{"title":"Retraction: A Porous Zn2(abct) Framework as an Efficient Carrier for 5‐Fu Delivery and Inhibiting Human Liver Cancer Cells","authors":"","doi":"10.1002/zaac.202400106","DOIUrl":"https://doi.org/10.1002/zaac.202400106","url":null,"abstract":"","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141746201","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":"Retraction: A 3D Luminescent Metal‐organic Framework Constructed from Cu4I4 Cubane Clusters and Triangular Imidazole Ligand","authors":"","doi":"10.1002/zaac.202400114","DOIUrl":"https://doi.org/10.1002/zaac.202400114","url":null,"abstract":"","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141744574","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}
The reactions of the dianion [Li2(Et2O)1.5][(SPh2P)2C] 1 with Se and Te were explored and shown to be dependent on the stoichiometry. The species, [Li2(THF)3(SPh2P)2CSe2] 2, [Li2(THF)4(SPh2P)2CSe4C(PPh2S)2] 3, [Li2(THF)3(SPh2P)2CTe2] 4 and [Li2(THF)3Et2O][(SPh2P)2CTe3C(PPh2S)2] 5 have been isolated and structurally characterized. While these products proved to be remarkably sensitive to light and air, the characterization of these products demonstrates that ability of the dianion to intercept short chalcogenide chains of E2‐4.
探讨了二元离子 [Li2(Et2O)1.5][(SPh2P)2C] 1 与 Se 和 Te 的反应，结果表明反应取决于化学计量学。已分离出[Li2(THF)3(SPh2P)2CSe2] 2、[Li2(THF)4(SPh2P)2CSe4C(PPh2S)2] 3、[Li2(THF)3(SPh2P)2CTe2] 4 和[Li2(THF)3Et2O][(SPh2P)2CTe3C(PPh2S)2] 5 物种，并对其进行了结构表征。事实证明，这些产物对光和空气非常敏感，同时，这些产物的表征也证明了二元离子拦截 E2-4 短链的能力。
{"title":"Reactions of the Geminal Dicarbanion Li2[C(SPPh2)2] with Selenium and Tellurium","authors":"Tongtong Wang, Maotong Xu, Douglas Wade Stephan","doi":"10.1002/zaac.202400083","DOIUrl":"https://doi.org/10.1002/zaac.202400083","url":null,"abstract":"The reactions of the dianion [Li2(Et2O)1.5][(SPh2P)2C] 1 with Se and Te were explored and shown to be dependent on the stoichiometry. The species, [Li2(THF)3(SPh2P)2CSe2] 2, [Li2(THF)4(SPh2P)2CSe4C(PPh2S)2] 3, [Li2(THF)3(SPh2P)2CTe2] 4 and [Li2(THF)3Et2O][(SPh2P)2CTe3C(PPh2S)2] 5 have been isolated and structurally characterized. While these products proved to be remarkably sensitive to light and air, the characterization of these products demonstrates that ability of the dianion to intercept short chalcogenide chains of E2‐4.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141744570","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":"Retraction: A InIII‐MOF with Imidazole Decorated Pores as 5‐Fu Delivery System to Inhibit Colon Cancer Cells Proliferation and Induce Cell Apoptosis in vitro and in vivo","authors":"","doi":"10.1002/zaac.202400104","DOIUrl":"https://doi.org/10.1002/zaac.202400104","url":null,"abstract":"","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141746200","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}
Utilizing the flexible carboxylic acid ligand, tri(4‐carboxybenzyl) amine (H3L), three new coordination polymers Na[Cd(L)]n·3nH2O (1), [Cd(HL)(4,4’‐bipy)0.5(H2O)]n (2) (4,4’‐bipy = 4,4’‐bipyridine) and [Cd(HL)(2,2’‐bipy)]n (3) (2,2’‐bipy = 2,2’‐bipyridine) have been successfully synthesized. Compounds 1 and 2 are all 2D structures with (3,6) 2‐nodal as kgd topology, while compound 3 is a 1D chain structure. The powder X‐ray diffraction and the thermal stabilities were studied for 1‐3. In addition, the solid‐state luminescence properties of compounds 1‐3 were also tested at room temperature, indicating their application prospects in fluorescent materials.
{"title":"Three metal organic frameworksof Cd(II) with tri(4‐carboxybenzyl) amine and their photoluminescence properties","authors":"Xiang He, Shuang Dong, Jie Jiang","doi":"10.1002/zaac.202400096","DOIUrl":"https://doi.org/10.1002/zaac.202400096","url":null,"abstract":"Utilizing the flexible carboxylic acid ligand, tri(4‐carboxybenzyl) amine (H3L), three new coordination polymers Na[Cd(L)]n·3nH2O (1), [Cd(HL)(4,4’‐bipy)0.5(H2O)]n (2) (4,4’‐bipy = 4,4’‐bipyridine) and [Cd(HL)(2,2’‐bipy)]n (3) (2,2’‐bipy = 2,2’‐bipyridine) have been successfully synthesized. Compounds 1 and 2 are all 2D structures with (3,6) 2‐nodal as kgd topology, while compound 3 is a 1D chain structure. The powder X‐ray diffraction and the thermal stabilities were studied for 1‐3. In addition, the solid‐state luminescence properties of compounds 1‐3 were also tested at room temperature, indicating their application prospects in fluorescent materials.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141650232","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}
Phosphaalkynes are the heavier congener of nitriles which feature a polarized Cδ−≡Pδ+ triple bond. Since the isolation of the first phosphaalkyne in 1981, these compounds have become important ligands for transition metals and valuable building blocks in synthetic chemistry. The reported reactivity with germylenes is rare, to expand this chemistry, we studied the reactivity of the recently developed gallium‐substituted germylene 1 ([LPhGe–Ga(Cl)LBDI] (LPh = PhC(NtBu)2; LBDI = [{2,6‐iPr2C6H3NCMe}2CH]) with tBuC≡P. Already at room temperature, insertion of the phosphaalkyne into the Ga–Ge bond occurred, resulting a metal‐functionalized (Z)‐phosphaalkenyl complex [LPhGe{C(tBu)=P}–Ga(Cl)LBDI] (2). Complex 2 was characterized by single crystal X‐ray diffraction analysis and spectroscopic methods (1H, 13C{1H}, 31P{1H} NMR and IR).
{"title":"Reactivity of phosphaalkyne tBuCP toward a Ga‐functionalized germylene","authors":"Xiaofei Sun, Peter Werner Roesky","doi":"10.1002/zaac.202400116","DOIUrl":"https://doi.org/10.1002/zaac.202400116","url":null,"abstract":"Phosphaalkynes are the heavier congener of nitriles which feature a polarized Cδ−≡Pδ+ triple bond. Since the isolation of the first phosphaalkyne in 1981, these compounds have become important ligands for transition metals and valuable building blocks in synthetic chemistry. The reported reactivity with germylenes is rare, to expand this chemistry, we studied the reactivity of the recently developed gallium‐substituted germylene 1 ([LPhGe–Ga(Cl)LBDI] (LPh = PhC(NtBu)2; LBDI = [{2,6‐iPr2C6H3NCMe}2CH]) with tBuC≡P. Already at room temperature, insertion of the phosphaalkyne into the Ga–Ge bond occurred, resulting a metal‐functionalized (Z)‐phosphaalkenyl complex [LPhGe{C(tBu)=P}–Ga(Cl)LBDI] (2). Complex 2 was characterized by single crystal X‐ray diffraction analysis and spectroscopic methods (1H, 13C{1H}, 31P{1H} NMR and IR).","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141608638","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}
Hannes Lukas Jacob, Jan Cramer, Robin Guthardt, Clemens Bruhn, Ulrich Siemeling
The diaminoferrocene derivative fc[NH(BMes2)]2 (1H2; fc = 1,1’‐ferrocenylene, Mes = mesityl) was prepared from fc(NH2)2 and Mes2BCl and used for the preparation of the N‐heterocyclic tetrylenes fc{[N(BMes2)]2E} (1E, E = Ge, Sn) via the sodium amide fc[NNa(BMes2)]2 (1Na2), which was obtained from 1H2 and NaN(SiMe3)2. 1H2 is inert towards LiN(SiMe3)2 or nBuLi. Its reaction with nBuLi in the presence of TMEDA afforded the TMEDA‐coordinated lithium amide 1Li2(TMEDA)2. Crystallisation of 1Na2 from THF furnished the adduct 1Na2(THF)3. The reaction of 1Na2 with Me3SiCl afforded 1(SiMe3)2. Attempts to obtain the thiourea fc{[N(BMes2)]2C=S} (1C=S) from 1Na2 and Cl2C=S were not successful. 1C=S is accessible from fc(NH3)Cl2, which is transformed to fc[(NH)2C=S] (2) by reaction with Cl2C=S and NEt3 (4 equiv.), followed by conversion of 2 to fc{[N(SiMe3)]2C=S} (3) with Me3SiCl and NEt3 (2 equiv.) and subsequent reaction of 3 with Mes2BCl. All new compounds except 1Na2 and 2 were structurally characterised by single‐crystal X‐ray diffraction. The N‐boryl substituents of 1E compete efficiently with the EII atom for nitrogen π‐donation, causing comparatively long EII–N bonds and small EII bond angles. 1C=S contains a four‐membered BNCS ring due to intramolecular adduct formation involving the Lewis basic S atom and a Lewis acidic B atom.
{"title":"An N‐Heterocyclic Germylene and Stannylene with a 1,1’‐Ferrocenylene Backbone and Dimesitylboryl N‐Substituents","authors":"Hannes Lukas Jacob, Jan Cramer, Robin Guthardt, Clemens Bruhn, Ulrich Siemeling","doi":"10.1002/zaac.202400111","DOIUrl":"https://doi.org/10.1002/zaac.202400111","url":null,"abstract":"The diaminoferrocene derivative fc[NH(BMes2)]2 (1H2; fc = 1,1’‐ferrocenylene, Mes = mesityl) was prepared from fc(NH2)2 and Mes2BCl and used for the preparation of the N‐heterocyclic tetrylenes fc{[N(BMes2)]2E} (1E, E = Ge, Sn) via the sodium amide fc[NNa(BMes2)]2 (1Na2), which was obtained from 1H2 and NaN(SiMe3)2. 1H2 is inert towards LiN(SiMe3)2 or nBuLi. Its reaction with nBuLi in the presence of TMEDA afforded the TMEDA‐coordinated lithium amide 1Li2(TMEDA)2. Crystallisation of 1Na2 from THF furnished the adduct 1Na2(THF)3. The reaction of 1Na2 with Me3SiCl afforded 1(SiMe3)2. Attempts to obtain the thiourea fc{[N(BMes2)]2C=S} (1C=S) from 1Na2 and Cl2C=S were not successful. 1C=S is accessible from fc(NH3)Cl2, which is transformed to fc[(NH)2C=S] (2) by reaction with Cl2C=S and NEt3 (4 equiv.), followed by conversion of 2 to fc{[N(SiMe3)]2C=S} (3) with Me3SiCl and NEt3 (2 equiv.) and subsequent reaction of 3 with Mes2BCl. All new compounds except 1Na2 and 2 were structurally characterised by single‐crystal X‐ray diffraction. The N‐boryl substituents of 1E compete efficiently with the EII atom for nitrogen π‐donation, causing comparatively long EII–N bonds and small EII bond angles. 1C=S contains a four‐membered BNCS ring due to intramolecular adduct formation involving the Lewis basic S atom and a Lewis acidic B atom.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141608628","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}
Aynura Mammadova, Clemens Bruhn, Rudolf Pietschnig
Reaction of two equivalents of ((CH3)3Si)2C(C6H5)SLi·3THF with SnCl2·IPr (IPr=:C[N(Diip)C(H)]2, Diip= 2,6 i‐(CH3)2CH(C6H5) led to fragmentation of the organolithium component and gave IPr·Sn(SPh)2, compound 3. The latter compound has been further prepared from Ph‐SSi(CH3)3 whereas disproportionation of the Sn(II) species was observed when starting from Ph‐SLi. Stannylene adduct 3 has been characterized spectroscopically and its structure was explored with single crystal X‐ray diffraction (SCXRD). The carbene donor in 3 can be displaced by chloride upon formal HCl addition giving rise to the ionic stannylene adduct 3a IPr+[SnCl(SPh)2]‐, the structure of which was investigated with SCXRD as well.
{"title":"Synthesis and characterization of NHC stabilized bis(phenylsulfanyl)stannylene","authors":"Aynura Mammadova, Clemens Bruhn, Rudolf Pietschnig","doi":"10.1002/zaac.202400119","DOIUrl":"https://doi.org/10.1002/zaac.202400119","url":null,"abstract":"Reaction of two equivalents of ((CH3)3Si)2C(C6H5)SLi·3THF with SnCl2·IPr (IPr=:C[N(Diip)C(H)]2, Diip= 2,6 i‐(CH3)2CH(C6H5) led to fragmentation of the organolithium component and gave IPr·Sn(SPh)2, compound 3. The latter compound has been further prepared from Ph‐SSi(CH3)3 whereas disproportionation of the Sn(II) species was observed when starting from Ph‐SLi. Stannylene adduct 3 has been characterized spectroscopically and its structure was explored with single crystal X‐ray diffraction (SCXRD). The carbene donor in 3 can be displaced by chloride upon formal HCl addition giving rise to the ionic stannylene adduct 3a IPr+[SnCl(SPh)2]‐, the structure of which was investigated with SCXRD as well.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141608627","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}
Fu-Wei Zheng, Lin Hua, Zhi-Yong He, Feng Geng, Yan Li, Long Wang, Xiang-Jun Zhu, Guo-Fang Li, Xian-Ying Duan, Hui-Qing Zhang, Hai-Tao Chen
Two butterfly‐like binuclear Gadolinium(III) (Gd) complex [Gd2(L1)2(H2L3)2(NO3)2] (1) and [Gd2(L2)2(H2L3)2(NO3)2] (2) were obtained by using 2‐hydroxybenzaldehyde or 2‐hydroxy‐1‐naphthaldehyde, 2‐aminophenol, pyridin‐2‐ylmethanamine and Gd(NO3)3·6H2O in CH3CN (H2L1 = (E)‐2‐((2‐hydroxybenzylidene)amino)phenol, H2L2 = (E)‐1‐(((2‐hydroxyphenyl)imino)methyl)naphthalen‐2‐ol, H2L3 = pyridin‐2‐ylmethanamine). Structural analysis suggests that all the ligands as protective units protect the central Gd(III) ions at the periphery. Magnetization studies exhibited magnetocaloric effect of 14.45 J·kg−1·K−1 at 4 K under ΔH = 7 T for complex 1 and 12.69 J·kg−1·K−1 at 2 K under ΔH = 7 T for complex 2. In complexes 1 and 2, although the coordination configurations are the same, the significant difference in MCE may be due to the adjustments of the peripheral ligands leading to changes in the coordination field strength. The electron affinity of the ligands can impact the interaction between the ligands and Gd(III) ions.
{"title":"Binuclear Gadolinium Complex by One‐Pot Method: Structure and Magnetic Property","authors":"Fu-Wei Zheng, Lin Hua, Zhi-Yong He, Feng Geng, Yan Li, Long Wang, Xiang-Jun Zhu, Guo-Fang Li, Xian-Ying Duan, Hui-Qing Zhang, Hai-Tao Chen","doi":"10.1002/zaac.202300238","DOIUrl":"https://doi.org/10.1002/zaac.202300238","url":null,"abstract":"Two butterfly‐like binuclear Gadolinium(III) (Gd) complex [Gd2(L1)2(H2L3)2(NO3)2] (1) and [Gd2(L2)2(H2L3)2(NO3)2] (2) were obtained by using 2‐hydroxybenzaldehyde or 2‐hydroxy‐1‐naphthaldehyde, 2‐aminophenol, pyridin‐2‐ylmethanamine and Gd(NO3)3·6H2O in CH3CN (H2L1 = (E)‐2‐((2‐hydroxybenzylidene)amino)phenol, H2L2 = (E)‐1‐(((2‐hydroxyphenyl)imino)methyl)naphthalen‐2‐ol, H2L3 = pyridin‐2‐ylmethanamine). Structural analysis suggests that all the ligands as protective units protect the central Gd(III) ions at the periphery. Magnetization studies exhibited magnetocaloric effect of 14.45 J·kg−1·K−1 at 4 K under ΔH = 7 T for complex 1 and 12.69 J·kg−1·K−1 at 2 K under ΔH = 7 T for complex 2. In complexes 1 and 2, although the coordination configurations are the same, the significant difference in MCE may be due to the adjustments of the peripheral ligands leading to changes in the coordination field strength. The electron affinity of the ligands can impact the interaction between the ligands and Gd(III) ions.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141608642","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}
Uli Kazmaier, Alexander Horn, Emanuel Papadopoulos, Thorsten Kinsinger, Jennifer Greve, Etienne Bickel, Stavroula Pachoula
Matteson homologation with sodium azide in DMF proved to be an excellent highly stereoselective tool for the synthesis of complex α‐azido and α‐amino acids. Both enantiomers are easily accessible via the choice of the chiral boronic ester auxiliary.
{"title":"Stereoselective Synthesis of α‐Azido Esters and α‐Amino Acid Derivatives via Matteson Homologation of Boronic Esters","authors":"Uli Kazmaier, Alexander Horn, Emanuel Papadopoulos, Thorsten Kinsinger, Jennifer Greve, Etienne Bickel, Stavroula Pachoula","doi":"10.1002/zaac.202400113","DOIUrl":"https://doi.org/10.1002/zaac.202400113","url":null,"abstract":"Matteson homologation with sodium azide in DMF proved to be an excellent highly stereoselective tool for the synthesis of complex α‐azido and α‐amino acids. Both enantiomers are easily accessible via the choice of the chiral boronic ester auxiliary.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141608640","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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