Pub Date : 2022-09-30DOI: 10.32362/2410-6593-2022-17-4-298-310
Y. Zotov, D. M. Zapravdina, E. V. Shishkin, Y. Popov
Objectives. The study aimed to develop new effective heat stabilizers based on glycerol esters of monocarboxylic acids for industrial chlorinated paraffins and to select of the optimal ratio of active ingredients in the stabilizing composition in order to provide the maximum thermostabilizing effect.Methods. The thermostabilizing effect of the studied samples on chlorinated paraffins was evaluated according to the standard method for determining the thermal stability of liquid chlorinated paraffins in terms of the mass fraction of split off hydrogen chloride. Quantitative and qualitative analysis of the obtained mixtures of monocarboxylic acid glycerides was carried out using chromato-mass spectrometry.Results. Glycerides of monocarboxylic acids (oleic, octanoic, hexanoic, and propionic acids) were obtained and identified, and the compositions of the resulting mixtures of mono-, di- and triesters were determined. The stabilizing effect of the obtained mixtures of glycerides of monocarboxylic acids in the amount of 0.5–2.0 wt parts per 100 wt parts of unstabilized industrial chlorinated paraffin CP-30 was determined. The combined use of glycerides of monocarboxylic acids with calcium-containing compounds as a complex stabilizer with a molar ratio of esters/Ca 0.93–0.86/0.07–0.14, respectively, was investigated. Chloroparaffin CP-470, stabilized by the developed complex stabilizer, was successfully used in a polyvinyl chloride composition for cable compound of the brand OM-40.Conclusions. A proposed variant of a complex stabilizer for chlorinated paraffins based on Russian raw materials for import substitution will expand the range of effective stabilizers for organochlorine substances. Glycerides of monocarboxylic acids are shown to exhibit a thermostabilizing effect on industrial chlorinated paraffins. The relationship between the length of the hydrocarbon substituent of the carboxylic acid in the ester and the thermostabilizing effect is obtained. With an increase in the number of carbon atoms in the hydrocarbon substituent of the carboxylic acid, the heat-stabilizing ability decreases. The minimum sufficient concentration of glycerides of carboxylic acids was 0.05 ± 0.005 mol/kg, above which no increase in the thermostabilizing effect on chloroparaffin was observed. A synergistic ratio of the components of the stabilizing mixture in terms of thermal stability—glycerides of monocarboxylic acids/calcium-containing compounds—was found equal to 0.85–0.9/0.15–0.1.
{"title":"Synthesis of stabilizers based on glycerides of monocarboxylic acids for industrial chloroparaffins","authors":"Y. Zotov, D. M. Zapravdina, E. V. Shishkin, Y. Popov","doi":"10.32362/2410-6593-2022-17-4-298-310","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-4-298-310","url":null,"abstract":"Objectives. The study aimed to develop new effective heat stabilizers based on glycerol esters of monocarboxylic acids for industrial chlorinated paraffins and to select of the optimal ratio of active ingredients in the stabilizing composition in order to provide the maximum thermostabilizing effect.Methods. The thermostabilizing effect of the studied samples on chlorinated paraffins was evaluated according to the standard method for determining the thermal stability of liquid chlorinated paraffins in terms of the mass fraction of split off hydrogen chloride. Quantitative and qualitative analysis of the obtained mixtures of monocarboxylic acid glycerides was carried out using chromato-mass spectrometry.Results. Glycerides of monocarboxylic acids (oleic, octanoic, hexanoic, and propionic acids) were obtained and identified, and the compositions of the resulting mixtures of mono-, di- and triesters were determined. The stabilizing effect of the obtained mixtures of glycerides of monocarboxylic acids in the amount of 0.5–2.0 wt parts per 100 wt parts of unstabilized industrial chlorinated paraffin CP-30 was determined. The combined use of glycerides of monocarboxylic acids with calcium-containing compounds as a complex stabilizer with a molar ratio of esters/Ca 0.93–0.86/0.07–0.14, respectively, was investigated. Chloroparaffin CP-470, stabilized by the developed complex stabilizer, was successfully used in a polyvinyl chloride composition for cable compound of the brand OM-40.Conclusions. A proposed variant of a complex stabilizer for chlorinated paraffins based on Russian raw materials for import substitution will expand the range of effective stabilizers for organochlorine substances. Glycerides of monocarboxylic acids are shown to exhibit a thermostabilizing effect on industrial chlorinated paraffins. The relationship between the length of the hydrocarbon substituent of the carboxylic acid in the ester and the thermostabilizing effect is obtained. With an increase in the number of carbon atoms in the hydrocarbon substituent of the carboxylic acid, the heat-stabilizing ability decreases. The minimum sufficient concentration of glycerides of carboxylic acids was 0.05 ± 0.005 mol/kg, above which no increase in the thermostabilizing effect on chloroparaffin was observed. A synergistic ratio of the components of the stabilizing mixture in terms of thermal stability—glycerides of monocarboxylic acids/calcium-containing compounds—was found equal to 0.85–0.9/0.15–0.1.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76156127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-09-30DOI: 10.32362/2410-6593-2022-17-4-357-368
O. Medennikov, N. Shabelskaya
Objectives. There is considerable economic demand for products obtained by processing phosphogypsum. In particular, calcium sulfide-based materials having luminescent properties are the object of intensive study due to the wide range of possibilities for their use. The alloying of the structure of calcium sulfide with cations of rare earth elements leads to the appearance of a glow having various colors. However, the high cost of such phosphorescent materials is due to the high chemical purity of the reagents required for their synthesis. The development of efficient methods for obtaining calcium sulfide-based luminescent materials from phosphogypsum is part of an integrated approach to solving the problem of synthesizing economically demanded materials from production waste.Methods. The synthesized materials were studied using X-ray phase analysis and scanning electron microscopy. Photos of the samples were taken under illumination with an incandescent lamp or a fluorescent ultraviolet lamp.Results. According to X-ray phase analysis, phosphogypsum is mainly comprised of calcium sulfate dihydrate and calcium sulfate hemihydrate. Heat treatment of a phosphogypsum sample at a temperature of 1073 K is accompanied by the formation of anhydrous calcium sulfate. In the presence of a reducing agent, a composite material is formed containing a phase of anhydrous calcium sulfate and calcium sulfide. Due to the calcium sulfide content, phosphogypsum has luminescent properties when heat-treated in the presence of various reducing agents, including activated carbon, wood charcoal, vegetable oil, citric acid, starch, and sucrose.Conclusions. Optimal technological conditions for obtaining a composite material exhibiting luminescent properties are revealed. The successful synthesis of phosphor from without nonpretreated phosphogypsum is demonstrated. Optimal technological conditions for obtaining a composite material exhibiting luminescent properties are as follows: heat treatment temperature is 1073–1173 K; isothermal holding time is 60 min; reducing agent quantity is 37–50% (mol). The study results are widely applicable to processing wastes obtained from large-scale chemical production involving the production of a highly demanded inorganic product.
{"title":"Technology for processing phosphogypsum into a fluorescent dye based on calcium sulfide","authors":"O. Medennikov, N. Shabelskaya","doi":"10.32362/2410-6593-2022-17-4-357-368","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-4-357-368","url":null,"abstract":"Objectives. There is considerable economic demand for products obtained by processing phosphogypsum. In particular, calcium sulfide-based materials having luminescent properties are the object of intensive study due to the wide range of possibilities for their use. The alloying of the structure of calcium sulfide with cations of rare earth elements leads to the appearance of a glow having various colors. However, the high cost of such phosphorescent materials is due to the high chemical purity of the reagents required for their synthesis. The development of efficient methods for obtaining calcium sulfide-based luminescent materials from phosphogypsum is part of an integrated approach to solving the problem of synthesizing economically demanded materials from production waste.Methods. The synthesized materials were studied using X-ray phase analysis and scanning electron microscopy. Photos of the samples were taken under illumination with an incandescent lamp or a fluorescent ultraviolet lamp.Results. According to X-ray phase analysis, phosphogypsum is mainly comprised of calcium sulfate dihydrate and calcium sulfate hemihydrate. Heat treatment of a phosphogypsum sample at a temperature of 1073 K is accompanied by the formation of anhydrous calcium sulfate. In the presence of a reducing agent, a composite material is formed containing a phase of anhydrous calcium sulfate and calcium sulfide. Due to the calcium sulfide content, phosphogypsum has luminescent properties when heat-treated in the presence of various reducing agents, including activated carbon, wood charcoal, vegetable oil, citric acid, starch, and sucrose.Conclusions. Optimal technological conditions for obtaining a composite material exhibiting luminescent properties are revealed. The successful synthesis of phosphor from without nonpretreated phosphogypsum is demonstrated. Optimal technological conditions for obtaining a composite material exhibiting luminescent properties are as follows: heat treatment temperature is 1073–1173 K; isothermal holding time is 60 min; reducing agent quantity is 37–50% (mol). The study results are widely applicable to processing wastes obtained from large-scale chemical production involving the production of a highly demanded inorganic product.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87415378","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-09-30DOI: 10.32362/2410-6593-2022-17-4-335-345
A. C. Ha, T. Nguyen, P. Nguyen, V. M. Nguyen
Objectives. The study aimed to synthesize the multifunctional materials silver-added titanates via reduction of sol-gel fabricating titanates (Fe2TiO5 and NiTiO3) with Jasminium subtriplinerve Blume leaf extract.Methods. The physicochemical characteristics of the obtained materials were determined by X-ray diffraction, energy dispersive X-Ray spectroscopy, Raman spectroscopy, Brunauer–Emmett–Teller specific surface area, scanning electron microscopy, and UV–Vis absorption spectroscopy.Results. The results demonstrated good dispersion of silver on the surface of Fe2TiO5 and NiTiO3 to create photocatalysts with two light-absorbing regions. The obtained materials were applied as antibacterial agents in polluted water. The Ag–Fe2TiO5 (Ag–FTO) samples showed better properties and antibacterial activity than Ag–NiTiO3 (Ag–NTO) due to the better dispersion of silver nanoparticles on the FTO surface. Besides, the antibacterial results exhibit increased inhibiting activity against gram-negative (−) bacteria as compared with gram-positive (+) bacteria.Conclusions. Nanomaterials Fe2TiO5 and NiTiO3 added Ag were successfully synthesized. These materials showed excellent inhibition against Baccilus cereus, Escherichia coli, Pseudomonas aeruginosa, Salmonella typhi, and Staphylococcus aureus. Additionally, the Ag–Fe2TiO5 samples showed much better antibacterial activity than the Ag–NiTiO3 sample.
{"title":"Antibacterial activity of green fabricated silver-doped titanates","authors":"A. C. Ha, T. Nguyen, P. Nguyen, V. M. Nguyen","doi":"10.32362/2410-6593-2022-17-4-335-345","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-4-335-345","url":null,"abstract":"Objectives. The study aimed to synthesize the multifunctional materials silver-added titanates via reduction of sol-gel fabricating titanates (Fe2TiO5 and NiTiO3) with Jasminium subtriplinerve Blume leaf extract.Methods. The physicochemical characteristics of the obtained materials were determined by X-ray diffraction, energy dispersive X-Ray spectroscopy, Raman spectroscopy, Brunauer–Emmett–Teller specific surface area, scanning electron microscopy, and UV–Vis absorption spectroscopy.Results. The results demonstrated good dispersion of silver on the surface of Fe2TiO5 and NiTiO3 to create photocatalysts with two light-absorbing regions. The obtained materials were applied as antibacterial agents in polluted water. The Ag–Fe2TiO5 (Ag–FTO) samples showed better properties and antibacterial activity than Ag–NiTiO3 (Ag–NTO) due to the better dispersion of silver nanoparticles on the FTO surface. Besides, the antibacterial results exhibit increased inhibiting activity against gram-negative (−) bacteria as compared with gram-positive (+) bacteria.Conclusions. Nanomaterials Fe2TiO5 and NiTiO3 added Ag were successfully synthesized. These materials showed excellent inhibition against Baccilus cereus, Escherichia coli, Pseudomonas aeruginosa, Salmonella typhi, and Staphylococcus aureus. Additionally, the Ag–Fe2TiO5 samples showed much better antibacterial activity than the Ag–NiTiO3 sample.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76592704","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-07-31DOI: 10.32362/2410-6593-2022-17-3-210-230
V. A. Sokhraneva, D. A. Yusupova, V. S. Boriskin, N. V. Groza
Objectives. With the growing resistance of pathogenic microorganisms to antibiotics, the development of new antimicrobial drugs offering specific mechanisms of action becomes an urgent task. Only few antimicrobials offer a broad spectrum of activity against gram-positive and gram-negative bacteria, molds, and yeasts. In this regard, the purpose of the work was to develop methods for synthesizing biologically active derivatives of alkyl-substituted phenols (reactions at the hydroxy group) to study their biological effect.Methods. The synthesis of imidazole acetates of substituted phenols was carried out in two stages. At the first stage, the chloroacetyl derivative of the selected compounds was obtained, to which imidazole was then added. O-acylation reactions at the first stage of the synthesis were carried out under varying conditions. The first version of the synthesis was carried out using chloroacetyl chloride as an acylating agent together with a high-boiling solvent. In the second variant, chloroacetic anhydride was used, along with an attempt to replace the solvent with a low-boiling one. A thymol methoxy derivative was additionally synthesized by a known method using methyl iodide and varying the reaction parameters.Results. The parameters of chloroacetylation and methoxylation of aromatic alcohols were optimized with rational selection of solvents and the ratio of reagents in the reactions. Synthesized thymol (2-isopropyl-5-methylphenol) and propofol (2,6-isopropylphenol) derivatives contained imidazole as an additional pharmacophore with affinity for microorganism cell membrane proteins. A thymol methoxy derivative comprising an aromatic ether exhibiting increased hydrophobicity was also obtained. The synthesized compounds were characterized by NMR spectroscopy.Conclusions. Chloroacetyl derivatives of aromatic alcohols can be effectively synthesized by cooling the reaction mixture using an excess quantity of an acylating agent and increasing the reaction time (compared to literature data). The yield of thymol chloroacetate was 75%, while that of propofol chloroacetate was 30%. This can be explained by the sterically hindered reaction of the propofol alcohol group, which has isopropyl substituents at the second and sixth positions of the benzene ring.
{"title":"Obtaining substituted phenol derivatives with potential antimicrobial activity","authors":"V. A. Sokhraneva, D. A. Yusupova, V. S. Boriskin, N. V. Groza","doi":"10.32362/2410-6593-2022-17-3-210-230","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-3-210-230","url":null,"abstract":"Objectives. With the growing resistance of pathogenic microorganisms to antibiotics, the development of new antimicrobial drugs offering specific mechanisms of action becomes an urgent task. Only few antimicrobials offer a broad spectrum of activity against gram-positive and gram-negative bacteria, molds, and yeasts. In this regard, the purpose of the work was to develop methods for synthesizing biologically active derivatives of alkyl-substituted phenols (reactions at the hydroxy group) to study their biological effect.Methods. The synthesis of imidazole acetates of substituted phenols was carried out in two stages. At the first stage, the chloroacetyl derivative of the selected compounds was obtained, to which imidazole was then added. O-acylation reactions at the first stage of the synthesis were carried out under varying conditions. The first version of the synthesis was carried out using chloroacetyl chloride as an acylating agent together with a high-boiling solvent. In the second variant, chloroacetic anhydride was used, along with an attempt to replace the solvent with a low-boiling one. A thymol methoxy derivative was additionally synthesized by a known method using methyl iodide and varying the reaction parameters.Results. The parameters of chloroacetylation and methoxylation of aromatic alcohols were optimized with rational selection of solvents and the ratio of reagents in the reactions. Synthesized thymol (2-isopropyl-5-methylphenol) and propofol (2,6-isopropylphenol) derivatives contained imidazole as an additional pharmacophore with affinity for microorganism cell membrane proteins. A thymol methoxy derivative comprising an aromatic ether exhibiting increased hydrophobicity was also obtained. The synthesized compounds were characterized by NMR spectroscopy.Conclusions. Chloroacetyl derivatives of aromatic alcohols can be effectively synthesized by cooling the reaction mixture using an excess quantity of an acylating agent and increasing the reaction time (compared to literature data). The yield of thymol chloroacetate was 75%, while that of propofol chloroacetate was 30%. This can be explained by the sterically hindered reaction of the propofol alcohol group, which has isopropyl substituents at the second and sixth positions of the benzene ring.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87016891","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-07-31DOI: 10.32362/2410-6593-2022-17-3-189-200
T. G. Korotkova, G. Kasyanov
Objectives. To apply an analytical method for the calculation of a distillation column for the production of D2O at a two-column Kuhn installation operating under vacuum: to simulate the Kuhn installation in the Hysys software; and to compare experimental and calculated data.Methods. Analytical method for the calculation of distillation columns “from stage to stage,” from the lower theoretical separation stage (TSS) to the upper stage. This method is based on phase equilibrium at the TSS with known data of input flows and component concentrations in the column bottoms. Hysys was used as modeling software.Results. Comparison of the calculation results with Kuhn’s experimental data testified to the high calculation accuracy of the vapor–liquid phase equilibrium for the H2O–D2O mixture at the TSS. The convergence of the D2O material balance for the entire installation was 0.005%. The identification parameter was the number of the column feed plate. Simulation of the Kuhn installation in the Hysys software showed a qualitative agreement of D2O concentrations in material flows. The UNIQUAC (UNIversal QUAsiChemical) model was used to calculate activity coefficients. The found values of the number of theoretical separation stages (NTSS) in both columns, were 88 and 153 taking into account the reboiler and condenser. This is less than the experimental 295 and 400, respectively. The discrepancy can be explained by the increased phase equilibrium H2O constant in the UNIQUAC model. However, the convergence of the material balance in terms of D2O was high and amounted to 1.38·10−6 %. The absolute error of the found concentrations in material flows did not exceed 0.12 mol %.Conclusions. The results obtained indicated the possible use of the Hysys modeling software when searching for and optimizing the operating mode of the block diagram of a cascade of distillation columns with direct and recycle flows to separate a mixture of water into light and heavy water. The final results obtained with regard to the operating mode, inlet and outlet material flows (flow rate, composition, temperature, and pressure drop across the column) are recommended for use in the analytical program for the calculation of the distillation column to refine the NTSS and distribution profile of the concentrations of the H2O and D2O components along the height of the column.
{"title":"Analysis of the rectifying separation of H2 O–D2 O mixture into light and heavy water by means of mathematical modeling","authors":"T. G. Korotkova, G. Kasyanov","doi":"10.32362/2410-6593-2022-17-3-189-200","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-3-189-200","url":null,"abstract":"Objectives. To apply an analytical method for the calculation of a distillation column for the production of D2O at a two-column Kuhn installation operating under vacuum: to simulate the Kuhn installation in the Hysys software; and to compare experimental and calculated data.Methods. Analytical method for the calculation of distillation columns “from stage to stage,” from the lower theoretical separation stage (TSS) to the upper stage. This method is based on phase equilibrium at the TSS with known data of input flows and component concentrations in the column bottoms. Hysys was used as modeling software.Results. Comparison of the calculation results with Kuhn’s experimental data testified to the high calculation accuracy of the vapor–liquid phase equilibrium for the H2O–D2O mixture at the TSS. The convergence of the D2O material balance for the entire installation was 0.005%. The identification parameter was the number of the column feed plate. Simulation of the Kuhn installation in the Hysys software showed a qualitative agreement of D2O concentrations in material flows. The UNIQUAC (UNIversal QUAsiChemical) model was used to calculate activity coefficients. The found values of the number of theoretical separation stages (NTSS) in both columns, were 88 and 153 taking into account the reboiler and condenser. This is less than the experimental 295 and 400, respectively. The discrepancy can be explained by the increased phase equilibrium H2O constant in the UNIQUAC model. However, the convergence of the material balance in terms of D2O was high and amounted to 1.38·10−6 %. The absolute error of the found concentrations in material flows did not exceed 0.12 mol %.Conclusions. The results obtained indicated the possible use of the Hysys modeling software when searching for and optimizing the operating mode of the block diagram of a cascade of distillation columns with direct and recycle flows to separate a mixture of water into light and heavy water. The final results obtained with regard to the operating mode, inlet and outlet material flows (flow rate, composition, temperature, and pressure drop across the column) are recommended for use in the analytical program for the calculation of the distillation column to refine the NTSS and distribution profile of the concentrations of the H2O and D2O components along the height of the column.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82274831","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-07-31DOI: 10.32362/2410-6593-2022-17-3-253-267
N. B. Savelieva, G. V. Ishutenko, A. Polosin, F. V. Radus, D. S. Polyansky, S. A. Kurbatkin, Y. Efimova, P. Postnikov
Objectives. To validate a new method for the quantitative determination of 31 potent and narcotic substances and their metabolites in urine that meets the requirements of ISO/IEC 17025 using a fast and highly sensitive method of chromato-mass spectrometry with a view to introducing such a method into the routine practice of the National Anti-Doping Laboratory of the Lomonosov Moscow State University (NADL MSU).Methods. Urine samples soldered with standard solutions were analyzed using ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC–MS/MS).Results. Diagnostic precursor/ion-product pairs and collision energies were established to allow unambiguous identification of the analyzed substances. During sample preparation, hydrolysis conditions were optimized. Selectivity, linearity, limits of qualitative determination, limit of quantitative determination (established under the contract with the customer firm), matrix effect, and measurement uncertainty were defined. Systematized data grouped by classes of analytes are given in the final table.Conclusions. The important advantages of the presented technique are the absence of complex and lengthy sample preparation, as well as the short time of the analysis method (about 10 min), which can significantly reduce duration along with labor and analysis costs. The addition of new analytes will ensure the versatility of the technique, as well as expanding its scope.
{"title":"Validation of a method for the quantitative determination of narcotic and psychotropic substances in urine by UHPLC–MS/MS","authors":"N. B. Savelieva, G. V. Ishutenko, A. Polosin, F. V. Radus, D. S. Polyansky, S. A. Kurbatkin, Y. Efimova, P. Postnikov","doi":"10.32362/2410-6593-2022-17-3-253-267","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-3-253-267","url":null,"abstract":"Objectives. To validate a new method for the quantitative determination of 31 potent and narcotic substances and their metabolites in urine that meets the requirements of ISO/IEC 17025 using a fast and highly sensitive method of chromato-mass spectrometry with a view to introducing such a method into the routine practice of the National Anti-Doping Laboratory of the Lomonosov Moscow State University (NADL MSU).Methods. Urine samples soldered with standard solutions were analyzed using ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC–MS/MS).Results. Diagnostic precursor/ion-product pairs and collision energies were established to allow unambiguous identification of the analyzed substances. During sample preparation, hydrolysis conditions were optimized. Selectivity, linearity, limits of qualitative determination, limit of quantitative determination (established under the contract with the customer firm), matrix effect, and measurement uncertainty were defined. Systematized data grouped by classes of analytes are given in the final table.Conclusions. The important advantages of the presented technique are the absence of complex and lengthy sample preparation, as well as the short time of the analysis method (about 10 min), which can significantly reduce duration along with labor and analysis costs. The addition of new analytes will ensure the versatility of the technique, as well as expanding its scope. ","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85337188","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-07-31DOI: 10.32362/2410-6593-2022-17-3-242-252
V. Gomzyak, N. V. Bychkov, A. S. Aduev, V. Ivanova, A. D. Koshelev, S. Chvalun
Objects. To synthesize monodisperse biodegradable hyperbranched polymers based on D,L-lactide in the presence of Boltorn™ H30 polyester polyol as a macroinitiator.Methods. 1H and 13C nuclear magnetic resonance (NMR) spectroscopy was used to study the chemical structure of the Boltorn™ H30 polyester polyol and (Boltorn™ H30)-PDLA hyperbranched copolymers. The molecular weight distribution of the polymers was studied by gel permeation chromatography (GPC). In order to study the thermal stability of Boltorn™ H30 polyester polyol, thermogravimetric analysis (TGA) was used. Polymerization of D,L-lactide was carried out in a block in the presence of Boltorn™ H30 polyester polyol.Results. The degree of branching of Boltorn™ H30 polyester polyol was calculated from NMR data, while the TGA method was used to determine the upper operational temperature range. The polymerization of D,L-lactide in the presence of Boltorn™ H30 polyester polyol used as a macroinitiator was studied. The molecular weight characteristics of the obtained copolymers were studied by NMR and GPC.Conclusions. Optimum conditions were determined for the polymerization of D,L-lactide when using Boltorn™ H30 polyester polyol as a macroinitiator. The possibility of synthesizing narrowly dispersed hyperbranched polymers (Boltorn™ H30)-PDLA under the described conditions was demonstrated.
对象。以Boltorn™H30聚酯多元醇为宏观引发剂，以D, l -丙交酯为原料合成单分散可生物降解的超支化聚合物。采用1H和13C核磁共振(NMR)谱对Boltorn™H30聚酯多元醇和(Boltorn™H30)-PDLA超支化共聚物的化学结构进行了研究。用凝胶渗透色谱法(GPC)研究了聚合物的分子量分布。为了研究Boltorn™H30聚酯多元醇的热稳定性，采用热重分析(TGA)方法。在Boltorn™H30聚酯多元醇的存在下，D, l -丙交酯在一个块中进行聚合。Boltorn™H30聚酯多元醇的支化度由NMR数据计算，TGA方法确定最高操作温度范围。以Boltorn™H30聚酯多元醇为高分子引发剂，研究了D, l -丙交酯的聚合反应。通过NMR和gpc对所得共聚物的分子量特性进行了研究。以Boltorn™H30聚酯多元醇为高分子引发剂，确定了D, l -丙交酯聚合的最佳条件。证明了在上述条件下合成窄分散超支化聚合物(Boltorn™H30)-PDLA的可能性。
{"title":"Polymerization of D,L-lactide in the presence of Boltorn™ polyester polyol","authors":"V. Gomzyak, N. V. Bychkov, A. S. Aduev, V. Ivanova, A. D. Koshelev, S. Chvalun","doi":"10.32362/2410-6593-2022-17-3-242-252","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-3-242-252","url":null,"abstract":"Objects. To synthesize monodisperse biodegradable hyperbranched polymers based on D,L-lactide in the presence of Boltorn™ H30 polyester polyol as a macroinitiator.Methods. 1H and 13C nuclear magnetic resonance (NMR) spectroscopy was used to study the chemical structure of the Boltorn™ H30 polyester polyol and (Boltorn™ H30)-PDLA hyperbranched copolymers. The molecular weight distribution of the polymers was studied by gel permeation chromatography (GPC). In order to study the thermal stability of Boltorn™ H30 polyester polyol, thermogravimetric analysis (TGA) was used. Polymerization of D,L-lactide was carried out in a block in the presence of Boltorn™ H30 polyester polyol.Results. The degree of branching of Boltorn™ H30 polyester polyol was calculated from NMR data, while the TGA method was used to determine the upper operational temperature range. The polymerization of D,L-lactide in the presence of Boltorn™ H30 polyester polyol used as a macroinitiator was studied. The molecular weight characteristics of the obtained copolymers were studied by NMR and GPC.Conclusions. Optimum conditions were determined for the polymerization of D,L-lactide when using Boltorn™ H30 polyester polyol as a macroinitiator. The possibility of synthesizing narrowly dispersed hyperbranched polymers (Boltorn™ H30)-PDLA under the described conditions was demonstrated.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76496556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-07-31DOI: 10.32362/2410-6593-2022-17-3-201-209
A. I. Musin, Y. Borisova, G. Raskil’dina, R. Daminev, A. R. Davletshin, S. S. Zlotskii
Objectives. To study the hydrogenation of substituted 5-acyl-1,3-dioxanes in the presence of metal-containing catalysts (Pt/Re, Pd/C, Ni/kieselguhr, and Ni/Mo).Methods. In order to determine the qualitative and quantitative composition of the reaction masses, the following analysis methods were used: gas-liquid chromatography (using the Kristall 2000 hardware complex); mass-spectroscopy (using Chromatec-Kristall 5000M device with NIST 2012); nuclear magnetic resonance (NMR) spectrometry (using Bruker AM-500 device with operating frequencies of 500 and 125 MHz).Results. Hydrogenation of substituted 5-acyl-1,3-dioxanes obtained by condensation of carbonyl compounds with paraformaldehyde and sulfuric acid was used to synthesize heterocyclic alcohols in the presence of metal-containing catalysts with a conversion of the initial ketones of 60–90% and a formation selectivity of target products of 70–90%. Substances were analyzed and confirmed by gas-liquid chromatography, mass spectrometry and NMR spectroscopy.Conclusions. The best catalyst for the reduction of substituted 5-acyl-1,3-dioxanes is Pd/C. By using this catalyst, it is possible to achieve a high selectivity for the formation of the corresponding heterocyclic alcohols at a conversion rate of the initial ketones of 60–90%.
{"title":"Heterogeneous catalytic reduction of substituted 5-acyl-1,3-dioxanes","authors":"A. I. Musin, Y. Borisova, G. Raskil’dina, R. Daminev, A. R. Davletshin, S. S. Zlotskii","doi":"10.32362/2410-6593-2022-17-3-201-209","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-3-201-209","url":null,"abstract":"Objectives. To study the hydrogenation of substituted 5-acyl-1,3-dioxanes in the presence of metal-containing catalysts (Pt/Re, Pd/C, Ni/kieselguhr, and Ni/Mo).Methods. In order to determine the qualitative and quantitative composition of the reaction masses, the following analysis methods were used: gas-liquid chromatography (using the Kristall 2000 hardware complex); mass-spectroscopy (using Chromatec-Kristall 5000M device with NIST 2012); nuclear magnetic resonance (NMR) spectrometry (using Bruker AM-500 device with operating frequencies of 500 and 125 MHz).Results. Hydrogenation of substituted 5-acyl-1,3-dioxanes obtained by condensation of carbonyl compounds with paraformaldehyde and sulfuric acid was used to synthesize heterocyclic alcohols in the presence of metal-containing catalysts with a conversion of the initial ketones of 60–90% and a formation selectivity of target products of 70–90%. Substances were analyzed and confirmed by gas-liquid chromatography, mass spectrometry and NMR spectroscopy.Conclusions. The best catalyst for the reduction of substituted 5-acyl-1,3-dioxanes is Pd/C. By using this catalyst, it is possible to achieve a high selectivity for the formation of the corresponding heterocyclic alcohols at a conversion rate of the initial ketones of 60–90%.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73134928","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-07-31DOI: 10.32362/2410-6593-2022-17-3-231-241
I. Vasilyev, V. Ananyev, M. Chernov
Objectives. To investigate the production and biological degradation of biodegradable hybrid compositions (BHCs), dispersed-filled with starch-containing products of various origins and distilled monoglycerides, along with the biodegradation of compositions based on low density polyethylene and thermoplastic starch (TPS) of various origins: corn, pea, and rice.Methods. Thermoplastic starch was obtained based on native starches of several types, which were processed in Brabender and MashkPlast (Russia) laboratory extruders. BHCs in the form of strands, granules, and films were obtained by mixing thermoplastic starches with polyethylene in extruders. Structural BHC parameters were studied by optical and electron scanning microscopy. The biodegradability of the composite films was evaluated by placing them in biohumus for six months; during storage, the change in water absorption of the films was determined. Before and after the biodegradation process, tensile fracture stress and elongation at rupture were determined to evaluate BHC performance (physical and mechanical characteristics of films). Changes in the chemical structure during biodegradation were determined by Fourier infrared spectroscopy.Results. The positive effect (acceleration of the biodegradation process) of using a novel type of starch plasticizer—monoglycerides distilled in TPS–polyethylene compositions—was confirmed. After six months, intensive sporulation of active microorganisms was observed on the surface of the samples. At the same time, water absorption by the samples reached 30%. The observed 60% decrease in strength and deformation properties indicates an intensive process of biodegradation.Conclusions. The biodegradation rate was shown to depend on the concentration and even distribution of the natural biodegradable filler in the synthetic polymer composition.
{"title":"Biodegradable packaging materials based on low density polyethylene, starch and monoglycerides","authors":"I. Vasilyev, V. Ananyev, M. Chernov","doi":"10.32362/2410-6593-2022-17-3-231-241","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-3-231-241","url":null,"abstract":"Objectives. To investigate the production and biological degradation of biodegradable hybrid compositions (BHCs), dispersed-filled with starch-containing products of various origins and distilled monoglycerides, along with the biodegradation of compositions based on low density polyethylene and thermoplastic starch (TPS) of various origins: corn, pea, and rice.Methods. Thermoplastic starch was obtained based on native starches of several types, which were processed in Brabender and MashkPlast (Russia) laboratory extruders. BHCs in the form of strands, granules, and films were obtained by mixing thermoplastic starches with polyethylene in extruders. Structural BHC parameters were studied by optical and electron scanning microscopy. The biodegradability of the composite films was evaluated by placing them in biohumus for six months; during storage, the change in water absorption of the films was determined. Before and after the biodegradation process, tensile fracture stress and elongation at rupture were determined to evaluate BHC performance (physical and mechanical characteristics of films). Changes in the chemical structure during biodegradation were determined by Fourier infrared spectroscopy.Results. The positive effect (acceleration of the biodegradation process) of using a novel type of starch plasticizer—monoglycerides distilled in TPS–polyethylene compositions—was confirmed. After six months, intensive sporulation of active microorganisms was observed on the surface of the samples. At the same time, water absorption by the samples reached 30%. The observed 60% decrease in strength and deformation properties indicates an intensive process of biodegradation.Conclusions. The biodegradation rate was shown to depend on the concentration and even distribution of the natural biodegradable filler in the synthetic polymer composition. ","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78182845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-06-01DOI: 10.32362/2410-6593-2022-17-2-164-171
K. Kirshanov, A. Gervald, R. Toms, A. Lobanov
Objects. Due to the polymer waste accumulation, the search for new directions for their utilization is urgent. Chemical recycling methods are of considerable interest, which allow one to obtain the original monomers or change the compositions of the copolymers. From the point of view of building a circular economy, a promising material is polyethylene terephthalate (PET), on the basis of which amorphous copolyesters can be obtained. The study aimed to analyze the simultaneous glycolysis and interchain exchange reactions of PET in the presence of the oligoethylene phthalate modifier with hydroxyl end groups and the study of isothermal crystallization of poly(ethylene phthalate-co-terephthalates) with different phthalate contents obtained in this way.Methods. Oligoethylene phthalate is synthesized by polycondensation. Poly(ethylene phthalateco-terephthalates) were obtained by the interaction of post-consumer PET with oligoethylene phthalate. The composition of the oligomer and copolymers was confirmed using Fourier-transform infrared spectroscopy, thermal characteristics and crystallization half-times were determined by differential scanning calorimetry.Results. In this work, the use of the post-consumer PET chemical recycling process, aimed at obtaining copolyesters under the influence of small modifier amounts was proposed. The process consisted in carrying out the combined interchain exchange and degradation with a complex oligoester different from PET. Poly(ethylene phthalate-co-terephthalate) copolymers were obtained via reaction of post-consumer poly(ethylene terephthalate) flakes and synthesized oligoethylene phthalate resin in the melt phase in the absence of catalyst. The effect of phthalate concentration in polymer on the isothermal crystallization of phthalate substituted poly(ethylene terephthalate) was estimated.Conclusions. The hypothesis about the possibility of using an oligoester modifier to obtain the PET-based copolymer at the high rate and without reducing the molecular weight to values characteristic of a monomer or oligomer has been confirmed. The process can be used to obtain random copolyesters based on post-consumer PET. The phthalate unit concentration increase is followed by decrease in the glass transition temperature, temperature and heat of fusion, and increase in crystallization half-times. Phthalate has a better ability to retard PET crystallization than 2-methyl-1,3-propanediol or furandicarboxylic acid, but is inferior to some of the other modifiers known.
{"title":"Obtaining phthalate substituted post-consumer polyethylene terephthalate and its isothermal crystallization","authors":"K. Kirshanov, A. Gervald, R. Toms, A. Lobanov","doi":"10.32362/2410-6593-2022-17-2-164-171","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-2-164-171","url":null,"abstract":"Objects. Due to the polymer waste accumulation, the search for new directions for their utilization is urgent. Chemical recycling methods are of considerable interest, which allow one to obtain the original monomers or change the compositions of the copolymers. From the point of view of building a circular economy, a promising material is polyethylene terephthalate (PET), on the basis of which amorphous copolyesters can be obtained. The study aimed to analyze the simultaneous glycolysis and interchain exchange reactions of PET in the presence of the oligoethylene phthalate modifier with hydroxyl end groups and the study of isothermal crystallization of poly(ethylene phthalate-co-terephthalates) with different phthalate contents obtained in this way.Methods. Oligoethylene phthalate is synthesized by polycondensation. Poly(ethylene phthalateco-terephthalates) were obtained by the interaction of post-consumer PET with oligoethylene phthalate. The composition of the oligomer and copolymers was confirmed using Fourier-transform infrared spectroscopy, thermal characteristics and crystallization half-times were determined by differential scanning calorimetry.Results. In this work, the use of the post-consumer PET chemical recycling process, aimed at obtaining copolyesters under the influence of small modifier amounts was proposed. The process consisted in carrying out the combined interchain exchange and degradation with a complex oligoester different from PET. Poly(ethylene phthalate-co-terephthalate) copolymers were obtained via reaction of post-consumer poly(ethylene terephthalate) flakes and synthesized oligoethylene phthalate resin in the melt phase in the absence of catalyst. The effect of phthalate concentration in polymer on the isothermal crystallization of phthalate substituted poly(ethylene terephthalate) was estimated.Conclusions. The hypothesis about the possibility of using an oligoester modifier to obtain the PET-based copolymer at the high rate and without reducing the molecular weight to values characteristic of a monomer or oligomer has been confirmed. The process can be used to obtain random copolyesters based on post-consumer PET. The phthalate unit concentration increase is followed by decrease in the glass transition temperature, temperature and heat of fusion, and increase in crystallization half-times. Phthalate has a better ability to retard PET crystallization than 2-methyl-1,3-propanediol or furandicarboxylic acid, but is inferior to some of the other modifiers known.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82423684","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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