聚脱氧腺苷酸/还原石墨烯纳米复合膜电化学传感器检测核黄素

doi:10.7503/cjcu20150184

摘要/Abstract

摘要：

以含32个碱基的聚脱氧腺苷酸(A₃₂)作为黏合剂, 将水合肼还原的石墨烯(RGO)固定在金(Au)电极表面, 制备A₃₂/RGO纳米复合膜电化学传感器. 利用循环伏安法和交流阻抗法对传感器制备过程进行表征, 并用循环伏安法和微分脉冲伏安法研究了该传感器的电化学行为. 研究结果表明, 与裸Au电极和A₃₂修饰的Au电极相比, RGO/A₃₂/Au电极对核黄素有较高的电化学活性, 其还原峰电流与核黄素的浓度在0.025~2.75 μmol/L范围内呈线性关系, 检出限(S/N=3) 为15 nmol/L. 该传感器具有灵敏度高、抗干扰能力强及稳定性好等优点, 可用于人尿中核黄素的分析测定.

关键词: 还原石墨烯, 核黄素, 聚脱氧腺苷酸, 电化学传感器

Abstract:

A novel electrochemical sensor to detect riboflavin was constructed using 32-mer polydeoxyadenylic acid(A₃₂) as an effective adhesive for binding with the hydrazine hydrate-reduced graphene oxide(RGO) and the gold(Au) electrode. The fabrication process of the sensor was characterized by cyclic voltammetry and electrochemical impedance spectroscopy, and its electrochemical behaviour was studied by cyclic voltammetry and differential pulse voltammetry. The experimental results showed that compared with the bare Au electrode and the A₃₂/Au electrode, the RGO/A₃₂/Au electrode displayed excellent electrochemical activity towards riboflavin, and the cathodic peak current increased linearly with the increasing concentration of riboflavin from 0.025 μmol/L to 2.75 μmol/L with a low detection limit of 15 nmol/L(S/N=3). The sensor possesses high sensitivity, strong anti-interference ability and good stability, and can be used for the analysis of riboflavin in human urine samples.

Key words: Reduced graphene oxide, Riboflavin, Polydeoxyadenylic acid, Electrochemical sensor

中图分类号:

O657

TrendMD:

庄欠粉, 王勇, 倪永年. 聚脱氧腺苷酸/还原石墨烯纳米复合膜电化学传感器检测核黄素. 高等学校化学学报, 2015, 36(9): 1674.

ZHUANG Qianfen, WANG Yong, NI Yongnian. Electrochemical Sensor for the Detection of Riboflavin Based on Nanocomposite Film of Polydeoxyadenylic Acid/Reduced Graphene Oxide^†. Chem. J. Chinese Universities, 2015, 36(9): 1674.

图/表 11

Scheme 1 Schematic representation of the fabrication procedure of the RGO/A32/Au electrode and its application for the detection of riboflavin

Fig.1 TEM image of RGO

Fig.2 XRD pattern of RGO

Fig.3 CV curves(A) and EIS responses(B) of different electrodes in 5.0 mmol/L [Fe(CN)6]3-/[Fe(CN)6]4-(1∶1) solution containing 0.1 mol/L KCla. Bare Au electrode; b. A32/Au electrode; c. RGO/A32/Au electrode; d. rMoS2-graphene/A32/Au electrode.

Fig.4 CV(A) and DPV(B) curves of different electrodes in the N2-saturated electrochemistry buffer solution containing 2.0 μmol/L riboflavina. Bare Au electrode; b. A32/Au electrode; c. RGO/A32/Au electrode.

Fig.5 CVs curves of RGO/A32/Au electrode with different scan rates in the N2-saturated electrochemistry buffer solution containing 2.0 μmol/L riboflavin(A), and the linear relationship between the anodic peak current and the square root of scan rate(B)Scan rates from inner to outer curves/(V·s-1): 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2.

Fig.6 DPV curves of the RGO/ A32/Au electrode with different concentrations of riboflavin in the N2-saturated electrochemistry buffer solutionConcentrations of riboflavin from a to y/(μmol·L-1): 0, 0.025, 0.05, 0.1, 0.25, 0.5, 0.75, 1.0, 1.25, 1.5, 1.75, 2.0, 2.25, 2.5, 2.75, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0.

Fig.7 Plot of cathodic peak current for the RGO/ A32/Au electrode against riboflavin concentration in the N2-saturated electrochemistry buffer solutionInset: calibration curve of the electrode for riboflavin. The error bar on each datum point represents mean value plus or minus one standard deviation.

Table 1 Comparison of determination of riboflavin using various sensors

Method	Linear range/(μmol·L^-1)	LOD/(μmol·L^-1)	Reference
Electrochemistry	0.1—200	0.05	[30]
Electrochemistry	1.33—186.0	0.903	[31]
Electrochemistry	0.323—40	0.187	[32]
Electrochemistry	0.2—100	0.107	[33]
Electrochemistry	0.009—55.9	0.001	[34]
Electrochemistry	0.3—0.8	0.10	[35]
Electrochemistry	0.025—2.25	0.02	[26]
Fluorescence	0.58—20	0.18	[36]
Fluorescence	0—265.7	1.59	[6]
Electrochemistry	0.025—2.75	0.015	This work

Fig.8 Plot of cathodic peak current for the RGO/ A32/Au electrode against riboflavin(2.0 μmol/L) with and without other bioactive substance(100.0 μmol/L)a. Riboflavin; b. riboflavin+ascorbic acid; c. riboflavin+vitamin B6; d. riboflavin+nicotinamide; e. riboflavin+thiamine; f. riboflavin+glucose; g. riboflavin+lysine; h. riboflavin+folic acid; i. riboflavin+uric acid.

Table 2 Determination of riboflavin spiked in urine samples(n=3)

Sample	Added/(μmol·L^-1)	Found^a/(μmol·L^-1)	Mean recovery^b(%)
1	0.25	0.26±0.02	104
2	1.0	1.07±0.08	107
3	2.0	1.96±0.04	98

参考文献 36

[1]	Foraker A. B., Khantwal C. M., Swaan P. W., Adv. Drug Deliv. Rev., 2003, 55(11), 1467—1483
[2]	Gastaldi G., Ferrari G., Verri A., Casirola D., Orsenigo M. N., Laforenza U., J. Nutr., 2000, 130(10), 2556—2561
[3]	Bishop A. M., Fernadndez C., Whitehead R. D., Morales P., Barr D. B., Wilder L. C., Baker S. E., J. Chromatogr. Technol. Biomed. Life Sci., 2011, 879(20), 1823—1826
[4]	Caelen I., Kalman A., Wahlstrom L., Anal. Chem., 2004, 76(1), 137—143
[5]	Aranda M., Morlock G., J. Chromatogr. A, 2006, 1131(1/2), 253—260
[6]	Kundu A., Nandi S., Layek R. K., Nandi A. K., ACS Appl. Mater. Interfaces, 2013, 5(15), 7392—7399
[7]	Yan Y., Xu J. G., Lin J., Chen G. Z., Chem. J. Chinese Universities, 1997, 18(6), 877—879
	(鄢远, 许金钩, 林江, 陈国珍. 高等学校化学学报, 1997, 18(6), 877—879)
[8]	Geim A. K., Science, 2009, 324(5934), 1530—1534
[9]	Wang Z. T., Xiao C. F., Zhao J., Hu X., Xu N. K., Chem. J. Chinese Universities, 2014, 35(11), 2410—2417
	(王子涛, 肖长发, 赵健, 胡霄, 徐乃库. 高等学校化学学报, 2014, 35(11), 2410—2417)
[10]	Chen Z. X., Lu H. B., Chem. J. Chinese Universities, 2013, 34(9), 2020—2033
	(陈仲欣, 卢红斌. 高等学校化学学报, 2013, 34(9), 2020—2033)
[11]	Chen Y., Wang J., Liu Z. M., Chin. J. Anal. Chem., 2012, 40(11), 1772—1779
	(陈钰, 王婕, 刘仲明. 分析化学, 2012, 40(11), 1772—1779)
[12]	Lawal A. T., Talanta, 2015, 131, 424—443
[13]	Ping J. F., Zhou Y. B., Wu Y. Y., Papper V., Boujday S., Marks R. S., Steele T. W. J., Biosens. Bioelectron., 2015, 64, 373—385
[14]	Liu J. Q., Liu Z., Barrow C. J., Yang W. R., Anal. Chim. Acta, 2015, 859, 1—19
[15]	Wang H. J., Cheng N. N., Yang X. Y., Li X. M., Zhu L. D., Chem. Res. Chinese Universities, 2013, 29(1), 132—138
[16]	An J., Li J. P., Chen W. X., Yang C. X., Hu F. D., Wang C. M., Chem. Res. Chinese Universities, 2013, 29(4), 798—805
[17]	Teller C., Willner I., Curr. Opin. Biotechnol., 2010, 21(4), 376—391
[18]	Tang Y. T., Ge B. X., Sen D., Yu H. Z., Chem. Soc. Rev., 2014, 43(2), 518—529
[19]	Opdahl A., Petrovykh D. Y., Kimura-Suda H., Tarlov M. J., Whitman L. J., Proc. Natl. Acad. Sci. USA, 2007, 104(1), 9—14
[20]	Liu J. W., Phys. Chem. Chem. Phys., 2012, 14(30), 10485—10496
[21]	Varghese N., Mogera U., Govindaraj A., Das A., Chem. Phys. Chem., 2009, 10(1), 206—210
[22]	Marcano D. C., Kosynkin D. V., Berlin J. M., Sinitskii A., Sun Z. Z., Slesarev A., Alemany L. B., Lu W., Tour J. M., ACS Nano, 2010, 4(8), 4806—4814
[23]	Stankovich S., Dikin D. A., Piner R. D., Kohlhaas K. A., Kleinhammes A., Jia Y. Y., Wu Y., Nguyen S. T., Ruoff R. S., Carbon, 2007, 45(7), 1558—1565
[24]	Dutta S., Sarkar S., Ray C., Pal T., RSC Adv., 2013, 3(44), 21475—21483
[25]	Some S., Kim Y., Yoon Y., Yoo H., Lee S., Park Y., Lee H., Sci. Rep., 2013,3, 1929
[26]	Wang Y., Zhuang Q. F., Ni Y. N., J. Electroanal. Chem., 2015, 736, 47—54
[27]	Huang G. C., Chen T., Chen W. X., Wang Z., Chang K., Ma L., Huang F. H., Chen D. Y., Lee J. Y., Small, 2013, 9(21), 3693—3703
[28]	Chang K., Chen W. X., ACS Nano, 2011, 5(6), 4750—4728
[29]	Li J. L., Liu X. J., Pan L. K., Qin W., Chen T. Q., Sun Z., RSC Adv., 2014, 4(19), 9647—9651
[30]	Zhang H., Zhao J. S., Liu H. T., Wang H. S., Liu R. M., Liu J. F., Int. J. Electrochem. Sci., 2010, 5(3), 295—301
[31]	Ensafi A. A., Heydari-Bafrooei E., Amini M., Biosens. Bioelectron., 2012, 31(1), 376—381
[32]	Li Y., Hsu P. C., Chen S. M., Sens. Actuators A, 2012, 174, 427—435
[33]	Lavanya N., Radhakrishnan S., Sekar C., Navaneethan M., Hayakawa Y., Analyst, 2013, 138(7), 2061—2067
[34]	Kumar D. R., Manoj D., Santhanalakshmi J., Anal. Methods, 2014, 6(4), 1011—1020
[35]	Sa E. S., Da Silva P. S., Jost C. L., Spinelli A., Sens. Actuators A, 2015, 209, 423—430
[36]	Li P. P., Liu S. P., Wang X. D., Liu Z. Q., He Y. Q., Luminescence, 2013, 28(6), 910—914