EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, U.K.
J Am Chem Soc. 2015 Aug 19;137(32):10084-7. doi: 10.1021/jacs.5b05736. Epub 2015 Aug 5.
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—the solvophobic effect—although 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.
疏水效应在决定生物分子和材料的结构、活性和性质方面起着核心作用。相比之下，尽管这种现象在其他溶剂中的普遍表现——疏溶剂效应——被广泛引用，但由于缺乏普遍接受的描述符，目前还没有得到很好的定义。在这里，我们使用合成分子天平来测量溶剂对芳香族、脂肪族和全氟非极性相互作用的影响。我们的溶剂筛选数据与超分子缔合、单分子折叠和体相转移能量的独立实验测量结果相结合，都与溶剂的内聚能密度（CED）很好地相关。同时，溶剂内聚的其他度量，如表面张力和内压，相关性较差。因此，我们确定 CED 是一种在多种化学环境中易于获得的疏溶剂缔合的定量描述符。
