Vaidyanathan V G, Nair Balachandran Unni
Chemical Laboratory, Central Leather Research Institute, Adyar, Chennai, 600 020, India.
Dalton Trans. 2005 Sep 7(17):2842-8. doi: 10.1039/b502917a. Epub 2005 Jul 19.
Two mixed ligand complexes of ruthenium(ii) Ru(bzimpy)(bpy)(OH(2)) (1) and Ru(bzimpy)(phen)(OH(2)) (2) have been synthesized and characterized by FAB mass, (1)H NMR, cyclic voltammetry and spectroelectrochemical measurements. Controlled potential electrolysis of these complexes results in the conversion of ruthenium(ii) to ruthenium(iii) at 0.6 V and ruthenium(iii) to ruthenium(iv) at 0.8 V vs. SCE. The binding constant of these complexes with DNA has been determined electrochemically and found to be (3.58 +/- 0.25) x 10(4) and (2.87+/- 0.2) x 10(4) M(-1). Viscosity measurements suggest that these complexes bind with DNA through intercalation. Such intercalative binding to DNA has been found to induce chirality to the two complexes. Electrochemically generated ruthenium(iv) species of these complexes have been found to bring about oxidative cleavage in DNA.
已合成了两种钌(II)的混合配体配合物Ru(bzimpy)(bpy)(OH(2))(1)和Ru(bzimpy)(phen)(OH(2))(2),并通过快原子轰击质谱、核磁共振氢谱、循环伏安法和光谱电化学测量对其进行了表征。对这些配合物进行控制电位电解,结果表明,相对于饱和甘汞电极,在0.6 V时钌(II)会转化为钌(III),在0.8 V时钌(III)会转化为钌(IV)。已通过电化学方法测定了这些配合物与DNA的结合常数,结果分别为(3.58 +/- 0.25) x 10(4)和(2.87 +/- 0.2) x 10(4) M(-1)。粘度测量表明,这些配合物通过嵌入作用与DNA结合。已发现这种与DNA的嵌入结合会使这两种配合物产生手性。已发现这些配合物的电化学生成的钌(IV)物种会导致DNA发生氧化裂解。