Thermodynamics, phase diagram, structure and anomalies of supercooled aqueous solutions of trehalose: A molecular dynamics study

We perform molecular dynamics simulations of supercooled solutions of trehalose in TIP4P/2005 water, with concentrations of 20 and 40 wt% (weight percentage) in trehalose, a disaccharide often used in cryopreserving solutions. We analyze the thermodynamics and the structure of these solutions. From the isochores we find that in the 20 wt% solution the temperature of maximum density (TMD) line is still present and it is shifted to lower temperatures with respect to that of pure water. We also find that the Widom line and the liquid-liquid critical point (LLCP) are still present for this concentration and we estimate the position of the LLCP to be shifted at lower temperatures and slightly lower pressures with respect to that of pure water. In the 40 wt% solution we find that the TMD line still persists, but the region of density anomaly shrinks. No LLCP is observed down to the lowest temperature investigated, and maxima of the isothermal compressibility, used as proxy for the Widom line, become weaker. The water oxygen - water oxygen radial distribution functions keep on showing the typical distinction between high density and low density liquid found in pure water, but at low temperatures the presence of trehalose appears to favor the high density phase of water more than in pure water. The number of water molecules of the solvation shell confirms this picture. • Supercooled aqueous solutions of water and trehalose are useful for cryoprotection. • The phase diagram in the liquid and supercooled region still shows anomalies. • The liquid-liquid critical point is still present for the lowest concentration. • Trehalose favors the high density liquid phase of water.