Does Confinement Modify Preferential Solvation and H-Bond Fluctuation Dynamics? A Molecular Level Investigation through Simulations of a Bulk and Confined Three-Component Mixture.

Exploring the local environment around a dissolved solute in a bulk aqueous solution of alcohol and assessing the impact of confinement on the solvation structure is an important topic yet is much less studied. Such a study is important because it can provide critical information regarding the miscibility of an amphiphilic drug after delivery at a designated nanoscopic site and the subsequent release. The present molecular dynamics simulation study reports an in-depth investigation of the composition-dependent solvation structure around a dissolved hydrophobic solute, coumarin 153 (C153), in ambient binary mixtures of methanol and water in both bulk and under confinement. The confinement is a spherical sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelle with a diameter of 55 Å. Inter- and intraspecies H-bond fluctuation dynamics have been monitored and compared with those from the corresponding bulk binary mixtures. A systematic comparison of both solvation structure and H-bond dynamics between confined and bulk binary mixtures reveals modulation of both preferential solvation and H-bond relaxation times inside a nanoscopic environment. More specifically, confinement accentuates the preferential solvation phenomenon and facilitates di-mixing of mixture components. In addition, the present study reveals that the tetrahedral H-bond network of neat liquid water becomes severely affected upon addition of methanol, which becomes further distorted under confinement. Confinement severely affects the interspecies hydrogen bonds and makes the corresponding continuous hydrogen bonds much shorter-lived. Interestingly, structural hydrogen bond relaxation timescales become longer in confined binary mixtures than those in bulk binary mixtures.