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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (19): 2319-2327. 上一篇    下一篇

研究论文

香豆素-3-羧酸铒(III)一维配位聚合物[Er(CCA)3(H2O)2]n•2nH2O的溶剂热法合成、晶体结构及与牛血清白蛋白(BSA)的相互作用

杨树平*,1，韩立军2，王大奇3，潘燕4，余志群1，叶海燕1   

  1. (1 淮海工学院化学工程学院 连云港 222005)
    (2 淮海工学院数理学院 连云港 222005)
    (3 聊城大学化学工程学院 聊城 252059)
    ( 4北京大学医学部基础医学院药理系及国家天然仿生药物重点实验室 北京 100191)
  • 投稿日期:2011-04-19 修回日期:2011-05-24 发布日期:2011-06-02
  • 通讯作者: 杨树平 E-mail:spyang66381@yahoo.cn
  • 基金资助:

    国家自然科学基金

Solvothermal Synthesis, Crystal Structure of a 1D Coordination Polymer [Er(CCA)3(H2O)2]n•2nH2O (HCCA＝Coumarin-3-Carboxylic Acid) and the Interaction between the Polymer and Bovine Serum Albumin (BSA)

Yang Shuping*,1 Han Lijun2 Wang Daqi3 Pan Yan4 Yu Zhiqun1 Ye Haiyan1   

  1. (1 School of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005)
    (2 School of Mathematics and Science, Huaihai Institute of Technology, Lianyungang 222005)
    (3 School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059)
    (4 State Key Laboratory of Natural and Biomimetic Drugs, Department of Pharmacology, School of Basic Medical Sciences, Peking University and Institute of System Biomedicine, Peking University, Beijing 100191)
  • Received:2011-04-19 Revised:2011-05-24 Published:2011-06-02
  • Contact: Shu-Ping YANG E-mail:spyang66381@yahoo.cn

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利用溶剂热法合成了一维配位聚合物[Er(CCA)3(H2O)2]n•2nH2O (HCCA＝香豆素-3-羧酸), 通过元素分析和IR对配合物进行了表征, 用X-射线单晶衍射技术测定了其晶体结构. 标题配合物晶体属于单斜晶系, P21/c空间群: a＝0.6310(1) nm, b＝1.4165(2) nm, c＝3.1731(3) nm|β＝91.861(2)°, V＝2.8346(7) nm3, Dc＝1.890 g•cm－3, Z＝4, F(000)＝1596, 残差因子R1＝0.0525, wR2＝0.0930 [I＞2σ(I)], S＝1.290. 配合物的金属中心与来自配体(CCA)和配位水分子的8个氧原子进行配位, 形成了一个畸变的十二面体, 两个相邻的铒(III)离子通过一个羧基桥连成为一维聚合物. 用荧光光谱法研究了不同温度下配合物与牛血清白蛋白(BSA)的相互作用, 结果表明, 配合物对BSA 的荧光猝灭属于静态猝灭, 计算了不同温度下配合物与BSA间的结合常数(Ka), 结合位点(n)及相关热力学参数(ΔH＞0, ΔS＞0), 二者主要靠疏水作用力结合. 依据F?sters 非辐射能量转移理论, 求得给体(BSA)与受体(配合物)间的距离r＝2.85 nm, 说明配合物与BSA 之间发生了非辐射能量转移.

关键词: 铒(Ⅲ)配位聚合物, 香豆素-3-羧酸, 晶体结构, 牛血清白蛋白, 荧光光谱, 溶剂热法

A coordination polymer [Er(CCA)3(H2O)2]n•2nH2O (HCCA＝coumarin-3-carboxylic acid) has been prepared by solvent-thermal method and characterized by elemental analysis and IR spectra and single crystal X-ray diffraction. The crystal of erbium(III) complex belongs to monoclinic system with space group, P21/c, a＝0.6310(1) nm, b＝1.4165(2) nm, c＝3.1731(3) nm|β＝91.861(2)°, V＝2.8346(7) nm3, Dc＝1.890 g•cm－3, Z＝4, F(000)＝1596, residual factors R1＝0.0525, wR2＝0.0930 [I＞2σ(I)], S＝1.290. The Er(III) atom is eight-coordinated by eight O atoms from three ligands (CCA) and two coordinated water molecules, and the coordination polyhedron around the Er(III) atom can be best described as a distorted dodecahedron geometry. Two adjacent Er(III) atoms were bridged into a one-dimensional polymeric chain by the carboxylic group in a ligand (CCA). The interaction between complex and bovine serum albumin (BSA) was investigated by fluorescence spectroscopy at different temperature. The results indicated that the complex quenches the fluorescence of BSA through a static quenching procedure. The binding constants (Ka) and the number of binding sites (n) between the complex and BSA were calculated at different temperature. The corresponding thermodynamic parameters enthalpy changes (ΔH＞0) and entropy changes (ΔS＞0) were also obtained according to the vant Hoff equation. The primary binding pattern between complex and BSA was interpreted as hydrophobic interaction. The binding average distance r between the donor (BSA) and acceptor (complex) was obtained to be 2.85 nm based on the F?sters theory, which indicates the non-radiation energy transfer can occur from BSA to complex with high probability.

Key words: erbium(III) coordination polymer, coumarin-3-carboxylic acid, crystal structure, bovine serum albumin (BSA), fluorescence spectra, solvent-thermal method