4′-苯基-2，2′：6′，2″-三吡啶镍配合物的合成、结构及其与DNA键合作用的光谱研究(英文)  

Synthesis,Structure,and Interaction with DNA of Nickel(Ⅱ) Complexes Containing 4′-Phenyl-2 2′:6′,2″-terpyridine

作　　者：寇莹莹[1] 顾文[1] 刘慧[1] 马小芳[1] 李冬冬[1] 阎世平[1] 

机构地区：[1]南开大学化学系,天津300071

出　　处：《南开大学学报（自然科学版）》2008年第6期19-25,38,共8页Acta Scientiarum Naturalium Universitatis Nankaiensis

基　　金：Supported by the NNSF of China(20771063,20331020)

摘　　要：用多吡啶配体L(L=4′-苯基-2,2′:6′,2″-三吡啶)合成了两个镍配合物[Ni(L)_2](NO_3)_2(1)和[Ni (L)_2]Cl_2·10H_2O(2),其单晶结构均属于三斜晶系.中心镍离子与两个配体上的六个氮原子配位构成变形八面体结构.配合物2中由Cl_(2A)…O_(6A)…O_(5A)…Cl_(2B)…O_(6B)…O_(5B)构成的六员氢键环呈椅式构象.用电子光谱、荧光光谱研究了它们与小牛胸腺DNA之间的相互作用.随着DNA的加入,电子光谱的最大吸收峰明显红移(14 nm)并伴随有减色效应;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K_(app)分别为1.34×10~6和1.27×10~6mol^(-1)L.结果表明,两配合物均以较强的插入方式与DNA作用.Two nickel （Ⅱ） complexes ENi（L）2]（NO3）2（1） and ENi（L）2]Cl2.10H2O（2） （L=4′-phenyl-2, 2′ ：6′, 2′-terpyridine） have been synthesized and structurally characterized. Both of the complexes crystallize in the triclinic system, space group. The central Ni （ Ⅱ ） ions are coordinated by six nitrogen atoms from the two single tridentate ligands L and possess distorted octahedral geometry. Especially, in complex 2 the hexacyclic hydrogen-bonded ring adopted a chair conformation is constructed via the hydrogen bonds of Cl2A…O6A…O5A… Cl2B…O6B…O5B. Moreover, UV-vis spectra and fluorescence spectra of complexes with calf thymus （CT）-DNA have also been determined. Upon addition of an increasing amount of CT-DNA to the complexes, a remarkable hypochromism and a visible red shift （14 nm） were observed in UV-vis spectrum. The apparent binding constant （Kapp） values for complex 1 and 2 are 1.34×10^6 and 1.27×10^6 mol^-1L for the fluorescence quenching emission spectra of EB-DNA, respectively. The results suggest that the interaction of two complexes with CT- DNA is a strong intercalative mode.

关 键 词：镍(Ⅱ) 多吡啶配体 光谱性质 小牛胸腺DNA 

分 类 号：O164[理学—数学]