Scanning electrochemical microscopy (SECM) supplemented with potentiometric measurements was used to follow the time-dependent buildup of a steady-state diffusion layer at the aqueous-phase boundary of lead ion-selective electrodes (ISEs). Differential pulse voltammetry is adapted to SECM for probing the local concentration profiles at the sample side of solvent polymeric membranes. Major factors affecting the membrane transport-related surface concentrations were identified from SECM data and the potentiometric transients obtained under different experimental conditions (inner filling solution composition, membrane thickness, surface pretreatment). The amperometrically determined surface concentrations correlated well with the lower detection limits of the lead ion-selective electrodes.
The analytical characterization of a novel chromogenic calix [4]arene derivative based sodium selective, direct optode membranes has been investigated in detail. The dynamic concentration range, ion-selectivity, response time and reproducibility are discussed. The effect of the nature of the membrane matrix on the dynamic concentration range and the operation pH of the relevant optode membranes are explained. The sodium ion response is interpreted on the basis of the ion-exchange theory, which is underlined by the results of calixarene mediated ion-transport experiments.
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