Effect of hydrophobic environments on the hypothesized liquid-liquid critical point of water.

The complex behavior of liquid water, along with its anomalies and their crucial role in the existence of life, continue to attract the attention of researchers. The anomalous behavior of water is more pronounced at subfreezing temperatures and numerous theoretical and experimental studies are directed towards developing a coherent thermodynamic and dynamic framework for understanding supercooled water. The existence of a liquid-liquid critical point in the deep supercooled region has been related to the anomalous behavior of water. However, the experimental study of supercooled water at very low temperatures is hampered by the homogeneous nucleation of the crystal. Recently, water confined in nanoscopic structures or in solutions has attracted interest because nucleation can be delayed. These systems have a tremendous relevance also for current biological advances; e.g., supercooled water is often confined in cell membranes and acts as a solvent for biological molecules. In particular, considerable attention has been recently devoted to understanding hydrophobic interactions or the behavior of water in the presence of apolar interfaces due to their fundamental role in self-assembly of micelles, membrane formation and protein folding. This article reviews and compares two very recent computational works aimed at elucidating the changes in the thermodynamic behavior in the supercooled region and the liquid-liquid critical point phenomenon for water in contact with hydrophobic environments. The results are also compared to previous reports for water in hydrophobic environments.