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Differences between pair and bulk hydrophobic interactions.

R H Wood1, P T Thompson

  • 1Department of Chemistry, University of Delaware, Newark, DE 19716, USA.

Proceedings of the National Academy of Sciences of the United States of America
|February 1, 1990
PubMed
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Hydrocarbon pair interactions in water differ from bulk hydrophobic effects. These interactions are weaker in water than in gas, and contact configurations are more important than solvent-separated ones for larger hydrocarbons.

Area of Science:

  • Physical Chemistry
  • Solution Chemistry
  • Hydrophobic Interactions

Background:

  • The hydrophobic interaction is crucial in biochemistry, typically modeled as the transfer of nonpolar molecules from water to a nonpolar phase.
  • Pair interactions between hydrocarbon molecules in aqueous solutions exhibit unique characteristics distinct from bulk hydrophobic effects.

Purpose of the Study:

  • To analyze experimental data on hydrocarbon pair interactions in water using an empirical potential function.
  • To contrast these pair interactions with bulk hydrophobic interactions and existing theoretical models.

Main Methods:

  • Analysis of experimental data for hydrocarbon pair interactions in aqueous solutions.
  • Fitting data to a simple empirical potential function.
  • Comparison with surface free energy and cosphere overlap models.

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Main Results:

  • Existing models fail to accurately describe both pair and bulk hydrophobic interactions.
  • Hydrocarbon pair interactions in water are significantly weaker than in the gas phase, contrary to common assumptions.
  • For hydrocarbons with more than two carbon atoms, contact configurations dominate over solvent-separated configurations in aqueous solutions.

Conclusions:

  • Standard models for hydrophobic interactions are insufficient for describing pair interactions in water.
  • The attractive forces between hydrocarbon pairs in water are weaker than anticipated, challenging conventional understanding.
  • The relative importance of contact versus solvent-separated configurations depends on hydrocarbon size.