苯丙氨酸席夫碱邻菲咯啉铜(Ⅱ)配合物的合成、晶体结构及其与DNA作用研究  

Synthesis,Crystal Structure and DNA Interaction of a Copper(Ⅱ) Complex with Ligands of L-Phenylalanine Schiff Base and 1,10-Phenanthroline

作　　者：蒲雪炜[1] 李连之[1] 董建方[1,2] 黄蕾[1] 边琳[1] 

机构地区：[1]聊城大学化学化工学院,聊城252059 [2]山东工程技师学院材料科学系,聊城252027

出　　处：《化学学报》2011年第6期647-652,共6页Acta Chimica Sinica

基　　金：山东省自然科学基金(No.Y2004B02)资助项目

摘　　要：合成了一个新的L-苯丙氨酸邻香草醛席夫碱及邻菲咯啉混配铜(Ⅱ)配合物[Cu(o-van-phe)(phen)]·CH3OH.通过元素分析、红外光谱对其进行了表征.采用X射线单晶衍射测定其晶体结构,结果表明该配合物属于单斜晶系,C2空间群:a=1.15637(17)nm,b=1.8562(2)nm,c=1.34249(18)nm,β=98.385(2)°,V=2.8509(7)nm3,Dc=1.335 g/cm3,Z=4,F(000)=1188,最终的偏差因子为R1=0.0574,wR2=0.1540[Ⅰ>2σ(Ⅰ)].五配位的铜离子形成一个畸变的四方锥配位构型,相邻两主体分子之间通过氢键形成二聚体结构.紫外光谱、荧光光谱和圆二色光谱测定结果表明,配合物与小牛胸腺DNA(CT-DNA)以插入方式相互作用,结合常数Kb=9.697×103 L·mol-1.凝胶电泳研究表明,配合物可将环形质粒pBR322 DNA切割为缺刻型和线型DNA.A new copper（II） complex with mixed-ligands of a Schiff base derived from L-phenylalanine and o-vanillin and 1,10-phenanthroline,[Cu（o-van-phe）phen]·CH3OH,has been synthesized and character-ized by elemental analyses and IR spectra.Single crystal X-ray diffraction results suggest that the complex structure belongs to monoclinic crystal system,C2 space group with the cell dimensions： a=1.15637（17） nm,b=1.8562（2） nm,c=1.34249（18） nm,β=98.385（2）°,V=2.8509（7） nm3,Dc=1.335 g/cm3,Z=4,F（000）=1188,the final R1=0.0574,and wR2=0.1540 [Ⅰ2σ（Ⅰ）].The copper（Ⅱ） ion is five-coordinated and displays CuN3O2 distorted square-pyramid coordination geometry.The dimeric structure is formed by hy-drogen bonds of two adjacent molecules.The interaction of the complex with CT-DNA has been investi-gated by UV,fluorescence and circular dichroism（CD） spectra.Results show that this copper（Ⅱ） complex binds to calf thymus DNA（CT-DNA） in an intercalative mode and its intrinsic binding constant Kb is 9.697×103 L·mol-1.Furthermore,the DNA cleavage activity of this copper complex has also been studied by submarine gel electrophoresis,and it was found that this complex can cleave circular plasmid pBR322 DNA to both nicked and linear forms.

关 键 词：铜(Ⅱ)配合物 苯丙氨酸 席夫碱 晶体结构 DNA 

分 类 号：O627.12[理学—有机化学]