The relationship among pKa,pH, and binding constants in the interactions between boronic acids and diols -: it is not as simple as it appears
The relationship among pKa,pH, and binding constants in the interactions between boronic acids and diols -: it is not as simple as it appears
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DOI：
10.1016/j.tet.2004.08.051
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发表时间：
2004-11-29
期刊：
影响因子：
2.1
通讯作者：
Wang, BH
中科院分区：
文献类型：
--
作者：
Yan, J;Springsteen, G;Wang, BH
在我们持续努力设计识别细胞表面碳水化合物的基于硼酸的传感器中，有必要检查影响硼酸部分和二醇之间的结合亲和力的各种因素。目前流行的观点是，最强的硼酸/二醇复合物是由高溶液pH和低硼酸pK（a）的组合产生的。然而，从未系统地研究过结合常数、硼酸pK（a）和溶液pH值之间的关系。在这里，我们报告了我们的研究结果与一系列的25个芳基硼酸与各种取代基和它们的结合亲和力与二醇。我们发现：（1）单取代苯基硼酸与取代基的pK（a）之间的关系可用Hammet图来描述，（2）结合的最佳pH值并不总是高于硼酸的pK（a），而是受硼酸和二元醇的pK（a）值以及其它未知因素的影响;和（3）一般认为pK（a）值较低的硼酸对二醇显示出较大的结合亲和力并不总是正确的。(C)2004爱思唯尔有限公司保留所有权利。
In our continuing efforts into designing boronic acid-based sensors that recognize cell-surface carbohydrates, it has been necessary to examine various factors that affect the binding affinity between a boronic acid moiety and a diol. The current prevailing view is that the strongest boronic acid/diol complexes are generated by a combination of high solution pH and a low boronic acid pK(a). However, there has never been a systematic examination of the relationship among the binding constants, boronic acid pK(a), and the pH of the solution. Herein we report our findings with a series of 25 arylboronic acids with various substituents and their binding affinities with diols. We have found that (1) the relationship between the pK(a), of monosubstituted phenylboronic acid and its substituents can be described using a Hammet plot; (2) the optimal pH for binding is not always above the pK(a) of the boronic acid, and is affected by the pK(a) values of the boronic acid and the diol, and other unknown factors; and (3) the general belief that boronic acids with lower pK(a) values show greater binding affinities for diols is not always true. (C) 2004 Elsevier Ltd. All rights reserved.