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In this quasielastic neutron scattering (QENS) study we have investigated the relation between protein and solvent dynamics. Myoglobin in different water:glycerol mixtures has been studied in the temperature range of 260–320 K. In order to distinguish between solvent and protein dynamics we have measured protonated as well as partly deuterated samples. As commonly observed for bulk as well as for confined water, the dynamics of the surrounding solvent is well described by a jump diffusion model. The intermediate scattering function I(Q,t) from the protein (partly deuterated samples) was analyzed by fitting a single Kohlrausch–Williams–Watts (KWW) stretched exponential function to the data. However, due to the limited experimental time window, two different curve fitting approaches were used. The first one was performed with the assumption that I(Q,t) decays to zero at long times, i.e., it was assumed that all protein relaxations that are observed on the experimental time scale, as well as would be observed on longer time scales, can be described by a single KWW function. In the second approach we instead assumed that both the protein relaxation time τp and the stretching parameter βKWW were Q-independent, i.e., we assumed that the protein dynamics is dominated by more local motions. Advantages and disadvantages of both approaches are discussed. The first approach appears to work best at higher Q-values, indicating a power law relation of the Q-dependent protein dynamics for all samples and temperatures, whereas the second approach seems to work at lower Q-values, where the expected confined diffusion of hydrogen atoms in the protein gives the assumed Q-independent relaxation time. Independent of the chosen approach we find a significant correlation between the average relaxation time of the protein and the diffusion constant (or in this case the related relaxation time) of the solvent. However, the correlation is not perfect since the average relaxation time of the protein is more strongly dependent on the total amount of solvent than the diffusion constant of the solvent itself. Thus, the average relaxation time of the protein decreases not only with increasing solvent mobility, but also with increasing solvent content. [ABSTRACT FROM AUTHOR]

We have used dielectric spectroscopy and temperature modulated differential scanning calorimetry (TMDSC) to investigate the structural relaxation processes and phase transitions of water and lipids in multilamellar, planar phospholipids. At low hydration levels we observe the main structural relaxation related to the glass transition of the phospholipids. With increasing water content a more pronounced pretransition, attributed to a gel to ripple phase transition, is observed in the TMDSC data. In the proximity of this pretransition, a distinct change in the temperature dependence or alternatively a bifurcation into two processes is observed in the dielectric data. Around this temperature a crossover in the long-range ionic conductivity across the membranes is also observed, which is one of the key parameters for biological membranes. Thus, the major dynamical changes do not occur at the main, i.e., the gel to liquid structural phase transition, but at a pretransition that occurs roughly 20 K below the main transition. [ABSTRACT FROM AUTHOR]

The microscopic dynamics of the planar, multilamellar lipid bilayer system 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) has been investigated using quasielastic neutron scattering. The DMPC was hydrated to a level corresponding to approximately nine water molecules per lipid molecule. Selective deuteration has been used to separately extract the dynamics of the water, the acyl chains, and the polar head groups from the strong incoherent scattering of the remaining hydrogen atoms. Furthermore, the motions parallel and perpendicular to the bilayers were probed by using two different sample orientations relative to the incident neutron beam. For both sample orientations, the results showed an onset of water motions at 260 K on the experimental time scale of about 100 ps. From lack of wave-vector dependence of the onset temperature for water motions, it is evident that the observed water dynamics is of mainly rotational character at such low temperatures. At 290 K, i.e., slightly below the gel-to-liquid transition around 295 K, the nature of the water dynamics had changed to a more translational character, well described by a jump-diffusion model. On the limited experimental time and length (about 10 Å) scales, this jump-diffusion process was isotropic, despite the very anisotropic system. The acyl chains exhibited a weak onset of anharmonic motions already at 120 K, probably due to conformational changes (trans-gauche and/or syn-anti) in the plane of the lipid bilayers. Other anharmonic motions were not observed on the experimental time scale until temperature had been reached above the gel-to-liquid transition around 295 K, where the acyl chains start to show more substantial motions. [ABSTRACT FROM AUTHOR]

We have investigated the dynamical behavior of both the protein hemoglobin and its surrounding water during the denaturation process using modulated temperature differential scanning calorimetry, quasielastic neutron scattering, and frequency dependent conductivity measurements. To distinguish between the scattering from the protein and its surrounding water, neutron scattering measurements were performed on both a fully hydrogenated sample as well as a sample where the water and the exchangeable hydrogen atoms on the protein surface were deuterated. The experimental data show that the unfolding and aggregation processes are substantially overlapping in temperature. The unfolding process occurs in the approximate temperature range of 315–345 K, whereas the aggregation process starts around 330–335 K and is completed at 360 K. Furthermore, the results suggest that the secondary structure of the protein unfolds at about 325 K, and that this leads to an increased number of water molecule hydrogen bonded to the protein. Thus, the unfolding of the secondary structure reduces the number of mobile (on the experimental time scale of about 50–100 ps) water molecules. In contrast, the aggregation of protein molecules seems to have a minor effect on the dynamics of its surrounding water. In the case of the protein dynamics there are competing effects from unfolding and aggregation. The unfolding process increases the flexibility of the protein, whereas the initial aggregation reduces its dynamics. The conductivity seems to be negatively affected by both reduced water mobility and an aggregation of protein molecules. [ABSTRACT FROM AUTHOR]

The relaxation dynamics of dipropylene glycol and tripropylene glycol (nPG—n=2,3) water solutions on the nPG-rich side has been studied by broadband dielectric spectroscopy and differential scanning calorimetry in the temperature range of 130–280 K. Two relaxation processes are observed for all the hydration levels; the slower process (I) is related to the α relaxation of the solution whereas the faster one (II) is associated with the reorientation of water molecules in the mixture. Dielectric data for process (II) at temperatures between 150 and 200 K indicate the existence of a critical water concentration (xc) below which water mobility is highly restricted. Below xc, nPG-water domains drive the dielectric signal whereas above xc, water-water domains dominate the dielectric response at low temperatures. The results also show that process (II) at low temperatures is due to local motions of water molecules in the glassy frozen matrix. Additionally, we will show that the glass transition temperatures (Tg) for aqueous PG, 2PG, and 3PG solutions do not extrapolate to ∼136 K, regardless of the extrapolation method. Instead, we find that the extrapolated Tg value for water from these solutions lies in the neighborhood of 165 K. [ABSTRACT FROM AUTHOR]

The dynamics of propylene glycol (PG) and its oligomers 7-PG and poly-propylene glycol (PPG), with Mw=4000 (≈70 monomers), confined in a Na–vermiculite clay have been investigated by quasielastic neutron scattering. The liquids are confined to single molecular layers between clay platelets, giving a true two-dimensional liquid. Data from three different spectrometers of different resolutions were Fourier transformed to S(Q,t) and combined to give an extended dynamical time range of 0.3–2000 ps. An attempt was made to distinguish the diffusive motion from the methyl group rotation and a fast local motion of hydrogen in the polymer backbone. The results show that the average relaxation time 〈τd〉 of this diffusive process is, as expected, larger than the relaxation time 〈τ〉 averaged over all dynamical processes observed in the experimental time window. More interesting, it is evident that the severe confinement has a relatively small effect on 〈τd〉 at T=300 K, this holds particularly for the longest oligomer, PPG. The most significant difference is that the chain-length dependence of 〈τd〉 is weaker for the confined liquids, although the slowing down in bulk PG due to the formation of a three-dimensional network of OH-bonded end groups reduces this difference. The estimated average relaxation time 〈τ〉 at Q=0.92 Å-1 for all the observed processes is in excellent agreement with the previously reported dielectric α relaxation time in the studied temperature range of 260–380 K. The average relaxation time 〈τ〉 (as well as the dielectric α relaxation time) is also almost unaffected by the confinement to a single molecular layer, suggesting that the interaction with the clay surfaces is weak and that the reduced dimensionality has only a weak influence on the time scale of all the dynamical processes observed in this study. [ABSTRACT FROM AUTHOR]

A quasielastic neutron scattering study has been performed on a polymer gel electrolyte consisting of lithium perchlorate dissolved in ethylene carbonate/propylene carbonate and stabilized with poly(methyl methacrylate). The dynamics of the solvent, which is crucial for the ion conduction in this system, was probed using the hydrogen/deuterium contrast variation method with nondeuterated solvent and a deuterated polymer matrix. Two relaxation processes of the solvent were studied in the 10–400 μeV range at different temperatures. From analysis of the momentum transfer dependence of the processes we conclude that the faster process (∼100 μeV) is related to rotational diffusion of the solvent and the slower process (∼10 μeV) to translational diffusion of the solvent. The translational diffusion is found to be similar to the diffusion in the corresponding liquid electrolyte at short distances, but geometrically constrained by the polymer matrix at distances beyond ∼5 Å. The study indicates that the hindered diffusion of the solvent on a length scale of the polymer network interchain distance (∼5–20 Å) is sufficient to explain the reduced macroscopic diffusivity and ion conductivity of the gel electrolyte compared to the liquid electrolyte. [ABSTRACT FROM AUTHOR]

We have investigated the dynamics of water confined in a molecular sieve, with a cylindrical pore diameter of 10 Å, by means of quasielastic neutron scattering (QENS). Both the incoherent and coherent intermediate scattering functions I(Q,t) were determined by time-of-flight QENS and the neutron spin-echo technique, respectively. The results show that I(Q,t) is considerably more stretched in time with a slightly larger average relaxation time in the case of coherent scattering. From the Q dependence of I(Q,t) it is clear that the observed dynamics is almost of an ordinary translational nature. A comparison with previous dielectric measurements suggests a possible merging of the α and β relaxations of the confined water at T=185 K, although the α relaxation cannot be directly observed at lower temperatures due to the severe confinement. The present results are discussed in relation to previous results for water confined in a Na-vermiculite clay, where the average relaxation time from spin-echo measurements was found to be slower than in the present system (particularly at low temperatures). [ABSTRACT FROM AUTHOR]

The structure of an amorphous polymer electrolyte, poly(propylene oxide) (PPO) complexed with LiClO4, has been studied using reverse Monte Carlo (RMC) simulations. The simulations require no force field but are based on experimental data only, in this case from x-ray and neutron diffraction experiments. Excellent agreement between the experimental data and the structures resulting from the RMC simulation is obtained. Samples with ether-oxygen to lithium concentrations (molar ratios) O:Li=16:1 and 5:1 were studied and compared to results of pure PPO from a previous study. We focus on the effects of the solvated salt on the structure of the polymer matrix, the spatial distribution of ions, and the correlations between the anions and the polymer chains. Analyzing the structures produced in the simulations, we find that for a concentration 16:1, the interchain distance is approximately the same as in pure PPO but more well defined. For a concentration 5:1, we find a larger and less well-defined interchain distance compared to the 16:1 concentration. This signifies that at the 16:1 salt concentration, there is enough free volume in the polymer host to accommodate the ions, and that the solvation of salt induces ordering of the polymer matrix. At the higher salt concentration 5:1, the polymer network must expand and become less ordered to host the ions. We also note, in accordance with previous studies, that the solvation of salt changes the conformation of the polymer chain towards more gauche states. The simulations furthermore reveal marked correlations between the polymer chains and the anions, which we suggest arise predominantly from an interaction mediated via cations, which can simultaneously coordinate both ether oxygens in the polymer chains and anions. Interanionic distances at 5 Å, which are consistent with two or more anions being coordinated around the same cation, are also observed. On a larger scale, the RMC structure of PPO-LiClO4 16:1 clearly indicates the presence of salt-rich and salt-depleted domains having a length scale of <20 Å. In view of such a heterogeneous structure of PPO-LiClO4 16:1, it is plausible that the increased ordering of the polymer matrix is due to rather well-defined structural arrangements within the salt-rich domains, and that the characteristic interchain distance in the salt-rich domains is similar to that of the pure polymer.© 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The microscopic polymer dynamics in nanocomposite polymer electrolytes has been investigated using quasielastic neutron scattering experiments. Four samples based on the fully amorphous copolymer trihydroxy poly(ethylene oxide-co-propylene oxide) (3PEG) were investigated: 3PEG, 3PEG 1.5 mol/kg LiClO[sub 4], 3PEG 1.5 mol/kg LiClO[sub 4] 10 wt % TiO[sub 2], and 3PEG 1.5 mol/kg LiClO[sub 4] 20 wt % TiO[sub 2]. In addition to a slow relaxation giving rise to elastic scattering, at least two dynamical processes were observed: a fast, local chain motion and a slower diffusive segmental motion. No changes of the quasielastic peak widths could be observed between the filled or unfilled composites; however, the elastic scattering of the sample was found to increase upon addition of the filler to the polymer electrolyte. The results indicate the presence of a roughly 5-nm-thick immobilized polymer layer (∼5 vol %) around filler particles, while the dynamics of the bulk polymer (∼95 vol %) is not influenced by the filler. The results imply that the ionic conductivity increase observed in the nanocomposite polymer electrolyte cannot be attributed to enhanced polymer dynamics. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The dynamics of propylene glycol (PG) and its 7-mer confined in a Na-vermiculite clay have been investigated by quasielastic neutron scattering. Experiments were carried out in the temperature range 300-420 K and in two different scattering geometries in order to make the elastic Q-vector parallel and perpendicular to the clay platelets for a scattering angle of 90° (Q≈1.33 Å[sup -1]). The results indicate that at least three dynamical processes are present in the experimental time window of approximately 3-80 ps, although only two processes could be resolved at a given temperature. The fast process is independent of the chain length as well as the confinement, and in accordance with previous studies of the bulk liquids it is assigned to a rapid local motion of hydrogens in the polymeric backbone. The slow process has mainly a rotational character at T = 300 K and it is assigned to the methyl group rotation. At higher temperatures this rotational motion is hidden behind a Q-dependent jump diffusion process. The calculated diffusion constant is roughly the same for our confined PG and 7-PG, and also similar to the corresponding bulk liquids (except for PG at high temperatures where the bulk liquid shows a considerably faster diffusion). However, the diffusion seems to increase slightly faster for confined 7-PG with increasing temperature. This is an interesting finding since a clear opposite trend was observed for the bulk liquids. The methyl group rotation at low temperatures (≈300 K) is significantly faster in the confined liquids. Both the methyl group rotation and the jump diffusion process seem to be present also in the direction perpendicular to the clay platelets for the 7-mers, but not for the monomers where only the fast local motion of hydrogens is observed in that direction. Furthermore, the pure translational diffusion (with a quasielastic broadening proportional to Q²) observed for the bulk liquids was never obtained for... [ABSTRACT FROM AUTHOR]

The dynamics of propylene glycol (PG) and its 7-mer have been investigated by quasielastic neutron scattering (QENS). In the case of PG we used two techniques; ordinary QENS and neutron spin-echo (NSE). The QENS and NSE experiments were carried out at the temperature ranges 300-420 K and 260-340 K, respectively. The QENS results on both the monomer and the 7-mer showed three clear dynamical processes; a weakly temperature dependent fast local motion of hydrogens in the polymeric backbone, an almost temperature independent rotational motion of the methyl groups, and a strongly temperature dependent translational process. This latter motion exhibits a clear quasi-elastic broadening proportional to Q² at high temperatures (T≥380 K). At lower temperatures the diffusion becomes more difficult to characterize due to the contribution from the methyl group rotation. However, despite this difficulty it is no doubt about that the diffusion is faster for the 7-mers than for the monomers at low temperatures (T≤340 K). The reason for this anomalous behavior may be that the OH end groups of the monomers are linked together to a network at lower temperatures, which would slow down the translational diffusion. Another possible explanation can be that the dynamics of the 7-mers is dominated by segmental motions, which might be faster than the translational diffusion of single monomers at low temperatures. The NSE data on deuterated PG were described by the Kohlrausch-Williams-Watts (KWW) stretched exponential function, with a temperature independent stetching parameter/βKWW. The reason for the stretched behavior of the coherent intermediate scattering function I(Q,t) is most likely that several dynamical processes, such as the primary a-relaxation and secondary β-relaxations, are observed in the experimental time window (3-1500 ps), in accordance with the QENS results given above. An interesting observation is that the dynamics is slowest and the stetching... [ABSTRACT FROM AUTHOR]

We have investigated the dynamics of confined water in a fully hydrated Na-vermiculite clay using the neutron spin-echo (NSE) technique. NSE measures the intermediate self-scattering function, i.e., the dynamics directly in the time domain. In the present experiments we performed measurements, in the time range 3-3000 ps and temperature ranging from 254 to 323 K, on the essentially two-dimensional water with a layer thickness corresponding to only two molecular layers. The data can be described by the Kohlrausch-Williams-Watts (KWW) stretched exponential function, probably indicating a broad distribution of relaxation times. The reason for the very stretched behavior of the intermediate self-scattering function I[sub S](Q, t), particularly in the supercooled regime, is most likely that the water molecules have widely different local environments. Some water molecules are strongly interacting with the clay surfaces or the intercalated Na[sup +] ions, whereas the remaining molecules are interacting only with other water molecules. The average relaxation time for the dynamics observed in the experimental time window shows a pronounced non-Arrhenius temperature dependence, typical for the main relaxation of a “fragile” liquid, and a Q-dependence in reasonable agreement with the Gaussian jump-length distribution model for translational diffusion. The high temperature non-Arrhenius behavior of the relaxation time is in contrast to previous low temperature (125-215 K) dielectric results showing an Arrhenius temperature behavior, typical for a “strong” liquid. Although the NSE and dielectric data are not probing exactly the same water dynamics, the combined results suggests that our confined water undergoes a “fragile-strong” transition somewhere in the temperature range of 215-250 K. © 2001 American Institute of Physics. [DOI: 10.1063/1.1420728]. [ABSTRACT FROM AUTHOR]

Investigates the interlayer polymer structure of a four-component clay-polymer-salt-water system. Suitability of the system in the study of colloids; Part of the polymer chains directly bound to clay surfaces; Gaussian-like distribution of polymer segments; Displacement of water molecules by ethylene oxide segments.

Examines the structural characteristics of poly(propylene oxide) through neutron and x-ray diffraction experiments and reverse Monte Carlo simulation. Notation of neutron and x-ray diffraction; Details on the reverse Monte Carlo simulation; Analysis of chain conformation and interchain correlation.

In our recent article [R. Bergman et al., J. Chem. Phys. 132, 044504 (2010)] we investigated some polyalcohols, i.e., glycerol, xylitol, and sorbitol by dielectric spectroscopy. In the study, a low-frequency peak of Debye character that normally is hidden by the large low-frequency dispersion due to conductivity was revealed by analyzing the real part of the permittivity and by using a thin Teflon film to suppress the low-frequency dispersion. We agree with the comment by Paluch et al. [J. Chem. Phys. 134, 037101 (2011)] that the Teflon film setup will indeed create a peak due to the dc conductivity. However, due to the fact that the location of the peak was almost identical in measurement with and without Teflon, we unfortunately mainly showed the data measured with Teflon, despite that it could also be observed in the real part of the permittivity without using the Teflon setup, as shown in our original article [R. Bergman et al., J. Chem. Phys. 132, 044504 (2010)]. Here, we show that the low-frequency peak of Debye character can also be observed by subtracting the dc conductivity. Furthermore, we show that the modulus representation used in Paluch et al. [J. Chem. Phys. 134, 037101 (2011).] is also not suitable for detecting processes hidden by the conductivity. [ABSTRACT FROM AUTHOR]

In the foregoing Comment by Dyer [J. Chem. Phys.125, 077101 (2006)], it is claimed that the structure of our molecular sieve is identical to that of faujasite. However, this is not the case for the commercially produced molecular sieve 13X, as we used in our study. Therefore, we still have no reason to believe that we have provided incorrect information regarding the structure of the sample we used in our study. [ABSTRACT FROM AUTHOR]

© 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

A well-characterized Na-vermiculite clay, containing zero, one, or two molecular layers of water between the clay platelets, has been studied by quasielastic neutron scattering (QENS). Experiments were carried out at a temperature of 300 K in two different scattering geometries; the clay platelets being at 45 and 135° angles to the incident beam in order to make the elastic Q-vector perpendicular and parallel, respectively, to the clay platelets for a scattering angle of 90° (Qapprox. 1.33 Å[sup -1]). The resulting QENS spectra show that almost no hydrogen motion occurs perpendicular to the clay platelets on the experimental time scale (about 2-40 ps). The two-H[sub 2]O layer vermiculite exhibits a planar rotational motion of water molecules, forming hydration shells around the Na ions, and a basically two-dimensional translational jump-diffusion motion. The translational motion was modeled using the Gaussian jump-length distribution model, resulting in a mean jump length of 1.1 Å and an average residence time of 2.3 ps. Using these values we obtain an effective diffusion coefficient of 8.8[sup *]10[sup -10] m[sup 2]/s, which is only a factor 2-3 lower than for bulk water. The correlation time of the rotational motion was estimated to approximately 27 ps. In the case of the one-H[sub 2]O layer vermiculite we were only able to observe a planar rotational motion with a rotational correlation time of 16 ps, i.e., faster than in the two-H[sub 2]O layer vermiculite. This suggests that a smaller number of water molecules are involved in the rotational process in the one-H[sub 2]O layer vermiculite, and furthermore that the translational motion, if existent, is too slow to be observed on the experimental time scale. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We report results of dielectric spectroscopy on water confined in a two-dimensional layer-structured Na-vermiculite clay. Several relaxation processes of different origin can be discerned in the spectra. A strong dielectric loss peak is observed in the clay with two layers of water molecules between the rigid clay platelets at temperatures between 125 and 215 K. This loss peak is neither observed in bulk ice, nor in the dry clay or clay with only one water layer between platelets. The relaxation time is shown to have an Arrhenius temperature dependence which does not extrapolate to the high-temperature behavior. This behavior is in accordance with the proposed so-called "fragile-strong" transition of supercooled bulk water, which implies a change in the temperature dependence of the relaxation time from a high-temperature non-Arrhenius to low-temperature Arrhenius behavior. However, this transition is experimentally elusive as it would occur in an inaccessible (due to the ease of crystallization) temperature range of the supercooled bulk water. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]

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.

It is well-accepted that hydration water is crucial for the structure, dynamics, and function of proteins. However, the exact role of water for the motions and functions of proteins is still debated. Experiments have shown that protein and water dynamics are strongly coupled but with water motions occurring on a considerably faster time scale (the so-called slaving behavior). On the other hand, water also reduces the conformational entropy of proteins and thereby acts as a plasticizer of them. In this work, we analyze the dynamics (using broadband dielectric spectroscopy) of some specific non-biological water solutions in a broad concentration range to elucidate the role of water in the dynamics of the solutes. Our results demonstrate that at low water concentrations (less than 5 wt. %), the plasticization phenomenon prevails for all the materials analyzed. However, at higher water concentrations, two different scenarios can be observed: the slaving phenomenon or plasticization, depending on the solute analyzed. These results generalize the slaving phenomenon to some, but not all, non-biological solutions and allow us to analyze the key factors for observing the slaving behavior in protein solutions as well as to reshaping the slaving concept.

The molecular dynamics of solutions of di-propylene glycol methylether (2PGME) and H2O (or D2O) confined in 28 Å pores of MCM-41 have been studied by quasielastic neutron scattering and differential scanning calorimetry over the concentration range 0-90 wt.% water. This system is of particular interest due to its pronounced non-monotonic concentration dependent dynamics of 2PGME in the corresponding bulk system, showing the important role of hydrogen bonding for the dynamics. In this study we have elucidated how this non-monotonic concentration dependence is affected by the confined geometry. The results show that this behaviour is maintained in the confinement, but the slowest diffusive dynamics of 2PGME is now observed at a considerably higher water concentration; at 75 wt.% water in MCM-41 compared to 30 wt.% water in the corresponding bulk system. This difference can be explained by an improper mixing of the two confined liquids. The results suggest that water up to a concentration of about 20 wt.% is used to hydrate the hydrophilic hydroxyl surface groups of the silica pores, and that it is only at higher water contents the water becomes partly mixed with 2PGME. Hence, due to this partial micro-phase separation of the two liquids larger, and thereby slower relaxing, structural entities of hydrogen bonded water and 2PGME molecules can only be formed at higher water contents than in the bulk system. However, the Q-dependence is unchanged with confinement, showing that the nature of the molecular motions is preserved. Thus, there is no indication of localization of the dynamics at length scales of less than 20 Å. The dynamics of both water and 2PGME is strongly dominated by translational diffusion at a temperature of 280 K.

The molecular dynamics of aqueous solutions of propylene glycol (PG) and propylene glycol methylether (PGME) confined in a two-dimensional layer-structured Na-vermiculite clay has been studied by broadband dielectric spectroscopy and differential scanning calorimetry. As typical for liquids in confined geometries the intensity of the cooperative α-relaxation becomes considerably more suppressed than the more local β-like relaxation processes. In fact, at high water contents the calorimetric glass transition and related structural α-relaxation cannot even be observed, due to the confinement. Thus, the intensity of the viscosity related α-relaxation is dramatically reduced, but its time scale as well as the related glass transition temperature Tg are for both systems only weakly influenced by the confinement. In the case of the PGME-water solutions it is an important finding since in the corresponding bulk system a pronounced non-monotonic concentration dependence of the glass transition related dynamics has been observed due to the growth of hydrogen bonded relaxing entities of water bridging between PGME molecules [J. Sjöström, J. Mattsson, R. Bergman, and J. Swenson, Phys. Chem. B 115, 10013 (2011)]. The present results suggest that the same type of structural entities are formed in the quasi-two-dimensional space between the clay platelets. It is also observed that the main water relaxation cannot be distinguished from the β-relaxation of PG or PGME in the concentration range up to intermediate water contents. This suggests that these two processes are coupled and that the water molecules affect the time scale of the β-relaxation. However, this is most likely true also for the corresponding bulk solutions, which exhibit similar time scales of this combined relaxation process below Tg. Finally, it is found that at higher water contents the water relaxation does not merge with, or follow, the α-relaxation above Tg, but instead crosses the α-relaxation, indicating that the two relaxation processes are independent of each other. This can only occur if the two processes do not occur in the same parts of the confined solutions. Most likely the hydration shell of the interlayer Na(+) ions is causing this water relaxation, which does not participate in the α-relaxation at any temperature.

The structure of liquid 1-propanol is investigated as a function of temperature using neutron diffraction together with Empirical Potential Structure Refinement modelling. The combined diffraction and computer modelling analysis demonstrates that propanol molecules form hydrogen bonded clusters with a relatively wide size distribution, which broadens at lower temperatures. We find that the cluster size distribution is well described by a recently proposed statistical model for branched H-bonded networks [P. Sillrén, J. Bielecki, J. Mattsson, L. Börjesson, and A. Matic, J. Chem. Phys. 136, 094514 (2012)]. The average cluster size increases from ~3 to 7 molecules, whilst the standard deviation of the size distribution increases from 3.3 to 8.5 as the temperature is decreased from 293 to 155 K. The clusters are slightly branched, with a higher degree of branching towards lower temperatures. An analysis of the cluster gyration tensor (R(mn)) reveals an average elongated ellipsoidal shape with axes having proportions 1:1.4:1.9. We find that the average radius of gyration has a cluster size dependence consistent with that of fractal clusters, R(g) ∝ n(1/D), with a fractal dimension D ≈ 2.20, which is close to D = 2.00 expected for an ideal random walk or D = 2.11 expected for reaction limited aggregation. The characteristic angles between the H-bonded OH-groups that constitute the clusters show only a weak temperature dependence with O-H···O angles becoming more narrowly distributed around 180° at lower temperatures.

We present the first broadband dielectric spectroscopy (BDS) and differential scanning calorimetry study of supercooled xylitol-water mixtures in the whole concentration range and in wide frequency (10(-2)-10(6) Hz) and temperature (120-365 K) ranges. The calorimetric glass transition, T(g), decreases from 247 K for pure xylitol to about 181 K at a water concentration of approximately 37 wt. %. At water concentrations in the range 29-35 wt. % a plentiful calorimetric behaviour is observed. In addition to the glass transition, almost simultaneous crystallization and melting events occurring around 230-240 K. At higher water concentrations ice is formed during cooling and the glass transition temperature increases to a steady value of about 200 K for all higher water concentrations. This T(g) corresponds to an unfrozen xylitol-water solution containing 20 wt. % water. In addition to the true glass transition we also observed a glass transition-like feature at 220 K for all the ice containing samples. However, this feature is more likely due to ice dissolution [A. Inaba and O. Andersson, Thermochim. Acta, 461, 44 (2007)]. In the case of the BDS measurements the presence of water clearly has an effect on both the cooperative α-relaxation and the secondary β-relaxation. The α-relaxation shows a non-Arrhenius temperature dependence and becomes faster with increasing concentration of water. The fragility of the solutions, determined by the temperature dependence of the α-relaxation close to the dynamic glass transition, decreases with increasing water content up to about 26 wt. % water, where ice starts to form. This decrease in fragility with increasing water content is most likely caused by the increasing density of hydrogen bonds, forming a network-like structure in the deeply supercooled regime. The intensity of the secondary β-relaxation of xylitol decreases noticeably already at a water content of 2 wt. %, and at a water content above 5 wt. % it has been replaced by a considerably stronger water (w) relaxation at about the same frequency. However, the similarities in time scale and activation energy between the w-relaxation and the β-relaxation of xylitol at water contents below 13 wt. % suggest that the w-relaxation is governed, in some way, by the β-relaxation of xylitol, since clusters of water molecules are rare at these water concentrations. At higher water concentrations the intensity and relaxation rate of the w-relaxation increase rapidly with increasing water content (up to the concentration where ice starts to form), most likely due to a rapid increase of small water clusters where an increasing number of water molecules interacting with other water molecules.

Broadband dielectric relaxation measurements have been performed on monoalcohols confined in the quasi-two-dimensional space between clay platelets and the quasi-one-dimensional pores of approximately 10 Å diameter in a molecular sieve. Interestingly, the results show that the slow Debye-like process is present even in these severe confinements, proving that structural models that are based on two-dimensional or three-dimensional cluster formations as the structural origin of the Debye-like process can be excluded. Rather, the insensitivity of its time-scale to confinements suggests that it is of local character and in some way related to the lifetime or breaking and reformation of hydrogen bonds.

The hydrogen (H-) bonding interplay between water and other organic molecules is important both in nature and in a wide range of technological applications. Structural relaxation and, thus, diffusion in aqueous mixtures are generally dependent on both the strength and the structure of the H-bonds. To investigate diffusion in H-bonding mixtures, we present a quasielastic neutron scattering study of di-propylene glycol methylether (2PGME) mixed with H(2)O (or D(2)O) over the concentration range 0-90 wt.% water. We observe a nonmonotonic behavior of the dynamics with a maximum in average relaxation time for the mixture with 30 wt.% water, which is more than a factor 2 larger compared to that of either of the pure constituents. This is a result in qualitative agreement with previous calorimetric studies and the behavior of aqueous mixtures of simple mono-alcohols. More surprisingly, we notice that the dynamics of the 2PGME molecules in the mixture is slowed down by more than a factor 3 at 30 wt.% water but that the water dynamics indicates an almost monotonous behavior. Furthermore, in the low momentum transfer (Q) range of the 2PGME, where the intermediate scattering function I(Q,t) is considerably stretched in time (i.e., the stretching parameter β ≪ 1), it is evident for the 2PGME-D(2)O samples that the Q-dependence of the inverse average relaxation time, <τ>(-1), is greater than 2. This implies that the relaxation dynamics is partly homogenously stretched, i.e., the relaxation of each relaxing unit is somewhat intrinsically stretched in time.

Dielectric relaxation spectroscopy of glass forming liquids normally exhibits a relaxation scenario that seems to be surprisingly general. However, the relaxation dynamics is more complicated for hydrogen bonded liquids. For instance, the dielectric response of monoalcohols is dominated by a mysterious Debye-like process at lower frequencies than the structural alpha-relaxation that is normally dominating the spectra of glass formers. For polyalcohols this process has been thought to be absent or possibly obscured by a strong contribution from conductivity and polarization effects at low frequencies. We here show that the Debye-like process, although much less prominent, is also present in the response of polyalcohols. It can be observed in the derivative of the real part of the susceptibility or directly in the imaginary part if the conductivity contribution is reduced by covering the upper electrode with a thin Teflon layer. We report on results from broadband dielectric spectroscopy studies of several polyalcohols: glycerol, xylitol, and sorbitol. The findings are discussed in relation to other experimental observations of ultraslow (i.e., slower than the viscosity related alpha-relaxation) dynamics in glass formers.

Due to the widespread importance of water and the difficulty to study it in the so-called no man's land between 150 and 235 K, deeply supercooled bulk water is currently heavily debated. It speculates about its properties from extrapolations of experimental data on bulk water above 235 K and below 150 K, computer simulations, and experiments on confined water for which the finite size effects may prevent crystallization in the no man's land. However, it is far from obvious how experimental data on bulk water should be extrapolated to the temperature range of the no man's land or how relevant results from computer simulations and studies of confined water are for bulk water. In this paper the structural and dynamical properties of supercooled bulk water are tried to be understood from experimental results on confined water and comparisons with bulk water. We propose that a similar crossover from a high temperature alpha-relaxation to a low temperature beta-relaxation occurs also for bulk water but at a higher temperature than for confined water due to the larger average number of hydrogen bonds between the water molecules in bulk water. In the case of bulk water the crossover is expected to occur around the critical temperature T(s) approximately 228 K when the buildup of an icelike tetrahedral network structure is completed. The proposed interpretation is the simplest one that is able to explain many of the peculiar properties of supercooled water.

We use the reverse Monte Carlo modeling technique to fit two extreme structure models for water to available x-ray and neutron diffraction data in q space as well as to the electric field distribution as a representation of the OH stretch Raman spectrum of dilue HOD in D(2)O; the internal geometries were fitted to a quantum distribution. Forcing the fit to maximize the number of hydrogen (H) bonds results in a tetrahedral model with 74% double H-bond donors (DD) and 21% single donors (SD). Maximizing instead the number of SD species gives 81% SD and 18% DD, while still reproducing the experimental data and losing only 0.7-1.8 kJ/mole interaction energy. By decomposing the simulated Raman spectrum we can relate the models to the observed ultrafast frequency shifts in recent pump-probe measurements. Within the tetrahedral DD structure model the assumed connection between spectrum position and H-bonding indicates ultrafast dynamics in terms of breaking and reforming H bonds while in the strongly distorted model the observed frequency shifts do not necessarily imply H-bond changes. Both pictures are equally valid based on present diffraction and vibrational experimental data. There is thus no strict proof of tetrahedral water based on these data. We also note that the tetrahedral structure model must, to fit diffraction data, be less structured than most models obtained from molecular dynamics simulations.

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.

The molecular dynamics of oligomeric poly(propylene glycol) (PPG) liquids (MW=1000, 2000, and 4000 g/mol) confined in a two-dimensional layer-structured Na-vermiculite clay has been studied by broadband dielectric spectroscopy. The alpha-relaxation and the normal mode relaxation processes were studied for all samples in bulk and confinement. The most prominent experimental observation was that for the normal mode process: the relaxation rate in the clay is drastically shifted to lower frequencies compared to that of the bulk material. This slowing down is probably caused by the strongly reduced number of accessible chain conformations in two dimensions. Also the temperature dependence of the relaxation time for the normal mode process is strongly affected by the confinement. In contrast, for the alpha-relaxation of the confined polymers we observed only a slight increase of the relaxation rate at high temperatures compared to the corresponding bulk samples, and a decrease of its relaxation strength relative to the beta relaxation. Thus, the glass transition is unaffected by the 2D confinement, suggesting that the underlying phenomena responsible for the glass transition is the same as in bulk. Moreover, in the clay the intensity of the normal mode is stronger than that of the alpha-process, in contrast to the bulk samples where the opposite behavior is observed., ((c) 2004 American Institute of Physics)