基于Cu-TPA的电化学生物传感器对黄曲霉毒素B1的检测

doi:10.7503/cjcu20190233

摘要/Abstract

摘要：

利用对苯二甲酸铜(Cu-TPA)能产生强的电化学信号设计了一种灵敏的电化学生物传感器, 并将其用于测定黄曲霉毒素B1(AFB1). 信号探针中的Cu-TPA含有可产生电化学信号的Cu(Ⅱ), 当加入一定量的AFB1后, AFB1与探针中特定的适配体结合, 使信号探针脱落, 电化学信号降低. 根据电化学信号值的变化实现了对AFB1的检测. 在最佳条件下, 该传感器的检出限为4.2×10 ^-6 ng/mL(S/N=3), 线性范围为10 ^-5~10 ng/mL. 将该传感器用于啤酒中AFB1的检测, 回收率为95%~106%.

关键词: 对苯二甲酸铜, 适配体, 黄曲霉毒素B1, 电化学生物传感器

Abstract:

Copper-terephthalate(Cu-TPA), which could produce strong electrochemical signal, was used as a signal probe to design sensitive electrochemical biosensor for determination of aflatoxin B1(AFB1). Cu-TPA/AuNPs composites contain large amounts of Cu(Ⅱ), which can obtain strong electrochemical signal. When a certain amount of AFB1 was added, AFB1 and AFB1 aptamer combined to make the signal probe fall off and the electrochemical signal reduced. Under the optimized conditions, this electrochemical biosensor for AFB1 exhibited low detection limit of 4.2×10 ^-6 ng/mL(S/N=3) and wide linear range of 10 ^-5—10 ng/mL. The biosensor was also used to analyze AFB1 spiked beer sample and the recovery rate was 95%—106%.

Key words: Copper-terephthalate, Aptamer, Aflatoxin B1, Electrochemical biosensor

中图分类号:

O657.1
O646

TrendMD:

王春燕,蒋晓青,周泊. 基于Cu-TPA的电化学生物传感器对黄曲霉毒素B1的检测. 高等学校化学学报, 2019, 40(11): 2301.

WANG Chunyan,JIANG Xiaoqing,ZHOU Bo. An Electrochemical Biosensor Based on Cu-TPA for Determination of Aflatoxin B1 ^†. Chem. J. Chinese Universities, 2019, 40(11): 2301.

图/表 10

Scheme 1 Preparation procedure of Cu-TPA/AuNPs/S1

Scheme 2 Schematic illustration of the preparation of CuTPA/AuNPs/S1/S3/S2/GE electrochemical biosensor for AFB1 detection

Fig.1 XRD patterns of CuTPA×DMF(CCDC-687690)(a) and Cu-TPA(b)(A), chemical structure of Cu-TPA(B), IR spectra of HTPA(a), Cu-TPA(b) and Cu-TPA/AuNPs(C) and TEM image of Cu-TPA(D)

Fig.2 CV responses of the electrodes GE and Cu-TPA/GE in the scan range of -0.8—0.8 V(A) and DPV responses of the electrodes GE, Cu-TPA/GE and Cu-TPA/AuNPs/GE in Tris-HCl(pH=7.4) with a scan rate of 100 mV/s in the scan range of -0.1—0.5 V(B)

Fig.3 DPV responses of the CuTPA/AuNPs/S1/S3/S2/GE electrode to different concentrations of AFB1 in Tris-HCl(pH=7.4) with a scan rate of 100 mV/s and scan range of -0.1—0.5 V Concentration of AFB1/(ng·mL-1): a. 0; b. 0.001; c. 10.

Fig.4 CV(A) and EIS(B) results of the electrodes in different modification steps in 5.0 mmol/L K3[Fe(CN)6]/K4[Fe(CN)6] with a scan rate of 100 mV/s and in a scan range of -0.2—0.6 V a. Bare gold electrode; b. S2 immobilized on the electrode; c. S3 and S2 complementary paired on the electrode; d. S1 and S3 complementary paired on the electrode; e. adding 10 ng/mL AFB1 on the electrode.

Fig.5 Optimization of experimental parameters during the experiment (A) Concentration optimization of S3 binding to the electrode; (B) binding time of Cu-TPA/AuNPs/S1 to S3/S2/GE electrode; (C) combination time after the addition of AFB1 and S3. The concentration of AFB1 is 10 ng/mL.

Fig.6 DPV responses of the electrochemical biosensor to different concentrations of AFB1 under optimal experimental conditions(A) and the calibration curve between the peak current change and logarithm of AFB1 concentration(B) Concentration of AFBI/(ng·mL-1) from a to i: 10-6, 10-5, 10-4, 10-3, 10-2, 10-1, 1, 10, 100. The error bars in (B) are the standard deviations of the three experiments.

Table 1 Comparison of different methods for the detection of AFB1

Analytical method	Material	Linear range/(ng·mL^-1)	Detection limit/(ng·mL^-1)	Ref.
Electrochemical immunosensor	AFB1-BSA/Cu-apatite	10^-3—100	2.0×10^-4	[30]
Electrochemiluminoscence	DNA2/HRP/AuNR	5.0×10^-6—10	4.3×10^-7	[18]
Electrochemiluminescence	luminol-AgNPs @MC	10^-4—50	5.0×10^-5	[31]
Electrochemicalsensors	MIP-based polymer/AuNPs	10^-6—1000	3.0×10^-7	[32]
Electrochemicalsensors	MIPOPD-Au/PtNP-MCNT	10^-4—10	3.1×10^-5	[15]
Electrochemical biosensor	Cu-TPA/AuNPs/S1	10^-5—10	4.2×10^-6	This work

Table 2 Recovery of AFB1 spiked in beer sample

Spiked AFB1/(ng·mL^-1)	Detected AFB1/(ng·mL^-1)	Recovery(%)	RSD(%)
10	10.6	106	2.33
1	0.99	99	2.90
0.1	0.095	95	4.41

参考文献 32

[1]	Carson C. G., Hardcastle K., Schwartz J., Liu X., Hoffmann C., Gerhardt R. A., Tannenbaum R., Eur. J. Inorg. Chem., 2009,2009(16), 2338— 2343
[2]	Acheson R. J., Galwey A. K., J. Chem. Soc. A, 1967, 1174— 1178
[3]	Sherif F. G ., Ind. Eng. Chem. Prod. Res. Dev., 1970,9(3), 408— 412
[4]	Cueto S., Gramlich V., Petter W., Rys F. S., Rys P ., Acta Cryst., 1991,47(1), 75— 78
[5]	Chen Z., Xiang S., Zhao D., Chen B., Cryst. Growth Des., 2009,9(12), 5293— 5296
[6]	Cheng Y., Wang X., Jia C., Wang Y., Zhai L., Wang Q., Zhao D ., J. Membr. Sci., 2017,539, 213— 223
[7]	Elder A. C., Bhattacharyya S., Nair S., Orlando T. M., J. Phys. Chem. C, 2018,122(19), 10413— 10422
[8]	Zhang X., Dong W., Luan Y., Yang M., Tan L., Guo Y., Gao H., Tang Y., Dang R., Li J ., J. Mater. Chem. A, 2015,3(8), 4266— 4273
[9]	Brondani D., Zapp E., Heying R. S., De Souza B., Vieira I. C., Electroanalysis, 2017,29(12), 2810— 2817
[10]	Bai R. Y., Zhang K. L., Li D. L., Zhang Q., Liu T. Z., Liu Y., Hu R., Yang Y. H., Chin. J. Anal. Chem., 2017,45(1), 48— 55
	( 白茹燕, 张坤蕾, 李德蕾, 张茜, 刘婷知, 刘仪, 胡蓉, 杨云慧 , 分析化学, 2017,45(1), 48— 55)
[11]	Mak A. C., Osterfeld S. J., Yu H., Wang S. X., Davis R. W., Jejelowo O., Pourmand N ., Biosensors Bioelectron., 2010,25(7), 1635— 1639
[12]	Zheng W., Teng J., Cheng L., Ye Y., Pan D., Wu J., Xue F., Liu G., Chen W., Biosensors Bioelectron., 2016,80, 574— 581
[13]	Li X., Li P., Zhang Q., Li R., Zhang W., Zhang Z., Ding X., Tang X., Biosensors Bioelectron., 2013,49, 426— 432
[14]	Zhang J., Li Z., Zhao S., Lu Y ., Analyst, 2016,141(13), 4029— 4034
[15]	Wang Z., Li J., Xu L., Feng Y., Lu X ., J. Solid State Electrochem., 2014,18(9), 2487— 2496
[16]	Kuang H., Chen W., Xu D., Xu L., Zhu Y., Liu L., Chu H., Peng C., Xu C., Zhu S., Biosens. Bioelectron., 2011,26(2), 710— 716
[17]	Ge L., Wang W., Li F., Anal. Chem., 2017,89(21), 11560— 11567
[18]	Li Q., Lu Z., Tan X., Xiao X., Wang P., Wu L., Shao K., Yin W., Han H., Biosens Bioelectron., 2017,97, 59— 64
[19]	Wu L., Ding F., Yin W., Ma J., Wang B., Nie A., Han H., Anal. Chem., 2017,89(14), 7578— 7585
[20]	Adams R., Carson C., Ward J., Tannenbaum R., Koros W., Microporous Mesoporous Mater., 2010,131(1), 13— 20
[21]	Bai R., Zhang K., Delei L. I., Zhang X., Liu T., Liu Y., Rong H. U., Yang Y., Chinese Journal of Analytical Chemistry, 2017,45(1), 48— 55
[22]	Ji X., Song X., Li J., Bai Y., Yang W., Peng X ., J. Am. Chem. Soc., 2007,129(45), 13939— 13948
[23]	Zhang J., Song S., Wang L., Pan D., Fan C., Nat. Protoc., 2007,2(11), 2888— 2895
[24]	Goud K. Y., Catanante G., Hayat A., Satyanarayana M., Gobi K. V., Marty J. L., Sens. Actuators,B, 2016,235, 466— 473
[25]	Kubica P., Wolinska Grabczyk A., Grabiec E., Libera M., Wojtyniak M., Czajkowska S., Domański M., Microporous Mesoporous Mater., 2016,235, 120— 134
[26]	Elder A. C., Aleksandrov A. B., Nair S., Orlando T. M., Langmuir, 2017,33(39), 10153— 10160
[27]	Feijani E. A., Mahdavi H., Tavasoli A ., Chem. Eng. Res. Des., 2015,96, 87— 102
[28]	Yadav D. K., Ganesan V., Sonkar P. K., Gupta R., Rastogi P. K., Electrochim. Acta, 2016,200, 276— 282
[29]	Iqbal M., Ali S., Tahir M. N., Muhammad N., Shah N. A., Journal of Molecular Structure., 2015,1093, 135— 143
[30]	Wang H., Zhang Y., Chu Y., Ma H., Li Y., Wu D., Du B., Wei Q ., Talanta, 2016,147, 556— 560
[31]	Lv X., Li Y., Cao W., Yan T., Li Y., Du B., Wei Q., Sens. Actuators, B, 2014,202, 53— 59
[32]	Jiang M., Braiek M., Florea A., Chrouda A., Farre C., Bonhomme A., Bessueille F., Vocanson F., Zhang A., Jaffrezic R. N., Toxins, 2015,7(9), 3540— 3553