Hydrogen-bond dynamics of water in presence of an amphiphile, tetramethylurea: signature of confinement-induced effects

Abstract

Various experimental and simulation studies have suggested that the presence of amphiphilic molecules in aqueous solutions substantially perturbs the tetrahedral hydrogen-bond (H-bond) network of neat liquid water. Such structural perturbation is expected to impact H-bond lifetime of liquid water. Tetramethylurea (TMU) is an example of an amphiphile because it possesses both hydrophobic and hydrophilic moieties. Molecular dynamics simulations of (water+TMU) binary mixtures at various compositions have been performed in order to investigate the microscopic mechanism through which the amphiphiles influence the H-bond dynamics of liquid water at room temperature. Present simulations indicate lengthening of both water–water H-bond lifetime and H-bond structural relaxation time upon addition of TMU in aqueous solution. At the highest TMU mole fraction studied, H-bond lifetime and structural relaxation time are, respectively, ∼4 and ∼8 times longer than those in neat water. This is comparable with the slowing down of H-bond dynamics for water molecules confined in cyclodextrin cavities. Simulated relaxation profiles are multi-exponential in character at all mixture compositions, and simulated radial distribution functions suggest enhanced water–water and water–TMU interactions upon addition of TMU. No evidence for complete encapsulation of TMU by water H-bond network has been found.