Polina A. Yurova

Composite materials based on cation-exchange membranes MK-40 and ceria, including phosphate-functionalized, have been obtained and characterized by SEM, TGA, and IR spectroscopy. The conductivity of the membranes in the sodium form decreases from 6.2 to 3.5 mS/cm and in the calcium form, increases slightly from 1.3 to 1.6 mS/cm. It has been shown that selectivity to divalent ions grows. For example, during electrodialysis desalination selective permeability coefficients Р(Ca²⁺/Na⁺) and Р(Mg²⁺/Li⁺) increase to 3.6 and 6.6, respectively. Furthermore, additional phosphate functionalization of ceria improves the fouling resistance of the materials.

A growing interest in dental practice in intranasal anesthesia using tetracaine and oxymetazoline dictates the need for their simultaneous determination in combination drugs and human saliva. Potentiometric multisensory systems based on perfluorosulfonic acid membranes, including polyaniline‐modified ones, were developed for these purposes. A change in the distribution of the sensor sensitivity to the related analytes was achieved by variation of the conditions for concentration polarization at the membrane interface with a studied solution due to a change in the intrapore volume, nature, and availability of the sorption centers, as well as the hydrophilicity of the membrane surface that were specified by the conditions for their synthesis and subsequent hydrothermal treatment. Reversibility of the analyte sorption using the chosen conditions for regeneration provided long‐term stable work of both the sensors and the calibration equations established by multivariate linear regression. The membrane modification promoted their resistance to fouling. The relative errors of the simultaneous tetracaine and oxymetazoline determination in the combination drug solutions were no greater than 7% and 11%, while in the artificial saliva solutions, they were 15% and 17%, respectively, when an array of the cross‐sensitive sensors based on the composite membranes prepared by different methods was used. The analysis errors were reduced to 3%–6% when analyzing the drug and to 0.2%–6% when analyzing the artificial saliva if an array was organized with the sensors based on the membrane with the dopant and the membrane without it, due to the decreasing correlation between their responses.

A novel potentiometric multisensory system for the analysis of sulfamethoxazole and trimethoprim combination drugs was developed. The potentiometric sensors (Donnan potential (DP) was used as an analytical signal) with an inner reference solution were based on perfluorosulfonic acid (PFSA) membranes modified with polyaniline (PANI) by in situ oxidative polymerization. The order of the membrane treatment with precursor solutions and their concentrations was varied. Additionally, the PFSA/PANI composite membranes were hydrothermally treated at 120 °C. The influence of the preparation conditions and the composition of membranes on their sorption and transport properties was studied. We estimated the factors affecting the sensitivity of DP-sensors based on the PFSA/PANI composite membranes to ions of sulfamethoxazole and trimethoprim simultaneously presented in solutions. A developed multisensory system provided a simultaneous determination of two analytes in aqueous solutions without preliminary separation, derivatization, or probe treatment. The re-estimation of the calibration characteristics of the multisensory system did not show a statistically significant difference after a year of its use. The limits of detection of sulfamethoxazole and trimethoprim were 1.4 × 10⁻⁶ and 8.5 × 10⁻⁸ M, while the relative errors of their determination in the combination drug were 4 and 5% (at 5 and 6% relative standard deviation), respectively.

Ion exchange membranes are widely used for water treatment and ion separation by electrodialysis. One of the ways to increase the efficiency of industrial membranes is their modification with various dopants. To improve the membrane permselectivity, a simple strategy of the membrane surface modification was proposed. Heterogeneous RALEX-CM membranes were surface-modified by ceria with a phosphate-functionalized surface. Despite a decrease in ionic conductivity of the prepared composite membranes, their cation transport numbers slightly increase. Moreover, the modified membranes show a threefold increase in Ca²⁺/Na⁺ permselectivity (from 2.1 to 6.1) at low current densities.

The process of heterogeneous sulfonation of a radiation-grafted copolymer of polystyrene and polyvinylidene fluoride depending on the reaction time and the type of sulfonating agent (chlorosulfonic acid or its equimolar mixture with acetic acid) has been studied. The water uptake, ion-exchange capacity, and ionic conductivity of the prepared membranes have been characterized. In addition, composition and morphology of materials at different synthesis stages have been analyzed by FTIR, ¹Н NMR, and EPR spectroscopies, elemental analysis, and scanning electron microscopy combined with energy dispersive X-ray microanalysis. The ionic conductivity of the prepared materials exceeds that of Nafion®212 membranes. In addition, the mechanical properties and hydrogen gas permeability of the membrane with the highest ionic conductivity (52 mS/cm at 80°C in contact with water) are better than those of the Nafion®212 membrane.

The degradation of sulfacetamide with the formation of sulfanilamide leads to a deterioration in the quality of pharmaceuticals. In this work, potentiometric sensors for the simultaneous determination of sulfanilamide, sulfacetamide and inorganic ions, and for assessing the degradation of pharmaceuticals were developed. A multisensory approach was used for this purpose. The sensor cross-sensitivity to related analytes was achieved using perfluorosulfonic acid membranes with poly(3,4-ethylenedioxythiophene) or polyaniline as dopants. The composite membranes were prepared by oxidative polymerization and characterized using FTIR and UV-Vis spectroscopy, and SEM. The influence of the preparation procedure and the dopant concentration on the membrane hydrophilicity, ion-exchange capacity, water uptake, and transport properties was investigated. The characteristics of the potentiometric sensors in aqueous solutions containing sulfanilamide, sulfacetamide and alkali metals ions in a wide pH range were established. The introduction of proton-acceptor groups and π-conjugated moieties into the perfluorosulfonic acid membranes increased the sensor sensitivity to organic analytes. The relative errors of sulfacetamide and sulfanilamide determination in the UV-degraded eye drops were 1.2 to 1.4 and 1.7 to 4%, respectively, at relative standard deviation of 6 to 9%.