Wearable ion-selective sensors with rapid conditioning and extended stability achieved through modulation of water and ion transport

Solid-contact (SC) ion-selective electrodes (ISEs) are often employed in wearables for electrolytes detection owing to their simplicity and ease of miniaturization. However, to mitigate their inherently unstable open circuit potential signal, ISEs require long hours of conditioning and frequent calibration prior to and during operation, limiting their practicality in wearable applications. Inspired by strategies to address water crossover and flooding in polyelectrolyte fuel cells, we demonstrated a SCISE with minimal conditioning time and long-term stability by modulating the rate-limiting step between mass transfer of water and hydrated ions and redox kinetics in the conducting polymer (CP). Our strategy comprised a wearable ISE with a superhydrophobic CP, PEDOT:TFPB, which reduced water and ion fluxes within the ISE, resulting in a stable and less-swollen CP and diminished water layer formation while maintaining CP's high capacitance. Our PEDOT:TFPB based ISEs functioned after a short conditioning time of 30 min and exhibited extended stability with a reduced signal deviation of only 0.16 % per hour (0.02 mV h⁻¹) during 48 h of continuous measurement. Through systematic studies, we showed that ISE performance could be further tuned by tailoring the thickness of the ion-selective membrane as well as the hydrophobicity and polymerization charges of the CP. Without the need for recurrent calibration, our ISEs sustain high accuracy and prolonged stability upon integration into a wearable format for on-body perspiration analysis. Our strategy allows wearable ion-selective sensors with minimal maintenance at the user-end for long-term continuous monitoring, unveiling their potential in sports, healthcare, and diagnosis fields.