Electronic Structures, DNA-binding, SAR, and Spectral Properties of Ruthenium Methylimidazole Complexes [Ru（MeIm）4L]^2＋（L=iip,tip,2ntz）  

[Ru（MeIm）4L]^2＋（L=iip，tip，2ntz）的电子结构、DNA-键合、构效关系及光谱特征

作　　者：李国栋[1] 陈兰美[1] 王忻宇 巫玲凤 揭新明[3] 陈锦灿[3] 

机构地区：[1]广东医学院药学院,湛江524023 [2]广东医学院第一临床医学院,湛江524023 [3]广东医学院分析中心,湛江524023

出　　处：《Chinese Journal of Chemical Physics》2014年第2期159-167,I0003,共10页化学物理学报（英文）

基　　金：ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.20903027）, the Natural Science Foundation of Guangdong Province of China （No.9452402301001941）, the Medical Scientific Research Foundation of Guangdong Province of China （No.B2013297）, and the University Student in Guangdong Province Innovation and Entrepreneurship Train ing Program （No.1057112019 and No.1057112013）.

摘　　要：Theoretical studies on the electronic and geometric structures, the trend in DNA-binding affinities as well as the the structure-activity relationship （SAR） of a series of water-soluble Ru（II） methylimidazole complexes, i.e. [Ru（Mehn）4iip]^2＋ （1） （MeIm=l-methylimidazole, iip=2-（1H-imidazo-4-group）-lH-imidazo[n,5-f][1,10]phenanthroline）, [Ru（MeIm）4tip]^2＋ （2） （tip=2-（thiophene-2-group）-lH-imidazo[4,5-f] [i,10]phenanthroline）, and [Ru（Melm）42ntz]^2＋ （3） （2ntz=2-（2-nitro-l,3-thiazole-5-group）-lH-imidazo[4,5-f][1,10]phenanthroline）, were car- ried out using the density functional theory （DFT）. The electronic structures of these Ru（II） complexes were analyzed on the basis of their geometric structures optimized in aqueous solution, and the trend in the DNA-binding constants （Kb） was reasonably explained. The results show that the replacement of imidazole ligand by thiophene ligand can effectively improve the DNA-binding affinity of the complex. Meanwhile, it was found that introduc- ing the stronger electronegative N atom and NO2 group on terminal loop of intercalative ligand can obviously reduce the complex＇s LUMO and HOMO-LUMO gap energies. Based on these findings, the designed complex [Ru（MeIm）42ntz]^2＋ （3） can be expected to have the greatest Kb value in complexes 1-3. In addition, the structure-activity relationships and antitumor mechanism were also carefully discussed, and the antimetastatic activity of the designed complex 3 was predicted. Finally, the electronic absorption spectra of this series of complexes in aqueous solution were calculated, simulated and assigned using DFT/TDDFT methods as well as conductor-like polarizable continuum model （CPCM）, and were in good agreement with the experimental results.

关 键 词：Ruthenium methylimidazole complex DNA-BINDING Structure-activity rela- tionships Spectral property DFT calculation 

分 类 号：R-33[医药卫生]