Abstract:

A novel electrochemical sensor was constructed for detection of diethylstilbestrol (DES) based on molecularly imprinted polymer membrane on a glassy carbon electrode (GCE) modified with carboxyl-multi-walled carbon nanotubes (CMWCNTs) and Au nanoparticles (AuNPs). P-aminothiophenol (p-ATP) and DES were assembled on the surface of the modified GCE through the formation of Au—S bonds and hydrogen-bonding interactions, and the polymer membrane was formed by electropolymerization in a polymer solution containing p-ATP, DES, chloroauric acid and tetrabutyl ammonium perchlorate; and 50% ethanol-0.1mol/L sulfuric acid aqueous solution (1∶1，volume ratio) was used to elute template molecules. The imprinted effect and analysis performance of the sensor were researched by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), and the imprinted sensor was applied to rapid detection of DES in food. Under the optimal conditions, the linear response range of DES was 1.0×10^-9—1.0×10^-5mol/L, the limit of detection was 3.3×10^-10mol/L, the average recoveries were between 83.46% and 98.21%, and the relative standard deviations (RSDs) were between 1.01% and 3.74%. The sensor has the advantages of simple operation, rapid and sensitive detection, low cost, strong anti-interference ability and good stability, it is suitable for rapid detection of DES in real samples, and it has good application value.

Key words: diethylstilbestrol, nanomaterial, modified electrode, molecular imprinting polymer, electrochemical sensor

摘要：

通过自组装技术，分别以金硫键（Au—S）和氢键在羧基化多壁碳纳米管（CMWCNTs）和纳米金（AuNPs）修饰的电极表面成功组装功能单体对巯基苯胺（p-ATP）和模板分子己烯雌酚（DES），在含有p-ATP、DES、氯金酸和电聚合介质四丁基高氯酸铵的聚合液中采用电聚合的方法在组装电极表面形成聚合物膜，并用50%乙醇-0.1mol/L硫酸水溶液（1∶1，体积比）洗脱模板分子，成功制备了用于检测己烯雌酚的分子印迹电化学传感器。采用循环伏安法和差分脉冲伏安法研究印迹传感器的印迹效果和分析性能，并将该传感器应用于食品中己烯雌酚的快速检测。在最佳条件下，己烯雌酚的线性范围为1.0×10^-9～1.0×10^-5mol/L，检出限为3.3×10^-10mol/L，样品加标平均回收率为83.46%～98.21%，相对标准偏差（RSD）在1.01%～3.74%之间（n=5）。该传感器操作简单、检测快速灵敏、成本低、抗干扰能力强、稳定性好，有重要的应用价值。

关键词: 己烯雌酚, 纳米材料, 修饰电极, 分子印迹聚合物, 电化学传感器