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In this study, we investigated the cooperative molecular dynamics of poly(vinylpyrrolidone) (PVP), ice, and uncrystallized water (UCW) in partially crystallized PVP-water mixtures by means of broadband dielectric spectroscopy. Three relaxation processes, denoted I, II, and III, were observed at temperatures ranging from immediately below the crystallization temperature (Tc) to approximately 200 K. At temperatures of 173-193 K, processes I and II cannot be distinguished. Below 168 K, process II separates into two processes: process IV at higher frequencies and process V at lower frequencies. Process I contributes to process V. In partially crystallized mixtures, process I originates from UCW in an uncrystallized phase with PVP. Process II is attributed to ice in the mixture, with a relaxation time that is 2 orders of magnitude smaller than that of pure ice. The concentration dependence of the strength of process II and the relaxation time relative to that of ice in bovine serum albumin (BSA)-water and gelatin-water mixtures strongly support this conclusion. Observation of processes IV and V indicates the presence of multiple ice relaxation processes. Process III is attributed to the α process of PVP in the uncrystallized phase in 40 and 50 wt % PVP mixtures. For mixtures with 30 wt % PVP or less, process III is attributed not only to the α process of PVP but also to interfacial polarization.

The effect of hydrophobicity on thermal diffusion of acetylated dextran in aqueous solution was studied in the temperature range of 15–50 °C by optical beam deflection (OBD) technique. The hydrophobicity was controlled by substitution of hydroxyl groups on dextran chain with acetylated groups. The Soret coefficient ST and thermal diffusion coefficient DT significantly increased with an increase of temperature. The hydrophobicity plays an important role in the thermal diffusion behavior, i.e. ST and DT switch the sign from negative to positive magnitude with an increase of hydrophobic contents. We observed a correlation between the parameters obtained from Iacopini and Piazza equation (Europhy. Lett. 63 (2003) 247–253.) and the hydrophobic content of the binary aqueous solutions. A master curve can be used to describe the temperature dependence of ST and DT for acetylated samples. The ST linearly decreases with an increase of particle size for dextran whereas it scales linearly with the volume of particles for acetylated samples.

A novel polymer host from carboxymethyl cellulose (CMC)/poly(N-isopropylacrylamide) (PNiPAM) was developed for a high safety solid polymer electrolyte (SPE) in a zinc ion battery. Effects of the PNiPAM loading level in the range of 0–40% by weight ( wt%) on the chemical, mechanical, thermal, and morphological properties of the CMC/PNiPAMx films (where x is the wt% of PNiPAM) were symmetrically investigated. The obtained CMC/PNiPAMx films showed a high compatibility between the polymers. The CMC/PNiPAM20 blend showed the greatest tensile strength and modulus at 37.9 MPa and 2.1 GPa, respectively. Moreover, the thermal degradation of CMC was retarded by the addition of PNiPAM. Scanning electron microscopy images of CMC/PNiPAM20 revealed a porous structure that likely supported Zn2+ movement in the SPEs containing zinc triflate, resulting in the high Zn2+ ion transference number (0.56) and ionic conductivity (1.68 × 10–4 S cm−1). Interestingly, the presence of PNiPAM in the CMC/PNiPAMx blends showed a greater stability during charge–discharge cyclic tests, indicating the ability of PNiPAM to suppress dendrite formation from causing a short circuit. The developed CMC/PNiPAM20 based SPE is a promising material for high ionic conductivity and stability in a Zn ion battery.

This study investigates the cooperative molecular dynamics of poly(vinyl methyl ether) (PVME) at temperatures above and below the glass transition temperature, Tg, using differential scanning calor...

The dynamic behavior of water molecules in tofu gels is observed using dielectric spectroscopy (DS) and pulsed field gradient nuclear magnetic resonance (PFG-NMR) methods. The breaking stress of tofu gels are dependent on the heating time, which affects the water structures characterized by the dielectric relaxation time, τ. On the other hand, the inhomogeneity of the gel structures decreases with increasing coagulant concentration was reflected as decreasing of the dielectric broadening parameter, β, that related for a fluctuation of the dynamic water structure. In addition, a decrease in the translational diffusion coefficient of water molecules is obtained with increasing coagulant concentration suggesting a reduction of the free space for the diffusional motion of water molecules. Negative correlations between the broadening parameter, β, and the inverse of diffusion coefficient, 1/D, are found in tofu gels and soymilk with distinct correlation coefficients of −0.95 and −0.87, respectively. These results suggest that water dynamics analysis and complementary analysis using DS and PFG-NMR measuring techniques can be an effective tool to evaluate food gel physical properties. Further these technique could also explain the molecular mechanisms of gel and liquid structures and properties via dynamic water structures.

The dielectric relaxation process of water has been investigated for a partially crystallized poly(ethylene glycol) (PEG)–water mixture with PEG concentrations of up to 50 wt% at temperatures between −60 and 25 °C and over the frequency range of 1 MHz to 50 GHz. At subzero temperatures, most of the water is crystallized, and another portion of the water, uncrystallized water (UCW), remains in a liquid state with the polymer in an uncrystallized phase. The relaxation strength, Δɛ, of UCW for all PEG–water mixtures increased abruptly because of the melting of the eutectic of PEG and water. The Δɛ of UCW for 10–40 wt% PEG–water mixtures increased again because of the melting of ice, whereas the 50 wt% PEG–water mixture did not show any additional increase in Δɛ because it did not contain enough water to form ice crystals. The relaxation time of UCW in PEG–water mixtures is smaller than those observed in other polymer–water mixtures. The local fluctuation of the PEG chain, which has a smaller relaxation time than those of other polymers in water mixtures, and the characteristic hydration structure around the PEG chain prevent the formation of ice crystals even for water with a small relaxation time. The dielectric relaxation process of uncrystallized water (UCW) has been investigated for poly(ethylene glycol) (PEG)–water mixtures. The relaxation strength, Δɛ, of UCW for all PEG–water mixtures increased because of melting of the eutectic. For 10–40 wt% PEG–water mixtures, Δɛ increased again because of the melting of ice, whereas 50wt % PEG–water mixture did not show any additional increase because it did not contain enough water to form ice crystals.

Self-assembly of acetylated dextran (Ac-DEXs) was investigated with a modified dextran with acetic anhydride in the presence of pyridine. The effect of acetylation degree on solution properties has been investigated by static and dynamic light scattering (DLS). Molecular weight (Mw) and the radius of gyration (Rg) of dextran significantly increased with acetylation degree due to the aggregates formation. However, those aggregates noticeably reduced with further increase of acetylation degree. It suggested that the aggregates have shrinkage. The aggregate formation is clearly confirmed by DLS analysis in the presence of the bimodal relaxation distribution for Ac-DEXs. The hydrodynamic radius (Rh) of fast and slow mode is distinctly corresponded with single dextran macromolecules and aggregates, respectively. The Rh of aggregates varied slightly with increasing acetylation degree. The aggregates of Ac-DEXs represent hard spherical nanoparticles whereas the random coil structure is found in dextran. Formation of gel nanoparticles was monitored at the highest acetylated substitution.

Natural polysaccharides represent a renewable resource whose effective utilization is of increasing importance. Chemical modification is a powerful tool to transform them into processable materials but usually sacrifices the original structures and properties of value. Here we introduce a chemical modification of Curdlan, a β-1,3-glucan, via 4,6-acetalization. This modification has successfully combined a helix-forming ability of Curdlan with new solubility in organic media. Furthermore, it has operationalized efficient cohelical crossovers (CCs) among the helices to demonstrate the formation of an extensive supramolecular network that goes well beyond the nanoscopic regime, allowing for preparation of flexible self-supporting films with macroscopic dimensions. This protocol, which is now viewed as supramolecular polymerization of a helical polysaccharide macromer, can add a new dimension to "polysaccharide nanotechnology", opening a door for the creation of unconventional polymer materials based on the cohelical crossover network (CCN).

Background The dynamic behavior of water molecules remains an important subject for understanding human skin. The change in the dynamics of water molecules from those in bulk water can be effectively observed by dielectric spectroscopy. To study water in the human skin in vivo, non‐invasive and non‐destructive measurements are essential. Since many unknowns remain from previous research, in this report we employ a two‐layer dielectric model to evaluate the penetration depth of the electric field and use the results in measurements on human skin. Materials and Methods We used open‐ended coaxial probes with different diameters to perform time‐domain reflectometry (TDR) measurements for an acetone‐Teflon double‐layer model and for human skin from various parts of the body. Results The electric‐field penetration depth obtained from model measurements increases with the increasing outer diameter of open‐ended coaxial electrodes. For skin measurements, the relaxation strength corresponding to the water content shows a clear dependence on the epidermal thickness of the measured body parts. Conclusion We determined the depth distribution of the water content of skin from results of dielectric measurements obtained using electrodes with various electric‐field penetration depths. We found exponential decays with the thickness of the epidermis of each body part for several examinees. This study suggests an effective method for detailed evaluations of human skin.

The dynamics of a hydrogen bonding network (HBN) relating to macroscopic properties of hydrogen bonding liquids were observed as a significant relaxation process by dielectric spectroscopy measurements. In the cases of water and water rich mixtures including biological systems, a GHz frequency relaxation process appearing at around 20 GHz with the relaxation time of 8.2 ps is generally observed at 25 &deg, C. The GHz frequency process can be explained as a rate process of exchanges in hydrogen bond (HB) and the rate becomes higher with increasing HB density. In the present work, this study analyzed the GHz frequency process observed by suitable open-ended coaxial electrodes, and physical meanings of the fractal nature of water structures were clarified in various aqueous systems. Dynamic behaviors of HBN were characterized by a combination of the average relaxation time and the distribution of the relaxation time. This fractal analysis offered an available approach to both solution and dispersion systems with characterization of the aggregation or dispersion state of water molecules. In the case of polymer-water mixtures, the HBN and polymer networks penetrate each other, however, the HBN were segmented and isolated more by dispersed and aggregated particles in the case of dispersion systems. These HBN fragments were characterized by smaller values of the fractal dimension obtained from the fractal analysis. Some examples of actual usages suggest that the fractal analysis is now one of the most effective tools to understand the molecular mechanism of HBN in aqueous complex materials including biological systems.

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.

Dynamics of solvent molecules restricted in poly (acryl amide) gels immersed in solvent mixtures of acetone&ndash, 1,4-dioxane&ndash, and dimethyl sulfoxide&ndash, water were analyzed by the time domain reflectometry method of dielectric spectroscopy and the pulse field gradient method of nuclear magnetic resonance. Restrictions of dynamic behaviors of solvent molecules were evaluated from relaxation parameters such as the relaxation time, its distribution parameter, and the relaxation strength obtained by dielectric measurements, and similar behaviors with polymer concentration dependences for the solutions were obtained except for the high polymer concentration in collapsed gels. Scaling analyses for the relaxation time and diffusion coefficient respectively normalized by those for bulk solvent suggested that the scaling exponent determined from the scaling variable defined as a ratio of the size of solvent molecule to mesh size of polymer networks were three and unity, respectively, except for collapsed gels. The difference in these components reflects characteristic molecular interactions in the rotational and translational diffusions, and offered a physical picture of the restriction of solvent dynamics. A universal treatment of slow dynamics due to the restriction from polymer chains suggests a new methodology of characterization of water structures.

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.

Broadband dielectric spectroscopy measurements were performed on partially crystallized gelatin–water mixtures with gelatin concentrations of 1–5 wt % for temperatures between 123 and 298 K to study the dynamics of ice. These systems contain only hexagonal ice. Nevertheless, four dielectric relaxation processes of ice were observed. At temperatures below the crystallization temperature, a loss peak was observed, and it separated into four loss peaks at around 225 K. Using the temperature and concentration dependencies of these relaxation processes, we confirmed that these four processes originated from ice. For the relaxation time of ice, τice, the deviation of the temperature dependence of τice from the Arrhenius type is larger for the relaxation process at the higher-frequency side. For the temperature dependence of τice for the dominant process, three temperature ranges with different activation energies, Ea, were investigated. The intermediate-temperature range of τice with the smallest Ea decreased a...

The temperature-gradient induced migration of biomolecules, known as thermophoresis or thermodiffusion, changes upon ligand binding. In recent years, this effect has been used to determine protein-ligand binding constants. The mechanism through which thermodiffusive properties change when complexes are formed, however, is not understood. An important contribution to thermodiffusive properties originates from the thermal response of hydrogen bonds. Since there is a considerable difference between the degree of solvation of the protein-ligand complex and its isolated components, ligand-binding is accompanied by a significant change in hydration. The aim of the present work is therefore to investigate the role played by hydrogen bonding on the change in thermodiffusive behaviour upon ligand binding. As a model system we use cyclodextrins (CDs) and acetylsalicylic acid (ASA), where a quite significant change in hydration is expected, and where no conformational changes occur when a CD-ASA complex is formed in aqueous solution. Thermophoresis was investigated in a temperature range from 10 to 50°C by infrared thermal diffusion forced Rayleigh scattering (IR-TDFRS). NMR measurements were performed at 25°C to obtain information about the structure of the complexes. All CD-ASA complexes show a stronger affinity towards regions of lower temperature as compared to the free CDs. We found that the temperature sensitivity of thermophoresis correlates with the 1-octanol/water partition coefficient. This observation not only establishes the relation between thermodiffusion and the degree of hydrogen bonding, but also opens the possibility to relate thermodiffusive properties of complexes to their partition coefficient, which can not be determined otherwise. This concept is especially interesting for protein-ligand complexes where the protein undergoes a conformational change, different from the CD-ASA complexes, giving rise to additional changes in their hydrophilicity.

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.

Cyclodextrins are cyclic oligosaccharides which are interesting as drug delivery systems, because they can be used as containers for pharmaceutical substances. We studied the Ludwig-Soret effect of $\alpha$-, $\beta$-, $\gamma$- and methyl-$\beta$-cyclodextrin in water and formamide by infrared thermal diffusion forced Rayleigh scattering (IR-TDFRS).In water the Soret coefficient, $S_{\mathrm{T}}$, of $\alpha$-, $\beta$- and $\gamma$-cyclodextrin increases with increasing temperature and shows a sign change from negative to positive around $T=35^\circ$C, while $S_{\mathrm{T}}$ of methyl-$\beta$-cyclodextrin is positive in the entire investigated temperature. In formamide $S_{\mathrm{T}}$-values of all cyclodextrins coincide and show a slight decrease with temperature. We discuss the obtained results and relate the $S_{\mathrm{T}}$-values to the different hydrogen bonding capabilities of the cyclodextrins and the used solvents. It turns out that the change of $S_{\mathrm{T}}$ with temperature correlates with the partition coefficient, log~$P$, which indicates that more hydrophilic substances show a more pronounced temperature sensitivity of $S_{\mathrm{T}}$. Additionally we obtained a surprising result measuring the refractive index contrast factor with temperature, $(\partial n/\partial T)_{c,p}$ of cyclodextrins in formamide, which might be explained by a complex formation between cyclodextrins and formamide.

Dielectric relaxation process of ice-Ih has been investigated by many researchers. Pioneering studies focused on the temperature dependence of the dielectric relaxation time, τice, were reported by Auty in 1952 [ Auty, R. P.; Cole, R. H. J. Chem. Phys . 1952 , 120 , 1309 ] and Johari in 1981 [ Johari, G. P.; Whalley, E. J. Chem. Phys. 1981 , 75 , 1333 ]. However, the temperature dependences of τice found in these studies are not in agreement. While Auty et al. reported a single Arrhenius temperature dependence of τice for the entire 207-273 K temperature range, Johari et al. reported changes in the temperature dependence of τice at 230 and 140 K. In this study, the temperature dependence of τice is investigated by broadband dielectric spectroscopy for ice prepared by three different procedures. For all investigated ices, a dielectric relaxation process is observed, and τice decreases with increasing temperature. Temperature dependence of τice with rapid crystallization shows the same properties at temperatures down to 140 K as that reported by Johari et al. On the other hand, ice obtained by slow crystallization exhibits the same temperature dependence of τice as those reported by Auty et al. We suggest that the difference between the temperature dependences of τice found by Auty et al. and Johari et al. can be controlled by preparation conditions. That is, the growth rate of the ice crystal can affect τice because a slow growth speed of the ice crystal induces a smaller impurity content of ice, giving rise to an Arrhenius temperature dependence of τice.

Dielectric relaxation processes for mortar observed by broadband dielectric spectroscopy were analyzed in the drying and hydration processes for an aging sample in the frequency region from 1 MHz up to 2 MHz. At least two processes for structured water in the kHz frequency region and another mHz relaxation process affected by ionic behaviors were observed. Comparison of the relaxation parameters obtained for the drying and hydration processes suggests an existence of hierarchical water structures in the exchange of water molecules, which are originally exchanged from free water observed at around 20 GHz. The water molecules reflected in the lower frequency process of the two kHz relaxation processes are more restricted and take more homogeneous structures than the higher kHz relaxation process. These structured water usually hidden in large ionic behaviors for wood samples was observed by electrodes covered by a thin Teflon film, and hierarchical water structures were also suggested for wood samples. Dielectric spectroscopy technique is an effective tool to analyze the new concept of hierarchical water structures in complex materials.

Poly(tetrafluoroethylene) (PTFE) thin films were deposited onto a glass slide substrate by a heat-resistance type vacuum evaporation apparatus due to changing the evaporation conditions. Transparency of the PTFE thin films prepared by the vacuum evaporation depended on the deposition conditions, i.e., temperatures of the basket, and distance between the evaporation source and substrate. To elucidate relationship between the molecular structure and transparency of the PTFE thin film prepared by the vacuum evaporation, chemical structures, crystallinity and thermophysical property were investigated. The chemical bonding state of the PTFE thin film prepared by the vacuum evaporation was almost the same as that of the pristine PTFE, however, the crystalinity was different. Although the pristine PTFE was crystal structure, the transparent evaporated thin film was estimated to be microcrystal structure. In addition, endothermic peaks in a differential scanning calorimeter (DSC) spectrum of the PTFE thin film were different from that of the pristine PTFE. These endothermic peaks of the PTFE thin film prepared by the vacuum evaporation shifted lower temperature compared to the pristine PTFE, which suggests that molecular weight of the PTFE thin film prepared by the vacuum evaporation decreased compared with that of the pristine PTFE.

Opalescence of the aqueous solution of hydroxypropylmethylcellulose (HPMC) induced by heating has been studied in terms of the phase diagram and the phase separation dynamics. The cloud point curve and the sol-to-gel transition curve intersected with each other at about 55 °C . Just above the cloud-point curve at which the spinodal curve has its minimum, a ring-like scattering pattern appeared corresponding to the spinodal decomposition. Temporal growth of the scattering function in the course of phase separation was studied by a time-resolved light scattering technique. The gelation pinned the phase separation (spinodal decomposition) of the aqueous HPMC solution.