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Amperometric thyroxine sensor using a nanocomposite based on graphene modified with gold nanoparticles carrying a thiolated β-cyclodextrin

Microchimica Acta volume 183, pages 1579–1589 (2016)Cite this article

Abstract

This article reports a novel electrochemical sensor based on a nanocomposite for the sensitive determination of Thyroxine (T4), the active form of the hormone. Hydrodynamic amperometry is performed with a nanocomposite electrode based on the dispersion of a graphene–based filler hybrid-nanomaterial throughout an insulating epoxy resin in the optimum composition ratio (the near–percolation composition). This hybrid-nanomaterial consists of reduced graphene oxide tuned with gold nanoparticles and a biorecognition agent, the thiolated β-cyclodextrin. Recognition of T4 is accomplished via supramolecular chemistry, due to the formation of an inclusion complex between β-cyclodextrin and T4. The amperometric device operates at +0.85 V vs. Ag/AgCl, where the oxidation of T4 takes place on the electrode surface. The sensor covers the 1.00 nM to 14 nM T4concentration range in a 0.1 M HCl solution, with a detection limit of 1.00 ± 0.02 nM. The sensor can be easily reset by polishing. It exhibits the lowest detection limit regarding to any other electrochemical electrodes for T4 determination previously described in literature.

Step 1 consists on the in situ reduction of graphene oxide under the presence of Au3+ and the subsequently attachment of the thiolated β-cyclodextrin (β-CD-SH). In step 2, the conducting nanofiller is dispersed into epoxy resin, resulting in a nanocomposite that allows amperometric detection of thyroxine.

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References

  1. Epstein FH, Brent GA (1994) The molecular basis of thyroid hormone action. N Engl J Med 331(13):847–853

    Article  Google Scholar 

  2. Hall JE (2010) Guyton and hall textbook of medical physiology. Elsevier Health Sciences, Philadelphia

    Google Scholar 

  3. Karapitta CD, Xenakis A, Papadimitriou A, Sotiroudis TG (2001) A new homogeneous enzyme immunoassay for thyroxine using glycogen phosphorylase b–thyroxine conjugates. Clin Chim Acta 308(1):99–106

    Article  CAS  Google Scholar 

  4. Gök E, Ateş S (2004) Determination of thyroxine hormone by luminol chemiluminescence. Anal Chim Acta 505(1):125–127

    Article  Google Scholar 

  5. Kahric-Janicic N, Soldin SJ, Soldin OP, West T, Gu J, Jonklaas J (2007) Tandem mass spectrometry improves the accuracy of free thyroxine measurements during pregnancy. Thyroid 17(4):303–311

    Article  CAS  Google Scholar 

  6. Samanidou V, Gika H, Papadoyannis I (2000) Rapid HPLC analysis of thyroid gland hormones tri-iodothyronine (T3) and thyroxine (T4) in human biological fluids after SPE 23(5):681–692

  7. Jacobsen E, Fonahn W (1980) Determination of 1-thyroxdine sodium and 1-triiodo- thyronine sodium in tablets by differential pulse polarography. Anal Chim Acta 119(1):33–38

    Article  CAS  Google Scholar 

  8. Iwamoto M, Webber A, Osteryoung RA (1984) Cathodic reduction of thyroxine and related compounds on silver. Anal Chem 56(8):1202–1206

    Article  CAS  Google Scholar 

  9. Wang F, Fei J, Hu S (2004) The influence of cetyltrimethyl ammonium bromide on electrochemical properties of thyroxine reduction at carbon nanotubes modified electrode. Colloids Surf B: Biointerfaces 39(1–2):95–101

    Article  Google Scholar 

  10. He Q, Dang X, Hu C, Hu S (2004) The effect of cetyltrimethyl ammonium bromide on the electrochemical determination of thyroxine. Colloids Surf B: Biointerfaces 35(2):93–98

    Article  CAS  Google Scholar 

  11. Wu K, Ji X, Fei J, Hu S (2004) The fabrication of a carbon nanotube film on a glassy carbon electrode and its application to determining thyroxine. Nanotechnology 15(3):287

    Article  CAS  Google Scholar 

  12. Olivé-Monllau R, Pereira A, Bartrolí J, Baeza M, Céspedes F (2010) Highly sensitive CNT composite amperometric sensors integrated in an automated flow system for the determination of free chlorine in waters. Talanta 81(4):1593–1598

    Article  Google Scholar 

  13. Muñoz J, Bartrolí J, Céspedes F, Baeza M (2015) Influence of raw carbon nanotubes diameter for the optimization of the load composition ratio in epoxy amperometric composite sensors. J Mater Sci 50(2):652–661

    Article  Google Scholar 

  14. Muñoz J, Céspedes F, Baeza M (2015) Effect of carbon nanotubes purification on electroanalytical response of near-percolation amperometric nanocomposite sensors. J Electrochem Soc 162(8):B217–B224

    Article  Google Scholar 

  15. Martín A, Batalla P, Hernández-Ferrer J, Martínez MT, Escarpa A (2015) Graphene oxide nanoribbon-based sensors for the simultaneous bio-electrochemical enantiomeric resolution and analysis of amino acid biomarkers. Biosens Bioelectron 68:163–167

    Article  Google Scholar 

  16. Chen D, Tang L, Li J (2010) Graphene-based materials in electrochemistry. Chem Soc Rev 39(8):3157–3180

    Article  CAS  Google Scholar 

  17. Martín A, Escarpa A (2014) Graphene: the cutting–edge interaction between chemistry and electrochemistry. TrAC Trends Anal Chem 56:13–26

    Article  Google Scholar 

  18. Shin HJ, Kim KK, Benayad A, Yoon SM, Park HK, Jung IS, Jin MH, Jeong HK, Kim JM, Choi JY (2009) Efficient reduction of graphite oxide by sodium borohydride and its effect on electrical conductance. Adv Funct Mater 19(12):1987–1992

    Article  CAS  Google Scholar 

  19. Fan Y, Liu J-H, Yang C-P, Yu M, Liu P (2011) Graphene–polyaniline composite film modified electrode for voltammetric determination of 4-aminophenol. Sensors Actuators B Chem 157(2):669–674

    Article  CAS  Google Scholar 

  20. Compton OC, Nguyen ST (2010) Graphene oxide, highly reduced graphene oxide, and graphene: Versatile Building blocks for carbon-based materials. Small 6(6):711–723

    Article  CAS  Google Scholar 

  21. Jasuja K, Berry V (2009) Implantation and growth of dendritic gold nanostructures on graphene derivatives: electrical property tailoring and Raman enhancement. ACS Nano 3(8):2358–2366

    Article  CAS  Google Scholar 

  22. Fang Y, Guo S, Zhu C, Zhai Y, Wang E (2010) Self-assembly of cationic polyelectrolyte-functionalized graphene nanosheets and gold nanoparticles: A two-dimensional heterostructure for hydrogen peroxide sensing. Langmuir 26(13):11277–11282

    Article  CAS  Google Scholar 

  23. Shahgaldian P, Pieles U (2006) Cyclodextrin derivatives as chiral supramolecular receptors for enantioselective sensing. Sensors 6(6):593–615

    Article  CAS  Google Scholar 

  24. González-Campo A, Hsu S-H, Puig L, Huskens J, Reinhoudt DN, Velders AH (2010) Orthogonal covalent and noncovalent functionalization of cyclodextrin-alkyne patterned surfaces. J Am Chem Soc 132(33):11434–11436

    Article  Google Scholar 

  25. Shahgaldian P, Hegner M, Pieles U (2005) A cyclodextrin self-assembled monolayer (SAM) based surface Plasmon resonance (SPR) sensor for enantioselective analysis of thyroxine. J Incl Phenom Macrocycl Chem 53(1–2):35–39

    Article  CAS  Google Scholar 

  26. Rojas MT, Koeniger R, Stoddart JF, Kaifer AE (1995) Supported monolayers containing preformed binding sites. Synthesis and Interfacial Binding Properties of a Thiolated Beta-Cyclodextrin Derivative Journal of the American Chemical Society 117(1):336–343

    CAS  Google Scholar 

  27. Hummers WS Jr, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80(6):1339–1339

    Article  CAS  Google Scholar 

  28. Fernandez-Merino M, Guardia L, Paredes J, Villar-Rodil S, Solis-Fernandez P, Martinez-Alonso A, Tascon J (2010) Vitamin C is an ideal substitute for hydrazine in the reduction of graphene oxide suspensions. J Phys Chem C 114(14):6426–6432

    Article  CAS  Google Scholar 

  29. Tom RT, Suryanarayanan V, Reddy PG, Baskaran S, Pradeep T (2004) Ciprofloxacin-protected gold nanoparticles. Langmuir 20(5):1909–1914

    Article  CAS  Google Scholar 

  30. Pumera M, Merkoçi A, Alegret S (2006) Carbon nanotube-epoxy composites for electrochemical sensing. Sensors Actuators B Chem 113(2):617–622

    Article  CAS  Google Scholar 

  31. Chitravathi S, Kumara Swamy BE, Chandra U, Mamatha GP, Sherigara BS (2010) Electrocatalytic oxidation of sodium levothyroxine with phenyl hydrazine as a mediator at carbon paste electrode: A cyclic voltammetric study. J Electroanal Chem 645(1):10–15

    Article  CAS  Google Scholar 

  32. Muñoz J, Céspedes F, Baeza M (2015) Modified multiwalled carbon nanotube/epoxy amperometric nanocomposite sensors with CuO nanoparticles for electrocatalytic detection of free chlorine. Microchem J 122:189–196

    Article  Google Scholar 

  33. Zhao H, Ji X, Wang B, Wang N, Li X, Ni R, Ren J (2015) An Ultra-sensitive acetylcholinesterase biosensor based on reduced graphene oxide-Au nanoparticles-β-cyclodextrin/Prussian blue-chitosan nanocomposites for organophosphorus pesticides detection. Biosens Bioelectron 65:23–30

    Article  CAS  Google Scholar 

  34. Zhang J, Yang H, Shen G, Cheng P, Zhang J, Guo S (2010) Reduction of graphene oxide via L-ascorbic acid. Chem Commun 46(7):1112–1114

    Article  CAS  Google Scholar 

  35. Huang J, Zhang L, Chen B, Ji N, Chen F, Zhang Y, Zhang Z (2010) Nanocomposites of size-controlled gold nanoparticles and graphene oxide: formation and applications in SERS and catalysis. Nanoscale 2(12):2733–2738

    Article  CAS  Google Scholar 

  36. Martin C, Sandler J, Shaffer M, Schwarz M-K, Bauhofer W, Schulte K, Windle A (2004) Formation of percolating networks in multi-wall carbon-nanotube–epoxy composites. Compos Sci Technol 64(15):2309–2316

    Article  CAS  Google Scholar 

  37. Ramírez-García S, Alegret S, Céspedes F, Forster RJ (2004) Carbon composite microelectrodes: charge percolation and electroanalytical performance. Anal Chem 76(3):503–512

    Article  Google Scholar 

  38. Rao CN, Sood AK, Subrahmanyam KS, Govindaraj A (2009) Graphene: the new two-dimensional nanomaterial. Angew Chem Int Ed 48 (42):7752–7777

  39. Muñoz J, Bastos-Arrieta J, Muñoz M, Muraviev D, Céspedes F, Baeza M (2014) Simple green routes for the customized preparation of sensitive carbon nanotubes/epoxy nanocomposite electrodes with functional metal nanoparticles. RSC Advances 4(84):44517–44524

    Article  Google Scholar 

  40. Raj MA, John SA (2015) Assembly of gold nanoparticles on graphene film via electroless deposition: spontaneous reduction of Au 3+ ions by graphene film. RSC Advances 5(7):4964–4971

    Article  CAS  Google Scholar 

  41. Khafaji M, Shahrokhian S, Ghalkhani M (2011) Electrochemistry of levo-thyroxin on Edge-plane pyrolytic graphite electrode: application to sensitive analytical determinations. Electroanalysis 23(8):1875–1880

    Article  CAS  Google Scholar 

  42. Das A, Sangaranarayanan M (2014) Electroanalytical sensor based on unmodified screen-printed carbon electrode for the determination of levo-thyroxine. Electroanalysis 27(2):360–367

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the project CTQ2012-36165, MAT2013-47869-C4-2-P, the Science Foundation Ireland (SFI 12/IA/1300 and Amber project) and the Ministry of Education and Science of the Russian Federation (Grant no. 14.B25.31.0002). J. Muñoz thanks Universitat Autònoma de Barcelona (UAB) for the award of PIF studentship. M. Riba-Moliner and A. Gonzalez-Campo thank CSIC for the JAE-predoc and JAE-Doc grants.

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Authors and Affiliations

  1. Departament de Química, Facultat de Ciències, Edifici C-Nord, Universitat Autònoma de Barcelona, 08193, Cerdanyola del Vallès, Bellaterra, Spain

    Jose Muñoz, Francisco Céspedes & Mireia Baeza

  2. Functional Nanomaterials and Surfaces Group, Institut de Ciencia de Materials de Barcelona (ICMAB-CSIC), Campus de la UAB, 08193, Cerdanyola del Vallès, Bellaterra, Spain

    Marta Riba-Moliner & Arántzazu González-Campo

  3. School of Chemistry and CRANN Institute, Trinity College Dublin, Dublin 2, Ireland

    Lorcan J. Brennan & Yurii K. Gun’ko

  4. International Research and Education Center for Physics of Nanostructures, ITMO University, 197101, Saint Petersburg, Russia

    Yurii K. Gun’ko

Authors
  1. Jose Muñoz
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  2. Marta Riba-Moliner
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  3. Lorcan J. Brennan
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  6. Arántzazu González-Campo
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Correspondence to Arántzazu González-Campo or Mireia Baeza.

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Muñoz, J., Riba-Moliner, M., Brennan, L.J. et al. Amperometric thyroxine sensor using a nanocomposite based on graphene modified with gold nanoparticles carrying a thiolated β-cyclodextrin. Microchim Acta 183, 1579–1589 (2016). https://doi.org/10.1007/s00604-016-1783-x

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  • DOI: https://doi.org/10.1007/s00604-016-1783-x

Keywords

  • Nanocomposite
  • Near-percolation composition
  • High-Resolution Transmission Electron Microscopy
  • Biorecognition
  • Carbon filler
  • Epoxy resin