基于对巯基苯胺膜的高灵敏己烯雌酚印迹传感器的制备及应用

doi:10.16085/j.issn.1000-6613.2019-0131

摘要/Abstract

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

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

中图分类号:

O631.3

唐录华,秦思楠,高林,高文惠. 基于对巯基苯胺膜的高灵敏己烯雌酚印迹传感器的制备及应用[J]. 化工进展, 2019, 38(11): 5074-5083.

Luhua TANG,Sinan QIN,Lin GAO,Wenhui GAO. Preparation and application of sensitive diethylstilbestrol imprinting sensor based on p-aminothiophenol film[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 5074-5083.

图/表 15

图1 己烯雌酚结构式

图2 己烯雌酚在TBAP乙醇溶液中的CV曲线

图3 峰电流随电沉积液中HAuCl4·4H2O浓度的变化

图4 AuNPs电沉积时间与响应峰电流变化关系

图5 功能单体电聚合示意图

图6 分子印迹聚合过程示意图

图7 对巯基苯胺在TBAP乙醇溶液中CV曲线

图8 p-ATP、DES组装电极在聚合液中的CV曲线（01→10指从上至下的曲线为聚合圈数为1～10的CV曲线）

图9 洗脱剂的选择

图10 响应峰电流随洗脱时间的变化

图11 响应峰电流随吸附时间的变化

图12 不同电极在表征溶液中的DPV曲线a—GCE；b—MGCE；c—p-ATP和DES组装电极；d—MIP/MGCE；e—未洗脱模板分子的印迹电极；f—MIP/MGCE再吸附

图13 分子印迹电化学传感器的选择性a—己烯雌酚；b—双烯雌酚；c—雌二醇；d—双酚A；e—四环素

图14 不同浓度的己烯雌酚标准溶液DPV图

表1 样品加标回收率和精密度(n=5)

样品	浓度/mol·L^-1	回收率/%						相对标准偏差/%
样品	浓度/mol·L^-1	1	2	3	4	5	平均值	相对标准偏差/%
纯牛奶	1.0×10^-8	82.41	84.13	85.79	83.78	81.20	83.46	2.09
纯牛奶	1.0×10^-6	91.15	97.33	99.20	95.64	98.83	96.43	3.39
猪肉	1.0×10^-8	85.50	86.74	84.82	85.75	82.58	85.08	1.83
猪肉	1.0×10^-6	99.93	96.67	98.32	97.84	97.51	98.05	1.23
鲜虾	1.0×10^-8	83.34	82.71	84.47	81.63	85.19	83.47	1.69
鲜虾	1.0×10^-6	90.60	97.86	98.92	98.27	99.40	97.01	3.74
鸡蛋	1.0×10^-8	86.97	85.70	83.53	82.14	84.94	84.65	2.21
鸡蛋	1.0×10^-6	98.82	96.64	97.94	99.17	98.51	98.21	1.01

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