The Mechanism of Cleavage of RNA Phosphodiesters by a Gold Nanoparticle Nanozyme

被引：8

作者：

Czescik, Joanna ^{[1
,3
]}

Mancin, Fabrizio ^{[1
]}

Stromberg, Roger ^{[2
]}

Scrimin, Paolo ^{[1
]}

机构：

[1] Univ Padua, Dept Chem Sci, Via Marzolo 1, I-35131 Padua, Italy

[2] Karolinska Inst, NEO, S-14157 Huddinge, Sweden

[3] Aston Univ, Sch Life & Hlth Sci, Birmingham B4 7ET, W Midlands, England

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2021年 / 27卷 / 31期

基金：

欧盟地平线“2020”;

关键词：

Brø nsted plot; gold nanoparticles; metal ion catalysis; phosphate cleavage; RNA cleavage; ZN2+ COMPLEXES; METAL-IONS; CATALYSIS; BASE; BINDING; TRANSESTERIFICATION; MULTIVALENCY; RECOGNITION; HYDROLYSIS; ZINC(II);

D O I：

10.1002/chem.202100299

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The cleavage of uridine 3'-phosphodiesters bearing alcohols with pK(a) ranging from 7.14 to 14.5 catalyzed by AuNPs functionalized with 1,4,7-triazacyclononane-Zn(II) complexes has been studied to unravel the source of catalysis by these nanosystems (nanozymes). The results have been compared with those obtained with two Zn(II) dinuclear catalysts for which the mechanism is fairly understood. Binding to the Zn(II) ions by the substrate and the uracil of uridine was observed. The latter leads to inhibition of the process and formation of less productive binding complexes than in the absence of the nucleobase. The nanozyme operates with these substrates mostly via a nucleophilic mechanism with little stabilization of the pentacoordinated phosphorane and moderate assistance in leaving group departure. This is attributed to a decrease of binding strength of the substrate to the catalytic site in reaching the transition state due to an unfavorable binding mode with the uracil. The nanozyme favors substrates with better leaving groups than the less acidic ones.

引用

页码：8143 / 8148

页数：6

共 40 条

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