Visible and FTIR microscopic observation of bisthiourea ionophore aggregates in ion-selective electrode membranes

Since conventional response models for ionophore-based ISEs are based on the assumption of a homogeneous membrane phase, they cannot accurately predict the response of membranes containing self-aggregating ionophores. However, meaningful conclusions about the relationship between ionophore structure and potentiometric responses can only be drawn if ionophore aggregation is properly recognized. This study demonstrates that dark field visible microscopy and FTIR microspectroscopy are valuable tools for the observation of such ionophore self-aggregation and, thereby, the development of new ionophore-based ISEs. Sulfate selective electrodes with solvent polymeric membranes containing bisthiourea ionophores that differ only by peripheral nonpolar substituents were shown to exhibit very different interferences from the sample pH. On one hand, optimized electrodes based on an ionophore with a phenyl substituent on each thiourea group (1) do not respond to pH at all and function well as sulfate-selective electrodes. On the other hand, membranes containing a more lipophilic ionophore with two additional hexylsubstituted adamantyl groups (2) exhibit severe pH interference at pH values as low as pH 5. The observation of membranes containing ionophore 2 with dark field visible microscopy and FTIR microspectroscopy shows supramolecular aggregation, and explains the startling difference between the potentiometric responses of the two types of electrodes.