Journal
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, VOL 67
Volume 67, Issue -, Pages 617-+Publisher
ANNUAL REVIEWS
DOI: 10.1146/annurev-physchem-040215-112412
Keywords
hydrophobic; water-mediated; potential of mean force; free energy; enthalpy; entropy; compensation; crossover
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Funding
- Division Of Chemistry [1464904] Funding Source: National Science Foundation
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Hydrophobic interactions are driven by the combined influence of the direct attraction between oily solutes and an additional water-mediated interaction whose magnitude (and sign) depends sensitively on both solute size and attraction. The resulting delicate balance can lead to a slightly repulsive water-mediated interaction that drives oily molecules apart rather than pushing them together and thus opposes their direct (van der Waals) attraction for each other. As a consequence, competing solute size-dependent crossovers weaken hydrophobic interactions sufficiently that they are only expected to significantly exceed random thermal energy fluctuations for processes that bury more than similar to 1 nm(2) of water-exposed area.
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