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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%.

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Sulfamethoxazole and trimethoprim are synthetic bacteriostatic drugs. A potentiometric multisensory system for the analysis of sulfamethoxazole and trimethoprim combination drugs was developed. Perfluorosulfonic acid membranes containing functionalized CNTs were used as the sensor materials. The CNTs’ surface was modified by carboxyl, sulfonic acid, or (3-aminopropyl)trimethoxysilanol groups. The influence of the CNT concentration and the properties of their surface, as well as preliminary ultrasonic treatment of the polymer and CNT solution before the casting of hybrid membranes, on their ion-exchange capacity, water uptake, and transport properties was revealed. Cross-sensitivity of the sensors to the analytes was achieved due to ion exchange and hydrophobic interactions with hybrid membranes. An array of cross-sensitive sensors based on the membranes containing 1.0 wt% of CNTs with sulfonic acid or (3-aminopropyl)trimethoxysilanol groups enabled us to provide the simultaneous determination of sulfamethoxazole and trimethoprim in aqueous solutions with a concentration ranging from 1.0 × 10−5 to 1.0 × 10−3 M (pH 4.53–8.31). The detection limits of sulfamethoxazole and trimethoprim were 3.5 × 10−7 and 1.3 × 10−7 М. The relative errors of sulfamethoxazole and trimethoprim determination in the combination drug as compared with the content declared by the manufacturer were 4% (at 6% RSD) and 5% (at 7% RSD).

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The influence of incorporation of the dopants with proton-acceptor properties into perfluorosulfonic acid cation exchange membranes (MF-4SC and Nafion), and their treatment conditions on the characteristics of Donnan potential (DP)-sensors (analytical signal is the Donnan potential) in the aqueous solutions containing asparaginate and potassium ions in a wide pH range was investigated. A silica, surface modified by 3-aminopropyl and 3-(2-imidazolin-1-yl)-propyl groups, was used as the dopant. The membranes were subjected to mechanical deformation and thermal treatment at various relative humidities. The relationship between water uptake and diffusion permeability of membranes subjected to modification and treatment and the cross sensitivity of DP-sensors based on them to counter and co-ions was studied. The multisensory systems for the simultaneous determination of asparaginate and potassium ions in a concentration range from 1.0 × 10−4 to 1.0 × 10−2 M and pH range from 4 to 8 were developed. An array of cross-sensitive DP-sensors based on MF-4SC membranes containing 3 wt.% SiO2 modified by 10 mol.% 3-aminopropyl and 3-(2-imidazolin-1-yl)-propyl was used for the potassium asparaginate hemihydrate and magnesium asparaginate pentahydrate determination in Panangin® (with an error of 2 and 4%, respectively).