Skip to main content
Log in

Large-scale fabrication of ion-selective electrodes for simultaneous detection of Na+, K+, and Ca2+ in biofluids using a smartphone-based potentiometric sensing platform

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

Abstract

A significant bottleneck exists for mass-production of ion-selective electrodes despite recent developments in manufacturing technologies. Here, we present a fully-automated system for large-scale production of ISEs. Three materials, including polyvinyl chloride, polyethylene terephthalate and polyimide, were used as substrates for fabricating ion-selective electrodes (ISEs) using stencil printing, screen-printing and laser engraving, respectively. We compared sensitivities of the ISEs to determine the best material for the fabrication process of the ISEs. The electrode surfaces were modified with various carbon nanomaterials including multi-walled carbon nanotubes, graphene, carbon black, and their mixed suspensions as the intermediate layer to enhance sensitivities of the electrodes. An automated 3D-printed robot was used for the drop-cast procedure during ISE fabrication to eliminate manual steps. The sensor array was optimized, and the detection limits were 10–5 M, 10–5 M and 10–4 M for detection of K+, Na+ and Ca2+ ions, respectively. The sensor array integrated with a portable wireless potentiometer was used to detect K+, Na+ and Ca2+ in real urine and simulated sweat samples and results obtained were in agreement with ICP-OES with good recoveries. The developed sensing platform offers low-cost detection of electrolytes for point-of-care applications.

Graphical abstract

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
Fig. 7

Similar content being viewed by others

Data Availability

The datasets generated during and/or analyzed during the current study are available from the correspondingauthor on reasonable request.

References

  1. Bagheri N, Mazzaracchio V, Cinti S, Colozza N, Di Natale C, Netti PA et al (2021) Electroanalytical sensor based on gold-nanoparticle-decorated paper for sensitive detection of copper ions in sweat and serum. Anal Chem 93:5225–5233

    CAS  PubMed  Google Scholar 

  2. di Sant’Agnese PA, Darling RC, Perera GA, Shea E (1953) Abnormal electrolyte composition of sweat in cystic fibrosis of the pancreas: clinical significance and relationship to the disease. Pediatrics 12:549–563

    PubMed  Google Scholar 

  3. Mahendran V, Philip J (2013) Sensing of biologically important cations such as Na+, K+, Ca2+, Cu2+, and Fe3+ using magnetic nanoemulsions. Langmuir 29:4252–4258

    CAS  PubMed  Google Scholar 

  4. Riccardi D, Kemp PJ (2012) The calcium-sensing receptor beyond extracellular calcium homeostasis: conception, development, adult physiology, and disease. Annu Rev Physiol 74:271–297

    CAS  PubMed  Google Scholar 

  5. Lehnhardt A, Kemper MJ (2011) Pathogenesis, diagnosis and management of hyperkalemia. Pediatr Nephrol 26:377–384

    PubMed  Google Scholar 

  6. Donaldson SH, Boucher RC (2007) Sodium channels and cystic fibrosis. Chest 132:1631–1636

    CAS  PubMed  Google Scholar 

  7. Adams J, Badolato M, Pierce E, Cantrell A, Parker Z, Farzam D (2021) Short-Term Stability of Urine Electrolytes: Effect of Time and Storage Conditions. Int J Sport Nutr Exerc Metab 1:1–3

    Google Scholar 

  8. Bobacka J, Ivaska A, Lewenstam A (2008) Potentiometric ion sensors. Chem Rev 108:329–351

    CAS  PubMed  Google Scholar 

  9. Soda Y, Citterio D, Bakker E (2019) Equipment-free detection of K+ on microfluidic paper-based analytical devices based on exhaustive replacement with ionic dye in ion-selective capillary sensors. ACS sensors 4:670–677

    CAS  PubMed  Google Scholar 

  10. Shao Y, Ying Y, Ping J (2020) Recent advances in solid-contact ion-selective electrodes: Functional materials, transduction mechanisms, and development trends. Chem Soc Rev 49:4405–4465

    CAS  PubMed  Google Scholar 

  11. Yin T, Qin W (2013) Applications of nanomaterials in potentiometric sensors. TrAC, Trends Anal Chem 51:79–86

    CAS  Google Scholar 

  12. Paczosa-Bator B (2012) All-solid-state selective electrodes using carbon black. Talanta 93:424–427

    CAS  PubMed  Google Scholar 

  13. Ozer T, Henry CS (2022) All-solid-state potassium-selective sensor based on carbon black modified thermoplastic electrode. Electrochim Acta 404:139762

    CAS  Google Scholar 

  14. Crespo GA, Gugsa D, Macho S, Rius FX (2009) Solid-contact pH-selective electrode using multi-walled carbon nanotubes. Anal Bioanal Chem 395:2371–2376

    CAS  PubMed  Google Scholar 

  15. Ping J, Wang Y, Wu J, Ying Y (2011) Development of an all-solid-state potassium ion-selective electrode using graphene as the solid-contact transducer. Electrochem Commun 13:1529–1532

    CAS  Google Scholar 

  16. Bobacka J (2006) Conducting polymer-based solid-state ion-selective electrodes. Electroanalysis 18:7–18

    CAS  Google Scholar 

  17. Manjushree S, Adarakatti PS (2023) Recent advances in disposable electrochemical sensors. In: recent developments in green electrochemical sensors: design, performance, and applications. Am Chem Soc pp 1–21

  18. Hjort RG, Soares RR, Li J, Jing D, Hartfiel L, Chen B et al (2022) Hydrophobic laser-induced graphene potentiometric ion-selective electrodes for nitrate sensing. Microchim Acta 189:122

    CAS  Google Scholar 

  19. Lee C-W, Jeong S-Y, Kwon Y-W, Lee J-U, Cho S-C, Shin B-S (2022) Fabrication of laser-induced graphene-based multifunctional sensing platform for sweat ion and human motion monitoring. Sens Actuators A 334:113320

    CAS  Google Scholar 

  20. Liao J, Zhang X, Sun Z, Chen H, Fu J, Si H et al (2022) Laser-induced graphene-based wearable epidermal ion-selective sensors for noninvasive multiplexed sweat analysis. Biosensors 12:397

    CAS  PubMed  PubMed Central  Google Scholar 

  21. van de Velde L, d’Angremont E, Olthuis W (2016) Solid contact potassium selective electrodes for biomedical applications–a review. Talanta 160:56–65

    PubMed  Google Scholar 

  22. Ozer T, Agir I, Henry CS (2022) Rapid prototyping of ion-selective electrodes using a low-cost 3D printed internet-of-things (IoT) controlled robot. Talanta 247:123544

    CAS  PubMed  Google Scholar 

  23. Ozer T, Agir I, Henry CS (2022) Low-cost Internet of Things (IoT)-enabled a wireless wearable device for detecting potassium ions at the point of care. Sens Actuators B Chem 365:131961

    CAS  Google Scholar 

  24. Ozer T, Henry CS (2022) Microfluidic-based ion-selective thermoplastic electrode array for point-of-care detection of potassium and sodium ions. Microchim Acta 189:1–12

    Google Scholar 

  25. Ozer T (2022) Carbon composite thermoplastic electrodes integrated with mini-printed circuit board for wireless detection of calcium ions. Anal Sci 38:1233–1243

    CAS  PubMed  Google Scholar 

  26. Mikhelson KN (2013) Ionophore-Based ISEs. Springer, Ion-Selective Electrodes, pp 51–95

    Google Scholar 

  27. Lin J, Peng Z, Liu Y, Ruiz-Zepeda F, Ye R, Samuel EL et al (2014) Laser-induced porous graphene films from commercial polymers. Nat Commun 5:1–8

    Google Scholar 

  28. McNaught AD, Wilkinson A (1997) Compendium of chemical terminology. Blackwell Science, London

  29. Bakker E, Pretsch E (2005) Potentiometric sensors for trace-level analysis. TrAC, Trends Anal Chem 24:199–207

    CAS  Google Scholar 

  30. Bakker E, Bühlmann P, Pretsch E (1997) Carrier-based ion-selective electrodes and bulk optodes. 1. General characteristics. Chem Rev 97:3083–132

    CAS  PubMed  Google Scholar 

  31. Bühlmann P, Pretsch E, Bakker E (1998) Carrier-based ion-selective electrodes and bulk optodes. 2. Ionophores for potentiometric and optical sensors. Chem Rev 98:1593–688

    PubMed  Google Scholar 

  32. Mazzaracchio V, Serani A, Fiore L, Moscone D, Arduini F (2021) All-solid state ion-selective carbon black-modified printed electrode for sodium detection in sweat. Electrochim Acta 394:139050

    CAS  Google Scholar 

  33. Pięk M, Piech R, Paczosa-Bator B (2016) The complex crystal of NaTCNQ–TCNQ supported on different carbon materials as ion-to-electron transducer in all-solid-state sodium-selective electrode. J Electrochem Soc 163:B573

    Google Scholar 

  34. Kang YJ, Chung H, Kim M-S, Kim W (2015) Enhancement of CNT/PET film adhesion by nano-scale modification for flexible all-solid-state supercapacitors. Appl Surf Sci 355:160–165

    CAS  Google Scholar 

  35. Rostampour M, Lawrence Jr DJ, Hamid Z, Darensbourg J, Calvo‐Marzal P, Chumbimuni‐Torres KY (2023) Highly reproducible flexible ion‐selective electrodes for the detection of sodium and potassium in artificial sweat. Electroanalysis 35:2200121

  36. Choudhury S, Roy S, Bhattacharya G, Fishlock S, Deshmukh S, Bhowmick S et al (2021) Potentiometric ion-selective sensors based on UV-ozone irradiated laser-induced graphene electrode. Electrochim Acta 387:138341

    CAS  Google Scholar 

  37. Cinti S, Mazzaracchio V, Cacciotti I, Moscone D, Arduini F (2017) Carbon black-modified electrodes screen-printed onto paper towel, waxed paper and parafilm M®. Sensors 17:2267

    PubMed  PubMed Central  Google Scholar 

  38. Wan Z, Umer M, Lobino M, Thiel D, Nguyen N-T, Trinchi A et al (2020) Laser induced self-N-doped porous graphene as an electrochemical biosensor for femtomolar miRNA detection. Carbon 163:385–394

    CAS  Google Scholar 

  39. Lee J-H, Wee S-B, Kwon M-S, Kim H-H, Choi J-M, Song MS et al (2011) Strategic dispersion of carbon black and its application to ink-jet-printed lithium cobalt oxide electrodes for lithium ion batteries. J Power Sources 196:6449–6455

    CAS  Google Scholar 

  40. De Marco R, Veder J-P, Clarke G, Nelson A, Prince K, Pretsch E et al (2008) Evidence of a water layer in solid-contact polymeric ion sensors. Phys Chem Chem Phys 10:73–76

    PubMed  Google Scholar 

  41. Bobacka J (1999) Potential stability of all-solid-state ion-selective electrodes using conducting polymers as ion-to-electron transducers. Anal Chem 71:4932–4937

    CAS  PubMed  Google Scholar 

  42. Paczosa-Bator B, Cabaj L, Piech R, Skupień K (2012) Platinum nanoparticles intermediate layer in solid-state selective electrodes. Analyst 137:5272–5277

    CAS  PubMed  Google Scholar 

  43. Paczosa-Bator B, Pięk M, Piech R (2015) Application of nanostructured TCNQ to potentiometric ion-selective K+ and Na+ electrodes. Anal Chem 87:1718–1725

    CAS  PubMed  Google Scholar 

  44. Paczosa-Bator B (2014) Effects of type of nanosized carbon black on the performance of an all-solid-state potentiometric electrode for nitrate. Microchim Acta 181:1093–1099

    CAS  Google Scholar 

  45. Paczosa-Bator B, Cabaj L, Piech R, Skupień K (2013) Potentiometric sensors with carbon black supporting platinum nanoparticles. Anal Chem 85:10255–10261

    CAS  PubMed  Google Scholar 

  46. Rousseau CR, Bühlmann P (2021) Calibration-free potentiometric sensing with solid-contact ion-selective electrodes. TrAC, Trends Anal Chem 140:116277

    CAS  Google Scholar 

Download references

Acknowledgements

Kanyapat Teekayupak gratefully thanks to the 100th Anniversary Chulalongkorn University Fund for Doctoral Scholarship. This research was supported by National Research Council of Thailand (NRCT5-TRG63001-02). Additional support was provided by The Scientific and Technological Research Council of Turkey (TUBITAK) 122Z721 and 120N615. The author also gratefully acknowledges SciSpec Co., Ltd. for validation method with ICP-OES and Metabolic Disease in Gastrointestinal and Urinary System Research Unit, Department of Biochemistry, Faculty of Medicine, Chulalongkorn University for urine samples.

Author information

Authors and Affiliations

Authors

Contributions

Kanyapat Teekayupak: Formal analysis, Investigation, Methodology, Writing—Original Draft. Atchara Lomae: Formal analysis, Methodology, Writing—Original Draft. Ismail Agir: Investigation, Methodology, Software, Writing—Review & Editing. Natthaya Chuaypen: Real sample resource. Thasinas Dissayabutra: Real sample resource. Charles S. Henry: Investigation, Visualization, Writing—Review & Editing. Orawon Chailapakul: Investigation, Supervision. Tugba Ozer: Conceptualization, Supervision, Visualization, Writing—Review & Editing. Nipapan Ruecha: Conceptualization, Project administration, Supervision, Visualization, Writing—Review & Editing.

Corresponding authors

Correspondence to Orawon Chailapakul, Tugba Ozer or Nipapan Ruecha.

Ethics declarations

Competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Additional information

Publisher's note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (MOV 853 KB)

Supplementary file2 (MOV 181242 KB)

Supplementary file3 (MP4 35235 KB)

Supplementary file4 (DOCX 807 KB)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Teekayupak, K., Lomae, A., Agir, I. et al. Large-scale fabrication of ion-selective electrodes for simultaneous detection of Na+, K+, and Ca2+ in biofluids using a smartphone-based potentiometric sensing platform. Microchim Acta 190, 237 (2023). https://doi.org/10.1007/s00604-023-05818-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-023-05818-8

Keywords

Navigation