Pub Date : 2022-11-20DOI: 10.32362/2410-6593-2022-17-5-410-426
B. A. Buravov, A. Al-Khamzawi, E. S. Bochkarev, N. K. Grichishkina, S. Borisov, N. V. Sidorenko, O. Tuzhikov, O. O. Tuzhikov
Objectives. To synthesize phosphorus-containing oligoestermethacrylates spatially separated by spacers of aliphatic or aromatic structure and evaluate their effect on photocuring kinetics.Methods. For determining the qualitative and quantitative composition of the synthesized compounds, the following methods were used: thin layer chromatography; chromatographic and mass spectrometry; infrared spectroscopy; 1H, 13C, 31P nuclear magnetic resonance spectroscopy; differential scanning calorimetry. The dielectric loss tangent was determined on a specially designed optical cell with an ultraviolet (UV) light source to an immittance meter. Elemental analysis was performed on an energy dispersive X-ray fluorescence spectrometer.Results. Spatially separated oligoestermethacrylates based on phosphorus trichloride containing aliphatic or aromatic spacers in the structure were synthesized. During the interaction of glycidyl methacrylate with phosphorus trichloride in the mass of the latter, reaction products were shown to be formed both according to the Krasusky rule from the side of the α-carbon atom, as well as against this rule with the formation of isomeric products. Obtaining these compounds in bulk is possible only in the presence of a homopolymerization inhibitor. The influence of the spacer structure on the curing rate of oligoestermethacrylates under the action of UV radiation has been established. It has been shown that the introduction of a spacer into the oligomer structure is accompanied by an increase in the induction period by a factor of 39 compared to a sample without a spacer.Conclusions. The results obtained indicate the possibility of obtaining new oligoestermethacrylates with aliphatic and aromatic spacers in the structure. The influence of the structure of the spacer on the kinetics of photocuring is determined.
{"title":"Synthesis of new photo-cured phosphorus-containing oligoestermethacrylates with a spacer in the structure","authors":"B. A. Buravov, A. Al-Khamzawi, E. S. Bochkarev, N. K. Grichishkina, S. Borisov, N. V. Sidorenko, O. Tuzhikov, O. O. Tuzhikov","doi":"10.32362/2410-6593-2022-17-5-410-426","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-5-410-426","url":null,"abstract":"Objectives. To synthesize phosphorus-containing oligoestermethacrylates spatially separated by spacers of aliphatic or aromatic structure and evaluate their effect on photocuring kinetics.Methods. For determining the qualitative and quantitative composition of the synthesized compounds, the following methods were used: thin layer chromatography; chromatographic and mass spectrometry; infrared spectroscopy; 1H, 13C, 31P nuclear magnetic resonance spectroscopy; differential scanning calorimetry. The dielectric loss tangent was determined on a specially designed optical cell with an ultraviolet (UV) light source to an immittance meter. Elemental analysis was performed on an energy dispersive X-ray fluorescence spectrometer.Results. Spatially separated oligoestermethacrylates based on phosphorus trichloride containing aliphatic or aromatic spacers in the structure were synthesized. During the interaction of glycidyl methacrylate with phosphorus trichloride in the mass of the latter, reaction products were shown to be formed both according to the Krasusky rule from the side of the α-carbon atom, as well as against this rule with the formation of isomeric products. Obtaining these compounds in bulk is possible only in the presence of a homopolymerization inhibitor. The influence of the spacer structure on the curing rate of oligoestermethacrylates under the action of UV radiation has been established. It has been shown that the introduction of a spacer into the oligomer structure is accompanied by an increase in the induction period by a factor of 39 compared to a sample without a spacer.Conclusions. The results obtained indicate the possibility of obtaining new oligoestermethacrylates with aliphatic and aromatic spacers in the structure. The influence of the structure of the spacer on the kinetics of photocuring is determined.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91170538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-11-20DOI: 10.32362/2410-6593-2022-17-5-420-421
A. Polivanova, I. Solovieva, D. O. Botev, D. Y. Yuriev, A. Mylnikova, M. S. Oshchepkov
Page 126, in Acknowledgments instead of
第126页，在致谢部分，而不是
{"title":"Erratum to the article: “Bifunctional gallium cation chelators”","authors":"A. Polivanova, I. Solovieva, D. O. Botev, D. Y. Yuriev, A. Mylnikova, M. S. Oshchepkov","doi":"10.32362/2410-6593-2022-17-5-420-421","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-5-420-421","url":null,"abstract":"Page 126, in Acknowledgments instead of","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83246446","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-11-20DOI: 10.32362/2410-6593-2022-17-5-394-409
P. Poluboyarinov, N. Shchetinina, I. Moiseeva, N. I. Mikulyak, N. Golubkina, A. Kaplun
Objectives. While organic and inorganic derivatives of selenium like thiol poisons are known to activate enzymes in cells of different organisms, the mechanism of enzyme activity induction is poorly studied. Therefore, the aim of the study was to investigate the effect of selenium compounds on peroxidase activity induction in maize tissues.Methods. Mechanism of sulfhydryl groups blocking in selenium derivatives was studied on maize in comparison with fungicide tolylfluanid—a typical thiol poison. Electrolytes leakage was determined using conductometry and capillary electrophoresis, protein fractions—by the Ermakov–Durinina method, protein concentration—according to Bradford protein essay, and peroxidase activity—by the Boyarkin method.Results. Diacetophenolylselenide (DAPS-25) was shown to react with SH-groups similarly with tolylfluanid fungicide. DAPS-25 increased K+ and leakage by 58 and 14 times, while appropriate increases for tolylfluanid were 4.4 and 1.5 times as compared to control. Increased total protein content—especially albumins—was due to electrolyte leakage from maize cells. DAPS-25 increased albumins concentration by 2.4–4.5 times, and tolylfluanid application by 2 times. Similar increase of peroxidase activity in maize roots and sprouts as a result of DAPS-25 (by 63% and 112%) and tolylfluanid (by 73% and 63%) application indicates close mechanism of their effect. Under DAPS-25 loading L-cysteine decreases peroxidase activity, which records the removal of SH-groups blockage. A less intensive effect was registered for sodium selenite and L-selenocystin, also capable of reacting with SH-groups. L-cysteine supplementation to DAPS-25 solution decreases selenium concentration in maize, indicating the decrease of selenium bioavailability.Conclusions. The results indicated that selenium containing compounds react with SH-groups of maize cells increasing electrolytes leakage, protein content and especially albumins resulting in the increase of peroxidase activity.
{"title":"Thiol-dependent mechanisms of selenium-containing preparations and thiolylfluanide effect on electrolytes leaching and peroxidase activity in Zea mays L.","authors":"P. Poluboyarinov, N. Shchetinina, I. Moiseeva, N. I. Mikulyak, N. Golubkina, A. Kaplun","doi":"10.32362/2410-6593-2022-17-5-394-409","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-5-394-409","url":null,"abstract":"Objectives. While organic and inorganic derivatives of selenium like thiol poisons are known to activate enzymes in cells of different organisms, the mechanism of enzyme activity induction is poorly studied. Therefore, the aim of the study was to investigate the effect of selenium compounds on peroxidase activity induction in maize tissues.Methods. Mechanism of sulfhydryl groups blocking in selenium derivatives was studied on maize in comparison with fungicide tolylfluanid—a typical thiol poison. Electrolytes leakage was determined using conductometry and capillary electrophoresis, protein fractions—by the Ermakov–Durinina method, protein concentration—according to Bradford protein essay, and peroxidase activity—by the Boyarkin method.Results. Diacetophenolylselenide (DAPS-25) was shown to react with SH-groups similarly with tolylfluanid fungicide. DAPS-25 increased K+ and leakage by 58 and 14 times, while appropriate increases for tolylfluanid were 4.4 and 1.5 times as compared to control. Increased total protein content—especially albumins—was due to electrolyte leakage from maize cells. DAPS-25 increased albumins concentration by 2.4–4.5 times, and tolylfluanid application by 2 times. Similar increase of peroxidase activity in maize roots and sprouts as a result of DAPS-25 (by 63% and 112%) and tolylfluanid (by 73% and 63%) application indicates close mechanism of their effect. Under DAPS-25 loading L-cysteine decreases peroxidase activity, which records the removal of SH-groups blockage. A less intensive effect was registered for sodium selenite and L-selenocystin, also capable of reacting with SH-groups. L-cysteine supplementation to DAPS-25 solution decreases selenium concentration in maize, indicating the decrease of selenium bioavailability.Conclusions. The results indicated that selenium containing compounds react with SH-groups of maize cells increasing electrolytes leakage, protein content and especially albumins resulting in the increase of peroxidase activity.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76901627","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-11-20DOI: 10.32362/2410-6593-2022-17-5-427-438
E. Matveev, S. S. Novikov, V. Y. Levitskaya, A. Nichugovskiy, I. E. Sokolov, K. Zhizhin, N. T. Kuznetsov
Objectives. One of the most promising methods of treating malignant tumors is 10B-neutron capture therapy. While compounds based on cluster boron anions [BnHn]2− (n = 10, 12) are often used as boron-containing agents due to the very high specific concentration of boron atoms per particle, the use of such compounds is associated with the need to develop new methods for the functionalization of boron clusters associated with the production of boron-containing derivatives containing biologically active functional groups. One of the most convenient methods of modification of [BnHn]2− (n = 10, 12) anions is the interaction of their derivatives containing cyclic oxonium-type substituents with negatively charged or neutral nucleophilic reagents. The disclosure of substituents of this type leads to the formation of closo-borates with functional groups separated from the cluster by an alkoxyl spacer chain. The purpose of this study is to develop methods for the synthesis of derivatives of the closo-decaborate anion [B10H10]2− with pendant nitrogen-containing groups.Methods. The general control of the reactions of the disclosure of cyclic substituents was carried out on the basis of 11B nuclear magnetic resonance (NMR) spectroscopy data. The structure of the obtained derivatives, including the nature of the attached functional groups, was determined using 1H, 13C attached proton test (APT) NMR and infrared (IR) spectroscopy data. The molecular weight of the synthesized compounds was confirmed by electrospray ionization mass-spectrometry (ESI–MS).Results. The interaction of the anion [2-B10H9O(CH2)4O]− with secondary amines (dimethylamine, dipropylamine, diallylamine, dibutylamine, diisobutylamine, morpholine, di-sec-butylamine) in an ethanol environment is investigated. As a result of the reactions, a cyclic substituent is shown to expand with the addition of a nucleophilic reagent. Seven new derivatives of the closodecaborate anion with pendant nitrogen-containing groups have been synthesized.Conclusions. A developed method for obtaining closo-decaborates with ammonium groups separated from the boron cluster by an alkoxyl spacer group is presented. It is shown that the use of amines of various structures does not fundamentally affect the course of the reactions, allowing the composition and structure of the target derivatives to be effectively regulated. The resulting compounds can be involved in further modification reactions due to a reactive pendant group, as well as being suitable for use as effective polydentate ligands. Closo-decaborates with pendant nitrogen-containing groups and their derivatives are of considerable interest in the synthesis of compounds for use in 10B-neutron capture therapy of malignant tumors.
{"title":"Interaction of the anion [2-B10H9O(CH2)4O]− with secondary amines","authors":"E. Matveev, S. S. Novikov, V. Y. Levitskaya, A. Nichugovskiy, I. E. Sokolov, K. Zhizhin, N. T. Kuznetsov","doi":"10.32362/2410-6593-2022-17-5-427-438","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-5-427-438","url":null,"abstract":"Objectives. One of the most promising methods of treating malignant tumors is 10B-neutron capture therapy. While compounds based on cluster boron anions [BnHn]2− (n = 10, 12) are often used as boron-containing agents due to the very high specific concentration of boron atoms per particle, the use of such compounds is associated with the need to develop new methods for the functionalization of boron clusters associated with the production of boron-containing derivatives containing biologically active functional groups. One of the most convenient methods of modification of [BnHn]2− (n = 10, 12) anions is the interaction of their derivatives containing cyclic oxonium-type substituents with negatively charged or neutral nucleophilic reagents. The disclosure of substituents of this type leads to the formation of closo-borates with functional groups separated from the cluster by an alkoxyl spacer chain. The purpose of this study is to develop methods for the synthesis of derivatives of the closo-decaborate anion [B10H10]2− with pendant nitrogen-containing groups.Methods. The general control of the reactions of the disclosure of cyclic substituents was carried out on the basis of 11B nuclear magnetic resonance (NMR) spectroscopy data. The structure of the obtained derivatives, including the nature of the attached functional groups, was determined using 1H, 13C attached proton test (APT) NMR and infrared (IR) spectroscopy data. The molecular weight of the synthesized compounds was confirmed by electrospray ionization mass-spectrometry (ESI–MS).Results. The interaction of the anion [2-B10H9O(CH2)4O]− with secondary amines (dimethylamine, dipropylamine, diallylamine, dibutylamine, diisobutylamine, morpholine, di-sec-butylamine) in an ethanol environment is investigated. As a result of the reactions, a cyclic substituent is shown to expand with the addition of a nucleophilic reagent. Seven new derivatives of the closodecaborate anion with pendant nitrogen-containing groups have been synthesized.Conclusions. A developed method for obtaining closo-decaborates with ammonium groups separated from the boron cluster by an alkoxyl spacer group is presented. It is shown that the use of amines of various structures does not fundamentally affect the course of the reactions, allowing the composition and structure of the target derivatives to be effectively regulated. The resulting compounds can be involved in further modification reactions due to a reactive pendant group, as well as being suitable for use as effective polydentate ligands. Closo-decaborates with pendant nitrogen-containing groups and their derivatives are of considerable interest in the synthesis of compounds for use in 10B-neutron capture therapy of malignant tumors.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76386371","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-11-20DOI: 10.32362/2410-6593-2022-17-5-384-393
A. V. Pak, E. Pashkov, N. Abramova, A. Poddubikov, F. G. Nagieva, E. Bogdanova, E. P. Pashkov, O. Svitich, V. Zverev
Objectives. To evaluate the dynamics of the expression level of IL-1β and IL-28β (IFN-λ3) genes as a result of complex knockdown of some cellular genes, whose expression products play an important role in the reproduction of the influenza virus.Methods. Following the collection of virus-containing liquid and cell lysate within three days from the moment of transfection and infection, the intensity of viral reproduction was assessed using the cytopathic effect titration method. The concentration of viral ribonucleic acid (vRNA) and change in the expression of IL-1β and IL-28β (IFN-λ3) were determined by real-time reverse transcription quantitative polymerase chain reaction (real-time RT-qPCR). The nonparametric Mann–Whitney test was used to statistically calculate significant differences between groups.Results. The use of each small interfering ribonucleic acid (siRNA) complex led to a decrease in viral reproduction on the first day at the multiplicity of infection (MOI) of 0.001. The use of complex A (FLT4.2 + Nup98.1) and D (FLT4.2 + Nup98.1 + Nup205) led to a decrease in viral titer by 2.8 lgTCID50/mL and by 2.1 lgTCID50/mL relative to the use of nonspecific L2 siRNA and viral control (p ≤ 0.05). Transfection of complexes B (Nup98.1 + Nup205) and C (FLT4.2 + Nup205) also reduced the viral titer by 1.5 lgTCID50/mL and 1.8 lgTCID50/mL relative to nonspecific L2 siRNA and viral control (p ≤ 0.05). When conducting real-time RT-qPCR, a significant decrease in the concentration of viral RNA was also noted. When using complexes B, C, and D, the concentration of vRNA decreased on the first day by 14.5, 4.1, and 15 times, respectively. On the second day, a decrease in vRNA was observed in cells with B and D complexes by 17.1 and 18.3 times (p ≤ 0.05). Along with a decrease in the viral titer and vRNA, an increase in the expression of the IL-1β and IL-28β genes was observed on the first day when using all siRNA complexes relative to nonspecific and viral controls (p ≤ 0.05). On the second day, an increase was also observed in cells with A and D complexes, while on the third day, there was an increase in the expression of these genes in cells with complex D (p ≤ 0.05).Conclusions. The use of siRNA complexes is shown to have a pronounced antiviral effect while simultaneously suppressing the activity of cellular genes (FLT4, Nup98 and Nup205). In parallel, the transfection of complexes that block the formation of expression products necessary for viral reproduction is demonstrated to lead to an increase in the level of expression of the IL-1β and IL-28β genes. These results indicate not only that the use of siRNA has antiviral activity, but also immunomodulatory activity, which can contribute to a more effective immune response of the body.
{"title":"Effect of antiviral siRNAs on the production of cytokines in vitro","authors":"A. V. Pak, E. Pashkov, N. Abramova, A. Poddubikov, F. G. Nagieva, E. Bogdanova, E. P. Pashkov, O. Svitich, V. Zverev","doi":"10.32362/2410-6593-2022-17-5-384-393","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-5-384-393","url":null,"abstract":"Objectives. To evaluate the dynamics of the expression level of IL-1β and IL-28β (IFN-λ3) genes as a result of complex knockdown of some cellular genes, whose expression products play an important role in the reproduction of the influenza virus.Methods. Following the collection of virus-containing liquid and cell lysate within three days from the moment of transfection and infection, the intensity of viral reproduction was assessed using the cytopathic effect titration method. The concentration of viral ribonucleic acid (vRNA) and change in the expression of IL-1β and IL-28β (IFN-λ3) were determined by real-time reverse transcription quantitative polymerase chain reaction (real-time RT-qPCR). The nonparametric Mann–Whitney test was used to statistically calculate significant differences between groups.Results. The use of each small interfering ribonucleic acid (siRNA) complex led to a decrease in viral reproduction on the first day at the multiplicity of infection (MOI) of 0.001. The use of complex A (FLT4.2 + Nup98.1) and D (FLT4.2 + Nup98.1 + Nup205) led to a decrease in viral titer by 2.8 lgTCID50/mL and by 2.1 lgTCID50/mL relative to the use of nonspecific L2 siRNA and viral control (p ≤ 0.05). Transfection of complexes B (Nup98.1 + Nup205) and C (FLT4.2 + Nup205) also reduced the viral titer by 1.5 lgTCID50/mL and 1.8 lgTCID50/mL relative to nonspecific L2 siRNA and viral control (p ≤ 0.05). When conducting real-time RT-qPCR, a significant decrease in the concentration of viral RNA was also noted. When using complexes B, C, and D, the concentration of vRNA decreased on the first day by 14.5, 4.1, and 15 times, respectively. On the second day, a decrease in vRNA was observed in cells with B and D complexes by 17.1 and 18.3 times (p ≤ 0.05). Along with a decrease in the viral titer and vRNA, an increase in the expression of the IL-1β and IL-28β genes was observed on the first day when using all siRNA complexes relative to nonspecific and viral controls (p ≤ 0.05). On the second day, an increase was also observed in cells with A and D complexes, while on the third day, there was an increase in the expression of these genes in cells with complex D (p ≤ 0.05).Conclusions. The use of siRNA complexes is shown to have a pronounced antiviral effect while simultaneously suppressing the activity of cellular genes (FLT4, Nup98 and Nup205). In parallel, the transfection of complexes that block the formation of expression products necessary for viral reproduction is demonstrated to lead to an increase in the level of expression of the IL-1β and IL-28β genes. These results indicate not only that the use of siRNA has antiviral activity, but also immunomodulatory activity, which can contribute to a more effective immune response of the body.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80947684","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-11-19DOI: 10.32362/2410-6593-2022-17-5-377-383
L. O. Belova, N. A. Golub, M. V. Pletneva, N. I. Kirilina, A. D. Kirilin
Objectives. To study the patterns of behavior of morpholine and its trimethylsilyl derivative in reactions with trimethylsilyl isocyanate.Methods. The study employed infrared and nuclear magnetic resonance spectroscopy, as well as elemental analysis.Results. The formation of mixtures of tautomeric forms of silicon-containing urea—N-(trimethylsilyl) morpholine-4-carboxamide and trimethylsilylmorpholine-4-carboximidoate—was established.Conclusions. It is shown that the composition and structure of the resulting products are determined both by the presence of a morpholine substituent at the nitrogen atom and by the type of isocyanate used. Unlike the trimethylsilyl derivative of morpholine, morpholine itself reacts with trimethylsilyl isocyanate to form a mixture of tautomeric forms.
{"title":"Behavior of morpholine and its trimethylsilyl derivative in reactions with trimethylsilyl isocyanate","authors":"L. O. Belova, N. A. Golub, M. V. Pletneva, N. I. Kirilina, A. D. Kirilin","doi":"10.32362/2410-6593-2022-17-5-377-383","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-5-377-383","url":null,"abstract":"Objectives. To study the patterns of behavior of morpholine and its trimethylsilyl derivative in reactions with trimethylsilyl isocyanate.Methods. The study employed infrared and nuclear magnetic resonance spectroscopy, as well as elemental analysis.Results. The formation of mixtures of tautomeric forms of silicon-containing urea—N-(trimethylsilyl) morpholine-4-carboxamide and trimethylsilylmorpholine-4-carboximidoate—was established.Conclusions. It is shown that the composition and structure of the resulting products are determined both by the presence of a morpholine substituent at the nitrogen atom and by the type of isocyanate used. Unlike the trimethylsilyl derivative of morpholine, morpholine itself reacts with trimethylsilyl isocyanate to form a mixture of tautomeric forms.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85321166","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-09-30DOI: 10.32362/2410-6593-2022-17-4-275-297
S. A. Durakov, A. Kolobov, V. Flid
Objectives. Catalytic processes involving norbornene (NBN) and norbornadiene (NBD) offer exceptional opportunities for the synthesis of a wide range of hard-to-reach polycyclic hydrocarbons. The problems of selectivity and manufacturability of these reactions are fundamentally important for their practical implementation. The aim of this review is to summarize the latest advances in the field of designing heterogeneous catalysts for the preparation and transformation of promising NBN- and NBD-derivatives with the maintenance of a strained carbocyclic framework in isomerization and dimerization reactions of these compounds.Results. Various strategies for the selection of catalysts and prospects for the development of heterogeneous catalysis for syntheses based on NBN and NBD derivatives were considered. The possibility of selective cyclic dimerization and isomerization of NBN and NBD was shown. The factors that affect the direction of the reactions and make it possible to maintain the strained norbornane structure were discussed.Conclusions. An analysis of the current state of this problem showed that at present, the technological parameters of the conversion of NBD and NBN derivatives with the participation of heterogeneous catalysts are significantly inferior to homogeneous systems. In order to improve the productivity of these processes and design catalyst regeneration, further investigations are required. However, some progress in these areas has already been made. In a number of processes, it is possible not only to maintain the strained carbocyclic framework, but also to establish ways to control regio- and stereo-selectivity. In some cases, the use of heterogeneous catalysts allows the process to be direct into a completely new path, which has no analogues for homogeneous systems.
{"title":"Features of heterogeneous catalytic transformations of strained carbocyclic compounds of the norbornene series","authors":"S. A. Durakov, A. Kolobov, V. Flid","doi":"10.32362/2410-6593-2022-17-4-275-297","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-4-275-297","url":null,"abstract":"Objectives. Catalytic processes involving norbornene (NBN) and norbornadiene (NBD) offer exceptional opportunities for the synthesis of a wide range of hard-to-reach polycyclic hydrocarbons. The problems of selectivity and manufacturability of these reactions are fundamentally important for their practical implementation. The aim of this review is to summarize the latest advances in the field of designing heterogeneous catalysts for the preparation and transformation of promising NBN- and NBD-derivatives with the maintenance of a strained carbocyclic framework in isomerization and dimerization reactions of these compounds.Results. Various strategies for the selection of catalysts and prospects for the development of heterogeneous catalysis for syntheses based on NBN and NBD derivatives were considered. The possibility of selective cyclic dimerization and isomerization of NBN and NBD was shown. The factors that affect the direction of the reactions and make it possible to maintain the strained norbornane structure were discussed.Conclusions. An analysis of the current state of this problem showed that at present, the technological parameters of the conversion of NBD and NBN derivatives with the participation of heterogeneous catalysts are significantly inferior to homogeneous systems. In order to improve the productivity of these processes and design catalyst regeneration, further investigations are required. However, some progress in these areas has already been made. In a number of processes, it is possible not only to maintain the strained carbocyclic framework, but also to establish ways to control regio- and stereo-selectivity. In some cases, the use of heterogeneous catalysts allows the process to be direct into a completely new path, which has no analogues for homogeneous systems.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79203456","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-09-30DOI: 10.32362/2410-6593-2022-17-4-346-356
A. Nikolaev, A. Kondratov
Objectives. To quantitatively describe the thermochromic properties of films of isotactic polypropylene, a large-tonnage polymer widely used in the production of flexible packaging for goods and foodstuffs, as well as substantiate the possibility of covert labeling of transparent packaging.Methods. Differential scanning calorimetry, polarization photometry, infrared Fourier spectrometry, gravimetry, temperature control, physical and mechanical strength testing.Results. The identified thermochromic effect of dichroism in polarized light on industrial samples of transparent biaxially oriented film of isotactic polypropylene was studied. A change in the phase composition of the film-forming composition during short-term heating during marking was established. The absence of heat shrinkage and change in transparency in non-polarized light was shown, which provides the possibility of hidden recording of information and its contrast manifestation in a passing light stream at a certain arrangement of light filters.Conclusions. The causes and optimal conditions of the thermochromic effect are established. It is proposed to use local contact heat treatment of a polypropylene film for covert recording of information and marking of product packaging in order to protect against counterfeiting.
{"title":"Method for hidden marking of transparent polypropylene film","authors":"A. Nikolaev, A. Kondratov","doi":"10.32362/2410-6593-2022-17-4-346-356","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-4-346-356","url":null,"abstract":"Objectives. To quantitatively describe the thermochromic properties of films of isotactic polypropylene, a large-tonnage polymer widely used in the production of flexible packaging for goods and foodstuffs, as well as substantiate the possibility of covert labeling of transparent packaging.Methods. Differential scanning calorimetry, polarization photometry, infrared Fourier spectrometry, gravimetry, temperature control, physical and mechanical strength testing.Results. The identified thermochromic effect of dichroism in polarized light on industrial samples of transparent biaxially oriented film of isotactic polypropylene was studied. A change in the phase composition of the film-forming composition during short-term heating during marking was established. The absence of heat shrinkage and change in transparency in non-polarized light was shown, which provides the possibility of hidden recording of information and its contrast manifestation in a passing light stream at a certain arrangement of light filters.Conclusions. The causes and optimal conditions of the thermochromic effect are established. It is proposed to use local contact heat treatment of a polypropylene film for covert recording of information and marking of product packaging in order to protect against counterfeiting.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87634823","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-09-30DOI: 10.32362/2410-6593-2022-17-4-311-322
L. E. Grebenkina, A. N. Prutkov, A. Matveev, M. Chudinov
Objectives. A key step in the synthesis of natural nucleoside analogs is the formation of a glycosidic bond between the carbohydrate fragment and the heterocyclic base. Glycosylation methods differ in terms of regio- and stereoselectivity. A promising method for the highly specific synthesis of new pharmacologically active compounds involves an enzymatic reaction catalyzed by genetically engineered nucleoside phosphorylases. This study is devoted to the synthesis of a library of analogs of nucleoside heterocyclic bases—5-oxymethyl-1,2,4-triazole- 3-carboxamides—in order to investigate the substrate specificity of genetically engineered nucleoside phosphorylases.Methods. A method of cyclization of acylamidrazones obtained from the single synthetic precursor β-N-tert-butyloxycarbonyl-oxalamidrazone was used to parallel-synthesize new 5-alkoxy/ aryloxymethyl-1,2,4-triazole-3-carboxamides. Silica gel column chromatography was used to isolate and purify the synthesized compounds. A complex of physicochemical analysis methods (nuclear magnetic resonance spectroscopy, chromatography, and mass spectrometry) confirmed the structure of the compounds obtained in the work.Results. 5-alkoxy/aryloxymethyl-1,2,4-triazole-3-carboxamides were obtained to study the substrate specificity of genetically engineered nucleoside phosphorylases. The possibility of obtaining new nucleoside analogs by the chemico-enzymatic method was demonstrated on the basis of preliminary assessment results.Conclusions. The physicochemical characteristics of a series of novel 5-alkoxy/aryloxymethyl- 1,2,4-triazole-3-carboxamides were studied along with their potential to act as substrates for the transglycosylation reaction catalyzed by nucleoside phosphorylases.
目标。合成天然核苷类似物的关键步骤是在碳水化合物片段和杂环碱基之间形成糖苷键。糖基化方法在区域选择性和立体选择性方面有所不同。一种有前途的高度特异性合成新药理活性化合物的方法涉及基因工程核苷磷酸化酶催化的酶促反应。本研究致力于核苷杂环碱基的类似物库的合成- 5-氧甲基-1,2,4-三唑- 3-羧酰胺-以研究基因工程核苷磷酸化酶的底物特异性。以单一合成前体β- n -叔丁基羰基草胺腙为原料，采用环化法平行合成新的5-烷氧基/芳基甲基-1,2,4-三唑-3-羧酰胺。采用硅胶柱层析对合成的化合物进行分离纯化。一个复杂的物理化学分析方法(核磁共振光谱、色谱和质谱)证实了在工作中获得的化合物的结构。得到5-烷氧基/芳基甲基-1,2,4-三唑-3-羧酰胺，研究基因工程核苷磷酸化酶的底物特异性。在初步评价结果的基础上，论证了化学酶法获得新的核苷类似物的可能性。研究了一系列新型5-烷氧基/芳基甲基- 1,2,4-三唑-3-羧酰胺的理化性质，以及它们作为核苷磷酸化酶催化的转糖基化反应底物的潜力。
{"title":"Synthesis of 5-oxymethyl-1,2,4-triazole-3-carboxamides","authors":"L. E. Grebenkina, A. N. Prutkov, A. Matveev, M. Chudinov","doi":"10.32362/2410-6593-2022-17-4-311-322","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-4-311-322","url":null,"abstract":"Objectives. A key step in the synthesis of natural nucleoside analogs is the formation of a glycosidic bond between the carbohydrate fragment and the heterocyclic base. Glycosylation methods differ in terms of regio- and stereoselectivity. A promising method for the highly specific synthesis of new pharmacologically active compounds involves an enzymatic reaction catalyzed by genetically engineered nucleoside phosphorylases. This study is devoted to the synthesis of a library of analogs of nucleoside heterocyclic bases—5-oxymethyl-1,2,4-triazole- 3-carboxamides—in order to investigate the substrate specificity of genetically engineered nucleoside phosphorylases.Methods. A method of cyclization of acylamidrazones obtained from the single synthetic precursor β-N-tert-butyloxycarbonyl-oxalamidrazone was used to parallel-synthesize new 5-alkoxy/ aryloxymethyl-1,2,4-triazole-3-carboxamides. Silica gel column chromatography was used to isolate and purify the synthesized compounds. A complex of physicochemical analysis methods (nuclear magnetic resonance spectroscopy, chromatography, and mass spectrometry) confirmed the structure of the compounds obtained in the work.Results. 5-alkoxy/aryloxymethyl-1,2,4-triazole-3-carboxamides were obtained to study the substrate specificity of genetically engineered nucleoside phosphorylases. The possibility of obtaining new nucleoside analogs by the chemico-enzymatic method was demonstrated on the basis of preliminary assessment results.Conclusions. The physicochemical characteristics of a series of novel 5-alkoxy/aryloxymethyl- 1,2,4-triazole-3-carboxamides were studied along with their potential to act as substrates for the transglycosylation reaction catalyzed by nucleoside phosphorylases.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89093756","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-09-30DOI: 10.32362/2410-6593-2022-17-4-323-334
E. Eshtukova-Shcheglova, K. Perevoshchikova, A. V. Eshtukov-Shcheglov, D. Cheshkov, M. Maslov
Objectives. Alkylated derivatives of polyamines are able to block the growth of cancer cells due to their embedding into the polyamine biosynthesis mechanisms. The study aimed to synthesize lipophilic derivatives of norspermine or triethylenetetramine based on the formation of a C–N bond during the opening of the oxirane ring by primary amines to expand a number of synthetic polyamine derivatives with antitumor activity.Methods. The starting compounds—glycidol alcoholate or epichlorohydrin—were reacted with hexadecyl bromide or sodium hexadecanolate to give glycidyl hexadecyl ether. The key reaction for the preparation of lipophilic polyamines was the amination of lipophilic epoxides with polyamines in the presence of calcium triflate. Acylation of the hydroxyl group formed during the opening of oxirane was carried out by the action of 4-dimethylaminopyridine and acetic anhydride. The introduction of an alkyl substituent in the presence of sodium hydride led to intramolecular cyclization with the formation of an oxoazolidine cycle. The regioselectivity of the oxirane ring opening reaction at the C(1) position of glycerol was confirmed by two-dimensional heteronuclear {1H,13C} nuclear magnetic resonance spectroscopy.Results. An approach to the synthesis of novel lipophilic polyamines based on the catalytic amination of epoxides was developed and tested. Compounds based on norspermine and triethylentetramine containing a hydroxyl group at the C(2) atom of the glycerin backbone were obtained. For norspermine derivatives, the hydroxyl group was modified: an acetyl substituent was introduced and a derivative containing an oxoazolidine cycle was obtained.Conclusions. The obtained lipophilic polyamines can be considered as potential antitumor agents, for which cytotoxicity against various cancer cells will be evaluated in the future.
{"title":"Amination of epoxides as a convenient approach for lipophilic polyamines synthesis","authors":"E. Eshtukova-Shcheglova, K. Perevoshchikova, A. V. Eshtukov-Shcheglov, D. Cheshkov, M. Maslov","doi":"10.32362/2410-6593-2022-17-4-323-334","DOIUrl":"https://doi.org/10.32362/2410-6593-2022-17-4-323-334","url":null,"abstract":"Objectives. Alkylated derivatives of polyamines are able to block the growth of cancer cells due to their embedding into the polyamine biosynthesis mechanisms. The study aimed to synthesize lipophilic derivatives of norspermine or triethylenetetramine based on the formation of a C–N bond during the opening of the oxirane ring by primary amines to expand a number of synthetic polyamine derivatives with antitumor activity.Methods. The starting compounds—glycidol alcoholate or epichlorohydrin—were reacted with hexadecyl bromide or sodium hexadecanolate to give glycidyl hexadecyl ether. The key reaction for the preparation of lipophilic polyamines was the amination of lipophilic epoxides with polyamines in the presence of calcium triflate. Acylation of the hydroxyl group formed during the opening of oxirane was carried out by the action of 4-dimethylaminopyridine and acetic anhydride. The introduction of an alkyl substituent in the presence of sodium hydride led to intramolecular cyclization with the formation of an oxoazolidine cycle. The regioselectivity of the oxirane ring opening reaction at the C(1) position of glycerol was confirmed by two-dimensional heteronuclear {1H,13C} nuclear magnetic resonance spectroscopy.Results. An approach to the synthesis of novel lipophilic polyamines based on the catalytic amination of epoxides was developed and tested. Compounds based on norspermine and triethylentetramine containing a hydroxyl group at the C(2) atom of the glycerin backbone were obtained. For norspermine derivatives, the hydroxyl group was modified: an acetyl substituent was introduced and a derivative containing an oxoazolidine cycle was obtained.Conclusions. The obtained lipophilic polyamines can be considered as potential antitumor agents, for which cytotoxicity against various cancer cells will be evaluated in the future.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78929138","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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