Advertisement

Food Analytical Methods

, Volume 10, Issue 10, pp 3375–3384 | Cite as

A Simple and Sensitive Method for the Voltammetric Analysis of Theobromine in Food Samples Using Nanobiocomposite Sensor

  • Yingqiong Peng
  • Wenjuan Zhang
  • Juan Chang
  • Yaoping Huang
  • Li Chen
  • Hong DengEmail author
  • Zhong Huang
  • Yangping WenEmail author
Article

Abstract

Theobromine (TB) is one of important natural methylxanthine alkaloids in plants and their products, but there were few reports on the electrochemistry of TB, especially electrochemical measurements using chemically modified electrode owing to its poor detectability. In this work, a simple and sensitive method for the voltammetric analysis of TB in green tea, chocolate, and coffee samples was successfully realized using nanobiohybrid sensor based on glassy carbon electrode (GCE) modified by both carboxyl-functionalized multiwalled carbon nanotubes (fMWCNTs) and soluble biopolymer sodium salt of carboxymethylcellulose (CMC). Water-dispersible nanonbiohybrids with fMWCNTs were successfully prepared using CMC assist, and CMC-fMWCNTs were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, transmission electron microscope, electrochemical impedance spectroscopy, and cyclic voltammetry. CMC-fMWCNTs/GCE showed enlarged electrochemically active surface area, good electrode stability, and enhanced electrocatalytic activity. The voltammetric behavior of TB demonstrated an irreversible electrochemical oxidation reaction involving two electrons and two protons, which could detect TB in a wider linear range from 0.5 to 80 μM with a lower limit of detection (LOD) of 0.21 μM. The developed method displayed a high sensitivity, low LOD, good sensing stability, remarkable feasibility, and satisfactory practicality.

Keywords

Voltammetric sensor Nanobiocomposite Theobromine Carbon nanotube Carboxymethyl cellulose 

Notes

Acknowledgements

The authors would like to appreciative of financial support from the National Science Foundation of China (31660492, 51662014), Jiangxi Provincial Department of Education (GJJ150428), China Postdoctoral Science Foundation (2015M571987), Special Funds for Jiangxi Province Postdoctoral Research Funds (2015KY44), and Jiangxi Provincial Innovation Fund of Postgraduates (No. YC2016-S183).

Compliance with Ethical Standards

Conflict of Interest

Yingqiong Peng declares that she has no conflict of interest. Wenjuan Zhang declares that she has no conflict of interest. Juan Chang declares that she has no conflict of interest. Yaoping Huang declares that she has no conflict of interest. Li Chen declares that she has no conflict of interest. Hong Deng declares that he has no conflict of interest. Zhong Huang declares that he has no conflict of interest. Yangping Wen declares that he has no conflict of interest.

Ethical Approval

This article does not contain any studies with human or animal subjects. This is an original research article that has neither been published previously nor considered presently for publication elsewhere. All authors named in the manuscript are entitled to the authorship and have approved the final version of the submitted manuscript.

Informed Consent

Not applicable.

References

  1. Álvarez C, Pérez E, Cros E, Lares M, Assemat S, Boulanger R, Davrieux F (2012) The use of near infrared spectroscopy to determine the fat, caffeine, theobromine and (−)-epicatechin contents in unfermented and sun-dried beans of Criollo cocoa. J Near Infrared Spectros 20:307–315. doi: 10.1255/jnirs.990 CrossRefGoogle Scholar
  2. Baggott MJ, Childs E, Hart AB, De Bruin E, Palmer AA, Wilkinson JE, De Wit H (2013) Psychopharmacology of theobromine in healthy volunteers. Psychopharmacology 228:109–118. doi: 10.1007/s00213-013-3021-0 CrossRefGoogle Scholar
  3. Blauch JL, Traka SM (1983) HPLC determination of caffeine and theobromine in coffee, tea, and instant hot cocoa mixes. J Food Sci 48:745–747. doi: 10.1111/j.1365-2621.1983.tb14888.x CrossRefGoogle Scholar
  4. Chang J, Xiao W, Liu P, Liao XN, Wen YP, Bai L, Li LJ, Li MF (2016) Carboxymethyl cellulose assisted preparation of water-processable halloysite nanotubular composites with carboxyl-functionalized multi-carbon nanotubes for simultaneous voltammetric detection of uric acid, guanine and adenine in biological samples. J Electroanal Chem 780:103–113. doi: 10.1016/j.jelechem.2016.09.013 CrossRefGoogle Scholar
  5. Gao C, Guo Z, Liu JH, Huang XJ (2012) The new age of carbon nanotubes: an updated review of functionalized carbon nanotubes in electrochemical sensors. Nano 4:1948–1963. doi: 10.1039/C2NR11757F Google Scholar
  6. Gooding JJ (2005) Nanostructuring electrodes with carbon nanotubes: a review on electrochemistry and applications for sensing. Electrochim Acta 50:3049–3060. doi: 10.1016/j.electacta.2004.08.052 CrossRefGoogle Scholar
  7. Gosser DK (1993) Cyclic voltammetry: simulation and analysis of reaction mechanisms. VCH: New York.p43Google Scholar
  8. Hansen BH, Dryhurst G (1971) Electrochemical oxidation of theobromine and caffeine at the pyrolytic graphite electrode. J Electroanal Chem 30:407–416. doi: 10.1016/0368-1874(71)87024-7 CrossRefGoogle Scholar
  9. Jacobs CB, Peairs MJ, Venton BJ (2010) Review: Carbon nanotube based electrochemical sensors for biomolecules. Anal Chim Acta 662:105–127. doi: 10.1016/j.aca.2010.01.009 CrossRefGoogle Scholar
  10. Laviron E (1974) Adsorption, autoinhibition and autocatalysis in polarography and in linear potential sweep voltammetry. J Electroanal Chem 52:355–393. doi: 10.1016/S0022-0728(74)80448-1 CrossRefGoogle Scholar
  11. Lind T, Siegbahn PEM, Crabtree RH (1999) A quantum chemical study of the mechanism of tyrosinase. J Phys Chem B103:1193–1202. doi: 10.1021/jp982321r CrossRefGoogle Scholar
  12. Llobet E (2013) Gas sensors using carbon nanomaterials: a review. Sens Actuat B 179:32–45. doi: 10.1016/j.snb.2012.11.014 CrossRefGoogle Scholar
  13. Lu S, Bai L, Wen YP, Li MF, Yan D, Zhang R, Chen KJ (2015) Water-dispersed carboxymethyl cellulose-montmorillonite-single walled carbon nanotube composite with enhanced sensing performance for simultaneous voltammetric determination of two trace phytohormones. J Solid State Electrochem 19:2023–2037. doi: 10.1007/s10008-014-2695-5 CrossRefGoogle Scholar
  14. Lukaszewicz JP (2006) Carbon materials for chemical sensors: a review. Sens Lett 4:53–98. doi: 10.1166/sl.2006.020 CrossRefGoogle Scholar
  15. Meyer A, Ngiruwonsanga T, Henze G (1996) Determination of adenine, caffeine, theophylline and theobromine by HPLC with amperometric detection. Fresenius J Anal Chem 356:284–287. doi: 10.1007/s0021663560284 Google Scholar
  16. Sahoo NG, Rana S, Cho JW, Li L, Chan SH (2010) Polymer nanocomposites based on functionalized carbon nanotubes. Prog Polym Sci 35:837–867. doi: 10.1016/j.progpolymsci.2010.03.002 CrossRefGoogle Scholar
  17. Saleh NB, Pfefferle LD, Elimelech M (2008) Aggregation kinetics of multiwalled carbon nanotubes in aquatic systems: measurements and environmental implications. Environ Sci Technol 42:7963–7969. doi: 10.1021/es801251c CrossRefGoogle Scholar
  18. Schack JA, Waxler SH (1949) An ultraviolet spectrophotometric method for the determination of theophylline and theobromine in blood and tissues. J Pharmacol Exp Ther 97:283–291Google Scholar
  19. Scheller F, Schubert F (1991) Biosensors. Elsevier Science Publishers B.V, AmsterdamGoogle Scholar
  20. Serp P, Figueiredo JL (2009) Carbon materials for catalysis. John Wiley & Sons, HobokenGoogle Scholar
  21. Serra A, Macià A, Romero MP, Piñol C, Motilva MJ (2011) Rapid methods to determine procyanidins, anthocyanins, theobromine and caffeine in rat tissues by liquid chromatography-tandem mass spectrometry. J Chromatogr B879:1519–1528. doi: 10.1016/j.jchromb.2011.03.042 Google Scholar
  22. Sharma V, Gulati A, Ravindranath SD, Kumar V (2005) A simple and convenient method for analysis of tea biochemicals by reverse phase HPLC. J Food Compos Anal 18:583–594. doi: 10.1016/j.jfca.2004.02.015 CrossRefGoogle Scholar
  23. Spataru N, Sarada BV, Tryk DA, Fujishima A (2002) Anodic voltammetry of xanthine, theophylline, theobromine and caffeine at conductive diamond electrodes and its analytical application. Electroanalysis 14:721–728. doi: 10.1002/1521-4109(200206)14:11<721::AID-ELAN721>3.0.CO;2-1 CrossRefGoogle Scholar
  24. Sugimoto N, Katakura M, Matsuzaki K, Ohno-Shosaku T, Yachie A, Shido O (2016) Theobromine, the primary methylxanthine found in Theobroma cacao, can pass through the blood-brain barrier in mice. FASEB J.30 (1 Supplement), lb635-lb635Google Scholar
  25. Thomas JB, Yen JH, Schantz MM, Porter BJ, Sharpless KE (2004) Determination of caffeine, theobromine, and theophylline in standard reference material 2384, baking chocolate, using reversed-phase liquid chromatography. J Agr Food Chem 52:3259–3263. doi: 10.1021/jf030817m CrossRefGoogle Scholar
  26. Vinjamuri AKK (2008) A selectivity study on the use of caffeine and theobromine imprinted polypyrrole surface electrodes Masters Theses:5Google Scholar
  27. Vinjamuri A, Burris SC, Dahl D (2008) Caffeine and theobromine selectivity using molecularly imprinted polypyrrole modified electrodes. ECS Trans 13:9–20. doi: 10.1149/1.3002805 CrossRefGoogle Scholar
  28. Wang J (2005) Carbon-nanotube based electrochemical biosensors: a review. Electroanalysis 17:7–14. doi: 10.1002/elan.200403113 CrossRefGoogle Scholar
  29. Xia Z, Ni Y, Kokot S (2013) Simultaneous determination of caffeine, theophylline and theobromine in food samples by a kinetic spectrophotometric method. Food Chem 141:4087–4093. doi: 10.1016/j.foodchem.2013.06.121 CrossRefGoogle Scholar
  30. Zhang H, Xu JK, Wen YP, Wang ZF, Zhang J, Ding WC (2015a) Conducting poly (3, 4-ethylenedioxythiophene): poly (styrene-sulfonate) film electrode with superior long-term electrode stability in water and synergistically enhanced electrocatalytic ability for application in electrochemical sensors. Synth Met 204:39–47. doi: 10.1016/j.synthmet.2015.03.010 CrossRefGoogle Scholar
  31. Zhang J, Xu JK, Wen YP, Wang ZF, Zhang H, Ding WC (2015b) Voltammetric determination of phytoinhibitor maleic hydrazide using PEDOT: PSS composite electrode.J. Electroanal Chem 751:65–74. doi: 10.1016/j.jelechem.2015.05.032 CrossRefGoogle Scholar
  32. Zhang ZX, Zhang J, Zhang H, Xu JK, Wen YP, Ding WC (2016) Characterization of PEDOT: PSS-reduced graphene oxide@Pd composite electrode and its application in voltammetric determination of vitamin K3. J Electroanal Chem 775:258–266. doi: 10.1016/j.jelechem.2016.06.005 CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2017

Authors and Affiliations

  • Yingqiong Peng
    • 1
  • Wenjuan Zhang
    • 1
    • 2
  • Juan Chang
    • 2
  • Yaoping Huang
    • 1
    • 2
  • Li Chen
    • 2
    • 3
  • Hong Deng
    • 1
    Email author
  • Zhong Huang
    • 2
  • Yangping Wen
    • 2
    • 3
    Email author
  1. 1.Colleges and Uuniversities of Jiangxi Province for Key Laboratory of Information Technology in AgricultureJiangxi Agriculture UniversityNanchangPeople’s Republic of China
  2. 2.Institute of Functional Materials and Agricultural Applied ChemistryJiangxi Agricultural UniversityNanchangPeople’s Republic of China
  3. 3.Key Laboratory of Crop Physiology, Ecology and Genetic Breeding, Ministry of EducationJiangxi Agricultural UniversityNanchangPeople’s Republic of China

Personalised recommendations