物理化学学报 >> 2012, Vol. 28 >> Issue (01): 73-77.doi: 10.3866/PKU.WHXB20122873

理论与计算化学 上一篇    下一篇

A-T碱基对单羟基自由基加成产物的单电子氧化还原性质

侯若冰, 孙彦丽, 王贝贝   

  1. 广西师范大学化学化工学院, 广西桂林 541004
  • 收稿日期:2011-08-01 修回日期:2011-10-24 发布日期:2011-12-29
  • 通讯作者: 侯若冰 E-mail:rbhou@163.com

One-Electron Redox Characteristics of One-Hydroxyl Radical Adducts of A-T Base Pairs

HOU Ruo-Bing, SUN Yan-Li, WANG Bei-Bei   

  1. College of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin 541004, Guangxi Province, P. R. China
  • Received:2011-08-01 Revised:2011-10-24 Published:2011-12-29
  • Contact: HOU Ruo-Bing E-mail:rbhou@163.com

摘要: 采用密度泛函理论在B3LYP/DZP++//B3LYP/6-31++G(d,p)水平上研究A-T 碱基对的单羟基加成产物的氧化还原性质. 计算表明, 所有8 种加成复合物都表现出显著的氧化性, 但其还原性却很弱. 加成复合物AC2-T、AC4-T、AC5-T 的俘获电子诱发T碱基N3位上的H原子向A碱基的N1位迁移, 产生这种氢迁移的根源在于A碱基俘获电子后电子密度较大, 有利于在A碱基上形成新的N-H键.

关键词: A-T碱基对, 加成反应, 羟基自由基, 电子亲合势, 单电子氧化还原

Abstract: The one-electron redox characteristics of one-hydroxyl radical adducts of adenine-thymine base pairs were calculated using density functional theory at the B3LYP/DZP ++//B3LYP/6-31 ++ G(d,p) level. The computational results indicate that all eight adducts are strong oxidizing agents and very weak reducing agents. For the AC2-T, AC4-T, and AC5-T adducts electron capture causes a hydrogen atom migration from the N3 site of thymine to the N1 site of adenine. The hydrogen atom transfer reactions in the anion adducts are attributable to a higher electron density of the adenine moiety. The higher electron density favors the formation of a new N-H bond on the adenine base.

Key words: Adenine-thymine base pair, Addition reaction, Hydroxyl radical, Electron affinity, One-electron redox

MSC2000: 

  • O641