摘要
结合大分子自组装和分子印迹技术制备了分子印迹聚合物胶束,并通过电沉积将其固载到电极表面得到分子印迹电化学传感器.首先以甲基丙烯酸二甲氨基乙酯(DMA)、丙烯酸羟乙酯(HEA)、丙烯酸二异辛酯(EHA)和苯乙烯(St)合成了共聚物poly(DMA-co-HEA-co-EHA-co-St),在其侧链接枝上双键得到可光交联的双亲共聚物.以水为沉淀剂诱发该双亲共聚物在含有对乙酰氨基苯酚的溶液中自组装,得到印迹有对乙酰氨基苯酚的聚合物胶束,利用动态激光光散射(DLS)和透射电镜(TEM)表征其尺寸和形貌.最后通过电沉积技术诱导印迹胶束在金电极表面组装,经紫外光辐照交联后,洗脱模板分子形成分子印迹膜,制备了对乙酰氨基苯酚分子印迹传感器,通过循环伏安法、差分脉冲溶出伏安法研究此印迹传感器的性能.实验结果表明,该传感器对对乙酰氨基苯酚具有良好的选择性和灵敏度,浓度响应线性范围为1×10-6到4×10-3mol/L,检测限为3.3×10-7mol/L.
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.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2013年第6期934-940,共7页
Acta Chimica Sinica
基金
国家自然科学基金(Nos.21174056 and 51103064)资助~~
