Photoelectrochemical Response and Application of ZnO Nanorods Photoelectrode to Riboflavin†

doi:10.7503/cjcu20160522

Abstract

Abstract:

In this work, based on the pre-reduction of riboflavin(RF) on the second working electrode, a new photoelectrochemical(PEC) system was fabricated by the reduced RF as an electron donor incorporated into PEC reaction process of zinc oxide nanorods photoelectrode(ZnONRP). After optimizing the electro-chemical preparation for ZnONRP and studying the reaction mechanism of RF with ZnONRP, a PEC method for the determination of RF was developed. Under the optimized conditions of pH=6.5, -0.40 V as pre-reduction potential, illumination at 365 nm and light energy of 450 μW/cm², the photocurrent at bias voltage 0.1 V is proportional to the logarithm of RF concentration in the range of 1.00×10^-5—1.00 μmol/L with sensitivity of 195.6 nA/lg[c(μmol/L)], and the detection limit was estimated to be 6.00×10^-7 μmol/L(S/N=3). Determination results for real samples showed that the relative standard deviation is less than 6.25% and the recovery rate is 99.0%—104%. Compared with other methods for the determination of RF, the proposed method has various advantages, such as wide measurement range, high sensitivity, simple equipment and convenient operation. And common biochemical substances were not interfering with the photocurrent response of RF.

Key words: Riboflavin, ZnO nanorods, Photoelectronchemical analysis, Four-electrode electrochemical system

CLC Number:

O657.1

TrendMD:

HE Yanyan, GE Junying, ZHAO Changzhi. Photoelectrochemical Response and Application of ZnO Nanorods Photoelectrode to Riboflavin^†[J]. Chem. J. Chinese Universities, 2016, 37(12): 2144.

Figures/Tables 9

Fig.1 SEM image of the cross-section of ZnONRPInset is the surface photography of ZnONRP.

Fig.2 SEM image of the cross-section of ITO electrode

Fig.3 XRD pattern of ZnONRP surface

Fig.4 Cyclic voltammograms of RF solution(1.00×10-4 mol/L) before(a) and after electrochemical reduction(b)Inset is the structural formula of RF.

Fig.5 Fluorescence spectra of RF solution(1.00×10-6 mol/L) before(a) and after electrochemical reduction(b)

Fig.6 Photoelectrochemical response mechanism of RF on ZnONRP(A) and photocurrent responses(B) of blank solution(a), the unreduced RF(b) and reduced RF(c) on ZnONRP

Fig.7 Photocurrent responses to various concentration of RFs(A) and response curve(B)(A) From left to right, cRF/(μmol·L-1): 0, 1.00×10-5, 1.00×10-4, 1.00×10-3, 1.00×10-2, 0.10, 0.50, 1.00. (B) Inset is the calibration curve on the photocurrent responses to concentration logarithm.

Fig.8 Reduction current curve of RF at GCE(a) and photocurrent response curve of RF at ZnONRP(b)

Table 1 Determination results of the riboflavin in millet

Sample	Found/(μg·g^-1)	RSD(%)	Fluorescence/(μg·g^-1)	Added(μg·g^-1)	Total/(μg·g^-1)	Recovery(%)
1	1.92	5.48	1.85	2.00	4.06	104
2	1.38	6.25	1.42	1.50	2.85	99.0
3	1.26	5.76	1.32	1.00	2.29	101

References 20

[1]	Zhang X., Guo Y., Liu M., Zhang S., RSC Adv., 2013, 9, 2846—2857
[2]	Zhao C. Z., Yu J., Zhao G. S., Jiao K., Scientic Sinica Chim., 2011, 41, 1075—1080
	(赵常志, 俞佳, 赵改爽, 焦奎.中国科学: 化学, 2011, 41, 1075—1080)
[3]	Xu R., Jiang Y., Xia L., Zhang T., Xu L., Zhang S., Liu D., Song H., Biosens. Bioelectronics, 2015, 74, 411—417
[4]	Wang G. L., Shu J. X., Dong Y. M., Wu X. M., Zhao W. W., Xu J. J., Chen H. Y., Anal. Chem., 2015, 87, 2892—2900
[5]	Zhang Z., Zhao C., Chinese J. Anal. Chem., 2013, 41(3), 436—444
	(张光霞, 赵常志. 分析化学,2013, 41(3), 436—444)
[6]	Abbas C. A., Sibirny A. A., Microbiology and Molecular Biology Reviews, 2011, 75, 321—360
[7]	Lienhart W. D., Gudipati V., Macheroux P., Archives of Biochemistry and Biophysics, 2013, 535, 150—162
[8]	Barile M., Giancaspero T. A., Brizio C., Panebianco C., Indiveri C., Galluccio M., Vergani L., Eberini I., Gianazza E., Current Pharmaceutical Design, 2013, 19, 2649—2675
[9]	Wen Q. X., Dong L., Sun X. Y., Zhuang J., Chen Z. M., Chem. Res. Chinese Universities, 2016, 32(3), 437—442
[10]	Arya S. K., Saha S., Ramirez-Vick J. E., Gupta V., Bhansali S., Singh S. P., Anal. Chim. Acta, 2012, 737, 1—21
[11]	Zhai Y., Zhai S., Chen G., Zhang K., Yue Q., Wang L., Liu J., Jia J., J. Electroanal. Chem., 2011, 656, 198—205
[12]	Lee C. T., Chiu Y. S., Ho S. C., Lee Y. J., Sensors, 2011, 11, 4648—4655
[13]	Kang Z., Gu Y., Yan X., Bai Z., Liu Y., Biosens. Bioelectronics, 2015, 64, 499—504
[14]	Weng J., Zhang Y., Han G., Zhang Y., Xu J., Huang X., Chen K., Thin Solid Films, 2005, 478, 25—29
[15]	Hambali N. A., Yahaya H., Mahmood M. R., Terasako T., Hashim A. M., Nanoscale Res. Lett., 2014, 9, 609—616
[16]	Zhou T. Y., Yu J. S., Chem. J. Chinese Universities, 1998, 19(2), 204—206
	(周桃玉, 于俊生. 高等学校化学学报,1998, 19(2), 204—206)
[17]	Pérez-Ruiz T., Martínez-Lozano C., Sanz A., Bravo E., Electrophoresis, 2001, 22, 1170—1174
[18]	Andrés-Lacueva C., Mattivi F., Tonon D., J. Chromatogr. A, 1998, 823, 355—363
[19]	Kang C., Wu H. L., Zhou C., Xiang S. X., Zhang X. H., Yu Y. J., Yu R Q., Anal. Chim. Acta, 2016, 910, 36—44
[20]	Kumar D. R., Manoj D., Santhanalakshmi J., Anal. Methods, 2014, 6, 1011—1020