ACS Organic & Inorganic Au最新文献

{"title":"<i>N</i>-Heterocyclic Carbene-Borane Adducts with Chiral (<i>R</i>)-Chloroethyl and Vinyl Substituents.","authors":"Germán Rodríguez-López, Tayde O Villaseñor-Granados, Sonia Sánchez-Ruiz, Adriana Esparza-Ruiz, Angelina Flores-Parra","doi":"10.1021/acsorginorgau.4c00088","DOIUrl":"10.1021/acsorginorgau.4c00088","url":null,"abstract":"<p><p>This research provides how chiral imidazolium salts {1,3-bis[1'-chloro-1'-phenylpropan-2'-yl]-imidazolium} (<b>1a</b>) and enantiopure {1,3-bis[(<i>R</i>)-1-chlorobutan-2-yl]-imidazolium} [<b>1b</b>] can be utilized in diverse synthetic pathways to obtain new carbene-borane adducts (<b>2a</b>-<b>2d</b>): {1,3-bis[1'-chloro-1'-phenylpropan-2'-yl]-imidazolyl-2-ylidene-borane} (<b>2a</b>), {1,3-bis[(<i>Z</i>)-1'-phenylpropen-2'-yl]-imidazolyl-2-ylidene-borane} (<b>2b</b>), {1,3-bis[(<i>R</i>)-1-chlorobutan-2-yl]-imidazolyl-2-ylidene-borane} (<b>2c</b>), and {1,3-bis[but-1-en-2-yl]-imidazolyl-2-ylidene-borane} (<b>2d</b>). The carbene-borane adducts were synthesized and characterized by ¹³C, ¹H, and ¹¹B nuclear magnetic resonance spectroscopy and time-of-flight mass spectrometry. The X-ray crystal analyses of compounds <b>2a</b> and <b>2b</b> were performed, and to understand the structure and interactions of <b>2a</b>, a computational study was carried out. The effect of <i>N</i>-substituents in the NHC-borane adducts was clearly observed in the C-B bond lengths obtained by single-crystal X-ray diffraction, where the C-B bond is longer for adducts with <i>N</i>-(<i>R</i>)-chloroethyl substituents than for vinyl substituents. The analysis of the reduced density gradient and the bond critical point calculations of <b>2a</b> showed intramolecular proton-hydride and Cl···N interactions. These chiral imidazolium salts could have applicability in the development of new materials and possibly in pharmaceutical research.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"136-143"},"PeriodicalIF":3.3,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11969273/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143796302","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":"N-Heterocyclic Carbene-Borane Adducts with Chiral (R)-Chloroethyl and Vinyl Substituents","authors":"Germán Rodríguez-López,&nbsp;Tayde O. Villaseñor-Granados,&nbsp;Sonia Sánchez-Ruiz,&nbsp;Adriana Esparza-Ruiz* and Angelina Flores-Parra*,&nbsp;","doi":"10.1021/acsorginorgau.4c0008810.1021/acsorginorgau.4c00088","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00088https://doi.org/10.1021/acsorginorgau.4c00088","url":null,"abstract":"<p >This research provides how chiral imidazolium salts {1,3-bis[1′-chloro-1′-phenylpropan-2′-yl]-imidazolium} (<b>1a</b>) and enantiopure {1,3-bis[(<i>R</i>)-1-chlorobutan-2-yl]-imidazolium} [<b>1b</b>] can be utilized in diverse synthetic pathways to obtain new carbene-borane adducts (<b>2a</b>–<b>2d</b>): {1,3-bis[1′-chloro-1′-phenylpropan-2′-yl]-imidazolyl-2-ylidene-borane} (<b>2a</b>), {1,3-bis[(<i>Z</i>)-1′-phenylpropen-2′-yl]-imidazolyl-2-ylidene-borane} (<b>2b</b>), {1,3-bis[(<i>R</i>)-1-chlorobutan-2-yl]-imidazolyl-2-ylidene-borane} (<b>2c</b>), and {1,3-bis[but-1-en-2-yl]-imidazolyl-2-ylidene-borane} (<b>2d</b>). The carbene-borane adducts were synthesized and characterized by ¹³C, ¹H, and ¹¹B nuclear magnetic resonance spectroscopy and time-of-flight mass spectrometry. The X-ray crystal analyses of compounds <b>2a</b> and <b>2b</b> were performed, and to understand the structure and interactions of <b>2a</b>, a computational study was carried out. The effect of <i>N</i>-substituents in the NHC-borane adducts was clearly observed in the C–B bond lengths obtained by single-crystal X-ray diffraction, where the C–B bond is longer for adducts with <i>N</i>-(<i>R</i>)-chloroethyl substituents than for vinyl substituents. The analysis of the reduced density gradient and the bond critical point calculations of <b>2a</b> showed intramolecular proton–hydride and Cl···N interactions. These chiral imidazolium salts could have applicability in the development of new materials and possibly in pharmaceutical research.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"136–143 136–143"},"PeriodicalIF":3.3,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00088","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745972","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":"Strategic Methodologies for Efficient Synthesis of Imidazo[1,5-a]pyridine and Benzazepine Analogs via the Unique Ritter-Type Reaction","authors":"Gunniga Tanomsiri,&nbsp;Suthimon Boonmee,&nbsp;Nattawadee Chaisan,&nbsp;Jumreang Tummatorn*,&nbsp;Charnsak Thongsornkleeb and Somsak Ruchirawat,&nbsp;","doi":"10.1021/acsorginorgau.4c0007510.1021/acsorginorgau.4c00075","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00075https://doi.org/10.1021/acsorginorgau.4c00075","url":null,"abstract":"<p >We have developed novel approaches for synthesizing imidazo[1,5-<i>a</i>]pyridine and benzazepine analogs through a Ritter-type reaction. These methods utilize bismuth(III) trifluoromethanesulfonate (Bi(OTf)₃), an efficient catalyst for converting benzylic alcohol into benzylic cations, in combination with <i>para</i>-toluenesulfonic acid (<i>p</i>-TsOH·H₂O). The procedures offer a wide substrate scope and deliver the desired products in yields ranging from moderate to excellent.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"117–135 117–135"},"PeriodicalIF":3.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00075","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745868","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":"Strategic Methodologies for Efficient Synthesis of Imidazo[1,5-<i>a</i>]pyridine and Benzazepine Analogs via the Unique Ritter-Type Reaction.","authors":"Gunniga Tanomsiri, Suthimon Boonmee, Nattawadee Chaisan, Jumreang Tummatorn, Charnsak Thongsornkleeb, Somsak Ruchirawat","doi":"10.1021/acsorginorgau.4c00075","DOIUrl":"10.1021/acsorginorgau.4c00075","url":null,"abstract":"<p><p>We have developed novel approaches for synthesizing imidazo[1,5-<i>a</i>]pyridine and benzazepine analogs through a Ritter-type reaction. These methods utilize bismuth(III) trifluoromethanesulfonate (Bi(OTf)₃), an efficient catalyst for converting benzylic alcohol into benzylic cations, in combination with <i>para</i>-toluenesulfonic acid (<i>p</i>-TsOH·H₂O). The procedures offer a wide substrate scope and deliver the desired products in yields ranging from moderate to excellent.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"117-135"},"PeriodicalIF":3.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11969277/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143796448","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":"Single-Ion-Conducting Polymer Electrolytes for Rechargeable Alkaline Ag-Zn Batteries.","authors":"Hunter O Ford, Brian L Chaloux, Nishani K Jayakody, Christopher A Klug, Eric G Ruzicka, Meghanne Tighe, Ryan H DeBlock, Jeffrey W Long, Debra R Rolison, Megan Bourg Sassin","doi":"10.1021/acsorginorgau.4c00053","DOIUrl":"10.1021/acsorginorgau.4c00053","url":null,"abstract":"<p><p>Recently, we reported on the synthesis and performance of a cross-linked single-anion-conducting solid-state electrolyte (SSE) based on quaternized poly(dimethylaminomethylstyrene) (pDMAMS⁺) via initiated chemical vapor deposition (iCVD). In the homopolymer pDMAMS⁺-based SSE, the cross-linking occurs at the positively charged ammonium cation sites, hindering ion transport and conductivity. To improve ionic conductivity, we now report on a copolymer system, comprising DMAMS and divinylbenzene (DVB). Incorporating DVB moves the cross-links to the polymer backbone leaving the quaternary ammonium cation and its paired anion with maximal dynamic freedom. We evaluate the structure-transport relationships of a series of p[DVB-DMAMS] copolymers with varying DVB content using electrochemical impedance spectroscopy, nuclear magnetic resonance spectroscopy, and small- and wide-angle X-ray scattering. Our best composition containing 2.5 wt % DVB provides 1 mS cm^-1 single-ion OH^- conductivity under hydrated conditions, a significant improvement over the 0.01 mS cm^-1 of the hydrated homopolymer pDMAMS⁺ SSE. All copolymer compositions support Zn-ZnO and Ag-Zn electrochemical reduction-oxidation (redox) chemistry, which demonstrates the feasibility of a Ag-Zn battery using an alkaline single-ion-conducting SSE. Galvanostatic cycling shows some transport of Ag through the polymer electrolyte, however the deleterious effects of Ag migration can be partially mitigated by transitioning from a two-dimensional (2D) planar electrode to a 3D sponge electrode. With these promising results, the foundation is laid for using single-anion-conducting SSEs within alkaline Zn batteries.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"37-46"},"PeriodicalIF":3.3,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11803467/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143383467","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":"Hydrogen Oxidation by Bioinspired Models of [FeFe]-Hydrogenase","authors":"Abhijit Nayek,&nbsp;Rabin Kumar Poria,&nbsp;Md Estak Ahmed,&nbsp;Suman Patra,&nbsp;Somdatta Ghosh Dey* and Abhishek Dey*,&nbsp;","doi":"10.1021/acsorginorgau.4c0007310.1021/acsorginorgau.4c00073","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00073https://doi.org/10.1021/acsorginorgau.4c00073","url":null,"abstract":"<p >Synthetic azadithiolate-bridged diiron clusters serve as structural analogues of the active site of [FeFe]-hydrogenases. Recently, an <i>o-</i>alkyl substitution of aniline-based azadithiolate bridge allowed these synthetic models to both oxidize H₂ and reduce H⁺, i.e., bidirectional catalysis. Hydrogen oxidation by synthetic analogues of hydrogenases is rare, and even rarer is the ability of diiron hexacarbonyls to oxidize H₂. A series of synthetic azadithiolate-bridged biomimetic diiron hexacarbonyl complexes are synthesized where the substitution in the <i>para</i> position of the <i>ortho-</i>methyl aniline in the azadithiolate bridge is systematically varied between electron-withdrawing and electron-donating groups to understand factors that control H₂ oxidation by diiron hexacarbonyl analogues of [FeFe]-hydrogenases. The results show that the substituents in the <i>para</i> position of the <i>ortho-</i>ethyl aniline affect the electronic structure of the azadithiolate bridge as well as that of the diiron cluster. The electron-withdrawing −NO₂ substituent results in faster H₂ oxidation relative to that of a −OCH₃ substituent.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"105–116 105–116"},"PeriodicalIF":3.3,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00073","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745870","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":"Hydrogen Oxidation by Bioinspired Models of [FeFe]-Hydrogenase.","authors":"Abhijit Nayek, Rabin Kumar Poria, Md Estak Ahmed, Suman Patra, Somdatta Ghosh Dey, Abhishek Dey","doi":"10.1021/acsorginorgau.4c00073","DOIUrl":"10.1021/acsorginorgau.4c00073","url":null,"abstract":"<p><p>Synthetic azadithiolate-bridged diiron clusters serve as structural analogues of the active site of [FeFe]-hydrogenases. Recently, an <i>o-</i>alkyl substitution of aniline-based azadithiolate bridge allowed these synthetic models to both oxidize H₂ and reduce H⁺, i.e., bidirectional catalysis. Hydrogen oxidation by synthetic analogues of hydrogenases is rare, and even rarer is the ability of diiron hexacarbonyls to oxidize H₂. A series of synthetic azadithiolate-bridged biomimetic diiron hexacarbonyl complexes are synthesized where the substitution in the <i>para</i> position of the <i>ortho-</i>methyl aniline in the azadithiolate bridge is systematically varied between electron-withdrawing and electron-donating groups to understand factors that control H₂ oxidation by diiron hexacarbonyl analogues of [FeFe]-hydrogenases. The results show that the substituents in the <i>para</i> position of the <i>ortho-</i>ethyl aniline affect the electronic structure of the azadithiolate bridge as well as that of the diiron cluster. The electron-withdrawing -NO₂ substituent results in faster H₂ oxidation relative to that of a -OCH₃ substituent.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"105-116"},"PeriodicalIF":3.3,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11969278/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143796338","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":"Single-Ion-Conducting Polymer Electrolytes for Rechargeable Alkaline Ag–Zn Batteries","authors":"Hunter O. Ford,&nbsp;Brian L. Chaloux,&nbsp;Nishani K. Jayakody,&nbsp;Christopher A. Klug,&nbsp;Eric G. Ruzicka,&nbsp;Meghanne Tighe,&nbsp;Ryan H. DeBlock,&nbsp;Jeffrey W. Long,&nbsp;Debra R. Rolison and Megan Bourg Sassin*,&nbsp;","doi":"10.1021/acsorginorgau.4c0005310.1021/acsorginorgau.4c00053","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00053https://doi.org/10.1021/acsorginorgau.4c00053","url":null,"abstract":"<p >Recently, we reported on the synthesis and performance of a cross-linked single-anion-conducting solid-state electrolyte (SSE) based on quaternized poly(dimethylaminomethylstyrene) (pDMAMS⁺) via initiated chemical vapor deposition (iCVD). In the homopolymer pDMAMS⁺-based SSE, the cross-linking occurs at the positively charged ammonium cation sites, hindering ion transport and conductivity. To improve ionic conductivity, we now report on a copolymer system, comprising DMAMS and divinylbenzene (DVB). Incorporating DVB moves the cross-links to the polymer backbone leaving the quaternary ammonium cation and its paired anion with maximal dynamic freedom. We evaluate the structure–transport relationships of a series of p[DVB-DMAMS] copolymers with varying DVB content using electrochemical impedance spectroscopy, nuclear magnetic resonance spectroscopy, and small- and wide-angle X-ray scattering. Our best composition containing 2.5 wt % DVB provides 1 mS cm^–1 single-ion OH^– conductivity under hydrated conditions, a significant improvement over the 0.01 mS cm^–1 of the hydrated homopolymer pDMAMS⁺ SSE. All copolymer compositions support Zn–ZnO and Ag–Zn electrochemical reduction–oxidation (redox) chemistry, which demonstrates the feasibility of a Ag–Zn battery using an alkaline single-ion-conducting SSE. Galvanostatic cycling shows some transport of Ag through the polymer electrolyte, however the deleterious effects of Ag migration can be partially mitigated by transitioning from a two-dimensional (2D) planar electrode to a 3D sponge electrode. With these promising results, the foundation is laid for using single-anion-conducting SSEs within alkaline Zn batteries.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"37–46 37–46"},"PeriodicalIF":3.3,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00053","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143126441","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":"Strategic Synthesis of Sulfinamides as Versatile S(IV) Intermediates","authors":"Subham Das,&nbsp;Amit Dhibar and Basudev Sahoo*,&nbsp;","doi":"10.1021/acsorginorgau.4c0007810.1021/acsorginorgau.4c00078","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00078https://doi.org/10.1021/acsorginorgau.4c00078","url":null,"abstract":"<p >Sulfinamides constitute adaptable S(IV) intermediates with a sulfur stereocenter, having emerging interest in divergent synthesis of high-valent S(VI) functional bioisosteres. Recent years have witnessed the strategic development of mild and selective synthetic routes for highly functionalized sulfinamides, employing stable organometallic reagents, carbon-centered radical precursors, and other abundant coupling partners merged with various sulfur reagents in the arena of metal, photoredox, and organocatalysis. Furthermore, asymmetric metal and organocatalysis have enabled the stereoselective synthesis of enantioenriched sulfinamides. In this Perspective, we present the recent (2021 to present) advancement of various synthetic methods toward sulfinamides.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"1–12 1–12"},"PeriodicalIF":3.3,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00078","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127449","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":"Strategic Synthesis of Sulfinamides as Versatile S(IV) Intermediates.","authors":"Subham Das, Amit Dhibar, Basudev Sahoo","doi":"10.1021/acsorginorgau.4c00078","DOIUrl":"10.1021/acsorginorgau.4c00078","url":null,"abstract":"<p><p>Sulfinamides constitute adaptable S(IV) intermediates with a sulfur stereocenter, having emerging interest in divergent synthesis of high-valent S(VI) functional bioisosteres. Recent years have witnessed the strategic development of mild and selective synthetic routes for highly functionalized sulfinamides, employing stable organometallic reagents, carbon-centered radical precursors, and other abundant coupling partners merged with various sulfur reagents in the arena of metal, photoredox, and organocatalysis. Furthermore, asymmetric metal and organocatalysis have enabled the stereoselective synthesis of enantioenriched sulfinamides. In this Perspective, we present the recent (2021 to present) advancement of various synthetic methods toward sulfinamides.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"1-12"},"PeriodicalIF":3.3,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11803471/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143383468","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}