Acta Chimica Sinica ›› 2013, Vol. 71 ›› Issue (06): 934-940.DOI: 10.6023/A12121113 Previous Articles     Next Articles



范存华, 杨逸群, 赵伟, 肖宇, 罗静, 刘晓亚   

  1. 江南大学食品胶体与生物技术教育部重点实验室 江南大学化学与材料工程学院 无锡 214122
  • 收稿日期:2012-12-29 出版日期:2013-06-14 发布日期:2013-04-03
  • 通讯作者: 刘晓亚,
  • 基金资助:

    项目受国家自然科学基金(Nos. 21174056 and 51103064)资助.

Research on Amphiphilic Copolymer MIP Micelles Electrochemical Sensor

Fan Cunhua, Yang Yiqun, Zhao Wei, Xiao Yu, Luo Jing, Liu Xiaoya   

  1. The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122
  • Received:2012-12-29 Online:2013-06-14 Published:2013-04-03
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Grant Nos. 21174056 and 51103064).

Novel molecularly imprinted polymeric (MIP) micelles were prepared via macromolecule self-assembly of a photo-crosslinkable copolymer, combined with molecular imprinting technique using 4-acetaminophenol as the template molecule. First, an acrylic copolymer poly(DMA-co-HEA-co-EHA-co-St) was synthesized via free radical polymerization using (dimethylamino)ethylmethacrylate (DMA), 2-hydroxy ethylacrylate (HEA), 2-ethylhexyl acrylate (EHA) and styrene (St). Further post functionalization introduced a cross-linkable acrylate side groups into the polymer to form the photo-crosslinkable copolymer using isophorone diisocyanate (IPDI) as bridges. The photo-crosslinkable copolymer and 4-acetaminophenol were dissolved to give copolymer mixed solution. Water as a non-solvent, was added to the mixed solution to induce the self-assembly micellization of the photo-crosslinkable copolymer, during which the template molecules (4-acetaminophenol) was entrapped in the micelles through the interactions between 4-acetaminophenol and the copolymer chain. The properties and morphology of MIP micelles were characterized by dynamic light scattering (DLS), zeta potential and transmission electron microscope (TEM). DLS results showed that the average hydrodynamic diameter was about 70 nm, which was supported by the result from the TEM measurements. The MIP micelle solution prepared was used as a bath solution for electrodeposition. A MIP film was formed in situ on the electrode surface by electrodeposition of the MIP micelles and then crosslinked by UV radiation to lock the structure and improve the stability of the film. Finally the template molecules were removed from the film by extraction, leading to 4-acetaminophenol imprinted electrode. The electrochemical performance of the MIP electrode was evaluated by cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV). The resulting MIP sensor showed good response and selectivity towards 4-acetaminophenol. In addition, this MIP sensor showed excellent selectivity to 4-acetaminophenol, and the interferences from structurely similar analogues were effectively avoided. The linear range was from 1×10-6~4×10-3 mol/L, and the limit of detection was 3.3×10-7 mol/L. The proposed method was novel, sensitive, easy to operate and low cost.

Key words: self-assembly, MIP, 4-acetaminophenol, micelles, electrodeposition, electrochemical sensor