Effect of hydrophobic interaction on structure, dynamics, and reactivity of water

Langmuir. 2013 Feb 12;29(6):1808-17. doi: 10.1021/la3042583. Epub 2013 Jan 28.

Abstract

The effect of hydrophobic interaction on water is still controversial and requires more detailed experimental and theoretical investigation. The interaction between organic-water molecular complexes might be indicative of the perturbation of hydrogen-bond network in the tetrahedral structure of bulk waters, due to hydrophobic effect. In this contribution, femto/picosecond-resolved solvation dynamics techniques have been adopted to explore the dynamical modification of water clusters in hydrophobic solvent methyl tert-butyl ether (MTBE). The dynamical evolution of water molecules at the surface of micelle-like MTBE has also been studied. Dynamic light scattering techniques have been employed to determine the size of the molecular clusters being formed in respective solvents. Fourier transform infrared (FTIR) spectroscopy well measures the changes in O-H vibration frequency of water induced by MTBE. We have also monitored temperature dependent picosecond-resolved solvation dynamics in order to explore the energetics associated with water solvation in bulk MTBE. Using detailed ab initio calculations at the MP2 level, our study attempts to predict the possible structures, energies, and thermochemical parameters of corresponding MTBE-water molecular complexes in more detail. The chemical reactivity of water further confirms the effect of the hydrophobic interaction on water molecules. The results impart an understanding on hydrophobic interaction imposed by a biomolecule on the structure and reactivity of water, significant for the in vivo cellular condition.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Benzoates / chemistry
  • Hydrophobic and Hydrophilic Interactions*
  • Kinetics
  • Methyl Ethers / chemistry
  • Models, Molecular
  • Molecular Conformation
  • Quantum Theory
  • Solvents / chemistry
  • Water / chemistry*

Substances

  • Benzoates
  • Methyl Ethers
  • Solvents
  • Water
  • methyl tert-butyl ether
  • benzoyl chloride