Pub Date : 2019-11-30DOI: 10.37952/roi-jbc-01/19-60-11-21
A. A. Damzina, L. Skvortsova, K. Bolgaru
Iron-containing metal-ceramic composites based on nitrogen and sialon nitrides, obtained by the method of self-propagated synthesis were studied in the process of photocatalytic oxidative destruction of eosin. The phase composition of the samples was established by the X-ray diffraction method. It was shown that, along with the main phases, the ceramic matrix of materials contains the phases of semiconductors: (SiC, TiN). The indicator method of Hammet and Tanabe assessed the surface acid-base centers of the composites. It was established that a large sorption of the dye is characteristic of samples based on silicon nitride and sialon and is associated with the participation of active Brensted acid sites. The photocatalytic activity of iron-containing composites was studied in the presence of H2O2 (photo-Fenton system), H2O2 and EDTA (peroxide-ferriccomplexon system), H2O2 and tartaric acid (peroxide-ferritartrate system). It was shown that the degree of oxidative destruction of eosin is significantly higher with the participation of Fe(II, III) complexes with EDTA and tartaric acid, than Fe(II, III) aquacomplexes in the photo-Feton system. The high activity of composites containing the semiconductor phase of titanium nitride (TiN) is due to the combination of homogeneous and heterogeneous catalysis with the participation of the ceramic matrix. The introduction of complexing agents shifts the optimal acidity (pH 2-4) for a homogeneous system of photo-Fenton with the participation of iron(II, III) aqua complexes in the weakly acidic region (pH 4-7) and leads to almost complete destruction of the dye in the peroxide-tartrate system.
{"title":"Oxidative photo-catalytic destruction of eosine with the application of iron-contalning metal-ceramic composites with additive complex-forming reagents","authors":"A. A. Damzina, L. Skvortsova, K. Bolgaru","doi":"10.37952/roi-jbc-01/19-60-11-21","DOIUrl":"https://doi.org/10.37952/roi-jbc-01/19-60-11-21","url":null,"abstract":"Iron-containing metal-ceramic composites based on nitrogen and sialon nitrides, obtained by the method of self-propagated synthesis were studied in the process of photocatalytic oxidative destruction of eosin. The phase composition of the samples was established by the X-ray diffraction method. It was shown that, along with the main phases, the ceramic matrix of materials contains the phases of semiconductors: (SiC, TiN). The indicator method of Hammet and Tanabe assessed the surface acid-base centers of the composites. It was established that a large sorption of the dye is characteristic of samples based on silicon nitride and sialon and is associated with the participation of active Brensted acid sites. The photocatalytic activity of iron-containing composites was studied in the presence of H2O2 (photo-Fenton system), H2O2 and EDTA (peroxide-ferriccomplexon system), H2O2 and tartaric acid (peroxide-ferritartrate system). It was shown that the degree of oxidative destruction of eosin is significantly higher with the participation of Fe(II, III) complexes with EDTA and tartaric acid, than Fe(II, III) aquacomplexes in the photo-Feton system. The high activity of composites containing the semiconductor phase of titanium nitride (TiN) is due to the combination of homogeneous and heterogeneous catalysis with the participation of the ceramic matrix. The introduction of complexing agents shifts the optimal acidity (pH 2-4) for a homogeneous system of photo-Fenton with the participation of iron(II, III) aqua complexes in the weakly acidic region (pH 4-7) and leads to almost complete destruction of the dye in the peroxide-tartrate system.","PeriodicalId":9405,"journal":{"name":"Butlerov Communications","volume":"9 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87640947","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 : 2019-11-30DOI: 10.37952/roi-jbc-01/19-60-11-56
Yu.V. Shcherbakova, F. Akhmadullina, K. Kazimova, Nasrulina K. Aydarovna
In this paper, authors studied the integral antioxidant activity of kefir for baby food and the effect of the product's expiry date on this indicator. The integral antioxidant activity of kefir was determined on an “Expert-006” coulometer using coulometric titration with electro-generated bromine using rutin as a standard. The following points were chosen as control points for carrying out analytical work: release date, end of the expiry date, the period of time during which the food product, subject to storage conditions, must retain all of its properties specified in the regulatory documentation and a week after the expiration date. Such a trip allows us to determine a sample of fermented milk products that is distinguished by the highest biochemical value and high-quality preservation, and also to identify the brand of kefir for baby food and, as a result, the manufacturer, who should be preferred when buying goods. The object of the study in this work was several kefirs for children produced by OJSC «Zelenodolsk milk processing plant», OJSC «Lactis», LLC «Wimm Bill Dann». Studies have shown that the highest initial antioxidant activity was characterized by all control samples of kefir brand «For Babies» with the lowest declared expiry date. Moreover, an increase in the declared expiry date of sour-milk products led to a decrease in the value of the above indicator. A similar trend was observed when studying changes in the biochemical value of all studied samples during storage. The effect of storage duration on the integrated antioxidant activity of commercial products was evaluated by the level of its decrease (%) at the time of determination relative to its initial value. It was revealed that the kefir produced by OJSC «Zelenodolsk milk processing plant" had the highest integral antioxidant activity and was subjected to the least changes in this indicator during storage among all children's kefirs studied in the work.
本文研究了婴儿食品用开菲尔的整体抗氧化活性，以及产品有效期对该指标的影响。用“Expert-006”库仑滴定法测定了开菲尔的整体抗氧化活性，以芦丁为标准品，用电生溴库仑滴定法测定了开菲尔的整体抗氧化活性。以下点被选为进行分析工作的控制点:放行日期、有效期结束日期、受储存条件限制的食品必须保留法规文件中规定的所有特性的时间以及有效期后一周。这样的旅行使我们能够确定发酵乳制品的样品，该样品具有最高的生化价值和高质量的保存，并且还可以确定婴儿食品的开菲尔品牌，从而确定购买商品时应该首选的制造商。这项工作的研究对象是由OJSC“Zelenodolsk牛奶加工厂”，OJSC“Lactis”，LLC“Wimm Bill Dann”生产的几种儿童克弗尔。研究表明，具有最高初始抗氧化活性的是所有宣布有效期最短的婴儿克非尔品牌的对照样品。此外，酸奶类产品的申报有效期延长导致上述指标的数值下降。在研究所有研究样品在储存期间的生化值变化时，也观察到类似的趋势。贮存时间对商业产品综合抗氧化活性的影响是通过测定时相对于其初始值的降低水平(%)来评价的。结果显示，OJSC“泽列诺多尔斯克牛奶加工厂”生产的开菲尔具有最高的整体抗氧化活性，并且在工作中研究的所有儿童开菲尔中，该指标在储存期间的变化最小。
{"title":"Integral antioxidant activity of kefir for baby food from different manufacturers","authors":"Yu.V. Shcherbakova, F. Akhmadullina, K. Kazimova, Nasrulina K. Aydarovna","doi":"10.37952/roi-jbc-01/19-60-11-56","DOIUrl":"https://doi.org/10.37952/roi-jbc-01/19-60-11-56","url":null,"abstract":"In this paper, authors studied the integral antioxidant activity of kefir for baby food and the effect of the product's expiry date on this indicator. The integral antioxidant activity of kefir was determined on an “Expert-006” coulometer using coulometric titration with electro-generated bromine using rutin as a standard. The following points were chosen as control points for carrying out analytical work: release date, end of the expiry date, the period of time during which the food product, subject to storage conditions, must retain all of its properties specified in the regulatory documentation and a week after the expiration date. Such a trip allows us to determine a sample of fermented milk products that is distinguished by the highest biochemical value and high-quality preservation, and also to identify the brand of kefir for baby food and, as a result, the manufacturer, who should be preferred when buying goods. The object of the study in this work was several kefirs for children produced by OJSC «Zelenodolsk milk processing plant», OJSC «Lactis», LLC «Wimm Bill Dann». Studies have shown that the highest initial antioxidant activity was characterized by all control samples of kefir brand «For Babies» with the lowest declared expiry date. Moreover, an increase in the declared expiry date of sour-milk products led to a decrease in the value of the above indicator. A similar trend was observed when studying changes in the biochemical value of all studied samples during storage. The effect of storage duration on the integrated antioxidant activity of commercial products was evaluated by the level of its decrease (%) at the time of determination relative to its initial value. It was revealed that the kefir produced by OJSC «Zelenodolsk milk processing plant\" had the highest integral antioxidant activity and was subjected to the least changes in this indicator during storage among all children's kefirs studied in the work.","PeriodicalId":9405,"journal":{"name":"Butlerov Communications","volume":"186 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91491712","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 : 2019-11-30DOI: 10.37952/roi-jbc-01/19-60-11-156
I. Ustinov, I. Shakhkeldyan, Y. Atroshchenko, Anastasia V. Glazunova, Georgy V. Pescov, K. I. Kobrakov
Currently, agricultural production is impossible without the use of chemical plant protection products, so the search for new effective fungicides is an important and urgent task. A significant part of the systemic fungicides and antimycotics used today are azole derivatives. Research conducted at the Department of Chemistry is devoted to the analysis of the fungicidal and biological activity of substances of various classes of organic compounds, including derivatives of azoles. Previously published data on the fungicidal activity of 2-methyl-5-nitrobenzoxazole and its derivatives showed that 2-methyl-5-nitrobenzoxazole shows the highest fungicidal activity for all types of fungal cultures used in the study. The second nitro group introduced into the 2-methyl-5-nitrobenzoxazole molecule reduces fungitoxicity by 1.5-2 times. Replacing the methyl group with phenyl significantly reduces the fungicidal activity. In continuation of these studies, tests of 5-(4'-chlorophenylazo)-7-nitro-8-hydroxyquinoline, 5-(3',5'-dimethoxyphenylazo)-7-nitro-8-hydroxyquinoline and 5-(3'-methyl-4'-nitrophenylazo)-7-nitro-8-hydroxyqui-noline with respect to V. inaequalis, the causative agent of apple scab, R. solani, the causative agent of rhi-zoctonia, F. oxysporum, F. moniliforme, causative agents of cereal crops, B. sorokiniana – causative agent of root rot and S. sclerotiorum – causative agent of white rot. The radial growth of mycelium was determined according to the method developed by NIITEKHIM, according to which the fungal cultures were sown in nutrient media with the addition of the studied substan-ces. In parallel, a control experiment was conducted in the aquatic environment. The growth of mycelia was controlled by measurements on days 3, 6 and 9. The percentage of inhibition of fungal growth was calculated using the Abbott formula. Analysis of the experimental data demonstrates a higher fungicidal activity of 5-(3',5'-dimethoxy-phenylazo)-7-nitro-8-hydroxyquinoline compared with other azoquinolines for all types of fungal cultures used in the study.
{"title":"Fungicidal activity of new 5-arylazo-7-nitro-8-hydroxyquinolines","authors":"I. Ustinov, I. Shakhkeldyan, Y. Atroshchenko, Anastasia V. Glazunova, Georgy V. Pescov, K. I. Kobrakov","doi":"10.37952/roi-jbc-01/19-60-11-156","DOIUrl":"https://doi.org/10.37952/roi-jbc-01/19-60-11-156","url":null,"abstract":"Currently, agricultural production is impossible without the use of chemical plant protection products, so the search for new effective fungicides is an important and urgent task. A significant part of the systemic fungicides and antimycotics used today are azole derivatives. Research conducted at the Department of Chemistry is devoted to the analysis of the fungicidal and biological activity of substances of various classes of organic compounds, including derivatives of azoles. Previously published data on the fungicidal activity of 2-methyl-5-nitrobenzoxazole and its derivatives showed that 2-methyl-5-nitrobenzoxazole shows the highest fungicidal activity for all types of fungal cultures used in the study. The second nitro group introduced into the 2-methyl-5-nitrobenzoxazole molecule reduces fungitoxicity by 1.5-2 times. Replacing the methyl group with phenyl significantly reduces the fungicidal activity. In continuation of these studies, tests of 5-(4'-chlorophenylazo)-7-nitro-8-hydroxyquinoline, 5-(3',5'-dimethoxyphenylazo)-7-nitro-8-hydroxyquinoline and 5-(3'-methyl-4'-nitrophenylazo)-7-nitro-8-hydroxyqui-noline with respect to V. inaequalis, the causative agent of apple scab, R. solani, the causative agent of rhi-zoctonia, F. oxysporum, F. moniliforme, causative agents of cereal crops, B. sorokiniana – causative agent of root rot and S. sclerotiorum – causative agent of white rot. The radial growth of mycelium was determined according to the method developed by NIITEKHIM, according to which the fungal cultures were sown in nutrient media with the addition of the studied substan-ces. In parallel, a control experiment was conducted in the aquatic environment. The growth of mycelia was controlled by measurements on days 3, 6 and 9. The percentage of inhibition of fungal growth was calculated using the Abbott formula. Analysis of the experimental data demonstrates a higher fungicidal activity of 5-(3',5'-dimethoxy-phenylazo)-7-nitro-8-hydroxyquinoline compared with other azoquinolines for all types of fungal cultures used in the study.","PeriodicalId":9405,"journal":{"name":"Butlerov Communications","volume":"154 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88513224","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 : 2019-11-30DOI: 10.37952/roi-jbc-01/19-60-11-128
A. Kourdioukov
The primary stages of the oxidation of model cyclohexane and 1,3-cyclohexadiene by triplet molecular oxygen and subsequent transformations involving triplet and singlet states were studied for the first time by the DFT method with the density functional B3LYP with the basis set 6-311++g(df,p). It was shown that, ceteris paribus, cyclohexane and 1,3-cyclohexadiene will be orders of magnitude more reactive compared to the activity of acyclic saturated hydrocarbons under SCF conditions when the oxidation process is initiated by the primary reaction with 3O2, which allows the propane-butane mixture to be effectively used as SCF conditions of heavy oils and use air purge to activate this process. The triplet associate complexes resulting from the oxidative cleavage of the secondary C–H bond of cyclohexane and 1,3-cyclohexadiene consist of hydrogen-bonded hydroperoxyl radical and cyclohexyl radical or 1,3-cyclohexadiene radical, respectively. These complexes can dissociate into unbound pairs of radicals, and therefore further reactions can proceed in the triplet or singlet direction. The singlet direction is characterized by hydrate-induced hydroperoxide-carbonyl transformation, as well as other hydrate-induced rearrangements. The triplet direction is characterized by the occurrence of triplet rearrangement, which in its essence is a triplet recombination of associated radicals. Associate triplet complexes can be agents of radical hydroperoxyl and alkyl activity, as well as agents of radical hydroxyl and alkoxyl activity. Most oxidative dehydrogenation reactions are absolutely real under a number of conditions, namely, they must take place under SCF conditions, as well as in the presence of an excess of SCF solvent necessary for the effective shift of thermodynamic equilibrium towards the target products in accordance with the Le Chatelier principle.
{"title":"Comparative DFT study of triplet and singlet elementary oxidation acts of the cyclohexane and 1,3-cyclohexadiene initiated by primary interaction with 3O2 under SCF conditions","authors":"A. Kourdioukov","doi":"10.37952/roi-jbc-01/19-60-11-128","DOIUrl":"https://doi.org/10.37952/roi-jbc-01/19-60-11-128","url":null,"abstract":"The primary stages of the oxidation of model cyclohexane and 1,3-cyclohexadiene by triplet molecular oxygen and subsequent transformations involving triplet and singlet states were studied for the first time by the DFT method with the density functional B3LYP with the basis set 6-311++g(df,p). It was shown that, ceteris paribus, cyclohexane and 1,3-cyclohexadiene will be orders of magnitude more reactive compared to the activity of acyclic saturated hydrocarbons under SCF conditions when the oxidation process is initiated by the primary reaction with 3O2, which allows the propane-butane mixture to be effectively used as SCF conditions of heavy oils and use air purge to activate this process. The triplet associate complexes resulting from the oxidative cleavage of the secondary C–H bond of cyclohexane and 1,3-cyclohexadiene consist of hydrogen-bonded hydroperoxyl radical and cyclohexyl radical or 1,3-cyclohexadiene radical, respectively. These complexes can dissociate into unbound pairs of radicals, and therefore further reactions can proceed in the triplet or singlet direction. The singlet direction is characterized by hydrate-induced hydroperoxide-carbonyl transformation, as well as other hydrate-induced rearrangements. The triplet direction is characterized by the occurrence of triplet rearrangement, which in its essence is a triplet recombination of associated radicals. Associate triplet complexes can be agents of radical hydroperoxyl and alkyl activity, as well as agents of radical hydroxyl and alkoxyl activity. Most oxidative dehydrogenation reactions are absolutely real under a number of conditions, namely, they must take place under SCF conditions, as well as in the presence of an excess of SCF solvent necessary for the effective shift of thermodynamic equilibrium towards the target products in accordance with the Le Chatelier principle.","PeriodicalId":9405,"journal":{"name":"Butlerov Communications","volume":"3 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89794467","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 : 2019-11-30DOI: 10.37952/roi-jbc-01/19-60-11-40
N. Smirnova
The interaction of sulfonate-containing aromatic poly- and copolyamides with acrylonitrile copolymers with N,N-dimethyl-N,N-diallylammonium chloride (DMDAAC) and N,N-diethylaminoethylmethacrylate (DEAEM) in organic and water-organic solutions was studied. It was shown that as a result of macromolecular reactions interpolyelectrolyte complexes (IPEC) forms. They are stabilized mainly by electrostatic forces. To characterize the interpolyelectrolyte complexes composition the φ parameter was used, that defines as the ratio of corresponding functional groups molar concentrations of interacting polyelectrolytes. The transformation degree in interpolymer reactions θ was calculated as the ratio of the salt bonds number between polyions to their maximum possible number. It was shown that the main factors determining the composition and structure of forming interpolyelectrolyte complexes are linear charge density of polyelectrolytes, the nature and composition of the solvent in which interpolymer reactions occurs. It is possible to obtain IPEC, the composition of which for the same polycation will vary from φ = 2.5 to φ = 1.0, changing these factors. It was found that at the complexation process is not accompanied by a change in the phase state of the interpolymer system, when the concentration of units with sulfonate groups in the macromolecular polyamide chain 5 mol.%. It was found that the introduction of polycation leads to the formation of IPEC structures in the form of particles with an average size of ~217.7 nm for poly-4,4'-(2-sodium sulfonate) – diphenylaminisophthalamide and ~248.1 nm in the case of poly-4,4'-(2-sodium sulfonate) -diphenylaminterephthalamide. It was shown that the decrease in the polymer content of units with sulfonate groups is accompanied by a decrease in the transformation degree from 0.65-0.66 to 0.18. It was found that the studied complexes can be transferred to the solution by increasing its ionic strength. The result obtained during this work can serve as a base for the development of for the manufacturing technology of film and membrane materials based on sulfonate-containing aromatic poly- and copolyamides.
{"title":"Effect of chemical structure and linear density charge of sulfonate-containing aromatic polyamides on interaction with polycations in organic and water-organic media","authors":"N. Smirnova","doi":"10.37952/roi-jbc-01/19-60-11-40","DOIUrl":"https://doi.org/10.37952/roi-jbc-01/19-60-11-40","url":null,"abstract":"The interaction of sulfonate-containing aromatic poly- and copolyamides with acrylonitrile copolymers with N,N-dimethyl-N,N-diallylammonium chloride (DMDAAC) and N,N-diethylaminoethylmethacrylate (DEAEM) in organic and water-organic solutions was studied. It was shown that as a result of macromolecular reactions interpolyelectrolyte complexes (IPEC) forms. They are stabilized mainly by electrostatic forces. To characterize the interpolyelectrolyte complexes composition the φ parameter was used, that defines as the ratio of corresponding functional groups molar concentrations of interacting polyelectrolytes. The transformation degree in interpolymer reactions θ was calculated as the ratio of the salt bonds number between polyions to their maximum possible number. It was shown that the main factors determining the composition and structure of forming interpolyelectrolyte complexes are linear charge density of polyelectrolytes, the nature and composition of the solvent in which interpolymer reactions occurs. It is possible to obtain IPEC, the composition of which for the same polycation will vary from φ = 2.5 to φ = 1.0, changing these factors. It was found that at the complexation process is not accompanied by a change in the phase state of the interpolymer system, when the concentration of units with sulfonate groups in the macromolecular polyamide chain 5 mol.%. It was found that the introduction of polycation leads to the formation of IPEC structures in the form of particles with an average size of ~217.7 nm for poly-4,4'-(2-sodium sulfonate) – diphenylaminisophthalamide and ~248.1 nm in the case of poly-4,4'-(2-sodium sulfonate) -diphenylaminterephthalamide. It was shown that the decrease in the polymer content of units with sulfonate groups is accompanied by a decrease in the transformation degree from 0.65-0.66 to 0.18. It was found that the studied complexes can be transferred to the solution by increasing its ionic strength. The result obtained during this work can serve as a base for the development of for the manufacturing technology of film and membrane materials based on sulfonate-containing aromatic poly- and copolyamides.","PeriodicalId":9405,"journal":{"name":"Butlerov Communications","volume":"61 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88810671","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 : 2019-11-30DOI: 10.37952/roi-jbc-01/19-60-11-31
V. V. Shcherbakov, S. Kurbatova, M. Zemtsova
The influence of the solvent nature on some physicochemical parameters of the quinoline derivatives molecules is investigated. It was noted that a variety of intermolecular interactions arising between the dissolved substance and the solvent and often accompanied by the phenomena of solvation, association, etc. leads to a variety of structural and energy changes in such systems and complicating their description. The most urgent problems of solutions include issues related to the solubility and bioavailability of biologically active compounds and drugs, the study of their ability to dissolve, the permeability of biological barriers, targeted delivery, etc., as well as the problems associated with the study of sorption of organic compounds from aqueous-organic eluents, for example, in liquid chromatography. Derivatives of quinoline (4-carboxy- and 4-aminoquinoline), known as potential drugs with various types of pharmacological action, were used as research objects. Using quantum chemical calculations, the dipole moment of the amino and carboxy derivatives of quinoline was determined, and the data obtained for vacuum and in solvents of various chemical nature were compared. A significant effect of solvent polarity on the dipole moment of quinoline derivatives dissolved in these solvents was found. The values of the solvation energy of quinoline derivatives in solvents of various chemical nature are calculated. It is shown that a change in the solvation energy is determined both by the structure of the molecules of the quinoline derivatives and by the polarity of the solvent. A nonlinear change in the energy of solvation with a change in the polarity of the solvent is established. A comparison is made of the values of the quinoline derivatives molecules polar surface area in solvents of various chemical nature. It was found that the polar surface area of the studied compounds changes slightly with a change in the nature of the solvent.
{"title":"The effect of the solvent nature on the quinoline derivatives physicochemical characteristics","authors":"V. V. Shcherbakov, S. Kurbatova, M. Zemtsova","doi":"10.37952/roi-jbc-01/19-60-11-31","DOIUrl":"https://doi.org/10.37952/roi-jbc-01/19-60-11-31","url":null,"abstract":"The influence of the solvent nature on some physicochemical parameters of the quinoline derivatives molecules is investigated. It was noted that a variety of intermolecular interactions arising between the dissolved substance and the solvent and often accompanied by the phenomena of solvation, association, etc. leads to a variety of structural and energy changes in such systems and complicating their description. The most urgent problems of solutions include issues related to the solubility and bioavailability of biologically active compounds and drugs, the study of their ability to dissolve, the permeability of biological barriers, targeted delivery, etc., as well as the problems associated with the study of sorption of organic compounds from aqueous-organic eluents, for example, in liquid chromatography. Derivatives of quinoline (4-carboxy- and 4-aminoquinoline), known as potential drugs with various types of pharmacological action, were used as research objects. Using quantum chemical calculations, the dipole moment of the amino and carboxy derivatives of quinoline was determined, and the data obtained for vacuum and in solvents of various chemical nature were compared. A significant effect of solvent polarity on the dipole moment of quinoline derivatives dissolved in these solvents was found. The values of the solvation energy of quinoline derivatives in solvents of various chemical nature are calculated. It is shown that a change in the solvation energy is determined both by the structure of the molecules of the quinoline derivatives and by the polarity of the solvent. A nonlinear change in the energy of solvation with a change in the polarity of the solvent is established. A comparison is made of the values of the quinoline derivatives molecules polar surface area in solvents of various chemical nature. It was found that the polar surface area of the studied compounds changes slightly with a change in the nature of the solvent.","PeriodicalId":9405,"journal":{"name":"Butlerov Communications","volume":"121 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88424783","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 : 2019-11-30DOI: 10.37952/roi-jbc-01/19-60-11-85
N. A. Panurin, Natalya Yu. Isaeva, E. Markova, T. F. Sheshko, Alexander G. Cherednechenko, A. S. Savchenko, Y. Samoilenko, G. Z. Kaziev
Carrying out heterogeneous acid catalysis with the use of heteropoly compounds has received considerable attention due to the great economic and environmental benefits. In spite of this, its industrial application is limited as there are difficulties in catalyst regeneration (settling) caused by its relatively low thermal stability. The aim of present work was to search and select catalysts related to the class of heteropoly compounds for propane cracking, to test the selectivity of the prosses as well as to discuss possible approaches for solving the problem of catalyst deactivation, that can contribute to achieve stable characteristics of solid heteropoly catalysts. Among these approaches are: the development of new catalysts with high thermal stability, the modification of catalysts to promote coke combustion, the inhibition of coke formation on heteropoly compound catalysts during the process, carrying out the reactions in supercritical media and also the cascade reactions using a multifunctional heteropoly catalyst. The obtained catalyst was also studied by physicochemical methods to get deep knowledge about which features of these compounds influence on the catalytic activity. A highly active and selective catalyst for ammonium octomolybdenocobaltate(II) ammonium (NH4)2[Co(H2O)4]2[Mo8O27]∙6H2O was synthesized for cracking associated petroleum gases. The qualitative, quantitative, and structural composition as well as the specific surface area of the obtained catalyst was established by the methods of X-ray diffraction, X-ray phase and fluorescence analysis. It was revealed that ammonium octomolybdenocobaltate(II) crystallizes in a triclinic syngony with cell parameters: а = 8.6292(9) Å b = 9.4795(10) Å c = 12.2071(13) Å α = 104.326(2)° β = 109.910(2)° γ = 100.820(2)°.
利用杂多化合物进行多相酸催化因其具有巨大的经济效益和环境效益而受到广泛关注。尽管如此，它的工业应用受到限制，因为它的热稳定性相对较低，导致催化剂再生(沉淀)困难。本工作的目的是寻找和选择与丙烷裂解相关的杂多化合物类型的催化剂，测试其工艺的选择性，并探讨解决催化剂失活问题的可能方法，从而有助于实现固体杂多催化剂的稳定特性。这些方法包括:开发具有高热稳定性的新型催化剂，对催化剂进行改性以促进焦炭燃烧，抑制杂多化合物催化剂在反应过程中生成焦炭，在超临界介质中进行反应，以及使用多功能杂多催化剂进行级联反应。用物理化学方法对所得催化剂进行了研究，以深入了解这些化合物的哪些特性对催化活性有影响。合成了一种高活性、选择性的八钼钴酸铵(II)铵(NH4)2[Co(H2O)4]2[Mo8O27]∙6H2O裂解伴生石油气体催化剂。通过x射线衍射、x射线物相和荧光分析等方法确定了催化剂的定性、定量、结构组成和比表面积。结果表明，八钼钴酸铵(II)的晶型为三斜晶型，晶型参数为:α = 8.6292(9) Å b = 9.4795(10) Å c = 12.2071(13) Å α = 104.326(2)°β = 109.910(2)°γ = 100.820(2)°。
{"title":"Efficiency of using heteropoly compounds of the type (NH4)2[Co(H2O)4]2[Mo8O27]∙6H2O as catalysts for the production of ethylene","authors":"N. A. Panurin, Natalya Yu. Isaeva, E. Markova, T. F. Sheshko, Alexander G. Cherednechenko, A. S. Savchenko, Y. Samoilenko, G. Z. Kaziev","doi":"10.37952/roi-jbc-01/19-60-11-85","DOIUrl":"https://doi.org/10.37952/roi-jbc-01/19-60-11-85","url":null,"abstract":"Carrying out heterogeneous acid catalysis with the use of heteropoly compounds has received considerable attention due to the great economic and environmental benefits. In spite of this, its industrial application is limited as there are difficulties in catalyst regeneration (settling) caused by its relatively low thermal stability. The aim of present work was to search and select catalysts related to the class of heteropoly compounds for propane cracking, to test the selectivity of the prosses as well as to discuss possible approaches for solving the problem of catalyst deactivation, that can contribute to achieve stable characteristics of solid heteropoly catalysts. Among these approaches are: the development of new catalysts with high thermal stability, the modification of catalysts to promote coke combustion, the inhibition of coke formation on heteropoly compound catalysts during the process, carrying out the reactions in supercritical media and also the cascade reactions using a multifunctional heteropoly catalyst. The obtained catalyst was also studied by physicochemical methods to get deep knowledge about which features of these compounds influence on the catalytic activity. A highly active and selective catalyst for ammonium octomolybdenocobaltate(II) ammonium (NH4)2[Co(H2O)4]2[Mo8O27]∙6H2O was synthesized for cracking associated petroleum gases. The qualitative, quantitative, and structural composition as well as the specific surface area of the obtained catalyst was established by the methods of X-ray diffraction, X-ray phase and fluorescence analysis. It was revealed that ammonium octomolybdenocobaltate(II) crystallizes in a triclinic syngony with cell parameters: а = 8.6292(9) Å b = 9.4795(10) Å c = 12.2071(13) Å α = 104.326(2)° β = 109.910(2)° γ = 100.820(2)°.","PeriodicalId":9405,"journal":{"name":"Butlerov Communications","volume":"6 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87509357","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 : 2019-11-30DOI: 10.37952/roi-jbc-01/19-60-11-114
A. Kourdioukov, Aynur F. Mingaliev, V. F. Khayrutdinov, F. Gumerov, A. R. Gabitova, I. Salikhov, V. G. Uryadov, E. N. Ofitserov, Alexey Trofimov
The primary oxidation stages of 3O2 model acyclic and cyclic alkanes and their subsequent triplet and singlet elementary events were studied for the first time by the DFT method with the density functional B3LYP and basis set 6-311++g(df,p). According to quantum chemical DFT calculations the C–H radical cleavage of the bonds of acyclic and cyclic alkanes upon interaction with 3O2 is almost completely thermodynamically shifted toward the initial state of the reaction system. This energy of primary oxidizing events explains the extremely low reactivity of saturated alkanes in comparison with asphaltene structural fragments under the conditions of SCF technology for the extraction of heavy oils and asphaltenes by a propane-butane mixture. It has been demonstrated that for all elementary acts of primary alkane oxidation the product of the direct reaction direction is not a free pair of radicals but a triplet hydrogen complex with a pronounced hydrogen bond between the hydroperoxyl radical and the radical form of the corresponding hydrocarbon. A new, previously not taken into account very exothermic (H = -29.25 – -30.77 kcal/mol) reaction direction is described which corresponds to triplet recombination of alkyl radicals and a hydroperoxyl radical in its oxygen-concentrated part. The products of this recombination are triplet forms of alkane hydroperoxides in which there is a fairly loosened triplet O---O bond with a length of 2.20-2.23 Å, which is ~0.72-0.77 Å more than bond length in the singlet state.
{"title":"DFT study of triplet and singlet elementary acts of acyclic and cyclic alkanes oxidation initiated by primary interaction with 3O2","authors":"A. Kourdioukov, Aynur F. Mingaliev, V. F. Khayrutdinov, F. Gumerov, A. R. Gabitova, I. Salikhov, V. G. Uryadov, E. N. Ofitserov, Alexey Trofimov","doi":"10.37952/roi-jbc-01/19-60-11-114","DOIUrl":"https://doi.org/10.37952/roi-jbc-01/19-60-11-114","url":null,"abstract":"The primary oxidation stages of 3O2 model acyclic and cyclic alkanes and their subsequent triplet and singlet elementary events were studied for the first time by the DFT method with the density functional B3LYP and basis set 6-311++g(df,p). According to quantum chemical DFT calculations the C–H radical cleavage of the bonds of acyclic and cyclic alkanes upon interaction with 3O2 is almost completely thermodynamically shifted toward the initial state of the reaction system. This energy of primary oxidizing events explains the extremely low reactivity of saturated alkanes in comparison with asphaltene structural fragments under the conditions of SCF technology for the extraction of heavy oils and asphaltenes by a propane-butane mixture. It has been demonstrated that for all elementary acts of primary alkane oxidation the product of the direct reaction direction is not a free pair of radicals but a triplet hydrogen complex with a pronounced hydrogen bond between the hydroperoxyl radical and the radical form of the corresponding hydrocarbon. A new, previously not taken into account very exothermic (H = -29.25 – -30.77 kcal/mol) reaction direction is described which corresponds to triplet recombination of alkyl radicals and a hydroperoxyl radical in its oxygen-concentrated part. The products of this recombination are triplet forms of alkane hydroperoxides in which there is a fairly loosened triplet O---O bond with a length of 2.20-2.23 Å, which is ~0.72-0.77 Å more than bond length in the singlet state.","PeriodicalId":9405,"journal":{"name":"Butlerov Communications","volume":"55 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79425836","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 : 2019-11-30DOI: 10.37952/roi-jbc-01/19-60-11-102
V. Y. Chuklanov, K. Smirnov, Natalia V. Chuklanova
In this work the synthesis process of soluble polymethylsilsesquioxane that is a valuable prepolymer in the production of ceramic products, high-temperature protective coatings for high-speed aircraft, primary product for the formation of LEDs and other elements of microelectronics was studied. The synthesis was carried out from methyltrichlorosilane in a binary system of polar and non-polar solvent under the water action. The possibility of polymethylsilsesquioxane with a sufficiently high seepage at atmospheric pressure synthesis was shown. The resulting compound was analyzed. The presence of polymethylsilsesquioxane bonds in the polymer was identified by infrared Fourier spectroscopy on the Bruker Tensor 27 spectrometer. The resulting polymer has all the characteristics of polymethylsilsesquioxane. This is confirmed in particular by the presence of a characteristic wide band over the range by 1050-1100 cm-1 in the spectrum. To find out the optimal synthesis conditions and obtain the maximum yield of polymethylsilsesquioxane, the experiment was planned using the Box-Wilson planning method. The influence of temperature, reaction time and nature of solvents on the yield of polymethylsilsesquioxane was also studied. The optimal conditions for the synthesis were found out. The highest yield of polymethylsilsesquioxane was observed at 10 °C with a 6 hours synthesis duration. When the temperature increased to 30 °C, a partial decrease in the polymer yield was observed. It is assumed that at a high temperature and a significant time of the process, a partial decrease in the yield of polymethylsilsesquioxane associated with a decrease in the soluble fraction begins to occur.
{"title":"Soluble polymethylsilsesquioxane synthesis in organic solvents","authors":"V. Y. Chuklanov, K. Smirnov, Natalia V. Chuklanova","doi":"10.37952/roi-jbc-01/19-60-11-102","DOIUrl":"https://doi.org/10.37952/roi-jbc-01/19-60-11-102","url":null,"abstract":"In this work the synthesis process of soluble polymethylsilsesquioxane that is a valuable prepolymer in the production of ceramic products, high-temperature protective coatings for high-speed aircraft, primary product for the formation of LEDs and other elements of microelectronics was studied. The synthesis was carried out from methyltrichlorosilane in a binary system of polar and non-polar solvent under the water action. The possibility of polymethylsilsesquioxane with a sufficiently high seepage at atmospheric pressure synthesis was shown. The resulting compound was analyzed. The presence of polymethylsilsesquioxane bonds in the polymer was identified by infrared Fourier spectroscopy on the Bruker Tensor 27 spectrometer. The resulting polymer has all the characteristics of polymethylsilsesquioxane. This is confirmed in particular by the presence of a characteristic wide band over the range by 1050-1100 cm-1 in the spectrum. To find out the optimal synthesis conditions and obtain the maximum yield of polymethylsilsesquioxane, the experiment was planned using the Box-Wilson planning method. The influence of temperature, reaction time and nature of solvents on the yield of polymethylsilsesquioxane was also studied. The optimal conditions for the synthesis were found out. The highest yield of polymethylsilsesquioxane was observed at 10 °C with a 6 hours synthesis duration. When the temperature increased to 30 °C, a partial decrease in the polymer yield was observed. It is assumed that at a high temperature and a significant time of the process, a partial decrease in the yield of polymethylsilsesquioxane associated with a decrease in the soluble fraction begins to occur.","PeriodicalId":9405,"journal":{"name":"Butlerov Communications","volume":"41 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74164962","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 : 2019-11-30DOI: 10.37952/roi-jbc-01/19-60-11-98
I. Ustinov, I. Shakhkeldyan, Nikolay V. Khlytin, Y. Atroshchenko, K. I. Kobrakov
The synthesis of new derivatives of 3-azabicyclononan is one of the urgent tasks of modern synthetic organic chemistry. 3-Azabicyclononan is a structural analogue of the cytisine alkaloid, which is a strong agonist of acetylcholine receptors. Among synthetic heterocycles containing a 3-azabicyclo[3.3.1]nonane fragment, compounds with different types of biological activity have been discovered at present: analgesic, anti-inflammatory, antimicrobial, antioxidant, and others. The introduction of a fragment of azabicyclononan into the amino acid structure can lead to a limitation of the conformational mobility of a new molecule, as a result of which the activity and selectivity of its interaction with the receptor will increase. We synthesized 2-(1,9-dinitro-8-oxo-6,11-diazatricyclo[7.3.1.02,7]trideca-2,4,6-trien-11-yl)acetic acid and 2-(1,9-dinitro-8-oxo-13-(2-oxopropyl)-6,11-diazatricyclo[7.3.1.02,7]trideca-2,4,6-trien-11-yl)acetic acid by the interaction of annionic σ-complexes 5,7-dinitro-8-hydroxyquinoline with glycine under Mannich condensation in high yield. At the beginning, when 5,7-dinitro-8-hydroxyquinoline NaBH4 was applied in DMF or acetone carbanion in DMSO, the corresponding anionic complexes were synthesized. The resulting adducts were isolated from the reaction mixture, dissolved in cold water, and an aminomethylating mixture consisting of formaldehyde and an amino acid was added. As a result, 3-azabicyclo[3.3.1]nonane derivatives are formed, annelated with a pyridine ring and containing an amino acid residue. By the methods of NMR and IR spectroscopy, as well as high-resolution mass spectrometry, the structure of the obtained compounds was proved. Thus, in the 1H NMR spectra of the synthesized compounds, a signal of the proton of the carboxyl group in the form of a broadened singlet is detected in a weak spectral region. Equatorial and axial protons of an alicyclic fragment form a characteristic system of signals in the range δ 3.20-3.60 ppm. In the IR spectra of these molecules, the vibrational bands of carbonyl groups at ν 1720 cm–1, as well as the vibrational bands of the C–O bond of the carboxyl group at ν 1198 cm–1, are fixed. The m/z values in the high resolution mass spectra correspond to the molecular weights of the synthesized diazatricycclotridecans.
{"title":"Amino acids in the double Mannich reaction with anionic σ-complexes of 5,7-dinitro-8-hydroxyquinoline","authors":"I. Ustinov, I. Shakhkeldyan, Nikolay V. Khlytin, Y. Atroshchenko, K. I. Kobrakov","doi":"10.37952/roi-jbc-01/19-60-11-98","DOIUrl":"https://doi.org/10.37952/roi-jbc-01/19-60-11-98","url":null,"abstract":"The synthesis of new derivatives of 3-azabicyclononan is one of the urgent tasks of modern synthetic organic chemistry. 3-Azabicyclononan is a structural analogue of the cytisine alkaloid, which is a strong agonist of acetylcholine receptors. Among synthetic heterocycles containing a 3-azabicyclo[3.3.1]nonane fragment, compounds with different types of biological activity have been discovered at present: analgesic, anti-inflammatory, antimicrobial, antioxidant, and others. The introduction of a fragment of azabicyclononan into the amino acid structure can lead to a limitation of the conformational mobility of a new molecule, as a result of which the activity and selectivity of its interaction with the receptor will increase. We synthesized 2-(1,9-dinitro-8-oxo-6,11-diazatricyclo[7.3.1.02,7]trideca-2,4,6-trien-11-yl)acetic acid and 2-(1,9-dinitro-8-oxo-13-(2-oxopropyl)-6,11-diazatricyclo[7.3.1.02,7]trideca-2,4,6-trien-11-yl)acetic acid by the interaction of annionic σ-complexes 5,7-dinitro-8-hydroxyquinoline with glycine under Mannich condensation in high yield. At the beginning, when 5,7-dinitro-8-hydroxyquinoline NaBH4 was applied in DMF or acetone carbanion in DMSO, the corresponding anionic complexes were synthesized. The resulting adducts were isolated from the reaction mixture, dissolved in cold water, and an aminomethylating mixture consisting of formaldehyde and an amino acid was added. As a result, 3-azabicyclo[3.3.1]nonane derivatives are formed, annelated with a pyridine ring and containing an amino acid residue. By the methods of NMR and IR spectroscopy, as well as high-resolution mass spectrometry, the structure of the obtained compounds was proved. Thus, in the 1H NMR spectra of the synthesized compounds, a signal of the proton of the carboxyl group in the form of a broadened singlet is detected in a weak spectral region. Equatorial and axial protons of an alicyclic fragment form a characteristic system of signals in the range δ 3.20-3.60 ppm. In the IR spectra of these molecules, the vibrational bands of carbonyl groups at ν 1720 cm–1, as well as the vibrational bands of the C–O bond of the carboxyl group at ν 1198 cm–1, are fixed. The m/z values in the high resolution mass spectra correspond to the molecular weights of the synthesized diazatricycclotridecans.","PeriodicalId":9405,"journal":{"name":"Butlerov Communications","volume":"31 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81102387","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：