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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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

A challenge in turn-on mode operating optodes application is elimination of pH sensitivity. The polyoctylthiophene based optodes response mechanism is not involving hydrogen ions exchange, thus paves the way for optodes applicable for sensing in wide pH range. We report on nanoptodes that can be used both in alkaline and in acidic pH range inaccessible for classical systems using pH sensitive dyes as transducers. The proposed sensors offer 6 orders of magnitude broad, linear dependence of emission intensity on logarithm of analyte (K + or Ca 2+ ) concentration, in turn on mode. However, the slopes of calibration plots are to some extent dependent on solution pH and oxygen presence/absence. It is shown that this effect is resulting from changes of solution redox potential maintained mainly by dissolved oxygen. The solution redox potential affects the oxidation state of the polymer and thus amount of the neutral, fluorescent form of polyoctylthiophene, ultimately affecting performance of the sensor especially in acidic pH. Tailoring composition of polyoctylthiophene optodes, including hydrogen binding compound in the polymer phase, effectively diminishes the effect of pH change on sensitivity of proposed optodes, as shown on model examples of potassium and calcium sensors. Thus polyoctylthiophene based nanosensors show equally high sensitivity for analyte cations concentration change both in acidic (pH = 4) and alkaline (pH = 9.2) media., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Liposome type nano-optodes are reported. Probe architecture allows tailored - yet spontaneous - positioning of the reporter dye with chromophore group facing the sample solution. As a result the emission signal - related to competition between analyte cations and hydrogen ions, ultimately leading to deprotonation of chromoionophore and emission increase - can be read instantly after contact of the sensor with sample but also allows observation of optical signal in unique for these sensors days' time scale, without loss of intensity. Possibility of optode signal observation in days' time scale allows exploration of solvatochromic properties of applied chromoionophore group and estimation of sensor sample contact time as minute change in the position of chromophore group emission maximum., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In this study the effect of nature of nanostructural materials used as colorimetric optical probes on the analytical performance of the resulting sensors is compared. Different effects related to the nanoprobe materials - probe structure and properties: surface charge and stability, but also effects related to the analyte - receptor interactions - complex formation kinetics and transport of ions from the sample to the probe were taken into account. Presence of charge on the nanostructural colorimetric sensor effectively hinders ions exchange between the probe and the sample, leading to a linear dependence of absorbance on logarithm of analyte concentration changes. Interestingly, both anionic and cationic micelles are offering linear dependence on logarithm of concentration, covering 2 logarithmic units. Nanostructures, e.g. prepared from amphiphilic polymer Pluronic F127, lead to absorbance dependence on concentration observed in rather narrow concentration range. In this respect crosslinked poly(maleic anhydride-alt-1-octadecene) nanostructures of pH tunable surface charge, due to the presence of carboxyl and amine group on the surface, seem an attractive alternative, offering also the lowest detection limits among tested systems. This system is stable even in the presence of high concentration of background electrolyte in the sample and offers the lowest detection limit, what makes it useful as e.g. indicator for titration. Generally from the results obtained it follows that inert complexes, hindering ion transport to the probe, can be used to expose a linear dependence of the optical signal on logarithm of concentration, whereas for labile complexes formed sigmoidal type dependences of higher sensitivity over limited concentration range are obtained., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Analytical benefits related to application of copolymeric microspheres containing different number of carboxylic acid mers have been studied on example of acrylate copolymers. These structures can be used as a reagent in heterogeneous pH titration, benefiting from different number of reactive groups - i.e. different concentration of a titrant - within the series of copolymers. Thus introducing the same amount of different microspheres from a series to the sample, different amount of the titrant is introduced. Copolymeric microspheres also can be used as optical sensors - in this respect the increasing number of reactive groups in the series is useful to improve the analytical performance of microprobes - sensitivity of determination or/and response range. The increase in ion-permeability of the spheres with increasing number of reactive mers is advantageous. It is shown that for pH sensitive microspheres containing higher number of carboxyl groups the higher sensitivity for alkaline pH samples is observed for an indicator present in the beads. The significant increase of optical responses is related to enhanced ion transport within the microspheres. For zinc or potassium ions model sensors tested it was shown that by choice of pH conditions and type of microspheres from the series, the optical responses can be tuned - to enhance sensitivity for analyte concentration change as well as to change the response pattern from sigmoidal (higher sensitivity, narrow range) to linear (broader response range). For classical optode systems (e.g. microspheres containing an optical transducer - pH sensitive dye and optically silent ionophore - receptor) copolymeric microspheres containing carboxylic acid mers in their structure allow application of the sensor in alkaline pH range, which is usually inaccessible for applied optical transducer., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Copolymeric acrylate microspheres were prepared from hexyl acrylate using different amounts of methacrylic acid, resulting in a series of microspheres of gradually changing properties. The distribution of carboxyl groups - between surface and bulk of microspheres was evaluated. Bulk reactive carboxyl groups were determined using reverse coulometric titration with H(+) ions, following hydroxide ions have been generated and allowed to react with microspheres in the first step. It was found that the number of reactive carboxyl groups available in copolymeric microspheres is lower compared to number of methacrylic acid units used for polymerization process. Moreover, there is correlation between the number of groups introduced and found to be reactive in microspheres. On the other hand, the number of surface reactive groups was proportional to the number of groups introduced in course of polymerization. Thus, the surface reactive groups can be used as reagent, in novel heterogeneous microtitration procedure, in which a constant number of microspheres of different carboxyl groups contents is introduced to the sample to react with the analyte. The applicability of novel proposed method was tested on the example of Ni(2+) determination., (Copyright © 2016. Published by Elsevier B.V.)