Hydrophobic effects on a molecular scale
- Los Alamos National Lab., NM (United States). Theoretical Div.
- Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemical Engineering
A theoretical approach is developed to quantify hydrophobic hydration and interactions on a molecular scale, with the goal of insight into the molecular origins of hydrophobic effects. The model is based on the fundamental relation between the probability for cavity formation in bulk water resulting from molecular-scale density fluctuations and the hydration free energy of the simplest hydrophobic solutes, hard particles. This probability is estimated using an information theory (IT) approach, incorporating experimentally available properties of bulk water: the density and radial distribution function. The IT approach reproduces the simplest hydrophobic effects: hydration of spherical nonpolar solutes, the potential of mean force (PMF) between methane molecules, and solvent contributions to the torsional equilibrium of butane. Applications of this approach to study temperature and pressure effects provide new insights into the thermodynamics and kinetics of protein folding. The IT model relates the hydrophobic-entropy convergence observed in protein unfolding experiments to the macroscopic isothermal compressibility of water. A novel explanation for pressure denaturation of proteins follows from an analysis of the pressure stability of hydrophobic aggregates, suggesting the water penetrates the hydrophobic core of proteins at high pressures. This resolves a long-standing puzzle, whether pressure denaturation contradicts the hydrophobic-core model of protein stability. Finally, issues of dewetting of molecularly large nonpolar solutes are discussed in the context of a recently developed perturbation theory approach.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- OSTI ID:
- 316053
- Journal Information:
- Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical, Vol. 102, Issue 51; Other Information: PBD: 17 Dec 1998
- Country of Publication:
- United States
- Language:
- English
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