物理化学学报 >> 2013, Vol. 29 >> Issue (09): 1937-1944.doi: 10.3866/PKU.WHXB201307023

理论与计算化学 上一篇    下一篇

2’-脱氧腺苷-5’-磷酸与羟基自由基反应所形成的自由基

侯若冰1, 唐宗湘2, 樊友军1, 义祥辉3, 王贝贝1, 孙彦丽1   

  1. 1 广西师范大学化学化工学院, 广西 桂林 541004;
    2 南京中医药大学基础医学院, 南京 210046;
    3 桂林师范高等专科学校, 广西 桂林 541002
  • 收稿日期:2013-05-08 修回日期:2013-07-01 发布日期:2013-08-28
  • 通讯作者: 侯若冰 E-mail:rbhou@163.com
  • 基金资助:

    国家自然科学基金(31271181, 21263002);江苏省自然科学基金(BK2011811);广西自然科学基金(2013GXNSFAA019024)资助项目

Radicals Created fromthe Reactions of 2’-Deoxyadenosine-5’-monophosphate with Hydroxyl Radical

HOU Ruo-Bing1, TANG Zong-Xiang2, FAN You-Jun1, YI Xiang-Hui3, WANG Bei-Bei1, SUN Yan-Li1   

  1. 1 College of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin 541004, Guangxi Province, P. R. China;
    2 College of Basic Medicine, Nanjing University of Chinese Medicine, Nanjing 210046, P. R. China;
    3 Guilin Normal College, Guilin 541002, Guangxi Province, P. R. China
  • Received:2013-05-08 Revised:2013-07-01 Published:2013-08-28
  • Contact: HOU Ruo-Bing E-mail:rbhou@163.com
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (31271181, 21263002), Natural Science Foundation of Jiangsu Province, China (BK2011811), and Guangxi Natural Science Foundation, China (2013GXNSFAA019024).

摘要:

运用可靠的B3LYP/DZP++方法研究了2'-脱氧腺苷-5'-单磷酸(dAMP)与羟基自由基(HO·)的反应中所产生的20余种自由基. 结果表明, 反应的初始产物包括HO·加成到dAMP碱基C8、C4位上所形成的羟基加合物自由基, 以及dAMP碱基环上氨基的脱氢自由基. 而且,反应最初形成的C4位羟基加合物自由基具有脱水产生dAMP碱基环上氨基脱氢自由基的热力学趋势, 脱水形成的两种氨基脱氢自由基都是强氧化剂.尽管HO·加成到dAMP碱基C2位上所形成的加成产物比C4位的加成产物更稳定, 但dAMP与HO·的氧原子间较强的静电排斥作用却使得HO·难以靠近C2原子, 导致C2位的羟基加成产物难以形成. 上述结论不但与有关实验结果一致, 而且还对一些实验现象作出了合理的解释.

关键词: 2’-脱氧腺苷-5’-磷酸, 羟基自由基, 加成反应, 脱氢反应

Abstract:

The radicals generated fromreactions of 2'-deoxyadenosine-5'-monophosphate (dAMP) with an HO· radical were studied by the reliable B3LYP/DZP++ method. The results show that the initial primary products are the radicals of HO· addition at the C8 and C4 sites of dAMP and those of dehydrogenation from the NH2 moiety of dAMP. Moreover, the initial radicals of the C4 site adducts of HO· tend thermodynamically to take place dehydration reactions that yields strong oxidizing, H-abstraction radicals fromthe NH2 group of dAMP. The electrostatic repeller interaction between the dAMP molecule and HO· results in HO· addition radicals of the C2 atomof dAMP to be a by-product, even if they are relative stable species. These theoretical results agree well with available experimental observations and give proper explanations for some experimental results.

Key words: 2’-Deoxyadenosine-5’-monophosphate, Hydroxyl radical, Addition reaction, Hydrogen abstraction reaction

MSC2000: 

  • O641