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Trehalose-glycerol mixtures are known to be effective in the long time preservation of proteins. However, the microscopic mechanism of their effective preservation abilities remains unclear. In this article we present a molecular dynamics simulation study of the short time, less than 1 ns, dynamics of four trehalose-glycerol mixtures at temperatures below the glass transition temperature. We found that a mixture of 5% glycerol and 95% trehalose has the most suppressed short time dynamics (fast dynamics). This result agrees with the experimental analysis of the mean-square displacement of the hydrogen atoms, as measured via neutron scattering, and correlates with the experimentally observed enhancement of the stability of some enzymes at this particular concentration. Our microscopic analysis suggests that the formation of a robust intermolecular hydrogen bonding network is most effective at this concentration and is the main mechanism for the suppression of the fast dynamics.

The transport of protons is critical in a variety of bio- and electro-chemical processes and technologies. The Grotthuss mechanism is considered to be the most efficient proton transport mechanism, generally implying a transfer of protons between 'chains' of host molecules via elementary reactions within the hydrogen bonds. Although Grotthuss proposed this concept more than 200 years ago, only indirect experimental evidence of the mechanism has been observed. Here we report the first experimental observation of proton transfer between the molecules in pure and 85% aqueous phosphoric acid. Employing dielectric spectroscopy, quasielastic neutron, and light scattering, and ab initio molecular dynamic simulations we determined that protons move by surprisingly short jumps of only ~0.5–0.7 Å, much smaller than the typical ion jump length in ionic liquids. Our analysis confirms the existence of correlations in these proton jumps. However, these correlations actually reduce the conductivity, in contrast to a desirable enhancement, as is usually assumed by a Grotthuss mechanism. Furthermore, our analysis suggests that the expected Grotthuss-like enhancement of conductivity cannot be realized in bulk liquids where ionic correlations always decrease conductivity. Although the Grotthuss mechanism of proton transfer is generally considered to be the most efficient means of proton transport, the search for experimental evidence of the mechanism has remained elusive and in certain cases confusing. Here, dielectric spectroscopy, quasieleastic neutron and light scattering, along with ab initio molecular dynamics simulations have been utilized to elucidate the mechanism of proton transfer in pure and 85% aqueous phosphoric acid. [ABSTRACT FROM AUTHOR]

The slow, Debye-like relaxation in hydrogen-bonded liquids has largely remained a dielectric phenomenon and has thus far eluded observation by other experimental techniques. Here we report the first observation of a slow, Debye-like relaxation by both depolarized dynamic light scattering (DLS) and dielectric spectroscopy in a model hydrogen-bonded liquid, 2-ethyl-4-methylimidazole (2E4MIm). The relaxation times obtained by these two techniques are in good agreement and can be well explained by the Debye model of rotational diffusion. On the one hand, 2E4MIm is analogous to the widely studied monohydroxy alcohols in which transient chain-like supramolecular structure can be formed by hydrogen bonding. On the other hand, the hydrogen-bonded backbone of 2E4MIm is much more optically polarizable, making it possible to apply light scattering to study the dynamics of the supramolecular structure. These findings provide the missing evidence of the slow, Debye-like relaxation in DLS and open the venue for the application of dynamic light scattering to the study of supramolecular structures in hydrogen-bonded liquids. [ABSTRACT FROM AUTHOR]

We explore possible molecular mechanisms behind the coupling of protein and solvent dynamics using atomistic molecular-dynamics simulations. For this purpose, we analyze the model protein lysozyme in glycerol, a well-known protein-preserving agent. We find that the dynamics of the hydrogen bond network between the solvent molecules in the first shell and the surface residues of the protein controls the structural relaxation (dynamics) of the whole protein. Specifically, we find a power-law relationship between the relaxation time of the aforementioned hydrogen bond network and the structural relaxation time of the protein obtained from the incoherent intermediate scattering function. We demonstrate that the relationship between the dynamics of the hydrogen bonds and the dynamics of the protein appears also in the dynamic transition temperature of the protein. A study of the dynamics of glycerol as a function of the distance from the surface of the protein indicates that the viscosity seen by the protein is not the one of the bulk solvent. The presence of the protein suppresses the dynamics of the surrounding solvent. This implies that the protein sees an effective viscosity higher than the one of the bulk solvent. We also found significant differences in the dynamics of surface and core residues of the protein. The former is found to follow the dynamics of the solvent more closely than the latter. These results allowed us to propose a molecular mechanism for the coupling of the solvent-protein dynamics. [ABSTRACT FROM AUTHOR]

Abstract: Utilization of self‐healing chemistry to develop synthetic polymer materials that can heal themselves with restored mechanical performance and functionality is of great interest. Self‐healable polymer elastomers with tunable mechanical properties are especially attractive for a variety of applications. Herein, a series of urea functionalized poly(dimethyl siloxane)‐based elastomers (U‐PDMS‐Es) are reported with extremely high stretchability, self‐healing mechanical properties, and recoverable gas‐separation performance. Tailoring the molecular weights of poly(dimethyl siloxane) or weight ratio of elastic cross‐linker offers tunable mechanical properties of the obtained U‐PDMS‐Es, such as ultimate elongation (from 984% to 5600%), Young's modulus, ultimate tensile strength, toughness, and elastic recovery. The U‐PDMS‐Es can serve as excellent acoustic and vibration damping materials over a broad range of temperature (over 100 °C). The strain‐dependent elastic recovery behavior of U‐PDMS‐Es is also studied. After mechanical damage, the U‐PDMS‐Es can be healed in 120 min at ambient temperature or in 20 min at 40 °C with completely restored mechanical performance. The U‐PDMS‐Es are also demonstrated to exhibit recoverable gas‐separation functionality with retained permeability/selectivity after being damaged. [ABSTRACT FROM AUTHOR]

We present the discovery of an unusually large isotope effect in the structural relaxation and the glass transition temperature Tg of water. Dielectric relaxation spectroscopy of low-density as well as of vapor-deposited amorphous water reveal Tg differences of 10 ± 2 K between H2O and D2O, sharply contrasting with other hydrogen-bonded liquids for which H/D exchange increases Tg by typically less than 1 K. We show that the large isotope effect and the unusual variation of relaxation times in water at low temperatures can be explained in terms of quantum effects. Thus, our findings shed new light on water's peculiar low-temperature dynamics and the possible role of quantum effects in its structural relaxation, and possibly in dynamics of other low-molecular-weight liquids. [ABSTRACT FROM AUTHOR]

Dielectric spectroscopy, rheology, and differential scanning calorimetry were employed to study the effect of chain-end hydrogen bonding on the dynamics of hydroxyl-terminated polydimethylsiloxane. We demonstrate that hydrogen bonding has a strong influence on both segmental and slower dynamics in the systems with low molecular weights. In particular, the decrease in the chain length leads to an increase of the glass transition temperature, viscosity, and fragility index, at variance with the usual behavior of nonassociating polymers. The supramolecular association of hydroxyl-terminated chains leads to the emergence in dielectric and mechanical relaxation spectra of the so-called Debye process traditionally observed in monohydroxy alcohols. Our analysis suggests that the hydroxyl-terminated PDMS oligomers may associate in brush-like or chain-like structures, depending on the size of their covalent chains. The effective length of the linear-associated chains was estimated from the rheological measurements. [ABSTRACT FROM AUTHOR]

Weanalyzed solute and solvent dynamics of sugars and peptidesaqueous solutions using extended depolarized light scattering (EDLS)and broadband dielectric spectroscopies (BDS). Spectra measured withboth techniques reveal the same mechanism of rotational diffusionof peptides molecules. In the case of sugars, this solute reorientationalrelaxation can be isolated by EDLS measurements, whereas its contributionto the dielectric spectra is almost negligible. In the presented analysis,we characterize the hydration water in terms of hydration number andretardation ratio ξ between relaxation times of hydration andbulk water. Both techniques provide similar estimates of ξ.The retardation imposed on the hydration water by sugars is ∼3.3± 1.3 and involves only water molecules hydrogen-bonded (HB)to solutes (∼3 water molecules per sugar OH-group). In contrast,polar peptides cause longer range perturbations beyond the first hydrationshell, and ξ between 2.8 and 8, increasing with the number ofchemical groups engaged in HB formation. We demonstrate that chemicalheterogeneity and specific HB interactions play a crucial role inhydration dynamics around polar solutes. The obtained results helpto disentangle the role of excluded volume and enthalpic contributionsin dynamics of hydration water at the interface with biological molecules. [ABSTRACT FROM AUTHOR]

Abstract: A self-complementary heteroditopic molecule composed of thymine and diamidopyridine end groups and a flexible aliphatic interconnecting chain has been synthesized. The glassy dynamics of this hydrogen-bonded supramolecule have been investigated by using dielectric and rheological measurements, in combination with infra-red spectroscopy and solid-state 13C NMR experiments. Decoupling of main dielectric relaxation from viscosity has been found in the vicinity of the glass transition and the temperature dependence of viscosity appears to be stronger than that of dielectric relaxation. The unusual dynamic decoupling phenomenon is ascribed to the chemical/dynamic heterogeneity and formation of hydrogen bonds in the supramolecules. [Copyright &y& Elsevier]