Hydrogen bond induced nonmonotonic composition behavior of the glass transition in aqueous binary mixtures.

The glass transition temperature, T(g), of a binary mixture commonly varies monotonically between the T(g)s of its two components. However, mixtures of strongly associating liquids can instead exhibit a nonmonotonic T(g) variation. The origins of such nonideal mixing behavior have often been correlated with composition dependent structural variations.

Role of solvent for the dynamics and the glass transition of proteins.

For the first time, a systematic investigation of the glass transition and its related dynamics of myoglobin in water-glycerol solvent mixtures of different water contents is presented. By a combination of broadband dielectric spectroscopy and differential scanning calorimetry (DSC), we have studied the relation between the protein and solvent dynamics with the aim to better understand the calorimetric glass transition, T(g), of proteins and the role of solvent for protein dynamics. The results show that both the viscosity related α-relaxation in the solvent as well as several different protein relaxations are involved in the calorimetric glass transition, and that the broadness (ΔT(g)) of the transition depends strongly on the total amount of solvent.

Effects of water contamination on the supercooled dynamics of a hydrogen-bonded model glass former.

Broad-band dielectric spectroscopy is a commonly used tool in the study of glass-forming liquids. The high sensitivity of the technique together with the wide range of probed time scales makes it a powerful method for investigating the relaxation spectra of liquids. One particularly important class of glass-forming liquids that is often studied using this technique consists of liquids dominated by hydrogen (H) bond interactions.

Dielectric secondary relaxation of water in aqueous binary glass-formers.

Glassy aqueous binary mixtures generally exhibit a water induced dielectric relaxation. The characteristic time-scale of this relaxation follows an Arrhenius temperature dependence with a nearly universal activation energy. We here demonstrate for a series of model aqueous mixtures that the relaxation time also follows a remarkably general exponential dependence on the weight fraction of water.

Hidden slow dynamics in water.

It is well known that the structural and dynamical properties of water are of central importance for life on our planet. However, despite this knowledge its structural and dynamical properties are still far from fully understood. In this Letter we show for the first time that water exhibits an anomalously slow relaxation process, which is about 4 orders of magnitude slower than the viscosity-related structural main relaxation.

Slow Debye-type peak observed in the dielectric response of polyalcohols.

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.

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.

Relaxation processes in supercooled confined water and implications for protein dynamics.

We show that the viscosity-related main (alpha) relaxation of confined water vanishes at a temperature where the volume required for the cooperative alpha relaxation becomes larger than the size of the geometrically confined water cluster. This occurs typically around 200 K, implying that above this temperature we observe a merged alpha-beta relaxation, whereas below it only a local (beta) relaxation remains. This also means that such confined supercooled water does not exhibit any true glass transition, in contrast to other liquids in similar confinements.

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).

Dielectric and calorimetric studies of hydrated purple membrane.

Purple membranes (PM) from halobacteria were hydrated to approximately 0.4 and approximately 0.2 g H(2)O/g of PM and studied by dielectric spectroscopy and differential scanning calorimetry between 120 and 300 K.

Glass transition and relaxation processes in supercooled water.

Many of water's peculiar physical properties are still not well understood, and one of the most important unresolved questions is its glass transition related dynamics. The consensus has been to accept a glass transition temperature (T(g)) around 136 K, but this value has been questioned and reassigned to about 165 K. We find evidence that the dielectric relaxation process of confined water that has been associated with the long accepted T(g) of water (130-140 K) must be a local process which is not related to the actual glass transition.

Relaxation dynamics of a polymer in a 2D confinement.

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.