Rotational fluctuations of water inside the nanopores of SBA-type molecular sieves

The rotational molecular dynamics of water confined to nanoporous molecular sieves of a regular hexagonal (SBA-15) and of a foamlike pore structure was studied by dielectric spectroscopy in the frequency range from 10(-2) to 10(9) Hz and in a broad temperature interval. Two relaxation processes were observed: the process at lower frequencies is related to water molecules forming a layer, which is strongly adsorbed at the pore surface, whereas the relaxation process at higher frequencies is assigned to fluctuations of water molecules situated close to the center of the pore. The relaxation times of the low-frequency process for both materials and of the high-frequency process for the SBA-15 material have an unusual saddlelike temperature dependence, reported here for the first time. To describe this temperature dependence, a model developed for water confined to nanoporous glasses by Ryabov et al. [J. Phys. Chem. B 2001, 105, 1845] was applied, which considers two competing effects. The characteristic features of these two competing processes were compared with those reported for other porous systems.     

Correlation of ion dynamics and structure of superionic tellurite glasses

Ion dynamics and structure of a series of superionic AgI-doped silver tellurite glasses have been investigated in this paper. The composition dependence of the dc conductivity and the activation energy of these glasses has been compared with those of AgI-doped silver phosphate and borate glasses. We have observed that the conductivity increases and the activation energy decreases with increase of AgI content and that the tellurite glasses have higher conductivity than those for phosphate or borate glasses. We have analyzed the ac electrical data in the framework of the power law and the electric modulus formalisms. We have established a correlation between the crossover rate of the mobile silver ions and the rearrangement of the structural units in tellurite glasses. The scaling of the conductivity spectra has been used to interpret the temperature and composition dependence of the relaxation dynamics. Analysis of the dielectric relaxation in the framework of modulus formalism indicates an increase in the ion-ion cooperation in the glass compositions with increasing AgI content.     

Investigating hydration dependence of dynamics of confined water: monolayer, hydration water and Maxwell-Wagner processes

The dynamics of water confined in silica matrices MCM-41 C10 and C18, with pore diameter of 21 and 36 A, respectively, is examined by broadband dielectric spectroscopy (10(-2)-10(9) Hz) and differential scanning calorimetry for a wide temperature interval (110-340 K). The dynamics from capillary condensed hydration water and surface monolayer of water are separated in the analysis. Contrary to previous reports, the rotational dynamics are shown to be virtually independent on the hydration level and pore size. Moreover, a third process, also reported for other systems, and exhibiting a saddlelike temperature dependence is investigated. We argue that this process is due to a Maxwell-Wagner process and not to strongly bound surface water as previously suggested in the literature. The dynamics of this process is strongly dependent on the amount of hydration water in the pores. The anomalous temperature dependence can then easily be explained by a loss of hydration water at high temperatures in contradiction to previous explanations.     

Relaxation process due to molecular inclusions in non-crystalline solids

The dielectric, thermodynamic and electric conduction behaviour of amorphous solids with three types of inclusions are described. In the first, or the self-inclusion in glasses, the features of dielectric relaxation due to localized rotational diffusion have a remarkable resemblance to those of the rotation of guest molecules in clathrate structures. But here, the availability of the various configurational states to molecules in the local regions makes a relatively greater contribution to the thermodynamic behaviour of a glass than is observed in clathrates. The number of such self-inclusions decreases as a glass spontaneously densifies on ageing. In this respect, the features attributable to such inclusions in a non-crystalline solid differ from those of a crystalline solid. In the second, - 20 A size inclusions or microdomains of strained a-AgI (bec lattice) are randomly distributed in AgI-AgP03 glasses. The electrical conductivity due to such inclusions follows a power law characteristic of site percolation with a percolation threshold of 0.3, critical exponent 3.3, vulnerability 4.8 and the number of contact sites 2.7. In the third, the part of the repeat unit of a randomly oriented poly(vinyl pyrrolidone) becomes incorporated as inclusions in the distorted, H-bonded, cage-like structures formed by the water molecules. The features of dielectric relaxation of water molecules in the solid aqueous solution of the polymer are similar to those of ice clathrates containing a guest molecule similar in size to pyrrolidone, but the respective temperature dependence of their rates differ.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.     

丙三醇水溶液玻璃结构松弛现象学研究

为了考察水含量对丙三醇水溶液玻璃体结构松弛行为的影响，利用差示扫描量热法(DSC)测量了五种高浓度丙三醇水溶液的玻璃化转变温度和玻璃化转变区域的比热容，利用TNM模型进行了结构松弛的现象学分析. 松弛时间的分析结果表明，水溶液玻璃中水含量越高，则松弛过程越快. TNM模型的计算结果表明，随着水含量的增加，玻璃体系的结构松弛活化能和非指数参数都有逐渐降低的趋势，而非线性参数和指前因子逐渐增加.     

Structure-dependent dc conductivity and relaxation time in the Debye-Stokes-Einstein equation

The basis for a modification of the Debye-Stokes-Einstein (DSE) equation between the dc conductivity, sigma(dc), and dielectric relaxation time, tau, has been examined by using broad-band dielectric spectroscopy of LiClO4 solutions in 5-methyl-2-hexanol and 1-propanol and of pure liquids. According to the DSE equation, the log sigma(dc)-log tau plots should have a slope of -1. We find that sigma(dc) begins to depend upon the structure of an electrolytic solution when a variation of solvent's equilibrium dielectric permittivity, epsilon(s), with temperature causes the ion population to vary. As a consequence of this intrinsic dependence, the log sigma(dc)-log tau plots do not obey the DSE equation. Inclusion of the effect of change in epsilon(s) on the DSE equation may be useful in analyzing the measured quantities in terms of Brownian diffusion of both ions and molecules in ultraviscous liquids. Proton translocation along a hydrogen bond contributes little to sigma(dc), which appears to be predominantly determined by the ion population in the two alcohols and the solutions. The effect is briefly discussed in the potential energy landscape paradigm of structure fluctuations, and it is suggested that the high-frequency shear modulus measurements of ionic solutions would help reveal the temperature-dependent deviation from the DSE equation.     

Relation between solvent and protein dynamics as studied by dielectric spectroscopy

We present results obtained by dielectric spectroscopy in wide frequency (10(-2)-10(9) Hz) and temperature ranges on human hemoglobin in the three different solvents water, glycerol, and methanol, at a solvent level of 0.8 g of solvent/g of protein. In this broad frequency region, there are motions on several time-scales in the measured temperature range (110-370 K for water, 170-410 K for glycerol, and 110-310 K for methanol). For all samples, the dielectric data shows at least four relaxation processes, with frequency dependences that are well described by the Havriliak-Negami or Cole-Cole functions. The fastest and most pronounced process in the dielectric spectra of hemoglobin in glycerol and methanol solutions is similar to the alpha-relaxation of the corresponding bulk solvent (but shifted to slower dynamics due to surface interactions). For water solutions, however, this process corresponds to earlier results obtained for water confined in various systems and it is most likely due to a local beta-relaxation. The slowing down of the glycerol and methanol relaxations and the good agreement with earlier results on confined water show that this process is affected by the interaction with the protein surface. The second fastest process is attributed to motions of polar side groups on the protein, with a possible contribution from tightly bound solvent molecules. This process is shifted to slower dynamics with increasing solvent viscosity, and it shows a crossover in its temperature dependence from Arrhenius behavior at low temperatures to non-Arrhenius behavior at higher temperatures where there seems to be an onset of cooperativity effects. The origins of the two slowest relaxation processes (visible at high temperatures and low frequencies), which show saddlelike temperature dependences for the solvents water and methanol, are most likely due to motions of the polypeptide backbone and an even more global motion in the protein molecule.     

Mechanism of Water Dynamics in Hyaluronic Dermal Fillers Revealed by Nuclear Magnetic Resonance Relaxometry

¹H spin−lattice nuclear magnetic resonance relaxation experiments were performed for five kinds of dermal fillers based on hyaluronic acid. The relaxation data were collected over a broad frequency range between 4 kHz and 40 MHz, at body temperature. Thanks to the frequency range encompassing four orders of magnitude, the dynamics of water confined in the polymeric matrix was revealed. It is demonstrated that translation diffusion of the confined water molecules exhibits a two-dimensional character and the diffusion process is slower than diffusion in bulk water by 3–4 orders of magnitude. As far as rotational dynamics of the confined water is concerned, it is shown that in all cases there is a water pool characterized by a rotational correlation time of about 4×10⁻⁹ s. In some of the dermal fillers a fraction of the confined water (about 10 %) forms a pool that exhibits considerably slower (by an order of magnitude) rotational dynamics. In addition, the water binding capacity of the dermal fillers was quantitatively compared.     

Translational diffusion of cumene and 3-methylpentane on free surfaces and pore walls studied by time-of-flight secondary ion mass spectrometry

Mobility of molecules in confined geometry has been studied extensively, but the origins of finite size effects on reduction of the glass transition temperature, T(g), are controversial especially for supported thin films. We investigate uptake of probe molecules in vapor-deposited thin films of cumene, 3-methylpentane, and heavy water using secondary ion mass spectrometry and discuss roles of individual molecular motion during structural relaxation and glass-liquid transition. The surface mobility is found to be enhanced for low-density glasses in the sub-T(g) region because of the diffusion of molecules on pore walls, resulting in densification of a film via pore collapse. Even for high-density glasses without pores, self-diffusion commences prior to the film morphology change at T(g), which is thought to be related to decoupling between translational diffusivity and viscosity. The diffusivity of deeply supercooled liquid tends to be enhanced when it is confined in pores of amorphous solid water. The diffusivity of molecules is further enhanced at temperatures higher than 1.2-1.3 T(g) irrespective of the confinement.     

Molecular exchange dynamics in partially filled microscale and nanoscale pores of silica glasses studied by field-cycling nuclear magnetic resonance relaxometry

Nuclear magnetic spin-lattice relaxation experiments have been performed in partially filled porous glasses with wetting and nonwetting fluids. The frequency dependence of the spin-lattice relaxation rate in Vycor (4 nm pores) and VitraPOR #5 (1 microm pores) silica glasses was studied as a function of the filling degree with the aid of field-cycling NMR relaxometry. The species of primary interest were water ("polar") and cyclohexane ("nonpolar"). Spin-lattice relaxation was examined in the frequency range from 1 kHz to 400 MHz with the aid of a field-cycling NMR relaxometer and an ordinary 400 MHz NMR spectrometer. Three different mobility states of the fluid molecules are distinguished: The adsorbed state at the pore walls, the bulklike liquid phase, and the vapor phase. The adsorbate spin-lattice relaxation rate is dominated by the "reorientation mediated by translational displacements" (RMTD) mechanism taking place at the adsorbate/matrix interface at frequencies low enough to neglect rotational diffusion of the molecules. The experimental data are analyzed in terms of molecular exchange between the different mobility states. Judged from the dependence of the spin-lattice relaxation rates on the filling degree, limits for slow and fast exchange (relative to the RMTD time scale) can be distinguished and identified. It is concluded that water always shows the features of slow exchange irrespective of the investigated pore sizes and filling degrees. This is in contrast to cyclohexane which is subject to slow exchange in micrometer pores, whereas fast exchange occurs in nanoscopic pores. The latter case implies that the vapor phase contributes to molecular dynamics in this case at low filling degrees while it is negligible otherwise.     

Thermodynamics of water entry in hydrophobic channels of carbon nanotubes

Experiments and computer simulations demonstrate that water spontaneously fills the hydrophobic cavity of a carbon nanotube. To gain a quantitative thermodynamic understanding of this phenomenon, we use the recently developed two phase thermodynamics method to compute translational and rotational entropies of confined water molecules inside single-walled carbon nanotubes and show that the increase in energy of a water molecule inside the nanotube is compensated by the gain in its rotational entropy. The confined water is in equilibrium with the bulk water and the Helmholtz free energy per water molecule of confined water is the same as that in the bulk within the accuracy of the simulation results. A comparison of translational and rotational spectra of water molecules confined in carbon nanotubes with that of bulk water shows significant shifts in the positions of the spectral peaks that are directly related to the tube radius.     

Dielectric spectroscopy of some heteronuclear amino alcohol complexes

The temperature dependent dielectric spectroscopic properties of two heteronuclear complexes of monoethanolamine (MEA) at a wide temperature range (303-413 K) were investigated by impedance spectroscopy, in the frequency range from 100 Hz to 100 kHz. The frequency dependence of the impedance spectra plotted in the complex plane shows semi-circles. The Cole-Cole diagrams have been used to determine the molecular relaxation time, tau. The temperature dependence of tau is expressed by thermally activated process. Relaxation frequencies corresponding to the rotation of the molecules about their long axes are expected to lie above 10 MHz and exhibit Arrhenius behavior, where a single slope is observed with activation energy values equal to 0.67 and 0.78 eV. The ac conductivity sigma(ac) (omega) is found to vary as omega(s) with the index s相似文献   

String-like propagation of the 5-coordinated defect state in supercooled water: molecular origin of dynamic and thermodynamic anomalies

We find that at low temperature water, large amplitude (~60°) rotational jumps propagate like a string, with the length of propagation increasing with lowering temperature. The strings are formed by mobile 5-coordinated water molecules which move like a Glarum defect (J. Chem. Phys., 1960, 33, 1371), causing water molecules on the path to change from 4-coordinated to 5-coordinated and again back to 4-coordinated water, and in the process cause the tagged water molecule to jump, by following essentially the Laage-Hynes mechanism (Science, 2006, 311, 832-835). The effects on relaxation of the propagating defect causing large amplitude jumps are manifested most dramatically in the mean square displacement (MSD) and also in the rotational time correlation function of the O-H bond of the molecule that is visited by the defect (transient transition to the 5-coordinated state). The MSD and the decay of rotational time correlation function, both remain quenched in the absence of any visit by the defect, as postulated by Glarum long time ago. We establish a direct connection between these propagating events and the known thermodynamic and dynamic anomalies in supercooled water. These strings are found largely in the regions that surround the relatively rigid domains of 4-coordinated water molecules. The propagating strings give rise to a noticeable dynamical heterogeneity, quantified here by a sharp rise in the peak of the four-point density response function, χ(4)(t). This dynamics heterogeneity is also responsible for the breakdown of the Stokes-Einstein relation.     

Dielectric losses in the composite cellulose–mineral oil–water nanoparticles: theoretical assumptions

The paper presents an analysis of test results by Frequency Domain Spectroscopy (FDS) of the loss tangent (tgδ) in electrotechnical pressboard impregnated with insulating oil and containing nanoparticles of water depending on the frequency of alternating current, sample temperature and degree of moisture. We found tgδ reduction in areas of low and ultra-low frequency. It is associated with relaxation due to the hopping conductivity (tunnelling) of electrons between moisture nanoparticles occurring in the cellulose impregnated with insulating oil. In frequency areas close to the local minimum of tgδ and higher, relaxation does not depend on the moisture content and is associated with other polar molecules which are part of the cellulose. We developed a new method converting experimental frequency dependence of the loss angle tangent, measured by the FDS method to the reference temperature of 293 K (20 °C), using the exponential dependence of the relaxation time on the temperature, was developed. The activation energy of the relaxation time was determined based on the loss angle tangent of moist electrotechnical pressboard impregnated with insulating oil. It was found that the variation in moisture content in the composite cellulose–mineral oil–water nanoparticles do not cause changes in the activation energy of the relaxation time. The conversion of experimental frequency dependence of the loss angle tangent determined by the FDS method to the reference temperature of 293 K (20 °C) eliminates the temperature dependence in the areas of ultra-low and low frequencies occurring in the runs made directly on the basis of the measurement results. After calculating the frequency dependence of the loss angle tangent to the reference temperature, all that remains is its dependence on the moisture content.     

2H-solid state NMR and DSC study of isobutyric acid in mesoporous silica materials

Solid state deuterium NMR has been used to study the molecular motion of d(6)-isobutyric acid (d(6)-iBA) in the pure (unconfined) state and confined in the cylindrical pores of two periodic mesoporous silica materials (MCM-41, pore size 3.3 nm and SBA-15, pore size 8 nm), and in a controlled pore glass (CPG-10-75, pore size ca. 10 nm). The line shape analysis of the spectra at different temperatures revealed three rotational states of the iBA molecules: liquid (fast anisotropic reorientation of the molecule), solid I (rotation of the methyl group) and solid II (no rotational motion on the time scale of the experiment). Transition temperatures between these states were determined from the temperature dependence of the fraction of molecules in these states. Whereas the solid I-solid II transition temperature is not affected by confinement, a significant lowering of the liquid-solid I transition temperature in the pores relative to the bulk acid was found for the three matrix materials, exhibiting an unusual dependence on pore size and pore morphology. Complementary DSC measurements on the same systems show that the rotational melting (solid I-liquid) of d(6)-iBA in the pores occurs at a temperature 20-45 K below the thermodynamic melting point. This finding indicated that the decoupling of rotational and translational degrees of freedom in phase transitions in confined systems previously found for benzene is not restricted to molecules with non-specific interactions, but represents a more general phenomenon.     

Recent progress in oxide thermoelectric materials: p-type Ca3Co4O9 and n-type SrTiO3(-)

Thermoelectric energy conversion technology to convert waste heat into electricity has received much attention. In addition, metal oxides have recently been considered as thermoelectric power generation materials that can operate at high temperatures on the basis of their potential advantages over heavy metallic alloys in chemical and thermal robustness. We have fabricated high-quality epitaxial films composed of oxide thermoelectric materials that are suitable for clarifying the intrinsic "real" properties. This review focuses on the thermoelectric properties of two representative oxide epitaxial films, p-type Ca 3Co 4O 9 and n-type SrTiO 3, which exhibit the best thermoelectric figures of merit, ZT (= S (2)sigma Tkappa (-1), S = Seebeck coefficient, sigma = electrical conductivity, kappa = thermal conductivity, and T = absolute temperature) among oxide thermoelectric materials reported to date. In addition, we introduce the recently discovered giant S of two-dimensional electrons confined within a unit cell layer thickness ( approximately 0.4 nm) of SrTiO 3.     

Solute rotational dynamics at the water liquid/vapor interface

The rotational dynamics of a number of diatomic molecules adsorbed at different locations at the interface between water and its own vapors are studied using classical molecular dynamics computer simulations. Both equilibrium orientational and energy correlations and nonequilibrium orientational and energy relaxation correlations are calculated. By varying the dipole moment of the molecule and its location, and by comparing the results with those in bulk water, the effects of dielectric and mechanical frictions on reorientation dynamics and on rotational energy relaxation can be studied. It is shown that for nonpolar and weekly polar solutes, the equilibrium orientational relaxation is much slower in the bulk than at the interface. As the solute becomes more polar, the rotation slows down and the surface and bulk dynamics become similar. The energy relaxation (both equilibrium and nonequilibrium) has the opposite trend with the solute dipole (larger dipoles relax faster), but here again the bulk and surface results converge as the solute dipole is increased. It is shown that these behaviors correlate with the peak value of the solvent-solute radial distribution function, which demonstrates the importance of the first hydration shell structure in determining the rotational dynamics and dependence of these dynamics on the solute dipole and location.     

Non-monotonic, distance-dependent relaxation of water in reverse micelles: propagation of surface induced frustration along hydrogen bond networks

Layer-wise, distance-dependent orientational relaxation of water confined in reverse micelles (RM) is studied using theoretical and computational tools. We use both a newly constructed "spins on a ring" (SOR) Ising-type model (with Shore-Zwanzig rotational dynamics) and atomistic simulations with explicit water. Our study explores the effect of reverse micelle size and role of intermolecular correlations, compromised by the presence of a highly polar surface, on the distance (from the interface) dependence of water relaxation. The "spins on a ring" model can capture some aspects of distance dependence of relaxation, such as acceleration of orientational relaxation at intermediate layers. In atomistic simulations, layer-wise decomposition of hydrogen bond formation pattern clearly reveals that hydrogen bond arrangement of water at a certain distance away from the surface can remain frustrated due to the interaction with the polar surface head groups. This layer-wise analysis also reveals the presence of a non-monotonic slow relaxation component which can be attributed to this frustration effect and which is accentuated in small to intermediate size RMs. For large size RMs, the long time component decreases monotonically from the interface to the interior of the RMs with slowest relaxation observed at the interface.     

NMR relaxation of rigid molecules in the nematic phase of a discotic liquid crystal

Frequency and temperature dependent NMR relaxation measurements were performed on deuteriated benzene, pyrene and triphenylene dissolved in the nematic phase of a discotic liquid crystal. The results show a strong frequency dependence of the spectral densities. Based on the symmetries of the system and the usual model for director fluctuations this frequency dependence should be equal for J₁ and J₂. From fitting the commonly used model of rotational diffusion and director fluctuations to the data we see that this is not the case for benzene and triphenylene, even though the fits themselves are satisfactory. Values for the elastic constants, effective viscosity and translational diffusion in similar discotic liquid crystals do not account quantitatively for the frequency dependence of benzene. For both pyrene and triphenylene quantitative comparison was impossible due to lack of translational diffusion data. We also find that the so-called cut-off wave-length is of the order of the dimensions of the liquid crystal molecules, just as in ordinary nematics.     

On the molecular mobility in amorphous polymers, inorganic glasses, and amorphous metal alloys in the glass transition range

The transition of kinetic units (atoms or groups of atoms) in amorphous media from one quasi-equilibrium state to another is determined by fluctuations of both energy and entropy of the system. In the glass transition range of liquids and polymers, the entropic mechanism plays a determining role: the fluctuation of packing of particles turns out to be more important than accumulation of energy. Above the glass transition range, the energy mechanism begins to play a dominant role. The procedure that is currently used to calculate the constant for the Bartenev equation, which relates the relaxation time to the cooling rate at the glass transition temperature, leads to overestimated values. A procedure for the calculation of this parameter was proposed with allowance for the temperature dependence of the entropy of activation in the region of the liquid-glass transition. The use of this equation in the relaxation spectrometry of amorphous polymers, inorganic glasses, and amorphous metal alloys is discussed.