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A glassy carbon electrode modified with graphene and tyrosinase immobilized on platinum nanoparticles for sensing organophosphorus pesticides

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Abstract

An amperometric biosensor is described for the detection of organophosphorus pesticides. It is based on the enzyme tyrosinase immobilized on platinum nanoparticles and the use of a glassy carbon electrode modified with graphene. Tyrosinase was immobilized on the electrode surface via electrostatic interaction between a monolayer of cysteamine and the enzyme. In the presence of catechol as a substrate, the pesticides chlorpyrifos, profenofos and malathion can be determined as a result of their inhibition of the enzyme which catalyzes the oxidation of catechol to o-quinone. Platinum nanoparticles and graphene effectively enhance the efficiency of the electrochemical reduction of o-quinone, thus improving sensitivity. Under optimum experimental conditions, the inhibition effect of the pesticides investigated is proportional to their concentrations in the lower ppb-range. The detection limits are 0.2, 0.8 and 3 ppb for chlorpyrifos, profenofos and malathion, respectively. The biosensor displays good repeatability and acceptable stability.

A tyrosinase-based biosensor was developed for determining organophosphorus pesticides. The biosensor owned high sensitivity by combining platinum nanoparticles and graphene, and the immobilized tyrosinase had a great affinity to catechol. Low detection limits and reasonable liner ranges were obtained. The biosensor also displayed good repeatability and acceptable stability.

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References

  1. Vanloon GW (2001) Environmental chemistry—a global perspective. University Press, Oxford

    Google Scholar 

  2. Yin HS, Ai SY, Xu J, Shi W, Zhu L (2009) Amperometric biosensor based on immobilized acetylcholinesterase on gold nanoparticles and silk fibroin modified platinum electrode for detection of methyl paraoxon, carbofuran and phoxim. J Electroanal Chem 637:21

    Article  CAS  Google Scholar 

  3. Jiang X, Li D, Xu X, Ying Y, Li Y, Ye Z, Wang J (2008) Immunosensors for detection of pesticide residues. Biosens Bioelectron 23:1577

    Article  CAS  Google Scholar 

  4. Padrón-Sanz C, Halko R, Sosa-Ferrera Z, Santana-Rodríguez JJ (2005) Combination of microwave assisted micellar extraction and liquid chromatography for the determination of organophosphorous pesticides in soil samples. J Chromatogr A 1078:13

    Article  Google Scholar 

  5. Tahboub YR, Zaater MF, Al-Talla ZA (2005) Determination of the limits of identification and quantitation of selected organochlorine and organophosphorous pesticide residues in surface water by full-scan gas chromatography/mass spectrometry. J Chromatogr A 1098:150

    Article  CAS  Google Scholar 

  6. Rial-Otero R, Gaspar EM, Moura I, Capelo JL (2007) Chromatographic-based methods for pesticide determination in honey: an overview. Talanta 71:503

    Article  CAS  Google Scholar 

  7. Amine A, Mohammadi H, Bourais I, Palleschi G (2006) Enzyme inhibition-based biosensors for food safety and environmental monitoring. Biosens Bioelectron 21:1405

    Article  CAS  Google Scholar 

  8. Vakurov A, Simpson CE, Daly CL, Gibson TD, Millner PA (2005) Acetylecholinesterase-based biosensor electrodes for organophosphate pesticide detection: II. Immobilization and stabilization of acetylecholinesterase. Biosens Bioelectron 20:2324

    Article  CAS  Google Scholar 

  9. Arduini F, Ricci F, Tuta CS, Moscone D, Amine A, Palleschi G (2006) Detection of carbamic and organophosphorous pesticides in water samples using a cholinesterase biosensor based on Prussian Blue-modified screen-printed electrode. Anal Chim Acta 580:155

    Article  CAS  Google Scholar 

  10. Arduini F, Amine A, Moscone D, Palleschi G (2010) Biosensors based on cholinesterase inhibition for insecticides, nerve agents and aflatoxin B1 detection (review). Microchim Acta 170:193

    Article  CAS  Google Scholar 

  11. Trojanowicz M, Hitchman ML (1996) Determination of pesticides using electrochemical biosensors. Trends Anal Chem 15:38

    CAS  Google Scholar 

  12. Smit MH, Rechnitz GA (1993) Toxin detection using a tyrosinase-coupled oxygen electrode. Anal Chem 65:380

    Article  CAS  Google Scholar 

  13. Besombes J-L, Cosnier S, Labbé P, Reverdy G (1995) A biosensor as warning device for the detection of cyanide, chlorophenols, atrazine and carbamate pesticides. Anal Chim Acta 311:255

    Article  CAS  Google Scholar 

  14. Anh TM, Dzyadevych SV, Van MC, Renault NJ, Duc CN, Chovelon J-M (2004) Conductometric tyrosinase biosensor for the detection of diuron, atrazine and its main metabolites. Talanta 63:365

    Article  CAS  Google Scholar 

  15. Tanimoto de Albuquerque YD, Ferreira LF (2007) Amperometric biosensing of carbamate and organophosphate pesticides utilizing screen-printed tyrosinase-modified electrodes. Anal Chim Acta 596:210

    Article  CAS  Google Scholar 

  16. Solé S, Merkoçi A, Alegret S (2003) Determination of Toxic Substances Based on Enzyme Inhibition. Part I. Electrochemical Biosensors for the Determination of Pesticides Using Batch Procedures. Crit Rev Anal Chem 33:89

    Article  Google Scholar 

  17. Chen J, ** Y (2010) Sensitive phenol determination based on co-modifying tyrosinase and palygorskite on glassy carbon electrode. Microchim Acta 169:249

    Article  CAS  Google Scholar 

  18. Sánchez-Ferrer Á, Neptuno Rodríguez-López J, García-Cánovas F, García-Carmona F (1995) Tyrosinase: a comprehensive review of its mechanism. Biochim Biophys Acta 1247:1

    Article  Google Scholar 

  19. Cortina-Puig M, Muñoz-Berbel X, Calas-Blanchard C, Marty J-L (2010) Diazonium-functionalized tyrosinase-based biosensor for the detection of tea polyphenols. Microchim Acta 171:187

    Article  CAS  Google Scholar 

  20. Li X, Zhang G, Bai X, Sun X, Wang X, Wang E, Dai H (2008) Highly conducting graphene sheets and Langmuir-Blodgett films. Nat Nano 3:538

    Article  CAS  Google Scholar 

  21. Wang X, Zhi L, Mullen K (2007) Transparent, conductive graphene electrodes for dye-sensitized solar cells. Nano Lett 8:323

    Article  Google Scholar 

  22. Stankovich S, Dikin DA, Dommett GHB, Kohlhaas KM, Zimney EJ, Stach EA, Piner RD, Nguyen ST, Ruoff RS (2006) Graphene-based composite materials. Nature 442:282

    Article  CAS  Google Scholar 

  23. Shan C, Yang H, Han D, Zhang Q, Ivaska A, Niu L (2010) Electrochemical determination of NADH and ethanol based on ionic liquid-functionalized graphene. Biosens Bioelectron 25:1504

    Article  CAS  Google Scholar 

  24. Kang X, Wang J, Wu H, Aksay IA, Liu J, Lin Y (2009) Glucose oxidase-graphene-chitosan modified electrode for direct electrochemistry and glucose sensing. Biosens Bioelectron 25:901

    Article  CAS  Google Scholar 

  25. Zhou K, Zhu Y, Yang X, Luo J, Li C, Luan S (2010) A novel hydrogen peroxide biosensor based on Au-graphene-HRP-chitosan biocomposites. Electrochim Acta 55:3055

    Article  CAS  Google Scholar 

  26. Wang F, Hu S (2009) Electrochemical sensors based on metal and semiconductor nanoparticles. Microchim Acta 165:1

    Article  CAS  Google Scholar 

  27. Y-l Y, Ding Y, Ye L-S, **a X-H (2006) Two-step pyrolysis process to synthesize highly dispersed Pt-Ru/carbon nanotube catalysts for methanol electrooxidation. Carbon 44:61

    Article  Google Scholar 

  28. Love JC, Estroff LA, Kriebel JK, Nuzzo RG, Whitesides GM (2005) Self-assembled monolayers of thiolates on metals as a form of nanotechnology. Chem Rev 105:1103

    Article  CAS  Google Scholar 

  29. Gomez S, Erades L, Philippot K, Chaudret B, Collière V, Balmes O, Bovin JO (2001) Platinum colloids stabilized by bifunctional ligands: self-organization and connection to gold. Chem Commun 1474:1475

    Google Scholar 

  30. Li Y, Wu Y (2009) Coassembly of graphene oxide and nanowires for large-area nanowire alignment. J Am Chem Soc 131:5851

    Article  CAS  Google Scholar 

  31. Lin X, Li Y (2006) A sensitive determination of estrogens with a Pt nano-clusters/multi-walled carbon nanotubes modified glassy carbon electrode. Biosens Bioelectron 22:253

    Article  CAS  Google Scholar 

  32. Yildiz HB, Castillo J, Guschin DA, Toppare L, Schuhmann W (2007) Phenol biosensor based on electrochemically controlled integration of tyrosinase in a redox polymer. Microchim Acta 159:27

    Article  CAS  Google Scholar 

  33. Portaccio M, Di Tuoro D, Arduini F, Lepore M, Mita DG, Diano N, Mita L, Moscone D (2010) A thionine-modified carbon paste amperometric biosensor for catechol and bisphenol A determination. Biosens Bioelectron 25:2003

    Article  CAS  Google Scholar 

  34. Kamin RA, Wilson GS (1980) Rotating ring-disk enzyme electrode for biocatalysis kinetic studies and characterization of the immobilized enzyme layer. Anal Chem 52:1198

    Article  CAS  Google Scholar 

  35. Wang S, Tan Y, Zhao D, Liu G (2008) Amperometric tyrosinase biosensor based on Fe3O4 nanoparticles-chitosan nanocomposite. Biosens Bioelectron 23:1781

    Article  CAS  Google Scholar 

  36. Wang L, Ran Q, Tian Y, Ye S, Xu J, **an Y, Peng R, ** L (2010) Covalent grafting tyrosinase and its application in phenolic compounds detection. Microchim Acta 171:217

    Article  CAS  Google Scholar 

  37. Wang Y, Hasebe Y (2009) Carbon felt-based biocatalytic enzymatic flow-through detectors: chemical modification of tyrosinase onto amino-functionalized carbon felt using various coupling reagents. Talanta 79:1135

    Article  Google Scholar 

  38. Zamfir L-G, Rotariu L, Bala C (2011) A novel, sensitive, reusable and low potential acetylcholinesterase biosensor for chlorpyrifos based on 1-butyl-3-methylimidazolium tetrafluoroborate/multiwalled carbon nanotubes gel. Biosens Bioelectron 26:3692

    Article  CAS  Google Scholar 

  39. Kuswandi B, Fikriyah CI, Gani AA (2008) An optical fiber biosensor for chlorpyrifos using a single sol-gel film containing acetylcholinesterase and bromothymol blue. Talanta 74:613

    Article  CAS  Google Scholar 

  40. Imato T, Ishibashi N (1995) Potentiometric butyrylcholine sensor for organophosphate pesticides. Biosens Bioelectron 10:435

    Article  CAS  Google Scholar 

  41. Campanella L, Lelo D, Martini E, Tomassetti M (2007) Organophosphorus and carbamate pesticide analysis using an inhibition tyrosinase organic phase enzyme sensor; comparison by butyrylcholinesterase + choline oxidase opee and application to natural waters. Anal Chim Acta 587:22

    Article  CAS  Google Scholar 

  42. Du D, Ye X, Cai J, Liu J, Zhang A (2010) Acetylcholinesterase biosensor design based on carbon nanotube-encapsulated polypyrrole and polyaniline copolymer for amperometric detection of organophosphates. Biosens Bioelectron 25:2503

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No.21075078) and Natural Science Foundation of Shandong province, China (ZR2010BM005).

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Authors and Affiliations

  1. College of Chemistry and Material Science, Shandong Agricultural University, Taian, Shandong, 271018, China

    Tao Liu, Minrong Xu, Huanshun Yin, Shiyun Ai, **ang** Qu & Shanshan Zong

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  1. Tao Liu
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  2. Minrong Xu
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  3. Huanshun Yin
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  4. Shiyun Ai
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Correspondence to Shiyun Ai.

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Liu, T., Xu, M., Yin, H. et al. A glassy carbon electrode modified with graphene and tyrosinase immobilized on platinum nanoparticles for sensing organophosphorus pesticides. Microchim Acta 175, 129–135 (2011). https://doi.org/10.1007/s00604-011-0665-5

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