Salvio Riccardo
Dipartimento di Chimica and IMC-CNR, Sezione Meccanismi di Reazione, La Sapienza Università di Roma, Piazzale Aldo Moro 5, 00185 (Italy).
Chemistry. 2015 Jul 27;21(31):10960-71. doi: 10.1002/chem.201500789. Epub 2015 May 4.
Examples of guanidinium-based artificial phosphodiesterases are illustrated in this review article. A wide set of collected catalytic systems are presented, from the early examples to the most recent developments of the use of this unit in the design of supramolecular catalysts. Special attention is dedicated to illustrate the operating catalytic mechanism and the role of guanidine/ium units in the catalysis. One or more of these units can act by themselves or in conjunction with other active units. The analogy with the mechanism of enzymatic systems is presented and discussed. In the last part of this overview, recent examples of guanidinophosphodiesterases based on nanostructured supports are reported, namely gold-monolayer-protected clusters and polymer brushes grafted to silica nanoparticles. The issue of the dependence of the catalytic performance on the preorganization of the spacer is tackled and discussed in terms of effective molarity, a parameter that can be taken as a quantitative measurement of this preorganization for both conventional molecular linker and nanosized supports.
本文综述了基于胍鎓的人工磷酸二酯酶的实例。展示了一系列收集到的催化体系，从早期实例到该单元在超分子催化剂设计中的最新进展。特别关注阐述其催化作用机制以及胍/鎓单元在催化中的作用。这些单元中的一个或多个可以单独起作用，也可以与其他活性单元协同作用。文中展示并讨论了与酶促体系机制的类比。在本综述的最后部分，报道了基于纳米结构载体的胍基磷酸二酯酶的最新实例，即金单层保护簇和接枝到二氧化硅纳米颗粒上的聚合物刷。从有效摩尔浓度的角度探讨并讨论了催化性能对间隔基预组织的依赖性问题，有效摩尔浓度是一个可用于定量测量传统分子连接体和纳米尺寸载体的这种预组织的参数。
