In this paper we report on the novel polymeric membranes for the liquid junction‐free reference electrodes. The membranes contain the ionic liquids (ILs) based on the amino acid anions, namely valine‐, leucine‐, lysine‐ and histidine‐anions, and 1‐butyl‐3‐methylimidazolium cation. Addition of the ILs, and especially of the valine‐based one, to the polymeric plasticized membranes allows significant stabilization of the electrode potential and makes it insensitive to the solution composition. A simple criterion based on the calculated lipophilicities of the cation and anion of the IL is proposed for a priori estimation of its applicability for potential stabilization. The addition of the IL as a microcomponent is found to be advantageous over plasticizing the membrane with the IL due to better potential stability, higher dissociation degree and mobility of the species. The resistance of the novel reference membranes can be tuned by addition of the lipophilic membrane electrolytes, e. g. ETH500. The applicability of the developed reference electrodes is verified in the potentiometric calibration of the indicator K+‐ and Ca2+‐selective electrodes. Implementation of the amino acid‐based ionic liquids with low environmental toxicity can make a significant contribution to the development of nature‐friendly potentiometry.

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Here, we report on systematic investigation of the impact of coextraction of the aqueous electrolyte and anion interference on the response of cation-selective bulk optodes. It is evident that to deliberately manage the properties of chemical sensors and to apply them in routine analysis, one should have exhaustive insight into their operation mechanism. Despite the extensive research in the field of ionophore-based optodes and numerous attempts for their practical application, the understanding of how coextraction of an aqueous electrolyte influences its response characteristics has not been developed thus far. Meanwhile, the electrolyte coextraction determines the detection limits of analogous ion-selective electrodes. A theoretical model based on phase distribution equilibrium is proposed to quantitatively describe the effect of Donnan exclusion failure on the response of polymeric plasticized optodes. The theoretical conclusions are confirmed by the results obtained with Na+/pH-selective optodes based on a neutral chromoionophore as a model system in solutions containing anions of various lipophilicities (Cl–, NO3 –, I–, SCN–, and ClO4 –). For the first time, it is shown that coextraction leads to a significant shift of the response range of the optodes as well as to nonmonotonic response curves due to the transition from cationic to anionic response. An approach to estimate the coextraction constants of electrolytes from the optode response curves is proposed. The limitations in the applicability of optodes due to co-ion interference are explored. It is found that neglecting anion interference can cause dramatic errors in the results of analyses with optical sensors.

It is demonstrated for the first time that the registration of the optode signal under nonequilibrium conditions reduces analysis time and shifts the sensor working range. The fabrication of optode-like color standards for digital color analysis (DCA) is described, and a multi-parameter color scale for calibration-free sensor arrays is proposed. Advantages and limitations of monochrome and color camera for DCA with colorimetric optodes are discussed.

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