Heat does not come in different colours:: entropy-enthalpy compensation, free energy windows, quantum confinement, pressure perturbation calorimetry, solvation and the multiple causes of heat capacity effects in biomolecular interactions
Heat does not come in different colours:: entropy-enthalpy compensation, free energy windows, quantum confinement, pressure perturbation calorimetry, solvation and the multiple causes of heat capacity effects in biomolecular interactions
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DOI：
10.1016/s0301-4622(01)00222-8
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发表时间：
2001-11-28
影响因子：
3.8
通讯作者：
Nöllmann, M
中科院分区：
文献类型：
--
作者：
Cooper, A;Johnson, CM;Nöllmann, M
现代微量热技术使我们能够直接测量在合理浓度下水溶液中生物分子过程的热变化和相关热力学。所有这些过程都涉及溶剂化/水合作用的变化，并且很自然地假设这些过程的热量应该以某种方式反映溶剂化的这种变化。然而，数据的解释仍然有些模糊，因为不同的非共价相互作用可能具有相似的热力学特征，并且分析受到大的熵-焓补偿效应的阻碍。热容量（Δ C（p））的变化与疏水水化和非极性可及表面积的变化有关，但最近的经验和理论工作表明，情况并非总是如此。熵-焓补偿是有限DeltaC（p）值的自然结果，并且更一般地，可以作为量子限制效应、多个弱相互作用和有限自由能窗口的结果而出现，从而产生可能具有进化和功能优势的热力学稳态。
Modem techniques in microcalorimetry allow us to measure directly the heat changes and associated thermodynamics for biomolecular processes in aqueous solution at reasonable concentrations. All these processes involve changes in solvation/hydration, and it is natural to assume that the heats for these processes should reflect, in some way, such changes in solvation. However, the interpretation of data is still somewhat ambiguous, since different non-covalent interactions may have similar thermodynamic signatures, and analysis is frustrated by large entropy-enthalpy compensation effects. Changes in heat capacity (DeltaC(p)) have been related to changes in hydrophobic hydration and non-polar accessible surface areas, but more recent empirical and theoretical work has shown how this need not always be the case. Entropy-enthalpy compensation is a natural consequence of finite DeltaC(p) values and, more generally, can arise as a result of quantum confinement effects, multiple weak interactions, and limited free energy windows, giving rise to thermodynamic homeostasis that may be of evolutionary and functional advantage.