The dewetting transition and the hydrophobic effect

Niharendu Choudhury, Bernard Pettitt

Research output: Contribution to journalArticle

112 Citations (Scopus)

Abstract

A molecular-level description of the behavior of water in hydrophobic spaces is presented in terms of the coupled effects of solute size and atomic solute-solvent interactions. For model solutes with surface areas near those of protein contacts, we identify three different regions of solute-water interaction to be associated with three distinctly different structural characteristics of water in the intersolute region: dry, oscillating, and wet. A first orderlike phase transition is confirmed from the wet to dry state bridged by a narrow region with liquid-vapor oscillations in the intersolute region as the strength of the solute-water attractive dispersion interaction decreases. We demonstrate that the recent idea that cavitation in the intersolute region of nanoscopic solutes is preceded by the formation of a vapor layer around an individual solute is not the general case. The appearance of density waves pulled up around and outside of a nanoscopic plate occurs at lower interaction strengths than are required to obtain a wet state between such plates. We further show that chemically reasonable estimates of the interaction strength lead to a microscopically wet state and a hydrophobic interaction characterized by traps and barriers to association and not by vacuum induced collapse.

Original languageEnglish (US)
Pages (from-to)4847-4852
Number of pages6
JournalJournal of the American Chemical Society
Volume129
Issue number15
DOIs
StatePublished - Apr 18 2007
Externally publishedYes

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Water
Vapors
Phase Transition
Vacuum
Hydrophobic and Hydrophilic Interactions
Cavitation
Phase transitions
Association reactions
Proteins
Liquids

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

The dewetting transition and the hydrophobic effect. / Choudhury, Niharendu; Pettitt, Bernard.

In: Journal of the American Chemical Society, Vol. 129, No. 15, 18.04.2007, p. 4847-4852.

Research output: Contribution to journalArticle

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