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.
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The datasets generated during and/or analyzed during the current study are available from the correspondingauthor on reasonable request.
References
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
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
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
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
Lehnhardt A, Kemper MJ (2011) Pathogenesis, diagnosis and management of hyperkalemia. Pediatr Nephrol 26:377–384
Donaldson SH, Boucher RC (2007) Sodium channels and cystic fibrosis. Chest 132:1631–1636
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
Bobacka J, Ivaska A, Lewenstam A (2008) Potentiometric ion sensors. Chem Rev 108:329–351
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
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
Yin T, Qin W (2013) Applications of nanomaterials in potentiometric sensors. TrAC, Trends Anal Chem 51:79–86
Paczosa-Bator B (2012) All-solid-state selective electrodes using carbon black. Talanta 93:424–427
Ozer T, Henry CS (2022) All-solid-state potassium-selective sensor based on carbon black modified thermoplastic electrode. Electrochim Acta 404:139762
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
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
Bobacka J (2006) Conducting polymer-based solid-state ion-selective electrodes. Electroanalysis 18:7–18
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
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
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
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
van de Velde L, d’Angremont E, Olthuis W (2016) Solid contact potassium selective electrodes for biomedical applications–a review. Talanta 160:56–65
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
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
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
Ozer T (2022) Carbon composite thermoplastic electrodes integrated with mini-printed circuit board for wireless detection of calcium ions. Anal Sci 38:1233–1243
Mikhelson KN (2013) Ionophore-Based ISEs. Springer, Ion-Selective Electrodes, pp 51–95
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
McNaught AD, Wilkinson A (1997) Compendium of chemical terminology. Blackwell Science, London
Bakker E, Pretsch E (2005) Potentiometric sensors for trace-level analysis. TrAC, Trends Anal Chem 24:199–207
Bakker E, Bühlmann P, Pretsch E (1997) Carrier-based ion-selective electrodes and bulk optodes. 1. General characteristics. Chem Rev 97:3083–132
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
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
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
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
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
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
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
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
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
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
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
Paczosa-Bator B, Cabaj L, Piech R, Skupień K (2012) Platinum nanoparticles intermediate layer in solid-state selective electrodes. Analyst 137:5272–5277
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
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
Paczosa-Bator B, Cabaj L, Piech R, Skupień K (2013) Potentiometric sensors with carbon black supporting platinum nanoparticles. Anal Chem 85:10255–10261
Rousseau CR, Bühlmann P (2021) Calibration-free potentiometric sensing with solid-contact ion-selective electrodes. TrAC, Trends Anal Chem 140:116277
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.
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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.
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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
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DOI: https://doi.org/10.1007/s00604-023-05818-8