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An idea of using ion-exchanger salt containing optically active cations to prepare ion-selective membranes is proposed. Although the presence of an ion-exchanger in the composition of neutral ionophore based sensors is necessary, the choice of available salts for cation-selective sensors preparation, is usually limited to sodium or potassium compounds. In this work we propose application of an alternative salt, using a cation optically active both in absorption and emission mode as a mobile one. Thus, coloured ion-selective membranes can be obtained. This in turn opens new possibilities of monitoring the state of the receptor layer as well as allows direct analytical application of ion-selective membranes in simple optical mode with all benefits related to eliminating the necessity of using reference electrodes. As a model system Nile blue derivative of tetrakis[3,5-bis(trifluoromethyl)phenyl]borate ion-exchanger was prepared and used to obtain potassium or calcium selective sensors. Selective exchange of ions between the membrane and solution, leading to an increase in optical signal of the solution, can be used to quantify the presence of analyte ions. Thus the sensor pretreatment process is becoming a source of analytical information. The applicability of this approach was verified in determining the presence of potassium ions in the vast majority of interfering ions, e.g. present as impurities in the reagent grade calcium chloride. The resulting potassium ions contents was well comparable with values obtained in course of ICP-MS approach., 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 © 2025 Elsevier B.V. All rights reserved.)

Nerve agents (G- and V-series) are a group of extremely toxic organophosphorus chemical warfare agents that we have had the opportunity to encounter many times on a massive scale (Matsumoto City, Tokyo subway and Gulf War). The threat of using nerve agents in terrorist attacks or military operations is still present, even with establishing the Chemical Weapons Convention as the legal framework. Understanding their environmental sustainability and health risks is critical to social security. Due to the risk of contact with dangerous nerve agents and animal welfare considerations, in silico methods were used to assess hydrolysis and biodegradation safely. The environmental fate of the examined nerve agents was elucidated using QSAR models. The results indicate that the investigated compounds released into the environment hydrolyse at a different rate, from extremely fast (<1 day) to very slow (over a year); V-agents undergo slower hydrolysis compared to G-agents. V-agents turned out to be relatively challenging to biodegrade, the ultimate biodegradation time frame of which was predicted as weeks to months, while for G-agents, the overwhelming majority was classified as weeks. In silico methods for predicting various parameters are critical to preparing for the forthcoming application of nerve agents., 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 © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

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.)

Novichoks constitute a relatively new class of nerve agents of extreme toxicity that we have had the opportunity to experience three times already. After the first case (Salisbury, UK), a public debate about Novichoks began, which resulted in the realisation of the nature of these chemicals. From a social security point of view, examining their properties, especially toxicological and environmental aspects, are crucial. After the CWC (Chemical Warfare Agent) list update, the candidate structures for the Novichoks may be over 10,000 compounds. It would be extremely laborious to conduct experimental research for each. Understanding their environmental persistence and health hazards is an essential national issue. Moreover, due to the high risk posed by contact with hazardous Novichok substances, in silico research was applied to estimate hydrolysis and biodegradation safely. The present study elucidates, using QSAR models, the environmental fate of the Novichoks studied (n = 17). The results indicate that Novichoks released into the environment hydrolyse at various rates, from extremely fast (<1 day) to very slow (more than a year). Furthermore, ultimate biodegradation from weeks to months is expected for most compounds, which classifies them as relatively difficult biodegradable. Applying reliable in silico methods (QSAR Toolbox and EPI Suite) for predicting various parameters is crucial to prepare for the upcoming usage of Novichoks., 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 The Authors. Published by Elsevier B.V. All rights reserved.)

A novel approach is explored to result in anion selective nanostructural optodes, that do not require the presence of selective ionophore. The sensing principle proposed is based on interactions of polarity sensitive dye with anions, leading to change of the chromophore group environment, resulting in increase of emission for increase of analyte concentration. To induce interactions of the analyte with the dye precise matching of properties of analyte and receptor is required. It is shown that the careful balancing of composition of nanostructural probes allows fine tuning of linear response range to cover lower concentration range. The model analyte studied was ibuprofen, due to its clinical and environmental relevance, lack of ionophore. As model probes rhodamine B octadecyl ester based nanostructures were prepared and applied. For optimized system turn-on responses were obtained for ibuprofen concentration change from 10 -4.3  M to 10 -2  M, with no effect of other anti-inflammatory drugs such as naproxen or salicylate., (Copyright © 2021 Elsevier B.V. All rights reserved.)

An alternative optical signal transduction mechanism for ion-selective optodes is proposed. The nanostructural sensors benefit from ion-selective reversing aggregation caused quenching yielding turn-on, bright and highly stable optical signals. Selective incorporation of analyte results in transformation of the polymer dye from aggregate to a micelle structure, affecting spatial arrangement of chromophore groups in the nanostructure. Formation of micelles, induced by ion-selective interactions, is coupled with pronounced increase of emission due to decrease of aggregation caused quenching, characteristic for dispersed phase formation. The formed micelles are highly stable in solution, offering constant in time (days scale) emission signal. The important difference from other known systems is that the analyte binding induced change does not affect the chromophore group, but occurs in distant, terminal position of the side chain of the polymer. As a model system calcium selective optodes have been prepared. Thus obtained probes were characterized with broad analyte concentration range (from 10 -7 to 10 -3  M) emission signal increase. The turn-on response was observed within broad range of pH (6.3-8.9), with no sign of optical signal deterioration during 5 days contact with the analyte or more than two weeks storage., (Copyright © 2020 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.)

Recently it was shown that optical nanosensors based on alternating polymers e.g. poly(maleic anhydride-alt-1-octadecene) were characterized by a linear dependence of emission intensity on logarithm of concentration over a few of orders of magnitude range. In this work we focus on the material used to prepare calcium selective nanosensors. It is shown that alternating polymer nanosensors offer competitive performance in the absence of calcium ionophore, due to interaction of the nanospheres building blocks with analyte ions. The emission increase corresponds to increase of calcium ions contents in the sample within the range from 10(-4) to 10(-1) M. Further improvement in sensitivity (from 10(-6) to 10(-1) M) and selectivity can be achieved by incorporating calcium ionophore in the nanospheres. The optimal results were obtained for core-shell nanospheres, where the core was prepared from poly(styrene-co-maleic anhydride) and the outer layer from poly(maleic anhydride-alt-1-octadecene). Thus obtained chemosensors were showing linear dependence of emission on logarithm of calcium ions concentration within the range from 10(-7) to 10(-1) M., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A novel approach to the quantification of relatively small amounts of water present in low polarity, aprotic solvents is proposed. This method takes advantage of protolitic reaction of 4-methylumbelliferone dissolved in the solvent with water, acting as a base. The low emission intensity neutral 4-methylumbelliferone is transformed in reaction with water to a highly fluorescent anionic form. Thus the increase in emission intensity is observed for increasing water contents in aprotic solvents. For low water contents and highly lipophilic solvents, this method yields (in practical conditions) higher sensitivity compared to biamperometric Karl Fischer titration method in volumetric mode. It is also shown that organic compounds of protolitic character (amines, acids) not only interfere with water contents determination but increase the sensitivity of emission vs. water contents dependence. Introduction of aqueous solution of strong acid or base (HCl or NaOH) has similar effect on the system as introduction of pure water., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Carboxy-functionalized graphene was used as a solid contact for potassium ion-selective electrodes with poly(vinyl chloride) based membrane. Transducer layers were obtained simply by application of a dispersion of graphene derivative in water. Analytical performance of thus obtained sensors was compared with that of all-solid-state sensors with typical transducer materials: poly(octylthiophene) applied as chloroform solution, conducting polymers available as aqueous dispersions of poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate) ions or polyaniline. It was found that all sensors tested were characterized with similar analytical parameters. Carboxy-functionalized graphene contact layer was in some respect similar to polyaniline one, what most probably results from the presence of pH sensitive groups in both materials., (Copyright © 2012 Elsevier B.V. All rights reserved.)

In this work a novel method for introduction of ionophore and ion-exchanger to the ion-selective polyacrylate based membrane is proposed. These compounds (and optionally primary ions) are introduced to polyacrylate microspheres, used to prepare ion-selective membrane. The approach proposed here can be used to prepare membranes containing primary ions equally distributed through the receptor phase, i.e. membranes that do not require conditioning in primary ions solution and are free from problems related to slow diffusion of primary ions. Thus obtained sensors were characterized with linear responses (also at relatively high activities) and high selectivities, despite considerable reduction of ionophore and ion-exchanger amount introduced to the membrane. To be able to prepare ion-selective membranes using this approach, a method for quantification of ionophore and ion-exchanger introduced into microspheres is required. In this work a novel method utilizing high performance liquid chromatography (HPLC) with DAD or FLD detection is proposed. Incorporation of ionophore and ion-exchanger into the microspheres was achieved either by absorption into ready spheres or in course of photopolymerization of polymeric beads. The obtained results have proven that both procedures led to incorporation of ionophore/ion-exchanger into polymeric spheres, however, the content of the compounds in the spheres post process is different from their ratio in solution from which they had been introduced. These effects need to be considered/compensated while preparing microspheres containing ion-selective membranes. As a model system poly(n-butyl acrylate) spheres, silver selective ionophore and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate were chosen, resulting ultimately in silver-selective electrodes., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Internal solution free ion-selective electrodes were prepared applying for the first time gold nanoparticles as a solid contact layer. The presence of a layer of gold nanoparticles stabilized with aliphatic thiols at the back side of the membrane resulted in highly stable potentiometric responses of the sensors, good selectivities and close to Nernstian slopes. Electrochemical studies have confirmed that the applied material is effectively working as capacitive solid contact, yielding high stability sensors., (Copyright © 2011 Elsevier B.V. All rights reserved.)

A new method of quantitative incorporation of primary cations into ion-selective membrane by means of galvanostatic cathodic polarization/conditioning, before measurement step, was proposed and tested on the example of potassium-selective electrode with ionophore - valinomycin in poly(vinyl chloride) based membrane and with polypyrrole solid contact. Open circuit potential values recorded after polarization can be quantitatively explained by changes of primary cations and ionophore concentration in the surface part of the membrane. The influence of potassium ions concentration in the membrane (in relation to ion exchange sites amount) on the shape of potentiometric calibration plots was also observed. Improved characteristics, with extended linear range, can be obtained for membrane of minor loading with primary cations (around 25%), the responses are relatively stable in course of following calibrations., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Comparison of potentials stability of different types of solid contact lead selective electrodes is presented. Conducting polymer based sensors (hydrophilic and conducting - poly(3,4-ethylenedioxythiophene) or hydrophobic and semiconducting-polyoctylthiophene) were studied in parallel with coated wire and hydrogel (poly(hydroxyethylmethacrylate)) contact electrodes. The within day and between days potential stability was compared, highlighting the effect of sensor storing conditions. The obtained results clearly demonstrate that different conclusions on stability of sensors' potential can be drawn depending on experimental protocol applied. Polyoctylthiophene based contacts show superior within day stability with no influence of dry storage. On the other hand, a chronopotentiometric method of stability evaluation clearly prefers poly(3,4-ethylenedioxythiophene) based sensors, pointing to smallest resistance and polarizability. It is clearly shown that the choice of experimental conditions applied to test stability can favor particular type of contact used. The inductively coupled plasma mass spectrometry with laser ablation (LA-ICP-MS) experiments conducted for different arrangements tested has shown that for poly(3,4-ethylenedioxythiophene) and poly(hydroxyethylmethacrylate) type contacts longer contact time with lead(II) solution results in changes in the elemental composition of the transducer layer. On the other hand, in line with high stability observed under potentiometric conditions, no changes were seen for polyoctylthiophene based transducer., (Copyright 2010 Elsevier B.V. All rights reserved.)

Poly(n-butyl acrylate) membranes for potentiometric ion-selective electrodes were developed and studied on example of lead-selective sensors. A novel approach resulting in Nernstian responses of tested sensor was proposed. Introduction of 5% (w/w) hydroxyethyl methacrylate into n-butyl acrylate moiety resulted in significant improvement of sensor analytical parameters. For the latter membrane material linear responses were obtained within lead activities range from 10(-2) to 10(-9) mol/dm(3), while for poly(n-butyl acrylate) based membranes pretreated in the same manner super-Nernstian behavior was obtained in a parallel experiment. Electrochemical impedance spectroscopy studies did not reveal significant differences between these two membranes, also similar lead ions diffusion coefficients were determined using inductively coupled plasma mass spectrometry with laser ablation.The difference between two kinds of membranes was found to concern higher Pb(II) ions contents in the surface part of the membrane with hydroxyethyl methacrylate, resulting in balanced Pb ions fluxes from/to the membrane.

A simple procedure of preparing low cost, planar and disposable reference electrodes for potentiometric applications is presented. This method is essentially the same as used for obtaining all-plastic ion-selective electrodes and thus promising for simple fabrication of complete cells. Commercially available aqueous dispersion of poly(3,4-ethylenedioxythiophene) doped by poly(4-styrenesulfonate) ions (PEDOT-PSS, Baytron P) is simply cast on a non-conducting plastic support (transparent foil for laser printers). This layer is covered by a non-selective poly(vinyl chloride) based membrane containing solid AgCl and KCl, added to obtain a stable potential. The conducting polymer layer plays a double role, of electrical contact and ion-to-electron transducer, enhancing the potential stability. The reference electrodes obtained exhibit independence of the kind and concentration of electrolyte applied as well as very low sensitivity to interferences: redox reactants and H+ ions; they are also characterized by both potential stability and low polarisability, sufficient for potentiometric applications. Cells of plastic electrodes (indicator and reference ones) are tested using an arrangement with Pb2+ or Ca2+ selective sensors. Potentiometric characteristic of such cells is satisfactory, well comparable with that using a classical electrode arrangement.

Conducting polymer (CP) films, used as ion-sensing membranes under open circuit potentiometric conditions, are usually characterised with rather high detection limit, in the range of 10(-4)-10(-5)moldm(-3). This effect is unfavourable, not only from the point of view of CP applications in potentiometry as ion sensitive membranes, but also when these materials are used as ion-to-electron transducers (solid contacts) for ion-selective electrodes. The theoretical considerations presented underline the crucial role of spontaneous processes of polymer charging/discharging-the source of observed high detection limit of sensors comprising CP layer under zero current conditions. Although the mechanism of occurring process is different from that observed for plastic, solvent polymeric based ion-selective electrodes, the ultimate result-alteration of activity of electrolyte at the membrane/solution interface leading to elevation of the detection limit-is the same. The method of estimation of parameters characterising spontaneous charge transfer processes is presented. The values obtained can be used to calculate the resulting polymer/solution interface activity of electrolyte ions, thus the detection limit of CP membrane can be theoretically predicted. A method of lowering of the detection limit of conducting polymer membranes, applying galvanostatic polarisation to compensate the spontaneous process of polymer charging/discharging, is presented. The experimental results obtained for poly(pyrrole), poly(N-methylpyrrole) and poly(3,4-ethylenedioxythiophene) are in good accordance with predictions of the presented model.