化学学报 ›› 2012, Vol. 70 ›› Issue (14): 1569-1575.DOI: 10.6023/A12030065 上一篇    下一篇

研究论文

沉淀聚合制备诺氟沙星-Zn2+分子印迹聚合物及其印迹方式的研究

孙妍, 王兵   

  1. 天津工业大学中空纤维膜材料与膜过程省部共建国家重点实验室培育基地, 天津工业大学环境与化学工程学院 天津 300160
  • 投稿日期:2012-03-28 发布日期:2012-05-23
  • 通讯作者: 王兵 E-mail:bingwang666@yahoo.com.cn
  • 基金资助:
    项目受天津市自然科学基金重点项目(No. 10JCZDJC21900)资助

Synthesis of Norfloxacin-Zinc (II) Imprinted Polymer by Precipitation Polymerization and Study on Its Imprinting Form

Sun Yan, Wang Bing   

  1. State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300160
  • Received:2012-03-28 Published:2012-05-23
  • Supported by:
    Project supported by the Natural Science Foundation of Tianjin (No. 10JCZDJC21900).

采用沉淀聚合的方式以诺氟沙星(NFA)-Zn2+为模板分子, 乙二醇二甲基丙烯酸酯为交联剂, 分别选取酸性功能单体甲基丙烯酸与碱性功能单体4-乙烯基吡啶制备了诺氟沙星-Zn2+的分子印迹聚合物. 通过紫外光谱研究发现诺氟沙星与Zn2+及两种功能单体均发生了金属配位印迹作用且形成了比例不同的印迹复合物. 红外光谱的功能基团的表征结果显示, 甲基丙烯酸与诺氟沙星-Zn2+形成了以诱导作用占优的三元配合物, 而4-乙烯基吡啶则与诺氟沙星-Zn2+形成了共轭作用占优的三元配合物. 扫描电镜及粒径分布实验表征了聚合物的物理特性, 结果显示印迹聚合物的表面存在孔及孔道结构而非印迹聚合物的表面较致密不存在孔且制备的印迹聚合物的粒径均在100 μm以下, 其平均粒径为39 μm. 等温结合及选择性实验的结果表明4-乙烯基吡啶为功能单体制备的印迹聚合物的选择性识别性能优于甲基丙烯酸为功能单体制备的印迹聚合物, 其特异性吸附容量和印迹指数分别为66.84 μmol/g 和4.207. 同时在混合溶液的选择性实验中以4-乙烯基吡啶(4-VP)为功能单体制备的印迹聚合物的选择识别诺氟沙星的能力优于以甲基丙烯酸为功能单体的聚合物, 其识别因子分别为3.408和2.909, 而非印迹聚合物对底物的吸附量较小且识别因子均接近于1, 说明非印迹聚合物对底物的识别为非选择性的.

关键词: 诺氟沙星-Zn2+, 沉淀聚合, 金属配位, 诱导作用, 共轭作用

A group of molecularly imprinted polymer (MIP) with specific molecule identification properties for norfloxacin (NFA) was prepared by precipitation polymerization using norfloxacin-Zn2+ as template molecule, ethyleneglycol dimethacrylant as the cross-linker, methacrylic acid and 4-vinyl pyridine as functional monomer respectively. The coordination proportion of the template molecule and functional monomer was studied by ultraviolet spectrum and the characterization of the molecularly imprinted polymer can be achieved by the infrared spectrum analysis. The result indicated that dominant induction imprinted complex with the ratio 1:1 was formed between norfloxacin-Zn2+ and methacrylic acid, while the dominant conjugation imprinted complex was formed by 4-vinyl pyridine as the functional monomer with the ratio of 1:2, and the ChemDraw pictures were used to display the imprinted form of the polymers. Then the scanning electron microscopy and the particle size distribution were used to characterize the physical properties of the molecularly imprinted polymer, the result showed irregular holes and porous scattered in the prepared molecularly imprinted polymer and the non-imprinted polymer surface was dense with no holes, then the particle size of the prepared polymer was less than 100 μm and the average particle size was 39 μm. The adsorption ability of the prepared polymer were researched by the isothermal combined experiment and the result revealed that the prepared molecularly imprinted polymer using 4-vinyl pyridine with the ring space structure as the functional monomer showed better selectivity recognition ability for norfloxacin than methacrylic acid with the chain structure, the specificity adsorption was 66.84 μmol/g and the imprinted index was 4.207, and it also showed better selective ability in the nofloxacin-Zn2+ and ofloxacin-Zn2+ mixture solution, the recognition factor was 3.408. Meanwhile the selective experiment displayed that the adsorption capacity of the non-imprinted polymer was small and closed to each other, therefore the recognition factor was close to 1, this indicated that the recognition ability of the non-imprinted polymer to the adsorption substrate was non selective.

Key words: norfloxacin-Zn2+, precipitation polymerization, metal coordination, induction, conjugation