Skip to main content
SpringerLink
Log in

Direct detection of ammonium ion by means of oxygen electrocatalysis at a copper-polyaniline composite on a screen-printed electrode

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

Abstract

We describe a composite material for use in electrochemical oxygen reduction. A screen-printed electrode (SPE) was consecutively modified with electrodeposited copper, a Nafion membrane and electropolymerized polyaniline (PANi) to give an electrocatalytic composite of type PANi/Nafion/Cu2O/SPE that displays good electrical conductivity at neutral pH values. It is found that the presence of ammonia causes complex formation with Cu(I), and this causes electroreduction of oxygen to result in an increased cathodic current. The finding was applied to the quantification of ammonium ions in the 1 to 1000 μM concentration range by amperometry at −0.45 V (vs. Ag/AgCl). This Faradaic phenomenon offers the advantage of direct voltammetric detection, one of the lowest known limits of detection (0.5 μM), and high sensitivity (250 mA∙M−1∙cm−2). It was applied to the determination of ammonium ion in human serum where it compared well with the photometric routine approach for clinical analysis using glutamate dehydrogenase.

An electrocatalytic material for oxygen reduction, based on polyaniline in combination with copper, is described. It is found that the presence of ammonia causes complex formation with copper, and this causes electroreduction of oxygen to result in an increased current. This phenomenon offers the advantage of direct detection, one of the lowest known limits of detection and high sensitivity, which was utilized for ammonium ion determination in human serum.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Scheme 1
Fig. 3

Similar content being viewed by others

References

  1. Abass AK, Hart JP, Cowell DC, Chappell A (1998) Development of an amperometric assay for NH4+ based on a chemically modified screen-printed NADH sensor. Anal Chim Acta 373:1–8

    Article  CAS  Google Scholar 

  2. Annamalai SK, Palani B, Pillai KC (2012) Highly stable and redox active nano copper species stbilized functionalized-multiwalled carbon nanotube/chitosan modified electrode for efficient hydrogen peroxide reduction. Colloids Surf A Physicochem Eng Asp 395:207–216

    Article  CAS  Google Scholar 

  3. Bertocchi P, Compagnone D, Palleschi G (1996) Amperometric ammonium ion and urea determination with enzyme-based probes. Biosensors & Bioelectronics 11:1–10

    Article  CAS  Google Scholar 

  4. Burke LD, Ahern MJG, Ryan TG (1990) An investigation of the anodic behaviour of copper and its anodically produced oxides in aqueous solutions of high pH. J Electrochem Soc 137:553–561

    Article  CAS  Google Scholar 

  5. Cho WJ, Huang HJ (1998) An amperometric urea biosensor based on a polyaniline-perfluorosulfonated ionomer composite electrode. Anal Chem 70:3946–3951

    Article  CAS  Google Scholar 

  6. Davis J, Moorcroft MJ, Wilkins SJ, Compton RG, Cardosi MF (2000) Electrochemical detection of nitrate and nitrite at a copper modified electrode. Analyst 125:737–741

    Article  CAS  Google Scholar 

  7. Deng AP, Cheng JT, Huang HJ (2002) Application of a polyaniline based ammonium sensor for the amperometric immunoassay of a urease conjugated Tal 1 protein. Anal Chim Acta 461:49–55

    Article  CAS  Google Scholar 

  8. Fogg AG, Scullion SP, Edmonds TE, Birch BJ (1991) Direct reductive amperometric determination of nitrate at a copper electrode formed ln situ In a capillary-fill sensor device. Analyst 116:573–579

    Article  CAS  Google Scholar 

  9. Giannopoulou I, Panias D, Paspaliaris I (2009) Electrochemical modeling and study of copper deposition from concentrated ammoniacal sulfate solutions. Hydrometallurgy 99:58–66

    Article  CAS  Google Scholar 

  10. Hamlaoui ML, Kherrat R, Marrakchi M, Jaffrezic-Renault N, Walcarius A (2002) Development of an ammonium ISFET sensor with a polymeric membrane including zeolite. Materials Science & Engineering C-Biomimetic And Supramolecular Systems 21:25–28

    Article  Google Scholar 

  11. Hamlaoui ML, Reybier K, Marrakchi M, Jaffrezic-Renault N, Martelet C, Kherrat R, Walcarius A (2002) Development of a urea biosensor based on a polymeric membrane including zeolite. Anal Chim Acta 466:39–45

    Article  CAS  Google Scholar 

  12. Heng LY, Alva S, Ahmad M (2004) Ammonium ion sensor based on photocured and self-plasticising acrylic films for the analysis of sewage. Sensors and Actuators B-Chemical 98:160–165

    Article  CAS  Google Scholar 

  13. Hirai T, Kuwabata S, Yoneyama H (1988) Electrochemical behaviors of polypyrrole, poly-3-methylthyophene and polyaniline deposited on nafion-coated electrodes. J Electrochem Soc 135:1132–1137

    Article  CAS  Google Scholar 

  14. Lockwood AH, McDonald JM, Reiman RE, Gelbard AS, Laughlin JS, Duffy TE, Plum F (1979) Dynamics of ammonia metabolism in man - effects of liver-disease and hyper-ammonemia. J Clin Investig 63:449–460

    Article  CAS  Google Scholar 

  15. Luo YC, Do JS (2004) Urea biosensor based on PANi(urease)-Nation (R)/Au composite electrode. Biosensors & Bioelectronics 20:15–23

    Article  CAS  Google Scholar 

  16. Nagasubramanian G, Distefano S, Moacanin J (1986) Electrochemical incorporation of poly(pyrrole) into nafion and comparison of the electrochemical properties of nafion poly(pyrrole) Amd poly(pyrrole) film. J Phys Chem 90:4447–4451

    Article  CAS  Google Scholar 

  17. Nicholls D (1973) Complexes and first-Row transition elements. Macmillan Press, London

    Google Scholar 

  18. Ribeiro JA, Silva F, Pereira CM (2012) Electrochemical sensing of ammonium ion at the water/1,6-dichlorohexane interface. Talanta 88:54–60

    Article  CAS  Google Scholar 

  19. Shin JH, Yoon SY, Yoon IJ, Choi SH, Lee SD, Nam H, Cha GS (1998) Potentiometric biosensors using immobilized enzyme layers mixed with hydrophilic polyurethane. Sensors and Actuators B-Chemical 50:19–26

    Article  CAS  Google Scholar 

  20. Silva R, Voiry D, Chhowalla M, Asefa T (2013) Efficient metal-free electrocatalysts for oxygen reduction: polyaniline-derived N- and O-doped mesoporous carbons. JACS 135:7823–7826

    Article  CAS  Google Scholar 

  21. Stasyuk N, Smutok O, Gayda G, Vus B, Koval'chuk Y, Gonchar M (2012) Bi-enzyme L-arginine-selective amperometric biosensor based on ammonium-sensing polyaniline-modified electrode. Biosensors & Bioelectronics 37:46–52

    Article  CAS  Google Scholar 

  22. Strehlitz B, Grundig B, Kopinke H (2000) Sensor for amperometric determination of ammonia and ammonia-forming enzyme reactions. Anal Chim Acta 403:11–23

    Article  CAS  Google Scholar 

  23. Thompson M, Krull UJ, Bendellyoung LI (1983) The bilayer lipid-membrane as a basis for a selective sensor for ammonia. Talanta 30:919–924

    Article  CAS  Google Scholar 

  24. Vanson M, Schothorst RC, Denboef G (1983) Determination of total ammoniacal nitrogen in water by flow-injection analysis and a gas-diffusion membrane. Anal Chim Acta 153:271–275

    Article  CAS  Google Scholar 

  25. Vazquez-Arenas J, Lazaro I, Cruz R (2007) Electrochemical study of binary and ternary copper complexes in ammonia-chloride medium. Electrochim Acta 52:6106–6117

    Article  CAS  Google Scholar 

  26. Vitousek PM, Aber JD, Howarth RW, Likens GE, Matson PA, Schindler DW, Schlesinger WH, Tilman D (1997) Human alteration of the global nitrogen cycle: sources and consequences. Ecol Appl 7:737–750

    Google Scholar 

  27. Whittingham MS, Zawodzinski T (2004) Introduction: batteries and fuel cells. Chem Rev 104:4243

    Article  CAS  Google Scholar 

  28. Winther-Jensen B, Winther-Jensen O, Forsyth M, Macfarlane DR (2008) High rates of oxygen reduction over a vapor phase-polymerized PEDOT electorde. Science 321:671

    Article  CAS  Google Scholar 

  29. Yuan Y, Ahmed J, Kim S (2011) Polyaniline/carbon black composite-supported iron phtalocyanine as an oxygen reduction catalyst for microbial fuel cell. J Power Sources 196:1103

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was partially funded by the “SMARTCANCERSENS” project from the European Community Seventh Framework Program under the Grant Agreement PIRSES-GA-2012-318053 and by the NATO Science for Peace (SFP) Project CBP.NUKR.SFPP 984173. Authors would like to thank also Dr. Olga Beloivan and Mr. Krishnakumar Pillai for SEM and EDX measurements.

Author information

Authors and Affiliations

  1. Institute of Molecular Biology and Genetics, NAS of Ukraine, Kyiv, 03680, Ukraine

    Mykhailo T. Zhybak & Yaroslav I. Korpan

  2. Department of Physics, Chemistry and Biology, Linköping University, -581 83, Linköping, SE, Sweden

    Mykhailo T. Zhybak, Mikhail Yu. Vagin, Xianjie Liu & Anthony P. F. Turner

  3. Laboratory of Organic Electronics, Department of Science and Technology, Linköping University, -601 74, Norrköping, SE, Sweden

    Mikhail Yu. Vagin

  4. ACREO Swedish ICT, -601 74, Norrköping, SE, Sweden

    Valerio Beni

  5. Centre for Research in Electroanalytical Technologies, Department of Science, Institute of Technology Tallaght, Tallaght, Dublin, Ireland

    Eithne Dempsey

Authors
  1. Mykhailo T. Zhybak
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mikhail Yu. Vagin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Valerio Beni
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xianjie Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Eithne Dempsey
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Anthony P. F. Turner
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yaroslav I. Korpan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Mikhail Yu. Vagin or Yaroslav I. Korpan.

Ethics declarations

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

Electronic supplementary material

ESM 1

(DOCX 1305 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhybak, M.T., Vagin, M.Y., Beni, V. et al. Direct detection of ammonium ion by means of oxygen electrocatalysis at a copper-polyaniline composite on a screen-printed electrode. Microchim Acta 183, 1981–1987 (2016). https://doi.org/10.1007/s00604-016-1834-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00604-016-1834-3

Keywords

Search

Navigation