Allosteric, Chelate, and Interannular Cooperativity: A Mise au Point
Allosteric, Chelate, and Interannular Cooperativity: A Mise au Point
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DOI：
10.1002/anie.201004201
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发表时间：
2011-01-01
影响因子：
16.6
通讯作者：
Schiaffino, Luca
中科院分区：
文献类型：
--
作者：
Ercolani, Gianfranco;Schiaffino, Luca
协同效应是生物学和超分子化学中调控复杂分子体系行为的重要机制。[1，2]然而，如果我们要对协同效应的现象有一个真正的定量的理解，那么关于不同类型的协同效应的定义和评估就必须解决一些基本问题。最近，Whitty [3]以及Hunter和安德森[4]描述了两种类型的协同效应，即变构协同效应和螯合协同效应。前一种现象是由两个或多个分子间结合相互作用的相互作用引起的，如氧与血红蛋白的结合[5]，而后者是由一个或多个分子内结合相互作用的存在引起的，即作为螯合效应（多价性）的结果。然而，虽然变构协同性是公认的，螯合协同性的评估仍然是不令人满意的，因为一些陷阱，没有得到充分强调。为了解决这个问题，我们报告的分析，一贯评估螯合物的协同性，并介绍了必要性，第三种类型的协同性，即环间协同性，这是由两个或两个以上的分子内结合相互作用的相互作用。
Cooperativity is a key mechanism that regulates the behavior of complex molecular systems in biology and supramolecular chemistry.[1, 2] There are, however, some basic issues concerning the definition and assessment of different types of cooperativity that must be addressed if we are to achieve a truly quantitative understanding of the phenomenon.Recently Whitty,[3] as well as Hunter and Anderson,[4] delineated two types of cooperativity, namely allosteric and chelate cooperativity. The former phenomenon arises from the interplay of two or more intermolecular binding interactions, as exemplified by the binding of oxygen to hemoglobin,[5] and the latter arises from the presence of one or more intramolecular binding interactions, that is, as a consequence of the chelate effect (multivalency). However, while allosteric cooperativity is well recognized, the assessment of chelate cooperativity is still unsatisfactory because of a number of pitfalls that have not been adequately highlighted. To remedy this problem, we report an analysis that consistently assesses chelate cooperativity and introduces, by necessity, a third type of cooperativity, namely interannular cooperativity, which arises from the interplay of two or more intramolecular binding interactions.