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关于水溶液中表征过程的焓-熵补偿特性

On Enthalpy-Entropy Compensation Characterizing Processes in Aqueous Solution.

作者信息

Mancini Fiorella, Graziano Giuseppe

机构信息

Dipartimento di Scienze e Tecnologie, Università del Sannio, Via Francesco de Sanctis snc, 82100 Benevento, Italy.

出版信息

Entropy (Basel). 2025 Jul 2;27(7):716. doi: 10.3390/e27070716.

DOI:10.3390/e27070716
PMID:40724433
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12295146/
Abstract

The phenomenon of enthalpy-entropy compensation emerges as a ubiquitous feature of processes occurring in water, especially those involving biological macromolecules. In writing the present study, the aim was not to review most of the rationalizations proposed so far but to focus on a general theory of hydration, partly developed and applied by one of us. This theory poses a physical condition for the occurrence of enthalpy-entropy compensation: the energetic strength of the solute-water attraction must be weak compared to that of water-water H-bonds. This condition is largely fulfilled in water due to the cooperativity of its three-dimensional H-bonded network.

摘要

焓-熵补偿现象是水中发生的过程普遍存在的特征,尤其是那些涉及生物大分子的过程。在撰写本研究时,目的不是回顾迄今为止提出的大多数合理解释,而是关注一种水化的一般理论,该理论部分由我们其中一人提出并应用。该理论为焓-熵补偿的发生提出了一个物理条件:溶质与水之间吸引力的能量强度必须比水与水之间氢键的能量强度弱。由于其三维氢键网络的协同作用,这一条件在水中基本得到满足。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9c/12295146/c6f50fff8a00/entropy-27-00716-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9c/12295146/e5b7ecaa4c2a/entropy-27-00716-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9c/12295146/091839d777b4/entropy-27-00716-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9c/12295146/97bf9c4bfbf5/entropy-27-00716-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9c/12295146/c6f50fff8a00/entropy-27-00716-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9c/12295146/e5b7ecaa4c2a/entropy-27-00716-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9c/12295146/091839d777b4/entropy-27-00716-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9c/12295146/97bf9c4bfbf5/entropy-27-00716-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9c/12295146/c6f50fff8a00/entropy-27-00716-g004.jpg

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本文引用的文献

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Structural Order in the Hydration Shell of Nonpolar Groups versus that in Bulk Water.
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Simple Accurate Verification of Enthalpy-Entropy Compensation and Isoequilibrium Relationship.简单准确地验证焓熵补偿和等平衡关系。
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Contrasting the hydration thermodynamics of methane and methanol.对比甲烷和甲醇的水合热力学。
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