聚乙烯亚胺功能化石墨烯修饰电极同时测定抗坏血酸、 多巴胺、尿酸和色氨酸

doi:10.7503/cjcu20141143

摘要/Abstract

摘要：

制备了聚乙烯亚胺(PEI)功能化的石墨烯(G)修饰电极以实现抗坏血酸(AA)、多巴胺(DA)、尿酸(UA)和色氨酸(Trp)的分离及同时测定. 采用红外光谱(FTIR)、紫外-可见吸收光谱(UV-Vis)、 X射线粉末衍射仪(XRD)和透射电子显微镜(TEM)对电极修饰材料进行了表征, 并优化了该修饰电极同时测定AA, DA, UA和Trp的实验条件. 在聚乙烯亚胺功能化石墨烯修饰的玻碳电极(PEI-G/GCE)上实现了AA, DA, UA 和Trp氧化峰的分离, AA-DA, DA-UA和UA-Trp的氧化峰电位差分别为298, 130和350 mV. 该修饰电极对AA, DA, UA和Trp的检测线性范围分别为50~5800, 30~2570, 0.05~400和6~1000 μmol/L; 检出限分别为16.67, 10, 0.017和2 μmol/L.

关键词: 聚乙烯亚胺, 石墨烯, 抗坏血酸, 多巴胺, 尿酸, 色氨酸

Abstract:

Ascorbic acid(AA), dopamine(DA), uric acid(UA) and tryptophan(Trp) are considered as crucial small biomolecules for physiological processes in human metabolism. Abnormal levels of these species will lead to the occurrence of some diseases and disorders. In this paper, polyethyleneimine(PEI) covalent functionalized graphene(PEI-G) was used to modify glassy carbon electrode and applied for the simultaneous and sensitive determination of the four molecules.The PEI-G nanocomposite was characterized by fourier-transform infrared spectroscopy(FTIR), ultraviolet-visible(UV-Vis), X-ray powder diffraction(XRD) and transmission electron microscopy(TEM). The electrochemical behaviors of AA, DA, UA and Trp on PEI-G modified electrode were studied in detail. And the optimal experimental conditions for the simultaneous determination of AA, DA, UA and Trp were explored. The results showed that the oxidation peaks of the four species could be well separated and the peak to peak separations were 298 mV(AA-DA), 130 mV(DA-UA) and 350 mV(UA-Trp), respectively. The linear response ranges for the simultaneous detection of AA, DA, UA and Trp were 50—5800 μmol/L, 30—2570 μmol/L, 0.05—400 μmol/L and 6—1000 μmol/L, with the detection limits of 16.67 μmol/L, 10 μmol/L, 0.017 μmol/L and 2 μmol/L, respectively. The proposed method provides a promising strategy for the simultaneous detection of these species in practical application.

Key words: Polyethyleneimine, Graphene, Ascorbic acid, Dopamine, Uric acid, Tryptophan

中图分类号:

O657.1

TrendMD:

李冲, 贾丽萍, 马荣娜, 贾文丽, 王怀生, 杨海涛, 郭爱香. 聚乙烯亚胺功能化石墨烯修饰电极同时测定抗坏血酸、多巴胺、尿酸和色氨酸. 高等学校化学学报, 2015, 36(7): 1282.

LI Chong, JIA Liping, MA Rongna, JIA Wenli, WANG Huaisheng, YANG Haitao, GUO Aixiang. Simultaneous Detection of Ascorbic Acid, Dopamine, Uric Acid and Tryptophan on the PEI-graphene Modified Electrode^†. Chem. J. Chinese Universities, 2015, 36(7): 1282.

图/表 11

Fig.1 FTIR(A) and UV-Vis(B) spectra of GO(a), PEI-G(b) and PEI(c)

Fig.2 TEM images of GO(A), PEI-G(B) and PEI(C)

Fig.3 XRD patterns of graphite(a), GO(b) and PEI-G(c)

Scheme 1 Schematic diagram of synthesis of PEI-functionalized graphene

Fig.4 CV curves of GO/GCE(a), bare GCE(b) and PEI-G/GCE(c) in 1 mmol/L [Fe(CN)6]3-/4- solution(containing 0.1 mol/L KCl)

Fig.5 CV curves of bare GCE(A), GO/GCE(B), G/GCE(C) and PEI-G/GCE(D) in 0.1 mol/L PBS(pH=4.0)containing 0.5 mmol/L AA, 0.4 mmol/L DA, 0.02 mmol/L UA and 0.03 mmol/L Trp, respectively

Fig.6 CV curves of 0.25 mmol/L AA(A), 0.20 mmol/L DA(B), 0.02 mmol/L UA(C) and 0.03 mmol/L Trp(D) at various scan ratesScan rate, a—g/(mV·s-1): 10, 30, 50, 100, 150, 200, 300. Insets show the plots of peak currents vs. scan rates.

Fig.7 Effects of pH on peak currents(A) and peak potentials(B) for the oxidation of 0.25 mmol/L AA(a), 0.20 mmol/L DA(b), 0.02 mmol/L UA(c) and 0.03 mmol/L Trp(d) in 0.1 mol/L PBS

Fig.8 CV curves of PEI-G modified GCE in 0.1 mol/L PBS containing 0.25 mmol/L AA, 0.20 mmol/L DA, 0.02mmol/L UA and 0.03 mmol/L Trp at different pH values

Fig.9 DPVs of the PEI-G modified GCE in 0.1 mol/L PBS(pH=4.0) with scan rate of 20 mV/s and pulse amplitude of 50 mV(A) 0.08 mmol/L DA+0.015 mmol/L UA+0.05 mmol/L Trp+different concentrations of AA; (B) 0.7 mmol/L AA+0.015 mmol/L UA+0.05 mmol/L Trp+different concentrations of DA; (C) 0.5 mmol/L AA+0.025 mmol/L DA+0.05 mmol/L Trp+different concentrations of UA; (D) 0.7 mmol/L AA+0.08 mmol/L DA+0.015 mmol/L UA+different concentrations of Trp. Insets: calibration plots of the anodic peak currents vs. concentration of AA, DA, UA and Trp, respectively.

Table 1 Comparison of analytical performance of PEI-G modified GCE with other modified electrodes in the literatures

Working electrode	Linear range/(μmol·L^-1)					Detection limit/(μmol·L^-1)				Ref.
Working electrode	AA	DA	UA		Trp		AA	DA	UA	Trp
GNPs/PImox	210—1010	5.0—268	6—486	3—34		2.0	0.08	0.5	0.7	[44]
				84—464
GS-PTCA	20—420	0.4—370	4—540	0.4—140		5.60	0.13	0.92	0.06	[45]
MWCNT-FeNAZ-CH	7.77—833	7.35—833	0.23—83.3	0.074—34.5		1.11	1.05	0.033	0.011	[46]
MWNTs/MGF	100—6000	0.3—10	5—100	5—30		18.28	0.06	0.93	0.87	[47]
			300—1000	60—500
Fe-Meso-PANI	10—300	10—300	10—300	10—300		6.5	9.8	5.3	5.2	[48]
PEI-G/GCE	50—5800	30—2570	0.05—1	6—150		16.67	10	0.017	2	This work
			2—400	200—1000

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