单核多吡啶配合物的合成及与DNA的相互作用  

Synthesis and interaction with DNA of mononuclear polypyridine complexes

作　　者：寇莹莹[1] 任相浩[1] 岳冠华[1] KOU Ying-ying;REN Xiang-hao;YUE Guan-hua(Key Laboratory of Urban Stormwater System and Water Environment,Beijing University of Civil Engineering and Architecture, Beijing 100044 , China)

机构地区：[1]北京建筑大学城市雨水系统与水环境教育部重点实验室,北京100044

出　　处：《化学研究与应用》2017年第2期217-226,共10页Chemical Research and Application

基　　金：北京建筑大学科研基地建设-科技创新平台-城市雨水环境教育部重点实验室项目(2013年)资助;北京建筑大学博士启动基金项目(00331614012)资助;北京市教育委员会2016年度科技计划一般项目(KM201610016006资助)

摘　　要：利用多吡啶配体Ptpy设计合成了4个新的单核多吡啶过渡金属配合物Ni(Ptpy)_2(NO_3)_2(1)、Ni(Ptpy)_2Cl_2·(10H_2O)(2)、Cd(Ptpy)_2(NO_3)_2·2H_2O(3)和Fe(Ptpy)2(NO_3)_2(4),用红外光谱和元素分析对其进行了表征、X-射线单晶衍射确定了其晶体结构。利用紫外吸收光谱、荧光光谱和圆二色谱等方法研究了配合物与CT DNA的相互作用。结果表明,配合物以插入方式与DNA结合,结合常数分别为7.64×10~3,3.22×10~4,4.13×10~3,7.42×10~3L·mol^(-1)。同时配合物也能较大程度淬灭EB-DNA复合物的荧光,表观键合常数均在105mol^(-1)左右,略小于经典键合常数107mol^(-1)。淬灭机理除配合物3为静态淬灭外,均为动态淬灭机理。CD谱的结果显示配合物的嵌入使DNA碱基的堆积和双螺旋结构变得松散,从而减弱了DNA的稳定性。Four new single nuclear transition metal complexes Ni(Ptpy)2(N03)2(1)>Ni(Ptpy)2C12?(10H20)(2)-^Cd(Ptpy)2(N03)2*2H20(3)和Fe(Ptpy)2(N03)2(4)were designed and synthesized by Ptpy.The composition of the complexes were char-acterized by infrared spectroscopy and elemental analysis,and the crystal structures were determined by X-ray single crystal diffrac-tion.The interaction of complexes with CT DNA was studied by UV absorption spectroscopy,fluorescence spectroscopy and circular dichroism spectroscopy.The spectrophotometric studies showed that the mode of binding could be intercalation and their binding constant Kh are7.64x103,3.22x104,4.13xlO3,7.42x103L?mol At the same time a large extent the complex could quench EB-DNA complexes.The apparent binding constant values for complexes were about105mol1,which was slightly less than the clas-sical bond constant l〇7mol In addition,the quenching mechanism of complexes were dynamic quenching except complex3.The results of CD spectra indicated that the embedding of the complex made the accumulation of DNA bases and the double helix struc-ture become loose,thus weakening the stability of the DNA.

关 键 词：单核 多吡啶配合物 晶体结构 DNA 键合 

分 类 号：O626.32[理学—有机化学]