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BIOREMEDIATION OF SOIL CONTAMINATED WITH SYNTHETIC COMPOUNDS A.V. Nazarov Received: 07.10.2020 Received in revised form: 07.10.2020 Published: 01.02.2021 Abstract:
The efficiency of using bacteria of the Rhodococcus wratislaviensis KT112-7 strain and the humic fertilizer "Gumikom" for bioremediation of soil contaminated with synthetic compounds has been investigated. Due to the activities of the chemical industry, to date, there has been an accumulation in the environment of xenobiotics, resistant to microbial decomposition, dangerous to human health. Therefore, to prevent the negative consequences of this pollution, it is necessary to develop methods for cleaning the environment from a complex of synthetic pollutants. The technogenic soil used in the experiment was taken from the territory of the former chemical enterprise "Sredne-Volzhsky Chemical Plant" in Chapayevsk, Samara Region. The soil contained the following xenobiotics: hexachlorobenzene, lindane, a mixture of polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloromethylmethane (DDT) and dichlorodiphenyltrichloromethylmethane (DDD), trialate, phthalic esters (dioctyl phthalate and dibutyl phthalate). Cells of bacteria of the R. wratislaviensis KT112-7 strain in the amount of 107 cells/g and the fertilizer "Gumikom" – 0.01, 0,1 and 1,0% were introduced into the soil, depending on the variant of the experiment, and after 2 weeks the content of residual pollutants. The concentration of xenobiotics was estimated using an Agilent 6890/5973N gas chromatography-mass spectrometer. Previously, the effect of humic fertilizer on the destruction of pesticides by bacteria-destructors in the soil has not been studied. The introduction of the "Gumikom" in doses of 0,1 and 1,0% reduced the concentration of trialate and phthalic acid esters in the contaminated soil relative to the variant without the addition of the humic fertilizer. The inoculation with R. wratislaviensis KT112-7 bacteria into the contaminated soil, compared with the option without the addition of destructive bacteria, reduced the concentration of lindane, a mixture of PCBs, DDT and DDD, triallate, phthalic acid esters. The maximum loss of most of the pollutants was observed when the drug "Gumikom" was added together with bacteria-destructors. With the introduction of "Gumikom" in doses of 0,1 and 1,0%, the greatest positive effect was observed on a decrease in the content of lindane, by 2,6 and 3,5, respectively, the least – on a decrease in the concentration of DDT and DDD – by 1,2 times. The data obtained can be used to develop biotechnologies for cleaning the environment from complex soil contamination with the studied xenobiotics. Keywords: pesticides, polychlorinated biphenyls (PCBs), phthalic esters (dioctyl phthalate and dibutyl phthalate), Rhodococcus wratislaviensis KT112-7, soil remediation. Authors:
Alexey V. Nazarov (Perm, Russian Federation) – Ph.D. in Biological Sciences, Associate Professor, Senior Researcher at the Institute of Ecology and Genetics of Microorganisms UB RAS (13, Goleva str., Perm, 614081, e-mail: nazarov@iegm.ru). References:
HALOTOLERANT BACTERIA OF A ACTINOBACTERIA CLASS – PRODUCERS OF THE OSMOPROTECTIVE COMPOUNDS (EKTOINE AND HYDROXYEKTOINE) L.N. Anan’ina, E.A. Shestakova Received: 30.10.2020 Received in revised form: 30.10.2020 Published: 01.02.2021 Abstract:
Ectoine has a wide range of applications in the chemical-pharmaceutical branch of the chemical industry. Ectoine is currently used in skin care products as an anti-drying agent for the skin and helps protect it from UV rays. Ectoine can find wide application in the production of drugs (bacteriophages, adenoviral vectors, etc.) due to the properties that increase the stability and shelf life of macromolecules such as proteins and DNA. Moreover, research is underway on the role of ectoine as a therapeutic agent in the treatment of diseases associated with impaired protein folding – amyloidosis (Alzheimer's disease). Ectoine is a compatible solute in eubacterial cells. In the course of the study, the ability of actinobacteria of different taxonomic groups, isolated from saline biotopes of the Verkhnekamsk salt deposit area, to biosynthesis of ectoine and hydroxyectoine was studied by the method of high-performance liquid chromatography. It was shown for the first time that bacteria of the genus Rhodococcus synthesize ectoine and hydroxyectoine in response to hyperosmotic stress. A representative of the genus Brevibacterium (strain Brevibacterium sp. U1) accumulated ectoine in the cells. And cells of the strain Microbacterium sp. Y6 were found to have low levels of ectoine and hydroxyectoine, which may indicate that other solutes are key osmoprotectors. A promising producer of ectoine can be the Brevibacterium sp. U1, while strains of the genus Rhodococcus can be used for hydroxyectoine synthesis. Keywords: ectoine, hydroxyectoine, halotolerant bacteria. Authors:
Lyudmila N. Anan'ina (Perm, Russian Federation) – Ph.D. in Biological Sciences, researcher of laboratory of molecular microbiology and biotechnology of Institute of Ecology and Genetics of Miñroorganisms UB RAS (13, Golev str., Perm, 614081; e-mail: ludaananyina@mail.ru). Elena A. Shestakova (Perm, Russian Federation) – Engineer of laboratory of molecular microbiology and biotechnology of Institute of Ecology and Genetics of Miñroorganisms UB RAS (13, Golev str., Perm, 614081; e-mail: sheanton@mail.ru). References:
BACTERIA-DESTRUCTORS OF BENZOIC ACID OF THE GENUS HALOMONAS ISOLATED FROM THE SALT-MINING REGION A.A. Pyankova, E.G. Plotnikova Received: 28.10.2020 Received in revised form: 28.10.2020 Published: 01.02.2021 Abstract:
The accumulation of benzoic acid in the environment is due to the widespread use of this compound in industrial processes. Decomposition of benzoic acid in nature is carried out mainly by aerobic bacteria. However, biodegradation under extreme conditions such as salinity can proceed at a slow rate or efficiency. Therefore, studies on the search for halophilic/halotolerant bacteria-destructors are relevant for the development of technologies for the restoration of contaminated areas with an increased salt content. In this work, we investigated the phylogenetic diversity of benzoic acid degrading bacteria isolated from various samples from the salt-mining region (Verkhnekamsky salt deposit, Perm krai). Phylogenetic analysis based on the 16S rRNA gene revealed that the studied bacteria are most closely related to the type strains of the genus Halomonas of the species H. alkaliantarctica, H. neptunia, H. olivaria, H. taeanensis, H. titanicae, H. ventosae, H. radices, and H. utahensis. Two strains show a low level of 16S rRNA similarity (98.59-98.84%) with the type strains of species with validly published names and may represent new taxons. Analysis by BOX-PCR revealed that the studied strains differ at the genome level. Cultivation of bacteria on media with different NaCl concentrations showed that the studied strains are halophilic and halotolerant organisms. It was found that the optimal growth of all the studied strains was observed at 70-150 g/l NaCl in the medium. A number of strains are capable to grow at higher concentrations of sodium chloride in the medium (200-250 g/l). All studied strains of the genus Halomonas are able to use benzoic acid as the only source of carbon and energy at increased salinity (30 g/l NaCl). In addition, the benA gene encoding the alpha subunit of benzoate 1,2-dioxygenase, the key enzyme for the destruction of benzoic acid, was detected in all bacteria by PCR. Keywords: bacteria-destructors, benzoic acid, Halomonas, PCR, 16S rRNA gene, benA, NaCl. Authors:
Anna A. Pyankova (Perm, Russian Federation) – Engineer of laboratory of molecular microbiology and biotechnology Institute of Ecology and Genetics of Microorganisms, Ural Branch of Russian Academy of Sciences (13, Golev str., Perm, 614081; e-mail: annpjankva@mail.ru). Elena G. Plotnikova (Perm, Russian Federation) – Doctor of biology, leading researcher of laboratory of molecular microbiology and biotechnology, Institute of Ecology and Genetics of Microorganisms, Ural Branch of Russian Academy of Sciences (13, Golev str., Perm, 614081; e-mail: peg_el@mail.ru). References: 1. Llamas I., Quesada E., Martínez-Cánovas M.J., Gronquist M., Eberhard A., González J.E. Quorum sensing in halophilic bacteria: detection of N-acyl-homoserine lactones in the exopolysaccharide-producing species of Halomonas. Extremophiles, 2005, vol. 9, no. 4, pp. 333–341. 2. Berlanga M., Miñana-Galbis D., Domènech O., Guerrero R. Enhanced polyhydroxyalkanoates accumulation by Halomonas spp. in artificial biofilms of alginate beads. Int. Microbiol., 2012, vol. 15, no. 4, pp. 191–199. 3 Kearl J., McNary C., Lowman J.S., Mei C., Aanderud Z.T., Smith S.T., West J., Colton E., Hamson M., Nielsen B.L. Salt-tolerant halophyte rhizosphere bacteria stimulate growth of alfalfa in salty soil. Front. Microbiol., 2019, no. 10, pp. 1849. 4. García M.T., Ventosa A., Mellado E. Catabolic versatility of aromatic compound-degrading halophilic bacteria. FEMS Microbiol. Ecol., 2005, vol. 54, no. 1, pp. 97–109. 5. Le Borgne S., Paniagua D., Vazquez-Duhalt R. Biodegradation of organic pollutants by halophilic bacteria and archaea. J. Mol. Microbiol. Biotechnol., 2008, vol. 15, no. 2-3, pp. 74–92. 6. Parales R.E., Resnick S.M. Aromatic ring hydroxylating dioxygenases. In: Pseudomonas. Eds Ramos J.L., Levesque R.C. Boston: Springer, 2006, pp. 287–340. 7. Rozanova E.P., Nazina T.N. Uglevodorodokislyayushchie bakterii i ih aktivnost' v neftyanyh plastah [Hydrocarbon oxidizing bacteria and their activity in oil reservoirs]. Mikrobiologiya, 1982, vol. 51, pp. 324–348. 8. Korsakova E.S., Anan'ina L.N., Nazarov A.V., Bachurin B.A., Plotnikova E.G. Raznoobrazie bakterij semejstva Halomonadaceae rajona razrabotok Verhnekamskogo mestorozhdeniya solej [Diversity of bacteria of the family Halomonadaceae in the development area of the Verkhnekamskoye salt deposit]. Mikrobiologiya, 2013, vol. 82, no. 2, pp. 247-250. 9. Korsakova E.S., Pyankova A.A., Nazarov A.V., Filogeneticheskoe raznoobrazie bakterij, vydelennyh iz rizosfery mari krasnoj (Shenopodium rubrum L.), proizrastayushchej v usloviyah zasoleniya na territorii solerazrabotok (g. Solikamsk, Permskij kraj) [Phylogenetic diversity of bacteria isolated from rhizosphere Chenopodium rubrum L., growing in saline conditions on the salt deposit area (Solikamsk, Perm region)]. Vestnik Permskogo universiteta. Seriya: Biologiya, 2013, no. 3, pp. 47–51. 10. Lane D.J. 16S/23S rRNA sequencing. In: Nucleic acid techniques in bacterial systematics. Eds Stackebrandt E., Goodfellow M. New York, John Wiley and Sons, 1991, pp. 115–175. 11. Versalovic J., Schneider M., de Bruijn F.J., Lupski J. Genomic fingerprinting of bacteria using repetitive sequence-based polymerase chain reaction. Meth. Cell. Mol. Biol., 1994, vol. 5, pp. 25–40. 12. Egorova D.O., Pyankova A.A. Skrining gena al'fa-sub"edinicy benzoat dioksigenazy v bakterial'nyh associaciyah, poluchennyh v rezul'tate selekcii na (hlor)aromaticheskih soedineniyah [Alpha-subunit benzoate dioxygenase gene screening in bacterial associations obtained by selection on (chlorine) aromatic compounds]. Vestnik Permskogo universiteta. Seriya: Biologiya, 2019, no. 4, pp. 464–470. 13. Sanchez-Porro C., Kaur B., Mann H., Ventosa A. Halomonas titanicae sp. nov., a halophilic bacterium isolated from the RMS Titanic. Int. J. Syst. Evol. Microbiol., 2010, vol. 60, pp. 2768–2774. 14. Poli A., Esposito E., Orlando P., Lama L., Giordano A., de Appolonia F., Nicolaus B., Gambacorta A. Halomonas alkaliantarctica sp. nov., isolated from saline lake Cape Russell in Antarctica, an alkalophilic moderately halophilic, exopolysaccharide-producing bacterium. Syst. Appl. Microbiol., 2007, no. 30, pp. 31–38. 15. Martinez-Canovas M.J., Quesada E., Llamas I., Bejar V. Halomonas ventosae sp. nov., a moderately halophilic, denitrifying, exopolysaccharide-producing bacterium. Int. J. Syst. Evol. Microbiol., 2004, no. 54, pp. 733–737. 16. Navarro-Torre S., Carro L., Rodriguez-Llorente I.D., Pajuelo E., Caviedes M.A., Igual J.M., Klenk H.P., Montero-Calasanz M.D.C. Halomonas radicis sp. nov., isolated from Arthrocnemum macrostachyum growing in the Odiel marshes (Spain) and emended descriptions of Halomonas xinjiangensis and Halomonas zincidurans. Int J Syst Evol Microbiol., 2020, no. 70, pp. 220–227. 17. Kushner D. Zhizn' mikrobov v ekstremal'nyh usloviyah [Microbial life in extreme environments]. Moscow: Mir, 1981, 365 p. 18. Baggi G., Bernasconi S., Zangrossi M., Cavalca L., Vincenza A. Co-metabolism of di- and trichlorobenzoates in a 2-chlorobenzoate-degrading bacterial culture: Effect of the position and number of halo-substituents. International Biodeterioration and Biodegradation, 2008, vol. 62, no. 1, pp. 57–64. 19. Oie C.S.I., Albaugh C.E., Peyton B.M. Benzoate and salicylate degradation by Halomonas campisalis, an alkaliphilic and moderately halophilic microorganism. Water Res., 2007, vol. 41, no. 6, pp. 1235–1242. 20. Monzón G.C., Nisenbaum M., Seitz M.K.H., Murialdo S.E. New findings on aromatic compounds' degradation and their metabolic pathways, the biosurfactant production and motility of the halophilic bacterium Halomonas sp. KHS3. Curr. Microbiol., 2018, vol. 75, no. 8, pp. 1108–1118. 21. Moreno M.D.L., Sánchez-Porro C., Piubeli F., Frias L., García M.T., Mellado E. Cloning, characterization and analysis of cat and ben genes from the phenol degrading halophilic bacterium Halomonas organivorans. PLoS One., 2011, vol. 6, no. 6, pp. e21049. 22. Nelson W.C., Maezato Y., Wu Y.-W., Romine M.F., Lindemann S.R. Identification and resolution of microdiversity through metagenomic sequencing of parallel consortia. Appl. Environ. Microbiol., 2015, vol. 82, no. 1, pp. 255–267. 23. O'Dell K.B., Woo H.L., Utturkar S., Klingeman D., Brown S.D., Hazen T.C. Genome sequence of Halomonas sp. strain KO116, an ionic liquid-tolerant marine bacterium isolated from a lignin-enriched seawater microcosm. Genome Announc., 2015, vol. 3, no. 3, pp. e00402-15. 24 Cui Y., Cheng B., Meng Y., Li C., Yin H., Xu P., Yang C. Expression and functional analysis of two NhaD type antiporters from the halotolerant and alkaliphilic Halomonas sp. Y2. Extremophiles, 2016, vol. 20, no. 5, pp. 631–639. A MODIFIED TITRIMETRIC METHOD FOR THE QUANTITATIVE DETERMINATION OF VITAMIN C IN COLORED PLANT EXTRACTS V.S. Popov, Yu.A. Smyatskaya Received: 23.09.2020 Received in revised form: 23.09.2020 Published: 01.02.2021 Abstract:
Vitamin C (ascorbic acid) is an irreplaceable food component. It takes an active part in various metabolic reactions, participates in the synthesis of collagen, regulates blood clotting and normalizes vascular permeability, enhances immunity, and helps to eliminate toxins and heavy metals from the body. Ascorbic acid is not synthesized by the human body and therefore must be consumed daily with food. There are many different methods for determining vitamin C in foods, usually of plant origin. However, the proposed methods for the determination of ascorbic acid in colored extracts are either insufficiently reliable and convenient for implementation, or require special equipment and reagents. We have developed a simple, reliable and affordable method for the determination of vitamin C in colored plant extracts, based on the titrimetric method with visual titration with 2,6-dichlorophenolindophenol with preliminary sorption of colored compounds that interfere with the analysis. The method uses the property of kaolin (white clay) to absorb anthocyanins from extracts, the main coloring pigments of many fruits and berries (black, red currants, cherries, sweet cherries, irga, plums, grapes, etc.). Also, based on the analysis of uncolored fruit and berry crops with and without sorbent, a coefficient was calculated that takes into account the loss of vitamin C during the sorption of colored compounds. Currently, great importance is attached to methods for determining the content of important biochemical components that increase their nutritional and biological value. The proposed method will make it possible to identify new interesting breeding material; it can be used in the mass analysis of fruit and berry and vegetable crops that produce colored extracts. Keywords: vitamin C, ascorbic acid, sorption, titrimetric method, 2,6-dichlorophenol-indophenol, colored extracts Authors:
Vitaly S. Popov (St. Petersburg, Russian Federation) – Ph.D. in Technical Sciences, Senior Researcher, N.I. Vavilov Research Institute of Plant Industry (42, 44, Bolshaya Morskaya, St. Petersburg, 190000; e-mail: popovitaly@yandex.ru). Yuliya A. Smyatskaya (St. Petersburg, Russian Federation) – Ph.D. in Technical Sciences, Peter the Great St. Petersburg Polytechnic University, Institute of Civil Engineering (29, Politechnical. St. Petersburg, 194064; e-mail: Makarovayulia169@mail.ru). References: 1. Vitamin C. Ascorbic acid, available at: URL: https://vitamini.ru/vse-o-vitaminakh/vitamin-c/ (accessed 22 September 2020). 2. Carr A.C., and Maggini S. Vitamin C and immune function. Nutrients, 2017, 9(11), pp. 1211. DOI: 10.3390/nu9111211 3. Atyabi N., Yasini S.P., Jalali S. M., and Shaygan H. Antioxidant effect of different vitamins on methemoglobin production: An in vitro study. Vet Res Forum, 2012, Spring, 3(2), pp. 97-101. 4. Poliakova N.P., Bokova T.I. Ispol'zovanie vitaminnykh preparatov v kachestve detoksikantov pri povyshennom soderzhanii tiazhelykh metallov v ratsione ptitsy [The use of vitamin preparations as detoxifying agents with an increased content of heavy metals in the diet of poultry]. Animal Husbandry and Feed Production. Achievements of Science and Technology of the Agro-Industrial Complex, 2016, vol. 30, no. 9, pp. 99-101. 5. Vitamin C. Ascorbic acid, available at: URL: https://www.smed.ru/ guides/162 (accessed 22 September 2020). 6. Caritá A.C., Fonseca-Santos B., Shultz J.D., et al. Vitamin C: One compound, several uses. Advances for delivery, efficiency and stability. Nanomedicine: Nanotechnology, Biology and Medicine, 2020, vol. 24, pp. 102-117. DOI: 10.1016/j.nano.2019.102117 7. Gamaiurova V.S., Rzhechitskaia L.E. Pishchevaia khimiia: uchebnik dlia studentov vuzov [Food chemistry: a textbook for university students]. Electronic Publication. Moscow, KDU, Dobrosvet, 2018, available at: URL: https://bookonlime.ru/node/1525/ (accessed 22 September 2020). 8. GOST 24556-89 Produkty pererabotki plodov i ovoshchei. Metody opredeleniia vitamina S [Products of fruits and vegetables processing. Methods for determination of vitamin C]. Moscow, Publishing House of Standards, 2003, 11 p. 9. Ermakov A.I., Arasimovich V.V., Iarosh N.P. et al. Metody biokhimicheskogo issledovaniia rastenii [Biochemical research methods of plants]. 3-d ed. Ed. A.I. Ermakov. Leningrad, Agropromizdat, 1987, 430 p. 10. Akah N.P., Onweluzo J.C. Evaluation of water-soluble vitamins and optimum cooking time of fresh edible portions of elephant grass (pennisetum purpureum L. Schumach) shoot. Nigerian Food Journal, 2014, vol. 32, iss. 2, pp. 120-127. DOI: 10.1016/S0189-7241(15)30127-2 11. Chupakhina G.N., Maslennikov P.V. Metody analiza vitaminov [Chupakhina G.N., Maslennikov P.V. Methods for the analysis of vitamins]. Kaliningrad, Workshop, Kazanskii gosudarstvennyi universitet, 2004, 36 p. 12. Deineka L.A. Zakonomernosti sorbtsii antotsianov prirodnymi glinami [Regularities of sorption of anthocyanins by natural clays]. Journal of Applied Chemistry, 2009, no. 5, pp. 742-748. 13. Chulkov A.N. Osobennosti sorbtsii i ochistki antotsianov na prirodnykh glinistykh mineralakh [Features of sorption and purification of anthocyanins on natural clay minerals]. XVIII Mendeleev Conference of Young Scientists, 22-26 April, Belgorod, 2008, pp. 140-141. STUDYING THE INFLUENCE OF BIOLOGICALLY ACTIVE SUBSTANCES OF GINGER ROOTS ON YEAST METABOLISM SACCHAROMYCES CEREVISIAE A.A. Vasileva, T.S. Kutpanova, T.M. Panova Received: 29.10.2020 Received in revised form: 29.10.2020 Published: 01.02.2021 Abstract:
In this work the possibility of producing craft beer with the addition of ginger root extract is considered. As an object we used crushed fresh ginger roots, on the basis of which aqueous and water-alcoholic extracts with hydromodule GM = 10 g/g were obtained. Extraction was carried out in ultrasonic bath ultrasonic bath UZV-1/100-TN with frequency 44 kHz and power 75 W at temperature 40 ... 80°C for1 hour. During the work the optimal temperature regime (50°C) and duration (30 min) of extraction were revealed. The concentration of aqueous and water-alcoholic extracts was 0,3%; 1%; 1,5%. The obtained extracts were used as additives in the fermentation process. Dry beer yeast of Safbrew S-33 of the Kosulinsky brewery was used as production agents. Fermentation was carried out periodically at a temperature of 8 ± 1oC for 15 days. During the fermentation process, samples were analyzed once a day for the content of substrate (sugar), basic metabolite (alcohol) and yeast growth. Analysis of digested wort was performed with the help of «Kolos-1» beer quality analyzer.On the basis of the conducted researches we recommended the use of water-alcoholic extract in the dosage of 1...1,5 %, which allows to increase fermentation activity of yeast by 12...14%, to increase economic coefficient by 2%, to decrease duration of fermentation process up to 4 days and to increase production capacity by 12...13% on the existing equipment. Besides, organoleptic properties and biological value of beer are improved due to useful substances contained in ginger roots. Keywords: periodic fermentation, ginger, beer yeast. Authors:
Alina A. Vasileva (Yekaterinburg, Russian Federation) – Undergraduate Student, Department of chemical technology of wood, biotechnology and nanomaterials, Ural State Forest Engineering University (37/5, Siberian tract str., Yekaterinburg, 620100; e-mail: voyc_alina@mail.ru). Tatyana S. Kutpanova (Yekaterinburg, Russian Federation) – Undergraduate Student, Department of Technology pulp and paper industries and polymer processing, Ural State Forest Engineering University (37/5, Siberian tract str., Yekaterinburg, 620100). Tatyana M. Panova (Yekaterinburg, Russian Federation) – Senior Teacher, Department of chemical technology of wood, biotechnology and nanomaterials, Ural State Forest Engineering University (37/5, Siberian tract str., Yekaterinburg, 620100; e-mail: ptm55@yandex.ru). References:
INFLUENCE OF VARIOUS FACTORS ON CHARACTERISTICS OF CHEMICAL AMMONIA AND HYDROGEN SULFUR ABSORBER A.N. Tsukanova, E.A. Farberova, N.B. Khodyashev, N.V. Limonov Received: 01.11.2020 Received in revised form: 01.11.2020 Published: 01.02.2021 Abstract:
The use of a chemical absorber of ammonia and hydrogen sulfide based on granular activated carbon in personal protective equipment for the respiratory system determines high requirements for the quality and effectiveness of this product. In the present work, the influence of various factors on the efficiency of a chemical absorber is investigated when it is obtained using the existing technology. The following key factors are considered: the amount of active additive of copper (II) sulfate in the composition of the absorber, the use of products of the wood-chemical and coke-chemical industries as a binder in the production of activated carbons (the basis of the absorber). It was empirically established that the sorption activity of the sorbent with respect to ammonia and hydrogen sulfide depends on the amount of water-soluble form of copper (II) sulfate applied to the carbon matrix. The optimal amount of a chemical additive in the composition of the absorber has been determined, which makes it possible to obtain a product with a high level of dynamic activity with respect to ammonia and hydrogen sulphide, while excluding the excessive consumption of raw materials - an impregnating additive. Using the method of correlation analysis, the influence of the raw components of the composite binder used in the preparation of granular activated carbons on the formation of the porous structure of the base and the qualitative characteristics of the chemical absorber of ammonia and hydrogen sulfide has been established. The use of a composite binder with a high content of coal tar in the composition leads to the production of activated carbon with a smaller volume of adsorption space and micropores, and also has a negative effect on the adsorption activity of the absorber obtained on the basis of such activated carbon. Also, using this method, a relationship was found between the level of efficiency of the sorbent and its granulometric composition. Keywords: carbon absorber of ammonia and hydrogen sulfide, granular activated carbon, copper sulfate, active form of copper sulfate, bound form of copper sulfate. Authors:
Anzhelika N. Tsukanova (Perm, Russian Federation) – Postgraduate student of the Department of Chemistry and Biotechnology, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990; e-mail: angi.tsukanova@gmail.com). Elena A. Farberova (Perm, Russian Federation) – Ph.D. in Chemical Sciences, Associate Professor of the Department of Chemistry and Biotechnology, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990; e-mail: elenafarb@gmail.com). Nikolaj B. Khodjashev (Perm, Russian Federation) – Doctor of Technical Sciences, Head of the Department of Chemistry and Biotechnology, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990; e-mail: nhodyashev@yandex.ru). Nikolaj V. Limonov (Perm, Russian Federation) – Ph.D. in Technical Sciences, acting technical director of JSC «Sorbent» (6, Halperina str., Perm, 614113; e-mail: nvlimonov@sorbent.su). References: 1. Glushankov K.V., Kobeleva A.R., Farberova E.A. Vliianie ul'trazvukovoi obrabotki na svoistva poglotitelia ammiaka, prednaznachennogo dlia sredstv individual'noi zashchity organov dykhaniia [Influence of ultrasonic treatment on the properties of an ammonia absorber intended for personal protective equipment of the respiratory system]. Khimiia. Ekologiia. Urbanistika. Tez. dokl. Vseros. nauch.-prakt. konf. molodykh uchenykh, aspirantov, studentov i shkol'nikov, 2017, pp. 472-476. 2. Tsukanova A.N, Zorina E.I., Limonov N.V. Poluchenie aktivnykh granulirovannykh uglei novogo pokoleniia [Obtaining active granular carbons of a new generation]. Khimiia. Ekologiia. Urbanistika. Tez. dokl. Vseros. nauch.-prakt. konf. molodykh uchenykh, aspirantov, studentov i shkol'nikov, 2019, pp. 423-427. 3. Shirkunov A.S., Farberova E.A., Riabov V.G., Limonov N.V., Zorina E.I., Velikii E.M. Issledovanie vozmozhnosti ispol'zovaniia al'ternativnykh vidov sviazuiushchikh pri proizvodstve granulirovannykh aktivnykh uglei [Investigation of the possibility of using alternative types of binders in the production of granular activated carbons] Nauchno-tekhnicheskii vestnik Povolzh'ia, 2013, no. 5, pp. 316-320. 4. Chuchalina A.D., Shirkunov A.S., Riabov V.G. Issledovanie primenimosti tiazhelykh neftianykh ostatkov v kachestve sviazuiushchikh dlia polucheniia granulirovannykh aktivnykh uglei [Study of the applicability of heavy oil residues as binders for the production of granular activated carbons]. Nauchno-tekhnicheskii vestnik Povolzh'ia, 2014, ¹ 5, pp. 340-344. 5. Arkhipova E.V. Sposoby polucheniia poglotitelei ammiaka [Methods for obtaining ammonia absorbers]. Sbornik nauchnykh statei molodykh uchenykh, aspirantov i studentov TGTU, Tambov, 2013, vol. IV. 6. Leikin Iu.A., Miasoedov B.F., Losev V.V., Kirillov E.A. Modifitsirovannye sorbenty dlia selektivnogo izvlecheniia ammiaka i ego proizvodnykh [Modified sorbents for selective extraction of ammonia and its derivatives]. Khim. fizika, 2007, vol. 25, no. 10, pp. 18-32. 7. Farberova E.A., Tin'gaeva E.A., Kuz'minykh K.G., Smirnov S.A. Usovershenstvovanie tekhnologii polucheniia uglerodnogo khimpoglotitelia ammiaka [Improvement of technology for producing carbon chemical absorbent ammonia]. Izvestiia vysshikh uchebnykh zavedenii. Khimiia i khimicheskaia tekhnologiia, 2019, vol. 62, no. 9, pp. 117-123. 8. Spiridonova E.A., Samonin V.V., Podviaznikov M.L., Morozova V.Iu. Poluchenie i issledovanie modifitsirovannogo fullerenami khimicheskogo poglotitelia ammiaka na osnove aktivnogo uglia [Preparation and investigation of a fullerene-modified chemical absorber of ammonia based on activated carbon]. Zhurnal prikladnoi khimii, 2020, vol. 93, no. 5, pp. 683-690. 9. Buluchevskii E.A., Lavrenov A.V., Dupliakin V.K. Sorbenty tipa «sol' v poristoi matritse» v protsesse pererabotki uglevodorodov [Sorbents of the "salt in a porous matrix" type in the process of hydrocarbon processing ]. Rossiiskii khimicheskii zhurnal, 2007, vol. LI, no. 4, pp. 85-91. 10. Ageeva S.V., Ksandrov N.V., Ozhogina O.R. Modifikatsiia aktivnogo uglia khloridom medi (II) dlia uvelicheniia ego adsorbtsionnoi emkosti po ammiaku [Modification of activated carbon with copper (II) chloride to increase its adsorption capacity for ammonia]. Sovremennye problemy nauki i obrazovaniia, 2013, no. 3, pp. 446–447. 11. Kudymova N.G., Farberova E.A., Vol'khin V.V., Galkin E.A. Issledovanie vliianiia uslovii sinteza na svoistva kompozitsionnogo uglerodnogo khemosorbenta ammiaka [Study of the effect of synthesis conditions on the properties of a composite carbon ammonia chemisorbent]. Molodezhnaia nauka Prikam'ia, 2002, vol. 2, pp. 151-156. 12. Farberova E.A., Tin'gaeva E.A., Kobeleva A.R. i dr. Poglotitel' ammiaka i serovodoroda na osnove aktivnykh uglei i issledovanie ego svoistv [Ammonia and hydrogen sulfide scavenger based on active carbons and research of its properties]. Butlerovskie soobshcheniia, 2017, vol. 50, no. 6, pp. 41-47. 13. Temukueva Zh.Kh. Korreliatsionno-regressionnyi analiz kak indikator otbora pokazatelei pri provedenii faktornogo ekonomicheskogo analiza [Correlation-regression analysis as an indicator of the selection of indicators when conducting factor economic analysis]. Problemy sovremennoi nauki i obrazovaniia, 2016, no. 19 (61), pp. 67-69. 14. Pogorelova M.Ia. Ekonomicheskii analiz: teoriia i praktika. Uchebnoe posobie [Economic analysis: theory and practice. Tutorial]. INFRA-M, 2014, 373 p. 15. Simonov A.A., Vysk N.D. Proverka statisticheskikh gipotez. Metodicheskie ukazaniia i varianty kursovykh zadanii [Testing statistical hypotheses. Methodical instructions and options for coursework]. Moscow, 2005, 48 p. STUDYING OF THE METHYL 3-BENZOYL-6- METHYL-4-OXO-1,4-DIHYDRO-2-QUINOLINECARBOXILATES REACTION WITH ETHANOLAMINE IN A FLASK AND IN A FLOW REACTOR A.À. Boteva, I.V. Fefilova, O.P. Krasnykh, A.V. Shmyrov Received: 01.11.2020 Received in revised form: 01.11.2020 Published: 01.02.2021 Abstract:
The flow chemistry has advanced significantly in recent years from simple laboratory technic of synthetic organic chemistry to complex multistage processes that are implemented in practice in the pharmaceutical industry and in fine organic synthesis. Carrying out reactions in flow not only has obvious advantages over reactions carried out in batch reactors, such as high-grade security, the possibility of automation and combination with other technologies as well as an easy scalability, but is also viewed as a technology that can change the approaches in synthetic thinking in general. Substituted 4-quinolones are used in medicine as effective antibacterial agents. Depending on the nature of the substituents in the quinolone structure, the spectrum of biological activity exhibited by a given molecules varies from "classical" antibacterial to anti-cancer, antiviral, etc. The synthetic scheme of biologically active [b]-annelated 4-quinolones from methyl 3-aroyl-4-oxo-1,4-dihydro-2-quinolinecarboxylates with ethanolamine makes it possible to obtain tri- and tetracyclic [b]-annelated 4-quinolones in different conditions. This paper presents the results of studying the reaction of methyl 3-benzoyl-6-methyl-4-oxo-1,4-dihydro-2-quinolinecarboxylates with ethanolamine in different conditions by HPLC and selection of optimal conditions for currying this reaction in a flow. As the key parameters were chosen the next: temperature, heating duration and presence of acetic acid. It was found that for a more efficient conversion of the starting compound 3 and increasing the yield of the target compound 4, it is necessary to carry out the synthesis at an elevated temperature. Acetic acid plays the role of a catalyst, contributing to the faster conversion of starting 3 into key compound 4. Even at an equimolar ratio of compound 3 and ethanolamine and regardless of the reaction conditions, the reaction product 1: 2 (compound 5) is the first to form in the reaction mass, which, upon further heating, transforms into the target product 4. Synthesis of compound 4 from 5 under HPLC control of the reaction allows to classify compound 5 as a kinetic product, and compound 4 as a thermodynamic reaction product. The reaction of methyl 3-benzoyl-6-methyl-4-oxo-1,4-dihydro-2-quinolinecarboxylates 3 with ethanolamine in a flow reactor (tube length 10 m, total reactor volume 6.7 ml) did not lead to complete conversion of the starting compound 3 into the desired product 4 under all used conditions, however, made it possible to draw a number of conclusions useful for further work. Despite the fact that it was previously shown that the reaction must be carried out at a high temperature, carrying out the reaction in a flow makes it impossible to raise the temperature above 85 ° C due to increased gas formation in the system at the temperature which is close to the boiling point of the solvent used (1,4 -dioxane). A way out of this situation is to replace the solvent or change the design of the flow reactor. Keywords: flow chemistry, 4-quinolones, methyl 3-aroyl-4-oxo-1,4-dihydro-2-quinolinecarboxylates, [b]-anelated 4-quinolones. Authors:
Anastasiya A. Boteva (Perm, Russian Federation) – Ph.D. in Pharmaseutical Sciences, Associate Professor, Department of Chemistry and Biotechnology, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990; e-mail: aboteva@pstu.ru). Irina V. Fefilova (Perm, Russian Federation) – Engineer, Research and Educational Center of Applied Chemical and Biological Research, Perm National Research Polytechnic University (21, Korolyova str., Perm, 614990; e-mail: magoartois@rambler.ru). Olga P. Krasnykh (Perm, Russian Federation) – Ph.D. in Chemical Sciences, Associate Professor, Department of Chemistry and Biotechnology, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990; e-mail: ol.krasnykh@gmail.com) Andrey V. Shmyrov (Perm, Russian Federation) – Junior researcher of laboratory of hydrodynamic stability, Institute of Continuous Media Mechanics of the Ural Branch of Russian Academy of Sciences (1, Korolyova str., Perm, 614013; e-mail: shmyrov@icmm.ru). References: 1. Gomollón-Bel Fernando. Ten chemical innovations that will change our world. Chemistry International, 2019, vol. 41, pp.12-17. 2. Riccardo Porta, Maurizio Benaglia, Alessandra Puglisi. Flow chemistry: recent developments in the synthesis of pharmaceutical products. Organic Process Research & Development, vol. 20, pp. 2-25. DOI: org/10.1021/acs.oprd.5b00325 3. Daniel E. Fitzpatrick, Claudio Battilocchio, Steven V. Ley. Enabling technologies for the future of chemical synthesis. ACS Central Science, 2016, vol. 2, pp. 31-138. DOI: org/10.1021/acscentsci.6b00015 4. Mara Guidi, Peter H. Seeberger, Kerry Gilmore. How to approach flow chemistry. Chemical Society Reviews, 2020. DOI: org/10.1039/C9CS00832B, available at: https://pubs.rsc.org/en/content/articlelanding/2020/cs/c9cs00832b#!divAbstract (accessed 20 October 2020). 5. Ryan L Hartman. Flow chemistry remains an opportunity for chemists and chemical engineers. Current Opinion in Chemical Engineering, 2020, vol. 29, pp. 1-9. DOI: org/10.1016/j.coche.2020.05.002 6. Jan Hartwig, Jan B. Metternich, Nikzad Nikbin, Andreas Kirschning, Steven V. Ley. Continuous flow chemistry: a discovery tool for new chemical reactivity patterns. Organic & Biomolecular Chemisrty, 2014, vol. 12, pp. 3611-3615. DOI: org/10.1039/c4ob00662c 7. Nathaniel Corrigan, Abdulrahman Almasri, Werner Taillades, Jiangtao Xu, Cyrille Boyer. Controlling molecular weight distributions through photoinduced flow polymerization. Macromolecules, 2017, vol. 50(21), pp. 8438-8448. DOI: org/10.1021/acs.macromol.7b01890 8. Nathaniel Corrigan, Dzulfadhli Rosli, Jesse Warren Jeffery Jones, Jiangtao Xu, Cyrille Boyer. Oxygen tolerance in living radical polymerization: investigation of mechanism and implementation in continuous flow polymerization. Macromolecules, 2016, vol. 49(18), pp. 6779-6789. DOI: org/10.1021/acs.macromol.6b01306 9. Lutz. F. Tietze, Deshan Liu. Continuous-flow microreactor multi-step synthesis of an aminonaphthalene derivative as starting material for the preparation of novel anticancer agents. Archive for Organic Chemistry, 2008, vol. 8, pp. 193-210. DOI: 10.3998/ark.5550190.0009.816 10. Daniel E. Fitzpatrick, Steven V. Ley. Engineering chemistry for the future of chemical synthesis. Tetrahedron, 2018, vol.74, pp. 3087-3100. DOI: org/10.1016/j.tet.2017.08.050 11. Romaric Gérardy, Damien P. Debecker, Julien Estager, Patricia Luis, Jean-Christophe M. Monbaliu. Continuous flow upgrading of selected C2−C6 platform chemicals derived from biomass. Chemical Reviews, 2020, vol. 120, 12. Amol A. Kulkarni. Continuous flow nitration in miniaturized devices. Beilstein Journal of Organic Chemistry, 2014, vol. 10, pp. 405–424. DOI:10.3762/bjoc.10.38
13. Jennifer Tsoung, Andrew R. Bogdan, Stanislaw Kantor, Ying Wang, Manwika Charaschanya, Stevan W. Djuric. Synthesis of fused pyrimidinone and quinolone derivatives in an automated high-temperature and high-pressure flow reactor. The Journal of Organic Chemistry, 2017, vol. 82, pp. 1073-1084. DOI: 10.1021/acs.joc.6b02520 14. Hooper D.C., Rubinstein E. Quinolone àntimicrobial àgents. 3rd ed. Washington, ASM Press, 2003, 592 ð. 15. Claudia Mugnaini, Serena Pasquini, Federico Corelli. The 4-quinolone-3-carboxylic acid motif as a multivalent scaffold in medicinal chemistry. // Current Medicinal Chemistry, 2009, vol. 16, pp. 1746-1767. DOI: 10.2174/092986709788186156 16. Chen Yue Lei Chen, Jeana Zacharias, Robert Vince, Robert J. Geraghty, Zhengqiang Wang. C-6 aryl substituted 4-quinolone-3-carboxylic acids as inhibitors of hepatitis C virus. Bioorganic & Medicinal Chemistry, 2012, vol. 20, pp. 4790-4800. DOI: 10.1016/j.bmc.2012.05.066 17. Abeer Ahmed, Mohsen Daneshtalab. Nonclassical biological activities of quinolone derivatives. Journal of Pharmacy and Pharmaceutical Sciences, 2012, vol. 15(1), pp. 52-72. DOI: 10.18433/J3302N 18. Kunihiko Mohri, Akihiko Kanie, Yoshie Horiguchi, Kimiaki Isobe. A synthesis of 4-quinolone-3-carboxylic acids via pyrolysis of N-aryldioxopyrrolines. Heterocycles, 1999, vol.51, no.10, pp. 2377-2384. DOI: 10.3987/COM-99-8629 19. Maslivets A.N., Krasnykh O.P., Smirnova L.I., Andreychikov Yu.S. Pyatichlennye dioksogeterotsikly. XII. Termoliz 1-aril-4-aroil-5-metoksikarbonil-2,3-digidro-2,3-pirroldionov [Five-membered 2,3-dioxoheterocycles. Thermolysis of 1-aryl-4-aroyl-5-methoxycarbonyl-2,3-dihydro-2,3-pyrroldione]. Zhurnal organicheskoj himii, 1989, no. 2, pp. 1045-1053. 20. Boteva A.A., Fefilova I.V., Krasnykh O.P., Babushkina E.B., Slepuhin P.A. Sintez, molekulyarnaya i kristallicheskaya struktura metil-3-aroil-4-okso-1,4-digidro-2-hinolinkarboksilatov [Synthesis, molecular and crystal structure of methyl-3-aroyl-4-oxo-1,4-dihydro-2-quinolinecarboxylates]. Izvestiya Akademii nauk. Seriya khimicheskaya, 2014, no. 3, pp. 731–738. 21. Boteva A.A., Krasnyh O.P., Solodnikov S.Yu., Francblau S., Van B. 1H-Pirrolo[3,4 – b]hinolin – 3,9(2H,4H) – diony, obladayushchie protivotuberkuleznoj aktivnost'yu i sposob ih polucheniya [1H-pyrrolo[3,4-b]quinoline-3,9(2H,4H)-diones exhibiting antituberculosis activity and mrthod for preparing them]. Patent 2457208 Rossiiskaia Federatsiia no. 2009125914/04 (2012). 22. Boteva A.A., Fefilova I.V., Krasnyh O.P., Lyushina G.A., Maslova V.V., Solodnikov S.Yu. Anal'geziruyushchee sredstvo [Analgesic means]. Patent 2634618 Rossiiskaia Federatsiia no. 2016117456 (2017). 23. Boteva A.A., Fefilova I.V., Triandafilova G.A., Maslova V.V., Solodnikov S.Yu. Synthesis and Analgesic Activity of [b]-Annelated 4-Quinolones. Pharmaceutical Chemistry Journal, 2019, 53, ð. 616–619. DOI: org/10.1007/s11094-019-02048-2 24. Boteva A.A. Sintez, modifikatsiya i biologicheskaya aktivnost' metil 3-(get)aroil-4-okso-1,4-digidro-2-khinolinkarboksilatov [Synthesis, modification and biological activity of methyl 3-(het)aroyl-4-oxo-1,4-dihydro-2-quinolinecarboxylates]. Abstract of Ph. D. thesis. Perm, 2008, 187 p. SYNTHESIS AND STUDY OF RADICALTRAPPING ACTIVITY OF METHYL 6-METHYL-3-CINNAMOYL-4-OXO-1,4-DIHYDRO-2-QUINOLINCARBOXYLATE ANT ITS ANALOGUES G.A. Triandafilova, À.À. Boteva, Î.P. Krasnykh Received: 01.11.2020 Received in revised form: 01.11.2020 Published: 01.02.2021 Abstract:
The thermal decarbonylation reaction of 5-methoxycarbonyl-1- (4-methylphenyl) -4-cinnamoyl-1H-pyrrole-2,3-dione (1) leads to the formation of methyl 6-methyl-3-cinnamoyl-4-oxo-1, 4-dihydro-2-quinolinecarboxylate (2), methyl 9-methyl-4-oxo-2-phenyl-3,4-dihydro-2H-pyrano [3,2-c] quinoline-5-carboxylate (3), formed as a result of intramolecular cyclization of 2 with the participation of the double bond of the cinnamoyl fragment and the carbonyl group at position 4, and methyl 9-methyl-4-oxo-2-phenyl-4H-pyrano [3,2-c] quinoline-5-carboxylate(4). The ratio of the products depends on the temperature conditions of the reaction: at 190°Ñ, products of all three types are obtained while an increase in temperature to 235°Ñ contributes to the formation of the most thermally stable compound 4. The ability of compounds 2 and 3, as well as a number of analogs, to trap free radicals was evaluated in two test systems: using a stable radical DPPH and AAPH (ORAC test) as generator of radicals. The tested compounds showed no activity in the first test. When evaluating the radical-binding action in the second test (ORAC) which is based on the change in fluorescein fluorescence in the presence of radical particles, a sharp decrease in fluorescence below background values was observed in the presence of compounds containing a 4-quinolone fragment. At the same time, the nature of substituents in 4-quinolone, as well as the presence of the [b]-fused pyrrolone fragment, have no practical effect on the degree of manifestation of this property: the decrease in fluorescein fluorescence compared to the background is 90-125%. An exception is the 4-quinolone containing the phenylazogroup at position 6, which showed an 8% reduction. It has been established that there is apparently no direct interaction of the studied substituted 4-quinolones with fluorescein under the conditions of the experiment, but the transformation of compounds containing the 4-quinolone fragment is possible under the action of excitating radiation. Keywords: decarbonylation, pyrrole-2,3-dione, 3-cynnamoyl-4-quinolone, cyclization, 3-cinnamoyl-4-quinolone, radical-trapping activity, fluorescence. Authors:
Galina A. Triandafilova (Perm, Russian Federation) – Postgraduate Student of Institute of Ecology and Genetics of Microorganisms, Ural Branch of Russian Academy of Sciences (13, Goleva str., Perm, 614081; e-mail: lindick@ya.ru). Anastasia A. Boteva (Perm, Russian Federation) – Ph.D. in Pharmaceutical Sciences, Associate Professor, Department of Chemistry and Biotechnology, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990;
Olgla P. Krasnykh (Perm, Russian Federation) – Ph.D. in Chemical Sciences, Associate Professor, Department of Chemistry and Biotechnology, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990; References: 1. Briehl H., Lukosch A., Wentrup C. Reactive nitrogenous molecules from Meldrum's acid derivatives, pyrrole-2,3-diones, and isoxazolones. J. Org. Chem., 1984, no. 15, pp. 2772–2779. 2. Issledovaniye mekhanizmov termoliza i nukleofil'nykh reaktsiy zameshcheniya 2,3-digidro-2,3-pirroldionov. [Investigation of the mechanisms of thermolysis and nucleophilic substitution reactions of 2,3-dihydro-2,3-pyrroldiones]. Andreychikov Yu.S., Kozlov A.P., Masliwets A.N., Krasnykh O.P., Perevozchikov L.I., Smirnova L.I. IV Vsesojuznajz konferencija po himii azotsoderzhashih geterociklicheskih soedinenij [IV All-union conference in chemistry of nitrogencontaining heterocyclic compounds. Book of abstracts], Tezisi dokladov, Novosibirsk, 1987, p. 221. 3. Maslivets A.N., Krasnykh O.P., Smirnova L.I., Pyatichlennye dioksogeterotsikly. XII. Termoliz 1-aril-4-aroil-5-metoksikarbonil-2,3-digidro-2,3-pirroldionov [Five-membered 2,3-dioxoheterocycles. Thermolysis of 1-aryl-4-aroyl-5-methoxycarbonyl-2,3-dihydro-2,3-pyrroldione]. Zhurnal organicheskoj himii, 1989, no. 2, pp. 1045-1053 4. Boteva A.A., Fefilova I.V., Krasnykh O.P., Babushkina E.B., Slepuhin P.A. Sintez, molekulyarnaya i kristallicheskaya struktura metil-3-aroil-4-okso-1,4-digidro-2-hinolinkarboksilatov [Synthesis, molecular and crystal structure of methyl-3-aroyl-4-oxo-1,4-dihydro-2-quinolinecarboxylates]. Izvestiya Akademii nauk. Seriya khimicheskaya, 2014, no. 3, pp. 731–738. 5. Mohri K., Kanie A., Horiguchi Y., Isobe K. A synthesis of 4-quinolone-3-carboxylic acids via pyrolysis of N-aryldioxopyrrolines. Heterocycles, 1999, no.10, pp. 2377-2384. 6. Krasnykh O.P., Devjatkina N.A., Boteva A.A., Masliwets A.N. Termoliticheskie reakcii zameshennih 4,5-diacil-2,3-digidro-2,3-pirroldionov: novie dannie. Tezisi dokladov Tretjego Vserossijskogo simpoziuma “Strategija i taktika organicheskogo sinteza” [Thermolytical reactions of substituted 4,5-diacyl-2,3-dihydro-2,3-pyrrolediones: novel data. Book of abstracts of Third All-Russia symposium “Strategy and tactics of organic synthesis”], Jaroslavl, 2001, p. 31. 7. Boteva A.A., Krasnyh O.P., Solodnikov S.Yu., Francblau S., Van B. 1H-Pirrolo[3,4 – b]hinolin – 3,9(2H,4H) – diony, obladayushchie protivotuberkuleznoj aktivnost'yu i sposob ih polucheniya [1H-pyrrolo[3,4-b]quinoline-3,9(2H,4H)-diones exhibiting antituberculosis activity and method for preparing them]. Patent Rossiiskaia Federatsiia no. 2009125914/04 (2012). 8. Filimonov V.O. Sintez, termoliticheskie i nukleofilnie prevrashenija 5-metoksikarbonil-4-cinnamoil-1H-pirrol-2,3dionov: diss. kand. him. nauk [Synthesis, thermolytical and nucleophilic transformations of 5-methoxycarbony-4-cinnamoyl-1Í-pyrrole-2,3-diones, PhD theses], 2014, 158 pp. 9. Boteva A.A., Fefilova I.V., Krasnyh O.P., Lyushina G.A., Maslova V.V., Solodnikov S.Yu. Anal'geziruyushchee sredstvo [Analgesic means]. Patent Rossiiskaia Federatsiia no. 2016117456 (2017). 10. Ghosh P., Das S. Synthesis and Functionalization of 4-Quinolones – A Progressing Story. Eur. J. Org. Chem., 2019, no. 28, pp. 4466–4516. 11. Kuznetsov V., Gorohovsky S., Levy A., Meir S., Shkoulev V., Menashe N., Greenwald M., Aizikovich A., Ofer D., Byk G., Gellerman G. Approaches for introducing high molecular diversity in scaffolds: Fast parallel synthesis of highly substituted 1H-quinolin-4-one libraries. Molecular Diversity, 2004, no.8, pp. 437–448. 12. Í Hooper D.C., Rubinstein E. Quinolone àntimicrobial àgents. 3rd ed. Washington, ASM Press, 2003, 592 ð. 13. Yadav V., Talwar Ð. Repositioning of fluoroquinolones from antibiotic to anti-cancer agents: An underestimated truth. Biomedicine & Pharmacotherapy, 2019, pp. 934-946. 14. Abeer Ahmed, Mohsen Daneshtalab. Nonclassical biological activities of quinolone derivatives. Journal of Pharmacy and Pharmaceutical Sciences, 2012, no.1, pp 52– 72. 15. Maignan J., Lichorowic C., Giarrusso J., Blake L., Casandra D., Mutka T., LaCrue A., Burrows J., Willis P., Kyle D., Manetsch R. ICI 56,780 Optimization: Structure−Activity Relationship Studies of 7‑(2-Phenoxyethoxy)-4(1H)‑quinolones with Antimalarial Activity. J. Med. Chem., 2016, pp. 6943−6960. DOI: 10.1021/acs.jmedchem.6b00759 16. Greeff J., Joubert J., Malan S., Dyk S. Antioxidant properties of 4-quinolones and structurally related flavones. Bioorganic Med. Chem., 2012, no. 2, pp. 809–818. 17. Wang X., Zhao X. Contribution of oxidative damage to antimicrobial lethality. Antimicrob. Agents Chemother., 2009, no. 4, pp. 1395–1402. 18. Michalak K., Sobolewska A., Wlodarczyk M., Sobolewska J., Wozniak P., Sobolewski B. Treatment of the Fluoroquinolone-Associated Disability: The Pathobiochemical Implications.. Oxid. Med. Cell. Longev., 2017, pp. 1-15. doi.org/10.1155/2017/8023935 19. Ferreira J., Cardoso S., Paz F., Silva A., Silva V. Synthesis of 2-aroylfuro[3,2-c]quinolines from quinolone-based chalcones and evaluation of their antioxidant and anticholinesterase activities. New J. Chem., 2020, pp. 6501-6509. 20. Marinova G., Batchvarov V. Evaluation of the methods for determination of the free radical scavenging activity by DPPH. Bulg. J. Agric. Sci., 2011, no. 1., pp. 11–24. 21. Ou B. Development and Validation of an Improved Oxygen Radical Absorbance Capacity Assay Using Fluorescein as the Fluorescent Probe. J. Agric. Food Chem., 2001, no. 49, pp. 4619-4626. 22. Hirano J., Hamase K., Fukuda K., Tomita H., Zaitsu K. Novel stable fluorophore, 6-methoxy-4-quinolone, with strong fluorescence in wide pH range of aqueous media, and its application as a fluorescent labeling reagent. Journal of Chromatography A., 2004, pp. 225–231. A NEW METHOD OF SYNTHESIS OF METHYL 4-ARYL-2- (1,5-DIMETHYL-3-OXO-2-PHENYL-2,3-DIHYDRO-1H- PYRAZOL-4-YLAMINO)-4-OXO-2-BUTENOATES V.A. Lyadov, E.S. Denislamova Received: 01.11.2020 Received in revised form: 01.11.2020 Published: 01.02.2021 Abstract:
Derivatives of aroylpyruvic acids are of great interest in the field of organic synthesis due to their multifaceted biological effects and low toxicity. Structural modification of these compounds allows you to expand the spectrum of pharmacological action. Of particular interest is the synthesis of derivatives of aroylpyruvic acids, including a heterocyclic structural fragment of compounds with biological activity. An example of such heterocyclic systems can be pyrazolone derivatives – antipyrine, pyramidone, analgin. The reaction of methyl esters of aroylpyruvic acids with 4-aminoantipyrine gave α-enaminoesters – methyl 4-aryl-2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylamino)-4-oxo-2-butenoates,which are crystalline compounds of red-orange color, hardly soluble in common organic solvents, readily soluble in DMF and DMSO, and insoluble in alkanes and water. The approach to the synthesis of biologically active compounds should include various aspects, including the simplicity of the procedure and economic feasibility. We have developed a simple, fast and effective method for the synthesis of methyl 4-aryl-2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylamino)-4-oxo-2-butenoates.The data on the analgesic properties of the obtained α-enaminoesters are presented. Subsequently, the obtained methyl 4-aryl-2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylamino)-4-oxo-2-butenoates can be used for the synthesis of new heterocyclic compounds of the pyrrole series containing an antipyryl fragment at the nitrogen atom. Keywords: 4-aminoantipyrine, methyl esters of aroylpyruvic acids, enaminoesters, analgesic activity, Schiff bases. Authors:
Vadim A. Lyadov (Perm, Russian Federation) – Undergraduate Student, Department of Chemical Technologies, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990, e-mail: vadim.lyadov2017@yandex.ru). Ekaterina S. Denislamova (Perm, Russian Federation) – Ph.D. in Chemical Sciences, Associate Professor, Department of Chemical Technologies, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990, References: 1. Andreichikov Iu.S., Gein V.L., Zalesov V.V. et al. Khimiia piatichlennykh 2,3-dioksogeterotsiklov [Chemistry of five-membered 2,3-dioxoheterocycles]. Perm', Izd-vo Perm. Un-ta, 1994, 210 p. 2. Koz'minykh V.O., Safonova N.V., Miliutin A.V. i dr. Amidy i gidrazidy aroilpirovinogradnykh kislot. Sintez i biologicheskaia aktivnost' nekotorykh arilidengidrazidov aroilpirovinogradnykh kislot [Amides and hydrazides of aroylpyruvic acids. Synthesis and biological activity of some arylidenehydrazides of aroylpyruvic acids]. Pharmaceutical Chemistry Journal, 1994, vol. 28, no. 3, pp. 42-45. 3. Gein V.L., Bobrovskaia O.V., Kovtonogova I.V., Seliverstov G.V., Russkikh A.A., Belonogova V.D., Anisimova A.G., Iagontseva T.A. Sintez i rostostimuliruiushchaia aktivnost' metil 4-aril-2-{[4-(N-R-sul'famoil)fenil]amino}-4-oksobut-2-enoatov [Synthesis and growth-stimulating activity of methyl 4-aryl-2 – {[4- (N-R-sulfamoyl) phenyl] amino} -4-oxobut-2-enoates]. Butlerovskie soobshcheniia, 2016, vol. 48, no. 12, pp. 26-31. 4. Gein V.L., Bobrovskaia O.V., Belonogova V.D., Anisimova A.G., Iagontseva T.A. Izuchenie rostostimuliruiushchei aktivnosti metil 4-aril-2-{[4-(N-R-sul'famoil)fenil]amino}-4-oksobut-2-enoatov i produktov ikh vzaimodeistviia s ningidrinom [Study of growth-stimulating activity of methyl 4-aryl-2 – {[4- (N-R-sulfamoyl) phenyl] amino} -4-oxobut-2-enoates and products of their interaction with ninhydrin]. Butlerovskie soobshcheniia, 2017, vol. 51, no. 9, pp. 83-88. 5. Galeev A.R., Dmitriev M.V., Mokrushin I.G., Mashevskaya I.V., Maslivets A.N. and Rubin M. Synthesis of: Meta-substituted anilines via a three-component reaction of acetone, amines, and 1,3-diketones. Biomolecular Chemistry, 2019, vol. 17, no. 47, pp. 10030-10044. 6. Koz’minykh E.N., Igidov N.M., Berezina E.S., Shavkunova G.A., Yakovlev I.B., Shelenkova S.A., Kolla V.E., E.V. Voronina and Koz’minykh V.O. 1,3,4,6 – Tetracarbonyl compounds. Sinthesis of biologically active 2-hydroxy-2,3-dihydro-3-pyrrolones and substituted amides of aroylpyruvicacids. Pharmaceutical Chemistry Journal, 1996, vol. 30, no. 7, pp. 31-35. 7. Kurkovskaya L.N., Shapet’ko N.N., Andreichikov Yu.S., Saraeva R.F. Investigation of the intramolecular hydrogen bond of a siries of carbalkoxyl derivatives of β-dicarbonyl compounds by the PMR method. J. Struct. Chem., 1973, vol. 13, no. 6, pp. 958-963. 8. Andreichikov Iu.S., Maslivets A.N., Smirnova L.I., Krasnykh O.P., KozlovA.P., Perevozchikova L.A. Piatichlennye 2,3-dioksogeterotsiklitsy.V. Sintez 1-aril-3-aroil-5-metoksikarbonil-2,3-digidro-2,3-pirroldionov, ikh vzaimodeistvie s vodoi i spirtami [Five-membered 2,3-dioxoheterocyclic. V. Synthesis of 1-aryl-3-aroyl-5-methoxycarbonyl-2,3-dihydro-2,3-pyrrolediones, their interaction with water and alcohols]. Zhurnal organicheskoi khimii, 1987, vol. 23, no. 7, pp. 1534-1543. 9. Denislamova E.S., Dubovtsev A.Iu., Makhmudov R.R., Maslivets A.N. Sposob polucheniia metil 1,7-diaril-9-aroil-4-benzoil-3-gidroksi-2,6-diokso-1,7-diazaspiro[4.4]non-3,8-dien-8-karboksilatov, proiavliaiushchikh anal'geticheskuiu aktivnost' [A method of obtaining methyl 1,7-diaryl-9-aroyl-4-benzoyl-3-hydroxy-2,6-dioxo-1,7-diazaspiro [4.4] non-3,8-diene-8-carboxylates exhibiting analgesic activity]. Patent Rossiiskaia Federatsiia no. 2013132700/04 (2015). 10. Denislamova E.S., Dubovtsev A.Yu., Slepukhin P.A., Maslivets A.N. Five-membered 2,3-dioxo heterocycles: Reaction of methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with methyl 2-arylamino-4-(2-naphthyl)-4-oxobut-2-enoates. Crystal and molecular structure of substituted 1,7-diazaspiro[4.4]nonane. Russian Journal of Organic Chemistry, 2014, vol. 50, no. 7, pp. 1017-1021. 11. Dubovtsev A.Yu., Denislamova E.S., Dmitriev M.V., Maslivets A.N. Spirobisheterocyclization of 5-(methoxycarbonyl)-1H-pyrrol-2,3-doines by the action of enaminoesters. Crystal and molecular structure of substituted 1,7-diazaspiro[4.4]nonane. Russian Journal of Organic Chemistry, 2016, vol. 52, no. 5, pp. 706-710. 12. Racheva N.L., Aliev Z.G., Maslivets A.N. Five-membered 2,3-dioxo heterocycles. Reaction of 3-aroyl-1H-pyrrol[2,1-c][1,4]benzoxazine-1,2,4-triones with α-enaminoesters. Crystalline and molecular structure of methyl 11-benzoyl-2-o-hydroxyphenyl-3,4,10-trioxo-6,9-diphenyl-7-oxa-2,9-diazatricyclo[6.2.1.01,5]undec-5-ene-8-carboxylate. Russian Journal of Organic Chemistry, 2008, vol. 44, no. 8, pp. 1197-1201. 13. Mashkovskii M.D. Lekarstvennye sredstva [Medicines]. 15th ed. Moscow, RIA «Novaia volna», 2007, 1206 p. 14. Surendra P., Agarwal R.K. Cobalt (II) complexes of various thiosemicarbazones of 4-aminoantipyrine: syntheses, spectral, thermal and antimicrobial studies. Transition Met. Chem., 2007, vol. 32, pp. 143. 15. Raman N., Dhabeel J., Raja S.J., Sathivel A. Synthesis, spectral characterization of Schiff base transition metal complexes: DNA cleavage and antimicrobial activity studies. Journal Chemical Science, 2007, vol. 119, no. 4, pp. 303-310. 16. Agrawal R.K., Chakraborti A. Synthesis spectral and biological studies of some bioactive metal coordination compounds of thoiosemicarbazones derived from 4-aminoantipyrine. Oriental Journal of Chemistry, 2002, vol. 18, no. 2, pp. 343-346. 17. Nair R., Shah A., Baluja S., Chanda S.V. Synthesis and antibacterial activity some Schiff bases derived from sulphonamide , 4-aminoantipyrine and acetophenone. Medical Chemistry Research, 2002, vol. 11, no. 8, pp. 463-479. 18. Roman N., Kulandaisamy A., Thangarajan Ch., Manisankur P., Viswanathan S., Vedhi Ch. Synthesis, structural characterization and electrochemical and antibacterial studies of Schiff base copper complexes. Transition Metal Chemistry, 2004, vol. 29, no. 2, pp. 129-135. 19. Krutikov V.I., Erkin A.V., Krutikova V.V., Zakharova E.S. Sintez protivogribkovykh i protivovirusnykh soedinenii v riadu proizvodnykh antipirina [Synthesis of antifungal and antiviral compounds in a series of antipyrine derivatives]. Izvestiia Sankt-Peterburgskogo gosudarstvennogo tekhnicheskogo instituta (tekhnicheskogo universiteta), 2014, vol. 52, no. 26, pp. 53-57. 20. Rubtsov A.E., Makhmudov R.R., Kovylyaeva N.V., Prosyanik N.I., Bobrov A.V., Zalesov V.V. Synthesis, anti-inflammatory and analgesic activity of 4-antipyrine derivatives. Pharmaceutical Chemistry Journal. – 2002. – T. 36, ¹ 11. – P. 31-35. 21. Rubtsov A.E., Zalesov V.V. Iminofuran Chemistry. Decyclization of N-substituted 5-aryl-3-imino-3H-furan-2-ones by the action of OH- and NH-nucleophiles. Russian Journal of Organic Chemistry, 2007, vol. 43, no. 5, pp. 739-744. 22. Espejo E.F. Structure of the rat's behaviour in the hot plate test. Behavioural brain research, 1993, vol. 56, no. 2, pp. 171–176. METHODS OF IMPROVING MANGANESE-CONTAINING CATALYSTS P.P. Bushkov, À.R. Kobeleva, E.O. Kuzina Received: 01.11.2020 Received in revised form: 01.11.2020 Published: 01.02.2021 Abstract:
Chemical engineering processes are often carried out under heterogeneous catalysis conditions. One of the promising ways to improve catalysts is to develop its complex chemical composition. Great attention is paid to catalytic processes in the field of neutralization of industrial gases. Catalysts for neutralization of gases are often metals and metal oxides, as well as mixtures of various metal oxides and non-metals. These catalysts can be used either in pure form or applied to various porous substrates. Catalysts based on manganese (IV) oxide have found wide application in this field. The main active component in these mixtures is g–MnO2. Other components added to the catalyst can improve the activity of manganese dioxide, help reduce or prevent the toxic effects of moisture and other catalytic poisons. Various methods are used to obtain active g–MnO2, but the monosyllabic catalyst does not meet the requirements for activity and other characteristics. Currently, work is underway to develop manganese catalysts of various complex chemical compositions that would not be exposed to water vapor poisoning, have a high specific surface area and activity, have a fairly high mechanical strength and abrasion resistance, and also be resistant to overheating and work in a wide temperature range. It is proposed to use metals and their oxides as modifying additives depending on the purpose of the catalytic process. Each new component introduced into the manganese catalyst composition generates new improved performance characteristics of the finished catalyst. Keywords: manganese, manganese oxide, manganese-containing catalyst, heterogeneous catalysis, activity, catalytic poisons, composition of catalysts. Authors:
Pavel P. Bushkov (Perm, Russian Federation) – Undergraduate Student of the Department of Chemical Technologies, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990, e-mail: pavel.bushkov.97@mail.ru). Asiya R. Kobeleva (Perm, Russian Federation) – Ph.D. in Technical Sciences, Associate Professor, Department of Chemical Technologies, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990, e-mail: ushtf@pstu.ru). Evgeniia O. Kuzina (Perm, Russian Federation) – Senior Lecturer, Department of Chemical Technologies, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990, e-mail: zena322myname@mail.ru). References: 1. Vetoshkin A.G. Osnovy inzhenernoi zashchity okruzhaiushchei sredy [Fundamentals of engineering protection of the environment]. Moscow, Infra-Inzheneriia, 2019, 460 p. 2. Kudriavtsev A.A., Kruglova M.A. Razrabotka termostabil'nykh Mn-soderzhashchikh katalizatorov dlia protsessov ochistki vykhlopnykh gazov ot organicheskikh primesei [Development of thermostable Mn-containing catalysts for the processes of cleaning exhaust gases from organic impurities]. Advances in chemistry and chemical technology, 2011, no. 2, pp. 15–18. 3. Ivanova N.D., Ivanov S.V., Boldyrev E.I., Makeeva I.S. Vysokoeffektivnye oksidnomargantsevye katalizatory reaktsii okisleniia CO [Highly efficient manganese oxide catalysts for the CO oxidation]. Journal of Applied Chemistry, 2002, no. 9, pp. 1452 – 1455. 4. Chen Khai-Iing, Reining Artur Dzh., Andersen Pol Dzh. Med'- i marganets soderzhashchie katalizatory na osnove neblagorodnykh metallov dlia okisleniia monooksida ugleroda i letuchikh organicheskikh soedinenii [Copper and manganese base metal catalysts for the oxidation of carbon monoxide and volatile organic compounds]. Patent Rossiiskaia Federatsiia no. 2011147128/04 (2014). 5. Kolesnikov I.M. Kataliz v gazoneftianoi otrasli. Teoriia i praktika [Catalysis in the gas and oil industry. Theory and practice]. Moscow, Neft' i gaz, 2012, 471 p. 6. Kochetkova R.P., Kochetkov A.Iu., Kovalenko N.A. Sposob biokataliticheskoi ochistki stochnykh vod [Method of biocatalytic wastewater treatment]. Patent Rossiiskaia Federatsiia no. 2002116855/15 (2005). 7. Chou S., Cheng F., Chen J. Electrodeposition synthesis and electrochemical properties of nanostructured γ-MnO2 films. Journal of Power Sources, 2006, vol. 162(1), pp. 727–734. DOI: org/10.1016/j.jpowsour.2006.06.033 8. Suib S. L. Sorption, catalysis, separation design. Chemical Innovation, 2000, vol. 30, pp. 27–33. 9. Kononov Iu.S., Zhizhaev A.M., Patrushev V.V Sposob polucheniia dioksida margantsa gamma-modifikatsii [A method of producing manganese dioxide of the gamma-modification] Patent Rossiiskaia Federatsiia no. 97121784/12 (2000). 10. Krylov O.V. Geterogennyi kataliz [Heterogeneous catalysis]. Moscow, Akademkniga, 2004, 679 p. 11. Kariakin Iu.V., Angelov I.I. Chistye khimicheskie veshchestva [Pure chemicals]. Moscow, Khimiia, 1974, 408 p. 12. Sibarov D.A., Smirnova D.A. Kataliz, kataliticheskie protsessy i reaktory [Catalysis, catalytic processes and reactors]. Moscow, Lan', 2018, 200 p. 13. Semenova T.A., Leites I.L. Ochistka tekhnologicheskikh gazov [Purification of process gases]. Moscow, Khimiia, 1977, 487 p. 14. Timonin A.S., Vetoshkin A.G. Inzhenerno-ekologicheskii spravochnik. Tom 1 [Engineering and environmental handbook. Vol. 1]. Kaluga, Izdatel'stvo N. Bochkarevoi, 2003, 917 p. 15. Krylov O. V. Uglekislotnaia konversiia metana v sintez-gaz [Carbon dioxide conversion of methane to synthesis gas]. Russian chemical journal, 2000, no. 1, pp. 19–33. 16. Eshchenko L.S. Tekhnologiia katalizatorov i adsorbentov [Technology of catalysts and adsorbents]. Minsk, Belorusskii gosudarstvennyi tekhnologicheskii universitet, 2015, 167 p. 17. Yang L., Yao G., Honggen P., Xianglan X., Yuanyuan W., Cheng P., Ning Z., Xiang W. Modifying Hopcalite catalyst by SnO2 addition: An effective way to improve its moisture tolerance and activity for low temperature CO oxidation. Applied Catalysis A: General, 2016, vol. 525, pp. 204–214. DOI: org/10.1016/j.apcata.2016.07.023 18. Lin J., Li Q., Lu S., Chen X., Liew K. M. Cu-Mn-Ce ternary oxide catalyst coupled with KOH sorbent for air pollution control in confined space. Journal of Hazardous Materials, 2020, Vol. 389, pp. 1–11. DOI: org/10.1016/j.jhazmat.2019.121946 19. Taranushich V.A., Savost'ianov A.P., Sulima S.I., Zemliakov N.D. Tekhnologiia katalizatorov [Catalyst technology]. Novocherkassk, Iuzhno-Rossiiskii gosudarstvennyi politekhnicheskii universitet, 2012, 216 p. 20. Ali S., Wu X., Zuhra Z., Ma Y., Abbas Y., Jin B., Ran R., Weng D. Cu-Mn-Ce mixed oxides catalysts for soot oxidation and their mechanistic chemistry. Applied Surface Science, 2020, Vol. 512, pp. 1–9. DOI: org/10.1016/j.apsusc.2020.145602 21. Danilova I.G., Zaikovskii V.I., Ivanova A.S., Tsybulia S.V., Boronin A.I., Slavinskaia E.M., Stonkus O.A., Guliaev R.V., Bulavchenko O.A. Nizkotemperaturnoe okislenie monooksida ugleroda na katalizatorakh (Mn1-xMx)O2 (M = Co, Pd) [Low-temperature oxidation of carbon monoxide on catalysts (Mn1-xMx)O2 STUDY OF COMMODITY CHARACTERISTICS OF CYCLONE DUST AND GRANULAR POTASSIUM CHLORIDE OBTAINED BY PELLETIZING UNDER VARIOUS CONDITIONS A.À. Khazeev, M.V. Cherepanova Received: 20.10.2020 Received in revised form: 20.10.2020 Published: 01.02.2021 Abstract:
Determining the product characteristics of fertilizers is very important for the development of the technological scheme of the process and the initial data for the design of production as a whole. It is also important to consider the relationship of characteristics when assessing the impact of storage and transportation conditions of fertilizers. The paper presents the results of determining the static strength, average particle size, angle of natural slope, duration of dissolution, hygroscopicity at different ambient humidity, the degree of compaction and caking of granular potassium chloride obtained by rolling from cyclone dust under various conditions. The most durable granules (12.3 and 14.2 N/granule) were obtained when using a 10% aqueous solution of potassium silicic acid with a content of 12.0% by weight as a binder and with an additional supply of a strengthening additive-potassium dihydroorthophosphate. When determining the angle of natural slope, it was found that the samples granulated with the Ê2SiO3·nH2O binder (with or without an additive) have a lower value of this indicator by 25-26 %. The longest duration of dissolution with and without mixing was observed in granular potassium chloride obtained using an effective binder and strengthening additive. I.e., an increase in the strength of granules increases the duration of their dissolution, and, consequently, reduces the need for their annual application to the soil. By increasing the exposure time (from 1 to 96 hours) and the relative humidity of the medium (70, 80, 90 %) in the desiccator, the hygroscopicity of all samples increases, while its maximum value is noted for cyclone dust. Granulated potassium chloride with high strength has minimal hygroscopicity, which is explained by the presence of a dense (caked) layer on the surface of the granules, which makes it difficult for moisture to penetrate into it. The degree of compaction of granular potassium chloride – samples No. 2-4 is almost 2 times higher than that of the original dust. The initial cyclone dust, when placed in a cuvette for analysis, has a high density, the particles are close to each other. The caking capacity of granulated potassium chloride, regardless of the type of binder used and the presence of a strengthening additive, is 35-50% lower than that of the original cyclone dust. The type of binder, and hence the quality of the granulate – the value of static strength, significantly affect the caking ability and have an inversely proportional relationship. In the course of the research, the relationship between the commodity characteristics of granular potassium chloride obtained by the pelletizing method was determined. High strength of granulated KS1 – 12-14 N/granule, favorably affects its other product characteristics. Keywords: granular potassium chloride, static strength, angle of natural slope, duration of dissolution, hygroscopicity, relative humidity, degree of compaction, caking.
Authors:
Aleksey A. Khazeev (Perm, Russian Federation) – student of the Department of Chemical Technology of the Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990, e-mail: a.xazeev@mail.ru). Maria V. Cherepanova (Perm, Russian Federation) – Ph.D. in Technical Sciences, Associate Professor of the Department of Chemical Technologies, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990, e-mail: syromyatnikova.maria@yandex.ru). References:
DEVELOPMENT OF AN ADAPTIVE FUZZY CONTROL SYSTEM FOR PLATE HEAT EXCHANGERS AND ITS MODELING IN MATLAB SIMULINK E.À. Muravyova, M.D. Kviring Received: 05.09.2020 Received in revised form: 05.09.2020 Published: 01.02.2021 Abstract:
Today, in many enterprises, one of the stages of production is heating the liquid. To achieve the required liquid temperature, plate heat exchangers are most often used, due to their high heat transfer, reliability, and smaller volume compared to other devices. However, due to the influence of external disturbances on the control object, the temperature of the liquid obtained at the outlet of the heat exchanger deviates from the target values. To maintain the required liquid temperature without errors in the heat exchanger system, it is proposed to use fuzzy controllers instead of PID controllers. Such regulators are able to compensate for the resulting disturbances to a greater extent, and get a more accurate result of the final temperature value. These fuzzy controllers are able to improve the quality of the control process, reduce the heating time of the liquid, taking into account external influences and mutual influences, and adapting to them, which leads to a stable quality of the products produced by the enterprise. This article describes the development of adaptive control of a system of interconnected plate heat exchangers based on fuzzy controllers. The technological scheme of operation of heat exchangers is presented and their interrelation is described. A method for calculating the temperature of the liquid at the outlet of heat exchangers depending on the specified input parameters is also implemented. The developed adaptive fuzzy control system is modeled and the results are compared with the calculated values. The process of modeling the developed system in the Matlab environment is described. The control system contains four fuzzy controls. For the operation of each of them, rules of fuzzy control are drawn up in the process of which the problem of heating the liquid to the required temperature is solved. Keywords: heat exchanger, fuzzy controller, parameter, temperature, valve, pressure, control. Authors:
Ålena A. Muravyova (Sterlitamak, Russian Federation) – Doctor of Technical Sciences, Professor, Head of the Department “Automated technological and information systems” of Ufa State oil Technical University, Branch in Sterlitamak (2, October av., Sterlitamak, 453118, e-mail: muraveva_ea@mail.ru).
Margarita D. Kviring (Sterlitamak, Russian Federation) – Undergraduate Student of the Department “Automated technological and information systems” of the Ufa State oil Technical University, Branch in Sterlitamak (2, October av., Sterlitamak, 453118, e-mail: kviringg@yandex.ru). References: 1. Solov'ev K.A., Murav'eva E.A., Sultanov R.G. Adaptacija nechetkogo reguljatora [Adaptation of a fuzzy controller]. Oil and Gas business, 2014, no 3, pp. 123-128. 2. Prjadko P.V., Murav'eva E.A. Sistema upravlenija sushil'noj pech'ju dlja ceolitsoderzhashhih katalizatorov na osnove 5-mernogo nechetkogo reguljatora s interval'noj neopredelennost'ju [Control system of a drying oven for zeolite-containing catalysts based on a 5-dimensional fuzzy controller with interval uncertainty]. 63rd scientific and technical conference of students, postgraduates and young scientists of USNTU, 2012, pp. 358. 3. Gabitov R.F., Kajashev A.I., Murav'eva E.A. Upravlenie pech'ju prokalki ceolitsoderzhashhih katalizatorov krekinga nefteproduktov metodom plavajushhego gorizonta s ispol'zovaniem nejrosetevoj modeli [Control of the furnace for calcining zeolite-containing catalysts for cracking petroleum products by the floating horizon method using a neural network model]. Automation, telemechanization and communication in the oil industry, 2010, no 12, pp. 12-19. 4. Murav'eva E.A., Radakina D.S., Sharipov M.I., Enikeeva Je.R., Artykaeva Je.M. Razrabotka metoda adaptacii nechetkogo reguljatora, prednaznachennogo dlja regulirovanija tehnologicheskih parametrov [Development of a method for adapting a fuzzy controller designed for regulating technological parameters]. Bulletin of the Chuvash University, 2018, no 1, pp. 137-145. 5. Jain M., Madeira A., Martins Manuel A. A Fuzzy Modal Logic for Fuzzy Transition Systems. Electronic Notes in Theoretical Computer Science, 2020, vol. 3481, pp. 85-103. 6. Hu Y., Yang Y., Li S., Zhou Y. Fuzzy controller design of micro-unmanned helicopter relying on improved genetic optimization algorithm. Erospace Science and Technology, 2020, vol. 98, no 105685. 7. Liang H., Zou J., Zuo K., Khan M. J An improved genetic algorithm optimization fuzzy controller applied to the wellhead back pressure control system. Mechanical Systems and Signal Processing, 2020, vol. 142, no 106708. 8. Talbi N. Design of Fuzzy Controller rule base using Bat Algorithm. Energy Procedia, 2019, vol. 162, pp. 241-250. 9. Lamamra K., Batat F., Mokhtari F. A new technique with improved control quality of nonlinear systems using an optimized fuzzy logic controller. Expert Systems with Applications, 2020, vol. 145, 1. no 113148. 10. Alsafadi L. A., Chulin N. A., Mironova I. V. Synthesis of Fuzzy Controller Based on Simple PID Controller. Procedia Computer Science, 2019, vol. 150, pp. 28-38. 11. Sreedharan D., Paul V., Thottungal R. Mathematical modelling of polymer electrolyte membrane fuel cell and fuzzy-based intelligent controllers for performance enhancement. Computers & Electrical Engineering, 2019, vol. 77, pp. 354-365. 12. Farajdadian, S. M. Hassan Hosseini Design of an optimal fuzzy controller to obtain maximum power in solar power generation system. Solar Energy, 2019, vol. 182, pp. 161-178. 13. Nazarov I.S. Matematicheskoe modelirovanie nechetkogo reguljatora [Mathematical modeling of a fuzzy controller]. In the collection of scientific papers of the V International scientific conference: Information technologies in science, management, social sphere and medicine, 2018, pp. 113-118. 14. Mefedova Ju.A., Moiseeva Ju.R. Primenenie nechetkoj logiki v sistemah upravlenija [Application of fuzzy logic in control systems]. Proceedings of the IV International scientific and practical conference: Actual problems and ways of development of energy, engineering and technologies, 2018, pp. 94-97. 15. Buzikaeva A.V., Chernyj S.P. Osobennosti modelirovanija nechetkih reguljatorov dlja sistem jelektroprivoda peremennogo toka [Features of modeling fuzzy controllers for alternating current electric drive systems]. SB.: electric Drive in transport and industry proceedings of the II all-Russian scientific and practical conference, 2018, pp. 271-275. 16. Karimov I.I. Konceptual'naja model' nechetkogo reguljatora dlja opredelenija vozmushhenij [Conceptual model of a fuzzy controller for determining perturbations]. In the collection: Modern technologies in oil and gas business-2019 proceedings of the international scientific and technical conference: in 2 volumes, 2019, pp. 300-302. 17. Alimova M.M. Nechetkaja model' upravlenija tehnologicheskimi parametrami teplogenerirujushhih ustanovok [Fuzzy model of control of technological parameters of heat generating plants]. Internauka, 2019, no 8 (90), pp. 34-35. 18. Karabcov R.D. Optimizacija nechjotkih sistem upravlenija s ispol'zovaniem geneticheskogo algoritma [Optimization of fuzzy control systems using a genetic algorithm]. Applied mathematics and fundamental computer science, 2018, vol. 5, no 2, pp. 43-50. 19. Shilkina S.V., Fokina E.N. Kontroller nechjotkoj logiki v upravlenii tehnologicheskimi processami [Controller of fuzzy logic in process control]. Bulletin of the Siberian state automobile and road University, 2018, vol. 15. no 1 (59), pp. 106-114. 20. Potapov N.S., Maslov A.A. Ocenka adekvatnosti modeli adaptivnoj sistemy upravlenija s primeneniem sredstv matematicheskogo modelirovanija [Assessment of the adequacy of the adaptive control system model using mathematical modeling tools], Nauka – proizvodstvu. Materialy mezhdunarodnoi konferentsii. Murmansk, 2018, pp. 77–84. OPTIMIZATION IN THE DESIGN AND MANAGEMENT OF THE TECHNOLOGICAL PROCESS OF FIELD OIL TREATMENT T.N. Karanevskaia, A.G. Shumikhin Received: 28.10.2020 Received in revised form: 28.10.2020 Published: 01.02.2021 Abstract:
The problem of optimizing the technological process of field oil treatment in order to obtain commercial oil that meets the requirements of GOST R 51858-2002 and to improve technical and economic indicators in the design and operation of oil treatment plants (UPN) is considered. An optimality criterion is developed in the form of an indicator of reduced costs in the design problem and net profit in the management problem of the current UPN. The problem of optimizing a multi-stage process with a criterion that is an additive function of the optimality criteria for each of the stages of oil preparation is formulated. A structural scheme of joint design and control of the technological process of preparation for obtaining the required quality and volume of commercial oil is proposed. When formulating the optimality criterion, models have been developed that link the indicator of reduced costs for the design task or net profit for the operation task (real-time management) with operating parameters and daily productivity at the stages of the technological process of oil preparation. Based on the analysis of experimental materials collected from the field, a neural network model has been developed that is trained on an expanded volume of laboratory research data and connects the quality indicator (degree of dehydration) with the operating parameters of the process (temperature, demulsifier consumption, time spent in the apparatus). Based on the calculation of material and heat balance of the main processes of oil treatment, presented in the form of a system of differential equations, and statistical processing results of the stages of the process, expressions of the dependence outputs of target products from daily productivity are obtained. Keywords: oil field preparation, technological process, design and management tasks, experimental and statistical models, optimization. Authors:
Tatiana N. Karanevskaia (Perm, Russian Federation) – Senior Lecturer, Department of Equipment and Automation of Chemical Production, Perm National Research Polytechnic University (9, Building B, Professor Pozdeyev str., Perm, 614013, e-mail: bormotova_tn@mail.ru).
Alexander G. Shumikhin (Perm, Russian Federation) – Doctor of Technical Sciences, Professor, Department of Equipment and Automation of Chemical Production, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990; e-mail: atp@pstu.ru).
References: 1. Tehnologija, jekonomika i avtomatizacija processov pererabotki nefti i gaza / S.A. Ahmetov, M.H. Ishmijarov, A.P. Verevkin, E.S. Dokuchaev, Ju.M. Malyshev; Pod red. S.A. Ahmetova [Technology, Economics and automation of oil and gas refining processes]. Moscow, 2005, 736 p. 2. Bojarinov A.I., Kafarov V.V. Metody optimizacii v himicheskoj tehnologii [Optimization methods in chemical technology]. Moscow, 1975, 576 p. 3. Karanevskaja T.N., Shumihin A.G. Optimizacija tehnologicheskih rezhimov pri upravlenii processami promyslovoj podgotovki nefti [Optimization of technological modes for managing oil production processes]. Inženernyj vestnik Dona [Electronic resource], 2019, no. 4, 12 p. available at: http://www.ivdon.ru/ uploads/article/pdf/IVD_67_Karanevskaya_Shumikhin_1.pdf_f3d4311164.pdf (accessed 23 October 2020). 4. Grzymala-Busse J. W., Mroczek T. Definability in Mining Incomplete Data. Procedia Computer Science, 2016, vol. 96, pp. 179–186. 5. Kruglov V.V. Iskusstvennye nejronnye seti. Teorija i praktika / Kruglov V.V., Borisov V.V. [Artificial neural network. Theory and practice]. 6. Shumihin A.G., Bojarshinova A.S. Algoritm vybora strukturnyh parametrov iskusstvennoj nejronnoj seti i ob#ema obuchajushhej vyborki pri approksimacii povedenija dinamicheskogo ob#ekta [Algorithm for selecting the structural parameters of an artificial neural network and the size of the training sample when approximating the behavior of a dynamic object]. Komp'juternye issledovanija i modelirovanie, 2015, vol. 7, no. 2, pp. 243-251. 7. Karanevskaya T. N., Shumikhin A. G. Modeling of technological processes for algorithmization of problem of management of oil field treatment facilities [Electronic resource]. Izvestiya Vysshikh Uchebnykh Zavedenii, Seriya Khimiya i Khimicheskaya Tekhnologiya, 2020, vol. 63, iss. 2, pp. 84-90. 8. Gartman T.N., Klushin D.V. Osnovy komp'juternogo modelirovanija himiko-tehnologicheskih processov [Fundamentals of computer modeling of chemical and technological processes]. Moscow, 2006, 416 p. 9. Sistemnyj analiz himiko-tehnologicheskih processov / A.V. Kravcov, Je.D. Ivanchina, E.N. Ivashkina, E.S. Sharova [System analysis of chemical and technological processes]. Tomsk, 2008, 96 p. 10. Tronov V.P. Promyslovaja podgotovka nefti [Oil field preparation]. Kazan, 2000, 416 p. 11. Prikladnoj statisticheskij analiz: ucheb. posobie dlja vuzov / 12. Karanevskaja T.N., Popova A.V. Avtomatizirovannyj vybor tehnologicheskih sistem sbora i promyslovoj podgotovki nefti na osnove modul'nogo podhoda k ih predstavleniju [Automated selection of technological systems for oil collection and field treatment based on a modular approach to their presentation]. Neft'. Gaz. Novacii, 2016, no. 5 (186), pp. 20-23. 13. Hachatrjan S.S., Arunjanc G.G. Avtomatizacija proektirovanija himicheskih proizvodstv [Automation of chemical production design]. Moscow, 1984, 208 p. 14. Verevkin A.P., El'cov I.D., Kirjushin O.V. K resheniju zadachi operativnogo upravlenija processami podgotovki nefti [To solve the problem of operational management of oil preparation processes]. Territorija Neftegaz, 2007, no. 2, pp. 13-15. 15. Lutoshkin G.S., Dunjushkin M.I. Sbornik zadach po sboru i podgotovke nefti, gaza i vody na promyslah [Collection of tasks for collecting and preparing oil, gas and water in the fields]. Moscow, 2007, 135 p. DEVELOPMENT OF AN ALGORITHM FOR CONTROLLING THE THICKNESS OF A POLYETHYLENE FILM DURING ITS PRODUCTION BY EXTRUSION S.N. Kondrashov, E.I. Beresnev Received: 19.10.2020 Received in revised form: 19.10.2020 Published: 01.02.2021 Abstract:
According to the study of the mode of operation and hardware design process of production of polyethylene film by extrusion and according to the information obtained by interviewing operators and experts highlighted two main factors, changes in which can disrupt the normal conduct of the process, and one control action to return the process in normal mode: factor 1 – the temperature of the melt before exiting the cylindrical nozzle; factor 2 – the thickness of the plastic film after crystallization, i.e. after the cooling air flows; control action-setting the percentage opening of the valve that regulates the air supply. Based on the analysis of production and literature sources, a method for forming control actions is proposed that contains five stages: stage 1-selection and description of technological parameters and possible control actions; stage 2-construction of fuzzy behavior diagrams (membership functions); stage 3 – development of the production rules base; stage 4 – synthesis of the control action; stage 5 – defasification and implementation of the control action. To implement the method, the values of input and output parameters are reduced to fuzzy gradations and for all parameter values in the selected range, membership functions are constructed in the form of triangles. Two fuzzy diagrams of the behavior of technological values of the parameters of the polyethylene film production process are constructed. A combination of fuzzy behavior diagrams of input and output technological parameters of the film production process is performed. A complete list of production rules for the synthesis and implementation of the control action has been compiled, containing 16 rules. A model of the control algorithm in the form of a scheme in the MATLAB package is constructed. In this work, the algorithm was tested in 6 stages, the results of the algorithm are presented in the form of graphs. When comparing two graphs of PID and fuzzy control, it was found that the developed control algorithm works better than the basic one and deviations from the norm are not significant. Also, when comparing two graphs of control actions, it can be seen that when the melt temperature changes, the fuzzy control system responds quickly to disturbances, allowing you to maintain the operation mode at the optimal level. A variant of integration of the developed algorithm for controlling the thickness of a polyethylene film into a distributed control system of an industrial installation is proposed. Keywords: polyethylene film production, film thickness, control system, production rules, accessory functions, control algorithm. Authors:
Sergei N. Kondrashov (Perm, Russian Federation) – Ph.D. in Technical Sciences, Associate Professor, Department of equipment and automation of chemical production, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990, e-mail: Sergej. Kondrashov@pnos.lukoil.com). Evgeny I. Beresnev (Perm, Russian Federation) – Undergraduate Student, Department of equipment and automation of chemical production, Perm National Research Polytechnic University (29, Komsomolsky av., Perm, 614990). References:
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