Esterolytic action of synthetic macromolecules
Esterolytic action of synthetic macromolecules
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合成大分子的酯解作用
DOI：
10.1021/ar50019a004
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发表时间：
1969
影响因子：
18.3
通讯作者：
J. C. Salamone
中科院分区：
文献类型：
--
作者：
C. Overberger;J. C. Salamone
利用合成大分子来改变低分子量物种的活性最近受到了相当大的关注，特别是因为这些反应可以作为更复杂的酶促过程的模型。虽然这些聚合催化剂的效率比酶催化剂低得多，但已经揭示了天然和合成大分子系统之间的一些相似之处。例如，合成聚合物物种可以具有以下特征：(a)比相应的单体体系具有更高的反应活性，2 (b)底物水解的特异性（特别是如果底物与聚合物上的带电基团的电荷相反），2-4 (c)与活性底物相似的物质的竞争性抑制，6·6 (d)涉及两个附属官能团和底物相互作用的双功能催化。2·4·7-9和(e)高分子量和低分子量试剂的饱和（络合）。总的来说，合成聚合物对低分子量化合物的行为有两种不同的类型。首先，如果两个低分子量离子是反应试剂，那么带有带电基团的聚合物将倾向于在其附近聚集和/或排斥一个或两个低分子量试剂，因此，将起到反应的抑制剂或加速器的作用。其次，如果将催化活性功能添加到含有带电基团的聚合物中，那么聚合物本身，而不是其反离子，能够与带电的或带电的反应
The utilization of synthetic macromolecules to change thereactivities of low molecular weight species has recently received considerable attention, 2 particu-larly since these reactions can serve as models for the more complex enzymatic processes. Although these polymeric catalysts are considerably less efficient than enzymic catalysts, several analogies between the natural and synthetic macromolecular systems have been revealed. For example, synthetic polymeric species can be characterized by (a) higher reactivities than corresponding monomeric systems, 2 (b) specificity of substrate hydrolysis (particularly if the substrate is of a charge opposite to that of the charged groups on the polymer), 2-4 (c) competitive inhibition by substances similar to the reactive substrate, 6· 6 (d) bifunctional catalysis involving the interactions of two pendent functional groups and substrate, 2· 4· 7-9 and (e) satura-tion (complexation) by high and low molecular weight reagents. 6· 10-14 In general, the behaviors of synthetic polymers toward low molecular weight compounds are of two different types. First, if two low molecular weight ionic species are the reactive reagents, a polymer with charged groups will tend to concentrate and/or repel one or both low molecular weight reagents in its vicinity and, consequently, will functon as either an inhibitor or an accelerator of the reaction. Secondly, if cata-lytically active functions are added to a polymer which contains charged groups, the polymer itself, and not its counterions, is able to react with either charged or