Quantifying Solvophobic Effects in Nonpolar Cohesive Interactions

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• 作者：Lixu Yang ; Catherine Adam ; Scott L. Cockroft
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：August 19, 2015
• 年：2015
• 卷：137
• 期：32
• 页码：10084-10087
• 全文大小：391K
• ISSN：1520-5126

文摘

The hydrophobic effect plays a central role in determining the structure, activity, and properties of biomolecules and materials. In contrast, the general manifestation of this phenomenon in other solvents鈥攖he solvophobic effect鈥攁lthough widely invoked, is currently poorly defined because of the lack of a universally accepted descriptor. Here we have used synthetic molecular balances to measure solvent effects on aromatic, aliphatic, and fluorous nonpolar interactions. Our solvent screening data combined with independent experimental measurements of supramolecular association, single-molecule folding, and bulk phase transfer energies were all found to correlate well with the cohesive energy density (ced) of the solvent. Meanwhile, other measures of solvent cohesion, such as surface tension and internal pressure, gave inferior correlations. Thus, we establish ced as a readily accessible, quantitative descriptor of solvophobic association in a range of chemical contexts.