Solid-Contact pH Sensor with Covalent Attachment of Ionophores and Ionic Sites to a Poly(decyl methacrylate) Matrix

With a view to improving the sensor lifetime, solid-contact ion-selective electrodes (ISEs) were prepared with a plasticizer-free and cross-linked poly(decyl methacrylate) matrix, to which only the ionic sites, only the ionophore, or both the ionic sites and ionophore were covalently attached. In earlier work with covalently attached ionophores or ionic sites, it was difficult to discount the presence of ionophores or ionic site impurities that were not covalently attached to the polymer backbone because the reagents used to introduce the ionophore or ionic sites had high hydrophobicities. In this work, we deliberately chose readily available hydrophilic reagents for the introduction of covalently attached H⁺ ionophores with tertiary amino groups and covalently attached sulfonate groups as ionic sites. This simplified the synthesis and made it possible to thoroughly remove ionophores and ionic sites not covalently attached to the polymer backbone. Our results confirm the expectation that hydrophobic ISE membranes with both covalently attached ionophores and ionic sites have impractically long response times. In contrast, ISEs with either covalently attached H⁺ ionophores or covalently attached ionic sites responded to pH with quick Nernstian responses and high selectivity. Both conventional plasticized poly(vinyl chloride) (PVC)-based ISEs and the new poly(decyl methacrylate) membranes were exposed to 90 °C heat for 2 h, 10% ethanol for 1 day, or undiluted blood serum for 5 days. In all three cases, the poly(decyl methacrylate) ISEs exhibited properties superior to conventional PVC-based ISEs, confirming the advantages of the covalent attachment.