In this work, for the first time, the potentiometric method was used to determine the antioxidant capacity (AOC) of compounds of different hydrophilicity in the joint presence using mixed solvents and surfactants. The AOC of model solutions of antioxidants of different hydrophilicity was determined separately and in the joint presence in the media of phosphate buffer-surfactant and mixed solvents-surfactant, using as an example the ascorbic acid and the α-tocopherol. It was shown that the surfactant Triton X-100 is able to solubilize α-tocopherol under the selected conditions, allows to obtain reproducible and accurate results, and has less effect on the equilibrium rate of the K3[Fe(CN)6]/K4[Fe(CN)6] system. Phosphate buffer-ethanol and phosphate buffer-acetonitrile media in the 3:2 ratio with Triton X-100 (5 mmol/dm3) were chosen as the analysis conditions (RSD ≤ 6%). The range of determined concentrations was (0.006-0.5) m mmol/dm3 in phosphate buffer-ethanol and (0.006-0.3) m mmol/dm3 in phosphate buffer-acetonitrile. AOC of raw materials infusions was determined in selected media. The positive correlation with the well-known Folin-Ciocalteu assay was obtained.

Obtaining analytical information about chemical species at interfaces is fundamentally important to improving our understanding of chemical reactions and biological processes. pH at solid-liquid interfaces is found to deviate from the bulk solution value, for example, in electrocatalytic reactions at surfaces or during the corrosion of metals. Also, in the vicinity of living cells, metabolic reactions or cellular responses cause changes in pH at the extracellular interface. In this review, we collect recent progress in the development of sensors with the capability to detect pH at or close to solid-liquid and bio interfaces, with spatial and time resolution. After the two main principles of pH detection are presented, the different classes of molecules and materials that are used as active components in these sensors are described. The review then focuses on the reported electroanalytical techniques for local pH sensing. As application examples, we discuss model studies that exploit local pH sensing in the area of electrocatalysis, corrosion, and cellular interfaces. We conclude with a discussion of key challenges for wider use of this analytical approach, which shows promise to improve the mechanistic understanding of reactions and processes at realistic interfaces.

In this study, a new potentiometric sensor was developed for the determination of the local anesthetic drug procaine in pharmaceutical samples. Procaine (Pr)-Tetraphenlyborate (TPB) ion-pair was synthesized and used as a sensor material. Potentiometric sensors using the synthesized ion pair (Pr-TPB), poly(vinyl chloride) (PVC) and o-nitrophenyloctyl ether (o-NPOE) in different proportions were prepared and their performance properties were tested. Among the prepared sensors, the best potentiometric response characteristics were obtained with the sensor composition Pr-TPB:PVC:o-NPOE in the ratio of 6.0:32.0:62.0 (w/w %). The new procaine sensor developed in the present study had a near-Nernstian behavior of 54.1 ± 3.3 mV/per decade and a low detection limit of 3.18 × 10-5 mol L-1 in the concentration range of 1.0 × 10-1-1.0 × 10-4 mol L-1. Additionally, the sensor had a response time of less than 10 s and could work in a wide pH range for two different concentration values without being affected by pH changes. Finally, the new procaine potentiometric sensor was used to detect procaine in injection samples and successfully determined procaine concentrations with high recoveries.

A binary system of uridine-5\'-diphosphoglucuronic acid with copper (II) ions was studied. Potentiometric studies in aqueous solutions using computer data analysis were carried out. The pH of dominance, the overall stability constants (logβ), and the equilibrium constants of the formation reaction (logKe) were determined for each complex compound formed in the studied system. Spectroscopic studies were carried out to determine the mode of coordination in the compounds studied. Cytotoxicity and metabolic activity tests of the compounds obtained showed an increase in the biological activity of the complexes tested against the free ligand. The current research may contribute to the knowledge of complex compounds of biomolecules found in the human body and may also contribute to the characterization of a group of complex compounds with potential anticancer properties.

Carbon nanomaterials were introduced into this research as modifiers for polymeric membranes for single-piece electrodes, and their properties were studied for the case of nitrate-selective sensors. The use of graphene, carbon black and carbon nanotubes is shown to significantly improve the potentiometric response, while no redox response was observed. The use of carbon nanomaterials results in a near-Nernstian response (54 mV/pNO3-) towards nitrate ions over a wide linear range (from 10-1 to 10-6 M NO3-). The results obtained by chronopotentiometry and electrochemical impedance spectroscopy reveal little resistance, and the capacitance parameter is as high as 0.9 mF (for graphene-based sensor). The high electrical capacity of electrodes results in the good stability of the potentiometric response and a low potential drift (0.065 mV/h). Introducing carbon nanomaterials into the polymetric membrane, instead of using them as separate layers, allows for the simplification of the sensors\' preparation procedure. With single-piece electrodes, one step of the procedure could be omitted, in comparison to the procedure for the preparation of solid-contact electrodes.

Ion-selective electrodes (ISEs) have widespread use in the fields of clinical and environmental analyses. Tetrahydrofuran (THF) is the most used solvent for the preparation of modern ISEs, equipped with ion-selective membranes (ISMs). Until now, the influence of impurities in THF toward potentiometric instability of ion-selective membrane based ISEs was probably associated with the presence of either residual water or peroxide. To address this issue, most literature recommends redistilling THF prior to use in the preparation of the potentiometric membranes. Current study reveals that the actual THF impurity that is responsible for potential instability in the ISM includes products from the oxidation of THF, which contains the hydroxyl group and possibly carbonyl group with a boiling point of above 200 °C. The density functional theory calculation supported pathway of the chemical reaction of THF oxidation, hence, the chemical structure of the uncertain impurities was predicted. The underlying reason for the deteriorating potential stability of the ISEs is proposed as the significant hydrophilicity of these impurities that affect the partitioning of the ion sensing components in the membrane, thus enhancing the leaching of the membrane components from the membrane phase. This finding explains why redistillation of aged THF is advised.

Miniaturization and mass-production of potentiometric sensor systems is paving the way towards distributed environmental sensing, on-body measurements and industrial process monitoring. Inkjet printing is gaining popularity as a highly adaptable and scalable production technique. Presented here is a scalable and low-cost route for flexible solid-contact ammonium ion-selective electrode fabrication by inkjet printing. Utilization of inkjet-printed melamine-intercalated graphene nanosheets as the solid-contact material significantly improved charge transport, while evading the detrimental water-layer formation. External polarization was investigated as a means of improving the inter-electrode reproducibility: the standard deviations of E0 values were reduced after electrode polarization, the linear region of the response was extended to the range 10-1-10-6 M of NH4Cl and LODs reduced to 0.88 ± 0.17 μM. Finally, we have shown that the electrodes are adequate for measurements in a complex real sample: ammonium concentration was determined in landfill leachate water, with less than 4 % deviation from the reference method.

Electrochemical sensors provide an affordable and reliable approach towards the detection and monitoring of important biological species ranging from simple ions to complex biomolecules. The ability to miniaturize electrochemical sensors, coupled with their affordability and simple equipment requirements for signal readout, permits the use of these sensors at the point-of-care where analysis using non-invasively obtainable biofluids is receiving growing interest by the research community. This paper describes the design, fabrication, and integration of a 3D printed Mg2+ potentiometric sensor into a 3D printed microfluidic device for the quantification of Mg2+ in low-sample volume biological fluids. The sensor employs a functionalized 3D printable photocurable methacrylate-based ion-selective membrane affixed to a carbon-mesh/epoxy solid-contact transducer for the selective determination of Mg2+ in sweat, saliva and urine. The 3D printed Mg2+ ion-selective electrode (3Dp-Mg2+-ISE) provided a Nernstian response of 27.5 mV per decade with a linear range of 10 mM to 39 μM, covering the normal physiological and clinically relevant levels of Mg2+ in biofluids. 3Dp-Mg2+-ISEs selectively measure Mg2+ over other biologically present cations - sodium, potassium, calcium, ammonium - as well as provide high stability in the analytical signal with a drift of just 13 μV h-1 over 10 hours. Comparison with poly(vinylchloride)-based Mg2+-ISEs showed distinct advantages to the use of 3Dp-Mg2+-ISEs, with respect to stability, resilience towards biofouling and importantly providing a streamlined and rapid approach towards mass production of selective and reliable sensors. The miniaturization capabilities of 3D printing coupled with the benefits of microfluidic analysis (i.e., low sample volumes, minimal reagent consumption, automation of multiple assays, etc.), provides exciting opportunities for the realization of the next-generation of point-of-care diagnostic devices.

Under ideal conditions, nanotubes with a fixed negative tube-wall charge will reject anions and transport-only cations. Because many proposed nanofluidic devices are optimized in this ideally cation-permselective state, it is important to know the experimental conditions that produce ideal responses. A parameter called Ccrit, the highest salt concentration in a contacting solution that still produces ideal cation permselectivity, is of particular importance. Pioneering potentiometric studies on gold nanotubes were interpreted using an electrostatic model that states that Ccrit should occur when the Debye length in the contacting salt solution becomes equivalent to the tube radius. Since this \"double-layer overlap model\" (DLOM), treats all same-charge ions as identical point charges, it predicts that all same-charged cations should produce the same Ccrit. However, the effect of cation on Ccrit in gold nanotubes was never investigated. This knowledge gap has become important because recent studies with a polymeric cation-permselective nanopore membrane showed that DLOM failed for every cation studied. To resolve this issue, we conducted potentiometric studies on the effect of salt cation on Ccrit for a 10 nm diameter gold nanotube membrane. Ccrit for all cations studied were, within experimental error, the same and identical, with values predicted by DLOM. The reason DLOM prevailed for the gold nanotubes but failed for the polymeric nanopores stems from the chemical difference between the fixed negative charges of these two membranes.

PdRuO2/PVP nanomaterial was synthesized using a straightforward method and characterized using advanced analytical methods such as TEM, XRD, XPS, elemental mapping and SEM. The synthesized PdRuO2/PVP nanomaterial was used as an ionophore in potentiometric sensor electrodes and successfully adapted to Cr3+ ion detection in a large number of aqueous samples. Several experimental parameters of the PdRuO2/PVP sensor such as potentiometric behavior, selectivity, repeatability, response time, pH, titration, and recovery in real samples were investigated. Potentiometric behavioral characteristics were performed in the concentration range 1 × 10-6-1.0 × 10-1 M. The repeated experiments performed six times showed that there was no deviation in the measurements. The limit of detection of the PdRuO2/PVP potentiometric sensor was very low with a value of 8.6 × 10-8 M. The potentiometric measurements showed that the synthesized PdRuO2/PVP ionophore was highly effective in detecting Cr3+ in a wide pH range of 2.0-8.0 and was found to have a shelf life of over 1 year. As a result, the synthesized PdRuO2/PVP electrode material was found to be highly selective, stable, and applicable for Cr3+ detection.