https://www.sciencedirect.com/science/article/pii/S0014305702003269},
}

@Article{CortezLemus2016,
  author   = {Norma A. Cortez-Lemus and Angel Licea-Claverie},
  journal  = {Progress in Polymer Science},
  title    = {Poly(N-vinylcaprolactam), a comprehensive review on a thermoresponsive polymer becoming popular},
  year     = {2016},
  issn     = {0079-6700},
  pages    = {1-51},
  volume   = {53},
  abstract = {Poly(N-vinylcaprolactam) (PNVCL) is a temperature-responsive polymer, only second to poly(N-isopropylacrylamide), the most popular temperature-responsive polymer. Its applications include its use in cosmetics, as an anticlogging agent in pipelines and increasingly, in biomedical applications. This review highlights the controlled synthesis of PNVCL in different architectures: random copolymers, block copolymers, graft copolymers, nanogels, and their applications in the biomedical field, e.g., drug delivery, cell detachment, entrapment of enzymes, tissue engineering, among others. Emerging applications in areas that are expected to grow are also presented where PNVCL will play a pivotal roll: nanotechnology and the environment.},
  doi      = {https://doi.org/10.1016/j.progpolymsci.2015.08.001},
  file     = {:CortezLemus2016 - Poly(N Vinylcaprolactam), a Comprehensive Review on a Thermoresponsive Polymer Becoming Popular.pdf:PDF},
  keywords = {Poly(-vinylcaprolactam), Thermoresponsive polymers, Polymer nanoparticles, Block copolymers, Nanogels, PNVCL, PVCL, poly(N-vinylcaprolactam), review},
  url      = {https://www.sciencedirect.com/science/article/pii/S007967001500091X},
}









@Article{Liu2015,
  author   = {Liu, Biaolan and Wang, Jian and Ru, Geying and Liu, Chaoyang and Feng, Jiwen},
  journal  = {Macromolecules},
  title    = {Phase Transition and Preferential Alcohol Adsorption of Poly(N,N-diethylacrylamide) Gel in Water/Alcohol Mixtures},
  year     = {2015},
  number   = {4},
  pages    = {1126-1133},
  volume   = {48},
  abstract = {The phase separation of poly(N,N-diethylacrylamide) (PDEA) gel network in water/alcohol (methanol, ethanol, isopropanol, and n-propanol) mixtures has been systematically investigated by variable-temperature high-resolution 1H MAS NMR. The PDEA gel exhibits the cononsolvency effect and reentrant phase transition in water/isopropanol and water/n-propanol mixtures with larger alcohol hydrophobic groups but not in the water/methanol and water/ethanol bearing smaller alcohol hydrophobic groups, in contrast to the case of poly(N-isopropylacrylamide) where the cononsolvency effect was observed in all water/alcohol solutions. In the present PDEA gel, the phase separation is characterized by dehydration of the hydrophobic alkyl groups of PDEA, resulting in two distinct types of water/alcohol solutions above the lower critical solution temperature: confined binary solvents (3–5 solvent molecules per PDEA repeating unit) inside the gel network and free binary solvents outside the gel. The alcohol concentration in confined mixture solvents is markedly higher than that in free mixture solvents and increases with increasing hydrophobicity of the alcohol moiety. Interestingly, the alcohol enrichment inside the shrunk network does not cause additional dehydration of the PDEA network. Besides, the side chain mobility of shrunk PDEA gel network is enhanced by the appearance of alcohol and increases with the hydrophobicity of alcohol moiety. Our results reveal that there exists a strong interaction between alcohol and gel network.},
  doi      = {10.1021/ma502393z},
  eprint   = {https://doi.org/10.1021/ma502393z},
  file     = {:Liu2015 - Phase Transition and Preferential Alcohol Adsorption of Poly(N,N Diethylacrylamide) Gel in Water_Alcohol Mixtures.pdf:PDF;:PhaseTransitionAndPreferentialAlcoholAdsorptionOfPolyNNDiethylacrylamideGelInWaterAlcoholMixtures_LiuEtAl_Macromol2015_SI.pdf:PDF},
  keywords = {NMR,PDEA,cononsolvency,MAS,1h-nmr,aqueous alcohol,ethanol,methanol,propanol,isopropanol,n-propanol},
  url      = {https://doi.org/10.1021/ma502393z},
}









@Article{Velychkivska2018,
  author   = {Velychkivska, Nadiia and Starovoytova, Larisa and Březina, Václav and Hanyková, Lenka and Hill, Jonathan P. and Labuta, Jan},
  journal  = {ACS Omega},
  title    = {Improving the Colloidal Stability of Temperature-Sensitive Poly(N-isopropylacrylamide) Solutions Using Low Molecular Weight Hydrophobic Additives},
  year     = {2018},
  note     = {PMID: 31459272},
  number   = {9},
  pages    = {11865-11873},
  volume   = {3},
  abstract = {Poly(N-isopropylacrylamide) (PNIPAM) is an important polymer with stimuli-responsive properties, making it suitable for various uses. Phase behavior of the temperature-sensitive PNIPAM polymer in the presence of four low-molecular weight additives tert-butylamine (t-BuAM), tert-butyl alcohol (t-BuOH), tert-butyl methyl ether (t-BuME), and tert-butyl methyl ketone (t-BuMK) was studied in water (D2O) using high-resolution nuclear magnetic resonance (NMR) spectroscopy and dynamic light scattering. Phase separation was thermodynamically modeled as a two-state process which resulted in a simple curve which can be used for fitting of NMR data and obtaining all important thermodynamic parameters using simple formulas presented in this paper. The model is based on a modified van’t Hoff equation. Phase separation temperatures Tp and thermodynamic parameters (enthalpy and entropy change) connected with the phase separation of PNIPAM were obtained using this method. It was determined that Tp is dependent on additives in the following order: Tp(t-BuAM) > Tp(t-BuOH) > Tp(t-BuME) > Tp(t-BuMK). Also, either increasing the additive concentration or increasing pKa of the additive leads to depression of Tp. Time-resolved 1H NMR spin–spin relaxation experiments (T2) performed above the phase separation temperature of PNIPAM revealed high colloidal stability of the phase-separated polymer induced by the additives (relative to the neat PNIPAM/D2O system). Small quantities of selected suitable additives can be used to optimize the properties of PNIPAM preparations including their phase separation temperatures, colloidal stabilities, and morphologies, thus improving the prospects for the application.},
  doi      = {10.1021/acsomega.8b01811},
  eprint   = {https://doi.org/10.1021/acsomega.8b01811},
  file     = {:Velychkivska2018 - Improving the Colloidal Stability of Temperature Sensitive Poly(N Isopropylacrylamide) Solutions Using Low Molecular Weight Hydrophobic Additives.pdf:PDF},
  keywords = {pNIPAM,cononsolvency,cosolvency,aqueous alcohols,NMR,DLS,enthalpy,entropy,pH value,pKa value,spin-spin relaxation,T2,kinetics},
  url      = {https://doi.org/10.1021/acsomega.8b01811},
}

@Article{Stastna2022,
  author         = {Šťastná, Julie and Ivaniuzhenkov, Vladislav and Hanyková, Lenka},
  journal        = {Gels},
  title          = {External Stimuli-Responsive Characteristics of Poly(N,N′-diethylacrylamide) Hydrogels: Effect of Double Network Structure},
  year           = {2022},
  issn           = {2310-2861},
  number         = {9},
  volume         = {8},
  abstract       = {Swelling experiments and NMR spectroscopy were combined to study effect of various stimuli on the behavior of hydrogels with a single- and double-network (DN) structure composed of poly(N,N′-diethylacrylamide) and polyacrylamide (PAAm). The sensitivity to stimuli in the DN hydrogel was found to be significantly affected by the introduction of the second component and the formation of the double network. The interpenetrating structure in the DN hydrogel causes the units of the component, which is insensitive to the given stimulus in the form of the single network (SN) hydrogel, to be partially formed as globular structures in DN hydrogel. Due to the hydrophilic PAAm groups, temperature- and salt-induced changes in the deswelling of the DN hydrogel are less intensive and gradual compared to those of the SN hydrogel. The swelling ratio of the DN hydrogel shows a significant decrease in the dependence on the acetone content in acetone–water mixtures. A certain portion of the solvent molecules bound in the globular structures was established from the measurements of the 1H NMR spin–spin relaxation times T2 for the studied DN hydrogel. The time-dependent deswelling and reswelling kinetics showed a two-step profile, corresponding to the solvent molecules being released and absorbed during two processes with different characteristic times.},
  article-number = {586},
  doi            = {10.3390/gels8090586},
  keywords       = {interpenetrating polymer network,IPN,PDEA,PAA,kinetics,ionic strength,acetone,aqueous acetone,NMR,spin-spin relaxation,T2},
  pubmedid       = {36135298},
  url            = {https://www.mdpi.com/2310-2861/8/9/586},
}









@Article{Karg2008,
  author       = {Karg, Matthias and Pastoriza-Santos, Isabel and Rodriguez-González, Benito and von Klitzing, Regine and Wellert, Stefan and Hellweg, T.},
  journal      = {Langmuir},
  title        = {Temperature, pH, and Ionic Strength Induced Changes of the Swelling Behavior of PNIPAM−Poly(allylacetic acid) Copolymer Microgels},
  year         = {2008},
  note         = {PMID: 18489184},
  number       = {12},
  pages        = {6300-6306},
  volume       = {24},
  abstract     = {The volume phase transition of colloidal microgels made of N-isopropylacrylamide (NIPAM) is well-studied and it is known that the transition temperature can be influenced by copolymerization. A series of poly(N-isopropylacrylamide-co-allylacetic acid) copolymers with different contents of allylacetic acid (AAA) was synthesized by means of a simple radical polymerization approach. The thermoresponsive behavior of these particles was studied using dynamic light scattering (DLS). Further characterization was done by employing transmission electron microscopy (TEM) and zeta potential measurements. TEM observations reveal the approximately spherical shape and low polydispersity of the copolymer particles. In addition, the measured zeta potentials provide information about the relative surface charge. Since these copolymers are much more sensitive to external stimuli such as pH and ionic strength than their pure PNIPAM counterparts, the volume phase transition was investigated at two different pH values and various salt concentrations. At pH 10 for the copolymer microgels with the highest AAA content, a significant shift of the volume phase transition temperature toward higher values is found. For higher AAA content, a change in pH from 8 to 10 can induce a change in radius of up to 100 nm making the particles interesting as pH controlled actuators.},
  creationdate = {2024-11-11T08:09:39},
  doi          = {10.1021/la702996p},
  eprint       = {https://doi.org/10.1021/la702996p},
  file         = {:Karg2008 - Temperature, PH, and Ionic Strength Induced Changes of the Swelling Behavior of PNIPAM−Poly(allylacetic Acid) Copolymer Microgels.pdf:PDF},
  keywords     = {von Klitzing,microgel,synthesis,pNIPAM},
  url          = {https://doi.org/10.1021/la702996p},
}

@PhdThesis{Witt2021,
  author       = {Marcus Ulf Witt},
  school       = {Tu Darmstadt},
  title        = {Poly-N-isopropylacrylamide Based Microgels: A Study on Magnetic Microgels and Their Structure},
  year         = {2021},
  month        = apr,
  type         = {phdthesis},
  creationdate = {2024-11-11T11:42:20},
  doi          = {10.26083/tuprints-00018563},
  file         = {:Witt2021 - Poly N Isopropylacrylamide Based Microgels_ a Study on Magnetic Microgels and Their Structure.pdf:PDF},
  keywords     = {microgel,pNIPAM,von Klitzing,Dissertation,synthesis,homogeneous cross-link},
  url          = {https://tuprints.ulb.tu-darmstadt.de/18563/},
}

@Misc{PubChem2005NIPPA,
  comment      = {115.17g/mol},
  creationdate = {2024-11-11T12:56:57},
  keywords     = {synthesis,molecular weights,NIPPA},
  url          = {https://pubchem.ncbi.nlm.nih.gov/compound/Propanamide_-N-isopropyl},
  urldate      = {2024-11-11},
}

@Misc{PubChem2005NIPAM,
  comment      = {113.16g/mol},
  creationdate = {2024-11-11T13:01:05},
  keywords     = {synthesis,molecular weights,NIPPA},
  url          = {https://pubchem.ncbi.nlm.nih.gov/compound/Propanamide_-N-isopropyl},
  urldate      = {2024-11-11},
}

@Software{MarvinDemo,
  comment      = {https://freetrial.marvin.cxn.io/},
  creationdate = {2024-11-14T14:47:35},
  lastvisited  = {2024-12-14T14:48:00},
  url          = {https://chemaxon.com/},
  version      = {24.3.115},
}

@Article{AlRawi1981,
  author       = {Al-Rawi, Jasim M. A. and Behnam, George Q. and Taha, Nihad I.},
  journal      = {Organic Magnetic Resonance},
  title        = {Deuterium nuclear magnetic resonance spectroscopy. 1—Larmor frequency ratio, referencing and chemical shift},
  year         = {1981},
  number       = {3},
  pages        = {198-201},
  volume       = {16},
  abstract     = {Precise values for the ratio of the Larmor frequencies, w1H/w2H, were measured at constant field for various organic compounds. The values of the Larmor frequency ratio depend on carbon-hydrogen bond hybridization. The best ratio for the ghost referencing of 2H NMR spectra was then determined (6.514399862). This value enables an accurate ghost reference for any 2H NMR spectrum to be derived from the observed 1H NMR frequency of the normal internal reference. Deuterium and proton chemical shifts measured from internal, partially deuteriated TMS under the same conditions are shown to be the same.},
  creationdate = {2024-11-22T13:05:05},
  doi          = {https://doi.org/10.1002/mrc.1270160306},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/mrc.1270160306},
  file         = {:AlRawi1981 - Deuterium Nuclear Magnetic Resonance Spectroscopy. 1—Larmor Frequency Ratio, Referencing and Chemical Shift.pdf:PDF},
  keywords     = {1h-nmr,2h-nmr,nmr,chemical shift,isotope effect},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/mrc.1270160306},
}

@Article{MartinezMoro2020,
  author       = {Marta Martinez-Moro and Jacek Jenczyk and Juan M. Giussi and Stefan Jurga and Sergio E. Moya},
  journal      = {Journal of Colloid and Interface Science},
  title        = {Kinetics of the thermal response of poly(N-isopropylacrylamide co methacrylic acid) hydrogel microparticles under different environmental stimuli: A time-lapse NMR study},
  year         = {2020},
  issn         = {0021-9797},
  pages        = {439-448},
  volume       = {580},
  abstract     = {Hypothesis
Hydrogels of N-isopropylacrylamide and methacrylic acid (P(NIPAm-co-MAA)) display pH sensitivity and complex positively charged molecules through carboxylate groups, while having a critical solution temperature at which they reduce in volume and dehydrate. We aimed to elucidate how the responsiveness of MAA to environmental changes alters PNIPAm hydrogels at the molecular level using nuclear magnetic resonance (NMR). Time-lapse NMR allows us to follow the evolution of NMR signal under a temperature stimulus, providing unique information on conformational freedom of the hydrogel polymers.
Experiments
We used time-lapse NMR to follow the evolution of the NMR signal with time over a temperature change from 25 to 40°C and to study the swelling/deswelling kinetics of P(NIPAm-co-MAA) microgels at different pH values and ionic strengths, and in the presence of positively charged molecules complexing carboxylate groups.
Findings
At acid pH, hydrogel collapse is favored over neutral pH, and at basic pH the carboxylates remain steadily hydrated during temperature increase. Increasing ionic strength results in a faster, more effective collapse than decreasing pH. Complexation of medium-sized molecules with several charges (spermine, spermidine) causes a faster collapse than complexation with large molecular weight poly(allylamine) hydrochloride, but similar to the collapse effected by large poly(diallyldimethylammonium) chloride. This work opens new perspectives to using time-lapse NMR to study thermoresponsive systems that respond to multiple stimuli, with particular relevance in designing hydrogels for drug delivery.},
  creationdate = {2024-11-22T13:08:21},
  doi          = {https://doi.org/10.1016/j.jcis.2020.07.049},
  file         = {:MartinezMoro2020 - Kinetics of the Thermal Response of Poly(N Isopropylacrylamide Co Methacrylic Acid) Hydrogel Microparticles under Different Environmental Stimuli_ a Time Lapse NMR Study.pdf:PDF},
  keywords     = {Time-lapse NMR,NIPAM-MAA microgels,Hydrogel collapse,Deswelling kinetics,Polyamines,NMR,pNIPAM,kinetics,microgel,ionic strength},
  url          = {https://www.sciencedirect.com/science/article/pii/S0021979720309279},
}

@Article{RamirezIrigoyen2023,
  author       = {Ramírez-Irigoyen, Andya J. and García-Verdugo, Karla F. and Castillo-Ortega, María Mónica and Rodríguez-Félix, Dora E. and Encinas, José Carmelo and Plascencia-Jatomea, Maribel and Argüelles-Monal, Waldo and Sauceda, Irela Santos and Pérez-González, Refugio and del Castillo-Castro, Teresa},
  journal      = {Journal of Applied Polymer Science},
  title        = {Study of thermal transitions of copolymers based on -isopropylacrylamide and acrylic acid with potential for curcumin controlled release},
  year         = {2023},
  number       = {35},
  pages        = {e54338},
  volume       = {140},
  abstract     = {Thermosensitive polymers based on poly(N-isopropylacrylamide) (pNIPAM) have been widely evaluated in a variety of biomedical applications due to their particular thermal behavior in aqueous solutions. Despite this, few works have focused on the complementary analysis of the thermal transitions of pNIPAM polymers in linear and crosslinked form. In this work, linear and crosslinked poly(N-isopropylacrylamide-co-acrylic acid) p(NIPAM-co-AA) copolymers were synthesized at similar NIPAM/AA feed composition and their thermosensitive behavior was studied by turbidimetric methods, FTIR spectroscopy analysis, and temperature-dependent swelling measurements. The intermolecular crosslinking hindered the hydrophobic aggregation of chain segments, leading to higher transition temperatures of synthesized polymers. AA units promoted the intersegment hydrogen bonds during heating and strengthened the hydrogen bond interactions water-network. The effect of the thermosensitive behavior of p(NIPAM-co-AA) copolymer on curcumin (CUR) release kinetic was also studied. The low uptake level of p(NIPAM-co-AA) hydrogel, partially shrunken at 37°C, produced a CUR sustained delivery, reaching the release equilibrium state up to 18 h. Hydrogels of p(NIPAM-co-AA) with a suitable composition exhibited a promising performance for the CUR controlled delivery at physiological conditions.},
  creationdate = {2024-11-22T13:20:26},
  doi          = {https://doi.org/10.1002/app.54338},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/app.54338},
  file         = {:RamirezIrigoyen2023 - Study of Thermal Transitions of Copolymers Based on Isopropylacrylamide and Acrylic Acid with Potential for Curcumin Controlled Release.pdf:PDF},
  keywords     = {biomedical,curcumin,polymer,responsive,tunable,pNIPAM,NMR,hydrogel,chemical shift},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/app.54338},
}

@Article{Jadhav2016,
  author       = {Jadhav, Sushilkumar A. and Brunella, Valentina and Miletto, Ivana and Berlier, Gloria and Scalarone, Dominique},
  journal      = {Journal of Applied Polymer Science},
  title        = {Synthesis of poly(N-isopropylacrylamide) by distillation precipitation polymerization and quantitative grafting on mesoporous silica},
  year         = {2016},
  number       = {44},
  volume       = {133},
  abstract     = {In this work, syntheses of thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) with different molecular weights were carried out in ethanol by distillation precipitation polymerization (DPP) technique. The synthesized polymers were fully characterized by attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy, nuclear magnetic resonance spectroscopy, and size exclusion chromatography techniques. The lower critical solution temperatures of the polymers were determined with differential scanning calorimetry. A simple and versatile method for the in situ synthesis and grafting of PNIPAM on mesoporus silica nanoparticles (MSNs) with improved control over quantitative grafting is devised. The PNIPAM grafted MSNs were characterized with ATR-FTIR, thermogravimetric analysis, transmission electron microscopy, and dynamic light scattering analyses. From the results obtained it is showed that quantitative grafting of PNIPAM on MSNs from 1 to 20\% by weight can be tuned by manipulating the in situ DPP reaction conditions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44181.},
  creationdate = {2024-11-22T13:27:58},
  doi          = {https://doi.org/10.1002/app.44181},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/app.44181},
  file         = {:Jadhav2016 - Synthesis of Poly(N Isopropylacrylamide) by Distillation Precipitation Polymerization and Quantitative Grafting on Mesoporous Silica.pdf:PDF},
  keywords     = {nanoparticles,nanowires and nanocrystals,radical polymerization,stimuli-sensitive polymers,surfaces and interfaces,synthesis,pNIPAM,chemical shift,ART-FTIR,infrared,DSC,spherical polymer brush},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/app.44181},
}

@Article{Lanzalaco2023,
  author       = {Lanzalaco, Sonia and Mingot, Júlia and Torras, Juan and Alemán, Carlos and Armelin, Elaine},
  journal      = {Advanced Engineering Materials},
  title        = {Recent Advances in Poly(N-isopropylacrylamide) Hydrogels and Derivatives as Promising Materials for Biomedical and Engineering Emerging Applications},
  year         = {2023},
  number       = {4},
  pages        = {2201303},
  volume       = {25},
  abstract     = {Temperature-sensitive (thermosensitive) hydrogels, which are part of the family of stimulus-sensitive hydrogels, consist of water-filled polymer networks that display a temperature-dependent degree of swelling. Thermosensitive hydrogels, which can undergo phase transition or swell/de-swell as temperature changes, have great potential in various technological and biomedical purposes for a number of reasons: their temperature response is reversible, hydrogels are stable and easy to prepare, they can be biocompatible and also be suitably combined with other organic and inorganic materials, resulting in new materials with outstanding properties. Among thermosensitive hydrogels poly(N-isopropylacrylamide) (PNIPAAm) is the most extensively studied because it brings together the best properties of these materials. Consequently, in the past few years, a wide number of applications and new chemical processes to prepare PNIPAAm and their derivatives are being proposed. The objective of this review is to summarize the fundamentals of thermosensitive hydrogels and recent advances in preparation and both technological and biomedical applications of thermosensitive hydrogel, with a special focus on PNIPAAm and their derivatives. Special attention has been given to the discussion of challenges and future research perspectives based on new horizons not yet considered.},
  creationdate = {2024-11-26T10:08:53},
  doi          = {https://doi.org/10.1002/adem.202201303},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/adem.202201303},
  file         = {:Lanzalaco2023 - Recent Advances in Poly(N Isopropylacrylamide) Hydrogels and Derivatives As Promising Materials for Biomedical and Engineering Emerging Applications.pdf:PDF},
  keywords     = {biomedical sensors, poly(N-isopropylacrylamide), thermosensitive hydrogels, water cleaning, pNIPAM, review, hydrogel, thermoresponsive, application-focused, application focused},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adem.202201303},
}

@Article{Neal2024,
  author       = {Christopher A. P. Neal and Abhishek M. Shetty and Jason D. Linn and Michelle C. Quan and Joseph D. Casas and Michelle A. Calabrese},
  journal      = {Rheologica Acta},
  title        = {Magnetic field-dependent rheological behavior of thermoresponsive poly(N-isopropylacrylamide) solutions},
  year         = {2024},
  pages        = {493--512},
  volume       = {63},
  creationdate = {2024-11-26T10:12:37},
  doi          = {https://doi.org/10.1007/s00397-024-01454-y},
  file         = {:Neal2024 - Magnetic Field Dependent Rheological Behavior of Thermoresponsive Poly(N Isopropylacrylamide) Solutions.pdf:PDF},
  keywords     = {pNIPAM,rheology,NMR,magnetic field-dependence},
  url          = {https://doi.org/10.1007/s00397-024-01454-y},
}









@Article{Wang2024a,
  author       = {Wang, Chi and Hashimoto, Takeji},
  journal      = {Macromolecules},
  title        = {Time-Resolved Light Scattering of Atactic Poly(N-isopropylacrylamide) in Water: Physical Gelation and Spinodal Temperature of the Hydrogel},
  year         = {2024},
  number       = {11},
  pages        = {5398-5408},
  volume       = {57},
  abstract     = {Aqueous solutions of atactic poly(N-isopropylacrylamide) (a-PNIPAM) exhibiting lower critical solution temperature behavior can form macroscopic gels at the gel temperature Tgel, which is lower than the binodal temperature Tb (Macromolecules 2023, 56, 6354). This study applied time-resolved light scattering (TRLS) for the first time to explore the structure evolution of the transparent gel at Ti (Tgel < Ti < Tb). In addition, via the subsequent T-jump from Ti to some selected temperatures Tx’s (≥Tb), the TRLS intensity profiles of the phase-separated a-PNIPAM gel were also acquired until the steady state is reached, at which point, the phase-separated structures, induced either by nucleation and growth (NG) or by spinodal decomposition (SD), were finally pinned. At each Tx, the scattered intensity profiles of a-PNIPAM gels with either pinned NG or pinned SD structures were further analyzed to obtain the scaled structure factor F(x). Judging from the Tx-dependent F(x) profiles, a novel approach is proposed to determine the spinodal temperature (Ts,gel) of the macroscopic gel. For the well-characterized 7 wt \% a-PNIPAM aqueous solution with Tb = 30.6 °C, the TRLS intensity profile of the macroscopic gel at Ti (=29.2 °C) exhibits a mass-fractal dimension of 2.0 ± 0.1. The derived Ts,gel by TRLS in this study is 31.2 ± 0.1 °C, which is also in good agreement with that derived previously from small-angle X-ray scattering based on the Ornstein–Zernike scattering function. Remarkably, an extremely small temperature gap (∼0.6 °C) exists between Tb and Ts,gel for the specific a-PNIPAM/H2O hydrogels studied.},
  creationdate = {2024-11-26T10:36:05},
  doi          = {10.1021/acs.macromol.4c00278},
  eprint       = {https://doi.org/10.1021/acs.macromol.4c00278},
  file         = {:Wang2024a - Time Resolved Light Scattering of Atactic Poly(N Isopropylacrylamide) in Water_ Physical Gelation and Spinodal Temperature of the Hydrogel.pdf:PDF;:TimeResolvedLightScatteringOfAtacticPolyNIsopropylacrylamideInWater-PhysicalGelationAndSpinodalTemperatureOfTheHydrogel_WangEtAl_Macromol2024_SI.pdf:PDF},
  keywords     = {pNIPAM,light scattering,physical gel,aggregation,kinetics,pearl necklace},
  url          = {https://doi.org/10.1021/acs.macromol.4c00278},
}

@Article{Sizaire1999,
  author       = {R. Sizaire and G. Lielens and I. Jaumain and R. Keunings and V. Legat},
  journal      = {Journal of Non-Newtonian Fluid Mechanics},
  title        = {On the hysteretic behaviour of dilute polymer solutions in relaxation following extensional flow},
  year         = {1999},
  issn         = {0377-0257},
  number       = {2},
  pages        = {233-253},
  volume       = {82},
  abstract     = {The hysteretic behaviour of dilute polymer solutions in relaxation following extensional flow is studied in the framework of three distinct theoretical models. For ideal kinematics of uniaxial elongation, we show that the kinetic theory of FENE dumbbells and its FENE-L approximation present a hysteresis when plotting polymer stress versus average molecular extension. Similar behaviour is obtained for ideal extensional kinematics using a FENE-P constitutive equation with a spectrum of finite extensibility parameters. Finally, a numerical simulation of the filament-stretching device shows that spatial inhomogeneities of the stress and average conformation fields also lead to hysteretic behaviour with a single-mode FENE-CR constitutive equation. In all three cases, hysteretic behaviour results from the combined effect of dispersity and non-linearity. We also address the validity of the stress-optic law for FENE dumbbells in relaxation following start-up of uniaxial extension. The simulation results show that the stress-optic coefficient remains constant at low strains only. Plots of stress-optic coefficient versus birefringence show hysteresis as well. This rules out a modified stress-optic law for FENE dumbbells wherein the stress-optic coefficient would be a function of the second moment of the configuration distribution function alone. Finally, it is shown in the Appendix that a proper selection of the spectrum of finite extensibilities can be made so that the multi-mode FENE-P model gives essentially the same stress response as the kinetic theory of FENE dumbbells in transient uniaxial extension.},
  creationdate = {2024-11-26T10:44:45},
  doi          = {https://doi.org/10.1016/S0377-0257(98)00164-5},
  file         = {:Sizaire1999 - On the Hysteretic Behaviour of Dilute Polymer Solutions in Relaxation Following Extensional Flow.pdf:PDF},
  keywords     = {hysteresis,polymer solution,external flow,kinetics},
  url          = {https://www.sciencedirect.com/science/article/pii/S0377025798001645},
}

@Article{Swier2003,
  author       = {Swier, Steven and Van Durme, Kurt and Van Mele, Bruno},
  journal      = {Journal of Polymer Science Part B: Polymer Physics},
  title        = {Modulated-temperature differential scanning calorimetry study of temperature-induced mixing and demixing in poly(vinylmethylether)/water},
  year         = {2003},
  number       = {15},
  pages        = {1824-1836},
  volume       = {41},
  abstract     = {The heat capacity or reversing heat flow signal from modulated-temperature differential scanning calorimetry can be used to measure the onset of phase separation in a poly(vinylmethylether)/water mixture, clearly showing the special type III lower critical solution temperature demixing behavior. Characteristic of this demixing behavior is a three-phase region, which is detected in the nonreversing heat flow signal. Stepwise quasi-isothermal measurements through the phase transition show large excess contributions in the (apparent) heat capacity signal, caused by demixing/remixing heat effects on the timescale of the modulation (fast process). These excess contributions and their time-dependent evolutions (slow process) are useful in understanding the kinetics of phase separation and the morphology (interphase) development. Care has to be taken, however, in interpreting the heat capacity signal derived from the amplitude of the modulated heat flow because nonlinear effects lead to the occurrence of higher harmonics. Therefore, the raw heat flow signal for quasi-isothermal demixing and remixing measurements is also examined in the time domain. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1824–1836, 2003},
  creationdate = {2024-11-26T10:57:18},
  doi          = {https://doi.org/10.1002/polb.10512},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.10512},
  file         = {:Swier2003 - Modulated Temperature Differential Scanning Calorimetry Study of Temperature Induced Mixing and Demixing in Poly(vinylmethylether)_water.pdf:PDF},
  keywords     = {modulated-temperature differential scanning calorimetry,apparent heat capacity,phase-separation,kinetics,hydrophilic polymer,DSC,PVME,heat capacity},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.10512},
}

@Article{Seuring2012,
  author       = {Seuring, Jan and Agarwal, Seema},
  journal      = {Macromolecular Rapid Communications},
  title        = {Polymers with Upper Critical Solution Temperature in Aqueous Solution},
  year         = {2012},
  number       = {22},
  pages        = {1898-1920},
  volume       = {33},
  abstract     = {This review focuses on polymers with upper critical solution temperature (UCST) in water or electrolyte solution and provides a detailed survey of the yet few existing examples. A guide for synthetic chemists for the design of novel UCST polymers is presented and possible handles to tune the phase transition temperature, sharpness of transition, hysteresis, and effectiveness of phase separation are discussed. This review tries to answer the question why polymers with UCST remained largely underrepresented in academic as well as applied research and what requirements have to be fulfilled to make these polymers suitable for the development of smart materials with a positive thermoresponse.},
  creationdate = {2024-11-26T10:59:38},
  doi          = {https://doi.org/10.1002/marc.201200433},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/marc.201200433},
  file         = {:Seuring2012 - Polymers with Upper Critical Solution Temperature in Aqueous Solution.pdf:PDF},
  keywords     = {smart polymers,stimuli-responsive polymers,thermoresponse,upper critical solution temperatures,UCST,review,thermoresponsive},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/marc.201200433},
}

@Article{VanDurme2005,
  author       = {Van Durme, Kurt and Delellio, Laureen and Kudryashov, Evgeny and Buckin, Vitaly and Van Mele, Bruno},
  journal      = {Journal of Polymer Science Part B: Polymer Physics},
  title        = {Exploration of high-resolution ultrasonic spectroscopy as an analytical tool to study demixing and remixing in poly(N-isopropyl acrylamide)/water solutions},
  year         = {2005},
  number       = {11},
  pages        = {1283-1295},
  volume       = {43},
  abstract     = {The ultrasonic properties of poly(N-isopropyl acrylamide) (PNIPAM)/water solutions, determined with high-resolution ultrasonic spectroscopy (HR-US), change during demixing and remixing. All HR-US measurements are discussed with respect to modulated temperature differential scanning calorimetry results. The lower critical solution temperature type of phase behavior, in combination with the glass-transition/composition curve of PNIPAM/water, determines the evolution of the ultrasonic signals. Three different temperature regions can be distinguished: a homogeneous region and a heterogeneous region, the latter subdivided into zones without and with interference of partial vitrification of the PNIPAM-rich phase. During phase separation, the ultrasonic velocity decreases because of a change in the hydration structure around the polymer chains, whereas the ultrasonic attenuation increases as aggregation sets in. Isothermal measurements clearly show time dependence for both the velocity and the attenuation. The observed timescales are different and can be related to a changing polymer/water interphase and aggregate formation, respectively. Partial vitrification of the PNIPAM-rich phase slows the demixing kinetics and especially the remixing kinetics. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1283–1295, 2005},
  creationdate = {2024-11-26T11:13:26},
  doi          = {https://doi.org/10.1002/polb.20423},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.20423},
  file         = {:VanDurme2005 - Exploration of High Resolution Ultrasonic Spectroscopy As an Analytical Tool to Study Demixing and Remixing in Poly(N Isopropyl Acrylamide)_water Solutions.pdf:PDF},
  keywords     = {glass transition,high-resolution ultrasonic spectroscopy,hydrophilic polymers,modulated temperature differential scanning calorimetry,phase-separation,poly(N-isopropyl acrylamide),pNIPAM,DSC,kinetics,remixing,demixing,aggregation},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.20423},
}

@Article{Lu2010,
  author       = {Lu, Yijie and Zhou, Kejin and Ding, Yanwei and Zhang, Guangzhao and Wu, Chi},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Origin of hysteresis observed in association and dissociation of polymer chains in water},
  year         = {2010},
  pages        = {3188-3194},
  volume       = {12},
  abstract     = {By choosing poly(N{,}N-diethylacrylamide) which lacks the possibility to form intra- or inter-chain hydrogen bonds{,} we studied its chain association and dissociation in water by using laser light scattering (LLS){,} ultrasensitive differential scanning calorimetry (US-DSC) and Fourier transform infrared spectroscopy (FTIR). As the solution temperature increases{,} the average hydrodynamic radius (〈Rh〉) and average radius of gyration (〈Rg〉) decrease{,} indicating the intrachain shrinking. When the temperature is higher than its lower critical solution temperature (LCST{,} ∼30 °C){,} the apparent weight-average molar mass (Mw{,}app) increases{,} reflecting the interchain association. At the same time{,} FTIR study reveals that as the temperature increases{,} the area ratio of two absorption peaks{,} respectively{,} associated to one hydrogen bonded carbonyl >CO⋯H–O–H and free carbonyl >CO groups increases{,} while that related to two hydrated hydrogen bonded carbonyl groups decreases{,} indicating heating-induced dehydration. In the reversible cooling process{,} 〈Rh〉{,} 〈Rg〉{,} Mw{,}app and area ratios of the absorption peak are similar to those in the heating process for each given temperature{,} indicating that there is no hysteresis in the interchain association and dissociation. This present study confirms that the hysteresis previously observed for a sister polymer{,} poly(N-isopropylacrylamide){,} is due to the formation of some additional hydrogen bonds in its collapsed state at temperatures higher than the LCST.},
  creationdate = {2024-11-26T11:32:20},
  doi          = {10.1039/B918969F},
  file         = {:Lu2010 - Origin of Hysteresis Observed in Association and Dissociation of Polymer Chains in Water.pdf:PDF},
  issue        = {13},
  keywords     = {pNDEMA,hysteresis,thermoresponsive,FTIR,infrared,DSC,light scattering,hydrogen bond,demixing,remixing,aggregation,kinetics},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/B918969F},
}









@Article{Maeda2002,
  author       = {Maeda, Yasushi and Nakamura, Tomoya and Ikeda, Isao},
  journal      = {Macromolecules},
  title        = {Change in Solvation of Poly(N,N-diethylacrylamide) during Phase Transition in Aqueous Solutions As Observed by IR Spectroscopy},
  year         = {2002},
  number       = {27},
  pages        = {10172-10177},
  volume       = {35},
  abstract     = {Phase transitions of poly(N,N-dimethylacrylamide) (PdEA) in water and methanol/water mixture were investigated by Fourier transform infrared (FTIR) spectroscopy. IR spectra of the solutions measured as a function of temperature exhibited critical changes upon the phase transition. The amide I band of PdEA consists of three components centered at 1638, 1619, and 1599 cm-1, which can be assigned to free carbonyl groups and those connected to one and two water molecules through hydrogen bonds, respectively. The relative areas of the 1619 and 1599 cm-1 components decrease and that of the 1638 cm-1 component increases above the phase transition temperature (Tp), but the change is relatively small and most of the amide CO groups remain hydrated even above Tp. The C−H stretching bands shift toward lower wavenumbers that are close to those measured in the neat solid state, indicating that the alkyl groups are almost fully dehydrated above Tp. In the methanol/water mixture, Tp is almost independent of methanol concentration up to ca. 20\% and increases steeply above ca. 30\%. The heat of transition (ΔH) decreased linearly with an increase of methanol concentration up to 30\% and is nearly zero above 40\%. The areas of the 1599 and 1638 cm-1 bands decrease with an increase in methanol concentration with a slight change in the 1619 cm-1 band. The result suggests that methanol replaces parts of the CO···H−O−H hydrogen bonds to form a CO···H−O−CH3 hydrogen bond, and its bulky methyl group prevents the carbonyl group to form the second hydrogen bond that is responsible for the 1599 cm-1 band.},
  creationdate = {2024-11-28T09:42:20},
  doi          = {10.1021/ma020945w},
  eprint       = {https://doi.org/10.1021/ma020945w},
  file         = {:Maeda2002 - Change in Solvation of Poly(N,N Diethylacrylamide) during Phase Transition in Aqueous Solutions As Observed by IR Spectroscopy.pdf:PDF},
  keywords     = {PDEAM,infrared,FTIR,cononsolvency,aqueous methanol},
  url          = {https://doi.org/10.1021/ma020945w},
}

@Article{Maeda2009,
  author       = {Yasushi Maeda and Masato Yamabe},
  journal      = {Polymer},
  title        = {A unique phase behavior of random copolymer of N-isopropylacrylamide and N,N-diethylacrylamide in water},
  year         = {2009},
  issn         = {0032-3861},
  number       = {2},
  pages        = {519-523},
  volume       = {50},
  abstract     = {Thermosensitive phase separation of aqueous solutions of the random copolymers of N-isopropylacrylamide (iPA) and N,N-diethylacrylamide (dEA) (PiPA–dEA) and of iPA and N-isopropylmethacrylamide(iPMA) (PiPA–iPMA) with different compositions has been investigated by using calorimetry, turbidimetry and infrared spectroscopy. Though the phase transition temperature (Tp) of PiPA–iPMA is a linear function of its composition, a deviation from additivity is observed for that of PiPA–dEA, that is, it has a minimum value at iPA/dEA=1 (mol/mol). IR spectrum at the amide II mode of the copolymer suggests that part of N–H groups of iPA units form a hydrogen bond with CO groups of dEA units at T>Tp as well as with those of the iPA units. Effects of methanol on Tp of these copolymers have also been studied.},
  creationdate = {2024-11-28T09:46:39},
  doi          = {https://doi.org/10.1016/j.polymer.2008.11.032},
  file         = {:Maeda2009 - A Unique Phase Behavior of Random Copolymer of N Isopropylacrylamide and N,N Diethylacrylamide in Water.pdf:PDF},
  keywords     = {Infrared spectroscopy,Phase separation,Thermosensitive polymer,infrared,PDEAM,FTIR,DSC,pNIPAM,pNIPMAM,copolymer,turbidimetry},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386108010185},
}









@Article{Pettersson2016,
  author       = {Pettersson, Lars Gunnar Moody and Henchman, Richard Humfry and Nilsson, Anders},
  journal      = {Chemical Reviews},
  title        = {Water—The Most Anomalous Liquid},
  year         = {2016},
  note         = {PMID: 27405667},
  number       = {13},
  pages        = {7459-7462},
  volume       = {116},
  creationdate = {2024-11-28T14:00:49},
  doi          = {10.1021/acs.chemrev.6b00363},
  eprint       = {https://doi.org/10.1021/acs.chemrev.6b00363},
  file         = {:Pettersson2016 - Water—The Most Anomalous Liquid.pdf:PDF},
  keywords     = {water,anomalies,review},
  url          = {https://doi.org/10.1021/acs.chemrev.6b00363},
}

@Article{Poole1992,
  author       = {Peter H. Poole and Francesco Sciortino and Ulrich Essmann and H. Eugene Stanley},
  journal      = {Nature},
  title        = {Phase behaviour of metastable water},
  year         = {1992},
  month        = nov,
  pages        = {324--328},
  volume       = {360},
  creationdate = {2024-11-28T14:12:37},
  doi          = {https://doi.org/10.1038/360324a0},
  file         = {:Poole1992 - Phase Behaviour of Metastable Water.pdf:PDF},
  keywords     = {water,no man's land,anomaly,second critical point,HDL,LDL},
  url          = {https://doi.org/10.1038/360324a0},
}






@Book{Pang2014,
  author       = {Pang, Xiao Feng},
  publisher    = {WORLD SCIENTIFIC},
  title        = {Water},
  year         = {2014},
  comment      = {in AG library},
  creationdate = {2024-11-28T14:33:17},
  doi          = {10.1142/8669},
  eprint       = {https://www.worldscientific.com/doi/pdf/10.1142/8669},
  keywords     = {book,water,anomalies,review},
  url          = {https://www.worldscientific.com/doi/abs/10.1142/8669},
}

@Article{Parke1999,
  author       = {Sneha A. Parke and Gordon G. Birch},
  journal      = {Food Chemistry},
  title        = {Solution properties of ethanol in water},
  year         = {1999},
  issn         = {0308-8146},
  number       = {3},
  pages        = {241-246},
  volume       = {67},
  abstract     = {The packing propensity of ethanol in aqueous solution is very unusual, yet ethanol finds extensive use both in the food and the pharmaceutical industry. An analysis of the solution properties of increasing concentrations of ethanol in water at 20° and 37°C reveals valuable information about its packing characteristics. Apparent molar and specific volumes provide information about the interaction of ethanol with surrounding water structure. Isentropic apparent molar and specific compressibilities indicate the extent to which the hydration layer around the ethanol molecules can be compressed. Compressibility hydration numbers show the number of water molecules that are displaced by the introduction of the ethanol to water. The enhanced packing efficiency of ethanol in water at low concentrations, is affected by the formation of cage-like structures around the hydrophobic end of the molecule. At high concentrations, however, linear chains or rings of ethanol molecules are formed which change its mode of packing within the three-dimensional structure of water. These effects may be used to help explain the mechanism of action of ethanol in food, pharmaceutical and other applications.},
  creationdate = {2024-11-28T16:14:29},
  doi          = {https://doi.org/10.1016/S0308-8146(99)00124-7},
  file         = {:Parke1999 - Solution Properties of Ethanol in Water.pdf:PDF},
  keywords     = {aqueous ethanol,volume contraction},
  url          = {https://www.sciencedirect.com/science/article/pii/S0308814699001247},
}

@Article{Frank1945,
  author       = {Frank, Henry S. and Evans, Marjorie W.},
  journal      = {The Journal of Chemical Physics},
  title        = {Free Volume and Entropy in Condensed Systems III. Entropy in Binary Liquid Mixtures; Partial Molal Entropy in Dilute Solutions; Structure and Thermodynamics in Aqueous Electrolytes},
  year         = {1945},
  issn         = {0021-9606},
  month        = {11},
  number       = {11},
  pages        = {507-532},
  volume       = {13},
  abstract     = {The ideas of the first and second papers in this series, which make it possible to interpret entropy data in terms of a physical picture, are applied to binary solutions, and equations are derived relating energy and volume changes when a solution is formed to the entropy change for the process. These equations are tested against data obtained by various authors on mixtures of normal liquids, and on solutions of non‐polar gases in normal solvents. Good general agreement is found, and it is concluded that in such solutions the physical picture of molecules moving in a ``normal'' manner in each others' force fields is adequate. As would be expected, permanent gases, when dissolved in normal liquids, loosen the forces on neighboring solvent molecules producing a solvent reaction which increases the partial molal entropy of the solute. Entropies of vaporization from aqueous solutions diverge strikingly from the normal behavior established for non‐aqueous solutions. The nature of the deviations found for non‐polar solutes in water, together with the large effect of temperature upon them, leads to the idea that the water forms frozen patches or microscopic icebergs around such solute molecules, the extent of the iceberg increasing with the size of the solute molecule. Such icebergs are apparently formed also about the non‐polar parts of the molecules of polar substances such as alcohols and amines dissolved in water, in agreement with Butler's observation that the increasing insolubility of large non‐polar molecules is an entropy effect. The entropies of hydration of ions are discussed from the same point of view, and the conclusion is reached that ions, to an extent which depends on their sizes and charges, may cause a breaking down of water structure as well as a freezing or saturation of the water nearest them. Various phenomena recorded in the literature are interpreted in these terms. The influence of temperature on certain salting‐out coefficients is interpreted in terms of entropy changes. It appears that the salting‐out phenomenon is at least partly a structural effect. It is suggested that structural influences modify the distribution of ions in an electrolyte solution, and reasons are given for postulating the existence of a super‐lattice structure in solutions of LaCl3 and of EuCl3. An example is given of a possible additional influence of structural factors upon reacting tendencies in aqueous solutions.},
  creationdate = {2024-11-28T16:41:19},
  doi          = {10.1063/1.1723985},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/13/11/507/18793850/507\_1\_online.pdf},
  file         = {:Frank1945 - Free Volume and Entropy in Condensed Systems III. Entropy in Binary Liquid Mixtures\; Partial Molal Entropy in Dilute Solutions\; Structure and Thermodynamics in Aqueous Electrolytes.pdf:PDF},
  keywords     = {aqueous alcohol,iceberg model},
  url          = {https://doi.org/10.1063/1.1723985},
}

@Article{Li2010,
  author       = {Zhengzheng Li and Yon-Hwan Kim and Hyun Su Min and Chang-Kwon Han and Kang Moo Huh},
  journal      = {Macromol. Res.},
  title        = {Molecular weight and end group effects on the thermo-responsive property of oligomeric N-isopropylacrylamide},
  year         = {2010},
  month        = jun,
  pages        = {618--621},
  volume       = {18},
  creationdate = {2024-11-29T09:05:51},
  doi          = {https://doi.org/10.1007/s13233-010-0609-7},
  keywords     = {pNIPAM,NIPAM,oligomer,molecular weight,end group,chain length dependence,synthesis},
  url          = {https://doi.org/10.1007/s13233-010-0609-7},
}

@Article{GarciaPenas2019,
  author       = {García-Peñas, Alberto and Biswas, Chandra Sekhar and Liang, Weijun and Wang, Yu and Stadler, Florian J.},
  journal      = {Macromolecular Chemistry and Physics},
  title        = {Lower Critical Solution Temperature in Poly(N-Isopropylacrylamide): Comparison of Detection Methods and Molar Mass Distribution Influence},
  year         = {2019},
  number       = {13},
  pages        = {1900129},
  volume       = {220},
  abstract     = {Poly(N-Isopropylacrylamide) has a broad potential range of biomedical applications owing to its lower critical solution temperature (LCST). This work tries to elucidate the real influence of several parameters on LCST by comparing homopolymers prepared by free radical polymerization and reversible addition–fragmentation chain transfer (RAFT) polymerization using conventional calorimetry, turbidimetry, and rheology as well as how three different methods can be used to detect the LCST. These methods are compared to gain a deeper understanding of the underlying processes and how they are related to molar mass and synthesis methods. The diverse interactions associated with the LCST transitions are more sensitive depending on the ratio defined between polymerization degrees and end-group effects. Thus, the selection of a high sensitive method for LCST detection depends on the molecular features defined from the homopolymer. In addition, this work shows also the importance of the RAFT agent selected for the synthesis, which can modify substantially the LCST in comparison with other methods reported where the use of chemicals, complex processes, and costs considerably increase.},
  creationdate = {2024-11-29T09:52:58},
  doi          = {https://doi.org/10.1002/macp.201900129},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/macp.201900129},
  file         = {:GarciaPenas2019 - Lower Critical Solution Temperature in Poly(N Isopropylacrylamide)_ Comparison of Detection Methods and Molar Mass Distribution Influence.pdf:PDF;:LowerCriticalSolutionTemperatureInPolyNIsopropylacrylamide-ComparisonOfDetectionMethodsAndMolarMassDistributionInfluence_SI_GarciaPenasEtAl_MacromolChemPhys2019.pdf:PDF},
  keywords     = {injectability,metallohydrogels,multistimulus-responsiveness,self-healing,supramolecular chemistry,pNIPAM,molecular weight,chain length dependence,synthesis,LCST,RAFT,DSC,turbidimetry,viscosity,rheology,end groups},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/macp.201900129},
}









@Article{Meewes1991,
  author       = {Meewes, M. and Ricka, J. and De Silva, M. and Nyffenegger, R. and Binkert, T.},
  journal      = {Macromolecules},
  title        = {Coil-globule transition of poly(N-isopropylacrylamide): a study of surfactant effects by light scattering},
  year         = {1991},
  number       = {21},
  pages        = {5811-5816},
  volume       = {24},
  creationdate = {2024-11-29T09:57:37},
  doi          = {10.1021/ma00021a014},
  eprint       = {https://doi.org/10.1021/ma00021a014},
  file         = {:Meewes1991 - Coil Globule Transition of Poly(N Isopropylacrylamide)_ a Study of Surfactant Effects by Light Scattering.pdf:PDF},
  keywords     = {pNIPAM,light scattering,surfactant,SDS},
  url          = {https://doi.org/10.1021/ma00021a014},
}

@Article{Motornov2010,
  author       = {Mikhail Motornov and Yuri Roiter and Ihor Tokarev and Sergiy Minko},
  journal      = {Progress in Polymer Science},
  title        = {Stimuli-responsive nanoparticles, nanogels and capsules for integrated multifunctional intelligent systems},
  year         = {2010},
  issn         = {0079-6700},
  note         = {Special Issue on Stimuli-Responsive Materials},
  number       = {1},
  pages        = {174-211},
  volume       = {35},
  abstract     = {In this review we provide an analysis of recent literature reports on the synthesis and applications of stimuli-responsive polymeric and hybrid nanostructured particles in a range of sizes from nanometers to a few micrometers: nano- and microgels, core–shell structures, polymerosomes, block-copolymer micelles, and more complex architectures. The review consists of two major parts: synthesis and applications of nanoparticles in colloidal dispersions, thin films, delivery devices and sensors. We also broadly discuss potential directions for further developments of this research area.},
  creationdate = {2024-11-29T13:36:05},
  doi          = {https://doi.org/10.1016/j.progpolymsci.2009.10.004},
  file         = {:Motornov2010 - Stimuli Responsive Nanoparticles, Nanogels and Capsules for Integrated Multifunctional Intelligent Systems.pdf:PDF},
  keywords     = {Responsive polymers, Colloidal dispersions, Self-healing materials, Self assembly, Drug delivery, Sensors, review, synthesis, pNIPAM, stimuli-responsive, application-focused, application focused},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079670009001026},
}









@Article{Maeda2003,
  author       = {Maeda, Yasushi and Yamamoto, Hiroki and Ikeda, Isao},
  journal      = {Macromolecules},
  title        = {Phase Separation of Aqueous Solutions of Poly(N-isopropylacrylamide) Investigated by Confocal Raman Microscopy},
  year         = {2003},
  number       = {14},
  pages        = {5055-5057},
  volume       = {36},
  abstract     = {[...] In this study, we use confocalRaman microscopy to investigate phase separation ofaqueous solutions of [poly(N-isopropylacrylamide)] and poly(N,N-diethylacrylamide) (PdEA). Changes in the distribution of thepolymers and additives in the aqueous two-phase sys-tems are discussed.},
  creationdate = {2024-12-02T08:24:31},
  doi          = {10.1021/ma034311g},
  eprint       = {https://doi.org/10.1021/ma034311g},
  file         = {:Maeda2003 - Phase Separation of Aqueous Solutions of Poly(N Isopropylacrylamide) Investigated by Confocal Raman Microscopy.pdf:PDF},
  keywords     = {pNIPAM,light scattering,raman},
  url          = {https://doi.org/10.1021/ma034311g},
}









@Article{Shibayama1996,
  author       = {Shibayama, Mitsuhiro and Suetoh, Yohsuke and Nomura, Shunji},
  journal      = {Macromolecules},
  title        = {Structure Relaxation of Hydrophobically Aggregated Poly(N-isopropylacrylamide) in Water},
  year         = {1996},
  number       = {21},
  pages        = {6966-6968},
  volume       = {29},
  creationdate = {2024-12-02T09:50:39},
  doi          = {10.1021/ma960866i},
  eprint       = {https://doi.org/10.1021/ma960866i},
  file         = {:Shibayama1996 - Structure Relaxation of Hydrophobically Aggregated Poly(N Isopropylacrylamide) in Water.pdf:PDF},
  keywords     = {pNIPAM,DSC,ageing,remixing,linear,microgel},
  url          = {https://doi.org/10.1021/ma960866i},
}

@Book{Griffiths1999,
  author       = {Griffiths, David J.},
  editor       = {Alison Reeves},
  publisher    = {Prentice-Hall},
  title        = {Introduction to Electrodynamics},
  year         = {1999},
  edition      = {3},
  isbn         = {0-13-805326-X},
  creationdate = {2024-12-02T16:46:32},
  file         = {:Griffiths1999 - Introduction to Electrodynamics.pdf:PDF},
  keywords     = {book,theory},
  place        = {Cambridge},
}

@Article{Smith1992,
  author       = {Smith, Scott A. and Palke, William E. and Gerig, J. T.},
  journal      = {Concepts in Magnetic Resonance},
  title        = {The Hamiltonians of NMR. part I},
  year         = {1992},
  number       = {2},
  pages        = {107-144},
  volume       = {4},
  abstract     = {Nuclear magnetic resonance spectroscopy has evolved in complexity to the extent that it is often useful to carry out computer simulations of experiments as a way to refine experimental conditions, to maximize usable information, or to interpret results reliably. The starting point for such simulations is an appropriate quantum mechanical formulation. This article presents many of the physical ideas that are important in high-resolution NMR spectroscopy and then develops expressions for the contribution of each of these to the Hamiltonian for the system under consideration. The Hamiltonians for the Zeeman interaction, scalar coupling, and the chemical shielding effect are discussed with the aim of explaining the quantum mechanics of NMR in a manner understandable to a nontheoretician. Consequently, much of the discussion is explicit and includes points skimmed over in other presentations in the literature.},
  creationdate = {2024-10-25T18:59:04},
  doi          = {https://doi.org/10.1002/cmr.1820040202},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.1820040202},
  file         = {:Smith1992 - The Hamiltonians of NMR. Part I.pdf:PDF},
  keywords     = {NMR,theory},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.1820040202},
}

@Article{Smith1992a,
  author       = {Smith, Scott A. and Palke, William E. and Gerig, J. T.},
  journal      = {Concepts in Magnetic Resonance},
  title        = {The Hamiltonians of NMR. Part II},
  year         = {1992},
  number       = {3},
  pages        = {181-204},
  volume       = {4},
  abstract     = {The derivation of various components of the Hamiltonian operator used to describe high-resolution NMR experiments is presented, with an emphasis on time-dependent interactions that can produce relaxation of a spin system (dipole-dipole, chemical shift anisotropy) or that lead to excitation of a spin system (radio-frequency field).},
  creationdate = {2024-10-25T19:00:55},
  doi          = {https://doi.org/10.1002/cmr.1820040302},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.1820040302},
  file         = {:Smith1992a - The Hamiltonians of NMR. Part II.pdf:PDF},
  keywords     = {NMR,theory},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.1820040302},
}

@Article{Smith1993,
  author       = {Smith, Scott A. and Palke, William E. and Gerig, J. T.},
  journal      = {Concepts in Magnetic Resonance},
  title        = {The Hamiltonians of NMR. Part III},
  year         = {1993},
  number       = {2},
  pages        = {151-177},
  volume       = {5},
  abstract     = {Building on our previous discussions of the Hamiltonian operators that are important in the description of high-resolution NMR experiments, we use here the same symbolism and approach to develop formulations for time-dependent operators. These considerations lead to discussions of free precession and the influence of applied radio-frequency fields. As with the previous articles, the presentations are explicit, the mathematical operations are explained in detail, and all assumptions made are indicated.},
  creationdate = {2024-10-25T19:01:55},
  doi          = {https://doi.org/10.1002/cmr.1820050204},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.1820050204},
  file         = {:Smith1993 - The Hamiltonians of NMR. Part III.pdf:PDF},
  keywords     = {NMR,theory},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.1820050204},
}

@Article{Smith1994,
  author       = {Smith, Scott A. and Palke, William E. and Gerig, J. T.},
  journal      = {Concepts in Magnetic Resonance},
  title        = {The hamiltonians of NMR. Part IV: NMR relaxation},
  year         = {1994},
  number       = {2},
  pages        = {137-162},
  volume       = {6},
  abstract     = {Using the methods presented in our previous discussions of the Hamiltonians of NMR, we describe the processes that lead to relaxation of spin systems. The same nomenclature and methods of Parts I, II, and III have been used to develop a formulation of time-dependent operators.},
  creationdate = {2024-10-25T19:03:21},
  doi          = {https://doi.org/10.1002/cmr.1820060205},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.1820060205},
  file         = {:Smith1994 - The Hamiltonians of NMR. Part IV_ NMR Relaxation.pdf:PDF},
  keywords     = {NMR,theory},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.1820060205},
}

@Article{Suleimenov2017,
  author       = {Suleimenov, I. E. and Guven, O. and Mun, G. A. and Uzun, Ch. and Gabrielyan, O. A. and Kabdushev, Sh. B. and Agibaeva, L. and Nurtazin, A.},
  journal      = {Eurasian Chemico-Technological Journal},
  title        = {Hysteresis Effects During the Phase Transition in Solutions of Temperature Sensitive Polymers},
  year         = {2017},
  month        = jan,
  number       = {1},
  pages        = {41–46},
  volume       = {19},
  abstract     = {It is demonstrated, for the first time, that well-known phase transitions induced by changes in temperature in solutions of polymers containing both hydrophilic and hydrophobic functional groups could be followed by noticeable hysteresis effects. A well-known phase transitions accompanied by a sharp change in fluid properties, in particular its optical density can be induced by many external influences, including temperature changes occurring in the solutions of polymers containing both hydrophilic and hydrophobic functional groups. Since intensification subsequent hydrophobic interactions, leading to loss of solubility of the polymer molecules, resulting, in particular, a significant increase in the turbidity of the medium and are accompanied by a pronounced hysteresis phenomena. Hysteresis phenomena in the processes of molecular-scale play an important theoretical and practical interest in linkage with the development of advanced nano-level technology. In particular, the issue of the development of molecular &amp;quot;trigger&amp;quot; switches, and other analog electronic systems, implemented on submolecular level was actively discussed. In fact, under the same physical conditions of the environment of macromolecules system can be in two different states, which resolves the issue of programming such molecules. State of these polymers depends on their way of formation and thermodynamic variables. Observed effect could be utilized directly for information recording into the structure on the basis of stimulus-sensitive macromolecular chains. In fact, it is a first step towards creating memory of quasi-biological elements.},
  creationdate = {2024-11-26T10:47:28},
  doi          = {10.18321/ectj501},
  file         = {:Suleimenov2017 - Hysteresis Effects during the Phase Transition in Solutions of Temperature Sensitive Polymers.pdf:PDF},
  keywords     = {thermoresponsive,hysteresis,pNIPAM},
  url          = {https://ect-journal.kz/index.php/ectj/article/view/130},
}

@Article{Hughes2016,
  author       = {Colan E. Hughes and Kenneth D.M. Harris},
  journal      = {Solid State Nuclear Magnetic Resonance},
  title        = {Calculation of solid-state NMR lineshapes using contour analysis},
  year         = {2016},
  issn         = {0926-2040},
  pages        = {7-13},
  volume       = {80},
  abstract     = {Two new methods for calculating lineshapes in solid-state NMR spectra are described. The first method, which we refer to as semi-analytical, allows the rapid calculation of quadrupolar central-transition lineshapes in both static and magic-angle spinning cases. The second method, which is fully numerical, allows the calculation of lineshapes resulting from any combination of interactions, including quadrupolar, dipolar and chemical shift anisotropy, and is not restricted to cases in which the principal axis systems for the different interactions are aligned. Both methods are derived from consideration of the contour lines on a plot of the resonance frequency against the Euler angles, allowing the intensity of the lineshape to be calculated at each frequency. Consequently, highly accurate lineshapes can be calculated more rapidly than previously possible, since only orientations contributing to each specific frequency are considered. For our semi-analytical method, the intensity of each point in the lineshape can be directly calculated in tens of milliseconds on a standard PC. In contrast, established methods can take several hours to calculate the same lineshape.},
  creationdate = {2024-12-07T15:13:51},
  doi          = {https://doi.org/10.1016/j.ssnmr.2016.10.002},
  file         = {:Hughes2016 - Calculation of Solid State NMR Lineshapes Using Contour Analysis.pdf:PDF},
  keywords     = {NMR,lineshape,pake},
  url          = {https://www.sciencedirect.com/science/article/pii/S0926204016300613},
}

@Article{Jerschow2005,
  author       = {Alexej Jerschow},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {From nuclear structure to the quadrupolar NMR interaction and high-resolution spectroscopy},
  year         = {2005},
  issn         = {0079-6565},
  number       = {1},
  pages        = {63-78},
  volume       = {46},
  creationdate = {2024-12-07T15:15:13},
  doi          = {https://doi.org/10.1016/j.pnmrs.2004.12.001},
  file         = {:Jerschow2005 - From Nuclear Structure to the Quadrupolar NMR Interaction and High Resolution Spectroscopy.pdf:PDF},
  keywords     = {Nuclear structure and spin,Quadrupolar coupling,Nuclear quadrupole moment,Electric field gradient,Solid-state NMR,MQMAS,STMAS,DAS,DOR,NQR,NMR,lineshape,Pake},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079656504000615},
}

@Article{Kruk2011,
  author       = {Kruk, D. and Earle, K. A. and Mielczarek, A. and Kubica, A. and Milewska, A. and Moscicki, J.},
  journal      = {The Journal of Chemical Physics},
  title        = {Nuclear quadrupole resonance lineshape analysis for different motional models: Stochastic Liouville approach},
  year         = {2011},
  issn         = {0021-9606},
  month        = {12},
  number       = {22},
  pages        = {224511},
  volume       = {135},
  abstract     = {A general theory of lineshapes in nuclear quadrupole resonance (NQR), based on the stochastic Liouville equation, is presented. The description is valid for arbitrary motional conditions (particularly beyond the valid range of perturbation approaches) and interaction strengths. It can be applied to the computation of NQR spectra for any spin quantum number and for any applied magnetic field. The treatment presented here is an adaptation of the “Swedish slow motion theory,” [T. Nilsson and J. Kowalewski, J. Magn. Reson. 146, 345 (2000)10.1006/jmre.2000.2125] originally formulated for paramagnetic systems, to NQR spectral analysis. The description is formulated for simple (Brownian) diffusion, free diffusion, and jump diffusion models. The two latter models account for molecular cooperativity effects in dense systems (such as liquids of high viscosity or molecular glasses). The sensitivity of NQR slow motion spectra to the mechanism of the motional processes modulating the nuclear quadrupole interaction is discussed.},
  creationdate = {2024-12-07T15:22:56},
  doi          = {10.1063/1.3664783},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.3664783/15445917/224511\_1\_online.pdf},
  file         = {:Kruk2011 - Nuclear Quadrupole Resonance Lineshape Analysis for Different Motional Models_ Stochastic Liouville Approach.pdf:PDF},
  keywords     = {NMR,lineshape,Pake,anisotropic motion},
  url          = {https://doi.org/10.1063/1.3664783},
}

@Article{Pake1948,
  author       = {Pake, G. E.},
  journal      = {The Journal of Chemical Physics},
  title        = {Nuclear Resonance Absorption in Hydrated Crystals: Fine Structure of the Proton Line},
  year         = {1948},
  issn         = {0021-9606},
  month        = {04},
  number       = {4},
  pages        = {327-336},
  volume       = {16},
  abstract     = {Fine structure has been observed in the nuclear paramagnetic resonance absorption line for protons in crystalline hydrates. The magnetic field of 6820 gauss was provided by a permanent magnet, the inherent stability of which facilitated detailed study of line shape. Measurements on a single crystal of CaSO4·2H2O show a splitting into four component lines with maximum separation varying from zero to 22 gauss, depending upon the direction of the externally applied magnetic field in the crystal. Both the number of component lines and the dependence of their spacing on field direction are calculated by treating the magnetic dipole‐dipole interaction as a perturbation of the proton two‐spin system within the water molecule; the effect of the more distant protons, neglected in this calculation, gives a finite width to the component lines. Variation of the splitting with field direction determines the orientation of the line joining protons in the water molecule, which is found to be consistent with positions ascribed to hydrogen nuclei in the lattice through simple considerations of chemical bonding. The distance between protons in the water molecule is measured by the splitting to be 1.58A for CaSO4·2H2O; if one assumes an H–O–H bond angle of 108°, the O–H distance is 0.98A. Powdered hydrates show a characteristic fine structure arising from isotropic distribution in solid angle of single crystal granules. This type of fine structure determines the proton‐proton distance somewhat less accurately than does the single crystal experiment.},
  creationdate = {2024-12-07T15:26:46},
  doi          = {10.1063/1.1746878},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/16/4/327/18795002/327\_1\_online.pdf},
  file         = {:Pake1948 - Nuclear Resonance Absorption in Hydrated Crystals_ Fine Structure of the Proton Line.pdf:PDF},
  keywords     = {NMR,lineshape,Pake},
  url          = {https://doi.org/10.1063/1.1746878},
}

@PhdThesis{Steinruecken2024,
  author       = {Elisa Steinr{\"u}cken},
  school       = {Technische Universit{\"a}t Darmstadt},
  title        = {Dynamik von Wasser in nanopor{\"o}sen Festk{\"o}rpern und nanostrukturierten Fl{\"u}ssigkeitsmischungen},
  year         = {2024},
  address      = {Darmstadt},
  month        = jun,
  abstract     = {Trotz seiner einfachen chemischen Struktur weist Wasser eine Vielzahl an Anomalien auf, deren Ursprung bis heute noch nicht vollst{\"a}ndig verstanden ist. Zur Erkl{\"a}rung der Anomalien wurde vorgeschlagen, dass Wasser einen zweiten kritischen Punkt besitzt, der im stark unterk{\"u}hlten Temperaturbereich liegt und die Phasengrenzlinie eines Phasen{\"u}bergangs zweier fl{\"u}ssiger Wasserphasen unterschiedlicher Dichte terminiert. Experimentell unterbindet allerdings Kristallisation die Untersuchung von unterk{\"u}hltem Wasser im Bereich zwischen 150 K und 230 K, dem sogenannten no-man's land, in welchem der postulierte zweite kritische Punkt verortet wurde. Um diesen Bereich zug{\"a}nglich zu machen, kann Wasser in stark eingeschr{\"a}nkten Geometrien, sogenannten Confinements, oder in Mischungen betrachtet werden, in welchen die Kristallisation teilweise oder vollst{\"a}ndig unterdr{\"u}ckt werden kann. Derartige Systeme sind jedoch auch aufgrund ihrer enormen Bedeutung in Natur und Technologie von gro{\ss}em Interesse. Um m{\"o}gliche Einfl{\"u}sse von verschiedenen Confinements zu untersuchen, wird in dieser Arbeit Wasser zum einen in verschiedenen Silikaconfinements und zum anderen in Mischungen mit ionischen Fl{\"u}ssigkeiten studiert. F{\"u}r die umfassende Charakterisierung der langreichweitigen Translations- und lokalen Rotationsdynamik in einem gro{\ss}en dynamischen Bereich kommen verschiedene Kernspinresonanz-Methoden sowie dielektrische Spektroskopie zum Einsatz. Dabei k{\"o}nnen durch die Isotopensensitivit{\"a}t der Kernspinresonanz einzelne Komponenten getrennt voneinander untersucht werden. In den Untersuchungen werden insbesondere die Gr{\"o}{\ss}e von hartem Confinement sowie die Beschaffenheit seiner inneren Oberfl{\"a}che systematisch variiert und es werden Ergebnisse f{\"u}r harte und weiche Confinements gegen{\"u}bergestellt. Die vorliegende Arbeit konzentriert sich vor allem auf eine Analyse der temperaturabh{\"a}ngigen Dynamik von Wasser, die als Sonde f{\"u}r strukturelle Ver{\"a}nderungen in Folge eines Fl{\"u}ssig-Fl{\"u}ssig-Phasen{\"u}bergangs angesehen wird. 	 In den kleinsten untersuchten Silikaporen mit einem Durchmesser von 2,1 nm wird die Kristallisation von Wasser vollst{\"a}ndig unterdr{\"u}ckt. So kann die Dynamik der Fl{\"u}ssigkeit von Raumtemperatur bis zum Glas{\"u}bergang ermittelt werden. Ein breiter {\"U}bergangsbereich trennt die Nicht-Arrhenius-Temperaturabh{\"a}ngigkeit der Korrelationszeiten bei T{\ensuremath{>}}215 K von einer Arrhenius-Temperaturabh{\"a}ngigkeit bei T{\ensuremath{<}}160 K. Der kontinuierliche {\"U}bergang in der Temperaturabh{\"a}ngigkeit wird begleitet von einem graduellen Wechsel von einer asymmetrischen Hochtemperaturform der dynamischen Suszeptibilit{\"a}t zu einer symmetrischen Tieftemperaturform. Im Tieftemperaturbereich zeigt sich eine Aktivierungsenergie von 0,5 eV und die Reorientierung des Wassers erfolgt in quasi-isotropen Gro{\ss}winkelspr{\"u}ngen. Diese Ergebnisse k{\"o}nnen durch einen {\"U}bergang von einer bulkartigen Dynamik zu einer grenzfl{\"a}chenbeeinflussten, nicht-kooperativen Relaxation erkl{\"a}rt werden. Somit bestehen Zweifel, dass die Ergebnisse eindeutige Hinweise auf die Eigenschaften von Wasser im Bulk liefern. In gr{\"o}{\ss}eren Silikaporen mit Durchmessern von 2,8 nm bzw. 5,4 nm kommt es, wie in vielen biologisch, geologisch und technologisch relevanten F{\"a}llen, zu einer partiellen Kristallisation, die zur Koexistenz einer fl{\"u}ssigen Wasserschicht an der Porenwand und einer Eisphase in der Porenmitte f{\"u}hrt. Die Dynamik der fl{\"u}ssigen Randschicht wird dabei stark durch die Wechselwirkung mit der statischen Energielandschaft der Silika- und Eisgrenzfl{\"a}chen ver{\"a}ndert, was sich insbesondere in einer ausgepr{\"a}gten dynamischen Heterogenit{\"a}t zeigt. Die Dynamik des internen Eises {\"a}hnelt dem Verhalten, das f{\"u}r Eis in verschiedenen anderen Confinements und Mischungen gefunden wurde. Dies legt die Schlussfolgerung nahe, dass sich in all diesen F{\"a}llen eine Eisphase mit {\"a}hnlicher Struktur und Dynamik bildet, wobei in der Literatur Kristalle mit hexagonal-kubischer Stapelfehlordnung diskutiert werden. Um die Abh{\"a}ngigkeit der Wasserdynamik von der Oberfl{\"a}chenbeschaffenheit der Silikaconfinements zu untersuchen, werden mit basischem Lysin, neutralem Alanin oder saurer Glutamins{\"a}ure funktionalisierte Silikaporen studiert. W{\"a}hrend der qualitative Verlauf der Korrelationszeiten des Wassers dem in nativem Silikaconfinement {\"a}hnelt, kommt es zu erheblichen Unterschieden in den Absolutwerten der Korrelationszeiten durch die Aminos{\"a}urenmodifikationen, die bis zu zwei Gr{\"o}{\ss}enordnungen an Verlangsamung umfassen. Dabei ist die Reorientierungsdynamik der Wasserrandschicht am st{\"a}rksten verlangsamt f{\"u}r die Lysin-Funktionalisierung, gefolgt von Alanin und Glutamins{\"a}ure. Diese Beobachtung impliziert f{\"u}r biologische und biomimetische Systeme, dass die Mobilit{\"a}t von Wasser entlang von Proteinoberfl{\"a}chen stark variiert.  Um unterk{\"u}hltes Wasser zudem in einem weichen Confinement zu untersuchen, wird Wasser in Mischungen mit ionischen Fl{\"u}ssigkeiten betrachtet, bei denen sich in Abh{\"a}ngigkeit der Konzentration nanoskalige Wassercluster ausbilden. Bereits reine ionische Fl{\"u}ssigkeiten weisen bei geeigneter Zusammensetzung polare und unpolare Dom{\"a}nen auf, f{\"u}r welche anhand von gezielter Variation des Ausma{\ss}es dieser strukturellen Heterogenit{\"a}ten gezeigt wird, dass sie zu einer Entkopplung von Rotations- und Translationsdynamik der Kationen f{\"u}hren. Dagegen tritt im Fall der Wassercluster in den Mischungen unter Variation der Wasserkonzentration keine dynamische Signatur dieser strukturellen Heterogenit{\"a}ten auf. Anders als in den harten Confinements wird f{\"u}r die unterk{\"u}hlte Wasserdynamik in den ionischen Fl{\"u}ssigkeiten im untersuchten Temperaturbereich bis zu 200 K kein dynamischer {\"U}bergang in der Temperaturabh{\"a}ngigkeit beobachtet. Dies ist vermutlich der Kopplung der Wasserdynamik an die mobile Matrix geschuldet, was den starken Einfluss der H{\"a}rte des Confinements zeigt.},
  creationdate = {2024-12-07T17:18:35},
  doi          = {https://doi.org/10.26083/tuprints-00027515},
  language     = {de},
  pages        = {ix, 216 Seiten},
  url          = {http://tuprints.ulb.tu-darmstadt.de/27515/},
}






@Article{Ba2011,
  author       = {Ba, Yong and Ripmeester, John A. and Ratcliffe, Christopher I.},
  journal      = {Canadian Journal of Chemistry},
  title        = {Water molecular reorientation in ice and tetrahydrofuran clathrate hydrate from lineshape analysis of 17O spin-echo NMR spectra},
  year         = {2011},
  number       = {9},
  pages        = {1055-1064},
  volume       = {89},
  abstract     = {Lineshape analysis of 17O spin-echo NMR spectra has been used to study water molecular reorientations in ice-Ih and THF Structure II clathrate hydrate. The kinetics was determined by the changes of the lineshapes of the 17O central transitions at different temperatures. A model involving 12 orientations and 4-step jumps of water molecular orientations was proposed. Semi-classical exchange formalism was employed to simulate the lineshape of the central transitions of the 17O nuclei. Lineshape analysis gave the quadrupolar coupling constant CQ = 6.43 MHz and the asymmetry parameter η = 0.935, for both ice-Ih and THF gas hydrate. The theoretical lineshape simulations resulted in activation energies of water molecular reorientations Ea = 55.2 ± 2.1 kJ mol–1 and Ea = 30.5 ± 0.8 kJ mol–1 for ice-Ih and THF hydrate, respectively. The range of dynamic rates in THF clathrate hydrate is such that before melting, a pseudo-isotropic lineshape is observed that retains a second-order quadrupolar shift. The water reorientation process is discussed in light of recent results on Bjerrum defect injection obtained from molecular dynamics simulation and structural studies.},
  comment      = {no access},
  creationdate = {2024-12-07T17:22:57},
  doi          = {10.1139/v11-040},
  eprint       = {https://doi.org/10.1139/v11-040},
  keywords     = {17o,qcc,quadrupole coupling constant,water,THF},
  url          = {https://doi.org/10.1139/v11-040},
}

@Article{Nicholas2010,
  author       = {Matthew P. Nicholas and Ertan Eryilmaz and Fabien Ferrage and David Cowburn and Ranajeet Ghose},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {Nuclear spin relaxation in isotropic and anisotropic media},
  year         = {2010},
  issn         = {0079-6565},
  number       = {2},
  pages        = {111-158},
  volume       = {57},
  creationdate = {2024-12-08T10:55:10},
  doi          = {https://doi.org/10.1016/j.pnmrs.2010.04.003},
  file         = {:Nicholas2010 - Nuclear Spin Relaxation in Isotropic and Anisotropic Media.pdf:PDF},
  keywords     = {Spin relaxation,Rotational diffusion,Stochastic processes,Chemical shift,Dipolar coupling,NMR,theory,density matrix,anisotropic,isotropic,review},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079656510000476},
}

@Article{Hubbard1969,
  author       = {Hubbard, Paul S.},
  journal      = {Phys. Rev.},
  title        = {Some Properties of Correlation Functions of Irreducible Tensor Operators},
  year         = {1969},
  month        = {Apr},
  pages        = {319--326},
  volume       = {180},
  creationdate = {2024-12-08T11:09:24},
  doi          = {10.1103/PhysRev.180.319},
  file         = {:Hubbard1969 - Some Properties of Correlation Functions of Irreducible Tensor Operators.pdf:PDF},
  issue        = {1},
  keywords     = {NMR,theory,spherical tensor operators,spectral density},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRev.180.319},
}

@Article{Wakisaka2006,
  author       = {Akihiro Wakisaka and Kazuo Matsuura},
  journal      = {Journal of Molecular Liquids},
  title        = {Microheterogeneity of ethanol–water binary mixtures observed at the cluster level},
  year         = {2006},
  issn         = {0167-7322},
  note         = {New Highlights of Solution Chemistry: Diffraction, Simulation and Theoretical Studies},
  number       = {1},
  pages        = {25-32},
  volume       = {129},
  abstract     = {The microscopic structures in ethanol–water binary mixtures were examined by analyzing the mass spectra of clusters generated through fragmentation of liquid droplets. From the effects of temperature and mixing ratios on the cluster structures, we have demonstrated that the ethanol–water binary mixtures have microscopic phase separation at the cluster level in wide mixing ratios: 10 vol.%<[EtOH]<90 vol.%. In this region, ethanol-rich clusters whose molecular composition is independent of the mixing ratio were observed at lower temperatures, and the ethanol-rich clusters interacted with water molecules with increasing temperature. Furthermore, we would like to present the mechanism for the formation of ethanol-rich clusters, induced by the contact with water molecules.},
  creationdate = {2024-12-08T16:01:45},
  doi          = {https://doi.org/10.1016/j.molliq.2006.08.010},
  file         = {:Wakisaka2006 - Microheterogeneity of Ethanol–water Binary Mixtures Observed at the Cluster Level.pdf:PDF},
  keywords     = {Microheterogeneity,Cluster,Phase separation,Ethanol,Mixture,aqueous alcohol,aqueous ethanol},
  url          = {https://www.sciencedirect.com/science/article/pii/S0167732206001838},
}









@Article{Shi2023,
  author       = {Shi, Yi and He, Xuehao},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Effect of Tacticity Sequence of the Poly(N-isopropyl\-acrylamide) Oligomer on Phase Transition Behavior in Aqueous Solution},
  year         = {2023},
  note         = {PMID: 37756642},
  number       = {40},
  pages        = {8660-8668},
  volume       = {127},
  abstract     = {The tacticity of poly(N-isopropylacrylamide) (PNIPAM) has a strong impact on the lower critical solution temperature (LCST) in aqueous solution. The sequence of meso diads (m) and racemo diads (r) further contributes to such an effect. In this work, the phase transition behaviors of poly(N-isopropylacrylamide) pentamers with four kinds of sequences, i.e., rrmm, rmmr, mrrm, and rmrm, in water were studied applying replica exchange molecular dynamics with a modified OPLS/AA force field. The difference in local component concentration in the system was used as an order parameter to quantitatively describe the phase separation extent. It was found that the phase separation degree of rrmm and rmmr is higher than that of mrrm and rmrm at the same temperature. The LCSTs of rrmm and rmmr are lower than those of mrrm and rmrm. The radial distribution function and hydrogen bond analysis revealed that the average values of hydrogen bonds between pentamers for rrmm and rmmr are greater than those of mrrm and rmrm, whereas the average values of hydrogen bonds between pentamers and water for rrmm and rmmr are less than those of mrrm and rmrm. It was demonstrated that the isotactic triad (mm) plays an important role in the thermosensitive behaviors of the PNIPAM pentamer. The increase of isotactic triad (mm) content in the PNIPAM chain promotes the formation of intermolecular hydrogen bonds between amide and amide and leads to a higher aggregation of the pentamer with the sequence of rrmm or rmmr. Finally, the effect of the isotactic triad was qualitatively explained with the mean-field theory.},
  creationdate = {2024-12-08T17:03:16},
  doi          = {10.1021/acs.jpcb.3c03765},
  eprint       = {https://doi.org/10.1021/acs.jpcb.3c03765},
  file         = {:Shi2023 - Effect of Tacticity Sequence of the Poly(N Isopropylacrylamide) Oligomer on Phase Transition Behavior in Aqueous Solution.pdf:PDF;:EffectOfTacticitySequenceOfThePolyNIsopropylacrylamideOligomerOnPhaseTransitionBehaviorInAqueousSolution_ShiEtAl_JPC2023_SI.pdf:PDF},
  keywords     = {pNIPAM,oligomer,chain length dependence,tacticity,simulation},
  url          = {https://doi.org/10.1021/acs.jpcb.3c03765},
}

@Article{Ashbrook2004,
  author       = {Sharon E. Ashbrook and Stephen Wimperis},
  journal      = {Progress in Nuclear Magnetic Resonance Spectroscopy},
  title        = {High-resolution NMR of quadrupolar nuclei in solids: the satellite-transition magic angle spinning (STMAS) experiment},
  year         = {2004},
  issn         = {0079-6565},
  number       = {1},
  pages        = {53-108},
  volume       = {45},
  creationdate = {2024-12-16T16:41:20},
  doi          = {https://doi.org/10.1016/j.pnmrs.2004.04.002},
  file         = {:Ashbrook2004 - High Resolution NMR of Quadrupolar Nuclei in Solids_ the Satellite Transition Magic Angle Spinning (STMAS) Experiment.pdf:PDF},
  keywords     = {NMR,STMAS,MQMAS,Satellite transition,Multiple quantum,Quadrupolar nuclei,Magic angle spinning,theory},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079656504000214},
}

@Book{Ernst1990,
  author       = {Ernst, Richard R and Bodenhausen, Geoffrey and Wokaun, Alexander},
  publisher    = {Oxford University Press},
  title        = {Principles of Nuclear Magnetic Resonance in One and Two Dimensions},
  year         = {1990},
  isbn         = {0-19-855647-0},
  abstract     = {Nuclear magnetic resonance spectroscopy is one of the most powerful and versatile techniques now available for the study of molecular structure and reaction mechanisms. Written by recognised experts in the field, this classic account of modern NMR spectroscopy was heralded on its first publication in 1987 as "the lasting text of its age" Nature. Now available in paperback, it provides a thoroughly comprehensive review of modern NMR techniques and the underlying principles. It describes the study of solutions and solids using one- and two-dimensional spectroscpy, providing both a solid theoretical foundation and a description of practical procedures. The material is presented in an intuitive manner within a rigorous mathematical framework, and is extensively illustrated throughout. This important work was written at the ETH in Zurich, one of the world's leading institutions in advanced NMR methods, which has played a key role in the development of Fourier spectroscopy, two-dimensional spectroscopy, and Fourier-transform NMR imaging. Available in paperback for the first time, the book provides the definitive account of the field, and is without question "a must.....for every self-respecting NMR spectroscopist" Journal of Magnetic Resonance.},
  comment      = {in AG library},
  creationdate = {2024-12-16T16:43:49},
  doi          = {10.1093/oso/9780198556473.001.0001},
  keywords     = {book,NMR,theory},
  url          = {https://doi.org/10.1093/oso/9780198556473.001.0001},
}









@Article{Tavagnacco2022,
  author       = {Tavagnacco, Letizia and Zaccarelli, Emanuela and Chiessi, Ester},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Modeling Solution Behavior of Poly(N-isopropylacrylamide): A Comparison between Water Models},
  year         = {2022},
  note         = {PMID: 35491838},
  number       = {20},
  pages        = {3778-3788},
  volume       = {126},
  abstract     = {Water is known to play a fundamental role in determining the structure and functionality of macromolecules. The same crucial contribution is also found in the in silico description of polymer aqueous solutions. In this work, we exploit the widely investigated synthetic polymer poly(N-isopropylacrylamide) (PNIPAM) to understand the effect of the adopted water model on its solution behavior and to refine the computational setup. By means of atomistic molecular dynamics simulations, we perform a comparative study of PNIPAM aqueous solution using two advanced water models: TIP4P/2005 and TIP4P/Ice. The conformation and hydration features of an atactic 30-mer at infinite dilution are probed at a range of temperature and pressure suitable to detect the coil-to-globule transition and to map the P–T phase diagram. Although both water models can reproduce the temperature-induced coil-to-globule transition at atmospheric pressure and the polymer hydration enhancement that occurs with increasing pressure, the PNIPAM–TIP4P/Ice solution shows better agreement with experimental findings. This result can be attributed to a stronger interaction of TIP4P/Ice water with both hydrophilic and hydrophobic groups of PNIPAM, as well as to a less favorable contribution of the solvent entropy to the coil-to-globule transition.},
  creationdate = {2024-12-20T10:35:27},
  doi          = {10.1021/acs.jpcb.2c00637},
  eprint       = {https://doi.org/10.1021/acs.jpcb.2c00637},
  file         = {:Tavagnacco2022 - Modeling Solution Behavior of Poly(N Isopropylacrylamide)_ a Comparison between Water Models.pdf:PDF;:ModelingSolutionBehaviorOfPolyNIsopropylacrylamide-AComparisonBetweenWaterModels_TavagnaccoEtAl_JPC2022_SI.pdf:PDF},
  keywords     = {pNIPAM,simulation,oligomer,water model,force fields},
  url          = {https://doi.org/10.1021/acs.jpcb.2c00637},
}









@Article{Kwok2013,
  author       = {Kwok, Man-hin and Li, Zifu and Ngai, To},
  journal      = {Langmuir},
  title        = {Controlling the Synthesis and Characterization of Micrometer-Sized PNIPAM Microgels with Tailored Morphologies},
  year         = {2013},
  note         = {PMID: 23829635},
  number       = {30},
  pages        = {9581-9591},
  volume       = {29},
  abstract     = {This Article presents the controlling synthesis and characterization of micrometer-sized, multiresponsive poly(N-isopropylacrylamide-co-methacrylic acid) (PNIPAM-MAA) microgel particles. By combining semibatch and temperature-programmed surfactant-free precipitation polymerization, we have successfully developed a novel approach to the preparation of temperature- and pH-responsive PNIPAM microgels with a dense-shell (DS), dense-core (DC), or homogeneous (HOMO) structure. We then investigated the interaction between the synthesized microgels and some fluorescent dye molecules using confocal laser scanning microscopy (CLSM). Our results have qualitatively revealed that the cross-linkers and the functional carboxylic groups (−COOH) could be homogeneously distributed, predominately localized inside the core, or concentrated near the surface of the synthesized microgels. Moreover, pH-responsive swelling behaviors of the microgels were investigated and discussed with titration and CLSM data. We found that the swelling capability is strongly dependent on the morphology of the PNIPAM microgel. Besides the absorption of fluorescent molecules, the synthesized microgels also showed a strong affinity for fluorescently labeled polypeptide, even at a relatively high salt concentration.},
  creationdate = {2025-01-06T10:24:51},
  doi          = {10.1021/la402062t},
  eprint       = {https://doi.org/10.1021/la402062t},
  file         = {:Kwok2013 - Controlling the Synthesis and Characterization of Micrometer Sized PNIPAM Microgels with Tailored Morphologies.pdf:PDF},
  keywords     = {pNIPAM,microgel,synthesis,surfactant-free},
  url          = {https://doi.org/10.1021/la402062t},
}

@Article{Andersson2006b,
  author       = {Andersson, Mirja and Maunu, Sirkka Liisa},
  journal      = {Journal of Polymer Science Part B: Polymer Physics},
  title        = {Structural studies of poly(N-isopropyl\-acrylamide) microgels: Effect of SDS surfactant concentration in the microgel synthesis},
  year         = {2006},
  number       = {23},
  pages        = {3305-3314},
  volume       = {44},
  abstract     = {Abstract Thermoresponsive colloidal microgels were prepared by polymerization of N-isopropylacrylamide (NIPAM) in the presence of a crosslinking monomer, N,N-methylenebisacrylamide, in water with varying concentrations (<CMC) of an anionic surfactant, sodium dodecylsulphate (SDS). Volume phase transitions of the prepared microgels were studied in D2O by 1H NMR spectroscopy including the measurements of spin–lattice (T1) and spin–spin (T2) relaxation times for the protons of poly(N-isopropylacrylamide) (PNIPAM) at temperature range 22–50 °C. In addition, microcalorimetry, turbidometry, dynamic light scattering, and electrophoretic mobility measurements were used to characterize the aqueous microgels. As expected, increasing SDS concentration in the polymerization batch decreased the hydrodynamic size of an aqueous microgel. Structures with high mobilities at temperatures above the LCST of PNIPAM were observed in the microgels prepared with small amount of SDS, as indicated by the relaxation times of different PNIPAM protons. It was concluded that the high mobility at high temperatures is in connection to a mobile surface layer with polyelectrolyte nature and with high local LCST. High SDS concentration in the synthesis was observed to prevent the formation of permanent, solid PNIPAM particles. The results from different characterization methods indicated that PNIPAM microgels prepared in high SDS concentrations appear to be more homogeneously structured than their correspondences prepared in low SDS concentration. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3305–3314, 2006},
  creationdate = {2025-01-06T10:29:55},
  doi          = {https://doi.org/10.1002/polb.20971},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.20971},
  file         = {:Andersson2006b - Structural Studies of Poly(N Isopropylacrylamide) Microgels_ Effect of SDS Surfactant Concentration in the Microgel Synthesis.pdf:PDF},
  keywords     = {1H NMR,internal structure,microgel,poly(N-isopropylacrylamide),SDS,pNIPAM,synthesis,surfactant},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.20971},
}

@Article{Borgia1995,
  author       = {Borgia, Giulio C. and Brown, Robert J. S. and Fantazzini, Paola},
  journal      = {Phys. Rev. E},
  title        = {Scaling of spin-echo amplitudes with frequency, diffusion coefficient, pore size, and susceptibility difference for the NMR of fluids in porous media and biological tissues},
  year         = {1995},
  month        = {Mar},
  pages        = {2104--2114},
  volume       = {51},
  creationdate = {2025-01-07T08:28:11},
  doi          = {10.1103/PhysRevE.51.2104},
  file         = {:Borgia1995 - Scaling of Spin Echo Amplitudes with Frequency, Diffusion Coefficient, Pore Size, and Susceptibility Difference for the NMR of Fluids in Porous Media and Biological Tissues.pdf:PDF},
  issue        = {3},
  keywords     = {CPMG,Susceptibility,porous},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevE.51.2104},
}

@Article{Srivastava2024,
  author       = {Srivastava, Deepansh J. and Giammar, Matthew and Venetos, Maxwell C. and McCarthy-Carney, Lexi and Grandinetti, Philip J.},
  journal      = {The Journal of Chemical Physics},
  title        = {MRSimulator: A cross-platform, object-oriented software package for rapid solid-state NMR spectral simulation and analysis},
  year         = {2024},
  issn         = {0021-9606},
  month        = {12},
  number       = {21},
  pages        = {212501},
  volume       = {161},
  abstract     = {The open-source Python package, MRSimulator, is presented as a simple-to-use, fast, versatile, and extendable package capable of simulating one- and higher-dimensional Nuclear Magnetic Resonance (NMR) spectra under static, magic-angle, and variable-angle conditions. High benchmarks in spectral simulations are achieved by assuming that there are no degeneracies in the energy eigenstates, i.e., all dipolar couplings are in the weak limit and that there are no rotational resonances during evolution periods. Under these assumptions, the symmetry pathway formalism is exploited to reduce an NMR method applied to a spin system into a sum of individual transition pathways, whose signals are more efficiently calculated individually than as part of a full-density matrix simulation. To increase numerical efficiencies further, our approach restricts coherence transfer among transitions to pure rotations about an axis in the x–y plane of the rotating frame or through an artificial total mixing operation between selected transitions of adjacent free evolution periods. The assumptions used in this approach are valid for most commonly used solid-state NMR methods. Details of the implementation, along with example code usage, are given, including a least-squares spectral analysis.},
  comment      = {https://github.com/deepanshs/mrsimulator>},
  creationdate = {2025-01-09T09:58:23},
  doi          = {10.1063/5.0237608},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/5.0237608/20274973/212501\_1\_5.0237608.pdf},
  file         = {:/autohome/saeckech/Promotion/Literatur/NMR/MRSimulator-ACrossPlatformObjectOrientedSoftwarePackageForRapidSolidStateNMRSpectralSimulationAndAnalysis_SrivastavaEtAl_JCP2024.pdf:PDF},
  keywords     = {NMR,theory,spectra,lineshape analysis,python,solid-state},
  url          = {https://doi.org/10.1063/5.0237608},
}

@Article{Hanykova2006,
  author       = {Lenka Hanyková and Jan Labuta and Jiří Spěváček},
  journal      = {Polymer},
  title        = {NMR study of temperature-induced phase separation and polymer–solvent interactions in poly(vinyl methyl ether)/D2O/ethanol solutions},
  year         = {2006},
  issn         = {0032-3861},
  number       = {17},
  pages        = {6107-6116},
  volume       = {47},
  abstract     = {The changes in the dynamic structure during temperature-induced phase transition in D2O/ethanol solutions of poly(vinyl methyl ether) (PVME) were studied using NMR methods. The effect of polymer concentration and ethanol (EtOH) content in D2O/EtOH mixtures on the appearance and extent of the phase separation was determined. Measurements of 1H and 13C spin–spin and spin–lattice relaxations showed the presence of two kinds of EtOH molecules: besides the free EtOH expelled from the PVME mesoglobules there are also EtOH molecules bound in PVME mesoglobules. The existence of two different types of EtOH molecules at temperatures above the phase transition was in solutions with polymer concentration 20wt% manifested by two well-resolved NMR signals (corresponding to free and bound EtOH) in 13C and 1H NMR spectra. With time the originally bound EtOH is slowly released from globular-like structures. From the point of view of polymer–solvent interactions in the phase-separated PVME solutions both EtOH and water (HDO) molecules show a similar behaviour so indicating that the decisive factor in this behaviour is a polar character of these molecules and hydrogen bonding.},
  creationdate = {2025-01-15T10:54:48},
  doi          = {10.1016/j.polymer.2006.06.061},
  file         = {:Hanykova2006 - NMR Study of Temperature Induced Phase Separation and Polymer–solvent Interactions in Poly(vinyl Methyl Ether)_D2O_ethanol Solutions.pdf:PDF},
  keywords     = {Poly(vinyl methyl ether)/DO/ethanol solutions,Temperature-induced phase separation,H and C NMR spectroscopy,cononsolvency,PVME,CPMG,t2,spin-spin relaxation,1h nmr},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386106008020},
}

@Article{Pelton1986,
  author       = {R.H. Pelton and P. Chibante},
  journal      = {Colloids and Surfaces},
  title        = {Preparation of aqueous latices with N-isopropyl\-acrylamide},
  year         = {1986},
  issn         = {0166-6622},
  number       = {3},
  pages        = {247-256},
  volume       = {20},
  abstract     = {The preparation and characterization of monodisperse aqueous latex dispersions prepared from mixtures of N-isopropylacrylamide (NIPAM), acrylamide and N,N′-methylenebisacrylamide are described. Latices were prepared with solid contents up to 2.5%; the maximum acrylamide concentration which gave a good latex was about 1%. Absorbance (i.e. light scattering) of the latices increased when the temperature was raised above the lower critical solution temperature (LCST) of poly(NIPAM). Electron microscopic evidence suggested the latices were swollen to about 1μm in diameter at low temperature but were contracted by about a factor of 10, in volume, when the temperature was raised above the LCST. In 0.1 M CaCl2 the latices had critical coagulation temperatures ranging from 33 to 44°C when the acrylamide charge in the preparation was increased from 0 to 1.24 g l−1.},
  creationdate = {2025-01-21T15:12:25},
  doi          = {https://doi.org/10.1016/0166-6622(86)80274-8},
  file         = {:Pelton1986 - Preparation of Aqueous Latices with N Isopropylacrylamide.pdf:PDF},
  keywords     = {synthesis,pNIPAM,hydrogel,surfactant-free precipitation polymerization,BIS,gel},
  url          = {https://www.sciencedirect.com/science/article/pii/0166662286802748},
}

@Article{Kuehnhammer2022,
  author       = {Kühnhammer, Matthias and Gräff, Kevin and Loran, Edwin and Soltwedel, Olaf and Löhmann, Oliver and Frielinghaus, Henrich and von Klitzing, Regine},
  journal      = {Soft Matter},
  title        = {Structure formation of PNIPAM microgels in foams and foam films},
  year         = {2022},
  pages        = {9249-9262},
  volume       = {18},
  abstract     = {Responsive aqueous foams are very interesting from a fundamental point of view and for various applications like foam flooding or foam flotation. In this study thermoresponsive microgels (MGs) made from poly(N-isopropyl-acrylamide) (PNIPAM) with varying cross-linker content{,} are used as foam stabilisers. The foams obtained are thermoresponsive and can be destabilised by increasing the temperature. The structuring of MGs inside the foam films is investigated with small-angle neutron scattering and in a thin film pressure balance. The foam films are inhomogeneous and form a network-like structure{,} in which thin and MG depleted zones with a thickness of ca. 30 nm are interspersed in a continuous network of thick MG containing areas with a thickness of several 100 nm. The thickness of this continuous network is related to the elastic modulus of the individual MGs{,} which was determined by atomic force microscopy indentation experiments. Both{,} the elastic moduli and foam film thicknesses{,} indicate a correlation to the network elasticity of the MGs predicted by the affine network model.},
  creationdate = {2025-01-21T15:15:01},
  doi          = {10.1039/D2SM01021F},
  file         = {:Kuehnhammer2022 - Structure Formation of PNIPAM Microgels in Foams and Foam Films.pdf:PDF;:StructureFormationOfPNIPAMMicrogelsInFoamsAndFoamFilms_KuehnhammerEtAl_SoftMatter2022_SI.pdf:PDF},
  issue        = {48},
  keywords     = {pNIPAM,synthesis,gel,foam,microgel,von Klitzing},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D2SM01021F},
}

@Article{Goodwin1973,
  author       = {Goodwin, J. W. and Hearn, J. and Ho, C. C. and Ottewill, R. H.},
  journal      = {British Polymer Journal},
  title        = {The preparation and characterisation of polymer latices formed in the absence of surface active agents},
  year         = {1973},
  number       = {5},
  pages        = {347-362},
  volume       = {5},
  abstract     = {Abstract Methods have been devised for the formation of monodisperse polystyrene latices in the absence of added surface active agents. The particles are stabilised, as a colloidal dispersion, by surface groupings which are an integral part of the particle and are not removed by dialysis. By suitable variation of the ionic strength of the aqueous phase, the initiator concentration and the polymerisation temperature, the final particle size obtained in single-stage reactions was varied between c. 0.15 and 1.0 μm. The coefficient of variation on particle diameters was usually less than 5\%. The ionic strength of the aqueous phase was found to play an important part in determining particle size; this was explained in terms of a limited coagulation process occurring at the stage involving the nucleation of polymer particles. Conductometric titration experiments revealed the presence of sulphate, carboxyl and hydroxyl groups on the particle surfaces. Molecular weight determination of the polystyrene formed showed that this was lower than that formed in conventional emulsion polymerisation.},
  creationdate = {2025-01-21T17:29:00},
  doi          = {https://doi.org/10.1002/pi.4980050503},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/pi.4980050503},
  file         = {:Goodwin1973 - The Preparation and Characterisation of Polymer Latices Formed in the Absence of Surface Active Agents.pdf:PDF},
  keywords     = {synthesis,surfactant-free precipitation polymerization},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/pi.4980050503},
}

@Article{Slomkowski2011,
  author       = {Stanislaw Slomkowski and José V. Alemán and Robert G. Gilbert and Michael Hess and Kazuyuki Horie and Richard G. Jones and Przemyslaw Kubisa and Ingrid Meisel and Werner Mormann and Stanisław Penczek and Robert F. T. Stepto},
  journal      = {Pure and Applied Chemistry},
  title        = {Terminology of polymers and polymerization processes in dispersed systems (IUPAC Recommendations 2011)},
  year         = {2011},
  number       = {12},
  pages        = {2229--2259},
  volume       = {83},
  creationdate = {2025-01-22T11:12:19},
  doi          = {doi:10.1351/PAC-REC-10-06-03},
  file         = {:Slomkowski2011 - Terminology of Polymers and Polymerization Processes in Dispersed Systems (IUPAC Recommendations 2011).pdf:PDF},
  keywords     = {iupac,definitions,dispersion},
  lastchecked  = {2025-01-22},
  url          = {https://doi.org/10.1351/PAC-REC-10-06-03},
}

@Book{Odian2004,
  author       = {Odian, George G.},
  publisher    = {Wiley Interscience},
  title        = {Principles of Polymerization},
  year         = {2004},
  address      = {New York},
  edition      = {Fourth},
  isbn         = {0-471-27400-3},
  creationdate = {2025-01-22T11:25:27},
  file         = {:Odian2004 - Principles of Polymerization.pdf:PDF},
  keywords     = {book,chemistry,polymerization},
}

@Article{GomezGalvan2014,
  author       = {F. Gómez-Galván and H. Mercado-Uribe},
  journal      = {Phase Transitions},
  title        = {The phase transition of poly(N-isopropyl\-acrylamide): the effect of aging},
  year         = {2014},
  number       = {4},
  pages        = {336--343},
  volume       = {87},
  abstract     = {We study the effect of temporal and thermal aging of linear and hydrogel samples of poly(N-isopropylacrylamide) (PNIPAM). For this purpose, we designed a simple and inexpensive experimental device able to measure the optical density as a function of temperature. The samples were aged from 4 to 14\&nbsp;days at two temperatures: 24\&nbsp; and 37°C. We found that the phase transitions of linear PNIPAM samples shift to lower or higher temperatures, depending on the storage conditions, while the phase transitions of hydrogels always shift to higher temperatures. Structural differences between linear and hydrogel PNIPAMs and the formation of additional hydrogen bonds are behind these shifts.},
  creationdate = {2025-01-27T08:28:12},
  doi          = {10.1080/01411594.2013.837466},
  eprint       = {https://doi.org/10.1080/01411594.2013.837466},
  file         = {:Gómez-Galván03042014 - The Phase Transition of Poly(N Isopropylacrylamide)_ the Effect of Aging.pdf:PDF},
  keywords     = {pNIPAM,aging,ageing,storage,thermal cycling,linear,hydrogel,gel},
  publisher    = {Taylor \& Francis},
  url          = {https://doi.org/10.1080/01411594.2013.837466},
}

@Article{Li2003,
  author       = {Sai Kit Li and Antony D’Emanuele},
  journal      = {International Journal of Pharmaceutics},
  title        = {Effect of thermal cycling on the properties of thermoresponsive poly(N-isopropylacrylamide) hydrogels},
  year         = {2003},
  issn         = {0378-5173},
  number       = {1},
  pages        = {27-34},
  volume       = {267},
  abstract     = {Crosslinked poly(N-isopropylacrylamide) hydrogels have been widely studied for a variety of thermoresponsive applications, including chromatography, affinity precipitation, controlled biocatalysis, viable cell immobilisation, biomimetic actuators and, in particular, modulated drug delivery. The exploitation of crosslinked poly(N-isopropylacrylamide) hydrogels in all these applications relies on the well-known temperature-sensitive swelling properties of these hydrogels. The purpose of the current study was to determine the effects of repeated thermal cycling on the thermoresponsive swelling behaviour of crosslinked poly(N-isopropylacrylamide) hydrogels. The results show that repeated thermal cycling leads to the formation of cracks on the surface of the hydrogels. Repeated thermal cycling also results in a decreased degree of swelling in the crosslinked poly(N-isopropylacrylamide) hydrogels at temperatures below the volume phase transition temperature (VPTT).},
  creationdate = {2025-01-27T08:33:15},
  doi          = {10.1016/j.ijpharm.2003.07.009},
  file         = {:Li2003 - Effect of Thermal Cycling on the Properties of Thermoresponsive Poly(N Isopropylacrylamide) Hydrogels.pdf:PDF},
  keywords     = {Poly(-isopropylacrylamide),Hydrogels,Effect of thermal cycling,Thermoresponsive polymers,Responsive drug delivery,pNIPAM,thermal cycling,hydrogel,gel,aging,ageing},
  url          = {https://www.sciencedirect.com/science/article/pii/S0378517303004319},
}









@Article{Meng2009,
  author       = {Meng, Zhiyong and Cho, Jae Kyu and Breedveld, Victor and Lyon, L. Andrew},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Physical Aging and Phase Behavior of Multiresponsive Microgel Colloidal Dispersions},
  year         = {2009},
  note         = {PMID: 19298093},
  number       = {14},
  pages        = {4590-4599},
  volume       = {113},
  abstract     = {Quantitative microscopy measurements have been made on poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAm−AAc) microgel dispersions as a function of time, temperature, pH, and volume fraction. These studies reveal an extreme degree of complexity in the physical aging and phase behavior of the dispersions; this complexity arises from a convolution of the system energetics at the colloidal, polymer-chain, and molecular scales. Superficially, these dispersions display the classic colloidal phases observed for spherical particles (i.e., gas, fluid, crystal, and glass). However, unlike simple repulsive hard spheres, pNIPAm−AAc dispersions are observed to evolve from a diffusive, fluidlike state immediately after being introduced into rectangular capillary tubes, to very slow crystalline or glassy phases after days or weeks of aging. In addition to this structural evolution, the free volume accessible to the microgels in crystalline or glassy phases (i.e., the cage size) decreases with time, indicating that the physical aging process does not end following assembly, but instead continues to evolve as the dispersion slowly proceeds to an equilibrium state. The temperature dependence of pNIPAm−AAc microgel swelling and how it influences the colloidal assembly was evaluated during the aging process as well. These thermal melting experiments revealed an enhancement in the thermal stability (i.e., a decrease in the influence of temperature on the phase behavior) of the assemblies during the aging process that we associate with an evolution of attractive interparticle interactions during aging. These attractive interactions dictate the time scale for assembly (aging), the final phase adopted by the dispersion, the dynamics of the final state, and the ultimate thermal stability. The culmination of these studies is the pseudoequilibrium phase behavior of pNIPAm−AAc microgel dispersions, which we present as a function of pH and volume fraction following ∼1 month of aging. This diagram reveals highly complex dispersion characteristics that appear to be intrinsically tied to the degree of AAc protonation. In general, we find that, at pH < pKa, the final dispersions behave in a manner that can be associated with attractive interparticle interactions, whereas at pH > pKa, repulsive interactions appear to be dominant. These results are discussed in the context of the slow evolution of microgel swelling and attractive interaction potentials arising from reorganization and association of polymer chains via multiple weak hydrogen-bonding interactions.},
  creationdate = {2025-01-27T08:46:23},
  doi          = {10.1021/jp8104979},
  eprint       = {https://doi.org/10.1021/jp8104979},
  file         = {:Meng2009 - Physical Aging and Phase Behavior of Multiresponsive Microgel Colloidal Dispersions.pdf:PDF;:PhysicalAgingAndPhaseBehaviorOfMultiresponsiveMicrogelColloidalDispersions_MengEtAl_JPC2009_SI.pdf:PDF},
  keywords     = {pNIPAM,ageing,aging,microgel,gel,copolymer,pNIPAM-AAc,pH},
  url          = {https://doi.org/10.1021/jp8104979},
}

@Article{Halpern2020,
  author       = {Halpern, Jeffrey M and Roberge, Emma and Ren, Tianyu and LaFreniere, Joelle and Balog, Eva Rose M and Seitz, William Rudolf},
  journal      = {ECS Meeting Abstracts},
  title        = {Shifts of pNIPAM Lower Critical Solution Temperature in an Applied Electric Field},
  year         = {2020},
  month        = {may},
  number       = {43},
  pages        = {2513},
  volume       = {MA2020-01},
  abstract     = {Poly(N-isopropylacrylamide), or pNIPAM, is a free-radical polymer that is commonly studied for uses in surface coatings, tissue engineering, energy storage, biosensing, and more, due to its temperature responsiveness. Below its transition temperature, pNIPAM is dissolved in solution with a small particle size. Above the transition temperature, pNIPAM agglomerates and condenses out of solution. Dynamic Light Scattering (DLS) measures temperature induced agglomeration of pNIPAM by determining the transition temperature, which is typically 30-35oC for pNIPAM. We initially confirmed the lower critical solution temperature (LCST), or the point in which pNIPAM agglomerates, to be thermodynamically reversible and reproducible for both pNIPAM and an electrochemically active poly(N-isopropylacrylamide)-block-poly(ferrocenylmethyl methacrylate) block copolymer, or p(NIPAM-b-FMMA).

Applying a potential across the DLS light path, we expected p(NIPAM-b-FMMA) to cause a shift in the transition temperature and agglomeration behavior. However, we unexpectedly observed a shift in the transition behavior of pNIPAM. At an applied electric field of 400 mV/cm and above, the transition temperature of pNIPAM started to shift negative. Further, upon cooling, the pNIPAM never re-dissolves, indicating an irreversible agglomeration in the presence of an applied.

We have also started to investigate reasons on why this phenomenon might occur. We will discuss two primary hypotheses, including wetting behavior changes of the pNIPAM and further radicalization of the RAFT agents leading to cross-linking and irreversible behavior.

Acknowledgements: The authors would like to acknowledge the financial support from NIH (P20 GM113131), NSF (CBET 1638896), the Collaborative Research Excellence Initiative Pilot Research Program at the University of New Hampshire, and the Hamel Center of Undergraduate Research at the University of New Hampshire. The authors also would like to acknowledge the assistance of Dr. Seitz’s laboratory and Dr. Halpern’s laboratory},
  creationdate = {2025-01-27T08:58:45},
  doi          = {10.1149/MA2020-01432513mtgabs},
  publisher    = {The Electrochemical Society, Inc.},
  url          = {https://dx.doi.org/10.1149/MA2020-01432513mtgabs},
}

@Article{Deshmukh2013,
  author       = {Sanket A. Deshmukh and Ganesh Kamath and Derrick C. Mancini and Subramanian K. R. S. Sankaranarayanan},
  journal      = {MRS Online proceedings Library},
  title        = {Effect of Methanol/Water Mixtures on the Lower Critical Solution Temperature of Poly(N-isopropylacrylamide)},
  year         = {2013},
  pages        = {25--30},
  volume       = {1622},
  abstract     = {Poly(N-isopropylacrylamide) (PNIPAM) is a thermo-sensitive polymer that exhibits a lower critical solution temperature (LCST) around 305 K. Below the LCST, PNIPAM is soluble in water and above this temperature polymer chains collapse prior to aggregation. In the presence of methanol, electron paramagnetic resonance (EPR) spectroscopy suggests that, LCST of PNIPAM is depressed up to certain mole fraction of methanol (0.35 mole fraction) and it is speculated that addition of methanol affects the PNIPAM-water interactions. Above 0.35 mole fraction of methanol, LCST gets elevated to temperatures above ∼305 K (32°C) and cannot be detected up to 373 K (100 °C). The atomistic origin of this co-solvency effect on the LCST behavior is not completely understood. In the present study, we have used molecular dynamics (MD) simulations to investigate the effect of methanol-water mixtures on conformational transitions and the LCST of PNIPAM. We employ two different force fields i.e. polymer consistent force-field (PCFF) and CHARMM to study solvation dynamics and the PNIPAM LCST phase transition in various methanol-water mixture compositions (0.018, 0.09, 0.27, 0.5, and 0.98 mole fractions). Simulations are conducted at fully atomistic level for three different temperatures (260, 278, and 310 K) and radius of gyration (Rg) of PNIPAM chains was computed for determination of LCST behavior of PNIPAM.},
  comment      = {paywall},
  creationdate = {2025-01-27T09:02:34},
  doi          = {10.1557/opl.2014.276},
  keywords     = {pNIPAM,cononsolvency,aqueous alcohol,methanol,EPR,molecular dynamics simulation,simulation},
  url          = {https://doi.org/10.1557/opl.2014.276},
}

@Article{Umapathi2019,
  author       = {Reddicherla Umapathi and Payal Narang and Pannuru Venkatesu and Nirmala Deenadayalu},
  journal      = {Journal of Molecular Liquids},
  title        = {Profiling the molecular interactions between a promising thermoresponsive polymer and ionic liquid: A biophysical outlook},
  year         = {2019},
  issn         = {0167-7322},
  pages        = {716-721},
  volume       = {278},
  abstract     = {Thermoresponsive polymers (TRPs) that undergo significant conformation/aggregation changes in response to changes in temperature have extensive range of potential applications in various fields of science and technology. Among different types of TRPs, poly (N-isopropylacrylamide) (PNIPAM) is a suitable amphiphilic polymer for studying the conformational changes due to its biocompatible behavior with various additives. In order to get deeper insights of the TRPs in the presence of additives, we examined the collapse and aggregation of thermoresponsive polymer (PNIPAM) in aqueous solution containing variable amounts of 1-allyl-3-methylimidazolium bromide ([Amim][Br]). The influence of ionic liquid on the lower critical solution temperature (LCST) of PNIPAM aqueous solution were examined with the aid of comprehensive biophysical techniques such as UV–visible absorption spectroscopy, steady-state fluorescence spectroscopy, thermal fluorescence spectroscopy, viscosity (η) and dynamic light scattering (DLS) measurements. With the addition of 5 mg/mL of [Amim][Br] to the PNIPAM aqueous solution the LCST has been decreased towards lower temperatures. Further with the addition of higher concentration (10 and 15 mg/mL) of [Amim][Br] the decrease in the LCST of PNIPAM has been more pronounced towards lower temperatures. Our experimental results explicitly elucidated that the decrease in the LCST of the PNIPAM with increase in the concentration of [Amim][Br] is due to the substantial variations in the interactions among amide group of polymer, ions of ionic liquid and water molecules. The experimental results of the current investigation can be used for the design of smart polymer-based devices, as its LCST is close to body temperature. The results provide an alternative way to tune the phase transition temperature of the broadly accepted model PNIPAM polymer.},
  creationdate = {2025-01-27T09:40:21},
  doi          = {https://doi.org/10.1016/j.molliq.2019.01.087},
  file         = {:Umapathi2019 - Profiling the Molecular Interactions between a Promising Thermoresponsive Polymer and Ionic Liquid_ a Biophysical Outlook.pdf:PDF},
  keywords     = {Thermoresponsive polymers,Poly(-isopropylacrylamide),1-Allyl-3-methylimidazolium bromide,Phase transition behavior,Conformational changes,pNIPAM,ionic liquid,UV-vis,fluorescence spectroscopy,DLS,light scattering,rheology,viscosity,Amim-Br,aggregation},
  url          = {https://www.sciencedirect.com/science/article/pii/S0167732218348360},
}

@Article{LaFreniere2020,
  author       = {LaFreniere, Joelle and Roberge, Emma and Ren, Tianyu and Seitz, William Rudolf and Balog, Eva Rose M and Halpern, Jeffrey M},
  journal      = {ECS Transactions},
  title        = {Insights on the Lower Critical Solution Temperature Behavior of pNIPAM in an Applied Electric Field},
  year         = {2020},
  month        = {jun},
  number       = {7},
  pages        = {709},
  volume       = {97},
  abstract     = {Poly(N-isopropylacrylamide), or pNIPAM, is a free-radical polymer that is commonly studied for uses in surface coatings, tissue engineering, energy storage, biosensing, and more, due to its temperature responsiveness. pNIPAM is known to solubilize at temperatures below its lower critical solution temperature (LCST) and agglomerate above its LCST. This behavior has been shown to be reproducible and reversible. We confirmed this reversibility and the value of the LCST by performing dynamic light scattering (DLS) with a temperature sweep (increase and decrease). However, performing the same experiment under an applied voltage from copper electrodes, we observed a decrease in the LCST of pNIPAM and irreversible aggregation. Here we present preliminary data comparing the LCST behavior of pNIPAM in the presence of applied voltage using copper, aluminum, and carbon electrodes. We present data in support of the hypothesis that a phenomenon is occurring specifically with the use of copper electrodes that is altering pNIPAM LCST behavior.},
  comment      = {paywall},
  creationdate = {2025-01-27T09:44:28},
  doi          = {10.1149/09707.0709ecst},
  file         = {:LaFreniere2020 - Insights on the Lower Critical Solution Temperature Behavior of PNIPAM in an Applied Electric Field.pdf:PDF},
  keywords     = {pNIPAM,electric field,DLS,light scattering,aggregation,reversibility,hysteresis},
  publisher    = {The Electrochemical Society, Inc.},
  url          = {https://dx.doi.org/10.1149/09707.0709ecst},
}

@Article{Ding2009,
  author       = {Ding, Y. and Zhang, G.},
  journal      = {Chin. Sci. Bull.},
  title        = {Folding of a single polymer chain and phase transition},
  year         = {2009},
  pages        = {1908--1911},
  volume       = {54},
  abstract     = {Using an ultra-sensitive differential scanning calorimetry (US-DSC), we have investigated the folding and aggregation behaviors of poly(N-isopropylacrylamide) (PNIPAM) chains in dilute and semidilute solutions. In the heating process, the intrachain folding and interchain aggregation simultaneously occur in the dilute solutions, and the ratio of intrachain folding increases with decreasing concentration. In the semidilute solutions, PNIPAM chains show limited interchain aggregation with elevated temperature, because most of the PNIPAM chains have been collapsed at lower temperature. In an extremely dilute solution, PNIPAM chains undergo a single folding transition in the heating process. By extrapolating heating rate and concentration to zero, we have obtained the phase transition temperature (T S ) and enthalpy change (ΔH S ) of the single chain folding. ΔH S is higher than that for a phase transition involving intrachain collapse and interchain aggregation, indicating that a single chain folding can not be taken to be a macroscopic phase transition.},
  comment      = {paywall},
  creationdate = {2025-02-04T08:42:35},
  doi          = {10.1007/s11434-009-0278-0},
  file         = {:Ding2009 - Folding of a Single Polymer Chain and Phase Transition.pdf:PDF},
  keywords     = {pNIPAM,DSC,aggregation,kinetics,enthalpy,concentration dependence},
  url          = {https://doi.org/10.1007/s11434-009-0278-0},
}









@Article{Tucker2012,
  author       = {Tucker, Ashley K. and Stevens, Mark J.},
  journal      = {Macromolecules},
  title        = {Study of the Polymer Length Dependence of the Single Chain Transition Temperature in Syndiotactic Poly(N-isopropylacrylamide) Oligomers in Water},
  year         = {2012},
  number       = {16},
  pages        = {6697-6703},
  volume       = {45},
  abstract     = {Aqueous solutions of poly(N-isopropylacrylamide) (PNIPAM) exhibit a temperature responsive change in conformation. When the temperature is increased, the polymer transitions from an extended coil conformation to a collapsed structure. We performed molecular dynamics simulations of aqueous solutions of single chain, syndiotactic PNIPAM oligomers over a wide range of temperatures and varying degrees of polymerization to elucidate the effect of oligomer length on the single chain transition temperature, T1. We have reproduced recent measurements of the transition temperature increasing with decreasing oligomer chain length. Examination of the chain structure reveals that conformations above T1 bend to bring hydrophobic segments together to shield them from the water. The constraints of the dihedral dynamics require elevated temperatures for shorter chains to bend sharply enough in order to undergo the transition. This result is confirmed by calculations of the solvent accessible surface area, which shows an increase in shielding of the hydrophobic groups with increasing oligomer length above T1.},
  creationdate = {2025-02-04T08:47:05},
  doi          = {10.1021/ma300729z},
  eprint       = {https://doi.org/10.1021/ma300729z},
  file         = {:Tucker2012 - Study of the Polymer Length Dependence of the Single Chain Transition Temperature in Syndiotactic Poly(N Isopropylacrylamide) Oligomers in Water.pdf:PDF;:StudyOfThePolymerLengthDependenceOfTheSingleChainTransitionTemperatureInSyndiotacticPolyNIsopropylacrylamideOligomersInWater_TuckerEtAl_Macromol2012_SI.pdf:PDF},
  keywords     = {pNIPAM,chain length dependence,simulation,tacticity,oligomer,molecular dynamics simulation},
  url          = {https://doi.org/10.1021/ma300729z},
}

@Article{Mochizuki2016,
  author       = {Mochizuki, Kenji and Sumi, Tomonari and Koga, Kenichiro},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Driving forces for the pressure-induced aggregation of poly(N-isopropylacrylamide) in water},
  year         = {2016},
  pages        = {4697-4703},
  volume       = {18},
  abstract     = {Driving forces for the pressure-induced aggregation of poly(N-isopropylacrylamide) (PNiPA) in water are investigated by performing extensive molecular dynamics simulations. First{,} we observe that the model short oligomer of PNiPA with a modified OPLS-AA force field in water shrinks with increasing pressure. At varying pressures{,} the potentials of mean force (PMFs) between a pair of N-isopropylpropionamide (NiPPA) molecules{,} the repeating unit of PNiPA{,} are obtained and decomposed into the nonpolar and Coulombic contributions. The nonpolar contribution is the PMF between the hypothetical nonpolar NiPPA molecules in the solvent{,} which is mainly due to the molecular volume effect. The attractive force between NiPPA molecules is enhanced at higher pressures in agreement with the behavior of PNiPA. This pressure dependence of the PMF is caused by the growing nonpolar contribution at higher pressures. In contrast{,} the Coulombic contribution to the PMF becomes higher overall{,} making the mean force less attractive or more repulsive{,} with increasing pressure. The strength of the aggregation and its pressure dependence of the nonpolar contribution in water are closely reproduced even in nonpolar solvents. The degree of the pressure dependence is explained by the isothermal compressibility or the tightness of the solvation shell around an isolated solute{,} without regard to the existence and variation of hydrogen bond networks in a solvent. The role of hydrogen bonds in the aggregation of NiPPA and PNiPA molecules is also discussed.},
  creationdate = {2025-02-04T08:50:44},
  doi          = {10.1039/C5CP07674A},
  file         = {:Mochizuki2016 - Driving Forces for the Pressure Induced Aggregation of Poly(N Isopropylacrylamide) in Water.pdf:PDF},
  issue        = {6},
  keywords     = {NIPPA,pNIPAM,molecular dynamics simulation,pressure,OPLS,aggregation},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C5CP07674A},
}









@Article{Acharya2023,
  author       = {Acharya, Gobin Raj and Tyagi, Madhusudan and Mamontov, Eugene and Hoffmann, Peter M.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Diffusion Dynamics of Water and Ethanol in Graphene Oxide},
  year         = {2023},
  note         = {PMID: 37556231},
  number       = {33},
  pages        = {7384-7393},
  volume       = {127},
  abstract     = {We utilized the momentum transfer (Q)-dependence of quasi-elastic neutron scattering (QENS) to measure the dynamics of water and ethanol confined in graphene oxide (GO) powder or membranes at different temperatures and in different orientations. We found reduced diffusivities (up to 30\% in the case of water) and a depression of dynamic transition temperatures. While water showed near Arrhenius behavior with an almost bulk-like activation barrier in a temperature range of 280–310 K, the diffusivity of ethanol showed little temperature dependence. For both water and ethanol, we found evidence for immobile and mobile fractions of the confined liquid. The mobile fraction exhibited jump diffusion, with a jump length consistent with the expected average spacing of hydroxide groups in the GO surfaces. From anisotropy measurements, we found weak anisotropy in the diffusivity of the mobile species and in the fraction and geometry of immobile species.},
  comment      = {neat components, not mixtures},
  creationdate = {2025-02-10T09:39:17},
  doi          = {10.1021/acs.jpcb.2c08960},
  eprint       = {https://doi.org/10.1021/acs.jpcb.2c08960},
  file         = {:Acharya2023 - Diffusion Dynamics of Water and Ethanol in Graphene Oxide.pdf:PDF},
  keywords     = {cononsolvency,QENS,diffusion,activation energy,ethanol,water},
  url          = {https://doi.org/10.1021/acs.jpcb.2c08960},
}









@Article{Vikulina2020,
  author       = {Vikulina, Anna S. and Feoktistova, Natalia A. and Balabushevich, Nadezhda G. and von Klitzing, Regine and Volodkin, Dmitry},
  journal      = {ACS Applied Materials \& Interfaces},
  title        = {Cooling-Triggered Release from Mesoporous Poly(N-isopropylacrylamide) Microgels at Physiological Conditions},
  year         = {2020},
  note         = {PMID: 33290041},
  number       = {51},
  pages        = {57401-57409},
  volume       = {12},
  abstract     = {Poly(N-isopropylacrylamide) (pNIPAM) hydrogels have broad potential applications as drug delivery vehicles because of their thermoresponsive behavior. pNIPAM loading/release performances are directly affected by the gel network structure. Therefore, there is a need with the approaches for accurate design of 3D pNIPAM assemblies with the structure ordered at the nanoscale. This study demonstrates size-selective spontaneous loading of macromolecules (dextrans 10−500 kDa) into pNIPAM microgels by microgel heating from 22 to 35 °C (microgels collapse and trap dextrans) followed by the dextran release upon further cooling down to 22 °C (microgels swell back) . This temperature-mediated behavior is fully reversible. The structure of pNIPAM microgels was tailored via hard templating and cross-linking of the hydrogel using sacrificial mesoporous cores of vaterite CaCO3 microcrystals. In addition, the fabrication of hollow thermoresponsive pNIPAM microshells has been demonstrated, utilizing vaterite microcrystals that had narrower pores. The proposed approach for heating-triggered encapsulation and cooling-triggered release into/from pNIPAM microgels may pave the ways for applications of pNIPAM hydrogels for skin and transdermal cooling-responsive drug delivery in the future.},
  creationdate = {2025-02-10T09:54:05},
  doi          = {10.1021/acsami.0c15370},
  eprint       = {https://doi.org/10.1021/acsami.0c15370},
  file         = {:Vikulina2020 - Cooling Triggered Release from Mesoporous Poly(N Isopropylacrylamide) Microgels at Physiological Conditions.pdf:PDF;:CoolingTriggeredReleaseFromMesoporousPolyNIsopropylacrylamideMicrogelsAtPhysiologicalConditions_VikulinaEtAl_ApplMatInt2020_SI.pdf:PDF},
  keywords     = {von Klitzing, controlled release, drug delivery, pNIPAM, microgel, gel, dextrans, application-focused, application focused},
  url          = {https://doi.org/10.1021/acsami.0c15370},
}

@Article{Kim2024,
  author       = {Sungyun Kim and Dae-Duk Kim and Mrinmoy Karmakar and Hyun-Jong Cho},
  journal      = {Journal of Pharmaceutical Investigation},
  title        = {Injectable hydrogel systems for local cancer therapy},
  year         = {2024},
  month        = sep,
  pages        = {555--591},
  volume       = {54},
  creationdate = {2025-02-12T08:54:05},
  doi          = {10.1007/s40005-024-00678-7},
  file         = {:Kim2024 - Injectable Hydrogel Systems for Local Cancer Therapy.pdf:PDF},
  keywords     = {hydrogel, review, application-focused, application focused},
  url          = {https://doi.org/10.1007/s40005-024-00678-7},
}

@Article{Throat2024,
  author       = {Throat, Siddhi and Bhattacharya, Sankha},
  journal      = {Advances in Polymer Technology},
  title        = {Macromolecular Poly(N-isopropyl\-acryl\-amide) (PNIPAM) in Cancer Treatment and Beyond},
  year         = {2024},
  number       = {1},
  pages        = {1444990},
  volume       = {2024},
  abstract     = {Poly(N-isopropylacrylamide) (PNIPAM) is a versatile polymer known for its phase transition properties, exhibiting a lower critical solution temperature (LCST) of approximately 32°C. Below this temperature, PNIPAM is hydrophilic, while above it, the polymer becomes hydrophobic, making it ideal for thermosensitive drug delivery systems (DDSs). In tissue engineering, PNIPAM provides a biocompatible, nontoxic and stimuli-responsive surface for cell culture. Its nontoxic nature ensures safety in medical applications. PNIPAM enhances biosensing diagnostics through its affinity for biomolecules, improving accuracy. Widely used in hydrogels, smart textiles, soft robotics and various medical applications, PNIPAM adapts to environmental changes. Its straightforward synthesis allows for the creation of diverse copolymers and composites, applicable in selective reactions and conjugations with fluorescent tags or chemical modifications. PNIPAM’s versatility extends to pH-responsive alternatives, broadening its application spectrum. Practical examples include phase separation in water treatment and cleaning processes. This discussion explores PNIPAM’s biomedical and drug delivery applications, particularly in cancer treatment, photothermal therapy (PTT) and photodynamic therapy (PDT), gene delivery and medical imaging. Additionally, it highlights PNIPAM’s noncancerous applications, such as small interfering RNA (siRNA) targeting of oncogenes and detailed imaging of deep and tumour tissues.},
  creationdate = {2025-02-12T09:53:51},
  doi          = {https://doi.org/10.1155/2024/1444990},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1155/2024/1444990},
  file         = {:Throat2024 - Macromolecular Poly(N Isopropylacrylamide) (PNIPAM) in Cancer Treatment and beyond.pdf:PDF},
  keywords     = {biocompatibility, cancer therapy, drug delivery, poly(N-isopropylacrylamide) (PNIPAM), thermoresponsive, tissue engineering, review, pNIPAM, application-focused, application focused},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1155/2024/1444990},
}

@Article{Kutus2021,
  author       = {Kutus, Bence and Shalit, Andrey and Hamm, Peter and Hunger, Johannes},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Dielectric response of light{,} heavy and heavy-oxygen water: isotope effects on the hydrogen-bonding network{'}s collective relaxation dynamics},
  year         = {2021},
  pages        = {5467-5473},
  volume       = {23},
  abstract     = {Isotopic substitutions largely affect the dielectric relaxation dynamics of hydrogen-bonded liquid water; yet{,} the role of the altered molecular masses and nuclear quantum effects has not been fully established. To disentangle these two effects we study the dielectric relaxation of light (H216O){,} heavy (D216O) and heavy-oxygen (H218O) water at temperatures ranging from 278 to 338 K. Upon 16O/18O exchange{,} we find that the relaxation time of the collective orientational relaxation mode of water increases by 4–5%{,} in quantitative agreement with the enhancement of viscosity. Despite the rotational character of dielectric relaxation{,} the increase is consistent with a translational mass factor. For H/D substitution{,} the slow-down of the relaxation time is more pronounced and also shows a strong temperature dependence. In addition to the classical mass factor{,} the enhancement of the relaxation time for D216O can be described by an apparent temperature shift of 7.2 K relative to H216O{,} which is higher than the 6.5 K shift reported for viscosity. As this shift accounts for altered zero-point energies{,} the comparison suggests that the underlying thermally populated states relevant to the activation of viscous flow and dielectric relaxation differ.},
  creationdate = {2025-02-12T10:18:33},
  doi          = {10.1039/D0CP06460B},
  file         = {:Kutus2021 - Dielectric Response of Light, Heavy and Heavy Oxygen Water_ Isotope Effects on the Hydrogen Bonding Network's Collective Relaxation Dynamics.pdf:PDF;:DielectricResponseOfLightHeavyAndHeavyOxygenWater-IsotopeEffectsOnTheHydrogenBondingNetworksCollectiveRelaxationDynamics_KutusEtAl_PCCP2021_SI.pdf:PDF},
  issue        = {9},
  keywords     = {BDS,isotope effect,hydrogen bond,h-bond},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D0CP06460B},
}









@Article{Kogo2020,
  author       = {Kogo, Takuro and Shundo, Atsuomi and Wang, Chi and Tanaka, Keiji},
  journal      = {Macromolecules},
  title        = {Spatial Heterogeneity Accompanying Gel Formation of Poly(N-isopropylacrylamide) Aqueous Solution at a Temperature below Cloud Point},
  year         = {2020},
  number       = {24},
  pages        = {10964-10971},
  volume       = {53},
  abstract     = {Poly(N-isopropylacrylamide) (PNIPAM) is a representative thermoresponsive polymer, and its aqueous solution becomes phase-separated at a temperature higher than the cloud point (Tcp) at ∼304 K, which plays an important role in various biomedical applications. Thus, to further promote the use of PNIPAM as a functional material, it is necessary to gain a better understanding of its phase behavior especially at a temperature just below Tcp. To this end, we examined the local rheological properties of atactic PNIPAM solutions with a concentration of 10 wt \% by a particle tracking technique, in which the thermal motion of probe particles in the solution was tracked, in conjunction with Fourier-transform infrared spectroscopy, small-angle X-ray scattering measurements, fluorescence spectroscopy, and confocal laser scanning microscopy. At temperatures far below Tcp, the solution exhibited one-phase homogeneous characteristics. After the PNIPAM aqueous solution was left undisturbed at a temperature just below Tcp (302 K), it formed a physical gel. Changing the size of probe particles for the tracking measurements, we found that the resultant gel was spatially heterogeneous in terms of its rheological properties at a length scale of approximately 50–100 nm. The gelation of the solution promoted by the formation of hydrophobic pearls in PNIPAM chains led to the formation of network junctions with heterogeneity. The knowledge obtained here should be useful for understanding and controlling the phase behavior of the PNIPAM solution, thereby leading to the further development of thermoresponsive functional materials.},
  creationdate = {2025-02-13T17:03:45},
  doi          = {10.1021/acs.macromol.0c02292},
  eprint       = {https://doi.org/10.1021/acs.macromol.0c02292},
  file         = {:Kogo2020 - Spatial Heterogeneity Accompanying Gel Formation of Poly(N Isopropylacrylamide) Aqueous Solution at a Temperature below Cloud Point.pdf:PDF;:SpatialHeterogeneityAccompanyingGelFormationOfPolyNIsopropylacrylamideAqueousSolutionAtATemperatureBelowCloudPoint_KogoEtAl_Macromolecules2020_SI.pdf:PDF},
  keywords     = {pNIPAM,rheology,atactic,particle tracking,infrared,FTIR,SAXS,fluorescence,confocal laser scanning microscopy,gelation,aggregation,structure},
  url          = {https://doi.org/10.1021/acs.macromol.0c02292},
}









@Article{Millero1971,
  author       = {Millero, Frank J. and Dexter, Roger. and Hoff, Edward.},
  journal      = {Journal of Chemical \& Engineering Data},
  title        = {Density and viscosity of deuterium oxide solutions from 5-70.deg.},
  year         = {1971},
  number       = {1},
  pages        = {85-87},
  volume       = {16},
  creationdate = {2025-02-13T21:22:48},
  doi          = {10.1021/je60048a006},
  eprint       = {https://doi.org/10.1021/je60048a006},
  file         = {:Millero1971 - Density and Viscosity of Deuterium Oxide Solutions from 5 70.deg..pdf:PDF},
  keywords     = {water,d2o,viscosity,isotope effect},
  url          = {https://doi.org/10.1021/je60048a006},
}









@Article{Smithenry2001,
  author       = {Smithenry, Dennis W. and Kang, Mun-Sik and Gupta, Vinay K.},
  journal      = {Macromolecules},
  title        = {Telechelic Poly(N-isopropylacrylamide):  Polymerization and Chain Aggregation in Solution},
  year         = {2001},
  number       = {24},
  pages        = {8503-8511},
  volume       = {34},
  abstract     = {The synthesis of telechelic poly(N-isopropylacrylamide) (PNIPAM) with carboxylic acid termini was accomplished using the primary radical termination mechanism. Polymers with molecular weight (Mn) ranging from 32 to 5 kDa could be prepared by changing the monomer-to-initiator ratio and the time of polymerization. Modeling of the polymerization by a simple kinetic model based on radical initiation, propagation, and primary radical termination by initiator was performed. Prediction of the molecular weights by this model showed good agreement with the experimentally observed values. Characterization of the polymer revealed a complex aggregation phenomena in DMF solutions at temperatures of 60−70 °C. For samples with Mn between 8.3 and 12.2 kDa the presence of nanometer size aggregates was evident in the elution chromatogram, and the laser light scattered at right angles. It was found that the aggregation appeared at a polymer concentration that was far below the overlap concentration of the polymer chains, and the aggregates could not be broken up by either dilution of the solutions or addition of lithium bromide to DMF. The solvent was found to play a role, and aggregation was observed in another polar solvent such as N-methylpyrollidone but not in a nonpolar solvent such as tetrahydrofuran.},
  creationdate = {2025-02-14T09:21:22},
  doi          = {10.1021/ma010769b},
  eprint       = {https://doi.org/10.1021/ma010769b},
  file         = {:Smithenry2001 - Telechelic Poly(N Isopropylacrylamide)_ Polymerization and Chain Aggregation in Solution.pdf:PDF},
  keywords     = {pNIPAM,synthesis,aggregation,molecular weight,light scattering},
  url          = {https://doi.org/10.1021/ma010769b},
}

@Article{Paradossi2017,
  author         = {Paradossi, Gaio and Chiessi, Ester},
  journal        = {Gels},
  title          = {Tacticity-Dependent Interchain Interactions of Poly(N-Isopropylacrylamide) in Water: Toward the Molecular Dynamics Simulation of a Thermoresponsive Microgel},
  year           = {2017},
  issn           = {2310-2861},
  number         = {2},
  volume         = {3},
  abstract       = {The discovery that the lower critical solution temperature (LCST) of poly(N-Isopropylacrylamide) (PNIPAM) in water is affected by the tacticity opens the perspective to tune the volume phase transition temperature of PNIPAM microgels by changing the content of meso dyads in the polymer network. The increased hydrophobicity of isotactic-rich PNIPAM originates from self-assembly processes in aqueous solutions also below the LCST. The present work aims to detect the characteristics of the pair interaction between polymer chains, occurring in a concentration regime close to the chain overlap concentration, by comparing atactic and isotactic-rich PNIPAM solutions. Using atomistic molecular dynamics simulations, we successfully modelled the increased association ability of the meso-dyad-rich polymer in water below the LCST, and gain information on the features of the interchain junctions as a function of tacticity. Simulations carried out above the LCST display the PNIPAM transition to the insoluble state and do not detect a relevant influence of stereochemistry on the structure of the polymer ensemble. The results obtained at 323 K provide an estimate of the swelling ratio of non-stereocontrolled PNIPAM microgels which is in agreement with experimental findings for microgels prepared with low cross-linker/monomer feed ratios. This study represents the first step toward the atomistic modelling of PNIPAM microgels with a controlled tacticity.},
  article-number = {13},
  creationdate   = {2025-02-14T09:27:14},
  doi            = {10.3390/gels3020013},
  file           = {:Paradossi2017 - Tacticity Dependent Interchain Interactions of Poly(N Isopropylacrylamide) in Water_ toward the Molecular Dynamics Simulation of a Thermoresponsive Microgel.pdf:PDF},
  keywords       = {molecular dynamics simulation,tacticity,pNIPAM,stereoregularity,aggregation,microgel,overlap concentration},
  pubmedid       = {30920510},
  url            = {https://www.mdpi.com/2310-2861/3/2/13},
}

@Article{Graessley1980,
  author       = {William W. Graessley},
  journal      = {Polymer},
  title        = {Polymer chain dimensions and the dependence of viscoelastic properties on concentration, molecular weight and solvent power},
  year         = {1980},
  issn         = {0032-3861},
  number       = {3},
  pages        = {258-262},
  volume       = {21},
  abstract     = {The effects of polymer concentration on chain dimensions in good solvents is discussed in order to define the boundary between the semi-dilute and concentrated regimes. Based upon the screening principle of Edwards and de Gennes, it appears that chain dimensions should approach their unperturbed values for many systems at polymer volume fractions in the range of 0.05–0.20, independent of molecular weight. From these results we propose a method for correlating viscoelastic properties in the semi-dilute region which takes into account the contraction of dimensions with concentration. We also suggest the use of a concentration-molecular weight diagram to distinguish the several regions of viscoelastic behaviour.},
  creationdate = {2025-02-14T09:56:24},
  doi          = {https://doi.org/10.1016/0032-3861(80)90266-9},
  file         = {:Graessley1980 - Polymer Chain Dimensions and the Dependence of Viscoelastic Properties on Concentration, Molecular Weight and Solvent Power.pdf:PDF},
  keywords     = {polymer solution,overlap concentration,concentration dependence,molecular weight dependence},
  url          = {https://www.sciencedirect.com/science/article/pii/0032386180902669},
}

@Article{Peschier1993,
  author       = {L.J.C. Peschier and J.A. Bouwstra and J. {de Bleyser} and H.E. Junginger and J.C. Leyte},
  journal      = {Biomaterials},
  title        = {Water mobility and structure in poly[2-hydroxyethylmethacrylate] hydrogels by means of the pulsed field gradient NMR technique},
  year         = {1993},
  issn         = {0142-9612},
  number       = {12},
  pages        = {945-952},
  volume       = {14},
  abstract     = {The translational mobility of water in poly[2-hydroxyethylmethacrylate] (pHEMA) hydrogels, cross-linked with ethyleneglycoldimethacrylate, was studied by means of the pulsed field gradient (PFG) nuclear magnetic resonance (NMR) technique, which offers the opportunity to study the molecular displacements directly under well-defined equilibrium conditions, resulting in a determination of the self-diffusion coefficient. It is possible to check whether coexisting water phases with different mobilities (on a timescale of ca. 10 ms) are present. The dependence of the diffusion coefficient of water on the degree of hydration and the cross-linker concentration was measured. Magnetic interaction is found to cause cross-relaxation between the protons of water and those of the polymer matrix. This affects the data, rendering the evaluation by the standard equation invalid. An equation taking cross-relaxation into account has been derived. Amplitude measurements have shown that all the water in the gels contributes to the NMR signal. The PFG measurements have shown that the total water phase in a gel diffuses as one homogeneous phase, which can be characterized by a diffusion coefficient. The self-diffusion coefficient is strongly dependent on the degree of hydration of the gel; the cross-linker concentration has no measurable effect. The strong dependence of the diffusion of water on its concentration in the gel has consequences for the modelling of the swelling and drug-release dynamics of pHEMA and necessitates a revision of the present models describing these processes.},
  creationdate = {2025-02-17T11:02:43},
  doi          = {https://doi.org/10.1016/0142-9612(93)90137-Q},
  file         = {:Peschier1993 - Water Mobility and Structure in Poly[2 Hydroxyethylmethacrylate] Hydrogels by Means of the Pulsed Field Gradient NMR Technique.pdf:PDF},
  keywords     = {pHEMA,pulsed field gradient NMR,cross-linking,water diffusion,peschier,hydrogel,gel,nmr,pfg,diffusion,cross-relaxation,cross-linker concentration,controlled release,drug delivery},
  url          = {https://www.sciencedirect.com/science/article/pii/014296129390137Q},
}

@Article{Peschier1996,
  author       = {L.J.C. Peschier and J.A. Bouwstra and J. {de Bleyser} and H.E. Junginger and J.C. Leyte},
  journal      = {Journal of Magnetic Resonance, Series B},
  title        = {Cross-Relaxation Effects in Pulsed-Field-Gradient Stimulated-Echo Measurements on Water in a Macromolecular Matrix},
  year         = {1996},
  issn         = {1064-1866},
  number       = {2},
  pages        = {150-157},
  volume       = {110},
  abstract     = {Water diffusion in poly[2-hydroxyethyl-methacrylate] hydrogels has been measured by PFG NMR techniques, using both spin-echo and stimulated-echo methods. It is found that the results differ when evaluated using the standard equations for the echo attenuation. Furthermore, an apparent dependence of the diffusion coefficient on the diffusion time was found in stimulated-echo experiments. This effect is shown to be caused by cross relaxation between the protons of the water and those on the polymer matrix. An equation is derived describing the attenuation of a stimulated echo in the presence of cross relaxation. This equation shows that the additional damping due to cross relaxation depends on the gradient amplitude. If this equation is used with the measured cross-relaxation parameters, both methods are found to agree within experimental error, and no diffusion-time dependence is found for the stimulated-echo experiments. The equation predicts the effect of replacing part of the H2O by D2O; this has been experimentally verified. It is concluded that macromolecular systems should be checked for cross relaxation when stimulated-echo methods will be used for self-diffusion measurements.},
  creationdate = {2025-02-17T11:05:20},
  doi          = {https://doi.org/10.1006/jmrb.1996.0024},
  file         = {:Peschier1996 - Cross Relaxation Effects in Pulsed Field Gradient Stimulated Echo Measurements on Water in a Macromolecular Matrix.pdf:PDF},
  keywords     = {NMR,STE,Hahn Echo,PFG,peschier,pHEMA,cross-relaxation,hydrogel,gel,isotope effect,self-diffusion,diffusion},
  url          = {https://www.sciencedirect.com/science/article/pii/S1064186696900242},
}









@Article{Xia2006,
  author       = {Xia, Yan and Burke, Nicholas A. D. and St{\"o}ver, Harald D. H.},
  journal      = {Macromolecules},
  title        = {End Group Effect on the Thermal Response of Narrow-Disperse Poly(N-isopropylacrylamide) Prepared by Atom Transfer Radical Polymerization},
  year         = {2006},
  number       = {6},
  pages        = {2275--2283},
  volume       = {39},
  abstract     = {Four series of narrow-disperse poly(N-isopropylacrylamide) (PNIPAM) with well-controlled molecular weights and with end groups of varying hydrophobicity were synthesized by room temperature atom transfer radical polymerization in 2-propanol using the corresponding chloropropionate and chloropropionamide initiators. The thermal phase transitions of aqueous solutions of these PNIPAMs were studied by turbidimetry and high-sensitivity differential scanning calorimetry (HS-DSC) and showed an inverse molecular weight (MW) dependence of their cloud points. The magnitude of the MW dependence decreases when using more hydrophobic end groups. The choice of end group further affected the shape of the cloud point curves and the enthalpy of the phase transition. Above the cloud point, narrow-disperse PNIPAM sedimented more rapidly than polydisperse PNIPAM produced by conventional free radical polymerization, especially at concentrations above 1\%. Thus, multiple HS-DSC scans of PNIPAM prepared by ATRP typically gave repeatable results only at lower concentrations.},
  comment      = {sedimentation assumed based only on an extra dsc peak during slow heating or incubation above the lcst in preceding runs, which is stronger for low molecular weight samples},
  creationdate = {2025-02-17T17:51:41},
  doi          = {10.1021/ma0519617},
  eprint       = {https://doi.org/10.1021/ma0519617},
  file         = {:Xia2006 - End Group Effect on the Thermal Response of Narrow Disperse Poly(N Isopropylacrylamide) Prepared by Atom Transfer Radical Polymerization.pdf:PDF},
  keywords     = {pNIPAM,macroscopic phase separation,sedimentation,ATRP,synthesis,DSC,cloud point,end group,molecular weight dependence},
  url          = {https://doi.org/10.1021/ma0519617},
}

@Article{Deshmukh2014,
  author       = {Deshmukh, Sanket A. and Kamath, Ganesh and Suthar, Kamlesh J. and Mancini, Derrick C. and Sankaranarayanan, Subramanian K. R. S.},
  journal      = {Soft Matter},
  title        = {Non-equilibrium effects evidenced by vibrational spectra during the coil-to-globule transition in poly(N-isopropylacrylamide) subjected to an ultrafast heating–cooling cycle},
  year         = {2014},
  pages        = {1462-1480},
  volume       = {10},
  abstract     = {Molecular dynamics simulations in conjunction with finite element calculations are used to explore the conformational dynamics of a thermo-sensitive oligomer{,} namely poly(N-isopropylacrylamide) (PNIPAM){,} subjected to an ultra-fast heating–cooling cycle. Finite element (FE) calculations were used to predict the temperature profile resulting from laser-induced heating of the polymer–aqueous system. The heating rate (∼0.6 K ps−1) deduced from FE calculations was used to heat an aqueous solution of PNIPAM consisting of 30 monomeric units (30-mer) from 285 K to 315 K. Non-equilibrium effects arising from the ultra-fast heating–cooling cycle results in a hysteresis during the coil-to-globule transition. The corresponding atomic scale conformations were characterized by monitoring the changes in the vibrational spectra{,} which provided a reliable metric to study the coil-to-globule transition in PNIPAM and vice-versa across the LCST. The vibrational spectra of bonds involving atoms from the oligomer backbone and the various side-groups (amide I{,} amide II{,} and the isopropyl group of PNIPAM) of the oligomers were analyzed to study the conformational changes in the oligomer corresponding to the observed hysteresis. The differences in the vibrational spectra calculated at various temperatures during heating and cooling cycles were used to understand the coil-to-globule and globule-to-coil transitions in the PNIPAM oligomer and identify the changes in the relative interactions between various atoms in the backbone and in the side groups of the oligomer with water. The shifts in the computed vibrational spectral peaks and the changes in the intensity of peaks for the different regions of PNIPAM{,} seen across the LCST during the heating cycle{,} are in good agreement with previous experimental studies. The changes in the radius of gyration (Rg) and vibrational spectra for amide I and amide II regions of PNIPAM suggest a clear coil-to-globule transition at ∼301 K during the heating cycle from 285 K to 315 K. During the heating cycle{,} a comparison of the vibrational spectra of isopropyl groups in PNIPAM at 285 K and 315 K suggests dehydration of the isopropyl moieties at 315 K. This implies that the oligomer–water interactions are dominant below the LCST whereas oligomer–oligomer interactions pre-dominate above the LCST. On the other hand{,} during the cooling cycle minor changes in the Rg and vibrational spectra of the PNIPAM oligomer in going from 315 K to 285 K indicate that the interactions between oligomer–oligomer and between the oligomer and water are less perturbed during the cooling cycle. Our simulations suggest that the observed hysteresis is a consequence of ultrafast heating–cooling kinetics{,} which allows insufficient relaxation times for the solvated oligomer.},
  creationdate = {2025-02-17T18:55:56},
  doi          = {10.1039/C3SM51750K},
  file         = {:Deshmukh2014 - Non Equilibrium Effects Evidenced by Vibrational Spectra during the Coil to Globule Transition in Poly(N Isopropylacrylamide) Subjected to an Ultrafast Heating–cooling Cycle.pdf:PDF;:NonEquilibriumEffectsEvidencedByVibrationalSpectraDuringTheCoilToGlobuleTransitionInPolyNIsopropylacrylamideSubjectedToAnUltrafastHeatingCoolingCycle_DeshmukhEtAl_SoftMatter2014_SI.pdf:PDF},
  issue        = {10},
  keywords     = {pNIPAM,hysteresis,ageing,reversibility,molecular dynamics simulation,simulation,oligomer,kinetics},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C3SM51750K},
}









@Article{Ding2005,
  author       = {Ding, Yanwei and Ye, Xiaodong and Zhang, Guangzhao},
  journal      = {Macromolecules},
  title        = {Microcalorimetric Investigation on Aggregation and Dissolution of Poly(N-isopropylacrylamide) Chains in Water},
  year         = {2005},
  number       = {3},
  pages        = {904-908},
  volume       = {38},
  abstract     = {Aggregation and dissolution of poly(N-isopropylacrylamide) (PNIPAM) in water were investigated using an ultrasensitive differential scanning calorimetry (US-DSC) and a pressure perturbation calorimetry (PPC). US-DSC reveals that both the aggregation and dissolution of PNIPAM chains are greatly dependent on the scanning rate, indicating that the processes are kinetically controlled. The hysteresis in the dissolution process was found to have a nonequilibrium nature, which is thought to be related to the additional hydrogen bondings formed in the collapsed state of PNIPAM chains. A bimodal appearing in the cooling process at a slow scanning rate indicates the dissolution involves two different processes, i.e., the disruption of additional hydrogen bondings and the dissolution of the collapsed chains. PPC reveals that the solvent accessible surface area of PNIPAM chains in the cooling process is smaller than that in the heating process, which further indicates the dissolution of the PNIPAM aggregates involves such two processes.},
  creationdate = {2025-02-18T09:43:20},
  doi          = {10.1021/ma048460q},
  eprint       = {https://doi.org/10.1021/ma048460q},
  file         = {:Ding2005 - Microcalorimetric Investigation on Aggregation and Dissolution of Poly(N Isopropylacrylamide) Chains in Water.pdf:PDF},
  keywords     = {DSC,pNIPAM,remixing,kinetics,aggregation},
  url          = {https://doi.org/10.1021/ma048460q},
}

@Article{Wang2009a,
  author       = {Wang, Weinan and Metwalli, Ezzeldin and Perlich, Jan and Troll, Kordelia and Papadakis, Christine M. and Cubitt, Robert and Müller-Buschbaum, Peter},
  journal      = {Macromolecular Rapid Communications},
  title        = {Water Storage in Thin Films Maintaining the Total Film Thickness as Probed with in situ Neutron Reflectivity},
  year         = {2009},
  number       = {2},
  pages        = {114-119},
  volume       = {30},
  abstract     = {We investigate a new type of thin film material which allows for water storage without an increase in film thickness, whereas typically water storage in polymers and polymer films is accompanied with a strong swelling of the film, i.e., a strong increase in the film thickness. So these films will avoid problems related to strains which are caused by swelling. The basic key for the preparation of such thin films is the installation of a glassy network by the use of an asymmetric diblock copolymer polystyrene-block-poly(N-isopropylacrylamide) [P(S-b-NIPAM)] with a long PS and short PNIPAM block in combination with a solvent which is more equal in interaction with both the blocks as compared to water. With in situ neutron reflectivity the water storage and removal are probed. The total film thickness increases only by 2.5\% by allowing for a total water storage of 17.4\%. Thus the material can be used for coatings to reduce humidity in nano-applications, which might suffer from changes in the water content of the surrounding environment.},
  creationdate = {2025-02-18T10:44:30},
  doi          = {https://doi.org/10.1002/marc.200800576},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/marc.200800576},
  file         = {:Wang2009a - Water Storage in Thin Films Maintaining the Total Film Thickness As Probed with in Situ Neutron Reflectivity.pdf:PDF},
  keywords     = {diblock copolymer,in situ neutron reflectivity,structure,undeformable thin films,water storage,ageing,aging,pNIPAM,PS,polystyrene,block copolymer},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/marc.200800576},
}









@Article{Harrer2019,
  author       = {Harrer, Johannes and Rey, Marcel and Ciarella, Simone and L{\"o}wen, Hartmut and Janssen, Liesbeth M. C. and Vogel, Nicolas},
  journal      = {Langmuir},
  title        = {Stimuli-Responsive Behavior of PNiPAm Microgels under Interfacial Confinement},
  year         = {2019},
  note         = {PMID: 31304759},
  number       = {32},
  pages        = {10512-10521},
  volume       = {35},
  abstract     = {The volume phase transition of microgels is one of the most paradigmatic examples of stimuli-responsiveness, enabling a collapse from a highly swollen microgel state into a densely coiled state by an external stimulus. Although well characterized in bulk, it remains unclear how the phase transition is affected by the presence of a confining interface. Here, we demonstrate that the temperature-induced volume phase transition of poly(N-isopropylacrylamide) microgels, conventionally considered an intrinsic molecular property of the polymer, is in fact largely suppressed when the microgel is adsorbed to an air/liquid interface. We further observe a hysteresis in the core morphology and interfacial pressure between heating and cooling cycles. Our results, supported by molecular dynamics simulations, reveal that the dangling polymer chains of microgel particles, spread at the interface under the influence of surface tension, do not undergo any volume phase transition. The balance in free energy responsible for the volume phase transition is fundamentally altered by interfacial confinement. These results imply that important technological properties of such systems, including the temperature-induced destabilization of emulsions, do not occur via a decrease in the interfacial coverage of the microgels.},
  creationdate = {2025-02-21T15:17:08},
  doi          = {10.1021/acs.langmuir.9b01208},
  eprint       = {https://doi.org/10.1021/acs.langmuir.9b01208},
  file         = {:Harrer2019 - Stimuli Responsive Behavior of PNiPAm Microgels under Interfacial Confinement.pdf:PDF;:StimuliResponsiveBehaviorOfPNiPAmMicrogelsUnderInterfacialConfinement_HarrerEtAl_Langmuir2019_SI.pdf:PDF},
  keywords     = {pNIPAM,microgel,adsorption,interface,reversibility,ageing,hysteresis},
  url          = {https://doi.org/10.1021/acs.langmuir.9b01208},
}









@Article{Bochenek2023,
  author       = {Bochenek, Steffen and Rudov, Andrey A. and Sassmann, Tim and Potemkin, Igor I. and Richtering, Walter},
  journal      = {Langmuir},
  title        = {Influence of Architecture on the Interfacial Properties of Polymers: Linear Chains, Stars, and Microgels},
  year         = {2023},
  note         = {PMID: 38059308},
  number       = {50},
  pages        = {18354-18365},
  volume       = {39},
  abstract     = {Surface-active polymers have important applications as effective and responsive emulsifiers, foaming agents, and coatings. In this contribution, we explore the impact of the polymer architecture on the behavior at oil–water interfaces by comparing different poly(N-isopropylacrylamide) (pNIPAM)-based systems, namely, monolayers of linear and star-shaped macromolecules, ultralow cross-linked, regular cross-linked, and hollow microgels. Compression isotherms were determined experimentally as well as by computer simulations. The latter provides information about the conformational changes of the individual macromolecules as well as the interfacial properties of the monolayer, including the surface structure and the density distribution of an ensemble of interacting macromolecules near an interface. Surprisingly, the isotherms of the linear polymer, of the star polymer, and of the ultralow cross-linked microgel have an identical shape that differs from the isotherms of regular and hollow microgels. We introduced the mass fraction of adsorbed polymer, which gives a measure of the polymer segments contributing to the isotherm in relation to the most flexible architecture, i.e., the linear polymer, and allows a comparison of polymers with different architectures. The data demonstrate that increasing the number of cross-links leads to a significantly lower amount of polymer in the proximity of the interface as the increase in cross-linker reduces the deformability or softness of the polymers at the interface. The volume fraction profiles along the normal to the interface are essentially different in the microgel monolayers as compared to those in the linear and star polymer. The profiles through the microgel contact line and their growth upon initial compression are similar to those of the linear chains. Herewith, the profiles through the center of mass practically do not change upon compression. Therefore, the initial growth in the microgel surface pressure reveals the polymer-like behavior and is related to the deformation of the peripheral part of the microgel. Further compression of the microgel monolayer leads to 3D interactions of the microgels within the aqueous side of the interface and soft colloid-like behavior.},
  creationdate = {2025-02-21T15:24:31},
  doi          = {10.1021/acs.langmuir.3c02470},
  eprint       = {https://doi.org/10.1021/acs.langmuir.3c02470},
  file         = {:Bochenek2023 - Influence of Architecture on the Interfacial Properties of Polymers_ Linear Chains, Stars, and Microgels.pdf:PDF;:InfluenceOfArchitectureOnTheInterfacialPropertiesOfPolymers-LinearChainStarsAndMicrogels_BochenekEtAl_Langmuir2023_SI.pdf:PDF},
  keywords     = {pNIPAM,star polymer,linear,microgel,gel,simulation,compression isotherm,interface,langmuir trough,surface pressure,polymer architecture},
  url          = {https://doi.org/10.1021/acs.langmuir.3c02470},
}

@Article{Zhao2010,
  author       = {Rong-Li Zhao and Ke Lin and Xiao-Guo Zhou and Shi-Lin Liu},
  journal      = {ACTA PHYSICO-CHIMICA SINICA},
  title        = {Solubility of Poly(N-isopropylacrylamide) in Aqueous Methanol from Raman Spectroscopy},
  year         = {2010},
  month        = jul,
  number       = {7},
  pages        = {1915--1922},
  volume       = {26},
  abstract     = {We measured the non. coincidence effect (NCE) in the Raman spectrum of poly(N-isopropylacrylamide) (PNIPAM) in aqueous methanol at -13 degrees C (below the lower critical solution temperature, LCST). This was done to investigate the solubility of PINPAM in aqueous methanol by considering molecular interactions. Changes of NCE when adding PNIPAM to an aqueous methanol solution show that at the molar fraction of methanol x = 1.0-0.90, PNIPAM preferentially adsorbs methanol and at x = 0.80-0.50, PNIPAM preferentially adsorbs water. At x = 0.50-0.20, PNIPAM breaks down the ring structure composed of two methanol molecules and one water molecule. Further comparison between the changes of NCE when adding PNIPAM and its monomer NIPPA indicates that PNIPAM adsorbs methanol cooperatively through hydrophobic interactions. This cooperative interaction breaks down the methanol. water ring structure at low methanol concentrations. The cononsolvency phenomenon of PNIPAM in a methanol solution when heating above the LCST temperature is attributed to a reformation of the methanol-water ring structure.},
  comment      = {publication is not in English. Maybe Chinese.},
  creationdate = {2025-02-23T10:22:31},
  doi          = {10.3866/PKU.WHXB20100728},
  file         = {:Zhao2010 - Solubility of Poly(N Isopropylacrylamide) in Aqueous Methanol from Raman Spectroscopy.pdf:PDF},
  keywords     = {pNIPAM,aqueous methanol,cononsolvency,raman spectroscopy,preferential adsorption,Noncoincidence effect,Solubility,cooperative interaction,cooperativity,light scattering,hydration},
}









@Article{Zhang2025,
  author       = {Zhang, Pengfei},
  journal      = {Macromolecules},
  title        = {Phase Separation of Homopolymers in Binary Mixed Solvents: the Co-Solvency Effect},
  year         = {2025},
  number       = {0},
  pages        = {null},
  volume       = {0},
  abstract     = {As one of the most intriguing phenomena in polymer solutions, the co-solvency effect refers to the improved miscibility of polymers in mixtures of binary poor solvents. The physical mechanism underlying this phenomenon, however, remains obscure. In this work, by using the ternary Flory–Huggins theory, we examine the phase behaviors of polymers in mixtures of binary miscible poor solvents. We derive the general analytical conditions for the co-solvency and the related co-nonsolvency effect in the long chain limit. We find that a repulsion between the two solvents is required to induce the co-solvency effect. When this repulsion is weak, the binodal curve in the surface of polymer concentration and cosolvent composition x is of the hourglass type without a critical point. When this repulsion is modest, the binodal curve splits into two separate branches, with each having a single critical point. For x between these two branches, a solution is homogeneous over all polymer concentrations, and this type of co-solvency occurs for systems with a short chain length, modestly poor quality of both solvents to the polymer, and a relatively large repulsion between the two solvents. The phase behaviors of co-solvency systems differ significantly from those in mixtures of two good solvents and those in mixtures of a good solvent and a poor solvent. These findings, along with our previous results on the phase behaviors of polymers in mixtures of binary good solvents (Zhang, P., Macromolecules, 2024, 57, 4298), further demonstrate that the co-nonsolvency effect of poly-N-isopropylacrylamide in mixtures of water and small alcohol results from exclusively the preferential attraction of the polymer to the alcohol molecule over to the water molecule. Our findings not only afford the first complete picture of the mean–field phase behaviors of the co-solvency system but also provide a valuable guide in designing solvents to dissolve polymers for various applications such as fiber wet spinning and membrane fabrication.},
  comment      = {Attention: The title contains the word cosolvency. As in mixed solvents are of BETTER quality. Cononsolvency is also mentioned. Status of the article is "accepted" as of 2025-02-28. Should check again in a few weeks.},
  creationdate = {2025-02-28T16:31:00},
  doi          = {10.1021/acs.macromol.4c02724},
  eprint       = {https://doi.org/10.1021/acs.macromol.4c02724},
  file         = {:Zhang2025 - Phase Separation of Homopolymers in Binary Mixed Solvents_ the Co Solvency Effect.pdf:PDF;:PhaseSeparationOfHomopolymersInBinaryMixedSolvents-TheCosolvencyEffect_ZhangEtAl_Macromolecules2025_SI.pdf:PDF},
  keywords     = {cosolvency,cononsolvency,flory-huggins,ternary,preferential adsorption,pNIPAM,theory},
  url          = {https://doi.org/10.1021/acs.macromol.4c02724},
}

@Article{Wu1994,
  author       = {X. Wu and R. H. Pelon and A. E. Hamielec and D. R. Woods and W. McPhee},
  journal      = {Colloid Polym Sci},
  title        = {The kinetics of poly(N-isopropylacrylamide) microgel latex formation},
  year         = {1994},
  pages        = {467--477},
  volume       = {272},
  creationdate = {2025-03-05T07:58:14},
  doi          = {10.1007/BF00659460},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/TheKineticsOfPolyNIsopropylacrylamideMicrogelLatexFormation_WuEtAl_ColloidPolymSci1994.pdf:PDF},
  keywords     = {pNIPAM,microgel,cross-linker density,synthesis,reaction rate,cross-linker distribution},
  url          = {https://doi.org/10.1007/BF00659460},
}

@Article{Still2013,
  author       = {Tim Still and Ke Chen and Ahmed M. Alsayed and Kevin B. Aptowicz and A.G. Yodh},
  journal      = {Journal of Colloid and Interface Science},
  title        = {Synthesis of micrometer-size poly(N-isopropylacrylamide) microgel particles with homogeneous crosslinker density and diameter control},
  year         = {2013},
  issn         = {0021-9797},
  pages        = {96-102},
  volume       = {405},
  abstract     = {Poly(N-isopropylacrylamide) microgel particles are synthesized using a semi-batch surfactant-free emulsion polymerization method. Particle diameter can be precisely adjusted by controlling the initial conditions, the electrolyte concentration, and the monomer feeding rate and duration. Larger particles are obtained in the presence of small amounts of co-monomer with cationic amino groups that compete against the negative charges arising from the initiator. Monodisperse particles with uniform cross-linker density, homogeneous optical properties, and pronounced thermoresponsivity are readily produced with a wide variety of diameters ranging from several hundred nanometers to a few micrometers. The charge stabilization mechanisms that control particle growth are discussed.},
  creationdate = {2025-03-05T08:02:09},
  doi          = {https://doi.org/10.1016/j.jcis.2013.05.042},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/SynthesisOfMicrometerSizePolyNIsopropylacrylamideMicrogelParticlesWithHomogeneousCrosslinkerDensityAndDiameterConotrol_StillEtAl_JColloidInterfSci2013.pdf:PDF},
  keywords     = {Colloids,Polymers,Hydrogels,Synthesis,Thermoresponsive,pNIPAM,synthesis,cross-linker distribution,microgel,feed,semi-batch,starved-feed},
  url          = {https://www.sciencedirect.com/science/article/pii/S0021979713004815},
}









@Article{Acciaro2011,
  author       = {Acciaro, Roberta and Gilányi, Tibor and Varga, Imre},
  journal      = {Langmuir},
  title        = {Preparation of Monodisperse Poly(N-isopropylacrylamide) Microgel Particles with Homogenous Cross-Link Density Distribution},
  year         = {2011},
  note         = {PMID: 21591700},
  number       = {12},
  pages        = {7917-7925},
  volume       = {27},
  abstract     = {Monodisperse microgel latex with homogeneous cross-link density distribution within the particles was prepared by feeding the monomer and cross-linker into the reaction mixture in a regulated way during the polymerization. To determine the appropriate monomer feeding parameters, the kinetics of the particle formation was investigated by HPLC. The swelling and optical characteristics of the prepared homogenously cross-linked microgel particles were compared to the properties of inhomogenously cross-linked microgels prepared by the normal precipitation polymerization method. The distribution of the cross-link density within the particles inserts a great influence on the characteristics of the system. The degree of swelling of the homogeneous particles is significantly higher than that of the heterogeneous microgel particles. Furthermore, at room temperature the pNIPAm latex containing the homogeneously cross-linked particles is transparent, while the heterogeneously cross-linked particles form a highly turbid system at the same 0.1 wt \% concentration.},
  creationdate = {2025-03-05T08:06:33},
  doi          = {10.1021/la2010387},
  eprint       = {https://doi.org/10.1021/la2010387},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/PreparationOfMonodispersePolyNIsopropylacrylamideMicrogelParticlesWithHomogeneousCrossLinkingDensityDistribution_AcciaroEtAl_Langmuir2011.pdf:PDF},
  keywords     = {pNIPAM,synthesis,cross-linker distribution,feed,semi-batch,starved-feed},
  url          = {https://doi.org/10.1021/la2010387},
}









@Article{Varga2001,
  author       = {Varga, Imre and Gilányi, Tibor and M{\'e}száros, Róbert and Filipcsei, Genoveva and Zrínyi, Miklós},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Effect of Cross-Link Density on the Internal Structure of Poly(N-isopropylacrylamide) Microgels},
  year         = {2001},
  number       = {38},
  pages        = {9071-9076},
  volume       = {105},
  abstract     = {The effect of cross-link density on the structure of Poly-(N-isopropylacrylamide) microgel particles prepared by emulsion polymerization was investigated by static and dynamic light scattering measurements. According to these measurements the gel particles cannot be considered as homogeneous spheres. The structure of the gel particles strongly depends on the degree of cross-linking. At high cross-link density the particles can be described with a Gaussian segment density distribution. With decreasing cross-link density the structure of the microgel particles tends toward that of a highly branched coil.},
  creationdate = {2025-03-07T08:18:32},
  doi          = {10.1021/jp004600w},
  eprint       = {https://doi.org/10.1021/jp004600w},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/EffectOfCrossLinkDensityOnTheInternalStructureOfPolyNIsopropylacrylamideMicrogels_VargaEtAl_JPC2001.pdf:PDF},
  keywords     = {pNIPAM,microgel,emulsion polymerization,SLS,DLS,structure,cross-linker density,cross-linker distribution},
  url          = {https://doi.org/10.1021/jp004600w},
}

@Article{Hellweg2000,
  author       = {Hellweg, T. and Dewhurst, C. and Brückner, E. and Kratz, K. and Eimer, W.},
  journal      = {Colloid Polym Sci},
  title        = {Colloidal crystals made of poly(N-isopropylacrylamide) microgel particles},
  year         = {2000},
  month        = oct,
  pages        = {972--978},
  volume       = {278},
  abstract     = {Poly (N-isopropylacrylamide) microgel particles are found to form colloidal crystals similar to those occurring in typical hard-sphere colloids like poly(methyl-methacrylate) beads. Samples made of particles with dierent cross-linker concentrations are investigated and their deswelling ratio is  determined using dynamic light scattering. Small-angle neutron scattering data are also presented and analysed in terms of a face-centred-cubic crystal structure. The characteristic length, a, of the elementary cell is found to be 535 $\pm$ 16 and 495 $\pm$ 15 nm for the two systems investigated. This leads to particle radii of 189 $\pm$ 6 and 175 $\pm$ 5 nm, respectively. These values compare well to the radii determined using several dierent methods.},
  creationdate = {2025-03-07T08:22:05},
  doi          = {10.1007/s003960000350},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/ColloidalCrystalsMadeOfPolyNIsopropylacrylamideMicrogelParticles_HellwegEtAl_ColloidPolymSci2000.pdf:PDF},
  keywords     = {pNIPAM,microgel,cross-linker concentration,DLS,SANS,hydrodynamic radius},
  url          = {https://doi.org/10.1007/s003960000350},
}

@Article{Rzaev2007,
  author       = {Zakir M.O. Rzaev and Sevil Dinçer and Erhan Pişkin},
  journal      = {Progress in Polymer Science},
  title        = {Functional copolymers of N-isopropylacrylamide for bioengineering applications},
  year         = {2007},
  issn         = {0079-6700},
  number       = {5},
  pages        = {534-595},
  volume       = {32},
  abstract     = {Various kinds of stimuli–responsive N-isopropylacrylamide copolymers are among an important class of bioengineering materials that have been the subject of many extensive investigations in the field of modern macromolecular bioengineering and biotechnology. These materials are of special interest in the fields of cell and enzyme immobilization, controlled drug delivery and gene delivery, bioconjugation, and protein dehydration process. This review summarizes the main advances published over the last 15 years, outlining the synthesis, structural phenomena, unique properties and application areas of the bioengineering copolymers of N-isopropyl acrylamide with various types of comonomers. These copolymers include linear, end functionalized and crosslinked binary and ternary copolymers, graft and block copolymers exhibiting stimuli–responsive behavior, and reversible phase transitions. Particular attention is paid to the effects of hydrogen-bonding and complexing in copolymerization reactions, the formation of supramacromolecular structures, bioconjugates, physically and chemically crosslinkable copolymers, thermosensitive hydrogels and ion-exchange membrane systems, and other important bioengineering materials.},
  creationdate = {2025-03-09T15:28:12},
  doi          = {10.1016/j.progpolymsci.2007.01.006},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/FunctionalCopolymersOfNIsopropylacrylamideForBioengineeringApplications_RzaevEtAl_ProgrPolymSci2007.pdf:PDF},
  keywords     = {-isopropylacrylamide,Copolymerization,Stimuli-responsity,Hydrogen-bonding,Bioconjugates,review,pNIPAM,application-focussed,copolymer,synthesis},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079670007000093},
}

@Article{Inomata1995,
  author       = {H. Inomata and N. Wada and Y. Yagi and S. Goto and S. Saito},
  journal      = {Polymer},
  title        = {Swelling behaviours of N-alkylacrylamide gels in water: effects of copolymerization and crosslinking density},
  year         = {1995},
  issn         = {0032-3861},
  number       = {4},
  pages        = {875-877},
  volume       = {36},
  abstract     = {N-isopropylacrylamide (NIPA)/N-n-propylacrylamide (NNPA) copolymer gels of various molar ratios were prepared by radical polymerization and the relationship between the swelling behaviour of the gels and the copolymerization ratio was studied experimentally. The effect of a crosslinking point on the swelling behaviour of the NIPA gels was investigated by preparing the gels with various crosslinking densities. The results of our experiments revealed that the transition temperatures of the NIPA/NNPA copolymer gels were changed in proportion to the monomer ratio used in copolymerization and that the crosslinking density strongly affected the swelling ratios but not the transition temperatures of the gels.},
  creationdate = {2025-03-09T15:49:53},
  doi          = {https://doi.org/10.1016/0032-3861(95)93120-B},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/SwellingBehavioursOfNAlkylacrylamideGelsInWater-EffectsOfCopolymerizationAndCrosslinkingDensity_InomataEtAl_Polymer1995.pdf:PDF},
  keywords     = {-alkylacrylamide gels, swelling behaviour, crosslinking density},
  url          = {https://www.sciencedirect.com/science/article/pii/003238619593120B},
}









@Article{Wang2019,
  author       = {Wang, Jinghong and Liu, Yuping and Chen, Rui and Zhang, Zexin and Chen, Gaojian and Chen, Hong},
  journal      = {Langmuir},
  title        = {Ultralow Self-Cross-Linked Poly(N-isopropylacrylamide) Microgels Prepared by Solvent Exchange},
  year         = {2019},
  note         = {PMID: 31596589},
  number       = {43},
  pages        = {13991-13998},
  volume       = {35},
  abstract     = {We found that the poly(N-isopropylacrylamide) (PNIPAm) synthesized by free-radical polymerization in organic phase could also form stable microgels in water through solvent exchange without chemical cross-linkers. Dynamic light scattering and transmission electron microscopy showed the larger swelling ratio and higher deformability of these microgels. Nuclear magnetic resonance and infrared spectroscopy indicated that the self-cross-linking structures in these microgels were attributed to the hydrogen atom abstraction both from the isopropyl tert-carbon atoms and the vinyl tert-carbon atoms in PNIPAm chains and the organic solvents were important assistants in the hydrogen abstraction behavior. Our discovery revealed that the self-cross-linking of PNIPAm chains is a common phenomenon within their free-radical polymerization process, whether in aqueous phase or in organic phase. Besides, the addition of second monomers will not affect the cross-linkage of the PNIPAm portion, which may be of great significance for the synthesis of various functional ultralow cross-linking PNIPAm microgels.},
  creationdate = {2025-03-10T09:48:18},
  doi          = {10.1021/acs.langmuir.9b02722},
  eprint       = {https://doi.org/10.1021/acs.langmuir.9b02722},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/UltralowSelfCrossLinkedPolyNIsopropylacrylamideMicrogelsPreparedBySolventExchange_WangEtAl_Langmuir2019.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/UltralowSelfCrossLinkedPolyNIsopropylacrylamideMicrogelsPreparedBySolventExchange_WangEtAl_Langmuir2019_SI.pdf:PDF},
  keywords     = {pNIPAM,cross-linker concentration,cross-linker density,ultra-low cross-linking,self-cross-linking,microgel,DLS,TEM,NMR,infrared,copolymer,hydrogen abstraction},
  url          = {https://doi.org/10.1021/acs.langmuir.9b02722},
}

@Article{Bachman2015,
  author       = {Bachman, Haylee and Brown, Ashley C. and Clarke, Kimberly C. and Dhada, Kabir S. and Douglas, Alison and Hansen, Caroline E. and Herman, Emily and Hyatt, John S. and Kodlekere, Purva and Meng, Zhiyong and Saxena, Shalini and Spears Jr, Mark W. and Welsch, Nicole and Lyon, L. Andrew},
  journal      = {Soft Matter},
  title        = {Ultrasoft{,} highly deformable microgels},
  year         = {2015},
  pages        = {2018-2028},
  volume       = {11},
  abstract     = {Microgels are colloidally stable{,} hydrogel microparticles that have previously been used in a range of (soft) material applications due to their tunable mechanical and chemical properties. Most commonly{,} thermo and pH-responsive poly(N-isopropylacrylamide) (pNIPAm) microgels can be fabricated by precipitation polymerization in the presence of the co-monomer acrylic acid (AAc). Traditionally pNIPAm microgels are synthesized in the presence of a crosslinking agent{,} such as N{,}N′-methylenebisacrylamide (BIS){,} however{,} microgels can also be synthesized under ‘crosslinker free’ conditions. The resulting particles have extremely low (<0.5%){,} core-localized crosslinking resulting from rare chain transfer reactions. AFM nanoindentation of these ultralow crosslinked (ULC) particles indicate that they are soft relative to crosslinked microgels{,} with a Young{'}s modulus of ∼10 kPa. Furthermore{,} ULC microgels are highly deformable as indicated by a high degree of spreading on glass surfaces and the ability to translocate through nanopores significantly smaller than the hydrodynamic diameter of the particles. The size and charge of ULCs can be easily modulated by altering reaction conditions{,} such as temperature{,} monomer{,} surfactant and initiator concentrations{,} and through the addition of co-monomers. Microgels based on the widely utilized{,} biocompatible polymer polyethylene glycol (PEG) can also be synthesized under crosslinker free conditions. Due to their softness and deformability{,} ULC microgels are a unique base material for a wide variety of biomedical applications including biomaterials for drug delivery and regenerative medicine.},
  creationdate = {2025-03-10T09:54:29},
  doi          = {10.1039/C5SM00047E},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/UltrasoftHighlyDeformableMicrogels_BachmanEtAl_SoftMatter2015.pdf:PDF},
  issue        = {10},
  keywords     = {pNIPAM,ultra-low cross-linking,self-cross-linking,AFM,PEG,DLS,viscosimetry,hydrodynamic radius},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C5SM00047E},
}

@Article{Virtanen2016,
  author       = {Virtanen, O. L. J. and Mourran, A. and Pinard, P. T. and Richtering, W.},
  journal      = {Soft Matter},
  title        = {Persulfate initiated ultra-low cross-linked poly(N-isopropylacrylamide) microgels possess an unusual inverted cross-linking structure},
  year         = {2016},
  pages        = {3919-3928},
  volume       = {12},
  abstract     = {Cross-linking density and distribution are decisive for the mechanical and other properties of stimuli-sensitive poly(N-isopropylacrylamide) microgels. Here we investigate the structure of ultra-low cross-linked microgels by static light scattering and scanning force microscopy{,} and show that they have an inverted cross-linking structure with respect to conventional microgels{,} contrary to what has been assumed previously. The conventional microgels have the largest polymer volume fraction in the core from where the particle density decays radially outwards{,} whereas ultra-low cross-linked particles have the highest polymer volume fraction close to the surface. On a solid substrate these particles form buckled shapes at high surface coverage{,} as shown by scanning force micrographs. The special structure of ultra-low cross-linked microgels is attributed to cross-linking of the particle surface{,} which is exposed to hydrogen abstraction by radicals generated from persulfate initiators during and after polymerization. The particle core{,} which is less accessible to the diffusion of radicals{,} has consequently a lower polymer volume fraction in the swollen state. By systematic variation of the cross-linker concentration it is shown that the cross-linking contribution from peroxide under typical synthesis conditions is weaker than that from the use of 1 mol% N{,}N′-methylenebisacrylamide. Soft deformable hydrogel particles are of interest because they emulate biological tissues{,} and understanding the underlying synthesis principle enables tailoring the microgel structure for biomimetic applications. Deformability of microgels is usually controlled by the amount of added cross-linker; here we however highlight an alternative approach through structural softness.},
  creationdate = {2025-03-10T10:01:45},
  doi          = {10.1039/C6SM00140H},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/PersulfateInitiatedUltraLowCrossLinkedPolyNIsopropylacrylamideMicrogelsPossessAnUnusualInvertedCrossLinkingStructure_VirtanenEtAl_SoftMatter2016.pdf:PDF},
  issue        = {17},
  keywords     = {pNIPAM,microgel,synthesis,KPS,APS,SLS,DLS,SEM,AFM,ultra-low cross-linking,self-cross-linking},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C6SM00140H},
}

@Article{Senff2000,
  author       = {H. Senff and W. Richtering},
  journal      = {Colloid Polym Sci},
  title        = {Influence of cross-link density on rheological properties of temperature-sensitive microgel suspensions},
  year         = {2000},
  pages        = {830--840},
  volume       = {278},
  abstract     = {The influence of the cross-link density on rheological properties of thermosensitive microgels was investigated. The temperature-sensitive hydrogel particles consisted of poly (N-isopropylacrylamide) (PNiPAM) chemically cross-linked with several different molar ratios of N,N'-methylenebisacrylamide. The variation of cross-link density leads to soft spheres that possess a different particle interaction potential and a different swelling ratio. With increasing temperature the microgel particles decrease in size and with it the effective volume fraction, which leads to strong changes in rheological properties. The relative zero-shear viscosity and the plateau modulus at different temperatures superpose to mastercuvres when plotted versus the effective volume fraction. Up to an effective volume fraction of 0.5 the microgels behaved like hard spheres and the maximum volume fraction, as determined from the divergence of the zero-shear viscosity, was mainly dominated by the polydispersity of the spheres and not by the cross-link density. The plateau modulus, on the other hand, revealed soft-sphere behavior and the interaction potential became softer with decreasing cross-linker content.},
  creationdate = {2025-03-10T10:14:45},
  doi          = {10.1007/s003960000329},
  file         = {:Senff2000 - Influence of Cross Link Density on Rheological Properties of Temperature Sensitive Microgel Suspensions.pdf:PDF},
  keywords     = {pNIPAM,cross-linker density,cross-linker concentration,rheology,DLS,hydrodynamic radius,DSC},
  url          = {https://doi.org/10.1007/s003960000329},
}









@Article{Woodward2003,
  author       = {Woodward, Nicola C. and Chowdhry, Babur Z. and Snowden, Martin J. and Leharne, Stephen A. and Griffiths, P. C. and Winnington, Angie L.},
  journal      = {Langmuir},
  title        = {Calorimetric Investigation of the Influence of Cross-Linker Concentration on the Volume Phase Transition of Poly(N-isopropylacrylamide) Colloidal Microgels},
  year         = {2003},
  number       = {8},
  pages        = {3202-3211},
  volume       = {19},
  abstract     = {A series of poly(N-isopropylacrylamide) microgels were prepared, by a surfactant-free emulsion polymerization method, incorporating varying cross-linker concentrations (0.25−30.0\% of N,N‘-methylenebisacrylamide). Turbidimetric, light scattering, and differential scanning calorimetric (DSC) analyses of aqueous dispersions of these microgels show that the temperature and the half-width of the overall volume phase transition (VPT) of the colloidal dispersions increase with increasing cross-linker concentration. DSC analysis also reveals a decrease in the overall calorimetric enthalpy of the VPTs with increasing cross-linker concentration. The DSC thermograms have been deconvoluted into two component transitions; one is asymmetric and attributed to aggregation of “free” N-isopropylacrylamide monomers/oligomers, and a second, two-state conformational transition, is associated with the cross-linked microgels. Pulsed-gradient spin−echo NMR diffusion measurements show that the diffusion of water within the particles can be estimated and this diffusion rate decreases with increasing cross-link concentration. Complementary fluorescence studies show an increased hydrophobicity as the cross-linker density increases.},
  creationdate = {2025-03-10T10:31:50},
  doi          = {10.1021/la020881i},
  eprint       = {https://doi.org/10.1021/la020881i},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/CalorimetricInvestigationOfTheInfluenceOfCrossLinkerConcentrationOnTheVolumePhaseTransitionOfPolyNIsopropylacrylamideColloidalMicrogels_WoodwardEtAl_Langmuir2003.pdf:PDF},
  keywords     = {pNIPAM,microgel,DSC,cross-linker density,cross-linker concentration,PFG,NMR,self-diffusion coefficient,diffusion,fluorescence,turbidity,light scattering},
  url          = {https://doi.org/10.1021/la020881i},
}

@Misc{Merck_BIS,
  creationdate = {2025-03-10T11:00:30},
  keywords     = {N,N′-Methylenbis(acrylamid),Bis-acrylamid,synthesis,uncitable,sample preparation},
  lastvisited  = {2025-03-10T11:00:30},
  url          = {https://www.sigmaaldrich.com/DE/de/product/sial/146072?srsltid=AfmBOor7exfYJcBld9ScKo0eRnYBbToueCt0aouKEoY_u1NarEiEx0Me},
  urldate      = {2025-03-10T11:00:30},
}









@Article{Hazra2024,
  author       = {Hazra, Nabanita and Ninarello, Andrea and Scotti, Andrea and Houston, Judith E. and Mota-Santiago, Pablo and Zaccarelli, Emanuela and Crassous, J{\'e}rôme J.},
  journal      = {Macromolecules},
  title        = {Structure of Responsive Microgels down to Ultralow Cross-Linkings},
  year         = {2024},
  number       = {1},
  pages        = {339-355},
  volume       = {57},
  abstract     = {Although microgels have been widely used as model systems for soft colloids, their properties are still far from being completely understood. This stems from their heterogeneous structure strongly differing from that of an idealized polymeric network. Indeed, microgels synthesized by conventional precipitation polymerization exhibit not only a fuzzy structure with respect to the difference of reactivity between monomers and cross-linker molecules but also static heterogeneities related to the distribution in the length of the chains constituting their network. These features can be reproduced in computer simulations using the so-called in silico synthesis. Hereby, a designing force acting on the cross-linkers during the in silico synthesis allows us to finely adjust the radial density distribution and, thus, to reproduce both the fuzziness and local heterogeneities present in real microgel systems. In this study, poly(N-isopropylacrylamide) (PNIPAM) microgels were synthesized with different degrees of cross-linking ccross down to cross-linker free conditions corresponding to so-called ultralow cross-linked microgels (ULC microgels). The experimental characterization was accompanied by numerical simulations at different ccross with the same designing force, which is found to be independent of the cross-linker concentration, as well as the size of the microgels. For the ULC microgels, it was found that no designing force is needed, but the number density of the network is much smaller. The number of effective cross-linkers in this case is found to be ∼0.1\%. The form factors of all microgels were measured at different temperatures across their volume phase transition with both static light scattering and small-angle X-ray scattering, favorably comparing them to the simulated ones. Furthermore, the swelling behavior was experimentally determined by dynamic light scattering and viscosimetry and also compared to the simulated results. Finally, experimental and simulated results indicate that the cross-linking dependence of the swelling is well-described by theoretical predictions for the isotropic swelling of an ideal network despite the highly heterogeneous character of real microgels.},
  creationdate = {2025-03-10T15:31:25},
  doi          = {10.1021/acs.macromol.3c00766},
  eprint       = {https://doi.org/10.1021/acs.macromol.3c00766},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/StructureOfResponsiveMicrogelsDownToUltralowCrossLinkings_HazraEtAl_Macromol2024.pdf:PDF;:PhaseSeparationOfHomopolymersInBinaryMixedSolvents-TheCosolvencyEffect_ZhangEtAl_Macromolecules2025_SI.pdf:PDF},
  keywords     = {pNIPAM,microgel,simulation,ultra-low cross-linking,cross-linker concentration,cross-linker density,cross-linker distribution,SLS,DLS,SAXS,viscosimetry},
  url          = {https://doi.org/10.1021/acs.macromol.3c00766},
}









@Article{Saunders2004,
  author       = {Saunders, Brian R.},
  journal      = {Langmuir},
  title        = {On the Structure of Poly(N-isopropylacrylamide) Microgel Particles},
  year         = {2004},
  note         = {PMID: 15969381},
  number       = {10},
  pages        = {3925-3932},
  volume       = {20},
  abstract     = {This investigation presents a study of the internal structure of poly(NIPAM/xBA) microgel particles (NIPAM and BA are N-isopropylacrylamide and N,N‘-methylene bisacrylamide, respectively). In this study, x is the wt \% of BA used during microgel synthesis. Two values of x were used to prepare the microgels, 1 and 10. The microgel dispersions were investigated using photon correlation spectroscopy (PCS) and small-angle neutron scattering (SANS). These measurements were made as a function of temperature in the range 30−50 °C. Scattering maxima were observed for the microgels when the dispersion temperatures were less than their volume phase transition temperatures. The SANS data were fitted using a model which consisted of Porod and Ornstein−Zernike form factors. The analysis showed that the macroscopic hydrodynamic diameter of the microgel particles and the submicroscopic mesh size of the network are linearly related. This is the first study to demonstrate affine swelling for poly(NIPAM/xBA) microgels. Furthermore, the mesh size does not appear to be strongly affected by x. The data suggest that the swollen particles have a mostly homogeneous structure, although evidence for a thin, low segment density shell is presented. The study confirms that poly(NIPAM/xBA) microgel particles have a core−shell structure. The shell has an average thickness of ∼20 nm for poly(NIPAM/1BA) particles which appears to be independent of temperature over the range studied. The analysis suggests that the particles contained ∼50 vol \% water at 50 °C. The molar mass of the poly(NIPAM/1BA) microgel particles was estimated as 6 × 109 g mol-1.},
  creationdate = {2025-03-10T16:07:52},
  doi          = {10.1021/la036390v},
  eprint       = {https://doi.org/10.1021/la036390v},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/OnTheStructureOfPolyNIsopropylacrylamideMicrogelParticles_Saunders_Langmuir2004.pdf:PDF},
  keywords     = {pNIPAM,microgel,cross-linker concentration,cross-linker density,mesh size,SANS,PCS,hydrodynamic radius},
  url          = {https://doi.org/10.1021/la036390v},
}

@Article{Seelenmeyer2001,
  author       = {Seelenmeyer, S. and Deike, I. and Rosenfeldt, S. and Norhausen, Ch. and Dingenouts, N. and Ballauff, M. and Narayanan, T. and Lindner, P.},
  journal      = {The Journal of Chemical Physics},
  title        = {Small-angle x-ray and neutron scattering studies of the volume phase transition in thermosensitive core–shell colloids},
  year         = {2001},
  issn         = {0021-9606},
  month        = {06},
  number       = {23},
  pages        = {10471-10478},
  volume       = {114},
  abstract     = {The volume transition in thermosensitive colloidal core–shell particles is investigated by small-angle x-ray scattering (SAXS), small-angle Neutron scattering (SANS), and dynamic light scattering (DLS). The latex particles are dispersed in water and consist of a solid poly(styrene) core with a diameter of 100 nm. The thermosensitive shell is made up of poly(N-isopropylacrylamide) (PNIPA) chains crosslinked by 2.5 mol \% N,N’-methylenbisacrylamide (BIS). Water is a good solvent for PNIPA at room temperature but becomes a poor solvent above 32 °C. The PNIPA network of the shell undergoes a volume transition at this temperature. As a result the diameter of the particle shrinks. The scattering intensities of the particles measured by SAXS and SANS as a function of temperature may be decomposed into a part deriving from the overall structure and a part originating from the fluctuations within the network. The analysis of the overall structure leads to the volume fraction of the swollen network at different temperatures. SANS in conjunction with contrast variation demonstrates that the network is confined in a well-defined shell. SAXS and SANS data therefore allow the phase diagram of the network in the shell of the particles to be derived, i.e., the average volume fraction of the network in the shell can be determined as a function of temperature. DLS corroborates this result but demonstrates that there is a small fraction of chains exceeding the outer radius derived from SAXS and SANS. The static intensity caused by the fluctuations of the network becomes the leading contribution at high scattering angles. SAXS data show that this part can be described by a Lorentzian both below and above the volume transition. The analysis demonstrates that critical fluctuations of the network around the transition temperature are fully suppressed. This finding is explained by the strong steric constraint of the network by its confinement within a shell of colloidal dimension. The swelling and shrinking can only take place along the radial direction and the chains are bound to the solid surface of the cores which remains constant during the transition.},
  creationdate = {2025-03-10T16:42:47},
  doi          = {10.1063/1.1374633},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/114/23/10471/19105718/10471\_1\_online.pdf},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/SmallAngleXRayAndNeutronScatteringStudiesOfTheVolumePhaseTransitionInThermosensitiveCoreShellColloids_SeelenmeyerEtAl_JCP2001.pdf:PDF},
  keywords     = {mesh size,SANS,SAXS,core-shell,DLS,pNIPAM,PS,gel},
  url          = {https://doi.org/10.1063/1.1374633},
}









@Article{Li2021a,
  author       = {Li, Gen and Varga, Imre and Kardos, Attila and Dobryden, Illia and Claesson, Per M.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Nanoscale Mechanical Properties of Core–Shell-like Poly-NIPAm Microgel Particles: Effect of Temperature and Cross-Linking Density},
  year         = {2021},
  note         = {PMID: 34428041},
  number       = {34},
  pages        = {9860-9869},
  volume       = {125},
  abstract     = {Poly-NIPAm microgel particles with two different cross-linking densities were prepared with the classical batch polymerization process. These particles were adsorbed onto modified silica surfaces, and their nanomechanical properties were measured by means of atomic force microscopy. It was found that these particles have a hard core–soft shell structure both below and above the volume transition temperature. The core–shell-like structure appears due to a higher reaction rate of the cross-linker compared to that of the monomer, leading to depletion of cross-linker in the shell region. The microgel beads with lower average cross-linking density were found to be less stiff below the volume transition temperature than the microgel with higher cross-linking density. Increasing the temperature further to just above the volume transition temperature led to lower stiffness of the more highly cross-linked microgel compared to its less cross-linked counterpart. This effect is explained with the more gradual deswelling with temperature for the more cross-linked microgel particles. This phenomenon was confirmed by dynamic light scattering measurements in the bulk phase, which showed that the larger cross-linking density microgel showed a more gradual collapse in aqueous solution as the temperature was increased.},
  creationdate = {2025-03-10T17:39:51},
  doi          = {10.1021/acs.jpcb.1c04173},
  eprint       = {https://doi.org/10.1021/acs.jpcb.1c04173},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/NanoscaleMechanicalPropertiesOfCoreShellLikePolyNIPAmMicrogelParticles-EffectOfTemperatureAndCrossLinkingDensity_LiEtAl_JPC2021.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/NanoscaleMechanicalPropertiesOfCoreShellLikePolyNIPAmMicrogelParticles-EffectOfTemperatureAndCrossLinkingDensity_LiEtAl_JPC2021_SI.pdf:PDF},
  keywords     = {pNIPAM,cross-linker density,cross-linker concentration,AFM,core-shell,DLS,hydrodynamic radius,rheology},
  url          = {https://doi.org/10.1021/acs.jpcb.1c04173},
}

@Article{Kyrey2019,
  author       = {Kyrey, Tetyana and Witte, Judith and Feoktystov, Artem and Pipich, Vitaliy and Wu, Baohu and Pasini, Stefano and Radulescu, Aurel and Witt, Marcus U. and Kruteva, Margarita and von Klitzing, Regine and Wellert, Stefan and Holderer, Olaf},
  journal      = {Soft Matter},
  title        = {Inner structure and dynamics of microgels with low and medium crosslinker content prepared via surfactant-free precipitation polymerization and continuous monomer feeding approach},
  year         = {2019},
  pages        = {6536-6546},
  volume       = {15},
  abstract     = {The preparation of poly(N-isopropylacrylamide) microgels via classical precipitation polymerization (batch method) and a continuous monomer feeding approach (feeding method) leads to different internal crosslinker distributions{,} i.e.{,} from core–shell-like to a more homogeneous one. The internal structure and dynamics of these microgels with low and medium crosslinker concentrations are studied with dynamic light scattering and small-angle neutron scattering in a wide q-range below and above the volume phase transition temperature. The influence of the preparation method{,} and crosslinker and initiator concentration on the internal structure of the microgels is investigated. In contrast to the classical conception where polymer microgels possess a core–shell structure with the averaged internal polymer density distribution within the core part{,} a detailed view of the internal inhomogeneities of the PNIPAM microgels and the presence of internal domains even above the volume phase transition temperature{,} when polymer microgels are in the deswollen state{,} are presented. The correlation between initiator concentration and the size of internal domains that appear inside the microgel with temperature increase is demonstrated. Moreover{,} the influence of internal inhomogeneities on the dynamics of the batch- and feeding-microgels studied with neutron spin-echo spectroscopy is reported.},
  creationdate = {2025-03-11T16:27:24},
  doi          = {10.1039/C9SM01161G},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/InnerStructureAndDynamicsOfMicrogelsWithLowAndMediumCrosslinkerContentPreparedViaSurfactantFreePrecipitationPolymerizationAndContinuousMonomerFeedingApproach_KyreyEtAl_SoftMatter2019.pdf:PDF},
  issue        = {32},
  keywords     = {pNIPAM,mesh size,cross-linker density,cross-linker concentration,cross-linker distribution,DLS,SANS,NSE},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C9SM01161G},
}

@Article{Hoogenboom2009,
  author       = {Hoogenboom, Richard and Rogers, Sarah and Can, Aydin and Becer, C. Remzi and Guerrero-Sanchez, Carlos and Wouters, Daan and Hoeppener, Stephanie and Schubert, Ulrich S.},
  journal      = {Chem. Commun.},
  title        = {Self-assembly of double hydrophobic block copolymers in water–ethanol mixtures: from micelles to thermoresponsive micellar gels},
  year         = {2009},
  pages        = {5582-5584},
  abstract     = {Micellization and micellar gel formation of poly(styrene)-block-poly(methyl methacrylate) [PS-b-PMMA] are demonstrated in a water–ethanolsolvent mixture; full hydration of the PMMA causes a large radius of gyration resulting in micellar gel formation at only 1 wt% polymer concentration.},
  creationdate = {2025-03-19T10:45:30},
  doi          = {10.1039/B911858F},
  file         = {:/autohome/saeckech/Promotion/Literatur/Polymer_Networks_Microgels/SelfAssemblyOfDoubleHydrophobicBlockCopolymersInWaterEthanolMixtures-FromMicellesToThermoresponsiveMicellarGels_HoogenboomEtAl_ChemComm2009.pdf:PDF},
  issue        = {37},
  keywords     = {PMMA,aqueous alcohol,thermoresponsive,gel,self-assembly,PS,copolymer,radius of gyration,cosolvency},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/B911858F},
}









@Article{Katayama1984,
  author       = {Katayama, Seiji and Hirokawa, Yoshitsugu and Tanaka, Toyoichi},
  journal      = {Macromolecules},
  title        = {Reentrant phase transition in acrylamide-derivative copolymer gels},
  year         = {1984},
  number       = {12},
  pages        = {2641-2643},
  volume       = {17},
  abstract     = {N,N-Diethylacrylamide and N-isopropylacrylamide geld having ionizable groups were found to undergo a reentrant volume transition between swollen and collapsed states when the ratio of water to dimethyl sulfoxide in the solvent was monotonically varied. The behavior of the gels was interpreted by assuming the free energy of contact between polymer segments was not a linear function of the sovlent composition.},
  creationdate = {2025-03-19T10:57:38},
  doi          = {10.1021/ma00142a032},
  eprint       = {https://doi.org/10.1021/ma00142a032},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/ReentrantPhaseTransitionInAcrylamideDerivativeCopolymerGels_KatayamaEtAl_Macromol1984.pdf:PDF},
  keywords     = {pDEAM,pNIPAM,gel,UCST,reentrant transition,DMSO,volumetry},
  url          = {https://doi.org/10.1021/ma00142a032},
}

@Article{Amiya1987,
  author       = {Amiya, Takayuki and Hirokawa, Yoshitsugu and Hirose, Yoshiharu and Li, Yong and Tanaka, Toyoichi},
  journal      = {The Journal of Chemical Physics},
  title        = {Reentrant phase transition of N‐isopropylacrylamide gels in mixed solvents},
  year         = {1987},
  issn         = {0021-9606},
  month        = {02},
  number       = {4},
  pages        = {2375-2379},
  volume       = {86},
  abstract     = {Reentrant volume–phase transitions are observed in N‐isopropyoacrylamide gels in the methanol–water mixtures. When the solvent composition is varied systematically, the gel undergoes two transitions: a discontinuous collapsing followed by a discontinuous swelling. The reentrant transition defines a closed‐loop instability phase boundary having both upper and lower critical points. The closed‐loop phase boundary depends on temperature and diminishes to a point at approximately 0 °C. A simple mean field theory is presented to describe the phenomenon, which reveals an alteration of free energy of alcohol–water interaction by presence of polymer network. In the case of ethanol–water mixtures, there appear two closed‐loop phase boundaries, whose physico‐chemical basis are not yet clear.},
  creationdate = {2025-03-19T11:11:32},
  doi          = {10.1063/1.452740},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/86/4/2375/18963130/2375\_1\_online.pdf},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/ReentrantPhaseTransitionOfNIsopropylacrylamideGelsInMixedSolvents_AmiyaEtAl_JCP1987.pdf:PDF},
  keywords     = {pNIPAM,gel,UCST,cononsolvency,aqueous alcohol,aqueous methanol,aqueous ethanol,volumetry},
  url          = {https://doi.org/10.1063/1.452740},
}

@Article{Zhang2020,
  author       = {Zhang, Xiangyu and Zong, Jing and Meng, Dong},
  journal      = {Soft Matter},
  title        = {A unified understanding of the cononsolvency of polymers in binary solvent mixtures},
  year         = {2020},
  pages        = {7789-7796},
  volume       = {16},
  abstract     = {The standard random phase approximation (RPA) model is applied to investigate the cononsolvency of polymers in mixtures of two good solvents. It is shown that in the RPA framework{,} the two types of cononsolvency behaviors reported in previous theoretical studies can be unified under the same concept of mean-field density correlations. The two types of cononsolvency are distinguished by the solvent composition at which maximum immiscibility is predicted to occur. The maximum immiscibility occurs with the cosolvent being the minor solvent if the driving mechanism is the preferential solvation of polymers. For the cononsolvency driven by the preferential mixing of solvents{,} the maximum immiscibility is predicted at a symmetric solvent composition. An interplay of the two driving forces gives rise to a reentrant behavior in which the cononsolvency of the two types switches from one to the other{,} through a “conventional” region where the overall solvent quality varies monotonically with the solvent composition. The RPA model developed in this work provides a unified analytical framework for understanding the conformational and solubility transition of polymers in multi-solvent mixtures. Such findings highlight the complex role played by the solvents in polymer solutions{,} a problem of fundamental and practical interest in diverse applications of materials science.},
  creationdate = {2025-03-19T11:35:07},
  doi          = {10.1039/D0SM00811G},
  file         = {:/autohome/saeckech/Promotion/Literatur/Cononsolvency/AUnifiedUnderstandingOfTheCononsolvencyOfPolymersInBinarySolventMixtures_ZhangEtAl_SoftMatter2020.pdf:PDF},
  issue        = {33},
  keywords     = {cononsolvency,random phase approximation,theory,preferential adsorption,solvent complexation,UCST,reentrant,binary solvent},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D0SM00811G},
}

@Article{Mukherji2017,
  author       = {Mukherji, Debashish and Marques, Carlos M and Kremer, Kurt},
  journal      = {Journal of Physics: Condensed Matter},
  title        = {Collapse in two good solvents, swelling in two poor solvents: defying the laws of polymer solubility?},
  year         = {2017},
  month        = dec,
  number       = {2},
  pages        = {024002},
  volume       = {30},
  abstract     = {In this work we discuss two mirror but distinct phenomena of polymer paradoxical properties in mixed solvents: co-non-solvency and co-solvency. When a polymer collapses in a mixture of two miscible good solvents the phenomenon is known as co-non-solvency, while co-solvency is a phenomenon that is associated with the swelling of a polymer in poor solvent mixtures. A typical example of co-non-solvency is provided by poly(N-isopropylacrylamide) in aqueous alcohol, while poly(methyl methacrylate) in aqueous alcohol shows co-solvency. We discuss these two phenomena to compare their microscopic origins and show that both can be understood within generic universal concepts. A broad range of polymers is therefore expected to exhibit these phenomena where specific chemical details play a lesser role than the appropriate combination of interactions between the trio of molecular components.},
  creationdate = {2025-03-19T11:48:05},
  doi          = {10.1088/1361-648X/aa9c77},
  file         = {:/autohome/saeckech/Promotion/Literatur/Cononsolvency/CollapseInTwoGoodSolventsSwellingInTwoPoosSolvents-DefyingTheLawsOfPolymerSolubility_MukherjiEtAl_JPhysCondMatt2017.pdf:PDF},
  keywords     = {pNIPAM,pMPC,pAPOMe,cosolvency,cononsolvency,binary solvent,review},
  publisher    = {IOP Publishing},
  url          = {https://dx.doi.org/10.1088/1361-648X/aa9c77},
}









@Article{Zhang2024,
  author       = {Zhang, Pengfei},
  journal      = {Macromolecules},
  title        = {Phase Separation of Homopolymers in Binary Mixed Solvents─The Co-Nonsolvency Effect},
  year         = {2024},
  number       = {9},
  pages        = {4298-4311},
  volume       = {57},
  abstract     = {As one of the most intriguing phenomena in polymer solutions, the co-nonsolvency effect refers to the collapse of a homopolymer chain or phase separation of homopolymer solutions in mixtures of two good solvents. Despite decades of research, the molecular mechanism underlying the co-nonsolvency effect is still under debate. In this work, by using the ternary Flory–Huggins theory, we report the first complete mean-field phase behaviors of homopolymer solutions in binary mixtures of two miscible good solvents. We construct the binodal, spinodal, and critical points for several representative systems. Our calculations show that a homopolymer solution can separate into coexisting phases either when the quality difference between the two solvents is sufficiently large or in the presence of strong attractions between the two solvents. For both cases, the binodal and spinodal curves in the concentration plane of the polymer and the better solvent exhibit closed-loop features along with two critical points. However, the slope of the tie lines has the opposite sign in these two cases: it is positive in the former and negative in the latter. This suggests a convenient and decisive means to elucidate the physical mechanism of the co-nonsolvency effect. Moreover, we find that a phase-separated solution may undergo a re-entrant phenomenon while increasing the attractive strength between the two solvents.},
  creationdate = {2025-03-20T15:02:32},
  doi          = {10.1021/acs.macromol.4c00090},
  eprint       = {https://doi.org/10.1021/acs.macromol.4c00090},
  file         = {:/autohome/saeckech/Promotion/Literatur/Cononsolvency/PhaseSeparationOfHomopolymersInBinaryMixedSolvents-TheCononsolvencyEffect_Zhang_Macromol2024.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Cononsolvency/PhaseSeparationOfHomopolymersInBinaryMixedSolvents-TheCononsolvencyEffect_Zhang_Macromol2024_SI.pdf:PDF},
  keywords     = {cononsolvency,flory-huggins,ternary,preferential adsorption,pNIPAM,theory},
  url          = {https://doi.org/10.1021/acs.macromol.4c00090},
}

@InBook{Krueger2017,
  author       = {Krueger, Susan},
  editor       = {Chaudhuri, Barnali and Mu{\~{n}}oz, In{\'e}s G. and Qian, Shuo and Urban, Volker S.},
  pages        = {65--85},
  publisher    = {Springer Singapore},
  title        = {Designing and Performing Biological Solution Small-Angle Neutron Scattering Contrast Variation Experiments on Multi-component Assemblies},
  year         = {2017},
  address      = {Singapore},
  isbn         = {978-981-10-6038-0},
  abstract     = {Solution small-angle neutron scattering (SANS) combined with contrast variation provides information about the size and shape of individual components of a multi-component biological assembly, as well as the spatial arrangements between the components. The large difference in the neutron scattering properties between hydrogen and deuterium is key to the method. Isotopic substitution of deuterium for some or all of the hydrogen in either the molecule or the solvent can greatly alter the scattering properties of the biological assembly, often with little or no change to its biochemical properties. Thus, SANS with contrast variation provides unique information not easily obtained using other experimental techniques.},
  booktitle    = {Biological Small Angle Scattering: Techniques, Strategies and Tips},
  creationdate = {2025-03-24T12:52:57},
  doi          = {10.1007/978-981-10-6038-0_5},
  file         = {:/autohome/saeckech/Promotion/Literatur/Neutron_Spin_Echo/DesigningAndPerformingBiologicalSolutionSmallAngleNeutronScatteringContrastVariationExperimentsOnMultiComponentAssemblies_Krueger_BioSAS2017.pdf:PDF},
  keywords     = {SANS,book,theory,contrast variation,isotope effect},
  url          = {https://doi.org/10.1007/978-981-10-6038-0_5},
}

@Article{Kubo1966,
  author       = {R Kubo},
  journal      = {Reports on Progress in Physics},
  title        = {The fluctuation-dissipation theorem},
  year         = {1966},
  month        = {jan},
  number       = {1},
  pages        = {255},
  volume       = {29},
  abstract     = {The linear response theory has given a general proof of the fluctuation-dissipation theorem which states that the linear response of a given system to an external perturbation is expressed in terms of fluctuation properties of the system in thermal equilibrium. This theorem may be represented by a stochastic equation describing the fluctuation, which is a generalization of the familiar Langevin equation in the classical theory of Brownian motion. In this generalized equation the friction force becomes retarded or frequency-dependent and the random force is no more white. They are related to each other by a generalized Nyquist theorem which is in fact another expression of the fluctuation-dissipation theorem. This point of view can be applied to a wide class of irreversible process including collective modes in many-particle systems as has already been shown by Mori. As an illustrative example, the density response problem is briefly discussed.},
  creationdate = {2025-04-03T07:58:31},
  doi          = {10.1088/0034-4885/29/1/306},
  file         = {:/autohome/saeckech/Promotion/Literatur/NMR/TheFluctuationDissipationTheorem_Kubo_RepProgrPhys1966.pdf:PDF},
  keywords     = {fluctuation-dissipation theorem,theory,linear response,brownian motion,susceptibility},
  url          = {https://dx.doi.org/10.1088/0034-4885/29/1/306},
}

@Article{Auccaise2025,
  author       = {R. Auccaise},
  journal      = {Chemical Physics},
  title        = {Insights into NMR relaxation and susceptibility representation},
  year         = {2025},
  issn         = {0301-0104},
  pages        = {112583},
  volume       = {591},
  abstract     = {In this study, an analysis of the relaxation rate constant and the susceptibility definitions point out the most feasible setup to detect the non-exponential relaxation effects of longitudinal magnetization. The dipole–dipole interaction was considered the primary source of relaxation due to homonuclear or heteronuclear species. Some representative molecule systems were explored, such as Glycerol (alcohol), Butyltriethylammonium bis(Trifluoromethanesulfonyl)imide (ionic liquid), and Fluoroaniline (fluorines). Considering some physical and stoichiometric properties of these three molecule systems and applying the susceptibility representation, it can be concluded that the relaxation effects due to the dipole–dipole interaction of homonuclear species prevail against the heteronuclear species. Furthermore, the same analysis points out a range of frequency values in which the dipole–dipole interaction of heteronuclear species is favorable, even if the homonuclear one is available.},
  creationdate = {2025-04-03T08:20:17},
  doi          = {https://doi.org/10.1016/j.chemphys.2024.112583},
  file         = {:/autohome/saeckech/Promotion/Literatur/NMR/InsightsIntoNMRRelaxationAndSusceptibilityRepresentation_Auccaise_ChemPhys2025.pdf:PDF},
  keywords     = {Susceptibility,Relaxation rate constant,Heteronuclear spin system,Multi- exponential model,theory,review,dynamic heterogeneity},
  url          = {https://www.sciencedirect.com/science/article/pii/S0301010424004129},
}

@Article{Sillescu1999,
  author       = {Hans Sillescu},
  journal      = {Journal of Non-Crystalline Solids},
  title        = {Heterogeneity at the glass transition: a review},
  year         = {1999},
  issn         = {0022-3093},
  number       = {2},
  pages        = {81-108},
  volume       = {243},
  abstract     = {Theoretical concepts and experimental evidence of heterogeneity in glass-forming liquids and polymers are reviewed. The main purpose is to provide an introduction to theoretical developments and recent experiments which have led to rapidly increasing knowledge. Realizing that there is no consensus in regard to the various scenarios of the glass transition starting from rather different assumptions we try to give a balanced overview although we also compare and interrelate some of the approaches. The experimental part describes recent nuclear magnetic resonance, dielectric, and optical experiments from which dynamically distinguishable subensembles can be selected thus proving the existence of a well defined dynamical heterogeneity.},
  creationdate = {2025-04-03T10:57:34},
  doi          = {https://doi.org/10.1016/S0022-3093(98)00831-X},
  file         = {:/autohome/saeckech/Promotion/Literatur/GlassFormers/HeterogeneityAtTheGlassTransition-AReview_Sillescu_JNonCrystSolids1999.pdf:PDF},
  keywords     = {theory,review,dynamic heterogeneity,glass-former,NMR,viscous liquids},
  url          = {https://www.sciencedirect.com/science/article/pii/S002230939800831X},
}

@Article{Man2016,
  author       = {Man, Pascal P.},
  journal      = {Concepts in Magnetic Resonance Part A},
  title        = {Wigner active and passive rotation matrices applied to NMR tensor},
  year         = {2016},
  number       = {1},
  pages        = {e21385},
  volume       = {45A},
  abstract     = {Abstract NMR Hamiltonians are double contraction of two spherical rank-2 tensors, their space parts are represented by a spherical tensor and their spin parts are composed of spherical tensor operators. The comprehension of modern NMR experiments is very often based on the rotation of these tensors. We present the active and passive rotations in a progressive way from position vector to spherical tensor operator via space function, spherical harmonic, and vector operator. The passive rotation of a physical quantity is described by the rotation of coordinate system. Both the left- and right-handed rotation conventions are applied whereas the right-handed rotation convention is mainly used in the literature. Throughout the article, we explore the equivalence between the active rotation of a physical quantity in one direction and the rotation of the coordinate system in the opposite direction. The article presents redundant mathematical demonstrations between active and passive rotations, but they clarify the meanings of some important expressions not well developed in the literature.},
  creationdate = {2025-04-03T15:00:31},
  doi          = {https://doi.org/10.1002/cmr.a.21385},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/cmr.a.21385},
  file         = {:/autohome/saeckech/Promotion/Literatur/NMR/WignerActiveAndPassiveRotationMatricesAppliedToNMRTensor_Man_ConceptsMagnRes2016.pdf:PDF},
  keywords     = {active rotation,canonical transformation,Euler angles,passive rotation,Wigner rotation matrix,theory,hamiltonians,spherical tensor operator},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/cmr.a.21385},
}

@Article{Torchia1982,
  author       = {D.A Torchia and Attila Szabo},
  journal      = {Journal of Magnetic Resonance (1969)},
  title        = {Spin-lattice relaxation in solids},
  year         = {1982},
  issn         = {0022-2364},
  number       = {1},
  pages        = {107-121},
  volume       = {49},
  abstract     = {Spin-lattice relaxation times (T1) contain information about molecular motion. We present a formalism for extracting this information from T1 values measured for static and spinning polycrystalline solids. General equations are developed for orientation dependent line positions (frequencies) and values of T1. The correlation functions in the general T1 expressions are evaluated for various jump and diffusive models of motion, assuming an axially symmetric coupling mechanism. Explicit expressions for dipolar and quadrupolar values of T1 are presented for two- and three-site jumps, and for continuous diffusion about a symmetry axis. It is shown that T1measurements can readily distinguish between three-site jump and continuous diffusion models of methyl reorientation on the basis of the different angular dependence calculated for T1 in these two models. In general, T1 is axially asymmetric for the three-site jump model, resulting in nonexponential relaxation for the spectral lines in the axially symmetric powder pattern.},
  creationdate = {2025-04-03T17:02:36},
  doi          = {https://doi.org/10.1016/0022-2364(82)90301-8},
  file         = {:/autohome/saeckech/Promotion/Literatur/NMR/SpinLatticeRealxationInSolids_TorchiaEtAl_JMagnRse1969.pdf:PDF},
  keywords     = {NMR,T1,spin-lattice relaxation,theory,spherical tensor operator,non-exponential},
  url          = {https://www.sciencedirect.com/science/article/pii/0022236482903018},
}

@PhdThesis{Vogel2000,
  author       = {Michael Vogel},
  school       = {Universit{\"a}t Bayreuth},
  title        = {$^2$H-NMR-Untersuchung der Sekund{\"a}rrelaxation in organischen Glasbildnern},
  year         = {2000},
  month        = may,
  type         = {phdthesis},
  creationdate = {2025-04-04T10:52:35},
  file         = {:/autohome/saeckech/Promotion/Literatur/NMR/2HNMRUntersuchungDerSekundärrelaxationInOrganischenGlasbildnern_Vogel_Bayreuth2000.pdf:PDF},
  keywords     = {dissertation,nmr,2h,relaxation,theory,johari-goldstein,T1,T2,glas-former},
  url          = {https://eref.uni-bayreuth.de/id/eprint/28306},
}

@PhdThesis{Flaemig2020a,
  author       = {Max Fl{\"a}mig},
  school       = {Universität Bayreuth},
  title        = {A Field Cycling NMR Relaxometry Study on Molecular Liquids and Plastically Crystalline Phases},
  year         = {2020},
  type         = {phdthesis},
  creationdate = {2025-04-04T13:59:08},
  file         = {:/autohome/saeckech/Promotion/Literatur/NMR/AFieldCyclingNMRRelaxometryStudyOnMolecularLiquidsAndPlasticallyCrystallinePhases_Flämig_Bayreuth2020.pdf:PDF},
  keywords     = {NMR,field cycling,dissertation},
}

@Book{Gerven1977,
  editor       = {Lieven van Gerven},
  publisher    = {Springer},
  title        = {Nuclear Magnetic Resonance in Solids},
  year         = {2013},
  edition      = {First},
  isbn         = {978-1-4684-2808-7},
  series       = {NATO Science Series B},
  comment      = {Copyright: Plenum Press, New York 1977},
  creationdate = {2025-04-07T08:50:29},
  doi          = {10.1007/978-1-4684-2808-7},
  file         = {:/autohome/saeckech/Promotion/Literatur/NMR/NuclearMagneticResonanceInSolids_VanGerven_Springer1977.pdf:PDF},
  keywords     = {nmr,theory,book,quadrupole},
  url          = {https://link.springer.com/content/pdf/10.1007/978-1-4684-2808-7.pdf},
}









@Article{Reese2004,
  author       = {Reese, Chad E. and Mikhonin, Alexander V. and Kamenjicki, Marta and Tikhonov, Alexander and Asher, Sanford A.},
  journal      = {Journal of the American Chemical Society},
  title        = {Nanogel Nanosecond Photonic Crystal Optical Switching},
  year         = {2004},
  note         = {PMID: 14759207},
  number       = {5},
  pages        = {1493-1496},
  volume       = {126},
  abstract     = {We developed a robust nanosecond photonic crystal switching material by using poly(N-isopropylacrylamide) (PNIPAM) nanogel colloidal particles that self-assemble into crystalline colloidal arrays (CCAs). The CCA was polymerized into a loose-knit hydrogel which permits the individual embedded nanogel PNIPAM particles to coherently and synchronously undergo their thermally induced volume phase transitions. A laser T-jump from 30 to 35 °C actuates the nanogel particle shrinkage; the resulting increased diffraction decreases light transmission within 900 ns. Additional transmission decreases occur with characteristic times of 19 and 130 ns. Individual NIPAM sphere volume switching occurs in the ∼100 ns time regime. These nanogel nanosecond phenomena may be useful in the design of fast photonic crystal switches and optical limiting materials. Smaller nanogels will show even faster volume phase transitions.},
  creationdate = {2025-04-14T07:31:10},
  doi          = {10.1021/ja037118a},
  eprint       = {https://doi.org/10.1021/ja037118a},
  file         = {:Reese2004 - Nanogel Nanosecond Photonic Crystal Optical Switching.pdf:PDF;:NanogelNanosecondPhotonicCrystalOpticalSwitching_ReeseEtAl_JAmChemSoc2004_SI.pdf:PDF},
  keywords     = {pNIPAM,photonic crystal,kinetics,microgel,gel,transmission,transmittance,temperature jump},
  url          = {https://doi.org/10.1021/ja037118a},
}

@Article{Das2024,
  author       = {Das, Anubhab and Babu, Anashwara and Chakraborty, Sourav and Van Guyse, Joachim F. R. and Hoogenboom, Richard and Maji, Samarendra},
  journal      = {Advanced Functional Materials},
  title        = {Poly(N-isopropylacrylamide) and Its Copolymers: A Review on Recent Advances in the Areas of Sensing and Biosensing},
  year         = {2024},
  number       = {37},
  pages        = {2402432},
  volume       = {34},
  abstract     = {Stimuli-responsive polymers have received increasing attention for various applications due to their ability to adapt physical and chemical properties in response to external environmental stimuli. In this regard, poly(N-isopropylacrylamide) (PNIPAM) is the most extensively studied stimuli-responsive polymer and, consequently has been prominently featured in (bio)-sensor development, adaptive coating technology, drug delivery, wound healing, tissue regeneration, artificial actuator design, sensor technology, responsive coatings, and soft robotics. This success can be mainly attributed to the accessible and versatile nature of the PNIPAM platform, thus allowing the synthesis of a wide variety of copolymer architectures, topologies and compositions. Within this review, the structural and compositional features of PNIPAM-based materials in sensor and biosensor applications are discussed with a focus on the literature from 2016 until now. The reader is provided with the current state of the art regarding PNIPAM-based sensor development and their molecular design. Finally, the challenges ahead in the successful implementation of PNIPAM-based sensors are highlighted, as well as the opportunities in the rational design of improved PNIPAM-based sensors. Altogether, this review provides comprehensive insights into the exciting and rapidly expanding field of PNIPAM-based sensing systems, which will benefit the chemical, pharmaceutical, textile, and biotech industries is believed.},
  creationdate = {2024-05-24},
  doi          = {https://doi.org/10.1002/adfm.202402432},
  eprint       = {https://advanced.onlinelibrary.wiley.com/doi/pdf/10.1002/adfm.202402432},
  file         = {:Das - Poly(N Isopropylacrylamide) and Its Copolymers_ a Review on Recent Advances in the Areas of Sensing and Biosensing.pdf:PDF},
  keywords     = {biosensor, poly(N-isopropyl acrylamide), sensor, smart material, thermoresponsive polymer, pNIPAM, review, application-focused, application focused},
  url          = {https://advanced.onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202402432},
}

@Article{Li2009,
  author       = {Li, Haihong and O'Shea, John-Paul and Franks, George V.},
  journal      = {AIChE Journal},
  title        = {Effect of molecular weight of poly(N-isopropyl acrylamide) temperature-sensitive flocculants on dewatering},
  year         = {2009},
  number       = {8},
  pages        = {2070-2080},
  volume       = {55},
  abstract     = {Abstract The influence of molecular weight (MW) and dose of Poly(N-isopropyl acrylamide) (PNIPAM) (temperature-sensitive flocculant) on sedimentation rate, sediment density, and supernatant clarity of silica suspensions was investigated. The addition of PNIPAM resulted in rapid sedimentation (T > critical solution temperature, CST) and low sediment moisture (T < CST). Higher MW polymers resulted in more effective flocculation and sediment consolidation. At 10 ppm, PNIPAM (3.6 million Da) produced 20 m/h settling rate and 48 vol \% solids sediment density, whereas 0.23 million Da polymer produced 0.1 m/h settling rate. PNIPAM produces effective flocculation and consolidation by cycling the interparticle interactions between repulsion and attraction as temperature is cycled around the CST. The change in temperature produces a hydrophilic/hydrophobic transition of the polymer, influencing adsorption onto the surface and the inter-particle forces. Conventional polyacrylamide flocculants (not influenced by temperature), cannot be used to produce both rapid sedimentation and dense sediments. © 2009 American Institute of Chemical Engineers AIChE J, 2009},
  creationdate = {2025-04-14T08:12:59},
  doi          = {https://doi.org/10.1002/aic.11859},
  eprint       = {https://aiche.onlinelibrary.wiley.com/doi/pdf/10.1002/aic.11859},
  file         = {:Li2009 - Effect of Molecular Weight of Poly(N Isopropyl Acrylamide) Temperature Sensitive Flocculants on Dewatering.pdf:PDF},
  keywords     = {flocculation,temperature-sensitive polymer,solid–liquid separation,solids dewatering,pNIPAM,chain length,concentration-dependence,molecular weight de},
  url          = {https://aiche.onlinelibrary.wiley.com/doi/abs/10.1002/aic.11859},
}

@Article{Okay2021,
  author         = {Okay, Oguz},
  journal        = {Gels},
  title          = {Re-Entrant Conformation Transition in Hydrogels},
  year           = {2021},
  issn           = {2310-2861},
  number         = {3},
  volume         = {7},
  abstract       = {Hydrogels are attractive materials not only for their tremendous applications but also for theoretical studies as they provide macroscopic monitoring of the conformation change of polymer chains. The pioneering theoretical work of Dusek predicting the discontinuous volume phase transition in gels followed by the experimental observation of Tanaka opened up a new area, called smart hydrogels, in the gel science. Many ionic hydrogels exhibit a discontinuous volume phase transition due to the change of the polymer–solvent interaction parameter χ depending on the external stimuli such as temperature, pH, composition of the solvent, etc. The observation of a discontinuous volume phase transition in nonionic hydrogels or organogels is still a challenging task as it requires a polymer–solvent system with a strong polymer concentration dependent χ parameter. Such an observation may open up the use of organogels as smart and hydrophobic soft materials. The re-entrant phenomenon first observed by Tanaka is another characteristic of stimuli responsive hydrogels in which they are frustrated between the swollen and collapsed states in a given solvent mixture. Thus, the hydrogel first collapses and then reswells if an environmental parameter is continuously increased. The re-entrant phenomenon of hydrogels in water–cosolvent mixtures is due to the competitive hydrogen-bonding and hydrophobic interactions leading to flow-in and flow-out of the cosolvent molecules through the hydrogel moving boundary as the composition of the solvent mixture is varied. The experimental results reviewed here show that a re-entrant conformation transition in hydrogels requires a hydrophobically modified hydrophilic network, and a moderate hydrogen-bonding cosolvent having competitive attractions with water and polymer. The re-entrant phenomenon may widen the applications of the hydrogels in mechanochemical transducers, switches, memories, and sensors.},
  article-number = {98},
  creationdate   = {2025-04-18T12:41:30},
  doi            = {10.3390/gels7030098},
  file           = {:Okay2021 - Re Entrant Conformation Transition in Hydrogels.pdf:PDF},
  keywords       = {review,hydrogel,UCST,reentrant,cononsolvency,gel},
  pubmedid       = {34287329},
  url            = {https://www.mdpi.com/2310-2861/7/3/98},
}

@Article{Zhi2010,
  author       = {Dongyan Zhi and Yongmin Huang and Xia Han and Honglai Liu and Ying Hu},
  journal      = {Chemical Engineering Science},
  title        = {A molecular thermodynamic model for temperature- and solvent-sensitive hydrogels, application to the swelling behavior of PNIPAm hydrogels in ethanol/water mixtures},
  year         = {2010},
  issn         = {0009-2509},
  number       = {10},
  pages        = {3223-3230},
  volume       = {65},
  abstract     = {The swelling curves of poly-N-isopropylacrylamide (PNIPAm) hydrogels in ethanol/water mixtures were determined. A molecular thermodynamic model for swelling behavior of temperature- and solvent-sensitive hydrogels in solvent mixtures was developed by integrating a modified multiple lattice model developed previously for the mixing term and the Flory's Gaussian chain model for the elastic term. Three energy parameters and one volume parameter are included in this model for gel/solvent mixtures systems. Three of the four parameters can be determined from the swelling behavior of hydrogels in pure solvents. The energy parameter measuring the interaction between the two solvents is adjustable and expressed as a quadratic form of the inverse temperature. The calculated results for the swelling curves of PNIPAm hydrogels in ethanol/water mixtures at different temperatures are in good agreement with the experiments. In addition, the equilibrium concentrations of solvent mixtures inside and outside hydrogels can be predicted by this model, which is important for the application of hydrogels.},
  creationdate = {2025-04-18T14:55:58},
  doi          = {https://doi.org/10.1016/j.ces.2010.02.013},
  file         = {:Zhi2010 - A Molecular Thermodynamic Model for Temperature and Solvent Sensitive Hydrogels, Application to the Swelling Behavior of PNIPAm Hydrogels in Ethanol_water Mixtures.pdf:PDF},
  keywords     = {Hydrogel,Swelling behavior,Solvent mixtures,Molecular thermodynamic model,Temperature sensitive,Solvent sensitive,pNIPAM,aqueous ethanol,cononsolvency,theory,gel},
  url          = {https://www.sciencedirect.com/science/article/pii/S0009250910000795},
}

@Article{Mukherji2014,
  author       = {Debashish Mukherji and Carlos M. Marques and Kurt Kremer},
  journal      = {Nat Commun},
  title        = {Polymer collapse in miscible good solvents is a generic phenomenon driven by preferential adsorption},
  year         = {2014},
  pages        = {4882},
  volume       = {5},
  creationdate = {2025-04-18T16:11:52},
  doi          = {10.1038/ncomms5882},
  file         = {:Mukherji2014 - Polymer Collapse in Miscible Good Solvents Is a Generic Phenomenon Driven by Preferential Adsorption.pdf:PDF},
  keywords     = {cononsolvency,preferential adsorption,theory,simulation,aqueous alcohol},
  url          = {https://doi.org/10.1038/ncomms5882},
}

@Article{Pica2016,
  author       = {Pica, Andrea and Graziano, Giuseppe},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {An alternative explanation of the cononsolvency of poly(N-isopropylacrylamide) in water–methanol solutions},
  year         = {2016},
  pages        = {25601-25608},
  volume       = {18},
  abstract     = {Cononsolvency refers to the experimental finding that poly(N-isopropylacrylamide){,} PNIPAM{,} has a coil conformation in both pure water and pure methanol{,} at 20 °C and 1 atm{,} but assumes a globule conformation in methanol–water solutions{,} over the 0.1 ≤ X(MeOH) ≤ 0.4 methanol molar fraction. This strange phenomenon has recently been rationalized by claiming that: (a) MeOH molecules are able to bind two distant monomers in the chain{,} driving collapse [Nat. Commun.{,} 2014{,} 5{,} 4882]; (b) the preferential binding of MeOH stabilizes globule conformations due to a conformational entropy gain of the chain [J. Phys. Chem. B{,} 2015{,} 119{,} 15780]. In the present work a self-consistent application of the approach already used to rationalize the effect of sodium salts{,} urea and tetramethylurea on PNIPAM collapse [Phys. Chem. Chem. Phys.{,} 2015{,} 17{,} 27750; 2016{,} 18{,} 14426] leads to a different explanation. The emerging scenario is that cononsolvency is caused by the fact that{,} on adding methanol{,} the competition between water and methanol molecules to make attractive interactions with PNIPAM surface causes a decrease in the magnitude of attractive energy with respect to the pure water situation{,} for basic geometric reasons. Polymer chains collapse to reduce this geometric frustration.},
  creationdate = {2025-04-18T16:55:10},
  doi          = {10.1039/C6CP04753J},
  file         = {:Pica2016 - An Alternative Explanation of the Cononsolvency of Poly(N Isopropylacrylamide) in Water–methanol Solutions.pdf:PDF},
  issue        = {36},
  keywords     = {pNIPAM,cononsolvency,aqueous alcohol,methanol,theory,geometric frustration},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C6CP04753J},
}

@Article{Nagasaka2024,
  author       = {Nagasaka, Masanari and Kumaki, Fumitoshi and Yao, Yifeng and Adachi, Jun-ichi and Mochizuki, Kenji},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Mechanism of poly(N-isopropylacrylamide) cononsolvency in aqueous methanol solutions explored via oxygen K-edge X-ray absorption spectroscopy},
  year         = {2024},
  pages        = {13634-13638},
  volume       = {26},
  abstract     = {The cononsolvency mechanism of poly(N-isopropylacrylamide) (PNIPAM){,} dissolving in pure methanol (MeOH) and water (H2O) but being insoluble in MeOH–H2O mixtures{,} was investigated by O K-edge X-ray absorption spectroscopy (XAS). The cononsolvency emerges from the aggregation of PNIPAM with MeOH clusters{,} leading to the collapse of the hydrophobic hydration of PNIPAM.},
  creationdate = {2025-04-22T07:08:39},
  doi          = {10.1039/D4CP00676C},
  file         = {:Nagasaka2024 - Mechanism of Poly(N Isopropylacrylamide) Cononsolvency in Aqueous Methanol Solutions Explored Via Oxygen K Edge X Ray Absorption Spectroscopy.pdf:PDF},
  issue        = {18},
  keywords     = {pNIPAM,cononsolvency,aqueous alcohol,methanol,X-Ray,hydrophobic hydration},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D4CP00676C},
}









@Article{Dhabal2021,
  author       = {Dhabal, Debdas and Jiang, Zhitong and Pallath, Akash and Patel, Amish J.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Characterizing the Interplay between Polymer Solvation and Conformation},
  year         = {2021},
  note         = {PMID: 33978411},
  number       = {20},
  pages        = {5434-5442},
  volume       = {125},
  abstract     = {Conformational transitions of flexible molecules, especially those driven by hydrophobic effects, tend to be hindered by desolvation barriers. For such transitions, it is thus important to characterize and understand the interplay between solvation and conformation. Using specialized molecular simulations, here we perform such a characterization for a hydrophobic polymer solvated in water. We find that an external potential, which unfavorably perturbs the polymer hydration waters, can trigger a coil-to-globule or collapse transition, and that the relative stabilities of the collapsed and extended states can be quantified by the strength of the requisite potential. Our results also provide mechanistic insights into the collapse transition, highlighting that the bottleneck to polymer collapse is the formation of a sufficiently large cluster, and the collective dewetting of such a cluster. We also study the collapse of the hydrophobic polymer in octane, a nonpolar solvent, and interestingly, we find that the mechanistic details of the transition are qualitatively similar to that in water.},
  creationdate = {2025-04-22T07:13:05},
  doi          = {10.1021/acs.jpcb.1c02191},
  eprint       = {https://doi.org/10.1021/acs.jpcb.1c02191},
  file         = {:Dhabal2021 - Characterizing the Interplay between Polymer Solvation and Conformation.pdf:PDF;:CharacterizingTheInterplayBetweenPolymerSolvationAndConformation_DhabalEtAl_JPC2021_SI1.pdf:PDF;:CharacterizingTheInterplayBetweenPolymerSolvationAndConformation_DhabalEtAl_JPC2021_SI5.mp4:mp4;:CharacterizingTheInterplayBetweenPolymerSolvationAndConformation_DhabalEtAl_JPC2021_SI4.mp4:mp4;:CharacterizingTheInterplayBetweenPolymerSolvationAndConformation_DhabalEtAl_JPC2021_SI3.mp4:mp4;:CharacterizingTheInterplayBetweenPolymerSolvationAndConformation_DhabalEtAl_JPC2021_SI2.mp4:mp4},
  keywords     = {hydrophobic hydration,cooperativity,simulation,coil-to-globule,hydration shell},
  url          = {https://doi.org/10.1021/acs.jpcb.1c02191},
}









@Article{Nayar2018,
  author       = {Nayar, Divya and van der Vegt, Nico F. A.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Cosolvent Effects on Polymer Hydration Drive Hydrophobic Collapse},
  year         = {2018},
  note         = {PMID: 29443520},
  number       = {13},
  pages        = {3587-3595},
  volume       = {122},
  abstract     = {Water-mediated hydrophobic interactions play an important role in self-assembly processes, aqueous polymer solubility, and protein folding, to name a few. Cosolvents affect these interactions; however, the implications for hydrophobic polymer collapse and protein folding equilibria are not well-understood. This study examines cosolvent effects on the hydrophobic collapse equilibrium of a generic 32-mer hydrophobic polymer in urea, trimethylamine-N-oxide (TMAO), and acetone aqueous solutions using molecular dynamics simulations. Our results unveil a remarkable cosolvent-concentration-dependent behavior. Urea, TMAO, and acetone all shift the equilibrium toward collapsed structures below 2 M cosolvent concentration and, in turn, to unfolded structures at higher cosolvent concentrations, irrespective of the differences in cosolvent chemistry and the nature of cosolvent–water interactions. We find that weakly attractive polymer–water van der Waals interactions oppose polymer collapse in pure water, corroborating related observations reviewed by Ben-Amotz (Annu. Rev. Phys. Chem. 2016, 67, 617–638). The cosolvents studied in the present work adsorb at the polymer/water interface and expel water molecules into the bulk, thereby effectively removing the dehydration energy penalty that opposes polymer collapse in pure water. At low cosolvent concentrations, this leads to cosolvent-induced stabilization of collapsed polymer structures. Only at sufficiently high cosolvent concentrations, polymer–cosolvent interactions favor polymer unfolding.},
  creationdate = {2025-04-22T07:20:47},
  doi          = {10.1021/acs.jpcb.7b10780},
  eprint       = {https://doi.org/10.1021/acs.jpcb.7b10780},
  file         = {:Nayar2018 - Cosolvent Effects on Polymer Hydration Drive Hydrophobic Collapse.pdf:PDF},
  keywords     = {simulation,hydration shell,cononsolvency,hydrophobic hydration},
  url          = {https://doi.org/10.1021/acs.jpcb.7b10780},
}









@Article{Vegt2017,
  author       = {van der Vegt, Nico F. A. and Nayar, Divya},
  journal      = {The Journal of Physical Chemistry B},
  title        = {The Hydrophobic Effect and the Role of Cosolvents},
  year         = {2017},
  note         = {PMID: 28921974},
  number       = {43},
  pages        = {9986-9998},
  volume       = {121},
  abstract     = {Cosolvents modulate aqueous solubility, hydrophobic interactions, and the stability and function of most proteins in the living cell. Our molecular-level understanding of cosolvent effects is incomplete, not only at the level of complex systems such as proteins, but also at the level of very fundamental interactions that underlie the hydrophobic effect. This Feature Article discusses cosolvent effects on the aqueous solubility of nonpolar solutes, hydrophobic interactions, and hydrophobic self-assembly/collapse of aqueous polymers, recently studied with molecular dynamics simulations. It is shown that direct interactions of cosolvents with nonpolar solutes and aqueous polymers can strengthen hydrophobic interactions and can contribute to stabilizing collapsed globular structures. The molecular-level explanation of these observations requires a better understanding of the entropy associated with fluctuations of attractive solute–solvent interactions and of length-scale dependencies of this quantity.},
  creationdate = {2025-04-22T07:22:38},
  doi          = {10.1021/acs.jpcb.7b06453},
  eprint       = {https://doi.org/10.1021/acs.jpcb.7b06453},
  file         = {:Vegt2017 - The Hydrophobic Effect and the Role of Cosolvents.pdf:PDF},
  keywords     = {simulation,hydration shell,cononsolvency},
  url          = {https://doi.org/10.1021/acs.jpcb.7b06453},
}









@Article{Dalgicdir2017,
  author       = {Dalgicdir, Cahit and Rodríguez-Ropero, Francisco and van der Vegt, Nico F. A.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Computational Calorimetry of PNIPAM Cononsolvency in Water/Methanol Mixtures},
  year         = {2017},
  note         = {PMID: 28731710},
  number       = {32},
  pages        = {7741-7748},
  volume       = {121},
  abstract     = {We revisit the mechanism for cononsolvency of PNIPAM in water/methanol mixtures. Using extensive molecular dynamics simulations, we calculate the calorimetric enthalpy of the PNIPAM collapse transition and observe a unique fingerprint of PNIPAM cononsolvency which is analyzed in terms of microscopic interactions. We find that polymer hydration is the determining factor for PNIPAM collapse in the cononsolvency regime. In particular, it is shown that methanol frustrates the ability of water to form hydrogen bonds with the amide proton and therefore causes polymer collapse.},
  creationdate = {2025-04-22T07:25:33},
  doi          = {10.1021/acs.jpcb.7b05960},
  eprint       = {https://doi.org/10.1021/acs.jpcb.7b05960},
  file         = {:Dalgicdir2017 - Computational Calorimetry of PNIPAM Cononsolvency in Water_Methanol Mixtures.pdf:PDF;:ComputationalCalorimetryOfPNIPAMCononsolvencyInWaterMethanolMixtures_DalgicdirEtAl_JPC2017_SI.pdf:PDF;:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/ComputationalCalorimetryOfPNIPAMCononsolvencyInWaterMethanolMixtures_DalgicdirEtAl_JPC2017_Correction.pdf:PDF},
  keywords     = {simulation,calorimetry,DSC,cononsolvency,aqueous alcohol,methanol,geometric frustration},
  url          = {https://doi.org/10.1021/acs.jpcb.7b05960},
}

@Article{Bharadwaj2021,
  author       = {Bharadwaj, Swaminath and Nayar, Divya and Dalgicdir, Cahit and van der Vegt, Nico F. A.},
  journal      = {The Journal of Chemical Physics},
  title        = {An interplay of excluded-volume and polymer–(co)solvent attractive interactions regulates polymer collapse in mixed solvents},
  year         = {2021},
  issn         = {0021-9606},
  month        = {04},
  number       = {13},
  pages        = {134903},
  volume       = {154},
  abstract     = {Cosolvent effects on the coil–globule transitions in aqueous polymer solutions are not well understood, especially in the case of amphiphilic cosolvents that preferentially adsorb on the polymer and lead to both polymer swelling and collapse. Although a predominant focus in the literature has been placed on the role of polymer–cosolvent attractive interactions, our recent work has shown that excluded-volume interactions (repulsive interactions) can drive both preferential adsorption of the cosolvent and polymer collapse via a surfactant-like mechanism. Here, we further study the role of polymer–(co)solvent attractive interactions in two kinds of polymer solutions, namely, good solvent (water)–good cosolvent (alcohol) (GSGC) and poor solvent–good cosolvent (PSGC) solutions, both of which exhibit preferential adsorption of the cosolvent and a non-monotonic change in the polymer radius of gyration with the addition of the cosolvent. Interestingly, at low concentrations, the polymer–(co)solvent energetic interactions oppose polymer collapse in the GSGC solutions and contrarily support polymer collapse in the PSGC solutions, indicating the importance of the underlying polymer chemistry. Even though the alcohol molecules are preferentially adsorbed on the polymer, the trends of the energetic interactions at low cosolvent concentrations are dominated by the polymer–water energetic interactions in both the cases. Therefore, polymer–(co)solvent energetic interactions can either reinforce or compensate the surfactant-like mechanism, and it is this interplay that drives coil-to-globule transitions in polymer solutions. These results have implications for rationalizing the cononsolvency transitions in real systems such as polyacrylamides in aqueous alcohol solutions where the understanding of microscopic driving forces is still debatable.},
  creationdate = {2025-04-22T07:39:46},
  doi          = {10.1063/5.0046746},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/5.0046746/15590192/134903\_1\_online.pdf},
  file         = {:Bharadwaj2021 - An Interplay of Excluded Volume and Polymer–(co)solvent Attractive Interactions Regulates Polymer Collapse in Mixed Solvents.pdf:PDF},
  keywords     = {cononsolvency,simulation,preferential adsorption,excluded volume,surfactant,pNIPAM},
  url          = {https://doi.org/10.1063/5.0046746},
}

@Article{Higaki2023,
  author       = {Yuji Higaki and Naoki Kuraoka and Takumi Masuda and Mai Nakamura and Emi Hifumi},
  journal      = {Polym J},
  title        = {Cononsolvency of poly(carboxybetaine methacrylate) in water-ethanol mixed solvents},
  year         = {2023},
  pages        = {869--876},
  volume       = {55},
  creationdate = {2025-04-22T08:35:49},
  doi          = {10.1038/s41428-023-00780-x},
  file         = {:Higaki2023 - Cononsolvency of Poly(carboxybetaine Methacrylate) in Water Ethanol Mixed Solvents.pdf:PDF},
  keywords     = {cononsolvency,aqueous alcohol,ethanol,zwitterionic polymer,coil-to-globule,globule-to-coil,reentrant},
  url          = {https://doi.org/10.1038/s41428-023-00780-x},
}









@Article{Mills2019,
  author       = {Mills, Carolyn E. and Ding, Erika and Olsen, Bradley D.},
  journal      = {Biomacromolecules},
  title        = {Cononsolvency of Elastin-like Polypeptides in Water/Alcohol Solutions},
  year         = {2019},
  note         = {PMID: 31117367},
  number       = {6},
  pages        = {2167-2173},
  volume       = {20},
  abstract     = {Elastin-like polypeptides (ELPs) are one of the most widely-studied classes of protein material because of their lower critical solution temperature (LCST)-like thermoresponsive behavior in aqueous solutions. Here, it is shown that ELPs also exhibit cononsolvency effects, similar to many other water-soluble polymers. The effect of solvent composition on the dilute solution phase behavior of an elastin-like polypeptide is studied here in water/alcohol blends that contain 0–40 vol \% methanol, ethanol, isopropanol, or 1-propanol. In all systems studied, the ELP exhibits cononsolvency behavior at low alcohol content, as indicated by a decrease in the transition temperature of the ELP. When the alcohol added is ethanol, isopropanol, or 1-propanol, the decrease in transition temperature is followed by a region of complete ELP insolubility, and, finally, the emergence of upper-critical solution transition (UCST)-like behavior. The ELP is completely soluble at all temperatures measured at alcohol contents above 40 vol \%. The effect of sodium chloride on this ELP cononsolvency in water/ethanol blends was also studied. Unlike the previously studied polymer poly(N-isoropylacrylamide) (PNIPAM), ELP exhibits nonmonotonic changes in transition temperature with the addition of sodium chloride at ethanol contents that produce UCST-like transitions of the ELP. This discovery of ELP cononsolvency in water/alcohol systems introduces a new handle with which the solubility of ELPs can be tuned.},
  comment      = {paywall},
  creationdate = {2025-04-22T08:54:17},
  doi          = {10.1021/acs.biomac.8b01644},
  eprint       = {https://doi.org/10.1021/acs.biomac.8b01644},
  file         = {:Mills2019 - Cononsolvency of Elastin like Polypeptides in Water_Alcohol Solutions.pdf:PDF},
  keywords     = {cononsolvency,ELP,aqueous alcohol,methanol,ethanol,propanol,n-propanol,isopropanol,1-propanol,ionoic strength,sodium chloride,NaCl},
  url          = {https://doi.org/10.1021/acs.biomac.8b01644},
}

@Article{Hao2010,
  author       = {Hao, Jinkun and Cheng, He and Butler, Paul and Zhang, Li and Han, Charles C.},
  journal      = {The Journal of Chemical Physics},
  title        = {Origin of cononsolvency, based on the structure of tetrahydrofuran-water mixture},
  year         = {2010},
  issn         = {0021-9606},
  month        = {04},
  number       = {15},
  pages        = {154902},
  volume       = {132},
  abstract     = {The origin of poly(N-isopropylacrylamide) (PNIPAM) cononsolvency in tetrahydrofuran-water (THF-water) mixture was studied from the point of view of mixed solvent structure. The dynamic equilibrium of THF-water composition fluctuation in the mixed solvent system was found to be the main variable for this cononsolvency effect. Temperature and THF content dependences of composition fluctuation were studied by a combination of small angle neutron scattering (SANS), dynamic laser light scattering, and viscometry. A lower critical solution temperature (LCST) type phase diagram for THF-water mixture was established by SANS. The composition fluctuation in THF-water system reaches the maximum at about 20 mol \% THF content at constant temperature and increases with temperature as getting closer to the phase boundary. This kind of composition fluctuation induces PNIPAM cononsolvency. When the THF content is lower than 4.5 mol \%, the composition fluctuation influence of the THF-water structure is quite weak and most of water structure is not disturbed. Then, at low THF content, poly(N-isopropylacrylamide-co-ethylene glycol) (PNIPAM-co-PEG) microgel can still form hydrogen bonds with water and exist in the swollen state. The basic phase transition behavior of the microgel in THF-water is relatively similar to that in pure water, except for the shift of LCST to lower temperature. With THF content increasing to 20 mol \%, the influence of composition fluctuation in the THF-water mixture becomes dominant. Solvent-solvent interaction is stronger than mixed solvent-polymer interaction. So PNIPAM does not dissolve in the mixed solvent, and the microgel is in the collapsed state. Further increase in THF content abates the contribution of composition fluctuation, and the structures of mixed solvents tend to be that in pure THF. PNIPAM becomes soluble again via Van der Waals interaction between THF and polymer.},
  creationdate = {2025-04-22T09:12:33},
  doi          = {10.1063/1.3381177},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.3381177/15683420/154902\_1\_online.pdf},
  file         = {:Hao2010 - Origin of Cononsolvency, Based on the Structure of Tetrahydrofuran Water Mixture.pdf:PDF},
  keywords     = {cononsolvency,THF,pNIPAM,SANS,DLS,rheology,viscosity,light scattering,PEG,copolymer,solvent complexation},
  url          = {https://doi.org/10.1063/1.3381177},
}









@Article{Pooch2019,
  author       = {Pooch, Fabian and Teltevskij, Valerij and Karjalainen, Erno and Tenhu, Heikki and Winnik, Fran{\c{c}}oise M.},
  journal      = {Macromolecules},
  title        = {Poly(2-propyl-2-oxazoline)s in Aqueous Methanol: To Dissolve or not to Dissolve},
  year         = {2019},
  note         = {PMID: 31543552},
  number       = {17},
  pages        = {6361-6368},
  volume       = {52},
  abstract     = {At room temperature, poly(N-isopropylacrylamide) (PNIPAM) is soluble in water and methanol, but it is not soluble in certain water/methanol mixtures. This phenomenon, known as cononsolvency, has been explored in great detail experimentally and theoretically in an attempt to understand the complex interactions occurring in the ternary PNIPAM/water/co-nonsolvent system. Yet little is known about the effects of the polymer structure on cononsolvency. To address this point, we investigated the temperature-dependent solution properties in water, methanol, and mixtures of the two solvents of poly(2-cyclopropyl-2-oxazoline) (PcyPOx) and two structural isomers of PNIPAM (Mn ∼ 11 kg/mol): poly(2-isopropyl-2-oxazoline) (PiPOx) and poly(2-n-propyl-2-oxazoline) (PnPOx). The phase diagram of the ternary water/methanol/poly(2-propyl-2-oxazolines) (PPOx) systems, constructed based on cloud point (TCP) measurements, revealed that PnPOx exhibits cononsolvency in water/methanol mixtures. In contrast, methanol acts as a cosolvent for PiPOx and PcyPOx in water. The enthalpy, ΔH, and temperature, Tmax, of the coil-to-globule transition of the three polymers in various water/methanol mixtures were measured by high-sensitivity differential scanning calorimetry. Tmax follows the same trends as TCP, confirming the cononsolvency of PnPOx and the cosolvency of PiPOx and PcyPOx. ΔH decreases linearly as a function of the methanol content for all PPOx systems. Ancillary high-resolution 1H NMR spectroscopy studies of PPOx solutions in D2O and methanol-d4, coupled with DOSY and NOESY experiments revealed that the n-propyl group of PnPOx rotates freely in D2O, whereas the rotation of the isopropyl and cyclopropyl groups of PiPOx and PcyPOx, respectively, is limited due to steric restriction. This factor appears to play an important role in the case of the PPOxs/water/methanol ternary system.},
  creationdate = {2025-04-22T09:18:31},
  doi          = {10.1021/acs.macromol.9b01234},
  eprint       = {https://doi.org/10.1021/acs.macromol.9b01234},
  file         = {:Pooch2019 - Poly(2 Propyl 2 Oxazoline)s in Aqueous Methanol_ to Dissolve or Not to Dissolve.pdf:PDF;:Poly2Propyl2OxazolinesInAqueousMethanol-ToDissolveOrNotToDissolve_PoochEtAl_Macromol2019_SI.pdf:PDF},
  keywords     = {cononsolvency,pNIPAM,isomer,PcyPOx,PiPOx,PnPOx,PPOx,aqueous alcohol,methanol,1H,NMR,DOSY,NOESY,isotope effect,polymer structure,DSC},
  url          = {https://doi.org/10.1021/acs.macromol.9b01234},
}









@Article{Du2010,
  author       = {Du, Hongbo and Wickramasinghe, Ranil and Qian, Xianghong},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Effects of Salt on the Lower Critical Solution Temperature of Poly (N-Isopropylacrylamide)},
  year         = {2010},
  note         = {PMID: 21090725},
  number       = {49},
  pages        = {16594-16604},
  volume       = {114},
  abstract     = {Classical molecular dynamics simulations were performed to investigate the effects of salt on the lower critical solution temperature (LCST) of Poly (N-isopropylacrylamide) (PNIPAM). PNIPAM is often studied as a protein proxy due to the presence of a peptide bond in its monomer unit. PNIPAM is a temperature sensitive polymer which exhibits hydrophobic−hydrophilic phase transition at its LCST. The presence of salt in the solution will shift its LCST, typically to a lower temperature. This LCST shift follows the so-called Hofmeister series. Molecular dynamics (MD) simulations of PNIPAM in 1 M of NaCl, NaBr, NaI, and KCl were carried out to elucidate the effects of different salt on LCST and protein stability. Our results suggest that direct interactions between the salt cations and the polymer play a critical role in the shift of LCST and subsequently on protein stability. Further, cations have a much stronger affinity with the polymer, whereas anions bind weakly with the polymer. Moreover, the cation−polymer binding affinity is inversely correlated with the cation−anion contact pair association constant in solution.},
  creationdate = {2025-04-22T10:11:57},
  doi          = {10.1021/jp105652c},
  eprint       = {https://doi.org/10.1021/jp105652c},
  file         = {:Du2010 - Effects of Salt on the Lower Critical Solution Temperature of Poly (N Isopropylacrylamide).pdf:PDF},
  keywords     = {pNIPAM,ionic strength,simulation,molecular dynamics simulation,Hofmeister},
  url          = {https://doi.org/10.1021/jp105652c},
}

@Article{Wang2025,
  author       = {Wang, Peixi and Zheng, Tianle and Reitenbach, Julija and Wegener, Simon A. and Huber, Linus F. and Kreuzer, Lucas P. and Liang, Suzhe and Cubitt, Robert and Cheng, Ya-Jun and Xu, Tonghui and Hildebrand, Viet and Laschewsky, André and Papadakis, Christine M. and Müller-Buschbaum, Peter},
  journal      = {Advanced Science},
  title        = {Solvation Dynamics of Thermoresponsive Polymer Films: The Influence of Salt Series in Water and Mixed Water/Methanol Atmosphere},
  year         = {2025},
  number       = {8},
  pages        = {2408073},
  volume       = {12},
  abstract     = {Abstract Understanding the salt effects on solvation behaviors of thermoresponsive polymers is crucial for designing and optimizing responsive systems suitable for diverse environments. In this work, the effect of potassium salts (CH3COOK, KCl, KBr, KI, and KNO3) on solvation dynamics of poly(4-(N-(3'-methacrylamidopropyl)-N,N-dimethylammonio) butane-1-sulfonate) (PSBP), poly(N-isopropylmethacrylamide) (PNIPMAM), and PSBP-b-PNIPMAM films is investigated under saturated water and mixed water/methanol vapor via advanced in situ neutron/optical characterization techniques. These findings reveal that potassium salts enhance the films' hygroscopicity or methanol-induced swellability. Interestingly, the anions effects do not mirror the empirical Hofmeister series, which describes the salting-in effects for such polymers in dilute aqueous solution, particularly evident in PSBP films with an approximately inverted order. PNIPMAM and PSBP-b-PNIPMAM exhibit pronounced deviations from such an inverted correlation and vary somewhat for water-rich and methanol-rich atmospheres. Molecular dynamics (MD) simulations suggest that the observed orders of solvation result from the accessibility of the hydrated solvation shells close to the PSBP-b-PNIPMAM chains.},
  creationdate = {2025-04-22T10:16:43},
  doi          = {https://doi.org/10.1002/advs.202408073},
  eprint       = {https://advanced.onlinelibrary.wiley.com/doi/pdf/10.1002/advs.202408073},
  file         = {:Wang2025 - Solvation Dynamics of Thermoresponsive Polymer Films_ the Influence of Salt Series in Water and Mixed Water_Methanol Atmosphere.pdf:PDF},
  keywords     = {Hofmeister series,hydration shell,neutron reflectivity,potassium salt,solvation sequence,thermoresponsive polymer,ionic strength,cononsolvency,aqueous alcohol,methanol,thin film,pNIPMAM,molecular dynamics simulation},
  url          = {https://advanced.onlinelibrary.wiley.com/doi/abs/10.1002/advs.202408073},
}

@Article{Pagonis2006,
  author       = {Pagonis, Konstantinos and Bokias, Georgios},
  journal      = {Polymer International},
  title        = {Simultaneous lower and upper critical solution temperature-type co-nonsolvency behaviour exhibited in water–dioxane mixtures by linear copolymers and hydrogels containing N-isopropylacrylamide and N,N-dimethylacrylamide},
  year         = {2006},
  number       = {11},
  pages        = {1254-1258},
  volume       = {55},
  abstract     = {Abstract The co-nonsolvency behaviour in water–dioxane mixtures of linear copolymers and hydrogels consisting of N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide (DMAM) was studied as a function of solvent composition and temperature. The composition of the copolymers, P(NIPAM-co-DMAMx), in DMAM units, x, varies from x = 0 up to x = 100\%. It is shown that the copolymers combine the lower critical solution temperature (LCST)-type co-nonsolvency behaviour of poly-NIPAM with the upper critical solution temperature (UCST)-type co-nonsolvency behaviour of poly-DMAM. Depending on x, both the LCST- and UCST-type co-nonsolvency behaviour may be simultaneously observed in water-rich and dioxane-rich solvent mixtures, respectively. Due to this complex phase separation behaviour, the variation of the reduced viscosity of the linear copolymers, as well as the swelling–deswelling behaviour of the respective hydrogels, are shown to be temperature- and solvent-sensitive. Copyright © 2006 Society of Chemical Industry},
  creationdate = {2025-04-22T10:21:40},
  doi          = {https://doi.org/10.1002/pi.2072},
  eprint       = {https://scijournals.onlinelibrary.wiley.com/doi/pdf/10.1002/pi.2072},
  file         = {:Pagonis2006 - Simultaneous Lower and Upper Critical Solution Temperature Type Co Nonsolvency Behaviour Exhibited in Water–dioxane Mixtures by Linear Copolymers and Hydrogels Containing N Isopropylacrylamide and N,N Dimethylacrylamide.pdf:PDF},
  keywords     = {poly(N-isopropylacrylamide),poly(N,N-dimethylacrylamide),co-nonsolvency,lower critical solution temperature (LCST),upper critical solution temperature (UCST),pNIPAM,cononsolvency,dioxane,binary solvent,aqueous solution,gel,PDEAM,copolymer,LCST,UCST},
  url          = {https://scijournals.onlinelibrary.wiley.com/doi/abs/10.1002/pi.2072},
}

@Article{MoralesMoctezuma2021,
  author       = {Morales-Moctezuma, Marissa D. and Spain, Sebastian G.},
  journal      = {Polym. Chem.},
  title        = {The effects of cononsolvents on the synthesis of responsive particles via polymerisation-induced thermal self-assembly},
  year         = {2021},
  pages        = {4696-4706},
  volume       = {12},
  abstract     = {Nanogels have emerged as innovative platforms for numerous biomedical applications including gene and drug delivery{,} biosensors{,} imaging{,} and tissue engineering. Polymerisation-induced thermal self-assembly (PITSA) has been shown to be a suitable route for the synthesis of temperature-responsive nanogels{,} and cononsolvents have been used to improve the solubility of comonomers. Here{,} we show that use of cononsolvents during synthesis also has significant effects on the properties of the final nanogels. Responsive nanogels consisting of a poly(acrylic acid) corona and a crosslinked poly(N-isopropylacrylamide) core were synthesised via RAFT-mediated PITSA in water and water/EtOH mixtures. Nanogels synthesised in water were found to increase in size as the degree of polymerisation (DPn) of the pNIPAM block was increased. For a fixed pNIPAM DPn{,} particle sizes were seen to decrease with increasing EtOH content in the synthesis solvent. This is rationalised by the decreasing solubility of the growing pNIPAM in the reaction medium resulting in earlier particle nucleation. The temperature response of the particles was also found to be dependent on the synthesis conditions with increasing EtOH content in the synthesis solvent increasing the volume phase transition temperature. Model poly(acrylic acid)-block-poly(N-isopropylacrylamide) copolymers synthesised under similar conditions were seen to have differing tacticities dependent on the synthesis solvent with increasing EtOH content resulting in increased syndiotacticity and increased cloud point temperatures. We propose that the tacticity changes are due to the PITSA process{,} with the constrained environment of the particle resulting in increased syndiotacticity.},
  creationdate = {2025-04-22T10:56:10},
  doi          = {10.1039/D1PY00396H},
  file         = {:MoralesMoctezuma2021 - The Effects of Cononsolvents on the Synthesis of Responsive Particles Via Polymerisation Induced Thermal Self Assembly.pdf:PDF},
  issue        = {32},
  keywords     = {cononsolvency,synthesis,pNIPAM,gel,aqueous alcohol,ethanol,RAFT,tacticity},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D1PY00396H},
}

@Article{Linn2024,
  author       = {Linn, Jason D. and Rodriguez, Fabian A. and Calabrese, Michelle A.},
  journal      = {Soft Matter},
  title        = {Cosolvent incorporation modulates the thermal and structural response of PNIPAM/silyl methacrylate copolymers},
  year         = {2024},
  pages        = {3322-3336},
  volume       = {20},
  abstract     = {Polymers functionalized with inorganic silane groups have been used in wide-ranging applications due to the silane reactivity{,} which enables formation of covalently-crosslinked polymeric structures. Utilizing stimuli-responsive polymers in these hybrid systems can lead to smart and tunable behavior for sensing{,} drug delivery{,} and optical coatings. Previously{,} the thermoresponsive polymer poly(N-isopropyl acrylamide) (PNIPAM) functionalized with 3-(trimethoxysilyl)propyl methacrylate (TMA) demonstrated unique aqueous self-assembly and optical responses following temperature elevation. Here{,} we investigate how cosolvent addition{,} particularly ethanol and N{,}N-dimethyl formamide (DMF){,} impacts these transition temperatures{,} optical clouding{,} and structure formation in NIPAM/TMA copolymers. Versus purely aqueous systems{,} these solvent mixtures can introduce additional phase transitions and can alter the two-phase region boundaries based on temperature and solvent composition. Interestingly{,} TMA incorporation strongly alters phase boundaries in the water-rich regime for DMF-containing systems but not for ethanol-containing systems. Cosolvent species and content also alter the aggregation and assembly of NIPAM/TMA copolymers{,} but these effects depend on polymer architecture. For example{,} localizing the TMA towards one chain end in ‘blocky’ domains leads to formation of uniform micelles with narrow dispersities above the cloud point for certain solvent compositions. In contrast{,} polydisperse aggregates form in random copolymer and PNIPAM homopolymer solutions – the size of which depends on solvent composition. The resulting optical responses and thermoreversibility also depend strongly on cosolvent content and copolymer architecture. Cosolvent incorporation thus increases the versatility of inorganic-functionalized responsive polymers for diverse applications by providing a simple way to tune the structure size and optical response.},
  creationdate = {2025-04-22T11:01:13},
  doi          = {10.1039/D4SM00246F},
  file         = {:Linn2024 - Cosolvent Incorporation Modulates the Thermal and Structural Response of PNIPAM_silyl Methacrylate Copolymers.pdf:PDF},
  issue        = {15},
  keywords     = {cononsolvency,pNIPAM,copolymer,cloud-point,DLS,reversibility,thermal cycle},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D4SM00246F},
}









@Article{Wang2012,
  author       = {Wang, Fei and Shi, Yi and Luo, Shuangjiang and Chen, Yongming and Zhao, Jiang},
  journal      = {Macromolecules},
  title        = {Conformational Transition of Poly(N-isopropylacrylamide) Single Chains in Its Cononsolvency Process: A Study by Fluorescence Correlation Spectroscopy and Scaling Analysis},
  year         = {2012},
  number       = {22},
  pages        = {9196-9204},
  volume       = {45},
  abstract     = {Fluorescence correlation spectroscopy (FCS) has been adopted to investigate the conformational transition of poly(N-isopropylacrylamide) (PNIPAM) single chains with moderate molecular weights in the cononsolvency process. A practical approach of performing accurate FCS measurements with the presence of the refractive index mismatch was developed. The practical and reliable FCS calibration facilitates the acquisition of the hydrodynamic radius (RH) of PNIPAM single chains with the change of the water–ethanol composition. By using the synthesized PNIPAM samples covering a range of degrees of polymerization (N), the scaling analysis in the relationship of RH ∼ Nν exhibits a progressive, re-entrant change of the scaling index (ν) between good solvent (0.57) and poor solvent (∼1/3) condition, which is a reflection of a re-entrant conformational transition of the polymers. Furthermore, the highly asymmetrical feature of the cononsolvency process of single PNIPAM chains was unveiled, which indicates a much stronger effect or interaction of the ethanol molecules to the PNIPAM chain. Comparisons of the present results with previous reports provided new information to the mechanism model of the PNIPAM cononsolvency.},
  creationdate = {2025-04-22T11:25:14},
  doi          = {10.1021/ma301780f},
  eprint       = {https://doi.org/10.1021/ma301780f},
  file         = {:Wang2012 - Conformational Transition of Poly(N Isopropylacrylamide) Single Chains in Its Cononsolvency Process_ a Study by Fluorescence Correlation Spectroscopy and Scaling Analysis.pdf:PDF},
  keywords     = {pNIPAM,cononsolvency,fluorescence spectroscopy,FCS,aqueous alcohol,ethanol,scaling law,preferential adsorption},
  url          = {https://doi.org/10.1021/ma301780f},
}

@Article{FernandezPierola1980,
  author       = {Fernandez-Pierola, Ines and Horta, Arturo},
  journal      = {Polymer Bulletin},
  title        = {Co-nonsolvency of PMMA},
  year         = {1980},
  pages        = {273--278},
  volume       = {3},
  creationdate = {2025-04-22T11:50:30},
  doi          = {10.1007/BF00254873},
  file         = {:FernandezPierola1980 - Co Nonsolvency of PMMA.pdf:PDF},
  keywords     = {cononsolvency,PMMA,solvent complexation},
  url          = {https://doi.org/10.1007/BF00254873},
}









@Article{Grinberg2020,
  author       = {Grinberg, Valerij Y. and Burova, Tatiana V. and Grinberg, Natalia V. and Moskalets, Alexander P. and Dubovik, Alexander S. and Plashchina, Irina G. and Khokhlov, Alexei R.},
  journal      = {Macromolecules},
  title        = {Energetics and Mechanisms of poly(N-isopropylacrylamide) Phase Transitions in Water–Methanol Solutions},
  year         = {2020},
  number       = {24},
  pages        = {10765-10772},
  volume       = {53},
  abstract     = {The phase transitions of poly(N-isopropylacrylamide) (PNIPAM) in water–methanol mixed solutions were studied in detail by high-sensitivity differential scanning calorimetry. From this study, the dependences of the transition temperature, enthalpy, heat capacity increment, and width on the methanol molar fraction (xMeOH) were obtained. The transition temperature passed through a minimum at the methanol molar fraction xMeOH* ∼ 0.35. At xMeOH < xMeOH*, the transition enthalpy decreased quickly with the methanol content and became so small that it could not be measured, even with an increase in the polymer concentration by a hundred times (up to 150 mg mL–1). Furthermore, over this xMeOH range, the transition heat capacity increment being negative remained practically constant, but the transition width sharply increased. The transition thermograms were quantitatively described by the Okada–Tanaka theory, which takes into account the role of the polymer–solvent interaction cooperativity in the polymer thermoresponsivity. In terms of this approach, it is assumed that over the defined range of methanol content, PNIPAM possesses the cooperative hydro-solvation structure in the form of water–methanol complexes. The energetics of this structure smoothly decreases with the increase in the methanol content up to a complete disappearance of the structure at xMeOH > xMeOH*. In this range of the methanol content, the phase behavior of PNIPAM seems to be dictated by regularities typical of polymer solutions in organic solvents, that is, how the Flory–Huggins parameter depends on temperature.},
  creationdate = {2025-04-23T07:35:17},
  doi          = {10.1021/acs.macromol.0c02253},
  eprint       = {https://doi.org/10.1021/acs.macromol.0c02253},
  file         = {:Grinberg2020 - Energetics and Mechanisms of Poly(N Isopropylacrylamide) Phase Transitions in Water–Methanol Solutions.pdf:PDF;:EnergeticsAndMechanismsOfPolyNIsopropylacrylamidePhaseTransitionsInWaterMethanolSolutions_GrinbergEtAl_Macromol2020_SI.pdf:PDF},
  keywords     = {pNIPAM,aqueous alcohol,methanol,cononsolvency,DSC,cooperative hydration,solvent complexes},
  url          = {https://doi.org/10.1021/acs.macromol.0c02253},
}

@Article{Nothdurft2019,
  author       = {Nothdurft, Katja and Müller, David H. and Brands, Thorsten and Bardow, André and Richtering, Walter},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Enrichment of methanol inside pNIPAM gels in the cononsolvency-induced collapse},
  year         = {2019},
  pages        = {22811-22818},
  volume       = {21},
  abstract     = {Crosslinked poly-N-isopropylacrylamide (pNIPAM) gels adapt to their environment by a unique transition from a flexible{,} swollen macromolecular network to a collapsed particle. pNIPAM gels are swollen in both{,} pure water and pure methanol (MeOH). However{,} a drastic volume loss is observed in mixtures of water and methanol over a wide composition range. This effect is referred to as cononsolvency. Cononsolvency couples the volume phase transition to the transport of the cosolvent into the polymeric network. So far{,} the mechanisms underlying cononsolvency have not been fully elucidated. To obtain insights on cononsolvency{,} Raman microspectroscopy was applied to capture spatially resolved spectra distinguishing between the surroundings and the inside of the gel. Here{,} we used Indirect Hard Modelling (IHM) for the spectral analysis. Mass balancing allowed the calculation of the solvent composition inside the pNIPAM gel. The results show an increased methanol fraction inside the collapsed gel as compared to its surroundings. Furthermore{,} the sensitivity of the vibrational bands of methanol to its local hydrogen bonding environment allow to derive information about the molecular interactions. The methanol peak shifts measured inside the gel point towards donor-type hydrogen bonds between methanol and the peptide group of pNIPAM in the cononsolvency-induced collapse. The presented data should enhance our understanding of cononsolvency.},
  creationdate = {2025-04-23T08:01:13},
  doi          = {10.1039/C9CP04383G},
  file         = {:Nothdurft2019 - Enrichment of Methanol inside PNIPAM Gels in the Cononsolvency Induced Collapse.pdf:PDF},
  issue        = {41},
  keywords     = {Raman,pNIPAM,cononsolvency,aqueous alcohol,methanol,gel},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C9CP04383G},
}

@Article{Lang2019,
  author       = {Xiaolong Lang and Erin X. Xu and Yuan Wei and Lauren N. Walters and Michael J.A. Hore},
  journal      = {Polymer},
  title        = {Isomeric and structural effects in polymer cononsolvent systems},
  year         = {2019},
  issn         = {0032-3861},
  pages        = {190-197},
  volume       = {170},
  abstract     = {Thermoresponsive poly (N-isopropylacrylamide) (PNIPAM) has many analogs that exhibit cononsolvency behavior in mixtures of water and an alcohol. Cononsolvency is characterized by a combination of good solvents for a polymer that results in decreased solubility. In this work, the cononsolvency behavior of linear PNIPAM, four-arm (4f) star PNIPAM, and linear poly(N-n-propylacrylamide) (PNnPAM), with terminal groups that vary in hydrophobicity, were investigated in mixtures of water and propanol. Polymers were synthesized by RAFT polymerization and subsequently functionalized with one pot aminolysis/thiol-ene chemistry. Turbidimetry measurements and dynamic light scattering (DLS) were used to study the cononsolvency behavior by determining the critical solution temperature (Tc). The measurements show that the size and shape of the hydrophobic region of both the solvent and n-alkyl acrylamide monomer affect Tc and the phase transition behavior. The findings suggest methods to impart multiresponsiveness to soft material systems.},
  creationdate = {2025-04-23T08:56:31},
  doi          = {https://doi.org/10.1016/j.polymer.2019.03.011},
  file         = {:Lang2019 - Isomeric and Structural Effects in Polymer Cononsolvent Systems.pdf:PDF},
  keywords     = {Cononsolvency,Thermoresponsive polymers,PNIPAM,pNIPAM,pNnPAM,isomer,aqueous alcohol,linear polymer,star polymer,polymer architecture,propanol,turbidimetry,DLS,isopropanol,n-propanol,1-propanol,2-propanol,geometric frustration},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386119302253},
}









@Article{Jia2016,
  author       = {Jia, Di and Zuo, Taisen and Rogers, Sarah and Cheng, He and Hammouda, Boualem and Han, Charles C.},
  journal      = {Macromolecules},
  title        = {Re-entrance of Poly(N,N-diethylacrylamide) in D2O/d-Ethanol Mixture at 27 °C},
  year         = {2016},
  number       = {14},
  pages        = {5152-5159},
  volume       = {49},
  abstract     = {The re-entrance of poly(N,N-diethylacrylamide) (PDEA) in D2O/d-ethanol mixtures (i.e., the coil-to-spherical aggregates-to-coil transition) has been observed at 27 °C by small-angle neutron scattering (SANS). PDEA has a lower critical solution temperature (LCST) phase diagram in the D2O-rich region and is soluble in the D2O-poor region for all of the observed temperature ranges. Its spinodal temperature decreases first from 33.5 °C in pure D2O to 26.7 °C in 80\% D2O/20\% d-ethanol and then increases to 283.1 °C in 50\% D2O/50\% d-ethanol. With the further decrease of D2O content, PDEA dissolves well, and its phase boundary can no longer be observed by SANS. Therefore, at 27 °C, PDEA dissolves as random coils when the D2O content is higher than 90\% and then collapses and aggregates to form the globule phase in 20\% D2O/80\% d-ethanol; finally, it reswells and behaves as random coils again with excluded volume in the D2O-poor region. The ternary random phase approximation model (RPA) is used to analyze the SANS profiles, and three Flory–Huggins interaction parameters (χPDEA–d-ethanol, χPDEA–D2O, and χd-ethanol–D2O) are obtained. When a small amount of d-ethanol is added to the system, it has a strong interaction with D2O, so it directly gets distributed into the water structure and makes a negative contribution to the dissolution of PDEA (χd-ethanol–D2O is much smaller than χPDEA–d-ethanol and χPDEA–D2O). With the addition of more d-ethanol, its interaction with water becomes weaker, but still stronger than those between PDEA–D2O and PDEA–d-ethanol. Neither d-ethanol nor D2O wants to help the dissolution of PDEA in the first place, until the structure of mixed solvents tends to be pure d-ethanol in the D2O-poor region.},
  creationdate = {2025-04-23T10:40:30},
  doi          = {10.1021/acs.macromol.6b00785},
  eprint       = {https://doi.org/10.1021/acs.macromol.6b00785},
  file         = {:Jia2016 - Re Entrance of Poly(N,N Diethylacrylamide) in D2O_d Ethanol Mixture at 27 °C.pdf:PDF;:ReentranceOfPolyNNDiethylacrylamideInD2ODEthanolMixtureAt27C_JiaEtAl_Macromol2016_SI.pdf:PDF},
  keywords     = {PDEAM,cononsolvency,ternary flory-huggins,SANS,random phase approximation},
  url          = {https://doi.org/10.1021/acs.macromol.6b00785},
}

@Article{Bharadwaj2018,
  author       = {Bharadwaj, Swaminath and Sunil Kumar, P. B. and Komura, Shigeyuki and Deshpande, Abhijit P.},
  journal      = {The Journal of Chemical Physics},
  title        = {Kosmotropic effect leads to LCST decrease in thermoresponsive polymer solutions},
  year         = {2018},
  issn         = {0021-9606},
  month        = {02},
  number       = {8},
  pages        = {084903},
  volume       = {148},
  abstract     = {We study the phenomena of decrease in lower critical solution temperature (LCST) with addition of kosmotropic (order-making) cosolvents in thermoresponsive polymer solutions. A combination of explicit solvent coarse-grained simulations and mean-field theory has been employed. The polymer-solvent LCST behavior in the theoretical models has been incorporated through the Kolomeisky-Widom solvophobic potential. Our results illustrate how the decrease in the LCST can be achieved by the reduction in the bulk solvent energy with the addition of cosolvent. It is shown that this effect of cosolvent is weaker with an increase in polymer hydrophilicity which can explain the absence of a LCST decrease in poly(N,N-diethylacrylamide), water, and methanol systems. The coarse-grained nature of the models indicates that a mean energetic representation of the system is sufficient to understand the phenomena of LCST decrease.},
  creationdate = {2025-04-23T11:20:39},
  doi          = {10.1063/1.5012838},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.5012838/13286661/084903\_1\_online.pdf},
  file         = {:Bharadwaj2018 - Kosmotropic Effect Leads to LCST Decrease in Thermoresponsive Polymer Solutions.pdf:PDF},
  keywords     = {cononsolvency,pDEAM,kosmotropic,chaotropic,structure-making,structure-breaking,simulations,thermoresponsive},
  url          = {https://doi.org/10.1063/1.5012838},
}









@Article{Sommer2017,
  author       = {Sommer, Jens-Uwe},
  journal      = {Macromolecules},
  title        = {Adsorption–Attraction Model for Co-Nonsolvency in Polymer Brushes},
  year         = {2017},
  number       = {5},
  pages        = {2219-2228},
  volume       = {50},
  abstract     = {We study the properties of a polymer brush exposed to a mixture of two solvents where one component, called the co-nonsolvent (CNS), has a stronger preference with respect to the polymer. The concept of preferential adsorption of CNS onto the polymer, as recently proposed by Mukherhi, Kremer, and Marques [Nat. Commun. 2014, 5, 4882], is combined with the mean-field Alexander–de Gennes approach for the polymer brush. The key assumption is that CNS can form bridges between two monomers which is associated with a further gain in free energy, thus leading to an effective monomer–monomer attraction. The adsorption equilibrium of CNS at a given value of the monomer concentration results in a concentration-dependent χ-function for the polymer brush which describes the effective interactions between the monomers in the mixed solvent. This in turn can lead to a discontinuous collapse transition and to a corresponding reentry transition at higher CNS concentrations. The problem can be analytically treated for a minimal model where the increase of self-volume of the monomers due to adsorption of CNS is neglected. In this case the collapse and the reswelling transition have the same signature. For low brush densities in the noncollapsed state we give an analytic approximation for the spinodal of the collapse. This also allows to define two scaling variables instead of the three control parameters which are the grafting density, the CNS–monomer selectivity, and the volume faction of CNS. The proposed effective free energy contribution resulting from the CNS adsorption equilibrium can be transferred to other systems such as to gels or dendrimers.},
  creationdate = {2025-04-23T15:59:09},
  doi          = {10.1021/acs.macromol.6b02231},
  eprint       = {https://doi.org/10.1021/acs.macromol.6b02231},
  file         = {:Sommer2017 - Adsorption–Attraction Model for Co Nonsolvency in Polymer Brushes.pdf:PDF},
  keywords     = {cononsolvency,theory,polymer brush,preferential adsorption,flory-huggins,enthalpic bridging,mean field},
  url          = {https://doi.org/10.1021/acs.macromol.6b02231},
}









@Article{Sommer2018,
  author       = {Sommer, Jens-Uwe},
  journal      = {Macromolecules},
  title        = {Gluonic and Regulatory Solvents: A Paradigm for Tunable Phase Segregation in Polymers},
  year         = {2018},
  number       = {8},
  pages        = {3066-3074},
  volume       = {51},
  abstract     = {A theoretical concept for phase segregation of polymers in the presence of multicomponent selective solvents is presented. Phase separation is caused by nonspecific attractive interactions between the polymers and a smaller component in the solution instead of repulsion between monomers and solvent molecules. We call the component that adsorbs on the polymers and thus causes condensation “gluonic”. It is shown that a discontinuous phase transition from a diluted or semidiluted state to the condensed state takes place if the fraction of the gluonic component is increased. The location of the phase coexistence can be shifted by influencing the binding efficiency of the gluonic component. This can be achieved by adding a regulator component to the solution. The latter is assumed to bind specifically to the polymer and interferes with the gluonic component. In this way a switching of the state of the polymer from dissolved to condensed can be achieved without changing the chemical properties of the system. Applications of this model range from co-nonsolvency in synthetic polymers, over polymer–nanoparticle systems, to biological systems such as the formation of protein–RNA droplets.},
  comment      = {keyword gluonic for connection to particle physics},
  creationdate = {2025-04-23T16:02:21},
  doi          = {10.1021/acs.macromol.8b00370},
  eprint       = {https://doi.org/10.1021/acs.macromol.8b00370},
  file         = {:Sommer2018 - Gluonic and Regulatory Solvents_ a Paradigm for Tunable Phase Segregation in Polymers.pdf:PDF},
  keywords     = {cononsolvency,theory,polymer brush,preferential adsorption,flory-huggins,enthalpic bridging},
  url          = {https://doi.org/10.1021/acs.macromol.8b00370},
}

@Article{Vegt2017a,
  author       = {van der Vegt, Nico F. A. and Rodríguez-Ropero, Francisco},
  journal      = {Soft Matter},
  title        = {Comment on “Relating side chain organization of PNIPAm with its conformation in aqueous methanol” by D. Mukherji{,} M. Wagner{,} M. D. Watson{,} S. Winzen{,} T. E. de Oliveira{,} C. M. Marques and K. Kremer{,} Soft Matter{,} 2016{,} 12{,} 7995},
  year         = {2017},
  pages        = {2289-2291},
  volume       = {13},
  abstract     = {In a recent paper{,} Mukherji et al. describe the collapse of poly(N-isopropyl acrylamide) in methanol–water mixtures based on experiments and molecular dynamics simulations. The conclusion of their work is that chain collapse is dominated by enthalpic bridging interactions while entropic effects play no major role. Here we show that this claim arises from an improper interpretation of preferential binding and the corresponding thermodynamic data presented. When interpreted correctly{,} the data instead provide evidence for repulsive enthalpic interactions of methanol with the polymer{,} supporting the emerging view of entropic chain collapse.},
  comment      = {criticizes Mukherji, Mukherji2016. Reply exists},
  creationdate = {2025-04-24T10:48:14},
  doi          = {10.1039/C6SM02139E},
  file         = {:Vegt2017a - Comment on “Relating Side Chain Organization of PNIPAm with Its Conformation in Aqueous Methanol” by D. Mukherji, M. Wagner, M. D. Watson, S. Winzen, T. E. De Oliveira, C. M. Marques and K. Kremer, Soft Matter, 2016, 12, 7995.pdf:PDF},
  issue        = {12},
  keywords     = {pNIPAM,cononsolvency,model,enthalpic bridge,hydrophobic hydration,preferential adsorption,aqueous alcohol,methanol},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C6SM02139E},
}









@Article{Dalgicdir2019,
  author       = {Dalgicdir, Cahit and van der Vegt, Nico F. A.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Improved Temperature Behavior of PNIPAM in Water with a Modified OPLS Model},
  year         = {2019},
  note         = {PMID: 30990715},
  number       = {17},
  pages        = {3875-3883},
  volume       = {123},
  abstract     = {We test the OPLS/AA force field for a single PNIPAM 40-mer in aqueous solution using replica exchange molecular dynamics simulations and find that the force field fails to reproduce the experimental temperature behavior. To resolve this issue, we apply a modification on the partial charges previously suggested to reproduce the liquid–liquid phase separation of NIPAM aqueous solutions. The modified force field features stronger amide–water electrostatic interactions than the original OPLS model, predicts a weaker water-mediated monomer–monomer attraction, and reproduces the experimental coil–globule collapse enthalpy of PNIPAM in water. We revisit the cononsolvency problem of PNIPAM in methanol/water mixtures with the modified model and show that the dependence of the coil–globule collapse enthalpy on methanol concentration follows the experimental trend of the lower critical solution temperature. The calculations with the modified force field confirm that polymer dehydration is the determining factor for chain collapse in the cononsolvency regime.},
  comment      = {correction was published, DOI: 10.1021/acs.jpcb.9b00306: ``In a recent publication, (1){#referenceLink} we mistakenly interchanged the NH--water/CO--water symbol legends and the NH--methanol/CO--methanol symbol legends in [Figure](https://pubs.acs.org/doi/10.1021/acs.jpcb.9b00306#fig4)[4](https://pubs.acs.org/doi/10.1021/acs.jpcb.9b00306#fig4)B. The corrected version of [Figure](https://pubs.acs.org/doi/10.1021/acs.jpcb.9b00306#fig4)[4](https://pubs.acs.org/doi/10.1021/acs.jpcb.9b00306#fig4)B is included here. The results shown in the corrected [Figure](https://pubs.acs.org/doi/10.1021/acs.jpcb.9b00306#fig4)[4](https://pubs.acs.org/doi/10.1021/acs.jpcb.9b00306#fig4)B indicate that cononsolvency of PNIPAM in water/methanol mixtures is driven by dehydration of the carbonyl group (CO), rather than by dehydration of the amide proton as concluded in ref (1){#referenceLink}. When the methanol concentration is increased in the cononsolvency region below 20% methanol, we observe that CO--water hydrogen bonds disappear much faster than CO--methanol hydrogen bonds are formed. The enthalpic effect that drives polymer collapse in the cononsolvency regime of PNIPAM/methanol/water solutions therefore results from frustrated CO--water hydrogen-bonding interactions caused by methanol partitioning to the polymer/solution interface.''},
  creationdate = {2025-04-24T11:01:58},
  doi          = {10.1021/acs.jpcb.9b01644},
  eprint       = {https://doi.org/10.1021/acs.jpcb.9b01644},
  file         = {:Dalgicdir2019 - Improved Temperature Behavior of PNIPAM in Water with a Modified OPLS Model.pdf:PDF},
  keywords     = {simulation,pNIPAM,OPLS,molecular dynamics simulaiton,charge scaling,cononsolvency,aqueous alcohol,methanol},
  url          = {https://doi.org/10.1021/acs.jpcb.9b01644},
}









@Article{Sagle2009,
  author       = {Sagle, Laura B. and Zhang, Yanjie and Litosh, Vladislav A. and Chen, Xin and Cho, Younhee and Cremer, Paul S.},
  journal      = {Journal of the American Chemical Society},
  title        = {Investigating the Hydrogen-Bonding Model of Urea Denaturation},
  year         = {2009},
  note         = {PMID: 19527028},
  number       = {26},
  pages        = {9304-9310},
  volume       = {131},
  abstract     = {The direct binding mechanism for urea-based denaturation of proteins was tested with a thermoresponsive polymer, poly(N-isopropylacrylamide) (PNIPAM). Thermodynamic measurements of the polymer’s hydrophobic collapse were complemented by Fourier transform infrared (FTIR) spectroscopy, Stokes radius measurements, and methylated urea experiments. It was found that the lower critical solution temperature (LCST) of PNIPAM decreased as urea was added to the solution. Therefore, urea actually facilitated the hydrophobic collapse of the macromolecule. Moreover, these thermodynamic measurements were strongly correlated with amide I band data which indicated that the decrease in the LCST was coupled to the direct hydrogen bonding of urea to the amide moieties of the polymer. In addition, the hydrogen bonding was found to be highly cooperative, which is consistent with a cross-linking (bivalent binding) mechanism. Cross-linking was confirmed by Stokes radius measurements below the polymer’s LCST using gel filtration chromatography. Finally, phase transition measurements with methylurea, dimethylurea, and tetramethylurea indicated that these substituted compounds caused the LCST of PNIPAM to rise with increasing methyl group content. No evidence could be found for the direct binding of any of these methylated ureas to the polymer amide moieties by FTIR. These results are inconsistent with a direct hydrogen-bonding mechanism for the urea-induced denaturation of proteins.},
  creationdate = {2025-04-24T11:33:48},
  doi          = {10.1021/ja9016057},
  eprint       = {https://doi.org/10.1021/ja9016057},
  file         = {:Sagle2009 - Investigating the Hydrogen Bonding Model of Urea Denaturation.pdf:PDF;:InvestigatingTheHydrogenBondingModelOfUreaDenaturation_SagleEtAl_JACS2009_SI.pdf:PDF},
  keywords     = {cononsolvency,urea,pNIPAM,FTIR,enthalpic bridge,model},
  url          = {https://doi.org/10.1021/ja9016057},
}

@Article{Nayar2017,
  author       = {Nayar, Divya and Folberth, Angelina and van der Vegt, Nico F. A.},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Molecular origin of urea driven hydrophobic polymer collapse and unfolding depending on side chain chemistry},
  year         = {2017},
  pages        = {18156-18161},
  volume       = {19},
  abstract     = {Osmolytes affect hydrophobic collapse and protein folding equilibria. The underlying mechanisms are{,} however{,} not well understood. We report large-scale conformational sampling of two hydrophobic polymers with secondary and tertiary amide side chains using extensive molecular dynamics simulations. The calculated free energy of unfolding increases with urea for the secondary amide{,} yet decreases for the tertiary amide{,} in agreement with experiment. The underlying mechanism is rooted in opposing entropic driving forces: while urea screens the hydrophobic macromolecular interface and drives unfolding of the tertiary amide{,} urea{'}s concomitant loss in configurational entropy drives collapse of the secondary amide. Only at sufficiently high urea concentrations bivalent urea hydrogen bonding interactions with the secondary amide lead to further stabilisation of its collapsed state. The observations provide a new angle on the interplay between side chain chemistry{,} urea hydrogen bonding{,} and the role of urea in attenuating or strengthening the hydrophobic effect.},
  creationdate = {2025-04-24T11:35:56},
  doi          = {10.1039/C7CP01743J},
  file         = {:Nayar2017 - Molecular Origin of Urea Driven Hydrophobic Polymer Collapse and Unfolding Depending on Side Chain Chemistry.pdf:PDF},
  issue        = {28},
  keywords     = {pNIPAM,cononsolvency,PDEAM,urea},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C7CP01743J},
}

@Article{Kyriakos2016a,
  author       = {Kyriakos, Konstantinos and Philipp, Martine and Lin, Che-Hung and Dyakonova, Margarita and Vishnevetskaya, Natalya and Grillo, Isabelle and Zaccone, Alessio and Miasnikova, Anna and Laschewsky, André and Müller-Buschbaum, Peter and Papadakis, Christine M.},
  journal      = {Macromolecular Rapid Communications},
  title        = {Quantifying the Interactions in the Aggregation of Thermoresponsive Polymers: The Effect of Cononsolvency},
  year         = {2016},
  number       = {5},
  pages        = {420-425},
  volume       = {37},
  abstract     = {The aggregation kinetics of thermoresponsive core–shell micelles with a poly(N-isopropyl acrylamide) shell in pure water or in mixtures of water with the cosolvents methanol or ethanol at mole fractions of 5\% is investigated during a temperature jump across the respective cloud point. Characteristically, these mixtures give rise to cononsolvency behavior. At the cloud point, aggregates are formed, and their growth is followed with time-resolved small-angle neutron scattering. Using the reversible association model, the interaction potential between the aggregates is determined from their growth rate in dependence on the cosolvents. The effect of the cosolvent is attributed to the interaction potential on the structured layer of hydration water around the aggregates. It is surmised that the latter is perturbed by the cosolvent and thus the residual repulsive hydration force between the aggregates is reduced. The larger the molar volume of the cosolvent, the more pronounced is the effect. This framework provides a molecular-level understanding of solvent-mediated effective interactions in polymer solutions and new opportunities for the rational control of self-assembly in complex soft matter systems.},
  creationdate = {2025-04-24T11:41:56},
  doi          = {https://doi.org/10.1002/marc.201500583},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/marc.201500583},
  file         = {:Kyriakos2016a - Quantifying the Interactions in the Aggregation of Thermoresponsive Polymers_ the Effect of Cononsolvency.pdf:PDF},
  keywords     = {colloidal aggregation,cononsolvency,interaction potential,polymer solutions,self-assembled micelles,thermoresponsive polymers,aggregation,pNIPAM,aqueous alcohol,methanol,ethanol,Polystyrene,SANS},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/marc.201500583},
}









@Article{Vegt2021,
  author       = {van der Vegt, Nico F. A.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Length-Scale Effects in Hydrophobic Polymer Collapse Transitions},
  year         = {2021},
  note         = {PMID: 33906353},
  number       = {20},
  pages        = {5191-5199},
  volume       = {125},
  abstract     = {The study of molecular mechanisms for cosolvent-driven hydrophobic polymer collapse transitions in water is of pivotal importance in the field of smart responsive materials. Computational studies together with complementary experimental data have led to the discovery and understanding of new phenomena in recent years. However, elementary mechanisms, generally contributing to polymer coil–globule transitions in different classes of cosolvent–water systems, remain elusive due to compensating energy–entropy effects. Herein, I discuss the role of length scales in polymer solubility problems. New ideas on surfactant mechanisms are discussed based on examples in which these mechanisms drive polymer swelling or collapse.},
  creationdate = {2025-04-24T12:52:46},
  doi          = {10.1021/acs.jpcb.1c01070},
  eprint       = {https://doi.org/10.1021/acs.jpcb.1c01070},
  file         = {:Vegt2021 - Length Scale Effects in Hydrophobic Polymer Collapse Transitions.pdf:PDF},
  keywords     = {simulation,cononsolvency,hydrophobic hydration,model},
  url          = {https://doi.org/10.1021/acs.jpcb.1c01070},
}

@Article{Marcus1999,
  author       = {Marcus, Yizhak},
  journal      = {Phys. Chem. Chem. Phys.},
  title        = {Preferential solvation in mixed solvents Part 8. Aqueous methanol from sub-ambient to elevated temperatures},
  year         = {1999},
  pages        = {2975-2983},
  volume       = {1},
  abstract     = {The inversed Kirkwood–Buff integral method is applied to mixtures of water and methanol from -13 to 250°C. Preferential solvation is deduced from these integrals and shown over the entire composition and temperature ranges. The self-preference of water increases with rising temperatures in both water- and methanol-rich mixtures{,} reaching a limiting value near the critical point of methanol. At the equimolar composition{,} though{,} this self-preference reaches a shallow maximum near 150 °C. The methanol self-preference in methanol-rich mixtures is slight{,} but this hydrophobic effect is considerable at 15 mol% of methanol{,} reaching a pronounced maximum near 150°C. The effect of the methanol on the structure of the water{,} the incorporation of water into the structure of methanol{,} and their changes with increasing temperatures are discussed.},
  creationdate = {2025-04-24T14:08:58},
  doi          = {10.1039/A900459I},
  file         = {:Marcus1999 - Preferential Solvation in Mixed Solvents Part 8. Aqueous Methanol from Sub Ambient to Elevated Temperatures.pdf:PDF},
  issue        = {12},
  keywords     = {aqueous alcohol,methanol,kirkwood-buff},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/A900459I},
}









@Article{Tanaka2022,
  author       = {Tanaka, Fumihiko},
  journal      = {Langmuir},
  title        = {Thermoreversible Gelation of Associating Polymers in Hydrogen-Bonding Mixed Solvents},
  year         = {2022},
  note         = {PMID: 34595927},
  number       = {17},
  pages        = {5098-5110},
  volume       = {38},
  abstract     = {The thermoreversible gelation of associating polymers in hydogen-bonding mixed solvents is studied theoretically on the basis of the model ternary solution in which polymers carrying functional group A are dissolved in a primary solvent SB (mainly water) and cosolvent SC. Functional group A forms intermolecular cross-links (A–A) leading to gelation. It can also form hydrogen bonds with either solvent molecule SB or SC (A–SB, A–SC). If bound to a solvent molecule, A becomes inert. Solvent molecules form complexes with variable association numbers (SB–SC). Ternary phase diagrams for sol–gel transition lines and their cross sections on the temperature–solvent composition plane are constructed. It is shown that a minimum in the polymer concentration along the sol–gel transition line appears at a special solvent composition which depends upon the structure of the complexes. At such an optimal gel point, the sol–gel transition temperature becomes the highest, thus leading to stable, strong gels. The degree of adsorption, preferential adsorption coefficient, average molecular weight of the complexes, and cross-link probability are calculated as functions of the solvent composition. At the optimal gel point, the preferential adsorption coefficient changes its sign and the average molecular weight of the complexes reaches a maximum. Results are compared with the experimental data on poly(vinyl alcohol) in a mixed solvent of water/dimethyl sulfoxide, dimethyl sulfoxide/urea, or water/methanol.},
  creationdate = {2025-04-24T14:13:41},
  doi          = {10.1021/acs.langmuir.1c02040},
  eprint       = {https://doi.org/10.1021/acs.langmuir.1c02040},
  file         = {:Tanaka2022 - Thermoreversible Gelation of Associating Polymers in Hydrogen Bonding Mixed Solvents.pdf:PDF},
  keywords     = {cononsolvency,model,solvent complexes,complexation,preferential adsorption,DMSO,urea,aqueous alcohol,methanol,PVA,gel,theory,ternary},
  url          = {https://doi.org/10.1021/acs.langmuir.1c02040},
}

@Article{Mukherji2017a,
  author       = {Mukherji, Debashish and Wagner, Manfred and Watson, Mark D. and Winzen, Svenja and de Oliveira, Tiago E. and Marques, Carlos M. and Kremer, Kurt},
  journal      = {Soft Matter},
  title        = {Reply to the ‘Comment on “Relating side chain organization of PNIPAm with its conformation in aqueous methanol”’ by N. van der Vegt and F. Rodriguez-Ropero{,} Soft Matter{,} 2017{,} 13{,} DOI: 10.1039/C6SM02139E},
  year         = {2017},
  pages        = {2292-2294},
  volume       = {13},
  abstract     = {In a comment van der Vegt and Rodriguez-Ropero (vdVRR) challenged our explanation of the co-non-solvency effect of PNIPAm in aqueous methanol solutions. They argue{,} based on a careful selection of published studies including some of their own{,} that direct repulsions between the different constituents are sufficient to understand this phenomenon. According to vdVRR{,} the emerging view of entropic collapse{,} put forward by Flory (1910–1985) to explain common polymers in poor solvents{,} would be enough to explain co-non-solvency. In this reply we attempt to bring this discussion into firmer grounds. We provide a more comprehensive view of available experimental{,} numerical and theoretical results and review basic concepts of physical chemistry and of statistical mechanics of polymer collapse that show how methanol mediated attractions between chain monomers are required to understand this fascinating behavior.},
  creationdate = {2025-04-24T14:23:29},
  doi          = {10.1039/C7SM00041C},
  file         = {:Mukherji2017a - Reply to the ‘Comment on “Relating Side Chain Organization of PNIPAm with Its Conformation in Aqueous Methanol”’ by N. Van Der Vegt and F. Rodriguez Ropero, Soft Matter, 2017, 13, DOI_ 10.1039_C6SM02139E.pdf:PDF},
  issue        = {12},
  keywords     = {cononsolvency,model,enthalpic bridging,pNIPAM,aqueous alcohol,methanol},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C7SM00041C},
}

@Article{Mukherji2017b,
  author       = {Mukherji, Debashish and Wagner, Manfred and Watson, Mark D. and Winzen, Svenja and de Oliveira, Tiago E. and Marques, Carlos M. and Kremer, Kurt},
  journal      = {Soft Matter},
  title        = {Reply to the ‘Comment on “Relating side chain organization of PNIPAm with its conformation in aqueous methanol”’ by A. Pica and G. Graziano{,} Soft Matter{,} 2017{,} 13{,} DOI: 10.1039/C7SM01065F},
  year         = {2017},
  pages        = {7701-7703},
  volume       = {13},
  abstract     = {We have recently proposed preferential binding by a cosolvent as the mechanism for chain collapse under co-non-solvency. Here we summarise our earlier works and provide further evidence that alcohol preferentially binds to PNIPAm{,} forming cosolvent bridges{,} and thus drives the transition. We also clarify some of the common misconceptions evoked in this debate with Pica and Graziano (PG){,} reinforcing the arguments of our earlier reply-comment [Soft Matter{,} 2017{,} 13{,} 2292] and published works.},
  creationdate = {2025-04-24T14:27:49},
  doi          = {10.1039/C7SM01880K},
  file         = {:Mukherji2017b - Reply to the ‘Comment on “Relating Side Chain Organization of PNIPAm with Its Conformation in Aqueous Methanol”’ by A. Pica and G. Graziano, Soft Matter, 2017, 13, DOI_ 10.1039_C7SM01065F.pdf:PDF},
  issue        = {42},
  keywords     = {cononsolvency,model,enthalpic bridging,pNIPAM,aqueous alcohol,methanol,preferential adsorption},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C7SM01880K},
}

@Article{Pica2017,
  author       = {Pica, Andrea and Graziano, Giuseppe},
  journal      = {Soft Matter},
  title        = {Comment on “Relating side chain organization of PNIPAm with its conformation in aqueous methanol” by D. Mukherji{,} M. Wagner{,} M. D. Watson{,} S. Winzen{,} T. E. de Oliveira{,} C. M. Marques and K. Kremer{,} Soft Matter{,} 2016{,} 12{,} 7995},
  year         = {2017},
  pages        = {7698-7700},
  volume       = {13},
  abstract     = {In a recent article{,} Kremer and co-workers have combined NMR measurements and very long{,} all-atom MD simulations to strengthen their original claim that PNIPAM cononsolvency in water–methanol solutions is driven by the ability of MeOH molecules to bridge different monomers far away along the polymeric chain. In this comment{,} the results presented by Kremer and co-workers are reviewed{,} analyzed{,} and questioned regarding their ability to provide support to the bridging mechanism. Here{,} some pieces of evidence are provided to show that: (1) the solvent-excluded volume effect plays always a fundamental role in polymer collapse; (2) PNIPAM cononsolvency is caused by the geometric-energetic frustration experienced by the polymer when it can interact with both water and methanol molecules at the same time.},
  creationdate = {2025-04-24T14:31:22},
  doi          = {10.1039/C7SM01065F},
  file         = {:Pica2017 - Comment on “Relating Side Chain Organization of PNIPAm with Its Conformation in Aqueous Methanol” by D. Mukherji, M. Wagner, M. D. Watson, S. Winzen, T. E. De Oliveira, C. M. Marques and K. Kremer, Soft Matter, 2016, 12, 7995.pdf:PDF},
  issue        = {42},
  keywords     = {pNIPAM,cononsolvency,model,aqueous alcohol,methanol},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C7SM01065F},
}









@Article{Lama1965,
  author       = {Lama, R. F. and Lu, Benjamin C.-Y.},
  journal      = {Journal of Chemical \& Engineering Data},
  title        = {Excess Thermodynamic Properties of Aqueous Alcohol Solutions.},
  year         = {1965},
  number       = {3},
  pages        = {216-219},
  volume       = {10},
  creationdate = {2025-04-25T15:59:21},
  doi          = {10.1021/je60026a003},
  eprint       = {https://doi.org/10.1021/je60026a003},
  file         = {:Lama1965 - Excess Thermodynamic Properties of Aqueous Alcohol Solutions..pdf:PDF},
  keywords     = {aqueous alcohol,methanol,ethanol,2-propanol,cononsolvency,calorimetry,DSC,1-propanol,propanol,isopropanol,n-propanol},
  url          = {https://doi.org/10.1021/je60026a003},
}

@Article{Vialetto2024,
  author       = {Jacopo Vialetto and Shivaprakash N. Ramakrishna and Sebastian Stock and Regine {von Klitzing} and Lucio Isa},
  journal      = {Journal of Colloid and Interface Science},
  title        = {Modulating the conformation of microgels by complexation with inorganic nanoparticles},
  year         = {2024},
  issn         = {0021-9797},
  pages        = {797-804},
  volume       = {672},
  abstract     = {Hypothesis
The complexation of microgels with rigid nanoparticles is an effective way to impart novel properties and functions to the resulting hybrid particles for applications such as in optics, catalysis, or for the stabilization of foams/emulsions. The nanoparticles affect the conformation of the polymer network, both in bulk aqueous environments and when the microgels are adsorbed at a fluid interface, in a non-trivial manner by modulating the microgel size, stiffness and apparent contact angle.
Experiments
Here, we provide a detailed investigation, using light scattering, in-situ atomic force microscopy and nano-indentation experiments, of the interaction between poly(N-isopropylacrylamide) microgels and hydrophobized silica nanoparticles after mixing in aqueous suspension to shed light on the network reorganization upon nanoparticle incorporation.
Findings
The addition of nanoparticles decreases the microgels' bulk swelling and thermal response. When adsorbed at an oil-water interface, a higher ratio of nanoparticles influences the microgel's stiffness as well as their hydrophobic/hydrophilic character by increasing their effective contact angle, consequently modulating the monolayer response upon interfacial compression. Overall, these results provide fundamental understanding on the complex conformation of hybrid microgels in different environments and give inspiration to design new materials where the combination of a soft polymer network and nanoparticles might result in additional functionalities.},
  creationdate = {2025-04-25T16:18:01},
  doi          = {https://doi.org/10.1016/j.jcis.2024.05.163},
  file         = {:Vialetto2024 - Modulating the Conformation of Microgels by Complexation with Inorganic Nanoparticles.pdf:PDF},
  keywords     = {Hybrid microgel,Atomic force microscopy,Fluid interface,Colloidal particle,Hydrophobicity,Mechanical properties,von Klitzing,nanoparticle,gel,microgel,light scattering,AFM,pNIPAM,DLS},
  url          = {https://www.sciencedirect.com/science/article/pii/S0021979724011494},
}









@Article{Zhao2020,
  author       = {Zhao, Yani and Singh, Manjesh K. and Kremer, Kurt and Cortes-Huerto, Robinson and Mukherji, Debashish},
  journal      = {Macromolecules},
  title        = {Why Do Elastin-Like Polypeptides Possibly Have Different Solvation Behaviors in Water–Ethanol and Water–Urea Mixtures?},
  year         = {2020},
  note         = {PMID: 32226139},
  number       = {6},
  pages        = {2101-2110},
  volume       = {53},
  abstract     = {The solvent quality determines the collapsed or the expanded state of a polymer. For example, a polymer dissolved in a poor solvent collapses, whereas in a good solvent it opens up. While this standard understanding is generally valid, there are examples when a polymer collapses even in a mixture of two good solvents. This phenomenon, commonly known as co-non-solvency, is usually associated with a wide range of synthetic (smart) polymers. Moreover, recent experiments have shown that some biopolymers, such as elastin-like polypeptides (ELPs) that exhibit lower critical solution behavior Tl in pure water, show co-non-solvency behavior in aqueous ethanol mixtures. In this study, we investigate the phase behavior of elastin-like polypeptides (ELPs) in aqueous binary mixtures using molecular dynamics simulations of all-atom and complementary explicit solvent generic models. The model is parameterized by mapping the solvation free energy obtained from the all-atom simulations onto the generic interaction parameters. For this purpose, we derive segment-based (monomer level) generic parameters for four different peptides, namely proline (P), valine (V), glycine (G), and alanine (A), where the first three constitute the basic building blocks of ELPs. Here, we compare the conformational behavior of two ELP sequences, namely -(VPGGG)- and -(VPGVG)-, in aqueous ethanol and -urea mixtures. Consistent with recent experiments, we find that ELPs show co-non-solvency in aqueous ethanol mixtures. Ethanol molecules have preferential binding with all ELP residues, with an interaction contrast of 6–8 kBT, and thus driving the coil-to-globule transition. On the contrary, ELP conformations show a weak variation in aqueous urea mixtures. Our simulations suggest that the glycine residues dictate the overall behavior of ELPs in aqueous urea, where urea molecules have a rather weak preferential binding with glycine as observed from the all atom simulations, i.e., less than kBT. This weak interaction dilutes the overall effect of other neighboring residues and thus ELPs exhibit a different conformational behavior in aqueous urea in comparison to aqueous ethanol mixtures. While the validation of the latter findings will require a more detailed experimental investigation, the results presented here may provide a new twist to the present understanding of cosolvent interactions with peptides and proteins.},
  creationdate = {2025-04-28T09:43:32},
  doi          = {10.1021/acs.macromol.9b02123},
  eprint       = {https://doi.org/10.1021/acs.macromol.9b02123},
  file         = {:Zhao2020 - Why Do Elastin like Polypeptides Possibly Have Different Solvation Behaviors in Water–Ethanol and Water–Urea Mixtures_.pdf:PDF},
  keywords     = {ELP,elastin-like polypeptide,cononsolvency,aqueous alcohol,ethanol,urea,binary solvent,pNIPAM-alternative,biopolymer,simulation,molecular dynamics simulation,all-atom,preferential adsorption},
  url          = {https://doi.org/10.1021/acs.macromol.9b02123},
}









@Article{Ashbaugh1996,
  author       = {Ashbaugh, Henry S. and Paulaitis, Michael E.},
  journal      = {The Journal of Physical Chemistry},
  title        = {Entropy of Hydrophobic Hydration:  Extension to Hydrophobic Chains},
  year         = {1996},
  number       = {5},
  pages        = {1900-1913},
  volume       = {100},
  abstract     = {A statistical mechanical formulation for the entropy in terms of multiparticle correlation functions, used previously to calculate entropies of the hydration of simple hydrophobic solutes, has been generalized to molecular solutes of arbitrary shape by recasting the correlation function expansion as a summation over sites that define the solute molecule. The new formulation for the entropy is applied to a Monte Carlo simulation study of normal alkanes at infinite dilution in water to calculate contributions to the entropy of hydration from water−solute site pair correlations and to examine the role these contributions play in stabilizing different solute conformations. In this implemention, the water−solute site pair correlations are determined only for individual water molecules with their nearest solute site and are defined by water orientational and water oxygen radial distributions around the site, independent of solute orientation relative to the water molecule. We show that these distribution functions give an accurate representation of water structure around the individual n-alkane sites for methane through normal butane, account for the large negative entropies of hydration of these alkanes at 25 °C, and predict the stabilization of gauche-butane relative to trans-butane in water on the basis of an entropically favorable (energetically unfavorable) trans → gauche transition. Contributions to the entropy of hydration arising from solute-induced perturbations in water−water correlations (i.e., water structure enhancement) have also been examined, and we show energy−entropy compensation of these contributions within the framework of the correlation function expansion for the entropy.},
  creationdate = {2025-04-28T09:58:37},
  doi          = {10.1021/jp952387b},
  eprint       = {https://doi.org/10.1021/jp952387b},
  file         = {:Ashbaugh1996 - Entropy of Hydrophobic Hydration_ Extension to Hydrophobic Chains.pdf:PDF},
  keywords     = {hydrophobic hydration,simulation,monte carlo,alkane,methane,ethane,propane,butane},
  url          = {https://doi.org/10.1021/jp952387b},
}

@Article{Wiggins1997,
  author       = {Philippa M. Wiggins},
  journal      = {Physica A: Statistical Mechanics and its Applications},
  title        = {Hydrophobic hydration, hydrophobic forces and protein folding},
  year         = {1997},
  issn         = {0378-4371},
  number       = {1},
  pages        = {113-128},
  volume       = {238},
  abstract     = {There is no general agreement about the molecular mechanism of hydrophobic hydration. The preferred models all consider only the state of single water molecules immediately adjacent to the hydrophobic solute to which they cannot hydrogen bond. Because, fortuitously, all experiments, until recently, have been done at room temperature, the large decrease in entropy accompanying hydrophobic hydration has been taken to mean that the phenomenon is “entropy driven” when common sense says that the effect of losing a whole hydrogen bond is a large increase in enthalpy. At higher temperatures, enthalpy does become positive, further confusing interpretation. When the cooperativity of water-water hydrogen bonding is taken into account, many of the conceptual difficulties of the nature of hydrophobic hydration, the magnitude of the hydrophobic force and its role in protein folding disappear. 1.(1) It accounts for the long-range over which the hydrophobic force can sometimes (but not always) act.2.(2) It suggests that an appreciable population of water molecules close to a hydrophobic surface, out-of-equilibrium with more distant populations compensate for their excess enthalpy by expanding and decreasing their local chemical potential. This explains the thermodynamics findings for transfer of hydrocarbons from the vapour phase to water as a function of temperature.3.(3) It offers a resolution of the current uncertainty as to whether the hydrophobic interaction stabilises or destabilises the folded conformation of proteins. The belief that it is destabilising is based on extensive calorimetric measurements of transfer of amino acids from the vapour phase to water as a model for the transfer of amino acids from the central core of a protein to contact with water. It is suggested that this is an inappropriate model.4.(4) It is shown that the true hydrophobic interaction which drives protein folding is not due to oil/water incompatibility as has always been assumed, but is due to oil/low-density water incompatibility. Low-density water, which has stronger hydrogen bonds and lower intrinsic entropy than normal water has been shown to form outside double layers of polyelectrolytes. This low-density water can overlap adjacent nonpolar amino acids, inducing a powerful driving force for their sequestration out of contact with low-density water.5.(5) It offers mechanisms for the effects of ions of the Hofmeister series and of compensatory solutes in the stabilisation and destabilisation of folded proteins and other structures.6.(6) Other biological structures such as micelles, lipid bilayers, polysaccharides and polynucleotides also have both hydrophobic and charged groups to generate the extreme oil/low-density water incompatibility which promotes structures of singular stability. and order.},
  creationdate = {2025-04-28T10:01:11},
  doi          = {https://doi.org/10.1016/S0378-4371(96)00431-1},
  file         = {:Wiggins1997 - Hydrophobic Hydration, Hydrophobic Forces and Protein Folding.pdf:PDF},
  keywords     = {Hydrophobic,Water,Protein folding,Lipid bilayers,Low-density water,hydrophobic hydration},
  url          = {https://www.sciencedirect.com/science/article/pii/S0378437196004311},
}









@Article{Besseling1997,
  author       = {Besseling, N. A. M. and Lyklema, J.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Molecular Thermodynamics of Hydrophobic Hydration},
  year         = {1997},
  number       = {38},
  pages        = {7604-7611},
  volume       = {101},
  abstract     = {We applied a previously introduced lattice fluid theory for water to study the dissolution of apolar solutes. The treatment is based on a model for the orientation-dependent intermolecular interactions of water. It involves not only the strong directional intermolecular attraction, known as the hydrogen bond, but repulsive interactions between water molecules, which operate at a similar intermolecular separation as hydrogen bonds but at different relative orientations of the molecules, are also important. All the peculiar observations on the dissolution of apolar molecules in water, i.e. temperature dependence of solubility, the Gibbs energy of transfer from apolar medium into water, and its entropic and enthalpic contributions, are reproduced by the theory. Furthermore, the relation between these phenomena and the orientation-dependent intermolecular interactions of water is clarified. Our analysis indicates that the peculiar temperature dependence of the solubility of apolar compounds in water and of the isobaric density of pure water have a common molecular origin. Upon a small expansion of pure water or upon dissolution of small apolar molecules, a subtle enhancement occurs of the type of structuring that is characteristic for water at ambient conditions. This is sufficient to explain the negative hydration entropy of apolar molecules. The negative hydration enthalpy of small apolar molecules is due to a decrease of the number of repulsive non-hydrogen-bonding interactions between neighboring water molecules. Calculations on water adjoining a planar hydrophobic surface indicate that the characteristic features of the dissolution of small apolar solutes do not occur with bulky particles.},
  creationdate = {2025-04-28T10:02:54},
  doi          = {10.1021/jp970474t},
  eprint       = {https://doi.org/10.1021/jp970474t},
  file         = {:Besseling1997 - Molecular Thermodynamics of Hydrophobic Hydration.pdf:PDF},
  keywords     = {hydrophobic hydration,theory,calculation},
  url          = {https://doi.org/10.1021/jp970474t},
}









@Article{Lazaridis2000,
  author       = {Lazaridis, Themis},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Solvent Reorganization Energy and Entropy in Hydrophobic Hydration},
  year         = {2000},
  number       = {20},
  pages        = {4964-4979},
  volume       = {104},
  abstract     = {Monte Carlo simulations of methane in water at 25, 65, and 160 °C are used to obtain the water binding energy as a function of distance from the solute, average water pair interaction energies in the first and second solvation shell, the triplet solute−water oxygen−water oxygen correlation function, the water orientational distribution with respect to the solute as a function of distance from the solute, and water−water orientational correlation functions in the first and second solvation shells. The calculated correlation functions are used in conjunction with the inhomogeneous forms of the energy equation and the correlation expansion for the entropy [Lazaridis, J. Phys. Chem. 1998, 102, 3531] to calculate the solvent reorganization energy and entropy. It is shown that these quantities contain two large contributions of opposite sign:  a positive contribution from the exclusion of solvent molecules by the solute and a negative contribution from the orientational arrangement of water next to the solute. The large magnitude of the heat capacity of hydration is due to flattening of the water orientational distribution with respect to the solute as the temperature increases, which leads to diminution of the orientational arrangement contribution and concomitant increase in both the enthalpy and the entropy of solvation.},
  creationdate = {2025-04-28T10:05:48},
  doi          = {10.1021/jp994261a},
  eprint       = {https://doi.org/10.1021/jp994261a},
  file         = {:Lazaridis2000 - Solvent Reorganization Energy and Entropy in Hydrophobic Hydration.pdf:PDF},
  keywords     = {hydrophobic hydration,simulation,monte carlo,calculation},
  url          = {https://doi.org/10.1021/jp994261a},
}









@Article{Godec2012,
  author       = {Godec, Aljaž and Merzel, Franci},
  journal      = {Journal of the American Chemical Society},
  title        = {Physical Origin Underlying the Entropy Loss upon Hydrophobic Hydration},
  year         = {2012},
  note         = {PMID: 23003674},
  number       = {42},
  pages        = {17574-17581},
  volume       = {134},
  abstract     = {The hydrophobic effect (HE) is commonly associated with the demixing of oil and water at ambient conditions and plays the leading role in determining the structure and stability of biomolecular assembly in aqueous solutions. On the molecular scale HE has an entropic origin. It is believed that hydrophobic particles induce order in the surrounding water by reducing the volume of configuration space available for hydrogen bonding. Here we show with computer simulation results that this traditional picture, based on average structural features of hydration water, configurational properties of single water molecules, and up to pairwise correlations, is not correct. Analyzing collective fluctuations in water clusters we are able to provide a fundamentally new picture of HE based on pronounced many-body correlations affecting the switching of hydrogen bonds (HBs) between molecules. These correlations emerge as a nonlocal compensation of reduced fluctuations of local electrostatic fields in the presence of an apolar solute. We propose an alternative view which may also be formulated as a maximization principle: The electrostatic noise acting on water molecules is maximized under the constraint that each water molecule on average maintains as many HBs as possible. In the presence of the solute the maximized electrostatic noise is a result of nonlocal fluctuations in the labile HB network giving rise to strong correlations among at least up to four water molecules.},
  creationdate = {2025-04-28T10:07:20},
  doi          = {10.1021/ja306464u},
  eprint       = {https://doi.org/10.1021/ja306464u},
  file         = {:Godec2012 - Physical Origin Underlying the Entropy Loss upon Hydrophobic Hydration.pdf:PDF;:PhysicalOriginUnderlyingTheEntropyLossUponHydrophobicHydration_GodecEtAl_JACS2012_SI.pdf:PDF},
  keywords     = {hydrophobic hydration,simulation},
  url          = {https://doi.org/10.1021/ja306464u},
}

@Article{Lee2011,
  author       = {Hyo Jin Lee and Arnold McAuley and Karl F. Schilke and Joseph McGuire},
  journal      = {Advanced Drug Delivery Reviews},
  title        = {Molecular origins of surfactant-mediated stabilization of protein drugs},
  year         = {2011},
  issn         = {0169-409X},
  note         = {Formulating biomolecules: mechanistics insights in molecular interactions},
  number       = {13},
  pages        = {1160-1171},
  volume       = {63},
  abstract     = {Loss of activity through aggregation and surface-induced denaturation is a significant problem in the production, formulation and administration of therapeutic proteins. Surfactants are commonly used in upstream and downstream processing and drug formulation. However, the effectiveness of a surfactant strongly depends on its mechanism(s) of action and properties of the protein and interfaces. Surfactants can modulate adsorption loss and aggregation by coating interfaces and/or participating in protein-surfactant associations. Minimizing protein loss from colloidal and interfacial interaction requires a fundamental understanding of the molecular factors underlying surfactant effectiveness and mechanism. These concepts provide direction for improvements in the manufacture and finishing of therapeutic proteins. We summarize the roles of surfactants, proteins, and surfactant-protein complexes in modulating interfacial behavior and aggregation. These events depend on surfactant properties that may be quantified using a thermodynamic model, to provide physical/chemical direction for surfactant selection or design, and to effectively reduce aggregation and adsorption loss.},
  creationdate = {2025-04-28T10:51:58},
  doi          = {https://doi.org/10.1016/j.addr.2011.06.015},
  file         = {:Lee2011 - Molecular Origins of Surfactant Mediated Stabilization of Protein Drugs.pdf:PDF},
  keywords     = {Adsorption,Aggregation,Formulation,Protein,Stabilization,Surfactant,application-focussed, drug delivery,surfactant mechanism},
  url          = {https://www.sciencedirect.com/science/article/pii/S0169409X1100189X},
}

@Article{Sharma2020,
  author       = {Vivek Sharma and Osvaldo Yañez and Melissa Alegría-Arcos and Ashish Kumar and Ramesh C. Thakur and Plinio Cantero-López},
  journal      = {The Journal of Chemical Thermodynamics},
  title        = {A physicochemical and conformational study of co-solvent effect on the molecular interactions between similarly charged protein surfactant (BSA-SDBS) system},
  year         = {2020},
  issn         = {0021-9614},
  pages        = {106022},
  volume       = {142},
  abstract     = {Use of surfactants in numerous household and industrial processes and their interaction with proteins in our day to day life has made protein-surfactant interactions a booming topic among the researchers of current era. Bovine serum albumin (BSA) being structural homologue to Human Serum albumin (HSA) allowed us to study its binding efficiency with anionic surfactant such as sodium dodecyl benzene sulfonate (SDBS). BSA is known as transport protein due its binding characteristics as well as transportation of hydrophobic drugs or ligands to different target areas (In Human body). Surfactants are also known as eminent constituents of pharmaceutical drug delivery systems. So, interactions of BSA-SDBS (Similarly charged protein-surfactant system) in presence of two industrially important co-solvents DMSO and Glycerol have decided its fate as a novel drug delivery system. These interactional studies were performed by means of myriad experimental and theoretical approaches i.e. conductivity, fluorescence, Ligand Simultaneous Docking (MLSD) and non-covalent interactions index (NCI). Results showed the dominance of Van der Waals interactions and hydrophobic forces with important changes in the preferred binding site.},
  creationdate = {2025-04-28T10:54:05},
  doi          = {https://doi.org/10.1016/j.jct.2019.106022},
  file         = {:Sharma2020 - A Physicochemical and Conformational Study of Co Solvent Effect on the Molecular Interactions between Similarly Charged Protein Surfactant (BSA SDBS) System.pdf:PDF},
  keywords     = {Anionic surfactant,BSA,Co-solvents,Protein surfactant interactions,SDBS,Fluorescence,Ligand Simultaneous Docking,surfactant mechanism,application-focussed,drug delivery,Bovine Serum Albumin,sodium dodecyl benzene sulfonate,DMSO,glycerol},
  url          = {https://www.sciencedirect.com/science/article/pii/S002196141930744X},
}

@Article{Mukherji2015,
  author       = {Mukherji, Debashish and Marques, Carlos M. and Stuehn, Torsten and Kremer, Kurt},
  journal      = {The Journal of Chemical Physics},
  title        = {Co-non-solvency: Mean-field polymer theory does not describe polymer collapse transition in a mixture of two competing good solvents},
  year         = {2015},
  issn         = {0021-9606},
  month        = {03},
  number       = {11},
  pages        = {114903},
  volume       = {142},
  abstract     = {Smart polymers are a modern class of polymeric materials that often exhibit unpredictable behavior in mixtures of solvents. One such phenomenon is co-non-solvency. Co-non-solvency occurs when two (perfectly) miscible and competing good solvents, for a given polymer, are mixed together. As a result, the same polymer collapses into a compact globule within intermediate mixing ratios. More interestingly, polymer collapses when the solvent quality remains good and even gets increasingly better by the addition of the better cosolvent. This is a puzzling phenomenon that is driven by strong local concentration fluctuations. Because of the discrete particle based nature of the interactions, Flory-Huggins type mean field arguments become unsuitable. In this work, we extend the analysis of the co-non-solvency effect presented earlier [D. Mukherji et al., Nat. Commun. 5, 4882 (2014)]. We explain why co-non-solvency is a generic phenomenon, which can only be understood by the thermodynamic treatment of the competitive displacement of (co)solvent components. This competition can result in a polymer collapse upon improvement of the solvent quality. Specific chemical details are not required to understand these complex conformational transitions. Therefore, a broad range of polymers are expected to exhibit similar reentrant coil-globule-coil transitions in competing good solvents.},
  creationdate = {2025-04-28T11:13:22},
  doi          = {10.1063/1.4914870},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4914870/15495523/114903\_1\_online.pdf},
  file         = {:Mukherji2015 - Co Non Solvency_ Mean Field Polymer Theory Does Not Describe Polymer Collapse Transition in a Mixture of Two Competing Good Solvents.pdf:PDF},
  keywords     = {cononsolvency,mechanism},
  url          = {https://doi.org/10.1063/1.4914870},
}

@Article{Dudowicz2013,
  author       = {Dudowicz, Jacek and Freed, Karl F. and Douglas, Jack F.},
  journal      = {The Journal of Chemical Physics},
  title        = {Solvation of polymers as mutual association. II. Basic thermodynamic properties},
  year         = {2013},
  issn         = {0021-9606},
  month        = {04},
  number       = {16},
  pages        = {164902},
  volume       = {138},
  abstract     = {The theory of equilibrium solvation of polymers B by a relatively low molar mass solvent A, developed in the simplest form in Paper I, is used to explore some essential trends in basic thermodynamic properties of solvated polymer solutions, such as the equilibrium concentrations of solvated polymers AiB and free solvent molecules A, the mass distribution \\documentclass[12pt]\{minimal\}\\begin\{document\}\$\\phi \_\{\{A\_\{i\}B\}\}(i)\$\\end\{document\}ϕAiB(i) of solvated clusters, the extent of solvation of the polymer Φsolv, the solvation transition lines \\documentclass[12pt]\{minimal\}\\begin\{document\}\$T\_\{solv\}(\\phi \_\{\{B\}\}^\{\\:o\})\$\\end\{document\}Tsolv(ϕBo), the specific heat CV, the osmotic second virial coefficient \\documentclass[12pt]\{minimal\}\\begin\{document\}\$\{\\cal B\}\_\{2\}\$\\end\{document\}B2, phase stability boundaries, and the critical temperatures associated with closed loop phase diagrams. We discuss the differences between the basic thermodynamic properties of solvated polymers and those derived previously for hierarchical mutual association processes involving the association of two different species A and B into AB complexes and the subsequent polymerization of these AB complexes into linear polymeric structures. The properties of solvated polymer solutions are also compared to those for solutions of polymers in a self-associating solvent. Closed loop phase diagrams for solvated polymer solutions arise in the theory from the competition between the associative and van der Waals interactions, a behavior also typical for dispersed molecular and nanoparticle species that strongly associate with the host fluid. Our analysis of the temperature dependence of the second osmotic virial coefficient reveals that the theory must be generalized to describe the association of multiple solvent molecules with each chain monomer, and this complex extension of the present model will be developed in subsequent papers aimed at a quantitative rather than qualitative treatment of solvated polymer solutions.},
  creationdate = {2025-04-28T11:31:03},
  doi          = {10.1063/1.4800082},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4800082/13137458/164902\_1\_online.pdf},
  file         = {:Dudowicz2013 - Solvation of Polymers As Mutual Association. II. Basic Thermodynamic Properties.pdf:PDF},
  keywords     = {flory-huggins,solvent complexation,theory,mean field,virial coefficient},
  url          = {https://doi.org/10.1063/1.4800082},
}

@Article{Dudowicz2015a,
  author       = {Dudowicz, Jacek and Freed, Karl F. and Douglas, Jack F.},
  journal      = {The Journal of Chemical Physics},
  title        = {Theory of competitive solvation of polymers by two solvents and entropy-enthalpy compensation in the solvation free energy upon dilution with the second solvent},
  year         = {2015},
  issn         = {0021-9606},
  month        = {06},
  number       = {21},
  pages        = {214906},
  volume       = {142},
  abstract     = {We develop a statistical mechanical lattice theory for polymer solvation by a pair of relatively low molar mass solvents that compete for binding to the polymer backbone. A theory for the equilibrium mixture of solvated polymer clusters \{AiBCj\} and free unassociated molecules A, B, and C is formulated in the spirit of Flory-Huggins mean-field approximation. This theoretical framework enables us to derive expressions for the boundaries for phase stability (spinodals) and other basic properties of these polymer solutions: the internal energy U, entropy S, specific heat CV, extent of solvation Φsolv, average degree of solvation 〈Nsolv〉, and second osmotic virial coefficient    B   2    as functions of temperature and the composition of the mixture. Our theory predicts many new phenomena, but the current paper applies the theory to describe the entropy-enthalpy compensation in the free energy of polymer solvation, a phenomenon observed for many years without theoretical explanation and with significant relevance to liquid chromatography and other polymer separation methods.},
  creationdate = {2025-04-28T11:34:03},
  doi          = {10.1063/1.4921373},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4921373/13254031/214906\_1\_online.pdf},
  file         = {:Dudowicz2015a - Theory of Competitive Solvation of Polymers by Two Solvents and Entropy Enthalpy Compensation in the Solvation Free Energy upon Dilution with the Second Solvent.pdf:PDF},
  keywords     = {cononsolvency,theory,flory-huggins,mean field},
  url          = {https://doi.org/10.1063/1.4921373},
}









@Article{Chen2017,
  author       = {Chen, Xueqian and Feng, Wei and Han, Xia and Liu, Honglai},
  journal      = {Langmuir},
  title        = {Possible Way to Study Cononsolvency in Confinement: A Lattice Density Functional Theory Approach},
  year         = {2017},
  note         = {PMID: 28930471},
  number       = {42},
  pages        = {11446-11456},
  volume       = {33},
  abstract     = {Polymer lattice density functional theory (PLDFT) is used to investigate the cononsolvency (CNS) phenomena related to polymer adsorption in a slit pore. Specifically, the two simplest types of CNS are examined: CNS1 with solvent–cosolvent binding as the dominant factor and CNS2 with polymer–cosolvent binding as the dominant factor. The simplified models for CNS1/CNS2 well capture the symmetrical/asymmetrical reentrant swelling transition of polymers positively/negatively adsorbed on the solid surface as confirmed by the calculation of PLDFT. To more deeply understand the mechanism of CNS in polymer adsorption, the essential difference and connection between the two types of CNS are analyzed by PLDFT via the quantities as the surface/middle swelling ratio defined for the aggregated layer of polymers in the slit. Further investigation of the effects of binding strength on the collapsing state of the polymer membrane shows the existence of the critical binding energy to trigger drastic collapse through the cosolvent for CNS1 or CNS2. The effects from polymer concentration on two types of CNS are also discussed, showing two important results for CNS2 in agreement with reported experiments. For application, this work indicated the possibility of employing CNS (CNS1) in adsorbed polymers for a tunable surface, as an alternative to polymer brushes.},
  creationdate = {2025-05-01T11:15:21},
  doi          = {10.1021/acs.langmuir.7b03134},
  eprint       = {https://doi.org/10.1021/acs.langmuir.7b03134},
  file         = {:Chen2017 - Possible Way to Study Cononsolvency in Confinement_ a Lattice Density Functional Theory Approach.pdf:PDF},
  keywords     = {cononsolvency,theory,model,calculations},
  url          = {https://doi.org/10.1021/acs.langmuir.7b03134},
}

@Article{Budkov2017,
  author       = {Budkov, Yu. A. and Kolesnikov, A. L.},
  journal      = {Soft Matter},
  title        = {Statistical description of co-nonsolvency suppression at high pressures},
  year         = {2017},
  pages        = {8362-8367},
  volume       = {13},
  abstract     = {We present an application of Flory-type theory of a flexible polymer chain dissolved in a binary mixture of solvents to theoretical description of co-nonsolvency. We show that our theoretical predictions are in good quantitative agreement with the recently published MD simulation results for the conformational behavior of a Lennard-Jones flexible chain in a binary mixture of the Lennard-Jones fluids. We show that our theory is able to describe co-nonsolvency suppression through pressure enhancement to extremely high values recently discovered in experiments and reproduced by full atomistic MD simulations. By analysing the co-solvent concentration in the internal polymer volume at different pressure values{,} we speculate that this phenomenon is caused by the suppression of the co-solvent preferential solvation of the polymer backbone at the rather high pressure imposed. We show that when the co-solvent-induced coil–globule transition takes place{,} the entropy and enthalpy contributions to the solvation free energy abruptly decrease{,} while the solvation free energy remains continuous.},
  creationdate = {2025-05-01T11:25:25},
  doi          = {10.1039/C7SM01637A},
  file         = {:Budkov2017 - Statistical Description of Co Nonsolvency Suppression at High Pressures.pdf:PDF},
  issue        = {45},
  keywords     = {cononsolvency,flory-huggins,theory,pressure},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C7SM01637A},
}

@Article{Hofmann2014,
  author       = {Christian H. Hofmann and Sebastian Grobelny and Mirko Erlkamp and Roland Winter and Walter Richtering},
  journal      = {Polymer},
  title        = {Influence of high-pressure on cononsolvency of poly(N-isopropyl\-acrylamide) nanogels in water/methanol mixtures},
  year         = {2014},
  issn         = {0032-3861},
  number       = {8},
  pages        = {2000-2007},
  volume       = {55},
  abstract     = {We show that the temperature-induced collapse of poly(N-isopropylacrylamide) (PNiPAm) nanogels in water/methanol mixtures can be reversed by excess hydrostatic pressure. Small angle X-ray scattering (SAXS) results reveal that first a swollen surface layer is established and then the particles swell homogeneously. A threshold pressure needed for rewelling fully collapsed nanogels indicates that hydrophobic interactions inside the nanogel have to be compensated to form a swollen surface layer. The size change is related to a change in polymer solvation detected by infrared (IR) spectroscopy. Pressure favours polymer/water hydrogen bonds to the cost of methanol/polymer bonds so that water is enriched inside the nanogel.},
  creationdate = {2025-05-01T11:37:24},
  doi          = {https://doi.org/10.1016/j.polymer.2014.03.006},
  file         = {:Hofmann2014 - Influence of High Pressure on Cononsolvency of Poly(N Isopropylacrylamide) Nanogels in Water_methanol Mixtures.pdf:PDF},
  keywords     = {Lower critical solution temperature,Microgel,gel,Phase behaviour,pressure,cononsolvency,pNIPAM,SAXS,aqueous alcohol,methanol},
  url          = {https://www.sciencedirect.com/science/article/pii/S0032386114002031},
}









@Article{Vrhovsek2011,
  author       = {Vrhovšek, Aleksander and Gereben, Orsolya and Jamnik, Andrej and Pusztai, László},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Hydrogen Bonding and Molecular Aggregates in Liquid Methanol, Ethanol, and 1-Propanol},
  year         = {2011},
  note         = {PMID: 21916497},
  number       = {46},
  pages        = {13473-13488},
  volume       = {115},
  abstract     = {We present a detailed and comprehensive structural study of molecular models of liquid methanol, ethanol, and 1-propanol that originate from a series of reverse Monte Carlo (RMC), molecular dynamics (MD), and united-atom Monte Carlo (UA:MC) simulations. We compare several modeling approaches: RMC simulations that employ experimental neutron and X-ray diffraction data as sole constraints, RMC with diffraction data complemented with partial radial distribution functions (PRDFs) from MD or UA:MC, and conventional MD and UA:MC simulations. The assessment is done in view of the structural parameters of the hydrogen bond and resulting morphological characteristics of molecular aggregates. To achieve these tasks, a computer program for structural analysis of molecular configurations together with the appropriate aggregate classification scheme has been developed. We have analyzed the morphology of clusters, their probability, and size distributions. Any cyclic structures that appeared in the configurations were extracted and characterized in the same manner. We found that MD and UA:MC simulations resulted in configurations with bulkier, more threadlike aggregates that were not entirely consistent with the experimental evidence from diffraction experiments. A combination of neutron and X-ray diffraction data with PRDFs from MD simulations, simultaneously applied as constraints in the RMC procedure, proved to be a modeling approach with the most conclusive results.},
  creationdate = {2025-05-01T12:19:23},
  doi          = {10.1021/jp206665w},
  eprint       = {https://doi.org/10.1021/jp206665w},
  keywords     = {aqueous alcohol,methanol,ethanol,1-propanol,n-propanol,molecular dynamics simulation,simulation,monte carlo,solvent complexes},
  url          = {https://doi.org/10.1021/jp206665w},
}









@Article{Mahendrakar2025,
  author       = {Mahendrakar, Tushar and Rane, Kaustubh},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Comparative Study of Polymer Globules and Liquid Droplets in Poor Solvents: Effects of Cosolvents and Solvent Quality},
  year         = {2025},
  note         = {PMID: 39788924},
  number       = {3},
  pages        = {979-989},
  volume       = {129},
  abstract     = {We compare the structures of polymer globules, composed of flexible polymer chains, with liquid droplets made of nonbonded monomers of the same polymer in poor solvents. This comparison is performed in three different poor solvents, with and without the addition of cosolvents. Molecular dynamics simulations are used to analyze the properties of the polymer globules, while semigrand canonical Monte Carlo simulations are used to form metastable liquid droplets of nonbonded monomers through homogeneous nucleation in the same solvents. Our findings show that both globules and droplets are nearly spherical, although droplets display slightly more anisotropy. In the absence of cosolvents, the surrounding solvent structures are similar for both globules and droplets. However, in the presence of cosolvents, significant differences arise in the liquid structure, with the disparities increasing as the solvent quality worsens. Cosolvents tend to accumulate near the surface of globules due to the restricted movement of bonded monomers, which partially immobilizes the cosolvents. This effect becomes more pronounced as the solvent quality declines. Interfacial free energy calculations reveal that cosolvents act like surfactants, promoting larger interfacial areas for both globules and droplets. This effect is more significant for globules due to the greater accumulation of cosolvents at their surface. Therefore, modeling polymer globules as liquid droplets may underestimate the impact of cosolvents on the stability of the globule state. Additionally, the transition states involved in polymer collapse in the presence of cosolvents differ from those involved in the nucleation of liquid droplets in the same solution.},
  creationdate = {2025-05-01T12:34:10},
  doi          = {10.1021/acs.jpcb.4c07137},
  eprint       = {https://doi.org/10.1021/acs.jpcb.4c07137},
  file         = {:Mahendrakar2025 - Comparative Study of Polymer Globules and Liquid Droplets in Poor Solvents_ Effects of Cosolvents and Solvent Quality.pdf:PDF;:ComparativeStudyOfPolymerGlobulesAndLiquidDropletsInPoorSolvents-EffectsOfCosolventsAndSolventQuality_MahendrakarEtAl_JPC2025_SI.pdf:PDF},
  keywords     = {cononsolvency,cooperativity,simulation,molecular dynamics,monte carlo,monomer},
  url          = {https://doi.org/10.1021/acs.jpcb.4c07137},
}

@Article{Marcato2024,
  author       = {Marcato, Davide and Giacometti, Achille and Maritan, Amos and Rosa, Angelo},
  journal      = {Phys. Rev. Mater.},
  title        = {Theory of polymers in binary solvent solutions: Mean-field free energy and phase behavior},
  year         = {2024},
  month        = dec,
  pages        = {125601},
  volume       = {8},
  creationdate = {2025-05-01T12:36:54},
  doi          = {10.1103/PhysRevMaterials.8.125601},
  file         = {:Marcato2024 - Theory of Polymers in Binary Solvent Solutions_ Mean Field Free Energy and Phase Behavior.pdf:PDF},
  issue        = {12},
  keywords     = {cononsolvency,theory,mean field,calculations,ternary flory-huggins},
  numpages     = {11},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRevMaterials.8.125601},
}

@Article{Otake1989,
  author       = {Otake, Katsuto and Inomata, Hiroshi and Konno, Mikio and Saito, Shozaburo},
  journal      = {The Journal of Chemical Physics},
  title        = {A new model for the thermally induced volume phase transition of gels},
  year         = {1989},
  issn         = {0021-9606},
  month        = {07},
  number       = {2},
  pages        = {1345-1350},
  volume       = {91},
  abstract     = {A theoretical model that considers hydrophobic interaction is proposed for the thermally induced discontinuous shrinkage of hydrogels. In this model, the free energy of a hydrogel is divided into four parts: the elastic free energy of networks formulated according to the theory which takes the limit of elongation into account, the free energy arising from osmotic pressure of dissociated counterions in the gel, the free energy of interactions except for the hydrophobic interaction represented by a virial‐type volume interaction equation, and the free energy of the hydrophobic interaction. By the former three terms, the thermally induced swelling of gels and the effects of aspect ratio of segment are expressed. The incorporation of the fourth hydrophobic interaction term makes it possible to explain the thermally induced shrinkage of gels, and suggests the possibility of an explanation of ‘‘convexo’’‐type volume phase transition by means of the hydrophobic interaction.},
  creationdate = {2025-05-02T10:17:40},
  doi          = {10.1063/1.457157},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/91/2/1345/18981496/1345\_1\_online.pdf},
  file         = {:Otake1989 - A New Model for the Thermally Induced Volume Phase Transition of Gels.pdf:PDF},
  keywords     = {thermoresponsive,theory,model,hydrophobic hydration,gel},
  url          = {https://doi.org/10.1063/1.457157},
}









@Article{Otake1990,
  author       = {Otake, Katsuto and Inomata, Hiroshi and Konno, Mikio and Saito, Shozaburo},
  journal      = {Macromolecules},
  title        = {Thermal analysis of the volume phase transition with N-isopropylacrylamide gels},
  year         = {1990},
  number       = {1},
  pages        = {283-289},
  volume       = {23},
  abstract     = {Experimental work was done to study the thermoshrinking-type volume phase transition of N-isopropylacrylamide (NIPA) gel in aqueous solutions. The experiments principally consisted of the application of thermal analysis with a differential scanning calorimeter (DSC) to NIPA gels and to aqueous solutions of linear NIPA polymer (PNIPA) and poly(vinyl methyl ether) (PVME), whose gel is characteristic of the thermoshrinking type. The transition temperatures of NIPA gel obtained from DSC analysis were compared with those usually obtained from standard swelling expreiments. This comparison clraified the efficiency of DSC for the determination of the trannsition temperature. For the linear polymer solutions, the transition temperatures obtained from DSC were staisfactorily consistent with their cloud points. Both the transition temperature and heat of the collapse of the NIPA gel showed similar values to those of the PNIPA solutions, which permitted the inference that the volume phase transition is controlled primarily by the same factors as the coil-globule transition of the linear polymer. The transition heat of collapse of the gel was endothermic and its absolute value was larger than those reported for nonpolar organis solution systems. Similar results were obtained with the linear polymer solutions. The experimental results were interpreted by using the concept of hydrophobic interaction. The addition of low molecular weight substances changed the transition temperature. This can be explained through the viscosity B coefficient},
  creationdate = {2025-05-02T10:19:57},
  doi          = {10.1021/ma00203a049},
  eprint       = {https://doi.org/10.1021/ma00203a049},
  keywords     = {pNIPAM,PVME,cononsolvency,DSC,thermoresponsive,gel,linear polymer,hydrophobic hydration,aqueous alcohol,methanol,ethanol,1-propanol,n-propanol,1-butanol,n-butanol,urea,glycerol, DMSO,cloud point},
  url          = {https://doi.org/10.1021/ma00203a049},
}

@Article{Orlov2006,
  author       = {Yury Orlov and Xiaoping Xu and Gerd Maurer},
  journal      = {Fluid Phase Equilibria},
  title        = {Equilibrium swelling of N-isopropyl acrylamide based ionic hydrogels in aqueous solutions of organic solvents: Comparison of experiment with theory},
  year         = {2006},
  issn         = {0378-3812},
  number       = {1},
  pages        = {6-16},
  volume       = {249},
  abstract     = {A series of polyelectrolyte hydrogels were synthesized by copolymerization of N-isopropyl acrylamide with the ionic monomer sodium methacrylate. The swelling behavior and the effect of electric charge on the composition-induced collapse of the resulting ionic hydrogels were investigated in aqueous solutions of five single organic solvents (acetone, ethanol, acetic acid, butanol and methyl isobutyl ketone) at 298K. The experimental results of some hydrogels were correlated applying a thermodynamic model, which combines an expression for the Gibbs energy of a liquid phase with an equation for the Helmholtz energy of an elastic network. The model was also successfully used to predict the swelling equilibrium of the other hydrogels in aqueous, organic solutions.},
  creationdate = {2025-05-02T10:37:41},
  doi          = {https://doi.org/10.1016/j.fluid.2006.08.015},
  file         = {:Orlov2006 - Equilibrium Swelling of N Isopropyl Acrylamide Based Ionic Hydrogels in Aqueous Solutions of Organic Solvents_ Comparison of Experiment with Theory.pdf:PDF},
  keywords     = {Synthetic chemically crosslinked ionic hydrogels,-isopropyl acrylamide,Sodium methacrylate,Swelling equilibrium in water and aqueous solutions,Acetone,Ethanol,Acetic acid,Butanol,Methyl isobutyl ketone experimental data,Modeling,pNIPAM,gel,cononsolvency,ionic strength,aqueous alcohol,ethanol,butanol,MEK,theory},
  url          = {https://www.sciencedirect.com/science/article/pii/S0378381206003670},
}

@Article{Poschlad2011,
  author       = {K. Poschlad and S. Enders},
  journal      = {The Journal of Chemical Thermodynamics},
  title        = {Thermodynamics of aqueous solutions containing poly (N-isopropylacrylamide)},
  year         = {2011},
  issn         = {0021-9614},
  number       = {3},
  pages        = {262-269},
  volume       = {43},
  abstract     = {Hydrogels undergo reversible and discontinuous volume changes in response to variation of solution conditions such as solvent composition, temperature, salt concentration, and pH. In this contribution we focus our attention on the experimental and theoretical investigation of these swelling equilibria of aqueous cross-linked poly (N-isopropylacrylamide) solutions as well as on the connected demixing behavior of the linear polymer dissolved in water. For the experimental study of the (liquid+liquid) equilibrium an alternative method based on refractive index measurements is suggested. In order to calculate the swelling behavior a model combining an expression for the Gibbs free energy of mixing with an expression for the elastic network is applied. As a model for the Gibbs free energy of mixing the UNIQUAC-approach and the Koningsveld–Kleintjens model are used. For the elastic network contribution again two different theories, namely the phantom network theory and the affine network theory, were applied. Whereas the type of network theory has only a small influence on the calculation results, the Gibbs free energy of mixing has a large impact. Using the UNIQUAC-approach the swelling equilibria can be correlated close to the experimental data, however, this model predicts a homogeneous mixture for linear polymer chains in water. In contrast to this situation the Koningsveld–Kleintjens model does a good job in calculating the swelling equilibria as well as the demixing curve, however, the adjustable parameter must be changed slightly.},
  creationdate = {2025-05-02T10:47:27},
  doi          = {https://doi.org/10.1016/j.jct.2010.09.007},
  keywords     = {Hydrogel,N-isopropylacrylamide,(Liquid+liquid) equilibrium,Modeling the hydrogel swelling,Koningsveld–Kleintjens model,UNIQUAC model,pNIPAM,gel,theory,refractive index},
  url          = {https://www.sciencedirect.com/science/article/pii/S0021961410002831},
}

@Article{HassanianMoghaddam2016,
  author       = {Hossein Hassanian-Moghaddam and Nasim Zamani},
  journal      = {Iranian Journal of Kidney Diseases},
  title        = {A Brief Review on Toxic Alcohols, Management Strategies},
  year         = {2016},
  month        = nov,
  number       = {6},
  pages        = {344–350},
  volume       = {10},
  abstract     = {The information on burden of alcohol abuse in Iran is scarce. However, the available data show that mortality rates and frequency of its use have increased in the Iranian community. In particular, Iran occupies the 1st rank in the number of outbreak incidents and victims of toxic alcohols such as methanol in the Middle East. Mortality and morbidity of toxic alcohols are high if prompt diagnosis and treatment are not initiated rapidly. On-time diagnosis, proper case finding, and standard treatment have an essential role to reduce mortality and morbidity of toxic alcohols particularly blindness and other physical and psychological disabilities. This review focuses on intoxication with methanol, ethylene glycol, and isopropanol, and their treatment.},
  creationdate = {2025-05-02T12:51:59},
  file         = {:HassanianMoghaddam2016 - A Brief Review on Toxic Alcohols, Management Strategies.pdf:PDF},
  keywords     = {toxic alcohols,medicine},
  url          = {https://ijkd.org/index.php/ijkd/article/view/2631},
}

﻿
@Article{Patocka2012,
  author       = {Patocka, Jiri and Kuca, Kamil},
  journal      = {Military Medical Science Letters},
  title        = {TOXIC ALCOHOLS: ALIPHATIC SATURATED ALCOHOLS},
  year         = {2012},
  issn         = {03727025},
  number       = {4},
  pages        = {142--163},
  volume       = {81},
  abstract     = {Toxic alcohols that clinicians commonly encounter are ethylene glycol, methanol, and isopropanol. Adults ingest these either for suicidal intent or to achieve inebriation, since these substances are readily available and cheaper than alcohol. Nevertheless, assorted alcohols are used very often in many applications and any alcohol can be toxic if ingested in large enough quantities. Toxic alcohols discussed here include all saturated aliphatic alcohols containing from 1 to 6 carbons in their molecules.},
  creationdate = {2025-05-02T12:55:30},
  doi          = {10.31482/mmsl.2012.022},
  file         = {:Patocka2012 - TOXIC ALCOHOLS_ ALIPHATIC SATURATED ALCOHOLS.pdf:PDF},
  keywords     = {toxic alcohols, methanol, ethanol, propanol, isopropanol, butanols, pentanols, hexanols, higher alcohols, medicine},
  url          = {https://mmsl.cz/artkey/mms-201204-0001.php},
}

@InBook{Fiesseler2012,
  author       = {Fiesseler, Frederick and Shih, Richard D.},
  editor       = {Vincent, Jean-Louis and Hall, Jesse B.},
  pages        = {2234--2238},
  publisher    = {Springer Berlin Heidelberg},
  title        = {Toxic Alcohols},
  year         = {2012},
  address      = {Berlin, Heidelberg},
  isbn         = {978-3-642-00418-6},
  booktitle    = {Encyclopedia of Intensive Care Medicine},
  creationdate = {2025-05-02T12:57:47},
  doi          = {10.1007/978-3-642-00418-6_861},
  file         = {:Fiesseler2012 - Toxic Alcohols.pdf:PDF},
  keywords     = {toxic alcohol,medicine},
  url          = {https://doi.org/10.1007/978-3-642-00418-6_861},
}

@Article{Warren1984,
  author       = {Warren, Warren S.},
  journal      = {The Journal of Chemical Physics},
  title        = {Effects of arbitrary laser or NMR pulse shapes on population inversion and coherence},
  year         = {1984},
  issn         = {0021-9606},
  month        = {12},
  number       = {12},
  pages        = {5437-5448},
  volume       = {81},
  abstract     = {We present a new perturbation expansion for calculating the effects of arbitrary pulse shapes in two‐level systems, even when the effects are grossly nonlinear. The first two terms have simple physical interpretations. This expansion converges rapidly for all values of resonance offset with simple shapes, and for any pulse shape far from resonance. We generate very simple, symmetric, single phase pulse shapes which produce uniform inversion or polarization and which can be combined into multiple pulse sequences. We also show that pulse shape modification is superior to construction of composite pulse sequences, since such sequences must become erratic far from resonance.},
  creationdate = {2025-05-08T15:49:18},
  doi          = {10.1063/1.447644},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/81/12/5437/18950760/5437\_1\_online.pdf},
  file         = {:Warren1984 - Effects of Arbitrary Laser or NMR Pulse Shapes on Population Inversion and Coherence.pdf:PDF},
  keywords     = {NMR,theory,pulse shape,pulse sequence,coherence},
  url          = {https://doi.org/10.1063/1.447644},
}

@Article{Bodenhausen1984,
  author       = {Geoffrey Bodenhausen and Herbert Kogler and R.R. Ernst},
  journal      = {Journal of Magnetic Resonance (1969)},
  title        = {Selection of coherence-transfer pathways in NMR pulse experiments},
  year         = {1984},
  issn         = {0022-2364},
  number       = {3},
  pages        = {370-388},
  volume       = {58},
  abstract     = {NMR pulse experiments are described in terms of pathways through various orders of coherence. A general procedure is indicated for the systematic design of phase cycles that select desirable coherence-transfer pathways.},
  creationdate = {2025-05-08T15:51:38},
  doi          = {https://doi.org/10.1016/0022-2364(84)90142-2},
  file         = {:Bodenhausen1984 - Selection of Coherence Transfer Pathways in NMR Pulse Experiments.pdf:PDF},
  keywords     = {NMR,theory,pulse sequence,phase cycle,coherence transfer pathways},
  url          = {https://www.sciencedirect.com/science/article/pii/0022236484901422},
}

@Article{Bain1984,
  author       = {Alex D Bain},
  journal      = {Journal of Magnetic Resonance (1969)},
  title        = {Coherence levels and coherence pathways in NMR. A simple way to design phase cycling procedures},
  year         = {1984},
  issn         = {0022-2364},
  number       = {3},
  pages        = {418-427},
  volume       = {56},
  abstract     = {The paper presents a simple way of calculating what a phase cycling procedure in a pulse NMR experiment does. This is done by exploiting the fact that if a pulse is phase shifted by angle φ and if it changes the coherence level by Δm, then the effect on the coherence is a multiplication by eiΔmφ The coherence level is a fundamental quantum number of the system-the z component of the Liouville space angular momentum—and is a generalization of the number of quanta in a multiple-quantum transition. The sequence of coherence levels that a signal passes through between the first pulse and the time it reaches the receiver is the coherence pathway. This pathway, combined with the above formula, provides a powerful method for analyzing pulse NMR experiments.},
  creationdate = {2025-05-08T15:53:57},
  doi          = {https://doi.org/10.1016/0022-2364(84)90305-6},
  file         = {:Bain1984 - Coherence Levels and Coherence Pathways in NMR. a Simple Way to Design Phase Cycling Procedures.pdf:PDF},
  keywords     = {NMR,theory,phase cycles,coherence transfer pathways,pulse sequences},
  url          = {https://www.sciencedirect.com/science/article/pii/0022236484903056},
}

@Article{Stejskal1974,
  author       = {E.O Stejskal and Jacob Schaefer},
  journal      = {Journal of Magnetic Resonance (1969)},
  title        = {Comparisons of quadrature and single-phase fourier transform NMR},
  year         = {1974},
  issn         = {0022-2364},
  number       = {2},
  pages        = {160-169},
  volume       = {14},
  abstract     = {Reflections of lines in time-averaged Fourier transform NMR spectra obtained by imperfect quadrature detection can be removed either by 90° rf phase shifting of the excitation pulse together with simple data routing, or by phase and amplitude manipulations of the two imperfect free induction decays after completion of data accumulation. The sensitivity of the resulting reflection-free spectra is comparable to that of spectra obtained by single-phase detection using a rf crystal filter to remove aliased noise. However, since the quadrature experiment involves data sampling rates half as fast as the comparable single-phase experiment, distortions associated with the finiterecovery time of the spectrometer areless severe. Even for fast-recovery spectrometers, asymmetric spectral distortions in Fourier transform experiments involving moderately broad lines can occur. In quadrature detection schemes, these distortions are less severe since they are not folded through the entire spectral width as occurs in single-phase experiments.},
  creationdate = {2025-05-08T15:56:17},
  doi          = {https://doi.org/10.1016/0022-2364(74)90270-4},
  file         = {:Stejskal1974 - Comparisons of Quadrature and Single Phase Fourier Transform NMR.pdf:PDF},
  keywords     = {nmr,theory,quadrature detection,phase cycle},
  url          = {https://www.sciencedirect.com/science/article/pii/0022236474902704},
}

@Article{Bloch1946,
  author       = {Bloch, F.},
  journal      = {Phys. Rev.},
  title        = {Nuclear Induction},
  year         = {1946},
  month        = {Oct},
  pages        = {460--474},
  volume       = {70},
  creationdate = {2025-05-08T16:05:59},
  doi          = {10.1103/PhysRev.70.460},
  file         = {:Bloch1946 - Nuclear Induction.pdf:PDF},
  issue        = {7-8},
  keywords     = {NMR,theory,bloch equation},
  numpages     = {0},
  publisher    = {American Physical Society},
  url          = {https://link.aps.org/doi/10.1103/PhysRev.70.460},
}

@Article{Luszczynski1959,
  author       = {K Luszczynski and J G Powles},
  journal      = {Journal of Scientific Instruments},
  title        = {Nuclear spin pulse apparatus},
  year         = {1959},
  month        = {feb},
  number       = {2},
  pages        = {57},
  volume       = {36},
  abstract     = {A detailed description including circuits and operating instructions, is given for the construction of a nuclear spin pulse apparatus which will measure nuclear spin-lattice relaxation times from 500 μs upwards and nuclear spin-spin relaxation times from 20 μs upwards over the temperature range -180° C to 220° C with an accuracy of better than ±5%. An Appendix lists where all published circuit diagrams and technical data suitable for spin echo apparatus may be found.},
  creationdate = {2025-05-08T16:11:12},
  doi          = {10.1088/0950-7671/36/2/301},
  file         = {:Luszczynski1959 - Nuclear Spin Pulse Apparatus.pdf:PDF},
  keywords     = {nmr,experimental setup,pulse},
  url          = {https://dx.doi.org/10.1088/0950-7671/36/2/301},
}

@Article{Haas1987,
  author       = {Roswitha T. Haas and Kevin C. O'Kane},
  journal      = {Computers & Chemistry},
  title        = {Typesetting chemical structure formulas with the text formatter TeX/LaTeX},
  year         = {1987},
  issn         = {0097-8485},
  number       = {4},
  pages        = {251-271},
  volume       = {11},
  abstract     = {Methods are described to incorporate chemical structure diagrams into manuscripts prepared with the widely used text formatter TeX, a program that specializes in mathematics typesetting. The graphics capabilities of the LaTeX macros are used to draw the diagrams. Structures are input with keyboard characters; no graphics hardware is needed. The TeX program produces device-independent ASCII files to send to output devices. About 30 macros were written to facilitate the typesetting of common structural fragments such as branching patterns and alicyclic and heterocyclic rings. These macros permit optional substituents and multiple bonds. Fragments from different macros can be combined.},
  creationdate = {2025-05-09T10:14:33},
  doi          = {https://doi.org/10.1016/0097-8485(87)85004-0},
  file         = {:Haas1987 - Typesetting Chemical Structure Formulas with the Text Formatter TeX_LaTeX.pdf:PDF},
  keywords     = {typesetting,misc,tex macro},
  url          = {https://www.sciencedirect.com/science/article/pii/0097848587850040},
}

@Article{Timoshenko2001,
  author       = {E. G. Timoshenko and Yu. A. Kuznetsov},
  journal      = {Europhysics Letters},
  title        = {Aggregation number distributions and mesoglobules in dilute solutions of diblock and triblock copolymers},
  year         = {2001},
  month        = feb,
  number       = {3},
  pages        = {322},
  volume       = {53},
  abstract     = {We investigate the aggregation number and size distributions  for inter-molecular clusters of amphiphilic diblock and triblock  copolymers in poor solvent at very low concentrations. Diblocks and triblocks with hydrophilic ends are shown to possess  narrow distributions corresponding to formation of monodispersed mesoglobules. Diblocks with hydrophobic ends are found to produce inter-cluster  multimers due to bridging by the hydrophilic middle blocks, resulting  in polydisperse distributions. Implications of these observations for the preparation of  monodispersed nanoparticles and, potentially, for the understanding of the  quaternary structure of proteins are discussed.},
  comment      = {defines the term ``mesoglobule'': Mesoglobules are essentially equally sized globules obtained by association of more than one and less than all polymer chains in the system and corresponding to, at least, a local minimum of the free energy. Thus, the term mesoglobules refers to the globules possessing a well-characterised size distribution, but not necessarily a well-defined conformational structure such as, e.g., in micelles.},
  creationdate = {2025-05-10T12:15:20},
  doi          = {10.1209/epl/i2001-00156-5},
  file         = {:Timoshenko2001 - Aggregation Number Distributions and Mesoglobules in Dilute Solutions of Diblock and Triblock Copolymers.pdf:PDF},
  keywords     = {pNIPAM,mesoglobule,copolymer},
  url          = {https://dx.doi.org/10.1209/epl/i2001-00156-5},
}

@Book{Hanson2019,
  editor       = {Malgorzata Hanson and Annna Wypych},
  publisher    = {ChemTec Publishing},
  title        = {Databook of curatives and crosslinkers},
  year         = {2019},
  isbn         = {978-1-927885-50-5},
  creationdate = {2025-05-11T13:01:34},
  file         = {:Hanson2019 - Databook of Curatives and Crosslinkers.pdf:PDF},
  keywords     = {cross-linker,chemistry},
}

@Article{Lam2016,
  author       = {Lam, Royce K. and Smith, Jacob W. and Saykally, Richard J.},
  journal      = {The Journal of Chemical Physics},
  title        = {Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy},
  year         = {2016},
  issn         = {0021-9606},
  month        = {05},
  number       = {19},
  pages        = {191103},
  volume       = {144},
  abstract     = {While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure. The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility.},
  creationdate = {2025-05-12T10:09:54},
  doi          = {10.1063/1.4951010},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4951010/15510520/191103\_1\_online.pdf},
  file         = {:Lam2016 - Communication_ Hydrogen Bonding Interactions in Water Alcohol Mixtures from X Ray Absorption Spectroscopy.pdf:PDF},
  keywords     = {aqueous alcohol,X-Ray,oxygen K-edge,methanol,ethanol,propanol,isopropanol,hydrophobic hydration},
  url          = {https://doi.org/10.1063/1.4951010},
}









@Article{Dolenko2015,
  author       = {Dolenko, Tatiana A. and Burikov, Sergey A. and Dolenko, Sergey A. and Efitorov, Alexander O. and Plastinin, Ivan V. and Yuzhakov, Viktor I. and Patsaeva, Svetlana V.},
  journal      = {The Journal of Physical Chemistry A},
  title        = {Raman Spectroscopy of Water–Ethanol Solutions: The Estimation of Hydrogen Bonding Energy and the Appearance of Clathrate-like Structures in Solutions},
  year         = {2015},
  note         = {PMID: 26465255},
  number       = {44},
  pages        = {10806-10815},
  volume       = {119},
  abstract     = {The structure of aqueous alcohol solutions at the molecular level for many decades has remained an intriguing topic in numerous theoretical and practical investigations. The aberrant thermodynamic properties of water–alcohol mixtures are believed to be caused by the differences in energy of hydrogen bonding between water–water, alcohol–alcohol, and alcohol–water molecules. We present the Raman scattering spectra of water, ethanol, and water–ethanol solutions with 20 and 70 vol \% of ethanol thoroughly measured and analyzed at temperatures varying from −10 to +70 °C. Application of the MCR-ALS method allowed for each spectrum to extract contributions of molecules with different strengths of hydrogen bonding. The energy (enthalpy) of formation/weakening of hydrogen bonds was calculated using the slope of Van’t Hoff plot. The energy of hydrogen bonding in 20 vol \% of ethanol was found the highest among all the samples. This finding further supports appearance of clathrate-like structures in water–ethanol solutions with concentrations around 20 vol \% of ethanol.},
  creationdate = {2025-05-12T10:16:38},
  doi          = {10.1021/acs.jpca.5b06678},
  eprint       = {https://doi.org/10.1021/acs.jpca.5b06678},
  file         = {:Dolenko2015 - Raman Spectroscopy of Water–Ethanol Solutions_ the Estimation of Hydrogen Bonding Energy and the Appearance of Clathrate like Structures in Solutions.pdf:PDF;:RamanSpectroscopyOfWaterEthanolSolutions-TheEstimationOfHydrogenBondingEnergyAndTheAppearanceOfClathrateLikeStructuresInSolutions_DolenkoEtAl_JPC2015_SI.pdf:PDF},
  keywords     = {aqueous alcohol,ethanol,raman scattering},
  url          = {https://doi.org/10.1021/acs.jpca.5b06678},
}









@Article{Nishi1995,
  author       = {Nishi, Nobuyuki and Takahashi, Satoru and Matsumoto, Masaki and Tanaka, Aki and Muraya, Keisuke and Takamuku, Toshiyuki and Yamaguchi, Toshio},
  journal      = {The Journal of Physical Chemistry},
  title        = {Hydrogen-Bonded Cluster Formation and Hydrophobic Solute Association in Aqueous Solutions of Ethanol},
  year         = {1995},
  number       = {1},
  pages        = {462-468},
  volume       = {99},
  abstract     = {Hydrogen bonding (HB) cluster formation of ethanol and water molecules in diluted aqueous solutions (x$_A$ $\leq$ 0.03) is investigated on the basis of infrared (IR) adsorption spectroscopy, mass spectrometric analyses of the clusters, and X-ray diffraction measurement. With increasing alcohol molar fraction (x$_A$ up to 0.03, IR spectra showed the intensity decrease on the high-frequency side of the O-H stretching band of water. The s*i(s) curve at x$_A$=0.02 showed striking resemblance to the reported pure water curve at 1 kbar. The X-ray radial distribution function exhibited the decrease of linear hydrogen bonds (LHB) at 2.85 {\AA} and the new peaks at 3.3. and 3.8 {\AA}. The new peaks correspond to the O-O distance of an angular hydrogen bond and the distance from an ethyl carbon to a water oxygen of the hydrogen-bonding cage, respectively. Mass spectra of the clusters revealed the dimerization of ethanol in a very diluted solution (x$_A$ $\approx$ 0.001) at 35 $^\circ$C. The clusters isolated from an x$_A$=0.02 solution were composed of water and ethanol molecules with an average molecular number ratio (water/ethanol) of 2($\pm$1). This indicates that the solute-solute association is highly preferable even at such diluted concentration. A hydrophobic core structure composed of coherent ethyl groups with a strong water hydrogen-bonding cage is presented to explain the observed results.},
  creationdate = {2025-05-12T10:21:23},
  doi          = {10.1021/j100001a068},
  eprint       = {https://doi.org/10.1021/j100001a068},
  file         = {:Nishi1995 - Hydrogen Bonded Cluster Formation and Hydrophobic Solute Association in Aqueous Solutions of Ethanol.pdf:PDF},
  keywords     = {aqueous alcohol,hydrogen bonding,ethanol,X-Ray,infrared,IR,clathrate},
  url          = {https://doi.org/10.1021/j100001a068},
}

@Article{Sun2019,
  author       = {Hao Sun and Christopher P. Kabb and Michael B. Sims and Brent S. Sumerlin},
  journal      = {Progress in Polymer Science},
  title        = {Architecture-transformable polymers: Reshaping the future of stimuli-responsive polymers},
  year         = {2019},
  issn         = {0079-6700},
  pages        = {61-75},
  volume       = {89},
  abstract     = {The field of stimuli-responsive, or smart polymers, has commanded significant interest over the past decade. However, most examples of stimuli-responsive polymers have relied on macroscopic changes that arise via simple alterations in chain conformation or changes in polymer-polymer or polymer-solvent interactions. In recent years, there has been an effort to expand the scope of modifiable variables to include the covalent architecture of a polymer through the use of reversible covalent bonds. Polymers capable of architectural transformation are those that can undergo changes in their chain topology (e.g., linear to branched, star to comb, etc.) via rearrangement in the chain structure. This approach has proven particularly interesting because it allows access to materials capable of dramatic macromolecular property changes that cannot be replicated by the more traditional approaches to responsive polymer systems, which often rely on solubility or swelling transitions in solution. This review aims to highlight the main synthetic strategies to architecture-transformable polymers, including dynamic-covalent and supramolecular chemistry approaches. In addition, the properties and applications of those smart polymers are highlighted. It is clear from recent research in this area that macromolecules capable of undergoing transformations in topology represent a paradigm shift in the field of stimuli-responsive materials.},
  creationdate = {2025-05-12T10:38:40},
  doi          = {https://doi.org/10.1016/j.progpolymsci.2018.09.006},
  file         = {:Sun2019 - Architecture Transformable Polymers_ Reshaping the Future of Stimuli Responsive Polymers.pdf:PDF},
  keywords     = {Macromolecular topological transformation,Stimuli-responsive polymer,Dynamic-covalent,Supramolecular chemistry,Structure-property relationships,dynamic bond,polymer architecture,review},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079670018302259},
}

@InCollection{SanchezFernandez2021,
  author       = {Adrian Sanchez-Fernandez and Andrew J. Jackson},
  booktitle    = {Eutectic Solvents and Stress in Plants},
  publisher    = {Academic Press},
  title        = {Chapter Four - Proteins in deep eutectic solvents: Structure, dynamics and interactions with the solvent},
  year         = {2021},
  editor       = {Robert Verpoorte and Geert-Jan Witkamp and Young Hae Choi},
  pages        = {69-94},
  series       = {Advances in Botanical Research},
  volume       = {97},
  abstract     = {The structure and dynamics of proteins in solution are closely related to their activity and, ultimately, to their performance in products and technologies, for example, drug formulations and enzymatic catalysis. With this in mind, the study of the fundamental behavior of proteins in deep eutectic solvents not only provides insight into a novel alternative to aqueous and molecular organic solvents, but also contributes to understanding the potential behavior of these macromolecules in non-aqueous environments. In particular, it has relevance for systems with high levels of dehydration, liquid phases for dispersions at cryogenic temperatures, or systems with high ionic strength. In this chapter, we will explore current knowledge of the physicochemical behavior of proteins in deep eutectic solvents. The local and global structure of proteins in these solvents will be presented and compared to those in aqueous solutions, organic solvents and ionic liquids. Furthermore, the characteristic behavior of proteins in deep eutectic solvents will be linked to solvation effects and the interaction of the macromolecules with the solvent, where specific electrostatic and hydrogen bond interactions can affect the structure and dynamics of proteins. Finally, challenges and opportunities in the field will be discussed, with the aim of guiding a common effort to develop a better understanding of the fundamental behavior of proteins in these interesting environments.},
  creationdate = {2025-05-12T10:45:04},
  doi          = {https://doi.org/10.1016/bs.abr.2020.09.003},
  file         = {:SanchezFernandez2021 - Chapter Four Proteins in Deep Eutectic Solvents_ Structure, Dynamics and Interactions with the Solvent.pdf:PDF},
  issn         = {0065-2296},
  keywords     = {Protein incorporation,Structure,Dynamics,Interactions,review},
  url          = {https://www.sciencedirect.com/science/article/pii/S006522962030046X},
}

@Article{Huang2006,
  author       = {Hao Huang and Giuseppe Melacini},
  journal      = {Analytica Chimica Acta},
  title        = {High-resolution protein hydration NMR experiments: Probing how protein surfaces interact with water and other non-covalent ligands},
  year         = {2006},
  issn         = {0003-2670},
  note         = {Analytical Methods for Proteomics},
  number       = {1},
  pages        = {1-9},
  volume       = {564},
  abstract     = {High-resolution solution NMR experiments are extremely useful to characterize the location and the dynamics of hydrating water molecules at atomic resolution. However, these methods are severely limited by undesired incoherent transfer pathways such as those arising from exchange-relayed intra-molecular cross-relaxation. Here, we review several complementary exchange network editing methods that can be used in conjunction with other types of NMR hydration experiments such as magnetic relaxation dispersion and 1JNC′ measurements to circumvent these limitations. We also review several recent contributions illustrating how the original solution hydration NMR pulse sequence architecture has inspired new approaches to map other types of non-covalent interactions going well beyond the initial scope of hydration. Specifically, we will show how hydration NMR methods have evolved and have been adapted to binding site mapping, ligand screening, protein–peptide and peptide–lipid interaction profiling.},
  creationdate = {2025-05-12T10:46:44},
  doi          = {https://doi.org/10.1016/j.aca.2005.10.049},
  file         = {:Huang2006 - High Resolution Protein Hydration NMR Experiments_ Probing How Protein Surfaces Interact with Water and Other Non Covalent Ligands.pdf:PDF},
  keywords     = {Protein,Water,Hydration,NMR,NOE,ROE,Surface,Screening,review},
  url          = {https://www.sciencedirect.com/science/article/pii/S0003267005017861},
}

@Article{Zhao2016,
  author       = {Zhao, Jing and Wang, Huiliang},
  journal      = {Journal of Polymer Science Part B: Polymer Physics},
  title        = {Exothermic nonreversing process in the phase transition of poly(N-isopropylacrylamide) studied with stochastic temperature-modulated DSC},
  year         = {2016},
  number       = {18},
  pages        = {1869-1877},
  volume       = {54},
  abstract     = {Exothermic nonreversing process is predicted to present in the phase transition of poly(N-isopropylacrylamide) (PNIPAM). By employing TOPEM-DSC, exothermic nonreversing heat flow peak is observed for the first time, and it usually appears under nonquasi-static conditions. The exothermic nonreversing heat flow is proved to be from the formation of hydrogen bonds by the comparative studies on the phase transition of poly(N,N-diethylacrylamide) (PDEAM) and cyclic heating and cooling of PDEAM and PNIPAM. Further TOPEM-DSC studies on the phase transition of poly(NIPAM-co-DEAM) and poly(NIPAM-co-AAm) prove that hydrophobic force rather than hydrogen bonding is the main driving force for the phase transition, and hydrophobic force is also the driving force for the formation of inter- and intrachain hydrogen bonding. However, the phase transition driven by only hydrophobic force is a slow process. The combined action of hydrogen bonding and hydrophobic force makes the phase transition occur much faster. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1869–1877},
  creationdate = {2025-05-12T14:41:46},
  doi          = {https://doi.org/10.1002/polb.24089},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/polb.24089},
  file         = {:Zhao2016 - Exothermic Nonreversing Process in the Phase Transition of Poly(N Isopropylacrylamide) Studied with Stochastic Temperature Modulated DSC.pdf:PDF},
  keywords     = {differential scanning calorimetry (DSC),hydrogen bonding,non-reversing heat flow,phase transition,transitions,poly(N-isopropylacrylamide),stimuli-sensitive polymers,pNIPAM,DSC,hysteresis,reversibility},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.24089},
}

@Article{Yuan2025,
  author       = {Yue Yuan and Qianqian Zhang and Shumiao Lin and Jinlong Li},
  journal      = {Progress in Materials Science},
  title        = {Water: The soul of hydrogels},
  year         = {2025},
  issn         = {0079-6425},
  pages        = {101378},
  volume       = {148},
  abstract     = {Hydrogels are soft and wet materials with a three-dimensional porous network structure, capable of swelling to retain a large volume of water and maintaining semi-solid integrity. In general, their diverse structures are mainly determined by the type of polymer matrix, the method and degree of crosslinking, and the three-dimensional structure. However, all different hydrogels share water as their core theme. The water content and organization, both at the surface and within the hydrogels, are crucial factors influencing their many physical properties. Over the past years, their formulations and applications have made transformative advances. But the construction of novel hydrogel systems requires understanding how water molecules or solutes interact with the hydrogel. Herein, this review reexamines hydrogels from the perspective of water and summarizes the states, distribution, and behavior of water within hydrogels, as well as the hydrogel properties imparted by water. We also enumerate the techniques for detecting water in hydrogels and discuss the latest progress in the regulation and design of water-hydrogel systems and their unique role in key applications. Thus, the role of water within hydrogels extends far beyond merely acting as a solvent; it is one of the key factors bridging the structure–function relationship in hydrogels.},
  creationdate = {2025-05-12T14:56:56},
  doi          = {https://doi.org/10.1016/j.pmatsci.2024.101378},
  file         = {:Yuan2025 - Water_ the Soul of Hydrogels.pdf:PDF},
  keywords     = {Hydrogel,Water states,Interaction,Water detecting technology,Water-hydrogel system,review},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079642524001476},
}

@Article{Yasunaga2002,
  author       = {H. Yasunaga and Y. Shirakawa and H. Urakawa and K. Kajiwara},
  journal      = {Journal of Molecular Structure},
  title        = {Dynamic behaviour of water in hydrogel containing hydrophobic side chains as studied by pulse 1H NMR},
  year         = {2002},
  issn         = {0022-2860},
  pages        = {399-404},
  volume       = {602-603},
  abstract     = {1H NMR measurements on spin–lattice relaxation time (T1) and spin–spin relaxation time (T2) were carried out on water contained in water-swollen copolymer gels prepared from hydrophilic methacrylic acid and hydrophobic stearyl methacrylate (SMA) or lauryl methacrylate (LMA). The degree of swelling of the copolymer gels decreases drastically with increasing component of hydrophobic monomers. 1H T1 and T2 of water show linear relationship with the cube root of the degree of swelling. Motion of water is restrained with the decreasing network size and the amount of hydrophobic groups in the network. T1 measurements with temperature change revealed that the hydrogen bondings in water are decreased by introducing hydrophobic groups into the hydro gel..},
  creationdate = {2025-05-12T15:23:02},
  doi          = {https://doi.org/10.1016/S0022-2860(01)00704-9},
  file         = {:Yasunaga2002 - Dynamic Behaviour of Water in Hydrogel Containing Hydrophobic Side Chains As Studied by Pulse 1H NMR.pdf:PDF},
  keywords     = {Hydrogen bonding,Hydrogel,Water,NMR,T1,T2,spin-spin relaxation,spin-lattice relaxation,1H-NMR},
  url          = {https://www.sciencedirect.com/science/article/pii/S0022286001007049},
}

@Article{Kogon2023,
  author       = {Rémi Kogon and David Faux and Ali Assifaoui and Philippe Bodart},
  journal      = {Carbohydrate Polymers},
  title        = {Advanced insight on the water dynamics of anisotropic hydrogels by field-cycling nuclear magnetic resonance: Application of 3-Tau model},
  year         = {2023},
  issn         = {0144-8617},
  pages        = {120922},
  volume       = {314},
  abstract     = {Fast field cycling (FFC) nuclear magnetic resonance (NMR) relaxometry is used to investigate an anisotropic polygalacturonate hydrogel formed by the diffusion of calcium ions from an external reservoir (external gelation). Such a hydrogel has a gradient of polymer density accompanied by a gradient of the mesh size of its 3D network. The NMR relaxation process is dominated by the interaction of proton spins between water molecules located at polymer interfaces and in nanoporous spaces. The FFC NMR experiment provides the spin-lattice relaxation rate R1ω as a function of Larmor frequency ω producing dispersion (NMRD) curves that are highly sensitive to the dynamics of the protons at the surfaces. The hydrogel is sliced into three parts and the NMR profile for each hydrogel slice is measured. The NMRD data for each slice is interpreted using the 3-Tau Model with the aid of user-friendly fitting software called 3TM. The key fit parameters include three nano-dynamical time constants and the average “mesh size” which collectively determine the bulk water and water surface layer contribution to the total relaxation rate. The results are consistent with independent studies where comparison is possible.},
  creationdate = {2025-05-12T15:35:23},
  doi          = {https://doi.org/10.1016/j.carbpol.2023.120922},
  file         = {:Kogon2023 - Advanced Insight on the Water Dynamics of Anisotropic Hydrogels by Field Cycling Nuclear Magnetic Resonance_ Application of 3 Tau Model.pdf:PDF},
  keywords     = {FFC NMR relaxometry,Nano-structured hydrogels,Mesh size,3-Tau model,Water dynamics,Polymer interface,field-cycling,NMR,hydrogel,water,NMRD},
  url          = {https://www.sciencedirect.com/science/article/pii/S0144861723003879},
}

@Article{YamadaNosaka1990,
  author       = {Yamada-Nosaka, Atsuko and Ishikiriyama, Kazuhiko and Todoki, Minoru and Tanzawa, Hiroshi},
  journal      = {Journal of Applied Polymer Science},
  title        = {1H-NMR studies on water in methacrylate hydrogels. I},
  year         = {1990},
  number       = {11-12},
  pages        = {2443-2452},
  volume       = {39},
  abstract     = {The behavior of water contained in a hydrophilic hydrogel poly(hydroxyethyl methacrylate) membrane and a hydrophobic hydrogel poly(methyl methacrylate) membrane was studied by proton nuclear magnetic resonance (NMR) spectroscopy. Significant differences between the two hydrogels were observed in their relaxation times, the temperature dependence, and frequency dependence of these relaxation times, and changes of signal intensity of water protons on freezing and thawing. The water in these hydrogels was classified into three states: free, intermediate, and bound states. Poly(hydroxyethyl methacrylate) contains relatively more water in bound and intermediate states than poly(methyl methacrylate). The mobility of water decreases in the order, free water, intermediate water, bound water. The correlation times of the three states were roughly estimated to be 10−11, 10−9, and 10−6 s, respectively. The mobility of water in poly(methyl methacrylate) is several orders of magnitude higher than that in poly(hydroxyethyl methacrylate). In poly(hydroxyethyl methacrylate), the exchange between intermediate and free water is slow in the NMR time scale: the apparent exchange rate and the activation energy were estimated to be 3.6 × 102 s−1 (28°C) and 2.0 kcal/mol, respectively.},
  creationdate = {2025-05-12T16:57:59},
  doi          = {https://doi.org/10.1002/app.1990.070391117},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/app.1990.070391117},
  file         = {:YamadaNosaka1990 - 1H NMR Studies on Water in Methacrylate Hydrogels. I.pdf:PDF},
  keywords     = {NMR,1H-NMR,hydrogel,PMMA},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/app.1990.070391117},
}

@Article{YamadaNosaka1991,
  author       = {Yamada-Nosaka, Atsuko and Tanzawa, Hiroshi},
  journal      = {Journal of Applied Polymer Science},
  title        = {1H-NMR studies on water in methacrylate hydrogels. II},
  year         = {1991},
  number       = {6},
  pages        = {1165-1170},
  volume       = {43},
  abstract     = {Properties of water in the wet membranes of a random copolymer of methyl methacrylate and methoxy poly(ethylene glycol)–monomethacrylate P(MMA-co-M100G) and of a graft copolymer of vinyl chloride and methoxy poly(ethylene glycol)–monomethacrylate P(VC-g-M100G) membranes were studied by proton NMR spectroscopy. Both polymers contain flexible polyoxyethylene side chains. Temperature and frequency dependences of relaxation times, changes of signal intensity of water protons on freezing and thawing, and saturation transfer were measured for both copolymers. These experimental results revealed that most of the bound water in these copolymers does not exist in a rigid state as suggested for the other hydrogels. The introduction of flexible hydrophilic side chains resulted in high mobility of the water molecules bound to the side chains (the apparent correlation time Tc ∼ 10−10 s). For the graft copolymer P(VC-g-M100G), hydrophilic polyoxyethylene side chains are contiguous to each other. Because of the interaction between the side chains, the mobility became more complex than that for the random copolymer P(MMA-co-M100G). The difference in the mode of mobility of water on the membrane surface may be related to the difference of the membrane characteristics of these copolymers.},
  creationdate = {2025-05-12T17:00:30},
  doi          = {https://doi.org/10.1002/app.1991.070430617},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/app.1991.070430617},
  file         = {:YamadaNosaka1991 - 1H NMR Studies on Water in Methacrylate Hydrogels. II.pdf:PDF},
  keywords     = {NMR,1H-NMR,hydrogel,PMMA,copolymer,PEG},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/app.1991.070430617},
}









@Article{Clop2012,
  author       = {Clop, Eduardo M. and Perillo, María A. and Chattah, Ana K.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {1H and 2H NMR Spin–Lattice Relaxation Probing Water: PEG Molecular Dynamics in Solution},
  year         = {2012},
  note         = {PMID: 22957770},
  number       = {39},
  pages        = {11953-11958},
  volume       = {116},
  abstract     = {Nuclear magnetic resonance spin–lattice relaxation times (T1) measurements were performed in aqueous solutions of poly(ethylene glycol) (PEG) of 6000 Da molecular mass to study the dynamical relation between PEG and water molecules at different solute concentrations. 1H–T1 experiments were carried on at a low magnetic field in the time domain (20 MHz) and at a high field (400 MHz) to obtain spectral resolution. Two contributing components were identified in each proton system, PEG and water, presenting values of T1 with very different orders of magnitude. The approximate matching between the shorter 1H–T1 values associated with water and PEG has lead us to conclude that there exists a network of interactions (hydrogen bonds) between the solute and the solvent, which results in the presence of an ordered and dehydrated structure of PEG folded or self-assembled in equilibrium with a more flexible monomer structure. Dynamic light scattering results were consistent with the formation of PEG aggregates, showing a mean size between 40 and 100 nm.},
  creationdate = {2025-05-12T17:03:24},
  doi          = {10.1021/jp304569a},
  eprint       = {https://doi.org/10.1021/jp304569a},
  file         = {:Clop2012 - 1H and 2H NMR Spin–Lattice Relaxation Probing Water_ PEG Molecular Dynamics in Solution.pdf:PDF},
  keywords     = {NMR,1H-NMR,2H-NMR,spin-lattice relaxation,T1,time-domain NMR,PEG,DLS},
  url          = {https://doi.org/10.1021/jp304569a},
}

@Article{Badi2017,
  author       = {Nezha Badi},
  journal      = {Progress in Polymer Science},
  title        = {Non-linear PEG-based thermoresponsive polymer systems},
  year         = {2017},
  issn         = {0079-6700},
  note         = {Topical Volume on Polymer Physics},
  pages        = {54-79},
  volume       = {66},
  abstract     = {Poly(ethylene glycol) (PEG) is one of the most used polymers in medical and biological applications. Its non-toxicity, non-immunogenicity, biocompatibility and solubility in a wide range of solvents offer various possibilities of utilization and explain the amount of studies dealing with this polymer. More recently, non-linear PEG-based monomers attracted much interest due to their thermal behavior. The present review aims at presenting many PEG-based thermoresponsive systems from structural and synthesis point of view and at highlighting all their fascinating properties from their behavior in solution, the fine-tuning of the transition temperature until the formation of smart materials.},
  creationdate = {2025-05-13T11:04:19},
  doi          = {https://doi.org/10.1016/j.progpolymsci.2016.12.006},
  file         = {:Badi2017 - Non Linear PEG Based Thermoresponsive Polymer Systems.pdf:PDF},
  keywords     = {Thermoresponsive polymers,LCST,UCST,Poly(ethylene glycol) derivatives,Smart materials,PEG,PEO,review,thermoresponsive,pNIPAM-alternative},
  url          = {https://www.sciencedirect.com/science/article/pii/S0079670016301162},
}

@Article{Eagland1993,
  author       = {D. Eagland and N.J. Crowther and C.J. Butler},
  journal      = {Polymer},
  title        = {Interaction of poly(oxyethylene) with water as a function of molar mass},
  year         = {1993},
  issn         = {0032-3861},
  number       = {13},
  pages        = {2804-2808},
  volume       = {34},
  abstract     = {Partial base molal volume values obtained from high-precision density measurements, in conjunction with heats of dilution data, derived from flow calorimetry measurements, have been obtained for a series of samples of poly(oxyethylene) (POE) of different molar masses, ranging from 200 to 35 000 Da. The results show that the state of solution of the POE is very much dependent upon the molar mass of the polymer; at low molar masses, pair and triplet interaction coefficients suggest that the hydrophobic interaction controls solution behaviour, while at higher molar masses, a helical conformation appears the most likely explanation.},
  creationdate = {2025-05-13T11:16:34},
  doi          = {https://doi.org/10.1016/0032-3861(93)90124-S},
  file         = {:Eagland1993 - Interaction of Poly(oxyethylene) with Water As a Function of Molar Mass.pdf:PDF},
  keywords     = {poly(ethylene oxide),molar mass,partial base molal volume,heat of dilution,pair and triplet interaction coefficients,PEG,PEO},
  url          = {https://www.sciencedirect.com/science/article/pii/003238619390124S},
}

@Article{Yuan2023,
  author       = {Yuan, Yichun and Raheja, Konpal and Milbrandt, Nathalie B. and Beilharz, Sophia and Tene, Steffy and Oshabaheebwa, Solomon and Gurkan, Umut A. and Samia, Anna Cristina S. and Karayilan, Metin},
  journal      = {RSC Appl. Polym.},
  title        = {Thermoresponsive polymers with LCST transition: synthesis{,} characterization{,} and their impact on biomedical frontiers},
  year         = {2023},
  pages        = {158-189},
  volume       = {1},
  abstract     = {Advances in thermoresponsive materials have significantly impacted many biomedical fields. The unique behavior of reversible phase transition close to the physiological temperatures makes these types of materials a great candidate for a wide variety of biomedical applications including bioimaging{,} biosensing{,} injectables{,} smart surfaces{,} adhesives{,} biomanufacturing{,} and tissue engineering. Thermoresponsive behavior{,} mainly lower critical solution temperature (LCST) can be easily tuned by shifting the balance between hydrophobicity and hydrophilicity (e.g.{,} by using comonomers or changing end groups) and modifying the molecular weight and architecture of the polymer. Hence{,} synthetic and characterization tools are critical in tailoring and precisely determining these properties. This review aims to show the full scope of the journey of thermoresponsive polymers from benchtop to potential applications. We especially intend to emphasize the effects of the structural heterogeneity of polymers on thermal transition and highlight the modern characterization techniques used to study thermoresponsive behavior. A better understanding of these structural effects and benchtop tools can help us design and implement more advanced materials for future applications in public health.},
  creationdate = {2025-05-13T11:21:39},
  doi          = {10.1039/D3LP00114H},
  file         = {:Yuan2023 - Thermoresponsive Polymers with LCST Transition_ Synthesis, Characterization, and Their Impact on Biomedical Frontiers.pdf:PDF},
  issue        = {2},
  keywords     = {pNIPAM-alternatives,review,pNIPAM,PEG,PEO,LCST,thermoresponsive,biomedical,copolymer},
  publisher    = {RSC},
  url          = {http://dx.doi.org/10.1039/D3LP00114H},
}

@Article{Saeki1976,
  author       = {Susumu Saeki and Nobuhiro Kuwahara and Mitsuo Nakata and Motozo Kaneko},
  journal      = {Polymer},
  title        = {Upper and lower critical solution temperatures in poly (ethylene glycol) solutions},
  year         = {1976},
  issn         = {0032-3861},
  number       = {8},
  pages        = {685-689},
  volume       = {17},
  abstract     = {Upper and lower critical solution temperatures have been determined for solutions of poly(ethylene glycol) in t-butyl acetate and water over the molecular weight range of Mη = 2.18 × 103 to ∼1020 × 103. The phase diagram for solutions of poly(ethylene glycol) (Mη = 719 × 103) in t-butyl acetate was expressed as the ‘hour glass’ type, while the phase diagram for solution of poly(ethylene glycol) (Mη = 2.18 × 103 to ∼2.29 × 103) in water was expressed as the ‘closed loop’ type. The value of the pressure dependence of the lower critical solution temperature (dTdP)c in the poly(ethylene glycol) (Mη = 1020 × 103)/water system over the pressure range of 0 to ∼50 atm was negligibly small and positive.},
  creationdate = {2025-05-13T11:30:47},
  doi          = {https://doi.org/10.1016/0032-3861(76)90208-1},
  file         = {:Saeki1976 - Upper and Lower Critical Solution Temperatures in Poly (ethylene Glycol) Solutions.pdf:PDF},
  keywords     = {PEG,PEO,thermoresponsive,LCST,tert-butyl acetate,water,chain-length dependence,phase diagram},
  url          = {https://www.sciencedirect.com/science/article/pii/0032386176902081},
}









@Article{Daley2017,
  author       = {Daley, Kimberly R. and Kubarych, Kevin J.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {An “Iceberg” Coating Preserves Bulk Hydration Dynamics in Aqueous PEG Solutions},
  year         = {2017},
  note         = {PMID: 29087711},
  number       = {46},
  pages        = {10574-10582},
  volume       = {121},
  abstract     = {Ultrafast picosecond time scale two-dimensional infrared (2D-IR) spectroscopy of a new water-soluble transition metal complex acting as a vibrational probe shows that over a range of concentration and poly(ethylene glycol) (PEG) molecular mass (2000, 8000, and 20000 Da) the time scale of the sensed hydration dynamics differs negligibly from bulk water (D2O). PEG is well-known to establish a highly stable hydration shell because the spacing between adjacent ethereal oxygens nearly matches water’s hydrogen-bonding network. Although these first-shell water molecules are likely significantly retarded, they present an interface to subsequent hydration shells and thus diminish the largely entropic perturbation to water’s orientational dynamics. In addition to the longer PEGs, a series of concentration-dependent 2D-IR measurements using aqueous PEG-400 show a pronounced hydration slowdown in the vicinity of the critical overlap concentration (c*). Comparison between these dynamical results and previously reported steady-state infrared spectroscopy of aqueous PEG-1000 solutions reveals a strikingly identical dependence on number of water molecules per ethylene oxide monomer, scaled according to the critical overlap concentration.},
  creationdate = {2025-05-13T13:56:40},
  doi          = {10.1021/acs.jpcb.7b08030},
  eprint       = {https://doi.org/10.1021/acs.jpcb.7b08030},
  file         = {:Daley2017 - An “Iceberg” Coating Preserves Bulk Hydration Dynamics in Aqueous PEG Solutions.pdf:PDF},
  keywords     = {infrared,PEG,hydration shell},
  url          = {https://doi.org/10.1021/acs.jpcb.7b08030},
}

@Article{Kato1997,
  author       = {Kato, Eiji},
  journal      = {The Journal of Chemical Physics},
  title        = {Volume-phase transition of N-isopropylacrylamide gels induced by hydrostatic pressure},
  year         = {1997},
  issn         = {0021-9606},
  month        = {03},
  number       = {9},
  pages        = {3792-3797},
  volume       = {106},
  abstract     = {Pressure-induced volume phase transitions in neutral and ionized N-isopropylacrylamide-water (NIPA) gels were investigated. When the pressure is increased, the gels which shrink at atmospheric pressure undergo two volume phase transitions. One is the continuous phase transition (for neutral gels) or the discontinuous phase transition (for ionized gels) from the shrunken state to the swollen state at low pressures of several tens MPa. Another is the gradual shrinking transition occurred in the high pressure region above 100 MPa. The former transition shows that the derivative of the pressure with respect to the volume at constant temperature, (∂P/∂V)T, is positive. The results are explained by considering the pressure effects on the hydrophobic interaction. The phase transition pressure increases with increase of the temperature, and the critical pressure and temperature exist. The P–T coexistence curve resembling the evaporation curve of a liquid–gas system is obtained. These pressure-induced phase transitions are qualitatively explained by taking account of the pressure effects on the hydrophobic and hydrophilic interactions. It is assumed that the polymer solvent interaction parameter χ is a function of the pressure as well as the temperature, χ(T,P)=χ0(T)+χ1(T)P+χ2(T)P2. χ1 represents the pressure effects on the interaction between water molecules and the hydrophobic parts of NIPA, and it is responsible for the phase transition at low pressure. χ2 represents the pressure effects on the association between water molecules and the hydrophilic parts of NIPA, and it is responsible for the gradual shrinking transition at high pressure.},
  creationdate = {2025-05-13T16:56:20},
  doi          = {10.1063/1.473432},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/106/9/3792/19113410/3792\_1\_online.pdf},
  file         = {:Kato1997 - Volume Phase Transition of N Isopropylacrylamide Gels Induced by Hydrostatic Pressure.pdf:PDF},
  keywords     = {pNIPAM,pressure,hydrogel,gel},
  url          = {https://doi.org/10.1063/1.473432},
}

@Article{Grobelny2013,
  author       = {Grobelny, Sebastian and Hofmann, Christian H. and Erlkamp, Mirko and Plamper, Felix A. and Richtering, Walter and Winter, Roland},
  journal      = {Soft Matter},
  title        = {Conformational changes upon high pressure induced hydration of poly(N-isopropylacrylamide) microgels},
  year         = {2013},
  pages        = {5862-5866},
  volume       = {9},
  abstract     = {We investigated thermosensitive poly(N-isopropylacrylamide) microgels by high-pressure small angle X-ray scattering and Fourier-transform infrared spectroscopy below and above the collapse temperature. The measurements reveal little pressure-induced deswelling below the volume phase transition temperature and clear re-swelling of the collapsed gels at temperatures above the VPTT.},
  creationdate = {2025-05-13T16:58:17},
  doi          = {10.1039/C3SM27653H},
  file         = {:Grobelny2013 - Conformational Changes upon High Pressure Induced Hydration of Poly(N Isopropylacrylamide) Microgels.pdf:PDF},
  issue        = {25},
  keywords     = {pNIPAM,pressure,gel,microgel},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C3SM27653H},
}









@Article{Ebeling2014,
  author       = {Ebeling, Bastian and Eggers, Steffen and Hendrich, Michael and Nitschke, Annika and Vana, Philipp},
  journal      = {Macromolecules},
  title        = {Flipping the Pressure- and Temperature-Dependent Cloud-Point Behavior in the Cononsolvency System of Poly(N-isopropylacrylamide) in Water and Ethanol},
  year         = {2014},
  number       = {4},
  pages        = {1462-1469},
  volume       = {47},
  abstract     = {It was demonstrated for several organic cononsolvents added to aqueous solutions of poly(N-isopropylacrylamide) that they lead to an increasing solubility of the polymer in the low-temperature/high-pressure region while reducing the solubility of the polymer and therefore its cloud temperature at atmospheric pressure. A complete inversion of the phase-separation behavior regarding both the effects of pressure and temperature was found by increasing the mole fraction of added ethanol over the whole cononsolvency range. As a special case, at a mole fraction of x = 0.23 the system cleared up independent of temperature at a constant pressure of about 1000 bar. The measurements were performed in an optical high-pressure cell up to pressures of 3000 bar and down to temperatures of −20 °C. The results are discussed in terms of solvent–solvent and solvent–polymer interactions.},
  creationdate = {2025-05-13T17:03:05},
  doi          = {10.1021/ma5001139},
  eprint       = {https://doi.org/10.1021/ma5001139},
  file         = {:Ebeling2014 - Flipping the Pressure and Temperature Dependent Cloud Point Behavior in the Cononsolvency System of Poly(N Isopropylacrylamide) in Water and Ethanol.pdf:PDF;:FlippingThePressureAndTemperatureDependentCloudPointBehaviorInTheCononsolvencySystemOfPolyNIsopropylacrylamideInWaterAndEthanol_EbelingEtAl_Macomol2014_SI.pdf:PDF},
  keywords     = {pNIPAM,pressure,cononsolvency,ethanol,aqueous alcohol,linear,methanol,n-propanol,1-propanol,n-butanol,n-pentanol},
  url          = {https://doi.org/10.1021/ma5001139},
}

@Article{Oliveira2015,
  author       = {de Oliveira, Tiago E. and Netz, Paulo A. and Mukherji, Debashish and Kremer, Kurt},
  journal      = {Soft Matter},
  title        = {Why does high pressure destroy co-non-solvency of PNIPAm in aqueous methanol?},
  year         = {2015},
  pages        = {8599-8604},
  volume       = {11},
  abstract     = {It is well known that poly(N-isopropylacrylamide) (PNIPAm) exhibits an interesting{,} yet puzzling{,} phenomenon of co-non-solvency. Co-non-solvency occurs when two competing good solvents for PNIPAm{,} such as water and alcohol{,} are mixed together. As a result{,} the same PNIPAm collapses within intermediate mixing ratios. This complex conformational transition is driven by preferential binding of methanol with PNIPAm. Interestingly{,} co-non-solvency can be destroyed when applying high hydrostatic pressures. In this work{,} using a large scale molecular dynamics simulation employing high pressures{,} we propose a microscopic picture behind the suppression of the co-non-solvency phenomenon. Based on thermodynamic and structural analysis{,} our results suggest that the preferential binding of methanol with PNIPAm gets partially lost at high pressures{,} making the background fluid reasonably homogeneous for the polymer. This is consistent with the hypothesis that the co-non-solvency phenomenon is driven by preferential binding and is not based on depletion effects.},
  creationdate = {2025-05-13T17:08:28},
  doi          = {10.1039/C5SM01772F},
  file         = {:Oliveira2015 - Why Does High Pressure Destroy Co Non Solvency of PNIPAm in Aqueous Methanol_.pdf:PDF},
  issue        = {44},
  keywords     = {pNIPAM,pressure,molecular dynamics simulation,cononsolvency,aqueous alcohol,methanol,preferential adsorption},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C5SM01772F},
}

@Article{Carver1972,
  author       = {J.P Carver and R.E Richards},
  journal      = {Journal of Magnetic Resonance (1969)},
  title        = {A general two-site solution for the chemical exchange produced dependence of T2 upon the carr-Purcell pulse separation},
  year         = {1972},
  issn         = {0022-2364},
  number       = {1},
  pages        = {89-105},
  volume       = {6},
  abstract     = {A general closed function for the tcp dependence of the transverse relaxation times of nuclei exchanging between two sites is described. Examination of the frequency and temperature dependence of this function demonstrates that, in contrast to T2's determined from line widths, this spin echo method permits the evaluation of the populations of nuclei in the two sites. As a result, an unequivocal determination of all the exchange parameters becomes possible. Numerical examples are discussed for systems where the relaxation mechanism in the bound site is: (i) in the white spectrum approximation, and (ii) in the nonwhite spectrum approximation.},
  creationdate = {2025-05-14T07:41:31},
  doi          = {https://doi.org/10.1016/0022-2364(72)90090-X},
  file         = {:Carver1972 - A General Two Site Solution for the Chemical Exchange Produced Dependence of T2 upon the Carr Purcell Pulse Separation.pdf:PDF},
  keywords     = {NMR,theory,CPMG,chemical exchange,spin-spin relaxation,T2},
  url          = {https://www.sciencedirect.com/science/article/pii/002223647290090X},
}

@Article{Kaatze2002,
  author       = {U. Kaatze and R. Behrends and R. Pottel},
  journal      = {Journal of Non-Crystalline Solids},
  title        = {Hydrogen network fluctuations and dielectric spectrometry of liquids},
  year         = {2002},
  issn         = {0022-3093},
  number       = {1},
  pages        = {19-28},
  volume       = {305},
  abstract     = {Complex dielectric spectra of associating liquids are presented and are discussed considering their relaxation properties. Particular emphasis is given to water and aqueous solutions and to alcohols and mixtures of alcohols with dipolar and non-polar solvents. The relaxation properties of the associating systems are examined in the light of a wait-and-switch model of dielectric relaxation in which the relaxation time is governed by the period for which a given ensemble of hydrogen bond partners within the hydrogen network has to wait until favorable conditions for a reorientation of a molecular permanent dipole exist. These conditions are provided by an additional molecule or group which firstly tends to lower the potential energy barrier for reorientation and which secondly, at the same time, offers a site for the formation of a new hydrogen bond. Some experimental findings are discussed in terms of the wait-and-switch model, among them the reduced dielectric relaxation time of water under hydrostatic pressure, effects of negative and hydrophobic hydration of ions, and the influence that water, on the one hand, and n-alkanes, on the other hand, act on the relaxation of alcohols.},
  creationdate = {2025-05-14T15:01:09},
  doi          = {https://doi.org/10.1016/S0022-3093(02)01084-0},
  file         = {:Kaatze2002 - Hydrogen Network Fluctuations and Dielectric Spectrometry of Liquids.pdf:PDF},
  keywords     = {hydrogen bond,wait-and-switch model,BDS,pressure,hydrophobic hydration},
  url          = {https://www.sciencedirect.com/science/article/pii/S0022309302010840},
}

@Article{Wei2017,
  author       = {Wei, Menglian and Gao, Yongfeng and Li, Xue and Serpe, Michael J.},
  journal      = {Polym. Chem.},
  title        = {Stimuli-responsive polymers and their applications},
  year         = {2017},
  pages        = {127-143},
  volume       = {8},
  abstract     = {Responsive polymer-based materials are capable of altering their chemical and/or physical properties upon exposure to external stimuli. These materials have been intensively studied over the years for a diverse range of applications{,} e.g.{,} for on-demand drug delivery{,} tissue generation/repair{,} biosensing{,} smart coatings{,} and artificial muscles. Here{,} we review recent advances in the areas of sensing and biosensing{,} drug delivery{,} and actuators. Specific examples are given in each of these areas{,} and we highlight our group{'}s work on poly(N-isopropylacrylamide)-based microgels and assemblies.},
  creationdate = {2025-05-14T21:11:45},
  doi          = {10.1039/C6PY01585A},
  file         = {:Wei2017 - Stimuli Responsive Polymers and Their Applications.pdf:PDF},
  issue        = {1},
  keywords     = {review,application-focussed,drug delivery,controlled release,biosensing,actuator,pNIPAM,microgel},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/C6PY01585A},
}









@Article{Wang2022a,
  author       = {Wang, Chi and Hashimoto, Takeji and Chuang, Ya-Chen and Tanaka, Keiji and Chang, Yen-Pin and Yang, Ting-Wei and Huang, Meng-Tse},
  journal      = {Macromolecules},
  title        = {Physical Gelation of Aqueous Solutions of Atactic Poly(N-isopropylacrylamide)},
  year         = {2022},
  number       = {20},
  pages        = {9152-9167},
  volume       = {55},
  abstract     = {Aqueous solutions of atactic poly(N-isopropylacrylamide) (PNIPAM) exhibit complex phase transitions at 20–33 °C, that is, the phase behaviors of lower critical solution temperature (LCST) and physical gelation. The LCST phase behavior has been successfully described by the “pearl-necklace” chain model (Macromolecules 2005, 38, 4465); however, the formation of the physical gel is still elusive. In this study, atactic PNIPAM (a-PNIPAM) was used and the gel point (GP) of semidilute solutions was validated by observing the frequency-independent loss tangent (Winter–Chambon criterion) from the oscillatory shear measurements to derive the gel temperature Tgel. It was found that the relaxation exponent n at GP is independent of solution concentration to be 0.76 with the fact that entanglement couplings play no effect on n. Tgel decreases with a-PNIPAM concentration from 29.5 °C for the 5 wt \% unentangled solution to 25 °C for the 12 wt \% entangled solution. The binodal point (Tb) was obtained from the extrapolated cloud-point temperature at zero heating rate, at which an initial drop of the light transmittance was observed. Based on these derived data, a phase diagram was constructed to show three typical phase domains composed of an one-phase solution at T < Tgel, a clear gel at Tgel < T < Tb, and an opaque gel at T > Tb. At 30 °C, the clear gels of 5 and 12 wt \% samples possess extremely low equilibrium moduli of 0.2 and 41 Pa, respectively, suggesting that many a-PNIPAM single chains are associated and connected in between two gel junctions. Synchrotron small-angle/wide-angle X-ray scattering was performed to disclose the radius of gyration of gel junctions (with functionality f ≥ 3) to be 30–55 Å above Tgel. Within the gel junctions, the collapsed subchains (pearls), which belong to different chains, become more compact with the interchain distance decreasing from 15 Å at 20 °C to 11 Å at 30 °C for the 12 wt \% solution. We proposed that the origin of physical gelation is relevant to the inter-amide hydrogen bonding between collapsed subchains in the gel junctions to develop a strong physical bonding for interchain connectivity. At an elevated temperature approaching the GP but still below the spinodal temperature, the physical crosslinking of the developing pregel clusters is further facilitated by the enhanced concentration fluctuations with a small-q Fourier-mode driven by the interchain associations, eventually giving rise to the critical gel at Tgel prior to solution phase separation.},
  creationdate = {2025-05-16T08:17:44},
  doi          = {10.1021/acs.macromol.1c02476},
  eprint       = {https://doi.org/10.1021/acs.macromol.1c02476},
  file         = {:Wang2022a - Physical Gelation of Aqueous Solutions of Atactic Poly(N Isopropylacrylamide).pdf:PDF;:PhysicalGelationOfAqueousSolutionsOfAtacticPolyNIsopropylacrylamide_WangEtAl_Macromol2022_SI.pdf:PDF},
  keywords     = {pNIPAM,preshrinking,pre-shrinking,gel,linear pNIPAM,binodal,spinodal},
  url          = {https://doi.org/10.1021/acs.macromol.1c02476},
}

@Article{Mathieu2024,
  author       = {Camille Mathieu and Samar Issa and Emmanuel Richaud},
  journal      = {Materials Today Chemistry},
  title        = {Effect of isothermal aging on Poly(N-isopropylacrylamide): Correlation between chemical structure and phase transition temperature property},
  year         = {2024},
  issn         = {2468-5194},
  pages        = {102127},
  volume       = {38},
  abstract     = {Poly(N-isopropylacrylamide) (PNIPAm) is a stimuli-responsive polymer with wide applications as a scaffold in biomedical applications. This study presents the PNIPAm's thermoresponsive behavior during storage and its stability in potential pharmaceutical formulations as a drug delivery excipient. Therefore, the turbidity curves of linear PNIPAm aqueous solutions are investigated before and after its thermal oxidation under air at 120°C and 130°C. First, PNIPAm aqueous phase separation diagram is determined for unaged polymer and then compared to thermally aged samples at two distinct points (1 and 10%(w/w)). After isothermal aging, the transition temperature has increased with a shift up to 4°C. The correlation between PNIPAm's chemical structure and phase transition temperature properties is illustrated in terms of chemical modifications, macromolecular changes as well as the polar/non-polar groups balance. It is observed that the water affinity and glass transition temperature (Tg) have increased at the macromolecular level. In addition, chains scissions are highlighted and seem to explain the shift of transition temperature. Chemical changes have revealed the presence of supplementary polar groups induced by aging. This multiscale study suggests a possible mechanism for the partial thermal oxidation based on all the observations.},
  creationdate = {2025-05-16T09:38:45},
  doi          = {https://doi.org/10.1016/j.mtchem.2024.102127},
  file         = {:Mathieu2024 - Effect of Isothermal Aging on Poly(N Isopropylacrylamide)_ Correlation between Chemical Structure and Phase Transition Temperature Property.pdf:PDF},
  keywords     = {Poly(N-isopropylacrylamide) (PNIPAm),Isothermal aging,Phase transition,Lower critical solution temperature (LCST),Chain scissions,pNIPAM,ageing,cloud point,turbidity,thermal oxidation},
  url          = {https://www.sciencedirect.com/science/article/pii/S2468519424002337},
}

@Article{Capella2019,
  author       = {Virginia Capella and Rebeca E. Rivero and Ana C. Liaudat and Luis E. Ibarra and Dardo A. Roma and Fabrisio Alustiza and Fernando Mañas and César A. Barbero and Pablo Bosch and Claudia R. Rivarola and Nancy Rodriguez},
  journal      = {Heliyon},
  title        = {Cytotoxicity and bioadhesive properties of poly-N-isopropylacrylamide hydrogel},
  year         = {2019},
  issn         = {2405-8440},
  number       = {4},
  pages        = {e01474},
  volume       = {5},
  abstract     = {Several hydrogel surfaces present properties that simulate the mechanical and physicochemical features of extracellular matrix (ECM), providing a platform that mimic the native cellular milieus. Poly-N-isopropylacrylamide (PNIPAM) hydrogels are receiving attention in biomedical field due to their thermosensibility and soft texture. However, more extensive biocompatibility and cellular interactions studies with cell lines are needed. Therefore, the aim of this study is focus on evaluating the biocompatibility of PNIPAM through cytotoxicity, genotoxicity, and proliferation tests in murine preadipose cells (3T3-L1), human embryonic kidney cells (HEK293) and human carcinoma-derived cells (A549) in presence of hydrogel surfaces. Bioadhesive capacity above PNIPAM surfaces was also analyzed. MTT and neutral red uptake assays shown non-cytotoxic effect of PNIPAM in the studied cell lines. Genotoxicity was evaluated by the single-cell gel electrophoresis assay, where DNA damages were not detected. [3H]-thymidine staining allowed to corroborate that cell proliferation had progressed correctly. Adopted morphologies for each cell line over PNIPAM were similar to cell growing observed on polystyrene, indicating that the surfaces favor the cell attachment during 5 days' culture. The good biocompatibility of PNIPAM surfaces make it an interesting scaffold with clinical potential in tissue regeneration engineering, and a possible adipose and kidney tissue-engineered construct.},
  creationdate = {2025-05-16T09:50:37},
  doi          = {10.1016/j.heliyon.2019.e01474},
  file         = {:Capella2019 - Cytotoxicity and Bioadhesive Properties of Poly N Isopropylacrylamide Hydrogel.pdf:PDF},
  keywords     = {Bioengineering,Biotechnology,Cell biology,pNIPAM,biocompatibility,toxicity,gel,hydrogel,cell stress},
  url          = {https://www.sciencedirect.com/science/article/pii/S2405844018387383},
}

@Article{Nagase2024,
  author       = {Nagase, Kenichi},
  journal      = {Analytical Sciences},
  title        = {Bioanalytical technologies using temperature-responsive polymers},
  year         = {2024},
  issn         = {1348-2246},
  number       = {5},
  pages        = {827--841},
  volume       = {40},
  abstract     = {In recent decades, various bioanalytical technologies have been investigated for appropriate medical treatment and effective therapy. Temperature-responsive chromatography is a promising bioanalytical technology owing to its functional properties. Temperature-responsive chromatography uses a poly(N-isopropylacrylamide)(PNIPAAm) modified stationary phase as the column packing material. The hydrophobic interactions between PNIPAAm and the analyte could be modulated by changing the column temperature because of the temperature-responsive hydrophobicity of PNIPAAm. Thus, the chromatography system does not require organic solvents in the mobile phase, making it suitable for therapeutic drug monitoring in medical settings such as hospitals. This review summarizes recent developments in temperature-responsive chromatography systems for therapeutic drug monitoring applications. In addition, separation methods for antibody drugs using PNIPAAm are also summarized because these methods apply to the therapeutic drug monitoring of biopharmaceutics. The temperature-responsive chromatography systems can also be utilized for clinical diagnosis, as they can assess multiple medicines simultaneously. This highlights the significant potential of temperature-responsive chromatography in medicine and healthcare.},
  creationdate = {2025-05-16T09:54:26},
  doi          = {10.1007/s44211-024-00545-3},
  file         = {:Nagase2024 - Bioanalytical Technologies Using Temperature Responsive Polymers.pdf:PDF},
  keywords     = {review,application-focussed,pNIPAM,chromatography,medicine,drug,biomedical,biomedicine},
  refid        = {Nagase2024},
  url          = {https://doi.org/10.1007/s44211-024-00545-3},
}

@Article{Caykara2006,
  author       = {Tuncer {\c{C}}aykara and Simin Kiper and G{\"{o}}khan Demirel},
  journal      = {Journal of Applied Polymer Science},
  title        = {Network parameters and volume phase transition behavior of poly(N-isopropylacrylamide) hydrogels},
  year         = {2006},
  number       = {3},
  pages        = {1756--1762},
  volume       = {101},
  abstract     = {Thermosensitive hydrogels were prepared by free radical polymerization in aqueous solution from N-isopropylacrylamide (NIPA) monomer and N,N-methylenebis(acrylamide) (MBAAm) crosslinker. The swelling equilibrium of the hydrogels in deionized water was investigated as a function of temperature and MBAAm content. The results indicated that the swelling behavior and temperature sensitivity of the hydrogels were affected by the amount of MBAAm content. The average molecular mass between crosslinks and polymer–solvent interaction parameter ($\chi$) of the hydrogels were determined from equilibrium swelling values. The swelling variations were explained according to swelling theory based on the hydrogel chemical structure. The swelling equilibrium of the hydrogels was also investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). In deionized water, the hydrogels showed a discontinuous volume phase transition at 32$^\circ$C. In SDS and DTAB solutions, the equilibrium swelling ratio and the volume phase transition temperature (lower critical solution temperature) of the hydrogels increased, which is ascribed to the conversion of nonionic PNIPA hydrogel into polyelectrolyte hydrogels because of binding of surfactant molecules through the hydrophobic interaction. Additionally, the amount of free SDS and DTAB ions was measured at different temperatures by a conductometric method; it was found that the electric conductivity of the PNIPA–surfactant systems depended strongly on both the type and concentration of surfactant solutions.},
  creationdate = {2025-03-10T09:10:57},
  doi          = {https://doi.org/10.1002/app.23513},
  eprint       = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/app.23513},
  file         = {:/autohome/saeckech/Promotion/Literatur/Probenspezifisch/PNIPAM/NetworkParametersAndVolumePhaseTransitionBehaviorOfPolyNIsopropylacrylamideHydrogels_CaykaraEtAl_JApplPolymSci2006.pdf:PDF},
  keywords     = {hydrogel,swelling,poly(N-isopropylacrylamide),surfactants,pNIPAM,cross-linker density,cross-linker concentration,SDS,DTAB,kinetics},
  url          = {https://onlinelibrary.wiley.com/doi/abs/10.1002/app.23513},
}









@Article{Doig1992,
  author       = {Doig, Andrew J. and Williams, Dudley H.},
  journal      = {Journal of the American Chemical Society},
  title        = {Binding energy of an amide-amide hydrogen bond in aqueous and nonpolar solvents},
  year         = {1992},
  number       = {1},
  pages        = {338-343},
  volume       = {114},
  creationdate = {2025-06-25T08:07:14},
  doi          = {10.1021/ja00027a044},
  eprint       = {https://doi.org/10.1021/ja00027a044},
  file         = {:Doig1992 - Binding Energy of an Amide Amide Hydrogen Bond in Aqueous and Nonpolar Solvents.pdf:PDF},
  keywords     = {hydrogen exchange,amide},
  url          = {https://doi.org/10.1021/ja00027a044},
}

@Article{Englander1996,
  author       = {S Walter Englander and Tobin R Sosnick and Joan J Englander and Leland Mayne},
  journal      = {Current Opinion in Structural Biology},
  title        = {Mechanisms and uses of hydrogen exchange},
  year         = {1996},
  issn         = {0959-440X},
  number       = {1},
  pages        = {18-23},
  volume       = {6},
  abstract     = {Recent work has largely completed our understanding of the hydrogen-exchange chemistry of unstructured proteins and nucleic acids. Some of the high-energy structural fluctuations that determine the hydrogen-exchange behavior of native macromolecules have been explained; others remain elusive. A growing number of applications are exploiting hydrogen-exchange behavior to study difficult molecular systems and elicit otherwise inaccessible information on protein structure, dynamics and energetics.},
  creationdate = {2025-06-25T08:19:04},
  doi          = {https://doi.org/10.1016/S0959-440X(96)80090-X},
  file         = {:Englander1996 - Mechanisms and Uses of Hydrogen Exchange.pdf:PDF},
  keywords     = {hydrogen exchange},
  url          = {https://www.sciencedirect.com/science/article/pii/S0959440X9680090X},
}

@Article{Syamjith2025,
  author       = {KS, Syamjith and Rout, Shubhasmita and Jacob, Alan R.},
  journal      = {The Journal of Chemical Physics},
  title        = {Revisiting crosslinking density effects on pNIPAM microgel properties: Size, electrophoretic mobility, and transition temperatures},
  year         = {2025},
  issn         = {0021-9606},
  month        = {05},
  number       = {18},
  pages        = {184903},
  volume       = {162},
  abstract     = {Poly(N-isopropylacrylamide) (pNIPAM) microgels exhibit a reversible thermoresponsive behavior, undergoing a volume phase transition. This property makes pNIPAM microgels highly appealing for diverse applications, including drug delivery, tissue engineering, and sensors, where temperature-triggered changes in size, charge, and mechanical properties are advantageous. However, a plethora of data available in the literature regarding the relationship between the crosslinking density and the above-mentioned properties of pNIPAM microgels necessitates a consolidation and re-examination. This study aims to address two key objectives: (1) elucidate the relationship between the crosslinking density and size/electrophoretic mobility of pNIPAM microgels, building upon existing knowledge, and (2) examine the influence of crosslinking density on transition temperatures, particularly the electrokinetic transition temperature, which is not well explored and understood. To achieve these objectives, we synthesized 20 batches of pNIPAM microgels using two distinct synthesis routes: 18 batches via conventional one-pot synthesis, with triplicate replicates for six crosslinking densities, and two batches of pNIPAM microgels via semi-batch synthesis, with a duplicate replicate for one crosslinking density. These microgels were characterized using a combination of dynamic light scattering to determine the size and thermoresponsive behavior, electrophoretic light scattering to analyze electrophoretic mobility, and atomic force microscopy to evaluate the structural morphology and assess stiffness. The insights from the characterization techniques enhance our understanding of how the crosslinking density influences the physical and electrokinetic properties of pNIPAM microgels, potentially creating a pathway for rational design of microgels tailored for specific applications.},
  creationdate = {2025-06-25T08:45:47},
  doi          = {10.1063/5.0269885},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/5.0269885/20519384/184903\_1\_5.0269885.pdf},
  file         = {:Syamjith2025 - Revisiting Crosslinking Density Effects on PNIPAM Microgel Properties_ Size, Electrophoretic Mobility, and Transition Temperatures.pdf:PDF},
  keywords     = {pNIPAM,cross-linking,crosslinking,semi-batch,crosslink distribution,homogeneous crosslinking,onepot,heterogeneous},
  url          = {https://doi.org/10.1063/5.0269885},
}









@Article{Chiefari1998,
  author       = {Chiefari, John and Chong, Y. K. (Bill) and Ercole, Frances and Krstina, Julia and Jeffery, Justine and Le, Tam P. T. and Mayadunne, Roshan T. A. and Meijs, Gordon F. and Moad, Catherine L. and Moad, Graeme and Rizzardo, Ezio and Thang, San H.},
  journal      = {Macromolecules},
  title        = {Living Free-Radical Polymerization by Reversible Addition−Fragmentation Chain Transfer:  The RAFT Process},
  year         = {1998},
  number       = {16},
  pages        = {5559-5562},
  volume       = {31},
  creationdate = {2025-06-25T11:00:38},
  doi          = {10.1021/ma9804951},
  eprint       = {https://doi.org/10.1021/ma9804951},
  file         = {:Chiefari1998 - Living Free Radical Polymerization by Reversible Addition−Fragmentation Chain Transfer_ the RAFT Process.pdf:PDF},
  keywords     = {synthesis,raft,living free-radical polymerization},
  url          = {https://doi.org/10.1021/ma9804951},
}

@Article{Garde2000,
  author       = {Garde, Shekhar and Khare, Rajesh and Hummer, Gerhard},
  journal      = {The Journal of Chemical Physics},
  title        = {Microscopic density fluctuations and solvation in polymeric fluids},
  year         = {2000},
  issn         = {0021-9606},
  month        = {01},
  number       = {3},
  pages        = {1574-1578},
  volume       = {112},
  abstract     = {The information theory approach is used to study molecular-scale density fluctuations and solvation of hard-core molecules in a condensed polymeric system, supported by extensive computer simulations. In contrast to simple liquids, it is found that the bond connectivity in polymers leads to non-Gaussian density fluctuations in molecular volumes. We define “renormalized” polymers with a reduced number of monomers of increased effective size. This reduces correlations between monomers and simplifies the effective density fluctuations. Chemical potentials of hard-core solutes in polyethylene can then be calculated accurately using information theory.},
  creationdate = {2025-07-04T10:23:52},
  doi          = {10.1063/1.480705},
  eprint       = {https://pubs.aip.org/aip/jcp/article-pdf/112/3/1574/19130620/1574\_1\_online.pdf},
  file         = {:Garde2000 - Microscopic Density Fluctuations and Solvation in Polymeric Fluids.pdf:PDF},
  keywords     = {density fluctuations,polymer solubility,simulation,theory},
  url          = {https://doi.org/10.1063/1.480705},
}


@Article{Jamadagni2011,
  author       = {Jamadagni, Sumanth N. and Godawat, Rahul and Garde, Shekhar},
  journal      = {Annual Review of Chemical and Biomolecular Engineering},
  title        = {Hydrophobicity of Proteins and Interfaces: Insights from Density Fluctuations},
  year         = {2011},
  issn         = {1947-5446},
  number       = {Volume 2, 2011},
  pages        = {147-171},
  volume       = {2},
  abstract     = {Macroscopic characterizations of hydrophobicity (e.g., contact angle measurements) do not extend to the surfaces of proteins and nanoparticles. Molecular measures of hydrophobicity of such surfaces need to account for the behavior of hydration water. Theory and state-of-the-art simulations suggest that water density fluctuations provide such a measure; fluctuations are enhanced near hydrophobic surfaces and quenched with increasing surface hydrophilicity. Fluctuations affect conformational equilibria and dynamics of molecules at interfaces. Enhanced fluctuations are reflected in enhanced cavity formation, more favorable binding of hydrophobic solutes, increased compressibility of hydration water, and enhanced water-water correlations at hydrophobic surfaces. These density fluctuation–based measures can be used to develop practical methods to map the hydrophobicity/philicity of heterogeneous surfaces including those of proteins. They highlight that the hydrophobicity of a group is context dependent and is significantly affected by its environment (e.g., chemistry and topography) and especially by confinement. The ability to include information about hydration water in mapping hydrophobicity is expected to significantly impact our understanding of protein-protein interactions as well as improve drug design and discovery methods and bioseparation processes.},
  creationdate = {2025-07-04T10:36:03},
  doi          = {https://doi.org/10.1146/annurev-chembioeng-061010-114156},
  file         = {:Jamadagni2011 - Hydrophobicity of Proteins and Interfaces_ Insights from Density Fluctuations.pdf:PDF},
  keywords     = {heterogeneous surfaces,hydrophobic interactions,wetting and adhesion,protein hydration,water structure,hydrophilicity,review,density fluctuations,hydrophobic hydration},
  publisher    = {Annual Reviews},
  type         = {Journal Article},
  url          = {https://www.annualreviews.org/content/journals/10.1146/annurev-chembioeng-061010-114156},
}


@Article{Rego2022,
  author       = {Rego, Nicholas B. and Patel, Amish J.},
  journal      = {Annual Review of Condensed Matter Physics},
  title        = {Understanding Hydrophobic Effects: Insights from Water Density Fluctuations},
  year         = {2022},
  issn         = {1947-5462},
  number       = {Volume 13, 2022},
  pages        = {303-324},
  volume       = {13},
  abstract     = {The aversion of hydrophobic solutes for water drives diverse interactions and assemblies across materials science, biology, and beyond. Here, we review the theoretical, computational, and experimental developments that underpin a contemporary understanding of hydrophobic effects. We discuss how an understanding of density fluctuations in bulk water can shed light on the fundamental differences in the hydration of molecular and macroscopic solutes; these differences, in turn, explain why hydrophobic interactions become stronger upon increasing temperature. We also illustrate the sensitive dependence of surface hydrophobicity on the chemical and topographical patterns the surface displays, which makes the use of approximate approaches for estimating hydrophobicity particularly challenging. Importantly, the hydrophobicity of complex surfaces, such as those of proteins, which display nanoscale heterogeneity, can nevertheless be characterized using interfacial water density fluctuations; such a characterization also informs protein regions that mediate their interactions. Finally, we build upon an understanding of hydrophobic hydration and the ability to characterize hydrophobicity to inform the context-dependent thermodynamic forces that drive hydrophobic interactions and the desolvation barriers that impede them.},
  creationdate = {2025-07-04T10:40:26},
  doi          = {https://doi.org/10.1146/annurev-conmatphys-040220-045516},
  file         = {:Rego2022 - Understanding Hydrophobic Effects_ Insights from Water Density Fluctuations.pdf:PDF},
  keywords     = {protein folding,solvation,dewetting,supramolecular chemistry,aqueous self-assembly,biomolecular interactions,contact angle,hydrophobic hydration,density fluctuations},
  publisher    = {Annual Reviews},
  type         = {Journal Article},
  url          = {https://www.annualreviews.org/content/journals/10.1146/annurev-conmatphys-040220-045516},
}









@Article{Lum1999,
  author       = {Lum, Ka and Chandler, David and Weeks, John D.},
  journal      = {The Journal of Physical Chemistry B},
  title        = {Hydrophobicity at Small and Large Length Scales},
  year         = {1999},
  number       = {22},
  pages        = {4570-4577},
  volume       = {103},
  abstract     = {We develop a unified and generally applicable theory of solvation of small and large apolar species in water. In the former, hydrogen bonding of water is hindered yet persists near the solutes. In the latter, hydrogen bonding is depleted, leading to drying of extended apolar surfaces, large forces of attraction, and hysteresis on mesoscopic length scales. The crossover occurs on nanometer length scales, when the local concentration of apolar units is sufficiently high, or when an apolar surface is sufficiently large. Our theory for the crossover has implications concerning the stability of protein assemblies and protein folding.},
  creationdate = {2025-07-04T11:00:10},
  doi          = {10.1021/jp984327m},
  eprint       = {https://doi.org/10.1021/jp984327m},
  file         = {:Lum1999 - Hydrophobicity at Small and Large Length Scales.pdf:PDF},
  keywords     = {hydrophobic hydration,density fluctuation,theory,hydration shell},
  url          = {https://doi.org/10.1021/jp984327m},
}

@Article{Ponomareva2022,
  author       = {Ponomareva, Ekaterina and Tadgell, Ben and Hildebrandt, Marco and Krüsmann, Marcel and Prévost, Sylvain and Mulvaney, Paul and Karg, Matthias},
  journal      = {Soft Matter},
  title        = {The fuzzy sphere morphology is responsible for the increase in light scattering during the shrinkage of thermoresponsive microgels},
  year         = {2022},
  pages        = {807-825},
  volume       = {18},
  abstract     = {Thermoresponsive microgels undergo a volume phase transition from a swollen state under good solvent conditions to a collapsed state under poor solvent conditions. The most prominent examples of such responsive systems are based on poly-(N-isopropylacrylamide). When cross-linked with N{,}N′-methylenebisacrylamide{,} such microgels typically possess a fuzzy-spherelike morphology with a higher cross-linked core and a loosely cross-linked fuzzy shell. Despite the efforts devoted to understanding the internal structure of microgels and their kinetics during collapse/swelling{,} the origins of the accompanying changes in light scattering intensity have barely been addressed. In this work{,} we study core–shell microgels that contain small gold nanoparticle cores with microgel shells of different thicknesses and cross-linker densities. All microgels are small enough to fulfill the Rayleigh-Debye-Gans criterion at all stages of swelling. Due to the high X-ray contrast of the gold cores{,} we can use absolute intensity small-angle X-ray scattering to determine the number density in the dilute dispersions. This allows us to extract polymer volume fractions of the microgels at different stages of swelling from form factor analysis of small-angle neutron scattering data. We match our findings to results from temperature-dependent absorbance measurements. The increase in absorbance during the shrinkage of the microgels is related to the transition from fuzzy spheres to hard sphere-like scattering objects with a rather homogeneous density profile. We provide a first attempt to model experimental spectra using finite difference time domain simulations that take into account the structural changes during the volume phase transition. Our findings significantly contribute to the understanding of the optical properties of thermoresponsive microgels. Further{,} we provide polymer volume fractions and microgel refractive indices as a function of the swelling state.},
  creationdate = {2025-07-04T17:21:36},
  doi          = {10.1039/D1SM01473K},
  file         = {:Ponomareva2022 - The Fuzzy Sphere Morphology Is Responsible for the Increase in Light Scattering during the Shrinkage of Thermoresponsive Microgels.pdf:PDF},
  issue        = {4},
  keywords     = {light scattering,pNIPAM,core-shell,microgel,fuzzy sphere},
  publisher    = {The Royal Society of Chemistry},
  url          = {http://dx.doi.org/10.1039/D1SM01473K},
}

@Article{Mompart1999,
  author       = {J. Mompart and R. Corbal{\'a}n},
  journal      = {Eur. Phys. J. D},
  title        = {Quantum-jump approach to dipole dephasing: Application to inversionless amplification},
  year         = {1999},
  issn         = {1434-6079},
  month        = feb,
  number       = {3},
  pages        = {351--356},
  volume       = {5},
  creationdate = {2025-09-16T17:49:52},
  doi          = {10.1007/PL00021600},
  file         = {:Mompart-Corbalán1999_Article_Quantum-jumpApproachToDipoleDe.pdf:PDF},
  publisher    = {Springer Science and Business Media LLC},
}

@Book{Becker2000,
  author       = {Edwin D. Becker},
  publisher    = {Academic Press},
  title        = {High Resolution NMR: Theory and Chemical Applications},
  year         = {2000},
  edition      = {Third},
  isbn         = {0-12-084662-4},
  creationdate = {2025-09-17T17:01:27},
  file         = {:Becker2000 - High Resolution NMR_ Theory and Chemical Applications.pdf:PDF;:Appendix-B---ABX-and-AA-XX--Spectra_2000_High-Resolution-NMR.pdf:PDF;:Appendix-C---Review-of-Relevant-Mathematics_2000_High-Resolution-NMR.pdf:PDF;:Appendix-D---Spin-Matrices_2000_High-Resolution-NMR.pdf:PDF;:Appendix-E---Selected-Answers-to-Problems_2000_High-Resolution-NMR.pdf:PDF;:Chapter-1---Introduction_2000_High-Resolution-NMR.pdf:PDF;:Chapter-2---The-Theory-of-NMR_2000_High-Resolution-NMR.pdf:PDF;:Chapter-3---Instrumentation-and-Techniques_2000_High-Resolution-NMR.pdf:PDF;:Chapter-4---Chemical-Shifts_2000_High-Resolution-NMR.pdf:PDF;:Chapter-5---Coupling-between-Pairs-of-Spins_2000_High-Resolution-NMR.pdf:PDF;:Chapter-6---Structure-and-Analysis-of-Complex-Spectr_2000_High-Resolution-NM.pdf:PDF;:Chapter-7---Spectra-of-Solids_2000_High-Resolution-NMR.pdf:PDF;:Chapter-8---Relaxation_2000_High-Resolution-NMR.pdf:PDF;:Chapter-9---Pulse-Sequences_2000_High-Resolution-NMR.pdf:PDF;:Chapter-10---Two-Dimensional-NMR_2000_High-Resolution-NMR.pdf:PDF;:Chapter-11---Density-Matrix-and-Product-Operator-Form_2000_High-Resolution-N.pdf:PDF;:Chapter-12---Selected-1D--2D--and-3D-Experiments--A-Fu_2000_High-Resolution-.pdf:PDF;:Chapter-13---Elucidation-of-Molecular-Structure-and-Macro_2000_High-Resoluti.pdf:PDF;:Chapter-14---NMR-Imaging-and-Spatially-Localized-Spect_2000_High-Resolution-.pdf:PDF;:Copyright_2000_High-Resolution-NMR.pdf:PDF;:Index_2000_High-Resolution-NMR.pdf:PDF;:Preface-to-the-Third-Edition_2000_High-Resolution-NMR.pdf:PDF;:References_2000_High-Resolution-NMR.pdf:PDF},
  keywords     = {book,NMR},
}

@Article{Braunbek1934,
  author       = {Werner Braunbek},
  journal      = {Z. für Phys.},
  title        = {Die Erzeugung weitgehend homogener Magnetfelder durch Kreisströme},
  year         = {1934},
  pages        = {399--402},
  volume       = {88},
  creationdate = {2025-09-18T11:25:05},
  doi          = {10.1007/BF01343500},
  file         = {:Braunbek1934 - Die Erzeugung Weitgehend Homogener Magnetfelder Durch Kreisströme.pdf:PDF},
  keywords     = {setup,b1-coil,NMR},
}

@Article{Wang2018,
  author       = {Pei Wang and Hua Liu and Xiang Cheng and Wanliang Zhao and Shaoliang Li and Yuxiang Cheng},
  journal      = {Journal of Shanghai Jiaotong University},
  title        = {Design of Braunbek Coil for Nuclear Magnetic Resonance Gyromagnetic Field Excitation},
  year         = {2018},
  pages        = {740--745},
  volume       = {23},
  creationdate = {2025-09-18T11:28:13},
  doi          = {10.1007/s12204-018-2000-3},
  file         = {:Wang2018 - Design of Braunbek Coil for Nuclear Magnetic Resonance Gyromagnetic Field Excitation.pdf:PDF},
  keywords     = {setup,NMR,b1-coil},
}

@Comment{jabref-meta: databaseType:bibtex;}

@Comment{jabref-meta: fileDirectory:/autohome/saeckech/Promotion/Literatur/Library;}

@Comment{jabref-meta: grouping:
0 AllEntriesGroup:;
1 KeywordGroup:Application Focused\;0\;keywords\;application focused\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Drug Delivery\;0\;keywords\;Drug Delivery\;0\;0\;1\;\;\;\;;
1 StaticGroup:Authors\;0\;1\;\;\;\;;
2 KeywordGroup:Balastre\;0\;author\;Balastre\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Ballauff\;0\;author\;Ballauff\;0\;0\;1\;0x8a8a8aff\;\;Reviews and current work on polymer brushes\;;
2 KeywordGroup:Biesalski\;0\;author\;Biesalski\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Borisov\;0\;author\;Borisov\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Cohen-Addad\;0\;author\;Cohen-Addad\;0\;0\;1\;0x8a8a8aff\;\;Pioneer work on NMR on polymers\;;
2 KeywordGroup:Deloche\;0\;author\;Deloche\;0\;0\;1\;0x8a8a8aff\;\;Co-author of THE paper\;;
2 KeywordGroup:Halle\;0\;author\;Halle\;0\;0\;1\;0x8a8a8aff\;\;Artikel mit der Beteiligung von Bertil Halle\;;
2 KeywordGroup:von Klitzing\;0\;author\;von Klitzing\;0\;0\;0\;\;\;\;;
2 KeywordGroup:Matyjaszewski\;0\;author\;Matyjaszewski\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Pincus\;0\;author\;Pincus\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Richtering\;0\;author\;Richtering\;0\;0\;0\;0x8a8a8aff\;\;\;;
2 KeywordGroup:Schönhoff\;0\;author\;Schönhoff, Schoenhoff, Sch{\\\\"{o}}nhoff\;0\;0\;0\;0x8a8a8aff\;\;PNIPAM NMR\;;
2 KeywordGroup:Schorr\;0\;author\;Schorr\;0\;0\;0\;\;\;\;;
2 KeywordGroup:Sierra-Martin\;0\;author\;Sierra-Martin\;0\;0\;0\;0x8a8a8aff\;\;PNIPAM microgels\;;
2 KeywordGroup:Spevacek\;0\;author\;Sp{\\\\v{e}}v{\\\\'{a}}{\\\\v{c}}ek\;0\;0\;1\;0x8a8a8aff\;\;\;;
2 KeywordGroup:Tanaka\;0\;author\;Tanaka\;0\;0\;0\;0x8a8a8aff\;\;cononsolvency, PNIPAM, cooperative hydration\;;
2 KeywordGroup:Tirrell\;0\;author\;Tirrell\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Papadakis\;0\;author\;papadakis\;0\;1\;1\;\;\;\;;
2 KeywordGroup:Müller-Buschbaum\;0\;author\;Müller-Buschbaum\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Winnik\;0\;author\;winnik\;0\;0\;1\;\;\;\;;
1 KeywordGroup:Books\;0\;keywords\;book\;0\;0\;0\;0x8a8a8aff\;\;\;;
1 KeywordGroup:Chemistry Basics\;0\;keywords\;chemistry basics\;0\;0\;1\;0x8a8a8aff\;\;\;;
1 KeywordGroup:Control Parameters\;0\;keywords\;control parameter\;0\;0\;0\;\;\;\;;
2 KeywordGroup:Grafting Densitiy\;0\;keywords\;grafting density\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Ionic Strength\;0\;keywords\;ionic strength\;0\;0\;1\;\;\;\;;
3 KeywordGroup:Salting-In, Salting-Out\;0\;keywords\;salting-in salting-out\;0\;0\;1\;\;\;\;;
3 KeywordGroup:Valency\;0\;keywords\;valency\;0\;0\;1\;\;\;\;;
2 StaticGroup:Other\;0\;1\;\;\;\;;
3 KeywordGroup:Photosensitive\;0\;keywords\;photosensitive\;0\;0\;1\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Pressure\;0\;keywords\;pressure\;0\;0\;1\;\;\;\;;
3 KeywordGroup:Electric Field\;0\;keywords\;electric field control\;0\;0\;1\;0x8a8a8aff\;\;Controlling the swelling of polymer systems via an external electric field\;;
2 KeywordGroup:pH Value\;0\;keywords\;pH control\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Solvent Quality\;0\;keywords\;solvent quality\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Thermoresponsive\;0\;keywords\;thermoresponsive\;0\;0\;1\;\;\;\;;
1 KeywordGroup:Copolymers\;0\;keywords\;copolymer\;0\;0\;0\;\;\;\;;
2 KeywordGroup:Block Copolymers\;0\;keywords\;block copolymer\;0\;0\;1\;\;\;\;;
1 KeywordGroup:Diffusion\;0\;keywords\;diffusion\;0\;0\;0\;\;\;\;;
2 KeywordGroup:Pulsed Field Gradient\;0\;keywords\;PFG diffusion\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Static Field Gradient\;0\;keywords\;SFG Diffusion\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Stokes Einstein Debye Relation\;0\;keywords\;SED\;0\;0\;1\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Stokes-Einstein Relation\;0\;keywords\;Stokes-Einstein\;0\;0\;1\;0x8a8a8aff\;\;\;;
1 SearchGroup:Cononsolvency\;0\;cononsolvency\;0\;0\;1\;\;\;Anything containing the word cononsolvency\;;
1 KeywordGroup:Experimental Methods\;0\;keywords\;experimental methods\;0\;0\;1\;0x8a8a8aff\;\;\;;
2 KeywordGroup:Atomic Force Microscopy\;0\;keywords\;AFM\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Dielectric Spectroscopy\;0\;keywords\;dielectric\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Dynamic Light Scattering\;0\;keywords\;DLS\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Ellipsometry\;0\;keywords\;ellipsometry\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Infrared\;0\;keywords\;infrared\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Neutrons\;0\;keywords\;neutron\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Nuclear Magnetic Resonance\;0\;keywords\;NMR\;0\;0\;1\;\;\;\;;
3 KeywordGroup:Chemical Shift\;0\;keywords\;chemical shift\;0\;0\;1\;\;\;\;;
2 StaticGroup:Other\;0\;1\;\;\;\;;
3 KeywordGroup:Calculations\;0\;keywords\;Calculation\;0\;0\;0\;\;\;\;;
3 KeywordGroup:Contact Angle\;0\;keywords\;contact anlge\;0\;0\;1\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Cyclic Voltametry\;0\;keywords\;cyclic voltametry\;0\;0\;1\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Dark Field Microscopy\;0\;keywords\;dark field\;0\;0\;1\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Direct Force\;0\;keywords\;direct force\;0\;0\;1\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Elasticity\;0\;keywords\;elasticity\;0\;0\;1\;\;\;\;;
3 KeywordGroup:Environmental Scanning Electron Microscopy\;0\;keywords\;Environmental Scanning Electron Microscopy\;0\;0\;1\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Flourescence\;0\;keywords\;flourescence\;0\;0\;1\;\;\;\;;
3 KeywordGroup:Interferometer\;0\;keywords\;interferometer\;0\;0\;1\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Mass Spectrometry\;0\;keywords\;mass spectrometry\;0\;0\;1\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Optical Tweezer\;0\;keywords\;optical tweezer\;0\;0\;1\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Photon Correlation Spectroscopy\;0\;keywords\;PCS\;0\;0\;1\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Rheology\;0\;keywords\;rheology\;0\;0\;1\;0x8a8a8aff\;\;Articles/books dealling with rheology\;;
3 KeywordGroup:Scanning Force Microscopy\;0\;keywords\;SFM\;0\;0\;1\;\;\;\;;
3 KeywordGroup:Surface Force Apparatus\;0\;keywords\;SFA\;0\;0\;1\;\;\;\;;
3 KeywordGroup:Surface Plasmon Resonance\;0\;keywords\;Surface Plasmon Resonance\;0\;0\;0\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Tensiometer\;0\;keywords\;tensiometer\;0\;0\;1\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Thermogravimetric Analysis\;0\;keywords\;thermogravimetric analysis\;0\;0\;1\;\;\;\;;
2 StaticGroup:Scattering\;0\;1\;\;\;\;;
3 KeywordGroup:SANS\;0\;keywords\;SANS\;0\;0\;1\;\;\;\;;
3 KeywordGroup:SAXS\;0\;keywords\;SAXS\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Simulation\;0\;keywords\;simulation\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Transmission Electron Microscopy\;0\;keywords\;TEM\;0\;0\;1\;\;\;\;;
3 KeywordGroup:cryogenic TEM\;0\;keywords\;cryo-TEM\;0\;0\;1\;\;\;\;;
2 KeywordGroup:X-Ray\;0\;keywords\;x-ray\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Calorimetry\;0\;keywords\;calorimetry\;0\;0\;0\;0x8a8a8aff\;\;supergroup for DSC and microcalorimetry\;;
3 KeywordGroup:Differential Scanning Calorimetry\;0\;keywords\;DSC\;0\;0\;1\;0x8a8a8aff\;\;\;;
3 KeywordGroup:Microcalorimetry\;0\;keywords\;microcalorimetry\;0\;0\;1\;0x8a8a8aff\;\;\;;
1 KeywordGroup:Gels and Networks\;0\;keywords\;gel\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Microgels\;0\;keywords\;microgel\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Polymer Networks\;0\;keywords\;polymer network\;0\;0\;1\;\;\;\;;
1 SearchGroup:hydrophobic hydration\;0\;keywords="hydrophobic hydration" OR keywords="hydration shell" OR keywords="hydration water" OR keywords="clathrate"\;0\;0\;1\;\;\;\;;
1 KeywordGroup:Key Articles\;0\;keywords\;key article\;0\;0\;1\;\;\;\;;
1 KeywordGroup:pH Value\;0\;keywords\;pH\;0\;0\;1\;\;\;\;;
1 KeywordGroup:Polymer Brushes\;0\;keywords\;brush\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Bottlebrush\;0\;keywords\;bottlebrush\;0\;0\;1\;0x8a8a8aff\;\;bottlebrushes a.k.a. cylindrical polymer brushes\;;
2 KeywordGroup:Charged Polymer Brush\;0\;keywords\;polyelectrolyte brush\;0\;0\;0\;\;\;\;;
3 KeywordGroup:Strong Polymer Brushes\;0\;keywords\;strong brush\;0\;0\;0\;\;\;\;;
3 KeywordGroup:Weak Polymer Brushes\;0\;keywords\;weak brush\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Multiarm Star Polymer\;0\;keywords\;multiarm\;0\;0\;1\;0x8a8a8aff\;\;\;;
2 KeywordGroup:Neutral Polymer Brushes\;0\;keywords\;neutral brush\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Planar Polymer Brushes\;0\;keywords\;planar brush\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Spherical Polymer Brushes\;0\;keywords\;spherical brush\;0\;0\;0\;\;\;\;;
3 KeywordGroup:Colloid Stabilization\;0\;keywords\;colloid stabilization\;0\;0\;1\;\;\;\;;
1 KeywordGroup:Polymer Melts\;0\;keywords\;polymer melt\;0\;0\;1\;\;\;\;;
1 KeywordGroup:Polymer Synthesis\;0\;keywords\;polymer synthesis\;0\;0\;0\;\;\;\;;
2 KeywordGroup:ATRP\;0\;keywords\;ATRP\;0\;0\;1\;\;\;\;;
3 KeywordGroup:SI-ATRP\;0\;keywords\;SI-ATRP\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Grafting-From\;0\;keywords\;grafting-from\;0\;0\;1\;0x8a8a8aff\;\;\;;
2 KeywordGroup:RAFT\;0\;keywords\;RAFT\;0\;0\;1\;0x8a8a8aff\;\;reversible addition - fragmentation chain transfer\;;
1 StaticGroup:Polymer Usage\;0\;1\;\;\;\;;
2 KeywordGroup:PAA\;0\;keywords\;PAA\;0\;0\;1\;0x8a8a8aff\;\;poly(acrylic acid)\;;
2 KeywordGroup:PAAm\;0\;keywords\;PAAm\;0\;0\;1\;0x8a8a8aff\;\;poly(acrylamide)\;;
2 KeywordGroup:PATAC\;0\;keywords\;PATAC\;0\;0\;1\;\;\;\;;
2 KeywordGroup:PDMAEMA\;0\;keywords\;PDMAEMA\;0\;0\;1\;\;\;\;;
2 KeywordGroup:PDMS\;0\;keywords\;PDMS\;0\;0\;1\;\;\;\;;
2 KeywordGroup:PHEAA\;0\;keywords\;PHEAA\;0\;0\;1\;0x8a8a8aff\;\;poly(N-hydroxyethyl acrylamide) (used in sample SPB1 from Zhishuang)\;;
2 KeywordGroup:PMAA\;0\;keywords\;PMAA\;0\;0\;1\;0x8a8a8aff\;\;poly(methacrylic acid)\;;
2 KeywordGroup:PMMA\;0\;keywords\;PMMA, Polymethylmethacrylat\;0\;0\;1\;0x8a8a8aff\;\;poly(methyl methacrylate)\;;
2 KeywordGroup:PNIPAM\;0\;keywords\;PNIPAM\;0\;0\;1\;\;\;\;;
2 KeywordGroup:Polystyrene\;0\;keywords\;polystyrene\;0\;0\;1\;\;\;\;;
2 KeywordGroup:PSS\;0\;keywords\;PSS\;0\;0\;0\;0x8a8a8aff\;\;polystyrenesulfonate\;;
2 KeywordGroup:PDADMAC\;0\;keywords\;PDADMAC\;0\;0\;1\;0x8a8a8aff\;\;Poly(diallyl dimethylammonium chloride)\;;
2 KeywordGroup:PAH\;0\;keywords\;PAH\;0\;0\;1\;0x8a8a8aff\;\;Poly(allalamine hydrochloride)\;;
2 KeywordGroup:PEI\;0\;keywords\;PEI\;0\;0\;1\;0x8a8a8aff\;\;poly(ethylene imine)\;;
2 KeywordGroup:PVCL\;0\;keywords\;PNVCL, PVCL, poly(N-vinylcaprolactam)\;0\;0\;1\;0x8a8a8aff\;\;poly(N-vinylcaprolactam)\;;
2 KeywordGroup:PEG\;0\;keywords\;PEG\;0\;0\;1\;\;\;poly(ethylene glycol) aka poly(ethylene oxide)\;;
1 KeywordGroup:Reviews\;0\;keywords\;review\;0\;0\;1\;\;\;\;;
1 KeywordGroup:Uncitable\;0\;keywords\;uncitable\;0\;0\;1\;\;\;\;;
}
