A mixed electronic-ionic conductor-based bifunctional sensing layer beyond ionophores for sweat electrolyte monitoring

Noninvasive and continuous monitoring of electrolytes in biofluids based on wearable biotechnology provides extensive health-related physiological information. The state-of-the-art wearable bioelectronic ion sensors depend on the organic ionophore-based solid-contact structure of potentiometric ion-selective electrodes. This structure contains two functional sensing layers, i.e., a solid contact (ion-to-electron signal transduction) and an ionophore-containing ion-selective membrane (ISM, ion recognition). However, the potential drift, biotoxicity, and expensive organic ionophores complicate practical wearable applications. These challenges intrinsically originate from the ISM. Herein, an ISM-free wearable ion sensor based on mixed electronic-ionic conductors of tungsten bronzes is reported. These materials can serve as a bifunctional sensing layer for simultaneous ion-to-electron transduction through the redox reaction of W6+/5+ and ion recognition through crystal ion exchange. The K- and Na-adjusted WO3 disclosed Nernstian responses toward NH4+ and H+, respectively. The selectivity is comparable to or even better than organic ionophores, such as ammonia ionophore of nonactin. Further, the on-body monitoring of sweat ammonia and pH was realized using an integrated ISM–free flexible sensor. Therefore, this work offers an ISM-free concept and emphasizes the importance of developing next-generation ISM-free wearable bioelectronic ion sensors.