Voltammetric Mechanism of Multiion Detection with Thin Ionophore-Based Polymeric Membrane

The capability to detect multianalyte ions in their mixed solution is an important advantage of voltammetry with an ionophore-based polymeric membrane against the potentiometric and optical counterparts. This advanced capability is highly attractive for the analysis of physiological ions at millimolar concentrations in biological and biomedical samples. Herein, we report on the comprehensive response mechanisms based on the voltammetric exchange and transfer of millimolar multiions at a thin polymeric membrane, where an ionophore is exhaustively depleted upon the transfer of the most favorable primary ion, I(zI). With a new voltammetric ion-exchange mechanism, the primary ion is exchanged with the secondary favorable ion, J(zJ), at more extreme potentials to transfer a net charge of |zJ|/nJ - |zI|/nI for each ionophore molecule, which forms 1:nI and 1:nJ complexes with the respective ions. Alternatively, an ion-transfer mechanism utilizes the second ionophore that independently transfers the secondary ion without ion exchange. Experimentally, a membrane is doped with a Na(+)- or Li(+)-selective ionophore to detect not only the primary ion, but also the secondary alkaline earth ion, based on the ion-exchange mechanism, where both ions form 1:1 complexes with the ionophores to transfer a net charge of +1. Interestingly, the resultant peak potentials of the secondary divalent ion vary with its sample activity to yield an apparently super-Nernstian slope as predicted theoretically. By contrast, the voltammetric exchange of calcium ion (nI = 3) with lithium ion (nJ = 1) by a Ca(2+)-selective ionophore is thermodynamically unfavorable, thereby requiring a Li(+)-selective ionophore for the ion-transfer mechanism.