Structure and slow dynamics of protein hydration water with cryopreserving DMSO and trehalose upon cooling.

We study, through molecular dynamics simulations, three aqueous solutions with one lysozyme protein and three different concentrations of trehalose and dimethyl sulfoxide (DMSO). We analyze the structural and dynamical properties of the protein hydration water upon cooling. We find that trehalose plays a major role in modifying the structure of the network of HBs between water molecules in the hydration layer of the protein. The dynamics of hydration water presents, in addition to the α-relaxation, typical of glass formers, a slower long-time relaxation process, which greatly slows down the dynamics of water, particularly in the systems with trehalose, where it becomes dominant at low temperatures. In all the solutions, we observe, from the behavior of the α-relaxation times, a shift of the Mode Coupling Theory crossover temperature and the fragile-to-strong crossover temperature toward higher values with respect to bulk water. We also observe a strong-to-strong crossover from the temperature behavior of the long-relaxation times. In the aqueous solution with only DMSO, the transition shifts to a lower temperature than in the case with only lysozyme reported in the literature. We observe that the addition of trehalose to the mixture has the opposite effect of restoring the original location of the strong-to-strong crossover. In all the solutions analyzed in this work, the observed temperature of the protein dynamical transition is slightly shifted at lower temperatures than that of the strong-to-strong crossover, but their relative order is the same, showing a correlation between the motion of the protein and that of the hydration water.

Phase Diagram of Aqueous Solutions of LiCl: a Study of Concentration Effects on the Anomalies of Water.

We perform molecular dynamics simulations in order to study thermodynamics and the structure of supercooled aqueous solutions of lithium chloride (LiCl) at concentrations c = 0.678 and 2.034 mol/kg. We model the solvent using the TIP4P/2005 potential and the ions using the Madrid-2019 force field, a force field particularly suited for studying this solution. We find that, for c = 0.678 mol/kg, the behavior of the equation of state, studied in the P-T plane, indicates the presence of a liquid-liquid phase transition, similar to what was previously found for bulk water. We estimate the position of the liquid-liquid critical point to be at Tc ≈ 174 K, Pc ≈ 1775 bar, and ρc ≈ 1.065 g/cm3. When the concentration is tripled to c = 2.034 mol/kg, no critical point is observed, indicating its possible disappearance at this concentration. We also study the water-water and water-ions structure in the two solutions, and we find that at the concentrations examined the effect of ions on the water-water structure is not strong, and all the features found in bulk water are preserved. We also calculate the hydration number of the Li and Cl ions, and in line with experiments, we find the value of 4 for Li+ and between 5.5 and 6 for Cl-, confirming the good performances of the Madrid-2019 force field.