Skip to main content
Log in

A glassy carbon electrode modified with amino-functionalized graphene oxide and molecularly imprinted polymer for electrochemical sensing of bisphenol A

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

Abstract

The main aim of the work was to develop an efficient strategy for preparing molecularly imprinted polymers (MIPs) on the surface of graphene oxide (GO) sheets. Amine functionalization of GO was accomplished by a facile and efficient procedure with 3-aminopropyltriethoxysilane (APTES). Then, the template was immobilized onto amino-functionalized GO in order to improve the recognition ability of MIP-based sensors. Also, prior to polymerization, ethylene glycol dimethacrylate was grafted onto the APTES coated graphene oxide sheets by the Michael addition reaction. In this way, many homogeneous imprinting sites were formed on the GO sheets. The resulting composite was placed on a glassy carbon electrode (GCE) which then was used for determination of bisphenol A (BPA) by electrochemical technique. The composite of amino-functionalized GO and MIP (GO/APTES–MIP) was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and energy dispersive X-ray spectroscopy. The electrochemical behaviors of the sensors were investigated by cyclic voltammetry and differential pulse voltammetry (DPV) techniques. Compared with non-imprinted polymer, the DPV current response of MIP sensor is about 4.6 times larger. Under the optimized conditions, GO/APTES–MIP sensor displays two linear ranges (from 0.006 to 0.1 μM and 0.2 to 20 μM) for determination of BPA, and the detection limit is 0.003 μM (at an S/N ratio of 3). The MIP-based sensor was applied to the in-situ determination of BPA in milk and mineralised water without any pre-treatment and matrix interfering effects.

Ethylene glycol dimethacrylate was grafted onto the amino-functionalized graphene oxide sheets. The template was already immobilized onto surface to improve the recognition ability of MIP-based sensor. The resulting composite was placed on a glassy carbon electrode for determination of bisphenol A by electrochemical technique.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Chang HS, Choo KH, Lee B, Choi SJ (2009) The methods of identification, analysis, and removal of endocrine disrupting compounds (EDCs) in water. J Hazard Mater 172:1

    Article  CAS  Google Scholar 

  2. Zhou W, Sun C, Zhou Y, Yang X, Yang W (2014) A facial electrochemical approach to determinate bisphenol A based on graphene-hypercrosslinked resin MN202 composite. Food Chem 158:81

    Article  CAS  Google Scholar 

  3. Inoue N, Ooya T, Toshifumi T (2013) Hydrophilic molecularly imprinted polymers for bisphenol A prepared in aqueous solution. Microchim Acta 180:1387

    Article  CAS  Google Scholar 

  4. Kang JH, Kondo F, Katayama Y (2006) Human exposure to bisphenol A. Toxicology 226:79

    Article  CAS  Google Scholar 

  5. Ferrer E, Santoni E, Vittori S, Font G, Mañes J, Sagratini G (2011) Simultaneous determination of bisphenol A, octylphenol, and nonylphenol by pressurised liquid extraction and liquid chromatography–tandem mass spectrometry in powdered milk and infant formulas. Food Chem 126:360

    Article  CAS  Google Scholar 

  6. Canale F, Cordero C, Baggiani C, Baravalle P, Giovannoli C, Bicchi C (2010) Development of a molecularly imprinted polymer for selective extraction of bisphenol A in water samples. J Sep Sci 33:1644

    Article  CAS  Google Scholar 

  7. Yuan L, Jiang L, Hui T, Jie L, Bingbin X, Feng Y, Yingchun L (2015) Fabrication of highly sensitive and selective electrochemical sensor by using optimized molecularly imprinted polymers on multi-walled carbon nanotubes for metronidazole measurement. Sensors Actuators B Chem 206:647

    Article  CAS  Google Scholar 

  8. Ma M, Tu X, Zhan G, Li C, Zhang S (2014) Electrochemical sensor for bisphenol A based on a nanoporous polymerized ionic liquid interface. Microchim Acta 181:565

    Article  CAS  Google Scholar 

  9. Han M, Qu Y, Chen S, Wang Y, Zhang Z, Ma M, Wang Z, Zhan G, Li C (2013) Amperometric biosensor for bisphenol A based on a glassy carbon electrode modified with a nanocomposite made from polylysine, single walled carbon nanotubes and tyrosinase. Microchim Acta 180:989

    Article  CAS  Google Scholar 

  10. Lin Y, Liu K, Liu C, Yin L, Kang Q, Li L, Li B (2014) Electrochemical sensing of bisphenol A based on polyglutamic acid/amino-functionalised carbon nanotubes nanocomposite. Electrochim Acta 133:492

    Article  CAS  Google Scholar 

  11. Zheng Z, Du Y, Wang Z, Feng Q, Wang C (2013) Pt/graphene–CNTs nanocomposite based electrochemical sensors for the determination of endocrine disruptor bisphenol A in thermal printing papers. Analyst 138:693

    Article  CAS  Google Scholar 

  12. Mosbach K, Ramstrom O (1996) The Emerging Technique of Molecular Imprinting and Its Future Impact on Biotechnology. Nat Biotech 14:163

    Article  CAS  Google Scholar 

  13. Sharma PS, Pietrzyk-Le A, D’Souza F, Kutner W (2012) Electrochemically synthesized polymers in molecular imprinting for chemical sensing. Anal Bioanal Chem 402:3177

    Article  CAS  Google Scholar 

  14. Zeng Y, Zhou Y, Kong L, Zhou T, Shi G (2013) A novel composite of SiO2-coated graphene oxide and molecularly imprinted polymers for electrochemical sensing dopamine. Biosens Bioelectron 45:25

    Article  CAS  Google Scholar 

  15. Sharma PS, Dabrowski M, D’Souza F, Kutner W (2013) Surface development of molecularly imprinted polymer films to enhance sensing signals. TrAC Trends Anal Chem 51:146

    Article  CAS  Google Scholar 

  16. Prasad BB, Prasad A, Tiwari MP, Madhuri R (2013) Multiwalled carbon nanotubes bearing ‘terminal monomeric unit’ for the fabrication of epinephrine imprinted polymer-based electrochemical sensor. Biosens Bioelectron 45:114

    Article  CAS  Google Scholar 

  17. Zhang D, Yu D, Zhao W, Yang Q, Kajiura H, Li Y, Zhou T, Shi G (2012) A molecularly imprinted polymer based on functionalized multiwalled carbon nanotubes for the electrochemical detection of parathion-methyl. Analyst 137:2629

    Article  CAS  Google Scholar 

  18. Moreira FTC, Dutra RAF, Noronha JPC, Sales MGF (2011) Myoglobin-biomimetic electroactive materials made by surface molecular imprinting on silica beads and their use as ionophores in polymeric membranes for potentiometric transduction. Biosens Bioelectron 26:4760

    Article  CAS  Google Scholar 

  19. Mehdinia A, Dadkhah S, Baradaran Kayyal T, Jabbari A (2014) Design of a surface-immobilized 4-nitrophenol molecularly imprinted polymer via pre-grafting amino functional materials on magnetic nanoparticles. J Chromatogr A 1364:12

    Article  CAS  Google Scholar 

  20. Marcano DC, Kosynkin DV, Berlin JM, Sinitskii A, Sun Z, Slesarev A, Alemany LB, Lu W, Tour JM (2010) Improved Synthesis of Graphene Oxide. ACS Nano 4:4806

    Article  CAS  Google Scholar 

  21. Lin Y, Jin J, Song M (2011) Preparation and characterisation of covalent polymer functionalized graphene oxide. J Mater Chem 21:3455

    Article  CAS  Google Scholar 

  22. Zheng D, Vashist SK, Al-Rubeaan K, Luong JHT, Sheu FS (2012) Mediatorless amperometric glucose biosensing using 3-aminopropyltriethoxysilane-functionalized graphene. Talanta 99:22

    Article  CAS  Google Scholar 

  23. Mather BD, Viswanathan K, Miller KM, Long TE (2006) Michael addition reactions in macromolecular design for emerging technologies. Prog Polym Sci 31:487

    Article  CAS  Google Scholar 

  24. Wang S, Wang R, Wu X, Wang Y, Xue C, Wu J, Hong J, Liu J, Zhou X (2012) Magnetic molecularly imprinted nanoparticles based on dendritic-grafting modification for determination of estrogens in plasma samples. J Chromatogr B 905:105

    Article  CAS  Google Scholar 

  25. Stankovich S, Piner RD, Nguyen ST, Ruoff RS (2006) Synthesis and exfoliation of isocyanate-treated graphene oxide nanoplatelets. Carbon 44:3342

    Article  CAS  Google Scholar 

  26. Hsiao VKS, Waldeisen JR, Zheng Y, Lloyd PF, Bunning TJ, Huang TJ (2007) Aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings: fabrication and application in biosensing. J Mater Chem 17:4896

    Article  CAS  Google Scholar 

  27. Niu X, Yang W, Wang G, Ren J, Guo H, Gao J (2013) A novel electrochemical sensor of bisphenol A based on stacked graphene nanofibers/gold nanoparticles composite modified glassy carbon electrode. Electrochim Acta 98:167

    Article  CAS  Google Scholar 

  28. Zhang Y, Cheng Y, Zhou Y, Li B, Gu W, Shi X, Xian Y (2013) Electrochemical sensor for bisphenol A based on magnetic nanoparticles decorated reduced graphene oxide. Talanta 107:211

    Article  CAS  Google Scholar 

  29. Deng P, Xu Z, Li J, Kuang Y (2013) Acetylene black paste electrode modified with a molecularly imprinted chitosan film for the detection of bisphenol A. Microchim Acta 180:861

    Article  CAS  Google Scholar 

  30. Wang Y, Yang Y, Xu L, Zhang J (2011) Bisphenol A sensing based on surface molecularly imprinted, ordered mesoporous silica. Electrochim Acta 56:2105

    Article  CAS  Google Scholar 

  31. Chen Z, Tang C, Zeng Y, Liu H, Yin Z, Li L (2014) Determination of bisphenol A using an electrochemical sensor based on a molecularly imprinted polymer-modified multiwalled carbon nanotube paste electrode. Anal Lett 47:996

    Article  CAS  Google Scholar 

  32. Zhu L, Cao Y, Cao G (2014) Electrochemical sensor based on magnetic molecularly imprinted nanoparticles at surfactant modified magnetic electrode for determination of bisphenol A. Biosens Bioelectron 54:258

    Article  CAS  Google Scholar 

  33. Huang J, Zhang X, Lin Q, He X, Xing X, Huai H, Lian W, Zhu H (2011) Electrochemical sensor based on imprinted sol–gel and nanomaterials for sensitive determination of bisphenol A. Food Control 22:786

    Article  CAS  Google Scholar 

  34. Huang J, Zhang X, Liu S, Lin Q, He X, Xing X, Lian W (2011) Electrochemical sensor for bisphenol A detection based on molecularly imprinted polymers and gold nanoparticles. J Appl Electrochem 41:1323

    Article  CAS  Google Scholar 

  35. Deng P, Xu Z, Kuang Y (2014) Electrochemical determination of bisphenol A in plastic bottled drinking water and canned beverages using a molecularly imprinted chitosan–graphene composite film modified electrode. Food Chem 157:490

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Ali Mehdinia.

Ethics declarations

The author(s) declare that they have no competing interests

Electronic supplementary material

ESM 1

(DOCX 565 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Dadkhah, S., Ziaei, E., Mehdinia, A. et al. A glassy carbon electrode modified with amino-functionalized graphene oxide and molecularly imprinted polymer for electrochemical sensing of bisphenol A. Microchim Acta 183, 1933–1941 (2016). https://doi.org/10.1007/s00604-016-1824-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00604-016-1824-5

Keywords

Navigation