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A theoretical analysis of the emf response of solkl-state lonselectlve electrodes (ISE) to Interfering Ions is presented.Different pathways of equilibration processes dictating ISE response are discussed and the quantitative predictions by use of diffusion-layer model formalism are shown. The treatment Is applied Irrespective of actual selectivity factor value (greater or smaller than one) and accounts for both selectivity coefficient changes and nonmonotonic overshoottype transient signals. A critical evaluation of existing concepts and the discussion of the limits of phenomenological Interpretation are given.
Competitive divalent (magnesium and calcium) or monovalent (potassium, lithium and sodium) ion exchange and its influence on a membrane potential formation was studied at biological ligands (BL) such as adenosine triphosphate (ATP), asparagine (Asn) and glutamine (Gln) sites. The sites are dispersed electrochemically in membranes made of the conducting polymers (CPs)poly(N-methylpyrrole) (PMPy) and poly(pyrrole) (PPy). The membranes are made sensitive to calcium and magnesium or to potassium, sodium and lithium by optimized electrodeposition and soaking procedures supported by the study of membrane topography and morphology. Distinctively different electrochemical responses, i.e. electrical potential transients or currents, are observed in the case of "antagonistic" calcium and magnesium or potassium and sodium/lithium ion pairs. Dissimilarity in the responses is ascribed to a difference between on site vs. bulk concentrations of ions, and is dictated by different transport properties of the ions, as shown by using the Nernst-Planck-Poisson (NPP) model and the diffusion-layer model (DLM). The method described allows inspecting potentialdependent competitive ion-exchange processes at the biologically active sites. It is suggested that this approach could be used as an auxiliary tool in study of potential dependent block in realistic membrane channels, such as Mg block in the N-methyl D-aspartate receptor channel (NMDA).
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