Lee B
Laboratory of Molecular Biology, National Cancer Institute, National Institutes of Health, Bethesda, MD 20892.
Biophys Chem. 1994 Aug;51(2-3):271-7; discussion 277-8. doi: 10.1016/0301-4622(94)00048-4.
Using Widom's potential distribution theory (J. Chem. Phys. 39 (1963) 2808; J. Phys. Chem. 86 (1982) 869), a general and a special theorems are derived, by means of which one can judge whether a particular sub-process of an overall process will produce compensating changes in enthalpy and entropy. The enthalpy-entropy compensation phenomena that are observed in the transfer process of a hydrophobic molecule from a non-aqueous phase to water are examined in the light of these theorems. It is concluded that most sub-processes involved in the hydrophobic transfer process are compensating except one, that of inserting a cavity corresponding to the solute molecule in the liquid. The reason that this process is non-compensating, and therefore most responsible for the hydrophobicity, is traced to the hard core overlap between solvent and the solute molecules.
运用维登的势能分布理论（《化学物理杂志》39卷（1963年）第2808页；《物理化学杂志》86卷（1982年）第869页），推导出一个一般性定理和一个特殊性定理，借助这两个定理可以判断一个总过程中的特定子过程是否会产生焓和熵的补偿性变化。根据这些定理，对疏水分子从非水相转移到水的过程中观察到的焓 - 熵补偿现象进行了研究。得出的结论是，疏水转移过程中涉及的大多数子过程是补偿性的，但有一个子过程除外，即在液体中插入与溶质分子对应的空穴的过程。这个过程是非补偿性的，因此对疏水性起主要作用，其原因可追溯到溶剂与溶质分子之间的硬核重叠。
