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Sprinkle formulations represent an interesting genre of medicinal products. A frequent problem, however, is the need to mask the unpleasant taste of these drug substances. In the present work, we propose the use of a novel sensor array based on solid-state ion-selective electrodes to evaluate the taste-masking efficiency of rosuvastatin (ROS) sprinkle formulations. Eight Multiple Unit Pellet Systems (MUPSs) were analyzed at two different doses (API_50) and (API_10), as well as pure Active Pharmaceutical Ingredient (API) as a bitter standard. Calcium phosphate-based starter pellets were coated with the mixture containing rosuvastatin. Some of them were additionally coated with hydroxypropyl methylcellulose, which was intended to separate the bitter substance and prevent it from coming into contact with the taste buds. The sensor array consisted of 16 prepared sensors with a polymer membrane that had a different selectivity towards rosuvastatin calcium. The main analytical parameters (sensitivity, selectivity, response time, pH dependence of potential, drift of potential, lifetime) of the constructed ion-selective electrodes sensitive for rosuvastatin were determined. The signals from the sensors array recorded during the experiments were processed using Principal Component Analysis (PCA). The results obtained, i.e., the chemical images of the pharmaceutical samples, indicated that the electronic tongue composed of the developed solid-state electrodes provided respective attributes as sensor signals, enabling both of various kinds of ROS pellets to be distinguished and their similarity to ROS bitterness standards to be tested. [ABSTRACT FROM AUTHOR]

Abstract Tulathromycin (TUL) is a widely used veterinary antibiotic for treating bovine and porcine respiratory infections. Consuming animal-derived food contaminated with this medication may jeopardize human health. This work adopted the first portable potentiometric platform for direct TUL sensing in pharmaceutical and food products. The sensor employed a plasticized PVC membrane on a glassy carbon electrode doped with calix[6]arene and multi-walled carbon nanotubes (MWCNT) in a single solid contact layer for selective binding and signal stability. Characterization via scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) confirmed the material’s integrity. The MWCNT-based sensor produced a stable Nernstian response (1.0 × 10−7 to 1.0 × 10−3 M) and a limit of detection (LOD) of 9.76 × 10–8 M with instantaneous response (8 ± 2 s). IUPAC validation revealed high selectivity for TUL against interfering ions, minimal drift (0.6 mV/h), and functionality over a broad pH range (2.0–7.0), allowing direct application to dosage form, spiked milk, and liver samples. Eco-Scale, AGREE, and Whiteness assessment proved the method's ecological sustainability, economic viability, and practical feasibility, surpassing traditional approaches. Graphical Abstract

Tulathromycin (TUL) is a widely used veterinary antibiotic for treating bovine and porcine respiratory infections. Consuming animal-derived food contaminated with this medication may jeopardize human health. This work adopted the first portable potentiometric platform for direct TUL sensing in pharmaceutical and food products. The sensor employed a plasticized PVC membrane on a glassy carbon electrode doped with calix[6]arene and multi-walled carbon nanotubes (MWCNT) in a single solid contact layer for selective binding and signal stability. Characterization via scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) confirmed the material's integrity. The MWCNT-based sensor produced a stable Nernstian response (1.0 × 10−7 to 1.0 × 10−3 M) and a limit of detection (LOD) of 9.76 × 10–8 M with instantaneous response (8 ± 2 s). IUPAC validation revealed high selectivity for TUL against interfering ions, minimal drift (0.6 mV/h), and functionality over a broad pH range (2.0–7.0), allowing direct application to dosage form, spiked milk, and liver samples. Eco-Scale, AGREE, and Whiteness assessment proved the method's ecological sustainability, economic viability, and practical feasibility, surpassing traditional approaches. [ABSTRACT FROM AUTHOR]

Ion-selective electrodes for tetrachloroaurate(III) have been developed for potentiometric monitoring of the reduction reaction of tetrachloroaurate(III). Three different plasticized polyvinyl chloride membranes containing tridodecymethylammonium chloride as an anion exchanger were investigated. These membranes differ in the plasticizer used, either 2-nitrophenyl octyl ether (NPOE) or tricresyl phosphate (TCP) or bis-(2-ethylhexyl) sebacate (DOS). The potentiometric response of the electrodes to the tetrachloroaurate(III) concentration was studied by two methods. In the first method, commonly used in the calibration of ion-selective electrodes, successive tetrachloroaurate(III) concentration increments were used and the potential was allowed to stabilize after each concentration step. The second method was developed to mimic the tetrachloroaurate(III) reduction reaction in which there is a continuous decrease in the concentration of tetrachloroaurate(III). This was achieved by continuously diluting an initial concentration of tetrachloroaurate(III) by pumping a diluent solution while keeping the sample volume constant. This method gave an excellent linear response to the tetrachloroaurate(III) concentration. The calibrated electrodes were used for the potentiometric monitoring of the kinetics of a newly observed reaction: the reduction of tetrachloroaurate(III) by hydroxylamine catalyzed by iodide. A mechanism for this reaction is proposed on the basis of the experimental results obtained. [ABSTRACT FROM AUTHOR]

Graphene oxide (GO) was used as an ion-to-electron transducer for all-solid-state nitrate electrodes based on an alkyl ammonium salt as the sensing element. Commercially available carbon screen-printed electrodes modified with GO were used as conductive substrates, whose morphology and distribution along the surface were evaluated by scanning electron microscopy and Raman spectroscopy. The potentiometric performance of the GO-based electrodes revealed a Nernstian slope of −53.5 ± 2.0 mV decade−1 (R2 = 0.9976 ± 0.0015) in the range from 3.0 × 10−6 to 10−2 M and a lower limit of detection of 1.9 × 10−6 M. An impressive reproducibility between equally prepared electrodes (n = 15) was demonstrated by a variation of <6% for the calibration parameters. Constant current chronopotentiometry and water layer tests were used to evaluate the potential signal stability, providing similar performance to previously published works with graphene-based ion-selective electrodes. Notably, the GO-based sensors showed the absence of a water layer, a long-term drift of 0.3 mV h−1, and a stable performance (LOD and sensitivity) over 3 months. The applicability of the proposed sensors was demonstrated in determining nitrate levels in water samples with great accuracy, yielding recovery values from 87.8 to 107.9%, and comparable (p > 0.05) results to a commercial nitrate probe. These findings demonstrate the use of GO as an alternative ion-to-electron transducer for the fabrication of all-solid-state potentiometric electrodes. [ABSTRACT FROM AUTHOR]

Plant-available nitrogen, often in the form of nitrate, is an essential nutrient for plant growth. However, excessive nitrate in the environment and watershed has harmful impacts on natural ecosystems and consequently human health. A distributed network of nitrate sensors could help to quantify and monitor nitrogen in agriculture and the environment. Here, we have developed fully printed potentiometric nitrate sensors and characterized their sensitivity and selectivity to nitrate. Each sensor comprises an ion-selective electrode and a reference electrode that are functionalized with polymeric membranes. The sensitivity of the printed ion-selective electrodes was characterized by measuring their potential with respect to a commercial silver/silver chloride reference electrode in varying concentrations of nitrate solutions. The sensitivity of the printed reference electrodes to nitrate was minimized with a membrane containing polyvinyl butyral (PVB), sodium chloride, and sodium nitrate. Selectivity studies with sulphate, chloride, phosphate, nitrite, ammonium, calcium, potassium, and magnesium showed that high concentrations of calcium can influence sensor behavior. The printed ion-selective and reference electrodes were combined to form a fully printed sensor with sensitivity of -48.0 ± 3.3 mV/dec between 0.62 and 6200 ppm nitrate in solution and -47 ± 4.1 mV/dec in peat soil.

The maintenance of ion balance in closed hydroponic solutions is essential to improve the crop quality and recycling efficiency of nutrient solutions. However, the absence of robust ion sensors for key ions such as P and Mg and the coupling of ions in fertilizer salts render it difficult to effectively manage ion-specific nutrient solutions. Although ion-specific dosing algorithms have been established, their effectiveness has been inadequately explored. In this study, a decision-tree-based dosing algorithm was developed to calculate the optimal volumes of individual nutrient stock solutions to be supplied for five major nutrient ions, i.e., NO3, K, Ca, P, and Mg, based on the concentrations of NO3, K, and Ca and remaining volume of the recycled nutrient solution. In the performance assessment based on five nutrient solution samples encompassing the typical concentration ranges for leafy vegetable cultivation, the ion-selective electrode array demonstrated feasible accuracies, with root mean square errors of 29.5, 10.1, and 6.1 mg·L-1 for NO3, K, and Ca, respectively. In a five-step replenishment test involving varying target concentrations and nutrient solution volumes, the system formulated nutrient solutions according to the specified targets, exhibiting average relative errors of 10.6 ± 8.0%, 7.9 ± 2.1%, 8.0 ± 11.0%, and 4.2 ± 3.7% for the Ca, K, and NO3 concentrations and volume of the nutrient solution, respectively. Furthermore, the decision tree method helped reduce the total fertilizer injections and carbon emissions by 12.8% and 20.6% in the stepwise test, respectively. The findings demonstrate that the decision-treebased dosing algorithm not only enables more efficient reuse of nutrient solution compared to the existing simplex method but also confirms the potential for reducing carbon emissions, indicating the possibility of sustainable agricultural development. [ABSTRACT FROM AUTHOR]

With the recent development in the field of electronics, it has made possible to continuous monitor health of patients and elderly and even of normal person. Since many years we are using bloodbased diagnosis for diagnosis of various health conditions and diseases. However, recent research done by many researchers shows that there are other potential biomarkers such as, sweat which can provide diagnosis of various health conditions and diseases. Sodium and chloride concentration in sweat provides status of hydration status in human body. Here we have designed a health monitoring device based on sweat analysis using different types of electrochemical sensors. Ion-selective electrodes for Na+ and Cl- are used which gives details about a person's hydration status and a glucose sensor is also used to measure the sweat glucose levels. The sensors are calibrated for artificial sweat solutions with different concentrations of Na+, Cl- and glucose. On body testing is done to confirm functionality of designed system for sweat analysis. The system is compact so can be used as a wearable device that is capable of continuously monitoring and wirelessly transmitting sensor data to the personal computer or smartphone. [ABSTRACT FROM AUTHOR]

In this paper, ion-selective electrodes sensitive to copper(II) ions are presented, in which new composite, synthesized from copper(II) oxide nanoparticles (CuONPs) and multi-walled carbon nanotubes (MWCNTs), was used as a solid contact. For comparison, electrodes obtained using separate components of the nanocomposite, i.e., CuONPs and MWCNTs, as well as unmodified electrodes, were also studied. The tested nanomaterials have been applied in two ways: as an intermediate layer placed between the ion-sensitive membrane and the internal electrode, and as an additional component of the ion-selective membrane mixture. To investigate the influence of the electrode's structure modification, the selected analytical parameters obtained by potentiometric measurements (slope, linearity range, detection limit, potential stability, and reversibility) and electrochemical impedance spectroscopy measurements (membrane resistance and charge transfer resistance as well as double layer capacitance) were determined and compared. It was found that the use of all nanomaterials improves the properties of the electrodes, with the effect being the strongest for electrodes modified with the CuO-MWCNTs nanocomposite. The nanocomposite-based electrodes, both those with an intermediate layer and those with a nanocomposite-modified membrane, showed a Nernstian slope of the characteristic, a wider working range and a lower detection limit compared to unmodified electrodes. Moreover, application of all nanomaterials, especially nanocomposite resulted in improvement of both, stability and reversibility of the sensor potential. Modification of the electrodes did not make them sensitive to changing external measurement conditions (lighting, presence of gasses, redox potential). The electrode with the best parameters (based on nanocomposite) was successfully used to determine the Cu2+ ions content in tap water and mineral water, obtaining satisfactory results. [ABSTRACT FROM AUTHOR]

Ion-selective electrodes for tetrachloroaurate(III) have been developed for potentiometric monitoring of the reduction reaction of tetrachloroaurate(III). Three different plasticized polyvinyl chloride membranes containing tridodecymethylammonium chloride as an anion exchanger were investigated. These membranes differ in the plasticizer used, either 2-nitrophenyl octyl ether (NPOE) or tricresyl phosphate (TCP) or bis-(2-ethylhexyl) sebacate (DOS). The potentiometric response of the electrodes to the tetrachloroaurate(III) concentration was studied by two methods. In the first method, commonly used in the calibration of ion-selective electrodes, successive tetrachloroaurate(III) concentration increments were used and the potential was allowed to stabilize after each concentration step. The second method was developed to mimic the tetrachloroaurate(III) reduction reaction in which there is a continuous decrease in the concentration of tetrachloroaurate(III). This was achieved by continuously diluting an initial concentration of tetrachloroaurate(III) by pumping a diluent solution while keeping the sample volume constant. This method gave an excellent linear response to the tetrachloroaurate(III) concentration. The calibrated electrodes were used for the potentiometric monitoring of the kinetics of a newly observed reaction: the reduction of tetrachloroaurate(III) by hydroxylamine catalyzed by iodide. A mechanism for this reaction is proposed on the basis of the experimental results obtained.

Graphene oxide (GO) was used as an ion-to-electron transducer for all-solid-state nitrate electrodes based on an alkyl ammonium salt as the sensing element. Commercially available carbon screen-printed electrodes modified with GO were used as conductive substrates, whose morphology and distribution along the surface were evaluated by scanning electron microscopy and Raman spectroscopy. The potentiometric performance of the GO-based electrodes revealed a Nernstian slope of −53.5 ± 2.0 mV decade−1 (R2 = 0.9976 ± 0.0015) in the range from 3.0 × 10−6 to 10−2 M and a lower limit of detection of 1.9 × 10−6 M. An impressive reproducibility between equally prepared electrodes (n = 15) was demonstrated by a variation of −1, and a stable performance (LOD and sensitivity) over 3 months. The applicability of the proposed sensors was demonstrated in determining nitrate levels in water samples with great accuracy, yielding recovery values from 87.8 to 107.9%, and comparable (p > 0.05) results to a commercial nitrate probe. These findings demonstrate the use of GO as an alternative ion-to-electron transducer for the fabrication of all-solid-state potentiometric electrodes.

Potentiometric ion-selective electrode (ISE) sensors are powerful electrochemical tools used in various applications in different fields, including the biological, clinical, and environmental fields, owing to their high selectivity, sensitivity, simplicity, and versatility. This review highlights recent advancements in ionophore-based polymeric ISE sensors over the past five years, with a particular focus on progress at the micro- and nanoscales. After discussing the conventional ISE configuration and its general operational principles, we explore the notable advancements in terms of the key ion-selective membrane components, such as ionophores, and other techniques combined with ISEs. These advancements have significantly improved the sensing performances and expanded the practical applications. We also examine the progress in the field of miniaturized solid-contact microelectrodes and the incorporation of novel functional materials for efficient ion-to-electron transduction. Miniaturized solid-state ISEs provide low limits of detection with reduced sample volume requirements, extended stability, and rapid response times. When combined with scanning electrochemical microscopy, ion-selective microelectrodes enable highly spatially resolved ion analyses. The integration of solid-contact ISEs into compact, portable, wearable devices has advanced the field of wearable on-body ISE sensors. Finally, we briefly introduce the development of ion-selective optode sensors as promising optical sensors based on ionophores that are particularly advantageous for cellular imaging.

Potentiometric sensors are the largest and most commonly used group of electrochemical sensors. Among them, ion-selective electrodes hold a prominent place. Since the end of the last century, their re-development has been observed, which is a consequence of the introduction of solid contact constructions, i.e., electrodes without an internal electrolyte solution. Research carried out in the field of potentiometric sensors primarily focuses on developing new variants of solid contact in order to obtain devices with better analytical parameters, and at the same time cheaper and easier to use, which has been made possible thanks to the achievements of material engineering. This paper presents an overview of new materials used as a solid contact in ion-selective electrodes over the past several years. These are primarily composite and hybrid materials that are a combination of carbon nanomaterials and polymers, as well as those obtained from carbon and polymer nanomaterials in combination with others, such as metal nanoparticles, metal oxides, ionic liquids and many others. Composite materials often have better mechanical, thermal, electrical, optical and chemical properties than the original components. With regard to their use in the construction of ion-selective electrodes, it is particularly important to increase the capacitance and surface area of the material, which makes them more effective in the process of charge transfer between the polymer membrane and the substrate material. This allows to obtain sensors with better analytical and operational parameters. Brief characteristics of electrodes with solid contact, their advantages and disadvantages, as well as research methods used to assess their parameters and analytical usefulness were presented. The work was divided into chapters according to the type of composite material, while the data in the table were arranged according to the type of ion. Selected basic analytical parameters of the obtained electrodes have been collected and summarized in order to better illustrate and compare the achievements that have been described till now in this field of analytical chemistry, which is potentiometry. This comprehensive review is a compendium of knowledge in the research area of functional composite materials and state-of-the-art SC-ISE construction technologies. [ABSTRACT FROM AUTHOR]

Electrochemical sensors have the ability to convert the electrochemical reaction that occurs between the analyte and the electrode into a useful signal. Potentiometric sensors, ion-selective electrodes, an important member of the electrochemical sensor family, have been the focus of much research for almost a century. Their constant development and combination with the development of other scientific and technological fields have given them a wide range of applications. Properties of ion-selective electrodes, such as simplicity of method, low cost, small sensor size, fast response, and reliability, have made them valuable competitors of other methods for determining the concentration of analytes in different real samples with minimal or no pretreatment of the samples. Considering the wide distribution and great importance of iron(III) cations in the human body and environment, there is a great need to develop analytical tools for their rapid and efficient determination. This paper, presents different literature sources dealing with the development of potentiometric sensors for the determination of iron(III) cations, focusing on scientific papers published in the last decade. The active centre of the sensor, its linear dynamic range, the limit of detection, and the change in potential depending on the change in analyte concentration are shown. It has been found that Fe3+ cations can be determined successfully in numerous real samples, such as pharmaceutical preparations, biological samples, different water samples (drinking, waste, mineral...), food products such as green and black tea, etc. Thanks to the wide linear range, low detection limits, and a wide range of real samples in which they can be applied, ion-selective electrodes are promising candidates for replacing some more sophisticated methods for the determination of iron(III) cations. [ABSTRACT FROM AUTHOR]

Nitrogen is a vital ingredient for plant development and growth. It is one of the most crucial indicators of soil fertility and crop growth conditions. For the monitoring of nitrogen loss patterns and the development of crop nitrogen fertilizer application strategies, an accurate determination of soil nitrogen concentration can be a valuable source of information. For the advancement of precision agriculture and the preservation of the natural ecological environment, an accurate, quick, and low-cost determination of soil nitrogen content and its variations is essential. This paper systematically analyzes and summarizes soil nitrogen detection methods by compiling and analyzing the relevant literature, comparing the advantages and disadvantages of various methods, and concluding with a discussion of the most significant challenges and future research trends in this field. This study provides a helpful resource for understanding the current status, application constraints, and future developments of nitrogen-sensing technologies in precision agriculture. [ABSTRACT FROM AUTHOR]

The evaluation of the biogenic amines (BAs) profile of different types of craft beers is herein presented. A previously developed and validated analytical method based on ion-pair chromatography coupled with potentiometric detection was used to determine the presence of 10 BAs. Good analytical features were obtained for all amines regarding linearity (R2 values from 0.9873 ± 0.0015 to 0.9973 ± 0.0015), intra- and inter-day precision (RSD lower than 6.9% and 9.7% for beer samples, respectively), and accuracy (recovery between 83.2–108.9%). Detection and quantification limits range from 9.3 to 60.5 and from 31.1 to 202.3 µg L−1, respectively. The validated method was applied to the analysis of four ale beers and one lager craft beer. Ethylamine, spermidine, spermine, and tyramine were detected in all analyzed samples while methylamine and phenylethylamine were not detected. Overall, pale ale beers had a significantly higher total content of BAs than those found in wheat pale and dark samples. A general least square regression model showed a good correlation between the total content of BAs and the brewing process, especially for Plato degree, mashing, and fermentation temperatures. Knowledge about the type of ingredients and manufacturing processes that contribute to higher concentrations of these compounds is crucial to ensuring consumer safety. [ABSTRACT FROM AUTHOR]

Epilepsy is a chronic neurological disease and its treatment requires the use of anti-epileptic drugs. The determination of anti-epileptic drugs in pharmaceutical and biological samples is carried out using various analytical methods. Potentiometric methods, which have a very important place in electroanalytical chemistry, are used extensively in the determination of various drugs in biological and pharmaceutical samples. In this study, we reviewed potentiometry-based sensors developed for the determination of anti-epileptic drug molecules in biological and pharmaceutical samples. [ABSTRACT FROM AUTHOR]

Epilepsy is a chronic neurological disease and its treatment requires the use of anti–epileptic drugs. The determination of anti–epileptic drugs in pharmaceutical and biological samples is carried out using various analytical methods. Potentiometric methods, which have a very important place in electroanalytical chemistry, are used extensively in the determination of various drugs in biological and pharmaceutical samples. In this study, we reviewed potentiometry–based sensors developed for the determination of anti–epileptic drug molecules in biological and pharmaceutical samples.

This work is a mini-review highlighting the relevance of the θ metallabis(dicarbollide) [3,3′-Co(1,2-C2B9H11)2]− with its peculiar and differentiating characteristics, among them the capacity to generate hydrogen and dihydrogen bonds, to generate micelles and vesicles, to be able to be dissolved in water or benzene, to have a wide range of redox reversible couples and many more, and to use these properties, in this case, for producing potentiometric membrane sensors to monitor amine-containing drugs or other nitrogen-containing molecules. Sensors have been produced with this monoanionic cluster [3,3′-Co(1,2-C2B9H11)2]−. Other monoanionic boron clusters are also discussed, but they are much fewer. It is noteworthy that most of the electrochemical sensor species incorporate an ammonium cation and that this cation is the species to be detected. Alternatively, the detection of the borate anion itself has also been studied, but with significantly fewer examples. The functions of the borate anion in the membrane are different, even as a doping agent for polypyrrole which was the conductive ground on which the PVC membrane was deposited. Apart from these cases related to closo borates, the bulk of the work has been devoted to sensors in which the θ metallabis (dicarbollide) [3,3′-Co(1,2-C2B9H11)2]− is the key element. The metallabis (dicarbollide) anion, [3,3′-Co(1,2-C2B9H11)2]−, has many applications; one of these is as new material used to prepare an ion-pair complex with bioactive protonable nitrogen containing compounds, [YH]x[3,3′-Co(1,2-C2B9H11)2]y as an active part of PVC membrane potentiometric sensors. The developed electrodes have Nernstian responses for target analytes, i.e., antibiotics, amino acids, neurotransmitters, analgesics, for some decades of concentrations, with a short response time, around 5 s, a good stability of membrane over 45 days, and an optimal selectivity, even for optical isomers, to be used also for real sample analysis and environmental, clinical, pharmaceutical and food analysis. [ABSTRACT FROM AUTHOR]

Many healthcare and environmental monitoring devices use electrochemical techniques to detect and quantify analytes. With sensors progressively becoming smaller—particularly in point‐of‐care (POC) devices and wearable platforms—it creates the opportunity to operate them using less energy than their predecessors. In fact, they may require so little power that can be extracted from the analyzed fluids themselves, for example, blood or sweat in case of physiological sensors and sources like river water in the case of environmental monitoring. Self‐powered electrochemical sensors (SPES) can generate a response by utilizing the available chemical species in the analyzed liquid sample. Though SPESs generate relatively low power, capable devices can be engineered by combining suitable reactions, miniaturized cell designs, and effective sensing approaches for deciphering analyte information. This review details various such sensing and engineering approaches adopted in different categories of SPES systems that solely use the power available in liquid sample for their operation. Specifically, the categories discussed in this review cover enzyme‐based systems, battery‐based systems, and ion‐selective electrode‐based systems. The review details the benefits and drawbacks with these approaches, as well as prospects of and challenges to accomplishing them. [ABSTRACT FROM AUTHOR]

Monitoring potassium ion (K + ) concentration is essential in veterinary medicine, particularly for preventing hypokalemia in dairy cows, which can severely impact their health and productivity. While traditional laboratory methods like atomic absorption spectrometry are accurate, they are also time-consuming and require complex sample preparation. Ion-selective electrodes (ISEs) provide an alternative that is faster and more suitable for field measurements, but their performance is often compromised under variable temperature conditions, leading to inaccuracies. To address this, we developed a novel screen-printed ion-selective electrode (SPE) with hydrophobic Ti 3 C 2 Mxene and gold nanoparticles (AuNPs), integrated with a temperature sensor. This design improves stability and accuracy across fluctuating temperatures by preventing water layer formation and enhancing conductivity. The sensor was validated across temperatures from 5 °C to 45 °C, achieving a linear detection range of 10 - ⁵ to 10 -1 M and a response time of approximately 15 s. It also demonstrated excellent repeatability, selectivity, and stability, making it a robust tool for K + monitoring in complex environments. This advancement could lead to broader applications in other temperature-sensitive analytical fields.

The aim of this paper is to investigate the influence of the molecules of conducting polymers on the properties of potentiometric sensors. Two conducting polymers, poly(3-octylthiophene-2,5-diyl) and poly(3,4-ethylene-1,4-dioxythiophene), were compared in the context of the design of ion-selective electrodes. This study offers a comparison of the most popular conducting polymers in the context of the design of potentiometric sensors. Firstly, the properties of both materials, such as their microstructure, electrical performance, wettability, and thermic properties, were examined. Subsequently, conducting polymers were applied as transducer layers in potassium-selective sensors. The properties of both groups of sensors were evaluated using the potentiometry method. Research has shown that the presence of poly(3-octylthiophene-2,5-diyl) (POT) in the transducer layer makes it superhydrophobic, leading to a long lifetime of sensors. On the other hand, the addition of poly(3,4-ethylene-1,4-dioxythiophene) polystyrene sulfonate (PEDOT:PSS) allows for the enhancement of electrical capacitance parameter values, which beneficially influence the stability of the potentiometric response of sensors. Both examined conducting polymers turned out to be perfect materials for transducer layers in potentiometric sensors, each being responsible for enhancing different properties of electrodes.

Abstract Many healthcare and environmental monitoring devices use electrochemical techniques to detect and quantify analytes. With sensors progressively becoming smaller—particularly in point‐of‐care (POC) devices and wearable platforms—it creates the opportunity to operate them using less energy than their predecessors. In fact, they may require so little power that can be extracted from the analyzed fluids themselves, for example, blood or sweat in case of physiological sensors and sources like river water in the case of environmental monitoring. Self‐powered electrochemical sensors (SPES) can generate a response by utilizing the available chemical species in the analyzed liquid sample. Though SPESs generate relatively low power, capable devices can be engineered by combining suitable reactions, miniaturized cell designs, and effective sensing approaches for deciphering analyte information. This review details various such sensing and engineering approaches adopted in different categories of SPES systems that solely use the power available in liquid sample for their operation. Specifically, the categories discussed in this review cover enzyme‐based systems, battery‐based systems, and ion‐selective electrode‐based systems. The review details the benefits and drawbacks with these approaches, as well as prospects of and challenges to accomplishing them.

The valence state of copper and the composition of the surface of the membranes of film electrodes with the composition CuI–AgI–As2Se3 are studied. Using X-ray photoelectron spectroscopy, it is shown that in CuI–AgI–As2Se3 chalcogenide films the copper atom is in the Cu(I) state. Auger-electron spectroscopy is used to prove the applicability of the modified surface layer model to explain the ion sensitivity of chalcogenide film sensors. [ABSTRACT FROM AUTHOR]

Potentiometric sensors are the largest and most commonly used group of electrochemical sensors. Among them, ion-selective electrodes hold a prominent place. Since the end of the last century, their re-development has been observed, which is a consequence of the introduction of solid contact constructions, i.e., electrodes without an internal electrolyte solution. Research carried out in the field of potentiometric sensors primarily focuses on developing new variants of solid contact in order to obtain devices with better analytical parameters, and at the same time cheaper and easier to use, which has been made possible thanks to the achievements of material engineering. This paper presents an overview of new materials used as a solid contact in ion-selective electrodes over the past several years. These are primarily composite and hybrid materials that are a combination of carbon nanomaterials and polymers, as well as those obtained from carbon and polymer nanomaterials in combination with others, such as metal nanoparticles, metal oxides, ionic liquids and many others. Composite materials often have better mechanical, thermal, electrical, optical and chemical properties than the original components. With regard to their use in the construction of ion-selective electrodes, it is particularly important to increase the capacitance and surface area of the material, which makes them more effective in the process of charge transfer between the polymer membrane and the substrate material. This allows to obtain sensors with better analytical and operational parameters. Brief characteristics of electrodes with solid contact, their advantages and disadvantages, as well as research methods used to assess their parameters and analytical usefulness were presented. The work was divided into chapters according to the type of composite material, while the data in the table were arranged according to the type of ion. Selected basic analytical parameters of the obtained electrodes have been collected and summarized in order to better illustrate and compare the achievements that have been described till now in this field of analytical chemistry, which is potentiometry. This comprehensive review is a compendium of knowledge in the research area of functional composite materials and state-of-the-art SC-ISE construction technologies.

The paper describes research on ion-selective electrodes sensitive to copper(II) ions, in which Schiff bases and their Cu(II) complexes were used as active components of ion-selective membranes. The Schiff bases differ in the type and amount of substituents in the benzene ring and/or in the aliphatic chain. A multi-stage process of optimization of the ion-selective membrane composition was carried out. Apart from the selection of the best ionophore, the influence of the type of plasticizer and lipophilic salt as well as the active substance content was also investigated. The best results were obtained for N,N′-bis(5-bromo-2-hydroxy-3-methoxybenzylidene)2-hydroxypropylene-1,3-diamine and its dinuclear copper(II) complex. The ion-selective membrane composition was optimized, resulting in obtaining electrodes with a very good slope of 29.68 mV/decade in a wide measuring range 1 × 10−6 – 1 × 10−1 mol L−1 and good potential stability and selectivity. The electrodes could successfully work in the pH range of 2.4–5.5 for a minimum period of 2 months. [ABSTRACT FROM AUTHOR]

The determination of chlortetracycline, doxycycline, oxytetracycline, and tetracycline in milk samples by HPLC coupled to a cucurbit[8]uril-based potentiometric sensor is herein presented. The new tetracycline-selective electrode is based on a polymeric membrane incorporating cucurbit[8]uril as a macrocyclic host, potassium tetrakis(p-chlorophenyl) borate as an ionic additive, 2-fluorophenyl 2-nitrophenyl ether as a plasticizer, and multi-walled carbon nanotubes as nanostructured materials. A microfluidic wall-jet flow-cell is implemented as a potentiometric detector after chromatographic separation by a C8 column using a gradient mobile phase of sulphuric acid and acetonitrile. The proposed methodology was validated following International Council for Harmonisation of Technical Requirements for Pharmaceuticals for Human Use (ICH) and European Union (EU) guidelines. Linear regression models provided R2 in the range from 0.9973 ± 0.0026 to 0.9987 ± 0.0012 for all tetracycline antibiotics. The limits of detection and quantification ranged from 13.3 to 46.0 μg L−1 and 44.4 to 92.1 μg L−1, respectively. Precision intra-day, inter-day, and inter-electrode showed relative standard deviation values lower than 12.5%, 13.5%, and 12.9%, respectively. Accuracy was assessed by analysis of spiked milk samples around the maximum residue limit, yielding recovery values in the range from 81.3 to 108.5%. The simple, sensitive, cost-effective, and reliable HPLC-ion-selective electrode method justifies its use as a competitive alternative for the analysis of tetracycline residues in the food quality control sector. [ABSTRACT FROM AUTHOR]

This mini review briefly describes (i) literature data on the non-zero current measurements with ionophore-based ion-selective electrodes (ISEs) aimed at fundamental studies of the mechanism of their potentiometric response, and (ii) the data on the possibilities of analytical applications of ISEs in voltametric and constant potential chronoamperometric/coulometric modes, in particular the K+ ion assay in blood serum with the sensitivity of 0.1%. A special attention is paid to the basics of voltammetry and chronoamperometry/coulometry with the ionophore-based ISEs, and to how and why these methods differ from the classical voltammetry and coulometry. [ABSTRACT FROM AUTHOR]

In this study, poly(vinly chloride) (PVC) membrane ion–selective electrodes for the determination of zinc(II) ions were prepared using potassium hydrotris(N-tert-butyl-2-thioimidazolyl)borate (L1), 1-[Bis(dimethylamino) methylen]-5-chlorobenzotriazolium-3-oxide hexafluorophosphate (L2), 1,4,8,12-tetraazacyclopentadecane (L3) and tetrabutylthiuram disulphide (L4) ionophores. Based on potentiometric performance properties, the optimum membrane composition was determined as 8.0% tetrabutylthiuram disulphide (L4), 58.0% o–nitrophenyloctylether (o–NPOE), 33.5% PVC and 0.5% potassium tetrakis (p–chlorophenyl) borate (KTpClPB). The electrode exhibits a wide concentration range from 1.0 ​× ​10−5 to 1.0 ​× ​10−1 ​M, and has a detection limit of 6.50 ​× ​10−6 ​M. The proposed electrode has a very quickly response time of 5s, good repeatability and selectivity. In addition, the electrode works in the wide pH range of 5.0–10.0 without being affected by pH changes. Finally, the developed zinc(II)–selective electrode was successfully used for the determination of zinc(II) in a drug sample. [ABSTRACT FROM AUTHOR]

Introduction: Recently, various modes of fluoride varnishes have evolved, each with its own recommended concentration, potentially active ingredients, and flavour, leading to a claim of additional preventive benefits. Differences in fluoride release patterns can potentially enhance or reduce the efficacy of fluoride varnishes. Numerous clinical trials have proven its ability in preventing and arresting dental caries. This study mainly focused on the investigations of the apatite demineralisation process under the effect of different fluoride varnishes by ion-selective electrodes (ISE), in an attempt to comprehend their mechanism in anti-caries. Methods: Four different fluoride varnishes (Fluor Protector S, Duraphat, ClinPro White, MI Varnish) were used to measure their effect on the demineralisation process of the hydroxyapatite (HAP) discs in 60ml pH 4.0 acetic solutions. The HAP discs were treated with these varnishes after 4-hours demineralisation and then immersed back into the same solutions for further demineralisation to observe the effect of the varnishes. Throughout the experiment, the calcium ISE was used to monitor the rate of calcium concentration. Results: The result demonstrated that ClinPro White varnish resulted in the most significant inhibition of demineralisation and signs of probable remineralisation throughout the experiment. Other fluoride varnishes treatment showed the ability to inhibit demineralisation. However, the rate of calcium dissolution was not significantly different from different varnishes. The fact that the ClinPro White showed evidence of remineralisation might be associated with the fact that the varnish contained a source of calcium and phosphate. Conclusion: The fluoride varnishes treatment is shown to be effective in inhibiting the demineralisation of apatite regardless of the difference in fluoride concentration and potentially active ingredients incorporated in some of the fluoride varnishes.

Objective: The aim of this study was to determine the concentration of fluoride ions present in var-ious solvent solutions and compare it to the label amount of fluoride concentration. Material and methods: The gel containing amine fluoride and sodium fluoride was compared to gel containing sodium fluoride only. The solvents used in this study were distilled water, redistilled water, tap water, 0.9% sodium chloride solution and the artificial saliva. The amount of fluoride ion (F -) was determined by the use of fluoride ion-selective electrode. The ANOVA and the Post hoc Tukey’s test were used. The significance level was α = 5%. Results: The differences between F –ion release in various solvents were statistically significant (p < 0.05). The F –ion concentrations measured in both gels’ redistilled water solutions were higher than the label concentration. There was a significant difference in fluo-ride ion release in sodium fluoride only gel solutions. Fluoride ion release was significantly different in combined fluoride gel solutions. Conclusions: Amine fluorides do not interact with other ions pres-ent in the solution, whereas F –ion release from sodium fluoride alters when other ions are dissolved in the same solution. Amine fluorides deliver F -ions for caries prevention more efficiently

In this study, poly(vinly chloride) (PVC) membrane ion–selective electrodes for the determination of zinc(II) ions were prepared using potassium hydrotris(N-tert-butyl-2-thioimidazolyl)borate (L1), 1-[Bis(dimethylamino)methylen]-5-chlorobenzotriazolium-3-oxide hexafluorophosphate (L2), 1,4,8,12-tetraazacyclopentadecane (L3) and tetrabutylthiuram disulphide (L4) ionophores. Based on potentiometric performance properties, the optimum membrane composition was determined as 8.0% tetrabutylthiuram disulphide (L4), 58.0% o–nitrophenyloctylether (o–NPOE), 33.5% PVC and 0.5% potassium tetrakis (p–chlorophenyl) borate (KTpClPB). The electrode exhibits a wide concentration range from 1.0 ​× ​10−5 to 1.0 ​× ​10−1 ​M, and has a detection limit of 6.50 ​× ​10−6 ​M. The proposed electrode has a very quickly response time of 5s, good repeatability and selectivity. In addition, the electrode works in the wide pH range of 5.0–10.0 without being affected by pH changes. Finally, the developed zinc(II)–selective electrode was successfully used for the determination of zinc(II) in a drug sample.

The level of hydrogen ions in sweat is one of the most important physiological indexes for the health state of the human body. As a type of two-dimensional (2D) material, MXene has the advantages of superior electrical conductivity, a large surface area, and rich functional groups on the surface. Herein, we report a type of Ti3C2Tx-based potentiometric pH sensor for wearable sweat pH analysis. The Ti3C2Tx was prepared by two etching methods, including a mild LiF/HCl mixture and HF solution, which was directly used as the pH-sensitive materials. Both etched Ti3C2Tx showed a typical lamellar structure and exhibited enhanced potentiometric pH responses compared with a pristine precursor of Ti3AlC2. The HF-Ti3C2Tx disclosed the sensitivities of −43.51 ± 0.53 mV pH–1 (pH 1–11) and −42.73 ± 0.61 mV pH–1 (pH 11–1). A series of electrochemical tests demonstrated that HF-Ti3C2Tx exhibited better analytical performances, including sensitivity, selectivity, and reversibility, owing to deep etching. The HF-Ti3C2Tx was thus further fabricated as a flexible potentiometric pH sensor by virtue of its 2D characteristic. Upon integrating with a solid-contact Ag/AgCl reference electrode, the flexible sensor realized real-time monitoring of pH level in human sweat. The result disclosed a relatively stable pH value of ~6.5 after perspiration, which was consistent with the ex situ sweat pH test. This work offers a type of MXene-based potentiometric pH sensor for wearable sweat pH monitoring.

The application of polyaniline nanofibers doped with chloride and nitrate ions (PANINFs-Cl and PANINFs-NO3) in potentiometry was described. Both kinds of nanofibers were used as an ion-to-electron transducer in ion-selective electrodes with solid contact (SCISEs). Extensive research on the properties of the nanofibers themselves (SEM, UV–Vis spectroscopy, FTIR) and the constructed electrodes (potentiometric methods, electrochemical impedance spectroscopy) has been carried out. Basic analytical parameters of electrodes containing various nanofibers contents in the ion-selective membrane and with nanofibers as an intermediate layer were determined. It was found that application of PANI nanofibers resulted in improvement of electrode performance (among others, better stability and reversibility of the electrode potential). The obtained sensors were characterized by a high slope of the calibration curve, a wide measuring range and a fast response time. Moreover, they were insensitive to change of redox potential, as well as light and the presence of oxygen in the solution, what is important from a practical point of view. They were also successfully used for nitrate determination in real environmental samples. [ABSTRACT FROM AUTHOR]

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The astrocyte water channel aquaporin-4 (AQP4) regulates extracellular space (ECS) K(+) concentration ([K(+)]e) and volume dynamics following neuronal activation. Here, we investigated how AQP4-mediated changes in [K(+)]e and ECS volume affect the velocity, frequency, and amplitude of cortical spreading depression (CSD) depolarizations produced by surface KCl application in wild-type (AQP4(+/+)) and AQP4-deficient (AQP4(-/-)) mice. In contrast to initial expectations, both the velocity and the frequency of CSD were significantly reduced in AQP4(-/-) mice when compared with AQP4(+/+) mice, by 22% and 32%, respectively. Measurement of [K(+)]e with K(+)-selective microelectrodes demonstrated an increase to ∼35 mM during spreading depolarizations in both AQP4(+/+) and AQP4(-/-) mice, but the rates of [K(+)]e increase (3.5 vs. 1.5 mM/s) and reuptake (t1/2 33 vs. 61 s) were significantly reduced in AQP4(-/-) mice. ECS volume fraction measured by tetramethylammonium iontophoresis was greatly reduced during depolarizations from 0.18 to 0.053 in AQP4(+/+) mice, and 0.23 to 0.063 in AQP4(-/-) mice. Analysis of the experimental data using a mathematical model of CSD propagation suggested that the reduced velocity of CSD depolarizations in AQP4(-/-) mice was primarily a consequence of the slowed increase in [K(+)]e during neuronal depolarization. These results demonstrate that AQP4 effects on [K(+)]e and ECS volume dynamics accelerate CSD propagation.

A new group of carbon nanomaterials modified with poly(3-octylthiophene-2,5-diyl) for solid-contact layers in ion-selective electrodes was obtained. The materials were characterized by scanning electron microscopy and measurement of the contact angle. The modification greatly improved the hydrophobicity of the materials, and the highest contact angle (175°) was obtained for a polymer-modified carbon nanofibers/nanotube nanocomposite. The electrical parameters of the electrodes were determined using the methods of chronopotentiometry and electrochemical impedance spectroscopy. The highest electrical charge capacity was obtained for polymer-modified carbon nanofibers (7.87 mF/cm2). For this material, the lowest detection limit (10−6.2 M) and the best potential reversibility (SD = 0.2 mV) were also obtained in potentiometric measurements.

The evaluation of the biogenic amines (BAs) profile of different types of craft beers is herein presented. A previously developed and validated analytical method based on ion-pair chromatography coupled with potentiometric detection was used to determine the presence of 10 BAs. Good analytical features were obtained for all amines regarding linearity (R2 values from 0.9873 ± 0.0015 to 0.9973 ± 0.0015), intra- and inter-day precision (RSD lower than 6.9% and 9.7% for beer samples, respectively), and accuracy (recovery between 83.2–108.9%). Detection and quantification limits range from 9.3 to 60.5 and from 31.1 to 202.3 µg L−1, respectively. The validated method was applied to the analysis of four ale beers and one lager craft beer. Ethylamine, spermidine, spermine, and tyramine were detected in all analyzed samples while methylamine and phenylethylamine were not detected. Overall, pale ale beers had a significantly higher total content of BAs than those found in wheat pale and dark samples. A general least square regression model showed a good correlation between the total content of BAs and the brewing process, especially for Plato degree, mashing, and fermentation temperatures. Knowledge about the type of ingredients and manufacturing processes that contribute to higher concentrations of these compounds is crucial to ensuring consumer safety.

This work is a mini-review highlighting the relevance of the θ metallabis(dicarbollide) [3,3′-Co(1,2-C2B9H11)2]− with its peculiar and differentiating characteristics, among them the capacity to generate hydrogen and dihydrogen bonds, to generate micelles and vesicles, to be able to be dissolved in water or benzene, to have a wide range of redox reversible couples and many more, and to use these properties, in this case, for producing potentiometric membrane sensors to monitor amine-containing drugs or other nitrogen-containing molecules. Sensors have been produced with this monoanionic cluster [3,3′-Co(1,2-C2B9H11)2]−. Other monoanionic boron clusters are also discussed, but they are much fewer. It is noteworthy that most of the electrochemical sensor species incorporate an ammonium cation and that this cation is the species to be detected. Alternatively, the detection of the borate anion itself has also been studied, but with significantly fewer examples. The functions of the borate anion in the membrane are different, even as a doping agent for polypyrrole which was the conductive ground on which the PVC membrane was deposited. Apart from these cases related to closo borates, the bulk of the work has been devoted to sensors in which the θ metallabis (dicarbollide) [3,3′-Co(1,2-C2B9H11)2]− is the key element. The metallabis (dicarbollide) anion, [3,3′-Co(1,2-C2B9H11)2]−, has many applications; one of these is as new material used to prepare an ion-pair complex with bioactive protonable nitrogen containing compounds, [YH]x[3,3′-Co(1,2-C2B9H11)2]y as an active part of PVC membrane potentiometric sensors. The developed electrodes have Nernstian responses for target analytes, i.e., antibiotics, amino acids, neurotransmitters, analgesics, for some decades of concentrations, with a short response time, around 5 s, a good stability of membrane over 45 days, and an optimal selectivity, even for optical isomers, to be used also for real sample analysis and environmental, clinical, pharmaceutical and food analysis.

Use of the nanocomposite of chloride-doped polyaniline nanofibers and multiwalled carbon nanotubes (PANINFs-Cl:MWCNTs) for construction of ion-selective electrodes with solid-contact sensitive to chloride ions has been described. Many types of electrodes were tested, differing in the quantitative and qualitative composition of the layer placed between the electrode material and the ion-selective membrane. Initial tests were carried out, including tests of electrical properties of intermediate solid-contact layers. The obtained ion-selective electrodes had a theoretical slope of the electrode characteristic curve (−61.3 mV dec−1), a wide range of linearity (5 × 10−6–1 × 10−1 mol L−1) and good potential stability resistant to changing measurement conditions (redox potential, light, oxygen). The chloride contents in the tap, mineral and river water samples were successfully determined using the electrodes.

The possibility of voltammetric ion sensing is demonstrated, for the first time, for ion-selective electrodes (ISEs) containing an internal aqueous solution. ISEs selective to calcium, lithium and potassium ions are used as model systems. The internal solution of the ISEs contains a chloride salt of the respective cation and a ferrocenemethanol or ferrocyanide/ferricyanide redox couple. A platinum wire is used as the internal reference electrode. It is shown, theoretically and experimentally, that the dependence of oxidation and reduction peak potentials on the sample composition obeys the Nernst law, while the peak currents virtually do not depend on the sample composition. Thus, the electrode behavior is similar to that reported by Bakker’s group for solid contact ISEs with ultra-thin membranes (200–300 nm). It is shown that the use of classical ISEs with relatively thick membranes (100–300 µm) and internal aqueous solution allows for the sensor lifetime of about one month. It is also shown that use of a suitable background electrolyte allows for improvement of the detection limits in voltammetric measurements with ISEs.

Abstract For fluoride to be effective in controlling caries, it should be bioavailable in commercial products, so that it can be released into the mouth in the products it contains. We chemically determined the available fluoride and pH in nine mouth rinses marketed in Chile, and eleven, in Brazil, and then discussed the legislation in force in both countries, regarding the anticaries potential of these oral hygiene products. The fluoride was analyzed with an ion-selective electrode (F-ISE), using the direct technique. The determinations were made in duplicate, and the results were expressed in ppm F (μg F/mL). The total fluoride concentration found in all the mouth rinses evaluated ranged from 94.7 to 233.5 ppm F, and closely matched what was declared by the manufacturers (100.0 to 226.2 ppm F). However, some mouth rinses showed lower fluoride concentrations (90 and 180 ppm F) in both countries. A Na2FPO3-formulated mouth rinse was found only in Chile, with 216.8 ppm F as the FPO32- ion, and 4.9 ppm F as the F-. The findings show that fluoride was potentially bioavailable in all the mouth rinses evaluated. Regarding the national legislations, although the mouthwashes sold in Brazil comply with the Brazilian legislation, discrepancies were found for Chile. However, neither country had a legislation matching the best available evidence on fluoride mouthwash efficacy for caries control. Thus, some products with low fluoride concentrations (below 226 ppm F), or manufactured with a fluoride salt other than NaF (Na2FPO3) are being sold in the Brazilian and Chilean markets.

The soil cover and soil salinity of the field were studied and the results are given in the article, the explored fileld is located within the Chervlenoye irrigated area belonging to Svetloyarskaya irrigation system (south of the Volgograd region). It was characterized by alternating dark and light wide strips visible on the satellite image. The field was irrigated until the mid-1990s and was subject to secondary salinization, since that time it has been used in dry-farming system. The soil combination is performed by steppe light chestnut solonetzic complex that was transformed due to the surface leveling and irrigation into agrozem accumulative-carbonate segregation saline (Sodic Endoprotosalic Cambisol (Loamic, Aric, Protocalcic, Ochric, Bathygypsic) and Cambic Calcisols (Loamic, Aric)) and deep saline, and agro-light-humus accumulative-carbonate stratified soil. The bright bands on the field mark soils rich in carbonates on the surface (12–13 % CaCO3) (Calcaric Cambisol (Loamic, Aric)) among the other soils that contain less carbonates on the surface by 5–10 times. All the soils are saline, but the salt content varies in space in a wave-like manner, wich disagrees with the satellite image. Two-dimensional distributions of carbonates and salts in the soil combination are discussed. The residual signs of secondary salinization are revealed in the form of calcium and magnesium chlorides two decades after the cessation of irrigation and drawdown of the groundwater curve deeper than 7 m.

While potentiometric, plasticized membrane sensors are known as convenient, portable and inexpensive analytical instruments, their development is time- and resource-consuming, with a poorly predictable outcome. In this study, we investigated the applicability of the QSPR (quantitative structure–property relationship) method for predicting the potentiometric sensitivity of plasticized polymeric membrane sensors, using the ionophore chemical structure as model input. The QSPR model was based on the literature data on sensitivity, from previously studied, structurally similar ionophores, and it has shown reasonably good metrics in relating ionophore structures to their sensitivities towards Cu2+, Cd2+ and Pb2+. The model predictions for four newly synthesized diphenylphosphoryl acetamide ionophores were compared with real potentiometric experimental data for these ionophores, and satisfactory agreement was observed, implying the validity of the proposed approach.

For fluoride to be effective in controlling caries, it should be bioavailable in commercial products, so that it can be released into the mouth in the products it contains. We chemically determined the available fluoride and pH in nine mouth rinses marketed in Chile, and eleven, in Brazil, and then discussed the legislation in force in both countries, regarding the anticaries potential of these oral hygiene products. The fluoride was analyzed with an ion-selective electrode (F-ISE), using the direct technique. The determinations were made in duplicate, and the results were expressed in ppm F (μg F/mL). The total fluoride concentration found in all the mouth rinses evaluated ranged from 94.7 to 233.5 ppm F, and closely matched what was declared by the manufacturers (100.0 to 226.2 ppm F). However, some mouth rinses showed lower fluoride concentrations (90 and 180 ppm F) in both countries. A Na2FPO3-formulated mouth rinse was found only in Chile, with 216.8 ppm F as the FPO3 2-ion, and 4.9 ppm F as the F-. The findings show that fluoride was potentially bioavailable in all the mouth rinses evaluated. Regarding the national legislations, although the mouthwashes sold in Brazil comply with the Brazilian legislation, discrepancies were found for Chile. However, neither country had a legislation matching the best available evidence on fluoride mouthwash efficacy for caries control. Thus, some products with low fluoride concentrations (below 226 ppm F), or manufactured with a fluoride salt other than NaF (Na2FPO3) are being sold in the Brazilian and Chilean markets. [ABSTRACT FROM AUTHOR]

Aim: To determine total fluoride (TF) concentration in Na2FPO3/Ca-based toothpastes, using fluoride ion selective electrode (F-ISE) by the direct technique, it is necessary to use acid (Ac+) to hydrolyze the FPO3 2- ion and to dissolve insoluble fluoride salts bound to the abrasive. For NaF/silicabased toothpastes, the use of acid is not necessary (Ac-) and a simplified protocol could be followed. Methods: Thus, we evaluated TF concentration in seven brands of NaF/silicabased toothpastes, following the validated conventional Cury’s protocol (Ac+) or a simplification of this protocol (Ac-). Fluoride was analyzed with ISE calibrated with fluoride standard solutions prepared in the same conditions as the samples (Ac+ or Ac-). Results: The mean (±SD; n=21) of TF concentrations (μg F/g) found by Ac+ (971.3±191.2) and Ac- (982.4±201.3) protocols were not statistically different (t test, p=0.22). The TF concentrations found agree with those declared by the manufacturers, except for one toothpaste imported from China. Conclusion: The findings suggest that the determination of fluoride in NaF/silica-based toothpastes can be accurately made using a simplified protocol of analysis.