Food Analytical Methods

, Volume 12, Issue 4, pp 1028–1039 | Cite as

Fabrication of a Structure-Specific Molecular Imprinted Polymer–Based Electrochemical Sensor Based on CuNP-Decorated Vinyl-Functionalized Graphene for the Detection of Parathion Methyl in Vegetable and Fruit Samples

  • M. P. Sooraj
  • Beena MathewEmail author


Molecular imprinted polymers on copper nanoparticle–decorated vinyl-functionalized graphene (CuNPs@GR-MIPs) are fabricated. The copper nanoparticles (CuNPs) are synthesized by the reduction of diaminopropane copper complexes (DAPCu) using sodium borohydride as reducing agent. The synthesized CuNPs are successfully decorated on vinyl-functionalized graphene (V-fGR) on which MIPs are fabricated. All intermediates during the synthesis of CuNPs@GR-MIP are characterized in detail by Fourier-transform infrared spectroscopy, ultraviolet-visible spectroscopy, powder X-ray diffraction analysis, transmission electron microscopy, and scanning electron microscopy techniques. The fabricated CuNPs@GR-MIPs are developed as a sensor for organophosphorus pesticide parathion methyl. The recognition cavities formed on CuNPs@GR-MIP during the synthesis are mainly responsible for the sensing property. The result of the electrochemical studies shows that CuNPs@GR-MIP material has good recognition and sensing capacity towards parathion methyl (PM). The sensitivity is found to be directly proportional to the amount of PM molecules in solution with a detection limit of 0.24 × 10−9 mol L−1 (S/N = 3). The selectivity studies of the fabricated CuNPs@GR-MIP sensor give a fine discrimination between PM and its structurally similar compounds such as 2,4-dinitrophenol, nitrobenzene, nitroaniline, p-nitrophenol, ascorbic, dopamine acid, and malathion. Most promisingly, the sensing capacity of the synthesized CuNPs@GR-MIP is successfully demonstrated in vegetables and fruits which shows us the real time applicability of the sensor in food analysis.


Parathion methyl Cyclic voltammetry Molecular imprinted polymer Graphene Copper nanoparticles 


Compliance with Ethical Standards

Conflict of Interest

Dr. Sooraj M. .P declares that there is no conflict of interest. Dr. Beena Mathew declares that there is no conflict of interest.

Ethical Approval

This article does not contain any studies with human participants or animals performed by any of the authors.

Informed Consent

Not applicable.


  1. Annu S, Suman B, Sanjeev A, Chopra S, Kanjilalet D (2011) Synthesis of copper nanoparticles in polycarbonate by ion implantation. Bull Mater Sci 34:645–649CrossRefGoogle Scholar
  2. Bin S, Wenjie C, Yazhen W (2016) A methyl parathion electrochemical sensor based on Nano-TiO graphene composite film modifyed electrode. Fullerenes Nanotubes Carbon Nanostruct 24:435–440. CrossRefGoogle Scholar
  3. Bowan W, Lijie H, Miao D, Tiantian Z, Zhihua W, Zhonghua X, Xiaoquan L (2014) A molecularly imprinted electrochemical enzymeless sensor based on functionalized gold nanoparticle decorated carbon nanotubes for methyl-parathion detection. RSC Adv 4:53701–53710. CrossRefGoogle Scholar
  4. Changyan X, Xiaomei S, An J, Lina S, Chen Z, Yunqi C (2015) Fabrication and characteristics of reduced graphene oxide produced with different green reductants. PLoS One 10:1–15. CrossRefGoogle Scholar
  5. Darlan FS, Francisco EPS, Fernanda GSS, Gilvanda SN, Mihaela B (2015) Direct determination of methyl parathion insecticide in rice samples by headspace solid-phase microextraction–gas chromatography–mass spectrometry. Pest Manag Sci 71:1497–1502. CrossRefGoogle Scholar
  6. Dau HA, Kritsananporn C, Jesdawan W, Werasak S (2011) A colorimetric assay for determination of methyl parathion using recombinant methyl parathion hydrolase. Biotechnol J 6:565–571. CrossRefGoogle Scholar
  7. Diagne M, Oturan N, Oturan MA (2007) Removal of methyl parathion from water by electrochemically generated Fenton’s reagent. Chemosphere 66:841–848CrossRefPubMedGoogle Scholar
  8. Edwards FL, Tchounwou PB (2005) Environmental toxicology and health effects associated with methyl parathion exposure – a scientific review. Int J Environ Res Public Health 2:430–441. CrossRefPubMedGoogle Scholar
  9. Fa-Ru W, Gang-Juan L, Neelamegan H, Jerry JW (2018) Electrochemical sensor using molecular imprinting polymerization modified electrodes to detect methyl parathion in environmental media. Electrocatalysis 9:1–9. CrossRefGoogle Scholar
  10. Fatima TJ, Jee WL, Woo GJ (2014) Facile and safe graphene preparation on solution based platform. J Ind Eng Chem 20:2883–2887CrossRefGoogle Scholar
  11. Ge C, Maojun J, Pengfei D, Chan Z, Xueyan C, Yudan Z, Yongxin S, Hua S, Fen J, Shanshan W, Lufei Z, Jing W (2017) A sensitive chemiluminescence enzyme immunoassay based on molecularly imprinted polymers solid-phase extraction of parathion. Anal Biochem 530:87–93. CrossRefGoogle Scholar
  12. Govindasamy M, Mani V, Chen SM, Chen TW, Sundramoorthy AK (2017a) Methyl parathion detection in vegetables and fruits using silver@graphene nanoribbons nanocomposite modified screen printed electrode. Sci Rep 7:46471. CrossRefPubMedPubMedCentralGoogle Scholar
  13. Govindasamy M, Subramanian S, Shen-Ming C, Te-Wei C, Anandaraj S, Johnson PM (2017b) Electroanalysis Reduced graphene oxide supported cobalt Bipyridyl complex for sensitive detection of methyl parathion in fruits and vegetables. Electroanalysis 29:1–12. CrossRefGoogle Scholar
  14. Hu TT, Lu CM, Li H, Zhang ZX, Zhao YH, Li J (2017) Determination of eleven organophosphorus pesticide residues in textiles by using HPLC-HRMS. Anal Sci 33:1027–1032. CrossRefPubMedGoogle Scholar
  15. Jung-Hoo S, Jonghyun C, Miyoung K, Seong-Hyeon H (2018) Comparative study on carbon nanotube- and reduced graphene oxide-reinforced alumina ceramic composites. Ceram Int 44:8350–8357. CrossRefGoogle Scholar
  16. Kanchanmala D, Rupesh KM, Sunil B (2011) Determination of methyl parathion in water and its removal on zirconia using optical enzyme assay. Appl Biochem Biotechnol 164:906–917. CrossRefGoogle Scholar
  17. Ling C, Xueping D, Youhong A, Huaixia C (2018) Preparation of an acryloyl β-cyclodextrin-silica hybrid monolithic column and its application in pipette tip solid-phase extraction and HPLC analysis of methyl parathion and fenthion. J Sep Sci 41:3508–3351. CrossRefGoogle Scholar
  18. Lipeng Y, Bo L, Kaidan Y, Guandong Y, Li H, Yehua N (2013) Biotin-streptavidin-enhanced enzyme-linked immunosorbent assay for the determination of parathion-methyl in vegetables. Anal Lett 46:1084–1096. CrossRefGoogle Scholar
  19. Liu X, Song B, Wang YZ (2014) Determination of residual parathion based on the graphene modified glassy carbon electrode. Chin J Anal Sci 30:509–512Google Scholar
  20. Minh P, Ngoc B, Seong SS (2015) Electrochemical analysis of parathion-ethyl using zirconium oxide–laponite nanocomposites-modified glassy carbon electrode. J Appl Electrochem 45:365–373. CrossRefGoogle Scholar
  21. Mohamed K, Haytham AA, Craig EB (2018) One-step green synthesis of colloidal gold nano particles: a potential electrocatalyst towards high sensitive electrochemical detection of methyl parathion in food samples non-enzymatic electrochemical platform for parathion pesticide sensing based on nanometer-sized nickel oxide modified screen-printed electrodes. Food Chem 255:104–111. CrossRefGoogle Scholar
  22. Rathnayake, Wijayasinghe, Pitawala, Masamichi Y, Hsin-Hui H (2017) Synthesis of graphene oxide and reduced graphene oxide by needle platy natural vein graphite. Appl Surf Sci 393:309–315. CrossRefGoogle Scholar
  23. Richard BC, Kaiwen H, Giuliana M, Marta C (2016) Intercalated species in multilayer graphene oxide: insights gained from in situ FTIR spectroscopy with probe molecule delivery. J Phys Chem C 120:23207–23211CrossRefGoogle Scholar
  24. Safina IJ, Zakir H (2015) Covalently functionalized graphene oxide characterization and its electrochemical performance. Int J Electrochem Sci 10:9475–9487Google Scholar
  25. Shengcheng X, Junfeng Z, Chunya L (2010) Electrochemical deposition of silicate–cetyltrimethylammonium bromide nanocomposite film on glassy carbon electrode for sensing of methyl parathion. Anal Bioanal Chem 396:697–705. CrossRefGoogle Scholar
  26. Sooraj MP, Archana SN, Suresh CP, Steven JH, Beena M (2018) CuNPs decorated molecular imprinted polymer on MWCNT for the electrochemical detection of L-DOPA. Arab J Chem.
  27. Susana G, Pieter D (2016) Review of analytical methods for the determination of pesticide residues in grapes. J Chromatogr A 1433:1–23. CrossRefGoogle Scholar
  28. Syed NA, Nidhi S, Lailesh K (2017) Synthesis of graphene oxide (GO) by modified Hummers method and its thermal reduction to obtain reduced graphene oxide (rGO). Graphene 6:1–18. CrossRefGoogle Scholar
  29. Turaj R, Ali H, Abbas A, Hasan B (2018) A novel and high-performance enzyme-less sensing layer for electrochemical detection of methyl parathion based on BSA templated au–ag bimetallic nanoclusters. New J Chem 42:7213–7222. CrossRefGoogle Scholar
  30. Xingyuan L (2011) Electrochemical sensor for determination of parathion based on electro polymerization poly(safranine) film electrode. Int J Electrochem 2011:6. CrossRefGoogle Scholar
  31. Zaaba NI, Foo KL, Hashim U, Tan SJ, Wei-Wen L, Voon CH (2017) Synthesis of graphene oxide using modified Hummers method: solvent influence. Procedia Eng 184:469–477. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Chemical SciencesMahatma Gandhi UniversityKottayamIndia
  2. 2.Advanced Molecular Materials Research CenterMahatma Gandhi UniversityKottayamIndia

Personalised recommendations