Cooperativity, partially bound states, and enthalpy-entropy compensation
Cooperativity, partially bound states, and enthalpy-entropy compensation
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DOI：
10.1016/j.chembiol.2003.10.009
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发表时间：
2003-11-01
影响因子：
--
通讯作者：
Tomas, S
中科院分区：
文献类型：
--
作者：
Hunter, CA;Tomas, S
努力发展一个定量的分子识别的理解依赖于个人的分子间相互作用的加和性，和协同性是主要的潜在绊脚石之一。化学双突变体循环已被用于实验测量复杂框架内的官能团相互作用之间的协同性。在合成的氢键复合物中，两个芳香基团之间的相互作用变化为0.2 +/- 0.4 kJ mol（-1），其整体稳定性相差8-13 kJ mol（-1）。在这些系统中，与单个分子间相互作用相关的自由能因此可以可靠地以加性方式处理。结果表明，其他的解释应考虑在其他系统中观察到的合作现象，并提出了一个合理的基础上的人口的部分束缚态的灵活分子的螯合效应和熵的补偿。
Efforts to develop a quantitative understanding of molecular recognition rely on the additivity of individual intermolecular interactions, and cooperativity represents one of the major potential stumbling blocks. A chemical double-mutant cycle has been used to experimentally measure cooperativity between functional group interactions within a complex framework. The interaction between two aromatic groups varies by 0.2 +/- 0.4 kJ mol(-1) in synthetic H-bonded complexes that differ by 8-13 kJ mol(-1) in overall stability. In these systems, the free energies associated with individual intermolecular interactions can therefore be reliably treated in an additive fashion. The results suggest that alternative explanations should be considered for cooperative phenomena observed in other systems, and a rationale based on the population of partially bound states in flexible molecules is proposed to account for the enthalpic chelate effect and enthalpy-entropy compensation.