MWCNTs-rGO/PDDA-AuNPs复合膜修饰电极对莱克多巴胺的灵敏检测

doi:10.7503/cjcu20160026

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (5): 835.doi: 10.7503/cjcu20160026

MWCNTs-rGO/PDDA-AuNPs复合膜修饰电极对莱克多巴胺的灵敏检测

寻艳, 曹忠(), 宋天铭, 吕超志, 刘峰, 何婧琳, 杨荣华

长沙理工大学化学与生物工程学院, 电力与交通材料保护湖南省重点实验室,微纳生物传感与食品安全检测协同创新中心, 长沙 410114

收稿日期:2016-01-13 出版日期:2016-05-10 发布日期:2016-04-15
作者简介:联系人简介: 曹忠, 男, 博士, 教授, 主要从事纳米生物传感与食品安全检测. E-mail:zhongcao2004@163.com
基金资助:
国家自然科学基金(批准号: 21275022, 21545010, 31527803)资助

MWCNTs-rGO/PDDA-AuNPs Nanocomposite Modified Electrode for Sensitive Detection of Ractopamine^†

XUN Yan, CAO Zhong^*(), SONG Tianming, LÜ Chaozhi, LIU Feng, HE Jinglin, YANG Ronghua

Collaborative Innovation Center of Micro/nano Bio-sensing and Food Safety Inspection, Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, School of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410114, China

Received:2016-01-13 Online:2016-05-10 Published:2016-04-15
Contact: CAO Zhong E-mail:zhongcao2004@163.com

摘要/Abstract

摘要：

采用自组装方法, 将聚二烯丙基二甲基氯化铵(PDDA)功能化的金纳米颗粒(AuNPs)负载于多壁碳纳米管(MWCNTs)-还原型氧化石墨烯(rGO)夹层, 再涂覆于玻碳电极(GCE)上, 制备了纳米复合膜修饰电极MWCNTs-rGO/PDDA-AuNPs/GCE. 采用透射电子显微镜(TEM)和紫外-可见光谱(UV-Vis)对修饰膜的形貌及结构进行表征. 探讨了其对莱克多巴胺(Rac)的循环伏安行为, 结果表明MWCNTs-rGO/PDDA-AuNPs纳米复合物对Rac表现出显著的电催化氧化特性. 采用差分脉冲伏安法测得该复合膜修饰电极对Rac检测的线性范围为0.036~4.5 μmol/L, 检出限为6.35 nmol/L(S/N≥3), 且显示出良好的抗干扰能力、稳定性及重现性. 采用该方法检测猪血清及猪尿样中的Rac, 回收率达95.4%~105.9%, 表明该复合膜修饰电极对实际样品中Rac的检测具有潜在应用价值.

关键词: 莱克多巴胺, 还原型氧化石墨烯, 聚二烯丙基二甲基氯化铵, MWCNTs-rGO/PDDA-AuNPs复合物, 食品安全检测

Abstract:

A nanocomposite film of MWCNTs-rGO/PDDA-AuNPs was fabricated through self-assembly method. The surface morphologies of different composite modified glassy carbon electrodes(GCEs) were characterized by means of TEM and UV-Vis spectroscopy, and the cyclic voltammetry behaviors of ractopamine(Rac) were investigated. The results showed that the MWCNTs-rGO/PDDA-AuNPs composite exhibited significantly electrocatalytic activity towards oxidation of Rac. The results of differential pulse voltammetry showed that the electrode possessed a linear range of 0.036—4.5 μmol/L and a detection limit of 6.35 nmol/L(S/N≥3) with good stability, reproducibility and selectivity. The electrode can be well applied to determination of Rac in pork serum and pork urine with a recovery rate of 95.4%—105.9%, suggesting a potential application for actual samples in food security field.

Key words: Ractopamine, Reductive graphene oxide, Poly(diallyldimethylammonium chloride), MWCNTs-rGO/PDDA-AuNPs composite, Food safety inspection

中图分类号:

TrendMD:

寻艳, 曹忠, 宋天铭, 吕超志, 刘峰, 何婧琳, 杨荣华. MWCNTs-rGO/PDDA-AuNPs复合膜修饰电极对莱克多巴胺的灵敏检测. 高等学校化学学报, 2016, 37(5): 835.

XUN Yan, CAO Zhong, SONG Tianming, LÜ Chaozhi, LIU Feng, HE Jinglin, YANG Ronghua. MWCNTs-rGO/PDDA-AuNPs Nanocomposite Modified Electrode for Sensitive Detection of Ractopamine^†. Chem. J. Chinese Universities, 2016, 37(5): 835.

图/表 10

Fig.1 TEM images of PDDA-AuNPs(A) and MWCNTs-rGO/PDDA-AuNPs hybrids(B)

Fig.2 UV-Vis absorption spectra of GO(a), PDDA-AuNPs(b), MWCNTs-GO(c), MWCNTs-rGO(d) and MWCNTs-rGO/PDDA-AuNPs hybrids(e)

Fig.3 Q-t curves for the bare GCE(a), MWCNTs-rGO/GCE(b) and MWCNTs-rGO/PDDA-AuNPs/GCE(c) in 0.2 mmol/L K3[Fe(CN)6] with pulse width of 0.25 s

Fig.4 CV curves for the oxidation of Rac at bare GCE without(a) and with(b) 3.6×10-6 mol/L Rac, and at PDDA-AuNPs/GCE(c), MWCNTs-rGO/GCE(d) and MWCNTs-rGO/PDDA-AuNPs/GCE(e) in PBS(0.01 mol/L, pH=6.5) containing 3.6×10-6 mol/L RacScan rate: 50 mV/s.

Fig.5 Effects of pH on the oxidation peak current(A) and peak potential(B) of 2.64×10-6 mol/L Rac in 0.01 mol/L PBS

Fig.6 CV curves of MWCNTs-rGO/PDDA-AuNPs/GCE responding to Rac at different scan rates(A), plots of peak current vs. scan rate(B) and peak potential vs. logarithmic scan rate(C)Scan rate/(mV·s-1): a. 10; b. 25; c. 50; d. 75; e. 100; f. 125.

Fig.7 Schematic diagram for preparation of MWCNTs-rGO/PDDA-AuNPs/GCE modified GCE and its detecting of Rac

Fig.8 DPV curves of MWCNTs-rGO/PDDA-AuNPs/GCE responding to different concentrations of Rac in 0.01 mol/L PBS(pH=6.5)(A) and linear plot of response current vs. concentration(B)c/(mol·L-1): a. 3.6×10-8; b. 6.60×10-8; c. 3.96×10-7; d. 7.92×10-7; e. 1.45×10-6; f. 2.90×10-6; g. 3.60×10-6; h. 4.50×10-6. Accumulation potential: -0.3 V, accumulation time: 120 s.

Fig.9 Effect of interferring substance on the modified electrodea. Rac; b. L-Leucine; c. L-Cysteine; d. L-Arginine; e. L-Alanine; f. L-Glycine; g. ascorbic acid; h. I-; i. NO3-; j. SO42-; k. K+; l. Zn2+; m. Cle; n. Sal; o. Pea.

Table 1 Application of MWCNTs-rGO/PDDA-AuNPs/GCE for determination of Rac in pork serum and urine samples

Sample	No.	Spiked/(μmol·L^-1)	Found/(μmol·L^-1)	Recovery(%)	RSD(%)
Pork serum	1	0.1850	0.1960	105.9	1.9
	2	0.6000	0.6055	100.9	3.4
	3	1.180	1.166	98.8	4.2
	4	1.980	2.019	102.0	5.8
	5	3.500	3.547	101.3	5.7
Pork urine	1	0.1850	0.1780	96.2	1.3
	2	0.6000	0.5722	95.4	2.3
	3	1.180	1.197	101.4	3.4
	4	1.980	1.937	97.8	4.1
	5	3.500	3.598	102.8	4.2

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MWCNTs-rGO/PDDA-AuNPs复合膜修饰电极对莱克多巴胺的灵敏检测

MWCNTs-rGO/PDDA-AuNPs Nanocomposite Modified Electrode for Sensitive Detection of Ractopamine^†

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MWCNTs-rGO/PDDA-AuNPs复合膜修饰电极对莱克多巴胺的灵敏检测

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