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Application of neutral ionophore based ion-selective sensors requires presence of ion-exchanger in the receptor phase, silently assuming that it is not only soluble but also dissociates to ions in the applied plasticizer. Although for typically applied ion-selective membrane constituents (plasticizers - ion-exchanger pairs) dissociation of ion-exchangers to ions is proven by theoretical (or close to) performance of resulting sensors, search for alternative plasticizers or ion-exchangers requires a method allowing estimation of the match of properties of involved compounds. In this work we propose a simple optical approach allowing estimation of ion-exchanger interactions with plasticizer. The results were confirmed by conductivity studies of model plasticizers solutions. The estimated dissociation constants of model ion-exchangers in plasticizers used are in excellent agreement with the results of optical studies. It was shown that solubility coupled with poor dissociation to ions of ion-exchanger affects performance of the resulting ion-selective membrane. Rational choice of properties of ion-exchanger and plasticizer allows finding a perfect match of the two, that results in improvements in performance of sensors (e.g. detection limits). As model sensors potassium and sodium ion-selective electrodes with poly(vinyl chloride) (PVC) based membranes, plasticized with classical plasticizer bis(2-ethylhexyl sebacate) or biodegradable alternative acetyl tributyl citrate, were prepared and studied using selected ion-exchangers. [Display omitted] • The effect of ion pair formation with the ion-selective receptor is studied with emphasis on sensor performance. • An optical approach allowing easy visualization of the dissociation of ion-exchanger in the plasticizer is proposed. • Ion pair formation between cation-exchanger and analyte cations affects performance of sensor. • The proposed optical approach can be helpful to predict suitability of ion-exchanger for the plasticizer. [ABSTRACT FROM AUTHOR]

Ion-selective membranes, as used in potentiometric sensors, are mixtures of a few important constituents in a carefully balanced proportion. The changes of composition of the ion-selective membrane, both qualitative and quantitative, affect the analytical performance of sensors. Different constructions and materials applied to improve sensors result in specific conditions of membrane formation, in consequence, potentially can result in uncontrolled modification of the membrane composition. Clearly, these effects need to be considered, especially if preparation of miniaturized, potentially disposable internal-solution free sensors is considered. Furthermore, membrane composition changes can occur during the normal operation of sensors—accumulation of species as well as release need to be taken into account, regardless of the construction of sensors used. Issues related to spontaneous changes of membrane composition that can occur during sensor construction, pre-treatment and their operation, seem to be underestimated in the subject literature. The aim of this work is to summarize available data related to potentiometric sensors and highlight the effects that can potentially be important also for other sensors using ion-selective membranes, e.g., optodes or voltammetric sensors. [ABSTRACT FROM AUTHOR]