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化学学报
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化学学报 ›› 2009, Vol. 67 ›› Issue (21): 2517-2522. 上一篇    下一篇

研究简报

三核铜(I/II)配合物[Cu(en)2][Cu(pht)2]2的合成、晶体结构及与DNA相互作用的研究

胡喜兰*,a   施鹏飞a   许兴友a    栾艳a   陈建平a   王大奇b   

  1. (a淮海工学院配位化学研究所 连云港 222005)   (b聊城大学化学化工学院 聊城 252059)
  • 投稿日期:2008-12-08 修回日期:2009-04-29 发布日期:2009-07-14
  • 通讯作者: 胡喜兰 E-mail:huxilan@hhit.edu.cn
  • 基金资助:

    江苏省高校自然科学重大基础研究基金(No.07KJA15011)、淮海工学院自然科学基金(No.KX07042)、淮海工学院引进人才启动基金(No.KK01060)资助项目

Synthesis, Crystal Structure and DNA-binding Studies of Cu(I/II) Complex [Cu(en)2]•[Cu(pht)2]2

Hu, Xilan*,a   Shi, Pengfeia    Xu, Xingyoua    Luan, Yana    Chen, Jianpinga    Wang, Daqib   

  1. (a Research Section of Coordination Chemistry, Huaihai Institute of Technology, Lianyungang 222005) (b College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059)
  • Received:2008-12-08 Revised:2009-04-29 Published:2009-07-14

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报道了多核铜配合物[Cu(en)2]•[Cu(pht)2]2 (Hpht: 苯妥英, 即5,5-二苯基-2,2-咪唑烷酮; en: 乙二胺)的溶剂热合成、晶体结构及其与DNA的相互作用. 该晶体属三斜晶系, Pī空间群, 晶胞参数: a＝0.8453(2) nm, b＝1.1878(3) nm, c＝1.5674(4) nm, α＝101.197(3)°, β＝97.690(3)°, γ＝103.283(3)°, V＝1.476(6) nm 3, Dc＝1.480 g/cm3, Z＝1, F(000)＝679, µ＝1.139 mm－1, R1＝0.0402, wR2＝0.0962[I＞2σ(I)], GOF＝1.035. XPS和X射线单晶衍射数据显示该配合物分子由混价铜组成, 包括两个一价铜和一个二价铜, 其中每个Cu(I)分别与两个苯妥英配体提供的氮原子配位, N—Cu(I)—N的夹角为177°, 一个Cu(II)与六个配位原子配位(CuN4O2), 形成一个稍变形八面体结构. 配合物与DNA相互作用研究表明, 该配合物主要是以插入方式与小牛胸腺DNA结合.

关键词: 苯妥英, 铜(I/II)配合物, 小牛胸腺DNA

The title complex [Cu(en)2]•[Cu(pht)2]2 (Hpht＝5,5-diphenylhydantoin, i.e. phenytoin; en＝ethylenediamine) was synthesized solvent-thermally and characterized by elemental analysis, IR, TG-DSC and single-crystal X-ray diffraction. The crystal of the complex belongs to triclinic system with space group Pī, a＝0.8453(2) nm, b＝1.1878(3) nm, c＝1.5674(4) nm, α＝101.197(3)°, β＝97.690(3)°, γ＝103.283(3)°, V＝1.476(6) nm 3, Dc＝1.480 g/cm3, Z＝1, F(000)＝679, µ＝1.139 mm－1, final R [I＞2σ(I)]: R1＝0.0402 , wR2＝0.0962 and GOF＝1.035. The XPS and single-crystal X-ray diffraction data demonstrated that the complex was mix-charged, including two Cu(I) and one Cu(II) metal centers. The Cu(I) atom was coordinated by two nitrogen atoms from two phenytoin ligands, and the angle of N—Cu(I)—N was 177°. The Cu(II) atom adopted a distorted CuN4O2 octahedron configuration when coordinated with two en and two phenytoin ligands. The interaction between the complex and CT-DNA was studied by UV spectroscopy, fluorescence spectroscopy and viscosity measurements, which confirmed the intercalation effect of the complex into DNA double helix.

Key words: 5,5-diphenylhydantoin, copper(I/II) complex, calf thymus DNA

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