基于纳米氧化铜修饰的异戊巴比妥的新型电化学传感器的制备与应用

doi:10.7503/cjcu20140638

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (10): 2078.doi: 10.7503/cjcu20140638

基于纳米氧化铜修饰的异戊巴比妥的新型电化学传感器的制备与应用

黄学艺¹, 余会成¹(), 韦贻春¹, 雷福厚¹, 谭学才¹, 吴海鹰²

1. 广西民族大学化学化工学院, 广西林产化学与工程重点实验室,广西高校食品安全与药物分析化学重点实验室, 南宁 530006
2. 广州有色金属研究院, 广州 510651

收稿日期:2014-07-09 出版日期:2014-10-10 发布日期:2014-09-19
作者简介:联系人简介: 余会成, 男, 博士, 副教授, 主要从事电化学传感器研究. E-mail: doyhc@126.com
基金资助:
国家自然科学基金(批准号: 21365004)、广西自然科学重点基金(批准号: 2013GXNSFDA019006)、广西高等学校高水平创新团队及卓越学者资助计划(批准号: 桂教人[2014]7 号)和广西研究生教育创新计划资助项目(批准号: YCSZ2014120)资助

Preparation and Application of Novel Amobarbital Electrochemical Sensor Based on CuO Nanoparticles Modified Glassy Carbon^†

HUANG Xueyi¹, YU Huicheng^1,^*(), WEI Yichun¹, LEI Fuhou¹, TAN Xuecai^1,^*, WU Haiying²

1. Guangxi Key Laboratory of Chemistry and Engineering of Forest Products,Key Laboratory of Guangxi Colleges and Universities for Food Safety and Pharmaceutical Analytical Chemistry,School of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning 530006, China
2. Guangzhou Research Institute of Nonferrous Metals, Guangzhou 510651, China

Received:2014-07-09 Online:2014-10-10 Published:2014-09-19
Contact: YU Huicheng,TAN Xuecai E-mail:doyhc@126.com
Supported by:
Supported by the National Natural Science Foundation of China(No.21365004), the Natural Science Key Foundation in Guangxi, China(No.2013GXNSFDA019006), the High-level-innovation Team and Outstanding Scholar Project of Guangxi Higher Education Institutes of China(No.guijiaoren[2014]7) and the Innovation Project of Graduate Education in Guangxi, China(No.YCSZ2014120)

摘要/Abstract

摘要：

在纳米氧化铜修饰的玻碳电极表面电聚合一种能够快速检测尿液中异戊巴比妥(AMB)的分子印迹敏感膜, 研究了该敏感膜的最佳成膜条件及最佳工作条件. 通过扫描电子显微镜(SEM)、循环伏安(CV)和电化学交流阻抗法(EIS)研究了印迹膜的表面形貌及性能. 电化学实验结果表明, 纳米氧化铜能提高传感器对AMB的灵敏度. 在最佳实验条件下, 铁氰化钾分子探针的差分脉冲伏安(DPV)峰电流响应值与AMB的浓度在1.0×10^-7~1.4×10^-4 mol/L范围内呈现良好的线性关系(线性相关系数R=0.9966); 检出限为2.1×10^-9 mol/L(S/N=3). 此印迹传感器可用于尿液中AMB的检测, 加标回收率为94.00%~104.67%.

关键词: 纳米氧化铜, 异戊巴比妥, 马来松香丙烯酸乙二醇酯, 电化学传感器

Abstract:

A novel sensor is developed for the detection of amobarbital in urines, which is based on an electropolymerized molecularly imprinted polymer(MIP) on the surface of the CuO nanoparticles modified glassy carbon electrode. The optimums film formed conditions and experimental conditions were explored. The surface feature and performance of the modified electrode were characterized by scanning electron microscope(SEM), cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS). The results of electrochemical measurements indicated that CuO nanoparticles had good sensitization effected for the molecularly imprinted sensor and it exhibits good sensitivity and selectivity to the template molecule amobarbital. Under the optimal conditions, the relative redox peak currents of hexacyanoferrate were linear. The concentration of amobarbital ranged from 1.0×10^-7 to 1.4×10^-4 mol/L, with a linear correlation coefficient of 0.9966. The detection limit was 2.1×10^-9 mol/L(S/N=3). The prepared sensor was applied to the determination of amobarbital in urine samples with recovery ranging from 94.00% to 104.67%.

Key words: CuO nanoparticle, Amobarbital, Ethylene glycol maleic rosinate acrylate, Electrochemical sensor

中图分类号:

O657
O613

TrendMD:

黄学艺, 余会成, 韦贻春, 雷福厚, 谭学才, 吴海鹰. 基于纳米氧化铜修饰的异戊巴比妥的新型电化学传感器的制备与应用. 高等学校化学学报, 2014, 35(10): 2078.

HUANG Xueyi, YU Huicheng, WEI Yichun, LEI Fuhou, TAN Xuecai, WU Haiying. Preparation and Application of Novel Amobarbital Electrochemical Sensor Based on CuO Nanoparticles Modified Glassy Carbon^†. Chem. J. Chinese Universities, 2014, 35(10): 2078.

图/表 9

Fig.1 Cyclic voltammograms for electropolymerization of imprinted film in the presence of AMB(A) and the nonimprinted membrance(B)

Fig.2 Effects of the elution time for MIP/CuO/GCE(a) and MIP/GCE(b) in 5.0 mmol/L K3[Fe(CN)6]-0.1 mol/L PBS

Fig.3 Effects of incubation time for the sensors CuO/MIP/GCE(A) and MIP/GCE(B) in 5.0 mmol/L K3[Fe(CN)6]-0.1 mol/L PBS (A) t/min, a—k: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11; (B) t/min, a—o: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15.

Fig.4 Cyclic voltammetries of different electrodes in 5.0×10-3 mol/L K3[Fe(CN)6]-0.1 mol/L PBS a. Bare GCE; b. MIP/CuO/GCE; c. MIP/GCE; d. MIP/CuO/GCE after interaction with 1.5×10-4mol/L AMB; e. NIP/CuO/GCE.

Fig.5 Electrochemical impedance spectra of different electrodes in 0.1 mol/L KCl-1.0×10-3 mol/L K3[Fe(CN)6]/K4[Fe(CN)6](1∶1, molar ratio) (A) a. Bare GCE; b. MIP/CuO/GCE; c. MIP/GCE; d. MIP/CuO/GCE after interaction with 5.0×10-5 mol/L AMB; e. NIP/CuO/GCE.

Fig.6 FESEM images of CuO modified bare GCE(A), and MIP/CuO/GCE electrodes before(B) and after(C) elution

Fig.7 Calibrations curve of AMB(A) and the differential pulse voltammetry incubation in different concentrations of AMB(B) in 5.0×10-3 mol/L K3[Fe(CN)6]-0.1 mol/L PBS (B) c/(μmol·L-1), a—j: 1.0×10-7, 5.0×10-7, 8.0×10-7, 2.0×10-6, 6.0×10-6, 1.5×10-5, 2.5×10-5, 5.0×10-5, 8.0×10-5, 1.4×10-4.

Fig.8 Determination results of interferences tested in 5.0×10-3 mol/L K3[Fe(CN)6]-0.1 mol/L PBS

Table 1 Determination results of recovery using the sensor

Sample	10⁵ Added/(mol·L^-1)	10⁵ Total found^* /(mol·L^-1)	Recovery(%)	RSD(%)
1	1.0	0.96	96.00	1.86
2	1.5	1.41	94.00	1.57
3	2.00	2.07	103.50	1.96
4	2.50	2.47	98.80	2.17
5	3.00	3.14	104.67	2.45

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基于纳米氧化铜修饰的异戊巴比妥的新型电化学传感器的制备与应用

Preparation and Application of Novel Amobarbital Electrochemical Sensor Based on CuO Nanoparticles Modified Glassy Carbon^†

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基于纳米氧化铜修饰的异戊巴比妥的新型电化学传感器的制备与应用

Preparation and Application of Novel Amobarbital Electrochemical Sensor Based on CuO Nanoparticles Modified Glassy Carbon†

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Preparation and Application of Novel Amobarbital Electrochemical Sensor Based on CuO Nanoparticles Modified Glassy Carbon^†