Isothermal Titration Calorimetry in Supramolecular Chemistry
Isothermal Titration Calorimetry in Supramolecular Chemistry
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DOI：
10.1002/9780470661345.smc024
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发表时间：
2012-03
影响因子：
--
通讯作者：
F. Schmidtchen
中科院分区：
文献类型：
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作者：
F. Schmidtchen
在测量溶液中分子相互作用的许多方法中，等温滴定微量热法（ITC）是一种几乎通用的、无标记的、操作快速的、完全计算机操作的、因此相当稳健的方法，可以获得表征分子间缔合能量学所需的所有热力学参数。如果分子相互作用伴随着焓响应，则可以在单次运行中确定自由能、摩尔焓，并且通过使用吉布斯-亥姆霍兹方程，还可以确定摩尔熵。本审查描述的基本概念，方法学方面的范围直接测定，其潜在的扩展。特别关注的是数据评估和内在的限制，将宏观仪器输出转化为分子场景上发生的微观事件的照明。ITC的范围作为一种手段来表征热力学平衡的说明与最近的应用程序的帮助下，从低分子主客体化学观察到的相变表面活性剂的多聚体组装。关键词：ITC;分子相互作用;主客体化学;热力学;量热法;缔合;超分子化学;焓;熵
Among the many options to measure molecular interactions in solution, isothermal titration microcalorimetry (ITC) stands out as an almost universal, label-free, operationally fast, fully computer-operated, and thus quite robust method to acquire all thermodynamic parameters necessary to characterize the energetics of intermolecular association. Provided that there is an enthalpic response accompanying the mutual molecular interaction, the free energy, molar enthalpy, and, by using the Gibbs–Helmholtz equation, also the molar entropy can be determined in a single run. The present review describes the fundamental concept, the methodological aspects concerning the range accessible to direct determinations, and its potential expansion. Special focus is on data evaluation and the intrinsic limits to translate the macroscopic instrumental output into the illumination of the microscopic events happening on the molecular scene. The scope of ITC as a means to characterize thermodynamic equilibria is illustrated with the help from recent applications spanning from low-molecular host–guest chemistry to multimeric assembly of surfactants observable as phase changes. Keywords: ITC; molecular interaction; host–guest chemistry; thermodynamics; calorimetry; association; supramolecular chemistry; enthalpy; entropy