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配合物[Ru(phen)2(6-OH-dppz)]2+和[Ru(phen)2(6-NO2-dppz)]2+的合成、表征、DNA结合及光切割作用

Synthesis, characterization, DNA-binding and photocleavage of complexes [Ru(phen)2(6-OH-dppz)]2+ and [Ru(phen)2(6-NO2-dppz)]2+.

作者信息

Liu Xue-Wen, Li Jun, Li Hong, Zheng Kang-Cheng, Chao Hui, Ji Liang-Nian

机构信息

Department of Chemistry, The Key Laboratory of Gene Engineering of Ministry of Education, State Key Laboratory of Optoelectronic Materials and Technologies, Zhongshan (Sun Yat-Sen) University, Guangzhou 510275, PR China.

出版信息

J Inorg Biochem. 2005 Dec;99(12):2372-80. doi: 10.1016/j.jinorgbio.2005.09.004. Epub 2005 Oct 27.

Abstract

Two new complexes, (Ru(phen)(2)(6-OH-dppz)) (1) and (Ru(phen)(2)(6-NO(2)-dppz)) (2) (phen=1,10-phenanthroline; 6-OH-dppz=6-hydroxyl-dipyrido[3,2-a:2',3'-c]phenazine; 6-NO(2)-dppz=6-nitro-dipyrido[3,2-a:2',3'-c]phenazine), have been synthesized and characterized by elemental analysis, ES-MS (electrospray mass spectra), (1)H NMR, UV-Vis (UV-visible) and CV (cyclic voltammetry). The DNA-binding behaviors of both complexes have been studied by spectroscopic methods and viscosity measurements. The results indicate that the two complexes all bind to calf thymus DNA (CT-DNA) in an intercalative mode, and the DNA-binding affinity of complex 2 is greater than that of complex 1. In addition, complex 1 can promote photocleavage of pBR322 DNA upon irradiation, whereas complex 2 can promote cleavage of pBR322 DNA both upon irradiation and in the dark, with more efficient cleavage occurring upon irradiation. Theoretical studies for these complexes have been also carried out with the density functional theory (DFT) method. The difference in the DNA-binding behaviors of the two complexes can be reasonably explained by the DFT calculations.

摘要

已合成了两种新的配合物,(Ru(phen)(2)(6-OH-dppz)) (1) 和 (Ru(phen)(2)(6-NO(2)-dppz)) (2)(phen = 1,10-菲咯啉;6-OH-dppz = 6-羟基-二吡啶并[3,2-a:2',3'-c]吩嗪;6-NO(2)-dppz = 6-硝基-二吡啶并[3,2-a:2',3'-c]吩嗪),并通过元素分析、电喷雾质谱(ES-MS)、核磁共振氢谱((1)H NMR)、紫外可见光谱(UV-Vis)和循环伏安法(CV)对其进行了表征。通过光谱方法和粘度测量研究了这两种配合物的DNA结合行为。结果表明,这两种配合物均以插入模式与小牛胸腺DNA(CT-DNA)结合,且配合物2的DNA结合亲和力大于配合物1。此外,配合物1在光照下可促进pBR322 DNA的光裂解,而配合物2在光照和黑暗条件下均可促进pBR322 DNA的裂解,光照时裂解更有效。还采用密度泛函理论(DFT)方法对这些配合物进行了理论研究。DFT计算能够合理地解释这两种配合物在DNA结合行为上的差异。

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