Dispersive Surface Free Energy of Adsorbents Modified by Supramolecular Structures of Heterocyclic Compounds

Received: 26.04.2024. Revised: 04.05.2024. Accepted: 04.05.2024. Available online: 13.05.2024.The classical Dorris-Gray method for dispersive surface free energy estimation cannot give reliable results.To calculate the dispersive component for adsorption materials, one should take inductive interactions into account.The dispersive component can be used to predict the properties of supramolecular layers.In the present work, the dispersive surface free energy was calculated by Dorris-Gray method for 30 samples of adsorbents modified with chiral supramolecular structures of uracil, 6-methyluracil, 5-hydroxy-6-methyluracil, 5-fluorouracil, thymine, melamine, cyanuric and barbirutic acids, and perylene-3,4,9,10-tetracarboxylic dianhydride. It was shown that the homologous series of n-alkanes is better suited for measuring dispersive surface free energy than the homologous series of alcohols. It was established that the classical Dorris-Gray method does not allow obtaining well interpretable data for the objects studied. This is due to a noticeable effect that inductive interactions of a polar surface as an inductor with nonpolar alkane molecules have on the calculated values. We suggested to modify the Dorris-Gray method, making it possible to obtain data on the dispersive component of the free energy of adsorption. It was shown that the changes in dispersive surface free energy as a result of the modification correlate well with data on the structure and properties of supramolecular ensembles of the modifiers used. The results obtained can be used to predict the enantioselectivity of chiral adsorbents.This work was supported by the Russian Science Foundation (grant no. 19-73-10079), https://www.rscf.ru/en

ВОЛЬТАМПЕРОМЕТРИЧЕСКОЕ ОПРЕДЕЛЕНИЕ ЭНАНТИОМЕРОВ ПРОПРАНОЛОЛА В МОДЕЛЬНЫХ РАСТВОРАХ ЛЕКАРСТВЕННЫХ ФОРМ И БИОЛОГИЧЕСКИХ ЖИДКОСТЯХ

The possibilities of new voltammetric sensors based on glassy carbon electrodes modified by the composites of polyarylenephthalide with melamine, cyanuric acid, α- and β-cyclodextrins for the determination of propranolol enantiomers in the model solutions of pharmaceutical and biological fluids were studied. The electrochemical and analytical characteristics of voltammograms of propranolol enantiomers and their pharmaceutical dosage forms on the modified electrodes were obtained. The voltamperograms of the propranolol enantiomers on these electrodes differ among themselves both in the values of the instantaneous currents and in the potentials of oxidation. The proposed sensors allowed determining the propranolol enantiomers in a racemic mixture and in a mixture with the predominance of one of the enantiomers. The dependence of the analytical signal on the concentration of propranolol was linear in the range from 0.021 to 0.675 mM, the detection limit was (5.28÷8.37)×10-6М in the solutions of enantiomers and (2.75÷5.57)×10-5М in pharmaceutical dosage forms respectively. The relative standard deviation for the pure solutions of propranolol enantiomers ranged from 0.011 to 0.064, and for pharmaceutical dosage forms of propranolol it ranged from 0.022 to 0.109. The auxiliary substances did not have a significant interfering effect. The developed enantioselective sensors were used for the determination of propranolol enantiomers in the biological fluids. The statistical evaluation of the results by the "spiked -found" method indicated that there was no significant systematic error. The relative standard deviation in the determination of propranolol enantiomers ranged from 0.071 to 0.109 in the urine, and from 0.116 to 0.146 in the plasma.Keywords: enantiomers, propranolol, voltammetry, polyarylenephthalide, melamine, cyanuric acid, cyclodextrins, composite electrodes, auxiliary substances, biological fluids DOI: http://dx.doi.org/10.15826/analitika.2018.22.3.012(Russian)R.A. Zilberg, Yu.A. Yarkaeva, Yu.R. Provorova, V.Yu. Gus’kov, V.N. MaistrenkoBashkir State University, Zaki Validi str. 32, Ufa, 450076, Russian FederationНовые вольтамперометрические сенсоры на основе стеклоуглеродных электродов, модифицированных композитами полиариленфталида с меламином, циануровой кислотой, α- и β-циклодекстринами, применены для определения энантиомеров пропранолола в рацемических смесях, модельных растворах лекарственных форм, плазме крови и моче. Изучены электрохимические и аналитические характеристики предложенных сенсоров при регистрации дифференциально-импульсных вольтамперограмм энантиомеров пропранолола. На полученных вольтамперограммах наблюдаются различия между энантиомерами пропранолола как по величинам мгновенных токов, так и по потенциалам окисления. Предложенные сенсоры позволяют проводить определение энантиомеров пропранолола в рацемической смеси и в смеси с преобладанием одного из энантиомеров. Изучено также влияние присутствующих в лекарственных формах в различных сочетаниях и концентрациях вспомогательных веществ на чувствительность сенсоров к энантиомерам пропранолола. Показано, что зависимость аналитического сигнала от концентрации линейна в диапазоне от 0.021 до 0.675 мМ с пределами обнаружения (5.28÷8.37)·10-6 М и (2.75÷5.57)·10-5 М в исходных растворах и модельных растворах лекарственных формах соответственно. Относительное стандартное отклонение для модельных растворов энантиомеров пропранолола изменяется в пределах от 0.011 до 0.064, а для лекарственных форм – от 0.022 до 0.109, вспомогательные вещества не оказывают существенного мешающего влияния на результаты определений. Относительное стандартное отклонение при определении энантиомеров пропранолола в моче изменяется в пределах 0.071 – 0.109, а в плазме крови – от 0.116 до 0.146. Статистическая оценка результатов определений методом «введено-найдено»        свидетельствует об отсутствии значимой систематической погрешности.Ключевые слова: энантиомеры, пропранолол, вольтамперометрия, полиариленфталид, меламин, циануровая кислота, циклодекстрины, композитные электроды, вспомогательные вещества, биологические жидкостиDOI: http://dx.doi.org/10.15826/analitika.2018.22.3.01

Evaluating the Effectiveness of the Original Designs of Immediate-Prostheses after Multiple Tooth Extraction: Clinical Cases

Background. Rehabilitation of patients with chronic periodontal diseases leading to multiple tooth loss can be carried out using the method of immediate prosthetics. However, the likelihood of atrophy of denture-supporting tissues under non-physiological load with removable dental prostheses imposes special requirements for their design features.Case description. Two patients seeking for dental surgical and prosthetic treatment for the diagnosis of chronic generalized periodontitis were treated in the dental clinic of Ryazan State Medical University named after academician I.P. Pavlov. Patient A. was mounted immediate prostheses made using additive technologies with the original design of the drug reservoir. Patient B. was mounted immediate prostheses with bases made of acrylic plastic, border ring of elastic polymer, and a drug reservoir made of polymethyl methacrylate. Patients underwent tooth extraction with immediate prosthetics. Patients were followed for 21 days. Criteria for the effectiveness of treatment included visual and palpatory control of extraction sites with a planimetric wound size analysis, assessment of microcirculation at the extraction site, control of the drug persistence in the reservoirs of prostheses.Conclusion. The observations at the stages of prosthodontic treatment revealed that immediate prostheses made with the help of 3D modeling and printing technologies resulted in a normal course of healing after tooth extraction with the normalization of microcirculatory parameters at the surgical wound sites. When using combined prosthetic structures, healing of postoperative wounds also proceeded favorably, however, congestion in the microcirculatory system was noted

Voltammetric determination of propranolol enantiomers in the model solutions of pharmaceutical forms and biological fluids

The possibilities of new voltammetric sensors based on glassy carbon electrodes modified by the composites of polyarylenephthalide with melamine, cyanuric acid, ?- and ?-cyclodextrins for the determination of propranolol enantiomers in the model solutions of pharmaceutical and biological fluids were studied. The electrochemical and analytical characteristics of voltammograms of propranolol enantiomers and their pharmaceutical dosage forms on the modified electrodes were obtained. The voltamperograms of the propranolol enantiomers on these electrodes differ among themselves both in the values of the instantaneous currents and in the potentials of oxidation. The proposed sensors allowed determining the propranolol enantiomers in a racemic mixture and in a mixture with the predominance of one of the enantiomers. The dependence of the analytical signal on the concentration of propranolol was linear in the range from 0.021 to 0.675 mM, the detection limit was (5.28?8.37)?10-6М in the solutions of enantiomers and (2.75?5.57)?10-5М in pharmaceutical dosage forms respectively. The relative standard deviation for the pure solutions of propranolol enantiomers ranged from 0.011 to 0.064, and for pharmaceutical dosage forms of propranolol it ranged from 0.022 to 0.109. The auxiliary substances did not have a significant interfering effect. The developed enantioselective sensors were used for the determination of propranolol enantiomers in the biological fluids. The statistical evaluation of the results by the ""spiked -found"" method indicated that there was no significant systematic error. The relative standard deviation in the determination of propranolol enantiomers ranged from 0.071 to 0.109 in the urine, and from 0.116 to 0.146 in the plasma.Новые вольтамперометрические сенсоры на основе стеклоуглеродных электродов, модифицированных композитами полиариленфталида с меламином, циануровой кислотой, ?- и ?-циклодекстринами, применены для определения энантиомеров пропранолола в рацемических смесях, модельных растворах лекарственных форм, плазме крови и моче. Изучены электрохимические и аналитические характеристики предложенных сенсоров при регистрации дифференциально-импульсных вольтамперограмм энантиомеров пропранолола. На полученных вольтамперограммах наблюдаются различия между энантиомерами пропранолола как по величинам мгновенных токов, так и по потенциалам окисления. Предложенные сенсоры позволяют проводить определение энантиомеров пропранолола в рацемической смеси и в смеси с преобладанием одного из энантиомеров. Изучено также влияние присутствующих в лекарственных формах в различных сочетаниях и концентрациях вспомогательных веществ на чувствительность сенсоров к энантиомерам пропранолола. Показано, что зависимость аналитического сигнала от концентрации линейна в диапазоне от 0.021 до 0.675 мМ с пределами обнаружения (5.28?8.37)·10-6 М и (2.75?5.57)·10-5 М в исходных растворах и модельных растворах лекарственных формах соответственно. Относительное стандартное отклонение для модельных растворов энантиомеров пропранолола изменяется в пределах от 0.011 до 0.064, а для лекарственных форм - от 0.022 до 0.109, вспомогательные вещества не оказывают существенного мешающего влияния на результаты определений. Относительное стандартное отклонение при определении энантиомеров пропранолола в моче изменяется в пределах 0.071 - 0.109, а в плазме крови - от 0.116 до 0.146. Статистическая оценка результатов определений методом «введено-найдено» свидетельствует об отсутствии значимой систематической погрешности.Авторы благодарят Российский научный фонд (грант № 16–13–10257) за финансовую поддержку исследования.The authors are thankful to The Russian Science Foundation (grant № 16–13–10257) for the financial support of the present research

Management of the Investigation and Detection of Legionellosis Agent in the Environmental Samples during the Preparation and Holding of the XXII Winter Olympics and XI Paralympics in Sochi

Provided are the data on the management and carrying out of the laboratory control over the hot-water supply systems of the sports venues and accommodation areas for the presence of Legionella pneumophila during the XXII Olympics and XI Paralympics in Sochi, 2014. Inspected have been 105 facilities. The samples from 37 of them showed positive. L. pneumophila DNA concentration varies between 2.19·102 and 3.92·107 genome equivalents (g.e.)/l. By means of bacteriological investigation detected have been legionella colonies in the water supply systems of 16 facilities, at one of the items - the loading is over 1·104 colony-forming units/l. Performed has been comparative analysis of the results obtained using PCR assay and bacteriological test. Based on the genotyping of 7 isolated strains serogroup 1 and 2 strains of 2-14 serogroups it is concluded that L. pneumophila strains circulating in the resort town Sochi are genetically heterogeneous