单取代大环多胺铜(Ⅱ)-铂(Ⅱ)异核配合物的合成、表征及其与DNA的作用
Preparation, Characterization, and DNA Binding Property of a Cu-Pt Heterodinuclear Complex Derived from Monosubstituted Cyclen
作者单位
杜 俊 南京大学化学化工学院配位化学国家重点实验室南京 210093
安徽师范大学化学与材料科学学院芜湖 241000 
吴子怡 南京大学化学化工学院配位化学国家重点实验室南京 210093 
贾 默 南京大学化学化工学院配位化学国家重点实验室南京 210093 
李一志 南京大学化学化工学院配位化学国家重点实验室南京 210093 
王晓勇 南京大学生命科学学院医药生物技术国家重点实验室南京 210093 
郭子建 南京大学化学化工学院配位化学国家重点实验室南京 210093 
摘要: 本文以1-[N-2′-(2″-吡啶基)乙基]甲氨酰甲基-1,4,7,10-四氮杂环十二烷为配体合成了一种铜(Ⅱ)-铂(Ⅱ)异核配合物,并用X-射线衍射单晶结构分析测定了配合物的晶体结构。该配合物晶体属三斜晶系,P1空间群,铜(Ⅱ)以五配位方式形成变形四方锥构型,铂(Ⅱ)以四配位方式形成平面四方构型。琼脂糖凝胶电泳实验证明配合物既能结合DNA,也能在还原剂存在下切割DNA。圆二色光谱表明配合物与DNA以非嵌入方式结合。
关键词: 铜-铂异核配合物  四氮杂环十二烷  晶体结构  DNA切割
基金项目: 
Abstract: A Cu-Pt heterodinuclear complex [CuPt(L-2H)Cl2]·5H2O (1) derived from 1-[N-(2′-(2″-pyridyl)ethyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane (L) has been synthesized and fully characterized. Complex 1 crystallizes in a triclinic system with space group P1, a=0.887 29(18) nm, b=1.028 9(2) nm, c=1.648 7(3) nm, α=85.128(2)°, β=83.975(3)° and γ=88.942(2)°. In the crystal structure, copper(Ⅱ) coordinates with four cyclic nitrogen atoms and a oxygen atom, forming a distorted square pyramid geometry with oxygen occupying the apical position. Platinum(Ⅱ) coordinates with two nitrogen atoms from carbamoyl and pyridyl respectively and two chloride ions, forming a square plane geometry with chloride ions adopting a cis configuration as in cisplatin. Agarose gel electrophoresis assay shows that complex 1 can bind to plasmid pUC19 DNA and cleave its supercoiled form into nicked form in the presence of ascorbate. Circular dichroism (CD) spectra obtained with CT-DNA suggests that the complex may interact with DNA by a non-intercalative mode. Crystallographic data have been deposited at the Cambridge Crystallographic Data Center with CCDC: 669337.
Keywords: Cu-Pt heterodinuclear complex  1,4,7,10-tetraazacyclododecane  crystal structure  DNA cleavage
 
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杜 俊,吴子怡,贾 默,李一志,王晓勇,郭子建.单取代大环多胺铜(Ⅱ)-铂(Ⅱ)异核配合物的合成、表征及其与DNA的作用[J].无机化学学报,2008,24(10):1669-1674.
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