脱氧核糖核苷酸阴离子的碱基和磷酸电子脱离能。

Base and phosphate electron detachment energies of deoxyribonucleotide anions.

作者信息

Zakjevskii Viatcheslav V, King Samuel J, Dolgounitcheva Olga, Zakrzewski Viatcheslav G, Ortiz Joseph Vincent

机构信息

Department of Chemistry, Kansas State University, Manhattan, KS 66506-3701, USA.

出版信息

J Am Chem Soc. 2006 Oct 18;128(41):13350-1. doi: 10.1021/ja064621p.

DOI:10.1021/ja064621p

PMID:17031935

Abstract

Photoelectron spectra of deoxyribonucleotide anions are interpreted with ab initio, electron propagator calculations. Ground-state structures display hydrogen bonds which are not present in less stable minima that resemble Watson-Crick fragment geometries. For the adenosine and thymidine anions, there are two vertical electron detachment energies (VEDEs) within 0.1 eV of each other that correspond to phosphate- and base-centered Dyson orbitals (DOs). The first VEDE of the cytidine anion belongs to a phosphate-centered DO. The anomalously low VEDE of the guanosine anion is assigned to a base-centered, pi DO. Higher VEDEs of all four anions also are assigned.

摘要

利用从头算电子传播子计算对脱氧核糖核苷酸阴离子的光电子能谱进行了解释。基态结构显示出氢键，而在不太稳定的极小值中不存在这种氢键，这些极小值类似于沃森-克里克片段的几何结构。对于腺苷和胸腺嘧啶阴离子，彼此之间在0.1 eV范围内有两个垂直电子脱离能（VEDEs），它们分别对应于以磷酸根和碱基为中心的戴森轨道（DOs）。胞嘧啶阴离子的第一个VEDE属于以磷酸根为中心的DO。鸟苷阴离子异常低的VEDE被归因于以碱基为中心的π DO。还对所有四种阴离子的较高VEDE进行了归属。