Preparation of HRP Molecularly Imprinted Electrochemical Sensor with Multi-walled Carbon Nanotubes as Sensitizing Materials and the Detection of H2O2 †

doi:10.7503/cjcu20190485

Abstract

Abstract:

Firstly, the pre-carboxylated multi-walled carbon nanotubes(MWCNTs) were electrodeposited on the surface of the glassy carbon electrode as sensitivity-enhanced materials. Then, a layer of polymeric film was formed on the modified electrode through the electropolymerization in the o-phenylenediamine(o-PD) monomer solution containing horseradish peroxidase template molecule. After removing the templates, the molecularly imprinted polymer membrane with specific recognition ability towards horseradish peroxidase was formed. The prepared molecularly imprinted electrochemical sensor had a good linear relationship with horseradish peroxidase(HRP) in the concentration range of 1.0×10 ^-10—1.0×10 ^-5 mg/mL, the correlation coefficient was 0.991, and the detection limit was 1.5×10 ^-11 mg/mL(S/N=3); and also exhibited a good linear response for H₂O₂ in the concentration range of 4.0×10 ^-7—1.4×10 ^-5 mol/L, with a correlation coefficient of 0.992 and a detection limit of 2.6×10 ^-7 mol/L(S/N=3). And this molecularly imprinted sensor was used for the detection of the actual sample, the recovery rate is between 91.2% and 97.1%. HRP and H₂O₂ bi-analyte sensor based on MIP film was successfully developed in this work. The developed method can also be applicable for enzyme and its enzymatic substrate bi-analyte sensor.

Key words: Molecularly imprinted polymer, Self-probe, Molecularly imprinted electrochemical enzyme sensor, Horseradish peroxidase, Hydrogen peroxide

TrendMD:

TENG Yu,YANG Shaoming,BAI Chaopeng,ZHANG Jian. Preparation of HRP Molecularly Imprinted Electrochemical Sensor with Multi-walled Carbon Nanotubes as Sensitizing Materials and the Detection of H₂O₂ ^†[J]. Chem. J. Chinese Universities, 2020, 41(1): 78.

Figures/Tables 11

Fig.1 SEM images of MWCNTs/GCE(A), POPD/GCE(B) and MIPs/MWCNTs/GCE before(C) and after(D) extracting HRP

Fig.2 EDS spectrum of MIPs/MWCNTs/GCE before extracting HRP

Fig.3 CV(A) and EIS(B) profiles of HRP molecularly imprinted sensor assembly process a. Bare GCE; b. MWCNTs/GCE; c. MIPs/MWCNTs/GCE before extracting HRP; d. MIPs/MWCNTs/GCE after rebinding HRP(1.0×10-7 mg/mL); e. MIPs/MWCNTs/GCE after extracting HRP.

Fig.4 CV(A—C) and EIS(D) profiles of different molecularly imprinted sensors a. MIPs/MWCNTs/GCE before extracting HRP; b. MIPs/MWCNTs/GCE after extracting HRP; c. MIPs/GCE before extracting HRP; d. MIPs/GCE after extracting HRP; e. NIPs/MWCNTs/GCE before extracting HRP; f. NIPs/MWCNTs/GCE after extracting HRP.

Fig.5 CV responses of MIPs/MWCNTs/GCE sensor with scan rates from 0.01 V/s to 1.0 V/s(A) and linear fitting curve between peak current to scan rate(B)

Fig.6 DPV response of MIPs/MWCNTs/GCE sensor to different concentrations of HRP(A) and corresponding linear fitting curve(B), I-t curve of the MIPs/MWCNTs/GCE modified electrode to successive addition of H2O2(C) and corresponding linear fitting curve(D) a. Blank; concentration of curve a—k: 10-10—10-5 mg/mL.

Electrode	Linear range/ (μmol·L^-1)	Sensitivity/ (μA·L·mol^-1)	Detection limit/ (μmol·L^-1)	Ref.
HRP/BSA/SPCNTE	5—100	0.104	0.85	[27]
HRP/AuNP/ITO	8—3000	0.4	2.0	[28]
HRP/LDH-CMC/GCE	20—6000	0.22	12.4	[29]
MIP/PANTs/HRP/GCE	0—10, 10—90	0.12, 0.049	0.01	[30]
MIP/MT-MWCNT/GCE	0.04—14	12.28	0.26	This work

Fig.7 Kinetic response curves of HRP at different sensors

Sensor	ΔI_pm/μA	k/min
MIPs/MWCNTs/GCE	-40.54	1.52
NIPs/MWCNTs/GCE	-4.75	0.06

Fig.8 Responses of MIPs/MWCNTs/GCE to different substances

c_original/(μmol·L^-1)	c_added/(μmol·L^-1)	c_found/(μmol·L^-1)	Recovery(%)
0.95	5.85	5.68	97.1
0.94	10.74	9.79	91.2
1.09	15.64	15.10	96.9

References 30

[1]	Chen L., Xu S., Li J., Chem. Soc. Rev., 2011,40(5), 2922— 2049 doi: 10.1039/c0cs00084a URL pmid: 21359355
[2]	Fan P. M., Wang B., Chem. J. Chinese Universities, 2009, 30(12), 2514—2520
	( 范培民, 王兵 . 高等学校化学学报, 2009,30(12), 2514— 2520)
[3]	Mao Y., Bao Y., Gan S., Li F., Niu L. Biosens. Bioelectron., 2011,28(1), 291— 297 doi: 10.1016/j.bios.2011.07.034 URL pmid: 21824760
[4]	Yao J., Chen M., Li N. N ., Liu C. H.,Yang M., Anal. Chim. Acta, 2019,1066, 36— 48 doi: 10.1016/j.aca.2019.03.051 URL pmid: 31027533
[5]	Duan D. D ., Yang H.,Ding Y. P.,Ye D. X.,Li L.,Ma G. H., Electrochim. Acta, 2018,261, 160— 166 doi: 10.1016/j.electacta.2017.12.146 URL
[6]	Sun B. H ., Ni X. J.,Cao Y. H.,Cao G. Q., Biosens. Bioelectron., 2017,91, 354— 358 doi: 10.1016/j.bios.2016.12.056 URL pmid: 28049107
[7]	Zhang X., Yang S., Sun L. Q ., Luo A. Q., J. Mater. Sci., 2016,51(12), 6075— 6085 doi: 10.1007/s10853-016-9914-7 URL
[8]	Kan X. W ., Xing Z. L.,Zhu A. H.,Zhao Z.,Xu G. L.,Li C.,Zhou H., Sens. Actuators B, 2012,168, 395— 401 doi: 10.1016/j.snb.2012.04.043 URL
[9]	Pacheco J. G ., Silva M. S. V.,Freitas M.,Nouws H. P. A.,Delerue-Matos C., Sens. Actuators B, 2018,256, 905— 912 doi: 10.1016/j.snb.2017.10.027 URL
[10]	Shen X. L ., Ma Y.,Zeng Q.,Huang J. Z.,Tao J.,Wang L. S.,. Chemistry Select, 2017,2, 6549— 6555
[11]	Shumyantseva V. V ., Bulko T. V.,Sigolaeva L. V.,Kuzikov A. V.,Archakov A. I., Biosens. Bioelectron., 2016,86, 330— 336 doi: 10.1016/j.bios.2016.05.101 URL pmid: 27392234
[12]	Tavares A. P. M ., Sales M. G. F., Electrochim. Acta, 2018,262, 214— 225 doi: 10.1016/j.electacta.2017.12.191 URL
[13]	Tang Y. Z., Chen X.,Yang X. J.,Shen R. F.,Yang X. D.,Xu C. Z., IEEE Sens. J., 2013,13(9), 3270— 3275 doi: 10.1109/JSEN.2013.2267233 URL
[14]	Goh M. S ., Pumera M., Anal. Bioanal. Chem., 2011,399(1), 127— 131 doi: 10.1007/s00216-010-4338-8 URL pmid: 21046081
[15]	Majouga A. G ., Russ. Chem. Rev., 2012,81(1), 65— 90 doi: 10.1070/RC2012v081n01ABEH004158 URL
[16]	Karimimaleh H., Curr. Anal. Chem., 2017,13(1), 4 doi: 10.2174/157341101301161226183935 URL
[17]	Ling W., Ran Y., Li J., Qu L ., Anal. Methods, 2014,6(10), 3449— 3455 doi: 10.1039/c4ay00684d URL
[18]	Li J., Qu J., Yang R., Qu L., Peter D. B. H ., Electroanal., 2016,28(6), 1322— 1330 doi: 10.1002/elan.201500490 URL
[19]	Gopal P., Reddy T. M ., Palakollu V. N.,. Chemistry Select, 2017,2(13), 3804— 3811
[20]	Ma P. C ., Wang S. Q.,Kim J. K.,Tang B. Z., J. Nanosci. Nanotechno., 2009,9(2), 749— 753 doi: 10.1166/jnn.2009.C017 URL
[21]	Ansaldo A., Castagnola E., Maggiolini E., Fadiga L., Ricci D ., ACS. Nano, 2011,5(3), 2206— 2214 doi: 10.1021/nn103445d URL pmid: 21341752
[22]	Chu D., Li Z., Yuan X., Li J., Wei X., Wan Y ., Electrochim. Acta, 2012,78(9), 644— 648 doi: 10.1016/j.electacta.2012.06.092 URL
[23]	Kim K. S ., Park S. J., Electrochim. Acta, 2011,56(3), 1629— 1635 doi: 10.1016/j.electacta.2010.10.043 URL
[24]	Liu Y., Huang L., Dong S., Biosens. Bioelectron., 2008,23(1), 35— 41 doi: 10.1016/j.bios.2007.03.009 URL pmid: 17459687
[25]	Chen C., Zhai W., Lu D., Zhang H. B ., Zheng W. G., Mater. Res. Bull., 2011,46(4), 583— 587 doi: 10.1016/j.materresbull.2010.12.024 URL
[26]	Feng L., Tu X. M., Zhao Y. J., Zou Y. Y., Jiangxi Chemical Industry, 2012,1, 97— 101
	( 冯莉, 涂新满, 赵英杰, 邹云云. 江西化工, 2012,1, 97— 101)
[27]	Xu S., Qin X., Zhang X., Zhang C ., Microchim. Acta, 2015,182(7/8), 1241— 1246 doi: 10.1007/s00604-014-1444-x URL
[28]	Wang J., Wang L., Di J., Tu Y ., Talanta, 2009,77(4), 1454— 1459 doi: 10.1016/j.talanta.2008.09.034 URL
[29]	Komathi S., Gopalan A. I ., Kim S. K.,Anand G. S.,Lee K. P., Electrochim. Acta, 2013,92(1), 71— 78 doi: 10.1016/j.electacta.2013.01.032 URL
[30]	Wang Q., Xue R., Guo H., Wei Y., Yang W ., J. Electroanal. Chem., 2018,817, 184— 194 doi: 10.1016/j.jelechem.2018.04.013 URL

Preparation of HRP Molecularly Imprinted Electrochemical Sensor with Multi-walled Carbon Nanotubes as Sensitizing Materials and the Detection of H₂O₂ ^†

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 11

References 30

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	WENG Meiqi, SHANG Guiming, WANG Jiatai, LI Shenghua, FAN Zhi, LIN Song, GUO Minjie. Template Simulation of Organophosphorus Nerve Agent Molecularly Imprinted Polymers [J]. Chem. J. Chinese Universities, 2022, 43(8): 20220136.
[2]	ZHU Haotian, JIN Meixiu, TANG Wensi, SU Fang, LI Yangguang. Properties of Transition Metal-biimidazole-Dawson-type Tungstophosphate Hybrid Compounds as Supports for Enzyme Immobilization [J]. Chem. J. Chinese Universities, 2022, 43(11): 20220328.
[3]	LI Jian, YU Mingming, SUN Yuan, FENG Wenhua, FENG Zhaochi, WU Jianfeng. Effect of Aqueous Solution pH on the Oxidation of Methane to Methanol at Low Temperature [J]. Chem. J. Chinese Universities, 2021, 42(3): 776.
[4]	GAO Xia,PAN Huibin,QIAO Chengfang,CHEN Fengying,ZHOU Yuan,YANG Wenhua. Construction of HRP Immobilized Enzyme Reactor Based on Hierarchically Porous Metal-organic Framework and Its Dye Degradation Application^† [J]. Chem. J. Chinese Universities, 2020, 41(7): 1591.
[5]	ZHANG Jingjing, JIN Rong, FANG Danjun, JIANG Dechen. Voltage Modulated Electrochemiluminescence for Highly Sensitive Detection [J]. Chem. J. Chinese Universities, 2020, 41(11): 2421.
[6]	WU Shanshan,WEI Chanling,ZHAO Lijuan,TIAN Yang,WANG Xia,GONG Bolin. Preparation and Enrichment Properties of Novel Magnetic Restricted Access Media-molecularly Imprinted Composites^† [J]. Chem. J. Chinese Universities, 2019, 40(6): 1150.
[7]	DONG Deming,ZHANG Ying,HUA Xiuyi,JIANG Xu,LIANG Dapeng,GUO Zhiyong. Effect of Dissolved Organic Matter on the Generation of H₂O₂ in Natural Biofilm Systems Under Illumination^† [J]. Chem. J. Chinese Universities, 2019, 40(4): 800.
[8]	FANG Chao,ZHU Hanyu,LIU Ye,ZHAO Waiou,LI Yapeng,WANG Jingyuan. Synthesis and Characterization of Nanoparticles with Hydrogen Peroxide Sensitivity, Targeting and Fluorscence for Atherosclerosis [J]. Chem. J. Chinese Universities, 2018, 39(9): 2071.
[9]	GUO Ming, ZHANG Xinge, ZENG Chuchu, YIN Xinxin. Preparation and Properties Characterization of Intelligent Molecularly Imprinted Polymer Based on Diles-Alder Reaction^† [J]. Chem. J. Chinese Universities, 2018, 39(3): 566.
[10]	MA Fangchen, LI Xin, REN Xiaohui. Ultrasensitive Detection of Malachite Green Using the Coupling Technique of Dummy Molecular Imprinting and Surface-enhanced Raman Scattering [J]. Chem. J. Chinese Universities, 2017, 38(8): 1347.
[11]	GAO Hongcheng, WANG Zhenlu, NIU Guiling, WEN Shoudong, WU Xiaonan, ZHANG Xiaofei, SU Pengchen, YAN Xin, QI Qiang, GAO Binbin. Preparation and Catalytic Olefin Epoxidation Properties of Carbon Nanotube/Polyoxometalates/Polypyrrole Composite Catalyst^† [J]. Chem. J. Chinese Universities, 2017, 38(7): 1223.
[12]	ZHANG Jinshuai, YU Fengli, TAO Renqing, XIE Congxia, YUAN Bing, YU Shitao. Selective Oxidation of Cyclopentene to Glutaraldehyde Catalyzed by Heteropolyphosphatotungstate Ionic Liquids^† [J]. Chem. J. Chinese Universities, 2017, 38(12): 2248.
[13]	GE Hao,HUANG Hailong,XU Min. Preparation and Properties of Surface Imprinted Magnetic Cellulose Microsphere with Highly Selective Adsorption^† [J]. Chem. J. Chinese Universities, 2016, 37(8): 1551.
[14]	ZHANG Yan, ZHENG Jing, WANG Juan, GUO Mandong. Preparation and Properties of Doxorubicin Hydrochloride Sensor Based on Molecularly Imprinted Polymer^† [J]. Chem. J. Chinese Universities, 2016, 37(5): 860.
[15]	TANG Xiaojian, WANG Yixue, KANG Chunli, LIU Hanfei, CHEN Baiyan, QIU Shilun. Photoconversion of Phenol in Ice with the Presence of H₂O₂ Under Simulated Solar Light^† [J]. Chem. J. Chinese Universities, 2015, 36(9): 1719.