物理化学学报 >> 2010, Vol. 26 >> Issue (12): 3322-3328.doi: 10.3866/PKU.WHXB20101215

量子化学及计算化学 上一篇    下一篇

金属离子(Na+、K+、Ca2+、Mg2+、Zn2+)与鸟嘌呤异构体配合物的稳定性

赵永平, 艾洪奇, 陈金鹏, 杨爱彬, 齐中囡   

  1. 济南大学化学化工学院, 济南250022
  • 收稿日期:2010-08-13 修回日期:2010-09-24 发布日期:2010-12-01
  • 通讯作者: 艾洪奇 E-mail:chm_aihq@ujn.edu.cn
  • 基金资助:

    国家自然科学基金(20973084, 20573047), 及山东省自然科学基金(Y2008B56)和优秀中青年科研奖励基金(2007BS02009)资助项目

Stability of Complexes Combined by Metal Ions (Na+, K+, Ca2+, Mg2+, Zn2+) and Guanine Isomers

ZHAO Yong-Ping, AI Hong-Qi, CHEN Jin-Peng, YANG Ai-Bin, QI Zhong-Nan   

  1. School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, P. R. China
  • Received:2010-08-13 Revised:2010-09-24 Published:2010-12-01
  • Contact: AI Hong-Qi E-mail:chm_aihq@ujn.edu.cn
  • Supported by:

    The project was supported by National Natural Science Foundation of China (20973084, 20573047), Natural Science Foundation of Shandong Province, China (Y2008B56) and Research Fund for Young and Middle-aged People of Shandong Province, China (2007BS02009).

摘要:

在B3LYP/6-311++G**水平上用极化连续介质模型(PCM)系统研究了金属离子(M+/2+=Na+, K+, Ca2+, Mg2+, Zn2+)和十三种鸟嘌呤异构体形成的配合物GnxM+/2+(n为鸟嘌呤异构体的编号, x表示M+/2+与鸟嘌呤异构体的结合位点)在气(g)液(a)两相中的稳定性顺序. 着重探讨了液相中配合物的稳定性差异, 并且从溶质-溶剂效应、结合能、形变能及异构体的相对能量等几个方面分析了造成稳定顺序发生变化的原因. 报道了溶液中这五种金属离子与鸟嘌呤异构体结合形成的六种基态配合物: aG1N2,N3Na+, aG1N2,N3K+, aG1O6,N7Ca2+, aG1N2,N3Mg2+(aG1O6,N7Mg2+), aG2N3,N9Zn2+. 可以看出, 除了在Zn2+配合物中鸟嘌呤异构体为G2 外, 构成其余四种金属离子配合物的鸟嘌呤异构体都是G1, 但结合位点不同. 同时对气相中各类配合物稳定性也进行了系统的排序, 并报道了几种较稳定的配合物, 如: gG3N1,O6K+, gG5N1,O6K+, gG3N1,O6Ca2+/Mg2+, gG4O6,N7Ca2+/Mg2+.

关键词: 鸟嘌呤异构体, 稳定性, 金属离子, 溶质-溶剂效应, 结合能

Abstract:

The order of stability for complexes of differently coordinated metal ions (M+/2+=Na+, K+, Ca2+, Mg2+, Zn2+) with thirteen guanine isomers in gas (g) and aqueous (a) phases was systematically investigated at the B3LYP/6-311++G** level in combination with the polarized continuum model (PCM). Special effort was devoted to differences in the order of stability for aGnxM+/2+ (n is the label of guanine isomers, x denotes binding site of M+/2+ and guanine isomers) complexes that were obtained in aqueous solutions. An analysis was also performed to determine the reason for these differences with respect to the solute-solvent effect, binding energy, deformation energy, and relative free energy of the guanine isomers. The most stable complexes generated by the five metal ions were: aG1N2,N3Na+ , aG1N2,N3K+ , aG1O6,N7Ca2+ , aG1N2,N3Mg2+ (aG1O6,N7Mg2+), and aG2N3,N9Zn2+. The isomer of guanine in the most stable Zn2+ complex in the aqueous solution was G2 whereas in the other four most stable complexes it was G1, i.e., the different active sites in G1 generate the four most stable complexes. Additionally, we report on stable complexes in the gas phase such as gG3N1,O6K+, gG5N1,O6K+, gG3N1,O6Ca2+/Mg2+, and gG4O6,N7Ca2+/Mg2+.

Key words: Guanine isomer, Stability, Metal ion, Solute-solvent effect, Binding energy

MSC2000: 

  • O641