新型双核配合物的形成、与DNA的作用机制及荧光性质研究

利用紫外、荧光和粘度等方法研究了含不同配体的钌(II)配合物Ru(phen)₂CImP]^2＋(CImP＝3,4-二羟基-咪唑并4,5-i]1,10]邻菲咯啉)和Ru(phen)₂TPPZ]^2＋(TPPZ＝四吡啶3,2-a:2',3'-c:3',2'-h:2',3'-j]吩嗪)与DNA的作用机制, 并研究了配合物与Zn^2＋配合后荧光性质变化. 结果表明Ru(phen)₂TPPZ]^2＋与DNA以插入模式作用, 而Ru(phen)₂CImP]^2＋与DNA则以沟面结合模式作用. 向配合物溶液中滴加Zn^2＋后, 配合物Ru(phen)₂TPPZ]^2＋和Ru(phen)₂CImP]^2＋均可以与Zn^2＋形成双核配合物Ru(phen)₂(TPPZ)Zn]^4＋和Ru(phen)₂(CImP)Zn]^4＋, 配合物的荧光减弱. 与DNA作用后, 配合物仍可以与Zn^2＋配位形成双核配合物, 但Ru(phen)₂(TPPZ)Zn]^4＋保持插入模式与DNA作用, 配合物的荧光减弱. 而Ru(phen)₂(CImP)Zn]^4＋与DNA则由沟面结合改为插入结合, 配合物的荧光增强.

Studies on the Formation, DNA-Binding and Luminescent Properties of New Heterobimetallic Complexes

The binding modes of polypyridyl ruthenium(II) complexes Ru(phen)2CImP]2 (CImP: 3,4-dihydroxyl-imidazo4,5-i](1,10-phenanthroline) and Ru(phen)2TPPZ]2 (TPPZ: tetrapyrido3,2-c:2', 3'-e:3',2'-j:2',3'-l]phenazine) with calf thymus DNA have been investigated by spectroscopic and viscosity methods. The luminescent properties of coordinated complexes with Zn2 were also studied. The experimental results indicated that Ru(phen)2TPPZ]2 bound to DNA by intercalation, while Ru(phen)2CImP]2 bound to DNA by groove binding mode. Both complexes could be coordinated with Zn2 to form the heterobimetallic complexes Ru(phen)2(TPPZ)Zn]4 and Ru(phen)2(CImP)Zn]4 , and the emission intensity of complexes decreased with increasing the amount of Zn2 . After binding to DNA, both original complexes could be coordinated with Zn2 to form the heterobimetallic complexes, and Ru(phen)2(TPPZ)Zn]4 kept binding to DNA by intercalation, with the emission intensity decreased, while the binding mode of Ru(phen)2(CImP)Zn]4 was changed from groove binding to intercalation, with increase of the emission intensity.