Abstract
Organophosphorus pesticides (OPs) are extensively used worldwide as agrochemicals; however, excess use may threaten the health of humans. Thus, it is an urgent need to develop a sensitive method for determination of OPs. Herein, a simple and sensitive split-type electrochemical method was developed by using MnO2 nanoflower-electron mediator as a signal transduction element. The MnO2 nanoflower-electron mediator was synthesized and shows an excellent electrochemical signal attributed to the high specific surface area of MnO2 nanoflower. Meanwhile, the inhibition of OPs on butyrylcholinesterase (BChE) was carried out in the homogeneous system. In the absence of target molecule, a large number of thiocholines (TCh) were yielded from hydrolysis of acetylthiocholine (ATCh) by BChE. The MnO2 nanoflower was cracked, and subsequently, multiple electron mediator molecules were released from the platform after treated with TCh, thus decreasing the electrochemical response. Furthermore, the inhibition of OPs on BChE resulted in the reduced generation of TCh, thus inducing the recovery of electrochemical signal. Under the optimal experimental, dichlorvos can be detected in a wide range of 10−6–10−10 M, with a detection limit of 3 × 10−10 M. Moreover, the assay was successfully used to analyze dichlorvos in cucumber juice and pear juice, showing a great promising potential for detecting organophosphorus pesticides in complex samples.
Similar content being viewed by others
References
Liu X, Song M, Hou T, Li F. Label-free homogeneous electroanalytical platform for pesticide detection based on acetylcholinesterase-mediated DNA conformational switch integrated with rolling circle amplification. ACS Sens. 2017;2(4):562–8.
Jokanovic M. Neurotoxic effects of organophosphorus pesticides and possible association with neurodegenerative diseases in man: a review. Toxicology. 2018;410:125–31.
Mol HGJ, van Dam RCJ, Steijger OM. Determination of polar organophosphorus pesticides in vegetables and fruits using liquid chromatography with tandem mass spectrometry: selection of extraction solvent. J Chromatogr A. 2003;1015(1–2):119–27.
Su R, Xu X, Wang X, Li D, Li X, Zhang H, et al. Determination of organophosphorus pesticides in peanut oil by dispersive solid phase extraction gas chromatography-mass spectrometry. J Chromatogr B Anal Technol Biomed Life Sci. 2011;879(30):3423–8.
Padrón Sanz C, Halko R, Sosa Ferrera Z, Santana Rodríguez JJ. Micellar extraction of organophosphorus pesticides and their determination by liquid chromatography. Anal Chim Acta. 2004;524(1–2):265–70.
Cao J, Wang M, Yu H, She Y, Cao Z, Ye J, et al. An overview on the mechanisms and applications of enzyme inhibition-based methods for determination of organophosphate and carbamate pesticides. J Agric Food Chem. 2020. https://doi.org/10.1021/acs.jafc.0c01962.
Hassani S, Momtaz S, Vakhshiteh F, Maghsoudi AS, Ganjali MR, Norouzi P, et al. Biosensors and their applications in detection of organophosphorus pesticides in the environment. Arch Toxicol. 2017;91(1):109–30.
Huang S, Yao J, Chu X, Liu Y, Xiao Q, Zhang Y. One-step facile synthesis of nitrogen-doped carbon dots: a ratiometric fluorescent probe for evaluation of acetylcholinesterase activity and detection of organophosphorus pesticides in tap water and food. J Agric Food Chem. 2019;67(40):11244–55.
Du D, Wang J, Wang L, Lu D, Smith JN, Timchalk C, et al. Magnetic electrochemical sensing platform for biomonitoring of exposure to organophosphorus pesticides and nerve agents based on simultaneous measurement of total enzyme amount and enzyme activity. Anal Chem. 2011;83(10):3770–7.
Chen H, Zhang H, Yuan R, Chen S. Novel double-potential electrochemiluminescence ratiometric strategy in enzyme-based inhibition biosensing for sensitive detection of organophosphorus pesticides. Anal Chem. 2017;89(5):2823–9.
Lu L, Xia Y. Enzymatic reaction modulated gold nanorod end-to-end self-assembly for ultrahigh sensitively colorimetric sensing of cholinesterase and organophosphate pesticides in human blood. Anal Chem. 2015;87(16):8584–91.
Zhang Q, Yu Y, Yun X, Luo B, Jiang H, Chen C, et al. Multicolor colorimetric sensor for detection of omethoate based on the inhibition of the enzyme-induced metallization of gold nanorods. ACS Appl Nano Mater. 2020;3:5212–9.
Dhull V, Gahlaut A, Dilbaghi N, Hooda V. Acetylcholinesterase biosensors for electrochemical detection of organophosphorus compounds: a review. Biochem Res Int. 2013;2013:731501.
Zhu C, Yang G, Li H, Du D, Lin Y. Electrochemical sensors and biosensors based on nanomaterials and nanostructures. Anal Chem. 2015;87(1):230–49.
Tang J, Huang Y, Zhang C, Liu H, Tang D. Amplified impedimetric immunosensor based on instant catalyst for sensitive determination of ochratoxin A. Biosens Bioelectron. 2016;86:386–92.
Tang J, Xiong P, Cheng Y, Chen Y, Peng S, Zhu ZQ. Enzymatic oxydate-triggered AgNPs etching: a novel signal-on photoelectrochemical immunosensing platform based on Ag@AgCl nanocubes loaded RGO plasmonic heterostructure. Biosens Bioelectron. 2019;130:125–31.
Shu J, Qiu Z, Zhou Q, Tang D. A chemiresistive thin-film translating biological recognition into electrical signals: an innovative signaling mode for contactless biosensing. Chem Commun (Camb). 2019;55(22):3262–5.
Lin Y, Zhou Q, Tang D, Niessner R, Knopp D. Signal-on photoelectrochemical immunoassay for Aflatoxin B1 based on enzymatic product-etching MnO2 nanosheets for dissociation of carbon dots. Anal Chem. 2017;89(10):5637–45.
Aveiro LR, da Silva AGM, Antonin VS, Candido EG, Parreira LS, Geonmonond RS, et al. Carbon-supported MnO2 nanoflowers: introducing oxygen vacancies for optimized volcano-type electrocatalytic activities towards H2O2 generation. Electrochim Acta. 2018;268:101–10.
Yan X, Song Y, Zhu C, Li H, Du D, Su X, et al. MnO2 nanosheet-carbon dots sensing platform for sensitive detection of organophosphorus pesticides. Anal Chem. 2018;90(4):2618–24.
Hou J, Dong G, Tian Z, Lu J, Wang Q, Ai S, et al. A sensitive fluorescent sensor for selective determination of dichlorvos based on the recovered fluorescence of carbon dots-Cu(II) system. Food Chem. 2016;202:81–7.
Di Tuoro D, Portaccio M, Lepore M, Arduini F, Moscone D, Bencivenga U, et al. An acetylcholinesterase biosensor for determination of low concentrations of paraoxon and dichlorvos. New Biotechnol. 2011;29(1):132–8.
Huang N, Qin Y, Li M, Chen T, Lu M, Zhao J. A sensitive fluorescence assay of organophosphorus pesticides using acetylcholinesterase and copper-catalyzed click chemistry. Analyst. 2019;144(10):3436–41.
Meng X, Wei J, Ren X, Ren J, Tang F. A simple and sensitive fluorescence biosensor for detection of organophosphorus pesticides using H2O2-sensitive quantum dots/bi-enzyme. Biosens Bioelectron. 2013;47:402–7.
Cui HF, Wu WW, Li MM, Song X, Lv Y, Zhang TT. A highly stable acetylcholinesterase biosensor based on chitosan-TiO2-graphene nanocomposites for detection of organophosphate pesticides. Biosens Bioelectron. 2018;99:223–9.
Yaneva M, Ivanov Y, Todorov N, Godjevargova T. Magnetic-nanoparticles-based fluorescent immunoassay for individual and simultaneous determination of dichlorvos and paraoxon in milk. Food Agric Immunol. 2017;29(1):228–43.
Hu Y, Li J, Li X. Leek-derived codoped carbon dots as efficient fluorescent probes for dichlorvos sensitive detection and cell multicolor imaging. Anal Bioanal Chem. 2019;411(29):7879–87.
Wei M, Wang J. A novel acetylcholinesterase biosensor based on ionic liquids-AuNPs-porous carbon composite matrix for detection of organophosphate pesticides. Sensors Actuators B Chem. 2015;211:290–6.
Lv S, Zhang K, Zhu L, Tang D. ZIF-8-assisted NaYF4:Yb,Tm@ZnO converter with exonuclease III-powered DNA walker for near-infrared light responsive biosensor. Anal Chem. 2020;92:1470–6.
Huang L, Chen J, Yu Z, Tang D. Self-powered temperature sensor with Seebeck effect transduction for photothermal-thermoelectric coupled immunoassay. Anal Chem. 2020;92:2809–14.
De Souza D, Machado SA. Electroanalytical method for determination of the pesticide dichlorvos using gold-disk microelectrodes. Anal Bioanal Chem. 2005;382(7):1720–5.
Funding
This work was financially supported by the National Natural Science Foundation of China (21864013) and the Open Project Program of Key Laboratory of Functional Small Organic Molecule, Ministry of Education, Jiangxi Normal University (No. KLFS-KF-201917).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Sun, Y., Xiong, P., Tang, J. et al. Ultrasensitive split-type electrochemical sensing platform for sensitive determination of organophosphorus pesticides based on MnO2 nanoflower-electron mediator as a signal transduction system. Anal Bioanal Chem 412, 6939–6945 (2020). https://doi.org/10.1007/s00216-020-02824-0
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-020-02824-0