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机构地区:[1]北京工业大学环境与能源工程学院,北京100022
出 处:《分析科学学报》2013年第4期493-496,共4页Journal of Analytical Science
基 金:国家自然科学基金(No.21005005);北京市教委科技发展基金重点项目(No.KZ201110005006);北京市自然科学基金(No.8102009)
摘 要:合成了含有嵌入配体二吡啶并[3,2-a:2′,3′-c]-吩嗪(dppz)的钌配合物二联吡啶二吡啶并[3,2-a;2′,3′-c]吩嗪钌([Ru(bpy)2dppz]2+),并对其结构和物理化学性质进行了表征。采用方波伏安法研究了[Ru(bpy)2dppz]2+与天然双链小牛胸腺DNA的相互作用,实验结果表明,[Ru(bpy)2dppz]2+配合物的嵌入配体会嵌入DNA的碱基对中,与DNA结合形成体积较大的"金属配合物-DNA"联合体,该联合体在电解质溶液中扩散速度较慢,导致溶液中游离的钌配合物分子减少,峰电流信号降低。计算得到[Ru(bpy)2dppz]2+与DNA的结合常数Ka=1.7×105 L/mol,结合位点n=0.84。The ruthenium complex with DPPZ (dipyrido[-3, 2-a: 2', 3'-c]-phenazine) as a ligand was prepared. TheERu(bpy)zdpp2]2+ (bpy=2,2-bipyridine, dppz=dipyrido[3,2-a:2',3'-c] phenazine) complex was characterized by UV-Vis,IH NMR,fluorescenee spectra and electrochemical analysis and was found to exhibit the expected propellerqike structure with significant intermolecular ~r-stacking interactions. The binding interaction of [Ru (bpy)a dppz]2+ with calf-thymus deoxyribonucleic acid (DNA) was studied by square wave voltammetry. The result showed that metallo-intercalators could intercalate into the double helix of DNA,and formed a "metallo-intercalators-DNA" complex. Due to the slow diffusion of the complex in the solution, anodic peak current decreased. The binding parameters, including the binding constant (K.) and the binding-site size (n), were obtained simultaneously by the analysis of bound and free [Ru(bpy)2dppz]2+ concentration corresponding to the limits of slow and fast binding kinetics compared to the experimental timescale. The binding constant(Ka) was 1.7×10s L/mol, and the calculated binding-site size(n) was 0.84 base pair,which was consistent with the reported values.
关 键 词:DNA [Ru(bpy)2dppz]2+ 伏安法 结合常数
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