The rapid progress in the chemistry of carboranes and other polyhedral boron compounds makes the development of methods for the synthesis of their various functional derivatives a high priority. The formation of cyclic oxonium derivatives followed by the ring opening is one of the most efficient methods for the preparation of these compounds. This review addresses the data on the use of the nucleophilic ring opening of cyclic oxonium derivatives based on cobalt and iron bis(dicarbollides), which have been extensively studied in recent years. Reactions involving O-, N-, S-, P- and C-nucleophiles are considered as a route to the targeted synthesis of a wide range of organic boron derivatives, in particular various boron-containing biologically active compounds. Possible applications of the reaction products are discussed. The bibliography includes 197 references.
{"title":"Cyclic oxonium derivatives of cobalt and iron bis(dicarbollides) and their use in organic synthesis","authors":"A. Druzina, A. Shmalko, I. Sivaev, V. Bregadze","doi":"10.1070/RCR5000","DOIUrl":"https://doi.org/10.1070/RCR5000","url":null,"abstract":"The rapid progress in the chemistry of carboranes and other polyhedral boron compounds makes the development of methods for the synthesis of their various functional derivatives a high priority. The formation of cyclic oxonium derivatives followed by the ring opening is one of the most efficient methods for the preparation of these compounds. This review addresses the data on the use of the nucleophilic ring opening of cyclic oxonium derivatives based on cobalt and iron bis(dicarbollides), which have been extensively studied in recent years. Reactions involving O-, N-, S-, P- and C-nucleophiles are considered as a route to the targeted synthesis of a wide range of organic boron derivatives, in particular various boron-containing biologically active compounds. Possible applications of the reaction products are discussed. The bibliography includes 197 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59009989","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The review focuses on variable-conductivity materials used to protect lithium-ion batteries from ignition. Examples of emergency situations arising in the operation of such batteries are given and their causes are considered. Thermal runaway that results in ignition of a lithium-ion battery and the chemical reactions accompanying this process are discussed. Internal battery protection using variable-resistance temperature- or voltage-sensitive components is described. Various approaches to the prevention of thermal runaway by modifying a battery with thermo- and voltage-resistive materials are summarized and analyzed. The advantages and drawbacks of various types of materials of this kind are demonstrated. Particular attention is paid to the practical significance of the creation and application of protective variable-resistance materials and approaches to the design of this kind of materials. The bibliography includes 165 references.
{"title":"Variable-resistance materials for lithium-ion batteries","authors":"E. Beletskii, E. Alekseeva, O. Levin","doi":"10.1070/RCR5030","DOIUrl":"https://doi.org/10.1070/RCR5030","url":null,"abstract":"The review focuses on variable-conductivity materials used to protect lithium-ion batteries from ignition. Examples of emergency situations arising in the operation of such batteries are given and their causes are considered. Thermal runaway that results in ignition of a lithium-ion battery and the chemical reactions accompanying this process are discussed. Internal battery protection using variable-resistance temperature- or voltage-sensitive components is described. Various approaches to the prevention of thermal runaway by modifying a battery with thermo- and voltage-resistive materials are summarized and analyzed. The advantages and drawbacks of various types of materials of this kind are demonstrated. Particular attention is paid to the practical significance of the creation and application of protective variable-resistance materials and approaches to the design of this kind of materials. The bibliography includes 165 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59011026","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
E. Alexandrov, A. P. Shevchenko, N. Nekrasova, V. Blatov
A comprehensive review of the methods for topological analysis of crystalline compounds as applied to the structures of coordination polymers is presented for the first time. The basic concepts of reticular chemistry, a new branch of science, which combines methods of synthetic chemistry with methods for topological design of polymer compounds, are considered. Reticular chemistry methods are illustrated with examples of the analysis and design of coordination polymers. The most complete classification of coordination polymers, which are similar in terms of various compositional and topological parameters, is given. This review describes and integrates information on the topological analysis tools, such as computer software and electronic databases. A special attention is paid to the application of topological methods in the machine analysis and the prediction of structures and properties of coordination polymers, in particular to the establishment of chemical composition–structure–property relationships and the development of knowledge bases and artificial intelligence systems. A procedure for the search for the general crystal-chemical features using automatic heuristic analysis of large sets of structural data is discussed. It is shown how this analysis can be used to determine the limits of applicability of reticular chemistry and the possibility of its extension to coordination polymers containing structurally, chemically and topologically complex building units with high conformational flexibility. Approaches of reticular chemistry are considered in detail in relation to the design of proton-conductive coordination polymers, which have received considerable attention in the past decade. The specific features of the topological structures of this class of compounds are described in a systematic way. The relationships between the chemical composition, structure and conductive properties of these compounds and the applicability of targeted design are discussed. The bibliography includes 303 references.
{"title":"Topological methods for analysis and design of coordination polymers","authors":"E. Alexandrov, A. P. Shevchenko, N. Nekrasova, V. Blatov","doi":"10.1070/RCR5032","DOIUrl":"https://doi.org/10.1070/RCR5032","url":null,"abstract":"A comprehensive review of the methods for topological analysis of crystalline compounds as applied to the structures of coordination polymers is presented for the first time. The basic concepts of reticular chemistry, a new branch of science, which combines methods of synthetic chemistry with methods for topological design of polymer compounds, are considered. Reticular chemistry methods are illustrated with examples of the analysis and design of coordination polymers. The most complete classification of coordination polymers, which are similar in terms of various compositional and topological parameters, is given. This review describes and integrates information on the topological analysis tools, such as computer software and electronic databases. A special attention is paid to the application of topological methods in the machine analysis and the prediction of structures and properties of coordination polymers, in particular to the establishment of chemical composition–structure–property relationships and the development of knowledge bases and artificial intelligence systems. A procedure for the search for the general crystal-chemical features using automatic heuristic analysis of large sets of structural data is discussed. It is shown how this analysis can be used to determine the limits of applicability of reticular chemistry and the possibility of its extension to coordination polymers containing structurally, chemically and topologically complex building units with high conformational flexibility. Approaches of reticular chemistry are considered in detail in relation to the design of proton-conductive coordination polymers, which have received considerable attention in the past decade. The specific features of the topological structures of this class of compounds are described in a systematic way. The relationships between the chemical composition, structure and conductive properties of these compounds and the applicability of targeted design are discussed. The bibliography includes 303 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59011163","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The review presents the general methodology of using sorption methods to solve problems of marine radiochemistry, including sampling, preconcentration and radiochemical preparation and methods for measuring the activity of radionuclides. The possible methodological errors at various stages of sampling and sample concentration are discussed. The most widely used artificial (90Sr, 134Cs, 137Cs, 239Pu, 240Pu), natural (210Pb, 210Po; radium quartet: 223Ra, 224Ra, 226Ra, 228Ra; thorium isotopes, mainly 234Th) and cosmogenic (7Be, 32P, 33P) radiotracers are considered. The sorption of uranium from seawater is not addressed, since its concentration in seawater is usually calculated from the known dependence of uranium concentration on seawater salinity. The bibliography includes 200 references.
{"title":"Sorption methods in marine radiochemistry","authors":"I. Dovhyi, N. Bezhin, I. Tananaev","doi":"10.1070/RCR5015","DOIUrl":"https://doi.org/10.1070/RCR5015","url":null,"abstract":"The review presents the general methodology of using sorption methods to solve problems of marine radiochemistry, including sampling, preconcentration and radiochemical preparation and methods for measuring the activity of radionuclides. The possible methodological errors at various stages of sampling and sample concentration are discussed. The most widely used artificial (90Sr, 134Cs, 137Cs, 239Pu, 240Pu), natural (210Pb, 210Po; radium quartet: 223Ra, 224Ra, 226Ra, 228Ra; thorium isotopes, mainly 234Th) and cosmogenic (7Be, 32P, 33P) radiotracers are considered. The sorption of uranium from seawater is not addressed, since its concentration in seawater is usually calculated from the known dependence of uranium concentration on seawater salinity. The bibliography includes 200 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59010389","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The review presents data on the use of porous metal-organic frameworks for the separation of some industrially important hydrocarbon mixtures, such as ethane and ethylene, propane and propylene, benzene and cyclohexane, and xylene isomers. It is shown that enhancing the efficiency of materials based on porous metal-organic frameworks relies on understanding the nature of adsorption sites in their structures, the specifics of interactions between the framework and a particular substrate, and the structural response of the framework (host) as it is filled with guest molecules. The achievements of fundamental studies and unresolved problems related to the use of porous metal-organic frameworks in industrial hydrocarbon separation processes are critically analyzed. The bibliography includes 183 references.
{"title":"Micro- and mesoporous metal-organic frameworks for hydrocarbon separation","authors":"K. Kovalenko, A. Potapov, V. Fedin","doi":"10.1070/RCR5026","DOIUrl":"https://doi.org/10.1070/RCR5026","url":null,"abstract":"The review presents data on the use of porous metal-organic frameworks for the separation of some industrially important hydrocarbon mixtures, such as ethane and ethylene, propane and propylene, benzene and cyclohexane, and xylene isomers. It is shown that enhancing the efficiency of materials based on porous metal-organic frameworks relies on understanding the nature of adsorption sites in their structures, the specifics of interactions between the framework and a particular substrate, and the structural response of the framework (host) as it is filled with guest molecules. The achievements of fundamental studies and unresolved problems related to the use of porous metal-organic frameworks in industrial hydrocarbon separation processes are critically analyzed. The bibliography includes 183 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59010976","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The results of studies related to the development of synthesis, determination of formation conditions and elucidation of the mechanism of palladium–carbon catalyst action are integrated and critically analyzed. The attention is focused on Pd/NGC compositions (NGC is nanoglobular carbon). Methods for NGC preparation with an emphasis on its most common form, carbon black, are considered. The following issues are addressed: mechanisms of formation of carbon nanoglobules and their aggregates, methods of varying the size of nanoglobules, functionalization of the NGC surface to make it suitable as a support for palladium nanoparticles, views on the formation mechanism of palladium clusters and nanoparticles on the carbon support surface and effect of the structure and surface chemistry of carbon nanoglobules on the state of palladium sites in Pd/NGC compositions. The published data on selective hydrogenation of organic compounds in the presence of Pd/NGC catalytic compositions are integrated and systematized. The catalytic properties of Pd/NGC are analyzed in comparison with the properties of palladium catalysts supported on other carbon materials (activated carbon, carbon nanotubes). The influence of preparation conditions of NGC-based palladium compositions on their catalytic properties in practically important hydrogenation reactions is discussed. Promising trends for further research on the development of molecular design methods, study of the genesis of Pd/NGC compositions and extension of their applications in hydrogenation processes are considered. The bibliography includes 623 references.
{"title":"Nanoglobular carbon and palladium–nanoglobular carbon catalysts for liquid-phase hydrogenation of organic compounds","authors":"R. Mironenko, V. Likholobov, O. Belskaya","doi":"10.1070/RCR5017","DOIUrl":"https://doi.org/10.1070/RCR5017","url":null,"abstract":"The results of studies related to the development of synthesis, determination of formation conditions and elucidation of the mechanism of palladium–carbon catalyst action are integrated and critically analyzed. The attention is focused on Pd/NGC compositions (NGC is nanoglobular carbon). Methods for NGC preparation with an emphasis on its most common form, carbon black, are considered. The following issues are addressed: mechanisms of formation of carbon nanoglobules and their aggregates, methods of varying the size of nanoglobules, functionalization of the NGC surface to make it suitable as a support for palladium nanoparticles, views on the formation mechanism of palladium clusters and nanoparticles on the carbon support surface and effect of the structure and surface chemistry of carbon nanoglobules on the state of palladium sites in Pd/NGC compositions. The published data on selective hydrogenation of organic compounds in the presence of Pd/NGC catalytic compositions are integrated and systematized. The catalytic properties of Pd/NGC are analyzed in comparison with the properties of palladium catalysts supported on other carbon materials (activated carbon, carbon nanotubes). The influence of preparation conditions of NGC-based palladium compositions on their catalytic properties in practically important hydrogenation reactions is discussed. Promising trends for further research on the development of molecular design methods, study of the genesis of Pd/NGC compositions and extension of their applications in hydrogenation processes are considered. The bibliography includes 623 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59010993","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The review considers general methods for the preparation of 3-amino-3-deoxy- and 4-amino-4-deoxyhexoses and their derivatives, including nitromethane condensation, reduction of 3- and 4-hexosulose oximes, epoxide opening with an azide ion, and nucleophilic substitution of sulfonates. The use of amino sugars of this type in the synthesis of natural carbohydrate-containing compounds and their analogues, including aminoglycoside antibiotics, glycosidase inhibitors, substrate analogues and inhibitors of glycan biosynthesis, galectin inhibitors, etc. is described. The bibliography includes 89 references.
{"title":"3-Amino-3-deoxy- and 4-amino-4-deoxyhexoses in the synthesis of natural carbohydrate compounds and their analogues","authors":"Y. Tsvetkov, O. Yudina, N. Nifantiev","doi":"10.1070/RCR4974","DOIUrl":"https://doi.org/10.1070/RCR4974","url":null,"abstract":"The review considers general methods for the preparation of 3-amino-3-deoxy- and 4-amino-4-deoxyhexoses and their derivatives, including nitromethane condensation, reduction of 3- and 4-hexosulose oximes, epoxide opening with an azide ion, and nucleophilic substitution of sulfonates. The use of amino sugars of this type in the synthesis of natural carbohydrate-containing compounds and their analogues, including aminoglycoside antibiotics, glycosidase inhibitors, substrate analogues and inhibitors of glycan biosynthesis, galectin inhibitors, etc. is described. The bibliography includes 89 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59008934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A. Smolobochkin, A. Gazizov, A. Burilov, Mikhael A. Pudovik, O. Sinyashin
The review systematizes and summarizes data on the synthesis of structurally diverse cyclic ureas published over the last 10 years. Saturated and unsaturated monocyclic ureas, as well as fused heterocycles containing one urea moiety, are considered. Data on the biological activity of selected compounds of this type are provided. The synthetic approaches to cyclic carbamides are classified in terms of the reaction type and the source of a carbonyl group. The bibliography includes 235 references.
{"title":"Advances in the synthesis of heterocycles bearing an endocyclic urea moiety","authors":"A. Smolobochkin, A. Gazizov, A. Burilov, Mikhael A. Pudovik, O. Sinyashin","doi":"10.1070/RCR4988","DOIUrl":"https://doi.org/10.1070/RCR4988","url":null,"abstract":"The review systematizes and summarizes data on the synthesis of structurally diverse cyclic ureas published over the last 10 years. Saturated and unsaturated monocyclic ureas, as well as fused heterocycles containing one urea moiety, are considered. Data on the biological activity of selected compounds of this type are provided. The synthetic approaches to cyclic carbamides are classified in terms of the reaction type and the source of a carbonyl group. The bibliography includes 235 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59009254","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The review deals with the main catalytic methods for the C(sp2)–N bond formation, including Buchwald–Hartwig palladium-catalyzed amination of aryl and heteroaryl halides, renaissance of the Ullmann chemistry, i.e., the application of catalysis by copper complexes to form the carbon–nitrogen bond, and Chan–Lam reactions of (hetero)arylboronic acids with amines. Also, oxidative amination with C–H activation, which has been booming during the last decade, is addressed. Particular attention is paid to achievements in the application of heterogenized catalysts. The bibliography includes 350 references.
{"title":"Metal-catalyzed reactions for the C(sp2)–N bond formation: achievements of recent years","authors":"I. Beletskaya, A. Averin","doi":"10.1070/RCR4999","DOIUrl":"https://doi.org/10.1070/RCR4999","url":null,"abstract":"The review deals with the main catalytic methods for the C(sp2)–N bond formation, including Buchwald–Hartwig palladium-catalyzed amination of aryl and heteroaryl halides, renaissance of the Ullmann chemistry, i.e., the application of catalysis by copper complexes to form the carbon–nitrogen bond, and Chan–Lam reactions of (hetero)arylboronic acids with amines. Also, oxidative amination with C–H activation, which has been booming during the last decade, is addressed. Particular attention is paid to achievements in the application of heterogenized catalysts. The bibliography includes 350 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59009921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Changes in the hydrostatic pressure may significantly affect the spin dynamics of magnetically active compounds. Hence, objects exhibiting spin transitions have attracted attention of researchers in different fields. Since these transitions are reversible and do not cause the chemical decomposition of the compounds, spin state conversions can be responsible for the functional activity of materials as data storage media, external stimulus sensors or actuators for certain solid-state processes. Moreover, multispin compounds can demonstrate specific structural dynamics that is not inherent in diamagnetic compounds, which is of independent interest. The review presents the analysis of recent data on the effect of hydrostatic pressure on the crystal structure and magnetic properties of metal complexes with organic diamagnetic and paramagnetic ligands, exhibiting spin transitions and valence tautomerism, organic paramagnets and single-molecule magnets. The bibliography includes 179 references.
{"title":"Effect of pressure on the structure of multispin complexes","authors":"G. Romanenko, G. Letyagin, V. Ovcharenko","doi":"10.1070/RCR5028","DOIUrl":"https://doi.org/10.1070/RCR5028","url":null,"abstract":"Changes in the hydrostatic pressure may significantly affect the spin dynamics of magnetically active compounds. Hence, objects exhibiting spin transitions have attracted attention of researchers in different fields. Since these transitions are reversible and do not cause the chemical decomposition of the compounds, spin state conversions can be responsible for the functional activity of materials as data storage media, external stimulus sensors or actuators for certain solid-state processes. Moreover, multispin compounds can demonstrate specific structural dynamics that is not inherent in diamagnetic compounds, which is of independent interest. The review presents the analysis of recent data on the effect of hydrostatic pressure on the crystal structure and magnetic properties of metal complexes with organic diamagnetic and paramagnetic ligands, exhibiting spin transitions and valence tautomerism, organic paramagnets and single-molecule magnets. The bibliography includes 179 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59010986","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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