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Solvent isotope effect on thermodynamics of hydration

机译:溶剂同位素对水合热力学的影响

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Partial molar heat capacities of five linear alcohols (methanol, ethanol, n-propanol, n-butanol, n-pentanol) and five N-substituted amides (n-propionamide, N-methylformamide, N-methylacetamide, N-methylpropionamide, N-ethylacetamide) in aqueous D2O solution have been measured at 25 degrees C. The heat capacities of transfer of these compounds from H2O to D2O were calculated using previously reported (Makhatadze et al., Biophys. Chem. 64 (1997) 93) values of partial heat capacities of alcohols and amides in aqueous H2O solutions. It is shown that the sign and magnitude of the heat capacity change upon transfer from H2O to D2O depends on the relative amount of polar and non-polar solvent accessible surface areas of solute. Analysis shows that transfer of non-polar surface from H2O to D2O is accompanied by a positive heat capacity change. In contrast, transfer of polar surface from H2O to D2O occurs with negative heat capacity change. Estimates show that the solvent isotope effect on the heat capacity changes upon protein unfolding can be predicted using the changes of the polar and non-polar surface area changes upon protein unfolding and the transfer data of model compounds. Analysis of the thermodynamic functions of transfer of non-polar compounds from H2O to D2O shows puzzling behavior which contradicts current definitions of the hydrophobic effect. (C) 1998 Elsevier Science B.V. All rights reserved. [References: 26]
机译:五个线性醇(甲醇,乙醇,正丙醇,正丁醇,正戊醇)和五个N-取代的酰胺(正丙酰胺,N-甲基甲酰胺,N-甲基乙酰胺,N-甲基丙酰胺,N-已在25°C下测量了D2O水溶液中的乙乙酰胺)。使用先前报道的(Makhatadze等人,Biophys.Chem.64(1997)93)值计算这些化合物从H2O到D2O的转移热容。 H2O水溶液中醇和酰胺的热容量。结果表明,当从H2O转移至D2O时,热容的符号和大小变化取决于溶质的极性和非极性溶剂可及表面积的相对量。分析表明,非极性表面从H2O到D2O的转移伴随着正热容变化。相反,极性表面从H2O向D2O的转移伴随负的热容变化而发生。估计表明,利用蛋白质解折叠时极性和非极性表面积的变化以及模型化合物的转移数据,可以预测溶剂同位素对蛋白质解折叠时热容量变化的影响。对非极性化合物从H2O转移至D2O的热力学函数的分析表明,令人费解的行为与当前对疏水作用的定义相矛盾。 (C)1998 Elsevier Science B.V.保留所有权利。 [参考:26]

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