Limashree Sahoo, Payal Panwar, Chivukula V. Sastri, Sam P. de Visser
{"title":"Unraveling Chlorite Oxidation Pathways in Equatorially Heteroatom-Substituted Nonheme Iron Complexes","authors":"Limashree Sahoo, Payal Panwar, Chivukula V. Sastri, Sam P. de Visser","doi":"10.1021/acsorginorgau.4c00045","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00045","url":null,"abstract":"The first-coordination sphere of catalysts is known to play a crucial role in reaction mechanisms, but details of how equatorial ligands influence the reactivity remain unknown. Heteroatom ligated to the equatorial position of iron centers in nonheme iron metalloenzymes modulates structure and reactivity. To investigate the impact of equatorial heteroatom substitution on chlorite oxidation, we synthesized and characterized three novel mononuclear nonheme iron(II) complexes with a pentadentate bispidine scaffold. These complexes feature systematic substitutions at the equatorial position in the bispidine ligand framework where the pyridine group is replaced with NMe<sub>2</sub>, SMe, and OMe groups. The three iron(II)–bispidine complexes were subjected to studies in chlorite oxidation reactions as a model pathway for oxygen atom transfer. Chlorine oxyanions, which have the halide in an oxidation state ranging from +1 to +7, have numerous applications but can contaminate water bodies, and this demands urgent environmental remediation. Chlorite, a common precursor to chlorine dioxide, is of particular interest due to the superior antimicrobial activity of chlorine dioxide. Moreover, its generation leads to fewer harmful byproducts in water treatment. Here, we demonstrate that these complexes can produce chlorine dioxide from chlorite in acetate buffer at room temperature and pH 5.0, oxidizing chlorite through the in situ formation of high-valent iron(IV)–oxo intermediates. This study establishes how subtle changes in the coordination sphere around iron can influence the reactivity.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142256822","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}
Henry P. DeGroot, Isaiah R. Speight, William W. Brennessel, Timothy P. Hanusa
{"title":"t-Butyl and Trimethylsilyl Substituents in Nickel Allyl Complexes: Similar but Not the Same","authors":"Henry P. DeGroot, Isaiah R. Speight, William W. Brennessel, Timothy P. Hanusa","doi":"10.1021/acsorginorgau.4c00044","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00044","url":null,"abstract":"Metal complexes with <i>t</i>-Bu-substituted allyl ligands are relatively rare, especially compared to their conceptually similar trimethylsilyl-substituted analogs. The scarcity partially stems from the few general synthetic entry points for the <i>t</i>-Bu versions. This situation was studied through a modified synthesis for the allyl ligand itself and by forming several mono(allyl)nickel derivatives. After 2,2,6,6-tetramethyl-4-hepten-3-one was converted to the related 5-bromo-2,2,6,6-tetramethylhept-3-ene (A<sup>2t</sup>Br), a mixture of Ni(COD)<sub>2</sub> and A<sup>2t</sup>Br in the presence of a neutral donor ligand such as MeCN was found to produce the dark red dimeric π-allyl complex [{A<sup>2t</sup>NiBr}<sub>2</sub>]. Both NMR and X-ray crystallographic data confirmed that the <i>t</i>-Bu substituents are in a <i>syn</i>, <i>syn</i>-conformation, like that in the previously described [{A′NiBr}<sub>2</sub>] (A′ = 1,3-(TMS)<sub>2</sub>C<sub>3</sub>H<sub>3</sub>) complex. [{A<sup>2t</sup>NiBr}<sub>2</sub>] will form adducts with neutral donors such as PPh<sub>3</sub> and IMes (IMes = 1,3-dimesitylimidazol-2-ylidene), but the resulting [A<sup>2t</sup>Ni(PPh<sub>3</sub>)Br] complex is not as stable as its trimethylsilyl analog. The [A<sup>2t</sup>Ni(IMes)Br] complex crystallizes from hexanes as a monomer, with an η<sup>3</sup>-coordinated [A<sup>2t</sup>] ligand, and in contrast to the starting arrangement in [{A<sup>2t</sup>NiBr}<sub>2</sub>], the <i>t</i>-Bu groups on the A<sup>2t</sup> ligand are in a <i>syn</i>, <i>anti-</i>relationship. This structure is paralleled in the trimethylsilyl analog [A′Ni(IMes)Br]. DFT calculations were used to compare the structures of <i>t</i>-Bu- and related trimethylsilyl-substituted complexes.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142256774","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}
ACS Organic & Inorganic AuPub Date : 2024-09-05DOI: 10.1021/acsorginorgau.4c0005710.1021/acsorginorgau.4c00057
Fellipe F. S. Farias*, Mateus Mittersteiner, Amanda M. Kieling, Priscila S. V. Lima, Gustavo H. Weimer, Helio G. Bonacorso, Nilo Zanatta and Marcos A. P. Martins*,
{"title":"The Persistence of Hydrogen Bonds in Pyrimidinones: From Solution to Crystal","authors":"Fellipe F. S. Farias*, Mateus Mittersteiner, Amanda M. Kieling, Priscila S. V. Lima, Gustavo H. Weimer, Helio G. Bonacorso, Nilo Zanatta and Marcos A. P. Martins*, ","doi":"10.1021/acsorginorgau.4c0005710.1021/acsorginorgau.4c00057","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00057https://doi.org/10.1021/acsorginorgau.4c00057","url":null,"abstract":"<p >Pyrimidinone scaffolds are present in a wide array of molecules with synthetic and pharmacological utility. The inherent properties of these compounds may be attributed to intermolecular interactions analogous to the interactions that molecules tend to establish with active sites. Pyrimidinones and their fused derivatives have garnered significant interest due to their structural features, which resemble nitrogenous bases, the foundational building blocks of DNA and RNA. Similarly, pyrimidinones are predisposed to forming N–H···O hydrogen bonds akin to nitrogenous bases. Given this context, this study explored the supramolecular features and the predisposition to form hydrogen bonds in a series of 18 substituted 4-(trihalomethyl)-2(1<i>H</i>)-pyrimidinones. The formation of hydrogen bonds was observed in solution via nuclear magnetic resonance (NMR) spectroscopy experiments, and subsequently confirmed in the crystalline solid state. Hence, the 18 compounds were crystallized through crystallization assays by slow solvent evaporation, followed by single-crystal X-ray diffraction (SC-XRD). The supramolecular cluster demarcation was employed to evaluate all intermolecular interactions, and all crystalline structures exhibited robust hydrogen bonds, with an average energy of approximately −21.64 kcal mol<sup>–1</sup> (∼19% of the total stabilization energy of the supramolecular clusters), irrespective of the substituents at positions 4, 5, or 6 of the pyrimidinone core. To elucidate the nature of these hydrogen bonds, an analysis based on the quantum theory of atoms in molecules (QTAIM) revealed that the predominant intermolecular interactions are N–H···O (average of −16.55 kcal mol<sup>–1</sup>) and C–H···O (average of −6.48 kcal mol<sup>–1</sup>). Through proposing crystallization mechanisms based on molecular stabilization energy data and contact areas between molecules and employing the supramolecular cluster and retrocrystallization concepts, it was determined that altering the halogen (F/Cl) at position 4 of the pyrimidinone nucleus modifies the crystallization mechanism pathway. Notably, the hydrogen bonds present in the initial proposed steps were confirmed by <sup>1</sup>H NMR experiments using concentration-dependent techniques.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00057","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142408197","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fellipe F. S. Farias, Mateus Mittersteiner, Amanda M. Kieling, Priscila S. V. Lima, Gustavo H. Weimer, Helio G. Bonacorso, Nilo Zanatta, Marcos A. P. Martins
{"title":"The Persistence of Hydrogen Bonds in Pyrimidinones: From Solution to Crystal","authors":"Fellipe F. S. Farias, Mateus Mittersteiner, Amanda M. Kieling, Priscila S. V. Lima, Gustavo H. Weimer, Helio G. Bonacorso, Nilo Zanatta, Marcos A. P. Martins","doi":"10.1021/acsorginorgau.4c00057","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00057","url":null,"abstract":"Pyrimidinone scaffolds are present in a wide array of molecules with synthetic and pharmacological utility. The inherent properties of these compounds may be attributed to intermolecular interactions analogous to the interactions that molecules tend to establish with active sites. Pyrimidinones and their fused derivatives have garnered significant interest due to their structural features, which resemble nitrogenous bases, the foundational building blocks of DNA and RNA. Similarly, pyrimidinones are predisposed to forming N–H···O hydrogen bonds akin to nitrogenous bases. Given this context, this study explored the supramolecular features and the predisposition to form hydrogen bonds in a series of 18 substituted 4-(trihalomethyl)-2(1<i>H</i>)-pyrimidinones. The formation of hydrogen bonds was observed in solution via nuclear magnetic resonance (NMR) spectroscopy experiments, and subsequently confirmed in the crystalline solid state. Hence, the 18 compounds were crystallized through crystallization assays by slow solvent evaporation, followed by single-crystal X-ray diffraction (SC-XRD). The supramolecular cluster demarcation was employed to evaluate all intermolecular interactions, and all crystalline structures exhibited robust hydrogen bonds, with an average energy of approximately −21.64 kcal mol<sup>–1</sup> (∼19% of the total stabilization energy of the supramolecular clusters), irrespective of the substituents at positions 4, 5, or 6 of the pyrimidinone core. To elucidate the nature of these hydrogen bonds, an analysis based on the quantum theory of atoms in molecules (QTAIM) revealed that the predominant intermolecular interactions are N–H···O (average of −16.55 kcal mol<sup>–1</sup>) and C–H···O (average of −6.48 kcal mol<sup>–1</sup>). Through proposing crystallization mechanisms based on molecular stabilization energy data and contact areas between molecules and employing the supramolecular cluster and retrocrystallization concepts, it was determined that altering the halogen (F/Cl) at position 4 of the pyrimidinone nucleus modifies the crystallization mechanism pathway. Notably, the hydrogen bonds present in the initial proposed steps were confirmed by <sup>1</sup>H NMR experiments using concentration-dependent techniques.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142219298","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}
{"title":"Anion-Exchange Membrane Oxygen Separator","authors":"Maisa Faour, Karam Yassin, Dario R. Dekel","doi":"10.1021/acsorginorgau.4c00052","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00052","url":null,"abstract":"Anion-exchange membranes (AEMs), known for enabling the high conductivity of hydroxide anions through dense polymeric structures, are pivotal components in fuel cells, electrolyzers, and other important electrochemical systems. This paper unveils an unprecedented utilization of AEMs in an electrochemical oxygen separation process, a new technology able to generate enriched oxygen from an O<sub>2</sub>/N<sub>2</sub> mixture using a small voltage input. We demonstrate a first-of-its-kind AEM-based electrochemical device that operates under mild conditions, is free of liquid electrolytes or sweep gases, and produces oxygen of over 96% purity. Additionally, we develop and apply a one-dimensional time-dependent and isothermal model, which accurately captures the unique operational dynamics of our device, demonstrates good agreement with the experimental data, and allows us to explore the device’s potential capabilities. This novel technology has far-reaching applications in many industrial processes, medical oxygen therapy, and other diverse fields while reducing operational complexity and environmental impact, thereby paving the way for sustainable on-site oxygen generation.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142219290","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}
ACS Organic & Inorganic AuPub Date : 2024-08-29DOI: 10.1021/acsorginorgau.4c0005210.1021/acsorginorgau.4c00052
Maisa Faour, Karam Yassin and Dario R. Dekel*,
{"title":"Anion-Exchange Membrane Oxygen Separator","authors":"Maisa Faour, Karam Yassin and Dario R. Dekel*, ","doi":"10.1021/acsorginorgau.4c0005210.1021/acsorginorgau.4c00052","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00052https://doi.org/10.1021/acsorginorgau.4c00052","url":null,"abstract":"<p >Anion-exchange membranes (AEMs), known for enabling the high conductivity of hydroxide anions through dense polymeric structures, are pivotal components in fuel cells, electrolyzers, and other important electrochemical systems. This paper unveils an unprecedented utilization of AEMs in an electrochemical oxygen separation process, a new technology able to generate enriched oxygen from an O<sub>2</sub>/N<sub>2</sub> mixture using a small voltage input. We demonstrate a first-of-its-kind AEM-based electrochemical device that operates under mild conditions, is free of liquid electrolytes or sweep gases, and produces oxygen of over 96% purity. Additionally, we develop and apply a one-dimensional time-dependent and isothermal model, which accurately captures the unique operational dynamics of our device, demonstrates good agreement with the experimental data, and allows us to explore the device’s potential capabilities. This novel technology has far-reaching applications in many industrial processes, medical oxygen therapy, and other diverse fields while reducing operational complexity and environmental impact, thereby paving the way for sustainable on-site oxygen generation.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00052","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142402688","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Corina Stoian, Fawaz Al Hussein, Wesley R. Browne, Emanuel Hupf, Jens Beckmann
{"title":"Electronic Coupling in Triferrocenylpnictogens","authors":"Corina Stoian, Fawaz Al Hussein, Wesley R. Browne, Emanuel Hupf, Jens Beckmann","doi":"10.1021/acsorginorgau.4c00034","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00034","url":null,"abstract":"From a fundamental perspective, studies of novel mixed-valent complexes containing ferrocenyl units are motivated by the prospect of improving and extending electron transfer models and theories. Here, the series of triferrocenylpnictogens Fc<sub>3</sub>E was extended to the heavier analogues (E = As, Sb, and Bi), and the influence of the bridging atom was investigated with Fc<sub>3</sub>P as a reference. Electrochemical studies elucidate the effect of electrostatic contribution on the large redox splitting (Δ<i>E</i><sub>1</sub>) exhibited by the compounds and solvent stabilization in the case of Fc<sub>3</sub>As. Structural characterization of the triferrocenylpnictogens combined with spectroelectrochemical studies indicates weak electronic couplings in the related cations [Fc<sub>3</sub>E]<sup>+</sup>, suggesting a through-space mechanism.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142219289","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}
ACS Organic & Inorganic AuPub Date : 2024-08-17DOI: 10.1021/acsorginorgau.4c0003410.1021/acsorginorgau.4c00034
Corina Stoian, Fawaz Al Hussein, Wesley R. Browne, Emanuel Hupf* and Jens Beckmann*,
{"title":"Electronic Coupling in Triferrocenylpnictogens","authors":"Corina Stoian, Fawaz Al Hussein, Wesley R. Browne, Emanuel Hupf* and Jens Beckmann*, ","doi":"10.1021/acsorginorgau.4c0003410.1021/acsorginorgau.4c00034","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00034https://doi.org/10.1021/acsorginorgau.4c00034","url":null,"abstract":"<p >From a fundamental perspective, studies of novel mixed-valent complexes containing ferrocenyl units are motivated by the prospect of improving and extending electron transfer models and theories. Here, the series of triferrocenylpnictogens Fc<sub>3</sub>E was extended to the heavier analogues (E = As, Sb, and Bi), and the influence of the bridging atom was investigated with Fc<sub>3</sub>P as a reference. Electrochemical studies elucidate the effect of electrostatic contribution on the large redox splitting (Δ<i>E</i><sub>1</sub>) exhibited by the compounds and solvent stabilization in the case of Fc<sub>3</sub>As. Structural characterization of the triferrocenylpnictogens combined with spectroelectrochemical studies indicates weak electronic couplings in the related cations [Fc<sub>3</sub>E]<sup>+</sup>, suggesting a through-space mechanism.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00034","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142407788","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Organic & Inorganic AuPub Date : 2024-08-08DOI: 10.1021/acsorginorgau.4c0003710.1021/acsorginorgau.4c00037
Sayan Ghosh, Samrat Mallick, Devika Karolly and Suman De Sarkar*,
{"title":"Easy Access to Fused Tricyclic Quinoline Derivatives through Metal-Free Electrocatalytic [4 + 2] Annulation","authors":"Sayan Ghosh, Samrat Mallick, Devika Karolly and Suman De Sarkar*, ","doi":"10.1021/acsorginorgau.4c0003710.1021/acsorginorgau.4c00037","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00037https://doi.org/10.1021/acsorginorgau.4c00037","url":null,"abstract":"<p >An efficient electrocatalytic cycloaddition approach for the construction of a lactone- or lactam-fused quinoline framework is documented. Diverse arrays of functionalities are well-compatible under this metal-free, mild, and scalable electro-redox protocol. Mechanistic studies indicate an iodide-mediated electro-oxidation of secondary amines to their corresponding imines and consequent [4 + 2] cycloaddition, fabricating C–C bonds followed by rapid aromatization leading to the six-membered core structure.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00037","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142408062","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Mechanochemistry for Organic and Inorganic Synthesis","authors":"Javier F. Reynes, Felix Leon, Felipe García","doi":"10.1021/acsorginorgau.4c00001","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00001","url":null,"abstract":"In recent years, mechanochemistry has become an innovative and sustainable alternative to traditional solvent-based synthesis. Mechanochemistry rapidly expanded across a wide range of chemistry fields, including diverse organic compounds and active pharmaceutical ingredients, coordination compounds, organometallic complexes, main group frameworks, and technologically relevant materials. This Review aims to highlight recent advancements and accomplishments in mechanochemistry, underscoring its potential as a viable and eco-friendly alternative to conventional solution-based methods in the field of synthetic chemistry.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141947619","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}