化学学报 ›› 2016, Vol. 74 ›› Issue (2): 199-207.DOI: 10.6023/A15090636 上一篇    

研究论文

双功能单体法制备磁性葡萄糖分子印迹聚合物及其吸附性能研究

智康康a,b, 董爱军a, 杨鑫a, 赵倩玉a, 赵海田a, 张华a, 王静a,b, 徐鹏飞a   

  1. a 哈尔滨工业大学 化工学院 黑龙江 哈尔滨 150000;
    b 中国农业科学院 农业质量标准与检测技术研究所 农业部农产品质量安全重点实验室 北京 100081
  • 投稿日期:2015-09-29 发布日期:2015-12-23
  • 通讯作者: 杨鑫, 王静 E-mail:yangxin@hit.edu.cn;w_jing2001@126.com
  • 基金资助:

    项目受哈尔滨学术带头人项目(No.2014RFXXJ113)资助.

Preparation and Adsorption Properties Study of Glucose Magnetic Molecularly Imprinted Polymers with Dual Functional Monomers

Zhi Kangkanga,b, Dong Aijuna, Yang Xina, Zhao Qianyua, Zhao Haitiana, Zhang Huaa, Wang Jinga,b, Xu Pengfeia   

  1. a School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150000, China;
    b Key Laboratory of Agro-Product Quality and Safety, Institute of Quality Standard and Testing Technology for Agro-Product, Chinese Academy of Agricultural Sciences, Beijing 100081, China
  • Received:2015-09-29 Published:2015-12-23
  • Supported by:

    Project supported by the Outstanding Academic Leaders of Harbin (No. 2014RFXXJ113).

采用表面分子印迹技术,以改性的磁纳米球作为载体,双功能单体分别为刀豆凝集素和3-氨基苯硼酸,交联剂为N,N'-亚甲基双丙烯酰胺,引发剂为过硫酸铵,采用二次接枝法成功合成了双功能单体的磁性葡萄糖分子印迹聚合物(MMIPs).通过多种表征技术:X射线衍射,扫描电子显微镜,红外光谱,振动样品磁强计,热重分析仪对合成的聚合物进行了表征分析.通过吸附动力学、热力学模型对实验数据进行拟合,探究了反应的吸附机理和吸附过程.合成的MMIPs的印迹因子能达到2.93,吸附量为9.112 mg/g.对其类特异性吸附的探索使得合成的聚合物还可应用于富含糖苷类化合物的提取与分离.

关键词: 双功能单体, 分子印迹, 葡萄糖, 类特异性, 葡萄糖苷, 超顺磁性纳米球

In this paper, dual functional monomers (concanavalin A and aminobenzeneboronic acid) method is applied to molecular imprinting technique, three synthetic methods of functional monomer were designed and their ability to adsorb glucose was evaluated. Step-by-step method (A1) was found to be a good synthetic method for selective adsorption, which could adsorb glucose powerfully. A kind of magnetic molecularly imprinted polymers (MMIPs) was synthesized by step-by-step method, in which superparamagnetic Fe3O4 nanoparticles were firstly synthesized by hydrothermal synthetic method and uniform SiO2-coated Fe3O4 (Fe3O4@SiO2) nanoparticles were prepared via Sol-gel method. The following Fe3O4@SiO2 reacted with (3-aminopropyl)triethoxysilane to produce Fe3O4@SiO2@NH2. The aminated nanoparticles combine with concanavalin A to form Fe3O4@SiO2@NH2@ConA in the presence of disuccinimidyl suberate. Subsequently, the single-functionalized nanoparticles binded with aminobenzeneboronic acid to form Fe3O4@SiO2@NH2@APBA-ConA in the presence of disuccinimidyl suberate. Eventually, the MMIPs for glucose selective recognition, with core-shell structure, were synthesized by surface molecular imprinting method, using glucose (Glu) as template molecule, concanavalin A (ConA) and aminobenzeneboronic acid (APBA) as dual functional monomers, N,N'-methylenebisacrylamide as the crosslinking agent, ammonium peroxydisulfate as the initiator, superparamagnetic nanoparticles as magnetic carrier. The MMIPs were characterized by X-ray diffraction (XRD), energy dispersive spectrometer (EDS), scanning electron microscopy (SEM), Fourier transform infrared spectra (FT-IR), vibrating sample magnetometer (VSM) and thermogravimetric analysis (TGA). The SEM showed the nanoparticles were highly dispersive and uniform. The EDS, FT-IR and TGA revealed the success of step-by-step method. The VSM demonstrated the saturation magnetization values of Fe3O4 and MMIPs were 96.661 emu/g and 45.064 emu/g, respectively. The study on kinetics of MMIPs showed that the adsorption reaction could be considered as a second order reaction. The thermodynamics research revealed that the adsorption of MMIPs was fitted to Langmuir isotherms. The study on selective adsorption displayed that MMIPs had maximum imprinting factor of 2.93 and best selectivity. The class specific study of MMIPs showed that it could be applied to extraction and separation of glucosides.

Key words: dual functional monomers, molecular imprinted, glucose, class specific, glucoside, superparamagnetic nanoparticles