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腺嘌呤-胸腺嘧啶碱基对中氢原子转移及其与电子重排的耦合的理论研究。协同与分步机制。

Theoretical investigation of hydrogen atom transfer in the adenine-thymine base pair and its coupling with the electronic rearrangement. Concerted vs. stepwise mechanism.

机构信息

Istituto per i Processi Chimico-Fisici, IPCF-CNR, Via G. Moruzzi, 1, I-56124 Pisa, Italy.

出版信息

Phys Chem Chem Phys. 2010 Mar 20;12(11):2664-9. doi: 10.1039/b917672a. Epub 2010 Jan 27.

DOI:10.1039/b917672a
PMID:20200744
Abstract

Two different mechanisms to obtain the imino-enol tautomer of the adenine-thymine base pair, a concerted hydrogen atom transfer and a stepwise process, have been studied and compared. The first mechanism includes both the concerted movement of two hydrogen atoms, in the bridges that bond the two bases, and an electronic reorganisation of the bonds. The stepwise mechanism is the simplest one where there is a correlation between the movement of the hydrogen atoms, but two or more steps can be identified. In this study, a different behaviour has been found when the first atom to move is the hydrogen in the N-N bridge or that in the N-O one.

摘要

已经研究并比较了两种获得腺嘌呤-胸腺嘧啶碱基对亚氨基-烯醇互变异构体的不同机制,即协同氢原子转移和逐步过程。第一种机制包括连接两个碱基的桥中两个氢原子的协同运动以及键的电子重新排列。逐步机制是最简单的机制,其中氢原子的运动存在相关性,但可以识别出两个或更多步骤。在这项研究中,当第一个移动的原子是 N-N 桥中的氢原子或 N-O 桥中的氢原子时,发现了不同的行为。

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