Inkjet-printed pH-independent paper-based calcium sensor with fluorescence signal readout relying on a solvatochromic dye

A challenge for paper-based cation sensors relying on classical carrier-based ion-selective optodes (ISOs) is their pH-cross response caused by the use of H⁺-sensitive chromoionophores as optical signal transducers. This work demonstrates fully pH-independent fluorescence-based calcium detection with a paper-based plasticizer-free ISO. To achieve a pH-independent assay, a solvatochromic dye (SD) instead of a traditional H⁺-sensitive chromoionophore has been applied to the paper-based ISO by means of inkjet printing technology. The detection principle depends on an ionophore-driven phase-transfer ion-exchange reaction between target cations and the positively charged SD, which no longer involves H⁺ in the optical signal transduction process. The developed paper-based ISOs with the SD resulted in Ca²⁺ concentration-dependent response curves not affected by the sample pH (pH 6.0, 7.0, and 8.0). The dynamic range obtained for Ca²⁺ detection was from 10⁻⁵ to 1 mol L⁻¹ with a detection limit of 19.3 μmol L⁻¹. Additionally, excellent selectivity derived from the used ionophore has been confirmed. As a simple practical application, the determination of Ca²⁺ in mineral water has been achieved without the pH-buffering process required for conventional cation-exchange ISOs.