Effect of ions on the hydrophobic interaction between two plates

被引:223
作者
Zangi, Ronen
Hagen, Morten
Berne, B. J. [1 ]
机构
[1] Columbia Univ, Dept Chem, New York, NY 10027 USA
[2] Columbia Univ, Ctr Biomol Simulat, New York, NY 10027 USA
关键词
D O I
10.1021/ja068305m
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We use molecular dynamics simulations to investigate the solvent mediated attraction and drying between two nanoscale hydrophobic surfaces in aqueous salt solutions. We study these effects as a function of the ionic charge density, that is, the ionic charge per unit ionic volume, while keeping the ionic diameter fixed. The attraction is expressed by a negative change in the free energy as the plates are brought together, with enthalpy and entropy changes that both promote aggregation. We find a strong correlation between the strength of the hydrophobic interaction and the degree of preferential binding/exclusion of the ions relative to the surfaces. The results show that amplification of the hydrophobic interaction, a phenomenon analogous to salting-out, is a purely entropic effect and is induced by high-charge-density ions that exhibit preferential exclusion. In contrast, a reduction of the hydrophobic interaction, analogous to salting-in, is induced by low-charge-density ions that exhibit preferential binding, the effect being either entropic or enthalpic. Our findings are relevant to phenomena long studied in solution chemistry, as we demonstrate the significant, yet subtle, effects of electrolytes on hydrophobic aggregation and collapse.
引用
收藏
页码:4678 / 4686
页数:9
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