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

doi:10.7503/cjcu20170643

Abstract

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

CLC Number:

O657.1

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2018, 39(4): 636.

Figures/Tables 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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