Nonenzymatic Electrochemical Determination of Paraoxon Ethyl in Water and Fruits by Graphene-Based NiFe Bimetallic Phosphosulfide Nanocomposite as a Superior Sensing Layer

  • Ali Aghaie
  • Akbar Khanmohammadi
  • Ali Hajian
  • Ulrich Schmid
  • Hasan BagheriEmail author


A highly sensitive nonenzymatic electrochemical sensor is designed for stripping voltammetric determination of paraoxon ethyl (PE) as a model for nitroaromatic organophosphates (OPs). Graphene-based NiFe bimetallic phosphosulfide nanocomposite is used for the first time as a novel electrocatalytic modifier for enhancing the electrochemical signal of PE. As a consequence of the efficient π-π stacking interactions between the aromatic structure of OPs and graphene and also due to the strong electrocatalytic properties of the bimetallic phosphosulfide, PE can strongly bind to the surface of modified glassy carbon electrodes and provide a dramatically enhanced voltammetric signal in a nonenzymatic determination method. Maximum square wave voltammetric (SWV) signals were obtained when the adsorption step was completed via 5-min convection at 1000 rpm in an analyte solution with the adjusted pH of 6. The SWV signal of PE was highly linear over the range of 12.3–10,000 nmol L−1 and with the detection limit of 3.7 nmol L−1 (S/N = 3). The developed sensor shows good reproducibility (RSD = 5.2%, N = 10). The study offers a promising application for bimetallic phosphosulfide compounds for developing fast, simple, and highly sensitive nonenzymatic determination protocol for nitroaromatic OPs.


Nonenzymatic determination Electrochemical sensor Paraoxon ethyl Organophosphates Modified electrodes Pesticide residual 



The authors gratefully acknowledge the support of this work by the Research Council of Baqiyatallah University of Medical Sciences.

Compliance with Ethical Standards

Conflict of Interest

Ali Aghaei declares that he has no conflict of interest. Akbar Khanmohammadi declares that he has no conflict of interest. Ali Hajian declares that he has no conflict of interest. Ulrich Schmid declares that he has no conflict of interest. Hasan Bagheri declares that he has no conflict of interest.

Ethics Approval

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

Informed Consent

For this type of study, informed consent is not required.


  1. Akbarzade S, Chamsaz M, Rounaghi GH, Ghorbani M (2018) Zero-valent Fe-reduced graphene oxide quantum dots as a novel magnetic dispersive solid phase microextraction sorbent for extraction of organophosphorus pesticides in real water and fruit juice samples prior to analysis by gas chromatography-mass spectrometry. Anal Bioanal Chem 410:429–439. CrossRefGoogle Scholar
  2. Arduini F, Forchielli M, Amine A, Neagu D, Cacciotti I, Nanni F, Moscone D, Palleschi G (2015) Screen-printed biosensor modified with carbon black nanoparticles for the determination of paraoxon based on the inhibition of butyrylcholinesterase. Microchim Acta 182:643–651CrossRefGoogle Scholar
  3. Asfaram A, Ghaedi M, Agarwal S, Tyagi I, Gupta VK (2015) Removal of basic dye Auramine-O by ZnS: Cu nanoparticles loaded on activated carbon: optimization of parameters using response surface methodology with central composite design. RSC Adv 5:18438–18450CrossRefGoogle Scholar
  4. Bagheri H, Afkhami A, Khoshsafar H, Hajian A, Shahriyari A (2017) Protein capped Cu nanoclusters-SWCNT nanocomposite as a novel candidate of high-performance platform for organophosphates enzymeless biosensor. Biosens Bioelectron 89:829–836CrossRefGoogle Scholar
  5. Cabán-Acevedo M, Stone ML, Schmidt JR, Thomas JG, Ding Q, Chang HC, Tsai ML, He JH, Jin S (2015) Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide. Nat Mater 14:1245–1251CrossRefGoogle Scholar
  6. Dhara K, Mahapatra DR (2017) Electrochemical nonenzymatic sensing of glucose using advanced nanomaterials. Microchim Acta 185:49. CrossRefGoogle Scholar
  7. Du D, Ye X, Zhang J, Zeng Y, Tu H, Zhang A, Liu D (2008) Stripping voltammetric analysis of organophosphate pesticides based on solid-phase extraction at zirconia nanoparticles modified electrode. Electrochem Commun 10:686–690. CrossRefGoogle Scholar
  8. Fang Z, Qiu X, Chen J, Qiu X (2011) Debromination of polybrominated diphenyl ethers by Ni/Fe bimetallic nanoparticles: influencing factors, kinetics, and mechanism. J Hazard Mater 185:958–969CrossRefGoogle Scholar
  9. Fujiwara N, S-i Y, Siroma Z, Ioroi T, Senoh H, Yasuda K (2009) Nonenzymatic glucose fuel cells with an anion exchange membrane as an electrolyte. Electrochem Commun 11:390–392CrossRefGoogle Scholar
  10. Gong J, Wang L, Song D, Zhu X, Zhang L (2009) Stripping voltammetric analysis of organophosphate pesticides using Ni/Al layered double hydroxides as solid-phase extraction. Biosens Bioelectron 25:493–496. CrossRefGoogle Scholar
  11. Gupta VK, Ganjali M, Norouzi P, Khani H, Nayak A, Agarwal S (2011a) Electrochemical analysis of some toxic metals by ion–selective electrodes. Crit Rev Anal Chem 41:282–313CrossRefGoogle Scholar
  12. Gupta VK, Nayak A, Agarwal S, Singhal B (2011b) Recent advances on potentiometric membrane sensors for pharmaceutical analysis. Comb Chem High Throughput Screen 14:284–302CrossRefGoogle Scholar
  13. Gupta VK, Kumar S, Singh R, Singh L, Shoora S, Sethi B (2014) Cadmium (II) ion sensing through p-tert-butyl calix [6] arene based potentiometric sensor. J Mol Liq 195:65–68CrossRefGoogle Scholar
  14. Gupta VK, Karimi-Maleh H, Sadegh R (2015) Simultaneous determination of hydroxylamine, phenol and sulfite in water and wastewater samples using a voltammetric nanosensor. Int J Electrochem Sci 10:303–316Google Scholar
  15. Gusmão R, Sofer Z, Sedmidubský D, Stpn H, Pumera M (2017) The role of the metal element in layered metal phosphorus triselenides upon their electrochemical sensing and energy applications. ACS Catal 7:8159–8170CrossRefGoogle Scholar
  16. Hryniewicz BM, Orth ES, Vidotti M (2018) Enzymeless PEDOT-based electrochemical sensor for the detection of nitrophenols and organophosphates. Sensors Actuators B Chem 257:570–578. CrossRefGoogle Scholar
  17. Huang Z, Lv C, Chen Z, Chen Z, Tian F, Zhang C (2015) One-pot synthesis of diiron phosphide/nitrogen-doped graphene nanocomposite for effective hydrogen generation. Nano Energy 12:666–674CrossRefGoogle Scholar
  18. Jiang T, Yan L, Meng Y, Xiao M, Wu Z, Tsiakaras P, Song S (2015) Glucose electrooxidation in alkaline medium: performance enhancement of PdAu/C synthesized by NH3 modified pulse microwave-assisted polyol method. Appl Catal B Environ 162:275–281CrossRefGoogle Scholar
  19. Karimi-Maleh H, Tahernejad-Javazmi F, Atar N, Yola ML, Gupta VK, Ensafi AA (2015) A novel DNA biosensor based on a pencil graphite electrode modified with polypyrrole/functionalized multiwalled carbon nanotubes for determination of 6-mercaptopurine anticancer drug. Ind Eng Chem Res 54:3634–3639CrossRefGoogle Scholar
  20. Karthik R, Vinoth Kumar J, Chen S-M, Kokulnathan T, Yang H-Y, Muthuraj V (2018) Design of novel ytterbium molybdate nano-flakes anchored carbon nanofibers: a challenging sustainable catalyst for the detection and degradation of assassination weapon (paraoxon-ethyl). ACS Sustain Chem Eng 6:8615–8630. CrossRefGoogle Scholar
  21. Kaur N, Prabhakar N (2017) Current scenario in organophosphates detection using electrochemical biosensors. TrAC Trends Anal Chem 92:62–85. CrossRefGoogle Scholar
  22. Khairy M, Ayoub HA, Banks CE (2018) 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
  23. Li C, Wang C, Wang C, Hu S (2006) Development of a parathion sensor based on molecularly imprinted nano-TiO2 self-assembled film electrode. Sensors Actuators B Chem 117:166–171. CrossRefGoogle Scholar
  24. Li H, Li J, Chen D, Qiu Y, Wang W (2015) Dual-functional cubic cuprous oxide for non-enzymatic and oxygen-sensitive photoelectrochemical sensing of glucose. Sensors Actuators B Chem 220:441–447. CrossRefGoogle Scholar
  25. Li D, Jiang M, Xu L, Qiao X, Xu Z (2017) Simultaneous determination of acephate and isocarbophos in vegetables by capillary electrophoresis using ionic liquid and sodium dodecyl sulfate as modifiers. Food Anal Methods 10:3368–3374. CrossRefGoogle Scholar
  26. Lin Y, Zhang R (1994) Liquid chromatography series dual-electrode amperometric detection for aromatic nitro compounds. Electroanalysis 6:1126–1131CrossRefGoogle Scholar
  27. Liu G, Lin Y (2005) Electrochemical stripping analysis of organophosphate pesticides and nerve agents. Electrochem Commun 7:339–343CrossRefGoogle Scholar
  28. Liu D, Chen T, Zhu W, Cui L, Asiri AM, Lu Q, Sun X (2016) Cobalt phosphide nanowires: an efficient electrocatalyst for enzymeless hydrogen peroxide detection. Nanotechnology 27:33LT01CrossRefGoogle Scholar
  29. Liu P, Zhang M, Xie S, Wang S, Cheng W, Cheng F (2017) Non-enzymatic glucose biosensor based on palladium-copper oxide nanocomposites synthesized via galvanic replacement reaction. Sensors Actuators B Chem 253:552–558. CrossRefGoogle Scholar
  30. Musameh MM, Gao Y, Hickey M, Kyratzis IL (2012) Application of carbon nanotubes in the extraction and electrochemical detection of organophosphate pesticides: a review. Anal Lett 45:783–803. CrossRefGoogle Scholar
  31. Oldham KB (1979) Analytical expressions for the reversible Randles-Sevcik function. J Electroanal Chem Interfacial Electrochem 105:373–375. CrossRefGoogle Scholar
  32. Pan Y, Chen Y, Lin Y, Cui P, Sun K, Liu Y, Liu C (2016) Cobalt nickel phosphide nanoparticles decorated carbon nanotubes as advanced hybrid catalysts for hydrogen evolution. J Mater Chem A 4:14675–14686CrossRefGoogle Scholar
  33. Qi P, Wang J, Wang Z, Wang X, Wang X, Xu X, Xu H, di S, Zhang H, Wang Q, Wang X (2018) Construction of a probe-immobilized molecularly imprinted electrochemical sensor with dual signal amplification of thiol graphene and gold nanoparticles for selective detection of tebuconazole in vegetable and fruit samples. Electrochim Acta 274:406–414. CrossRefGoogle Scholar
  34. Rahmani T, Hajian A, Afkhami A, Bagheri H (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 42:7213–7222CrossRefGoogle Scholar
  35. Ramnani P, Saucedo NM, Mulchandani A (2016) Carbon nanomaterial-based electrochemical biosensors for label-free sensing of environmental pollutants. Chemosphere 143:85–98. CrossRefGoogle Scholar
  36. Sgobbi LF, Machado SA (2018) Functionalized polyacrylamide as an acetylcholinesterase-inspired biomimetic device for electrochemical sensing of organophosphorus pesticides. Biosens Bioelectron 100:290–297CrossRefGoogle Scholar
  37. Song D, Wang Y, Lu X, Gao Y, Li Y, Gao F (2018) Ag nanoparticles-decorated nitrogen-fluorine co-doped monolayer MoS2 nanosheet for highly sensitive electrochemical sensing of organophosphorus pesticides. Sensors Actuators B Chem 267:5–13. CrossRefGoogle Scholar
  38. Stoytcheva M, Zlatev R, Montero G, Velkova Z, Gochev V (2017) Nanostructured platform for the sensitive determination of paraoxon by using an electrode modified with a film of graphite-immobilized bismuth. Microchim Acta 184:2707–2714CrossRefGoogle Scholar
  39. Talebianpoor MS, Khodadoust S, Mousavi A, Mahmoudi R, Nikbakht J, Mohammadi J (2017) Preconcentration of carbamate insecticides in water samples by using modified stir bar with ZnS nanoparticles loaded on activated carbon and their HPLC determination: response surface methodology. Microchem J 130:64–70. CrossRefGoogle Scholar
  40. Tankiewicz M, Biziuk M (2018) Fast, sensitive and reliable multi-residue method for routine determination of 34 pesticides from various chemical groups in water samples by using dispersive liquid–liquid microextraction coupled with gas chromatography-mass spectrometry. Anal Bioanal Chem 410:1533–1550CrossRefGoogle Scholar
  41. Tian X, Liu L, Li Y, Yang C, Zhou Z, Nie Y, Wang Y (2018) Nonenzymatic electrochemical sensor based on CuO-TiO2 for sensitive and selective detection of methyl parathion pesticide in groundwater. Sensors Actuators B Chem 256:135–142. CrossRefGoogle Scholar
  42. Tunesi MM, Kalwar N, Abbas MW, Karakus S, Soomro RA, Kilislioglu A, Abro MI, Hallam KR (2018) Functionalised CuO nanostructures for the detection of organophosphorus pesticides: a non-enzymatic inhibition approach coupled with nano-scale electrode engineering to improve electrode sensitivity. Sensors Actuators B Chem 260:480–489. CrossRefGoogle Scholar
  43. Uniyal S, Sharma RK (2018) Technological advancement in electrochemical biosensor based detection of organophosphate pesticide chlorpyrifos in the environment: a review of status and prospects. Biosens Bioelectron 116:37–50. CrossRefGoogle Scholar
  44. Wang J, Chatrathi MP, Mulchandani A, Chen W (2001) Capillary electrophoresis microchips for separation and detection of organophosphate nerve agents. Anal Chem 73:1804–1808CrossRefGoogle Scholar
  45. Wang M, Ma Z, Li J, Zhang Z, Tang B, Wang X (2018) Well-dispersed palladium nanoparticles on nickel- phosphorus nanosheets as efficient three-dimensional platform for superior catalytic glucose electro-oxidation and non-enzymatic sensing. J Colloid Interface Sci 511:355–364. CrossRefGoogle Scholar
  46. Xin Y, Kan X, Gan L-Y, Zhang Z (2017) Heterogeneous bimetallic phosphide/sulfide nanocomposite for efficient solar-energy-driven overall water splitting. ACS Nano 11:10303–10312CrossRefGoogle Scholar
  47. Yang Y, Tu H, Zhang A, Du D, Lin Y (2012) Preparation and characterization of Au–ZrO2–SiO2 nanocomposite spheres and their application in enrichment and detection of organophosphorus agents. J Mater Chem 22:4977–4981CrossRefGoogle Scholar
  48. Yola ML, Gupta VK, Eren T, Şen AE, Atar N (2014) A novel electro analytical nanosensor based on graphene oxide/silver nanoparticles for simultaneous determination of quercetin and morin. Electrochim Acta 120:204–211CrossRefGoogle Scholar
  49. Yu X-Y, Feng Y, Guan B, Lou XWD, Paik U (2016) Carbon coated porous nickel phosphides nanoplates for highly efficient oxygen evolution reaction. Energy Environ Sci 9:1246–1250CrossRefGoogle Scholar
  50. Zhang S, Liu X, Qin J’, Yang M, Zhao H, Wang Y, Guo W, Ma Z, Kong W (2017) Rapid gas chromatography with flame photometric detection of multiple organophosphorus pesticides in Salvia miltiorrhizae after ultrasonication assisted one-step extraction. J Chromatogr B 1068-1069:233–238. CrossRefGoogle Scholar
  51. Zhao Y, Zhang W, Lin Y, Du D (2013) The vital function of Fe3O4@Au nanocomposites for hydrolase biosensor design and its application in detection of methyl parathion. Nanoscale 5:1121–1126. CrossRefGoogle Scholar
  52. Zhao F, Wu J, Ying Y, She Y, Wang J, Ping J (2018) Carbon nanomaterial-enabled pesticide biosensors: design strategy, biosensing mechanism, and practical application. TrAC Trends Anal Chem 106:62–83. CrossRefGoogle Scholar

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

Authors and Affiliations

  1. 1.Chemical Injuries Research Center, Systems Biology and Poisonings InstituteBaqiyatallah University of Medical SciencesTehranIran
  2. 2.Institute of Sensor and Actuator SystemsTU WienViennaAustria

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