氧化石墨烯/三角形金纳米片/Nafion复合膜修饰电极对L-色氨酸的灵敏检测

doi:10.7503/cjcu20170643

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (4): 636.doi: 10.7503/cjcu20170643

氧化石墨烯/三角形金纳米片/Nafion复合膜修饰电极对L-色氨酸的灵敏检测

李雨晴¹, 朱钦¹, 肖忠良¹, 吕超志¹, 冯泽猛², 印遇龙², 曹忠¹()

1. 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
2. 中国科学院亚热带农业生态研究所, 长沙 410125

收稿日期:2017-09-26 出版日期:2018-04-10 发布日期:2018-03-22
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、环境与食品安全检测等方面的研究. E-mail:zhongcao2004@163.com
基金资助:
国家自然科学基金(批准号: 31527803, 21545010)和中国科学院科技服务网络(STS)计划项目(批准号: KFJ-SW-STS-173)资助

Graphene Oxide/Triangular Gold Nanoplates/Nafion Composite Modified Electrode Used for Sensitive Detection of L-Tryptophan^†

LI Yuqing¹, ZHU Qin¹, XIAO Zhongliang¹, LÜ Chaozhi¹, FENG Zemeng², YIN Yulong², CAO Zhong^1,^*()

1. 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
2. Institute of Subtropical Agriculture, Chinese Academy of Sciences, Changsha 410125, China

Received:2017-09-26 Online:2018-04-10 Published:2018-03-22
Contact: CAO Zhong E-mail:zhongcao2004@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.31527803, 21545010) and the Science and Technology Service-net(STS) Program of the Chinese Academy of Sciences, China(No.KFJ-SW-STS-173)

摘要/Abstract

摘要：

采用晶种生长法制备了形状均一、导电性良好的三角形金纳米片(Au TNPs), 并以氧化石墨烯(GO)为载体, 聚阴离子Nafion为保护剂, 将其修饰在玻碳电极(GCE)表面, 制得氧化石墨烯/三角形金纳米片/Nafion复合膜修饰电极(GO/Au TNPs/Nafion/GCE). 利用扫描电子显微镜和原子力显微镜对纳米复合材料的形貌进行表征, 采用循环伏安法(CV)和示差脉冲伏安法(DPV)探讨了L-色氨酸(L-Trp)在不同修饰电极上的电化学行为. 结果表明, GO/Au TNPs/Nafion/GCE对L-Trp表现出良好的电催化氧化特性. 在0.10 mol/L的PBS缓冲溶液(pH=3.5)中, 该修饰电极的响应峰电流与L-Trp的浓度存在良好的线性关系, 线性范围为4.000×10^-8~6.000×10^-5 mol/L, 检出限为1.000×10^-8 mol/L(S/N=3). 该电极具有良好的重现性、稳定性和抗干扰能力. 将该电极用于猪血清样品中L-Trp的测定, 回收率为93.1%~105.9%, 说明该电极在健康养殖生化检测领域有潜在的应用价值.

关键词: L-色氨酸, 三角形金纳米片, 氧化石墨烯, 纳米复合膜电极

Abstract:

Uniform triangular gold nanoplates(Au TNPs) with good conductivity were synthesized through a seeded growth process, and then modified on surface of glassy carbon electrode(GCE) using graphene oxide(GO) as carrier and Nafion polyanion as protecting agent, finally forming a nanocomposite modified electrode of GO/Au TNPs/Nafion/GCE. The morphologies of the nanocomposites were characterized by means of scanning electron microscopy and atomic force microscopy. The electrochemical behaviors of L-tryptophan(L-Trp) were investigated via cyclic voltammetry(CV) and differential pulse voltammetry(DPV), indicating that GO/Au TNPs/Nafion composite exhibited excellent electrocatalytic oxidation activity to L-Trp. The DPV method was employed for the determination of L-Trp in 0.10 mol/L PBS(pH=3.5), and a good linear relationship between the peak currents and the concentrations of L-Trp was obtained in the range from 4.000×10^-8 to 6.000×10^-5 mol/L, with a detection limit of 1.000×10^-8 mol/L(S/N=3). Furthermore, the modified electrode possessed good reproducibility, stability and selectivity, which can be used for the determination of L-Trp in pork serum samples with recoveries of 93.1%-105.9%, indicating that the proposed method is valuable in practical application on healthy breeding bio-analysis field.

Key words: L-Tryptophan, Triangular gold nanoplates, Graphene oxide, Nanocomposite electrode

中图分类号:

O657.1

TrendMD:

李雨晴, 朱钦, 肖忠良, 吕超志, 冯泽猛, 印遇龙, 曹忠. 氧化石墨烯/三角形金纳米片/Nafion复合膜修饰电极对L-色氨酸的灵敏检测. 高等学校化学学报, 2018, 39(4): 636.

LI Yuqing, ZHU Qin, XIAO Zhongliang, LÜ Chaozhi, FENG Zemeng, YIN Yulong, CAO Zhong. Graphene Oxide/Triangular Gold Nanoplates/Nafion Composite Modified Electrode Used for Sensitive Detection of L-Tryptophan^†. Chem. J. Chinese Universities, 2018, 39(4): 636.

图/表 10

Scheme 1 Schematic diagram for the construction of GO/Au TNPs/Nafion/GCE

Fig.1 SEM images of GO(A), Au TNPs(B, C) and GO/Au TNPs/Nafion hybrids(D), 3D tapping mode AFM image(E) of Au TNPs and its corresponding height profile(F)

Fig.2 DPV curves for the oxidation of L-Trp at bare GCE(a), GO/Nafion/GCE(b) and GO/Au TNPs/Nafion/GCE(c) in PBS(0.10 mol/L, pH=3.5) containing 1.000×10-5 mol/L L-TrpDPV conditions: amplitude, 0.05 V; pulse width, 0.2 s; sampling width, 0.02; pulse period, 0.5 s.

Fig.3 Effects of pH values on the oxidation peak current(A) and peak potential(B) of 1.000×10-5 mol/L L-Trp

Fig.4 CV curves of GO/Au TNPs/Nafion/GCE responding to L-Trp at different scan rates(A) and corresponding relation curve of oxidation peak potential vs. logarithmic scan rate(B)Inset of (A): relation curve of oxidation peak current vs. scan rate.

Scheme 2 Proposed oxidation mechanism of L-Trp at GO/Au TNPs/Nafion/GCE

Fig.5 DPV curves of GO/Au TNPs/Nafion/GCE responding to different concentrations of L-Trp(A) and the corresponding linear relation curve of response current vs. concentration of L-Trp(B)DPV conditions: amplitude, 0.05 V; pulse width, 0.2 s; sampling width, 0.02; pulse period, 0.5 s.

Table 1 Comparison of performance with different modified electrodes

Modified electrode	Analyte	Linear range/(μmol·L^-1)	LOD/(μmol·L^-1)	Reference
SnO₂/rGO/GCE^a	L-Trp	1-100	0.04	[17]
Nafion/TiO₂-GR/GCE^b	L-Trp	5-140	0.7	[18]
Co₃O₄/GR/Nafion/GCE	L-Trp	0.05-10	0.01	[19]
β-CD-MNPs/GCE^c	L-Trp	0.8-300	0.5	[20]
AuNPs-MWNT/ITO^d	L-Trp	0.5-90	0.025	[21]
Ag@C/GCE	L-Trp	0.1-100	0.04	[44]
AgNPs@EBT/GCE^e	L-Trp	0.1-100	0.0984	[45]
NiO-CuO/GR/GCE	L-Trp	0.3-40	0.1	[46]
Cu NPs/p-TA_ox/GCE^f	L-Trp	4.0-144.0	0.16	[47]
GO/Au TNPs/Nafion/GCE^g	L-Trp	0.04-60.00	0.01	This work

Fig.6 Effect of interferring substance on GO/Au TNPs/Nafion/GCEa. Trp; b. Met+Trp; c. Leu+Trp; d. Ala+Trp; e. Gly+Trp; f. Val+Trp; g. Pro+Trp; h. Thr+Trp; i. Asp+Trp; j. Glu+Trp.

Table 2 Application of GO/Au TNPs/Nafion/GCE to determination of L-Trp in pork serum samples(n=5)

Sample No.	Initial value/(μmol·L^-1)	Spiked/(μmol·L^-1)	Found/(μmol·L^-1)	Recovery(%)	RSD(%)
Serum 1	0.755	2.000	2.627	93.6	4.90
Serum 2	1.126	4.000	4.850	93.1	5.29
Serum 3	0.677	6.000	6.428	95.9	1.34
Serum 4	1.371	8.000	9.398	100.3	2.06
Serum 5	1.250	10.00	11.84	105.9	4.66

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氧化石墨烯/三角形金纳米片/Nafion复合膜修饰电极对L-色氨酸的灵敏检测

Graphene Oxide/Triangular Gold Nanoplates/Nafion Composite Modified Electrode Used for Sensitive Detection of L-Tryptophan^†

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氧化石墨烯/三角形金纳米片/Nafion复合膜修饰电极对L-色氨酸的灵敏检测

Graphene Oxide/Triangular Gold Nanoplates/Nafion Composite Modified Electrode Used for Sensitive Detection of L-Tryptophan†

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Graphene Oxide/Triangular Gold Nanoplates/Nafion Composite Modified Electrode Used for Sensitive Detection of L-Tryptophan^†