Alexey V. Eroshin, A. Otlyotov, Yuriy A. Zhabanov, Vladimir V. Veretennikov, M. Islyaikin
Equilibrium geometry and electronic structures of Ca(II), Ni(II) and Zn(II) complexes with hemiand dicarbahemiporphyrazines were determined by DFT calculations at PBE0/pcseg-2 level followed by natural bond orbital (NBO) analysis of the electron density distribution. Electronic structures of Ni(II) complexes in ground and low-lying excited electronic states were determined by complete active space (CASSCF) method with following accounting dynamic correlation by multiconfigurational quasidegenerate second-order perturbation theory (MCQDPT2). According to data obtained by MCQDPT2 method the complexes of hemiand dicarbahemiporphyrazine possess the ground states A1 and B1, respectively, and wave functions of the ground states have the form of a single determinant in the case of Ni(II) complex with hemiporphyrazine and the wave function for Ni(II) with dicarbahemiporphyrazine were found to possess a complex composition, therefore this complex could not be treated using single-reference DFT methods. The covalent component of metal-ligand bonding was found to increase significantly in the series: Ca(II) → Zn(II) → Ni(II). Large covalent contribution into Ni–N bonding is explained by additional LP(Np) → 3dx2-y2(Ni) and LP(Ni) → 3dx2-y2(Ni) interactions. The presence of agostic interactions -C–H∙∙∙Zn in the dicarbahemiporphyrazine complex was also confirmed.
{"title":"Complexes of Ca(II), Ni(II) and Zn(II) with Hemi- and Dicarbahemiporphyrazines: Molecular Structure and Features of Metal-Ligand Bonding","authors":"Alexey V. Eroshin, A. Otlyotov, Yuriy A. Zhabanov, Vladimir V. Veretennikov, M. Islyaikin","doi":"10.6060/mhc201026z","DOIUrl":"https://doi.org/10.6060/mhc201026z","url":null,"abstract":"Equilibrium geometry and electronic structures of Ca(II), Ni(II) and Zn(II) complexes with hemiand dicarbahemiporphyrazines were determined by DFT calculations at PBE0/pcseg-2 level followed by natural bond orbital (NBO) analysis of the electron density distribution. Electronic structures of Ni(II) complexes in ground and low-lying excited electronic states were determined by complete active space (CASSCF) method with following accounting dynamic correlation by multiconfigurational quasidegenerate second-order perturbation theory (MCQDPT2). According to data obtained by MCQDPT2 method the complexes of hemiand dicarbahemiporphyrazine possess the ground states A1 and B1, respectively, and wave functions of the ground states have the form of a single determinant in the case of Ni(II) complex with hemiporphyrazine and the wave function for Ni(II) with dicarbahemiporphyrazine were found to possess a complex composition, therefore this complex could not be treated using single-reference DFT methods. The covalent component of metal-ligand bonding was found to increase significantly in the series: Ca(II) → Zn(II) → Ni(II). Large covalent contribution into Ni–N bonding is explained by additional LP(Np) → 3dx2-y2(Ni) and LP(Ni) → 3dx2-y2(Ni) interactions. The presence of agostic interactions -C–H∙∙∙Zn in the dicarbahemiporphyrazine complex was also confirmed.","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":"43 1","pages":""},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71166380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
M. A. Gromova, Y. Kharitonov, T. Rybalova, E. Shults
The first macrocyclic pimarane type diterpenoids containing fragments of 1,2,3-triazole and tricyclic diterpenoid isopimaric acid moieties were synthesized. The key step was the CuAAC reaction of various diazides with the dialkyne derivative obtained from 16-(carboxyphenyl)isopimaric acid. The molecular structure of the macrocyclic compound with 1,5-diazopentane unit was determined by single crystal X-ray diffraction analysis.
{"title":"Click Synthesis of Triazole-Linked Polyazamacrocycles through Selective Isopimaric Acid Transformations","authors":"M. A. Gromova, Y. Kharitonov, T. Rybalova, E. Shults","doi":"10.6060/mhc200817s","DOIUrl":"https://doi.org/10.6060/mhc200817s","url":null,"abstract":"The first macrocyclic pimarane type diterpenoids containing fragments of 1,2,3-triazole and tricyclic diterpenoid isopimaric acid moieties were synthesized. The key step was the CuAAC reaction of various diazides with the dialkyne derivative obtained from 16-(carboxyphenyl)isopimaric acid. The molecular structure of the macrocyclic compound with 1,5-diazopentane unit was determined by single crystal X-ray diffraction analysis.","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":"1 1","pages":""},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71166487","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
T. Dubinina, P. Tychinsky, Е. А. Gorbunova, М. S. Belousov
Synthetic approaches to the phthalocyanines and their polynuclear and sandwich-type derivatives, bearing sulfur-containing functional groups, are classified. Additionally complexes, possessing an extended π-conjugation system (planar and sandwich-type 2,3-naphthalocyanines) are reviewed. Principal application areas are covered. Special attention is paid to the formation of conjugates with gold nanoparticles – prospective materials for organic electronics. Both approaches on substituted nitriles and methods for functional groups in the phthalocyanine macrocycle are Compounds of both planar and sandwich structures are considered.
{"title":"Phthalocyanines and Naphthalocyanines with Sulfur-Containing Functional Groups: Synthesis, Preparation of Hybrid Gold Nanoparticles and Some Application Areas","authors":"T. Dubinina, P. Tychinsky, Е. А. Gorbunova, М. S. Belousov","doi":"10.6060/MHC210232D","DOIUrl":"https://doi.org/10.6060/MHC210232D","url":null,"abstract":"Synthetic approaches to the phthalocyanines and their polynuclear and sandwich-type derivatives, bearing sulfur-containing functional groups, are classified. Additionally complexes, possessing an extended π-conjugation system (planar and sandwich-type 2,3-naphthalocyanines) are reviewed. Principal application areas are covered. Special attention is paid to the formation of conjugates with gold nanoparticles – prospective materials for organic electronics. Both approaches on substituted nitriles and methods for functional groups in the phthalocyanine macrocycle are Compounds of both planar and sandwich structures are considered.","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":"1 1","pages":""},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71166687","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mariia A. Gromova, Y. Kharitonov, T. S. Golubeva, E. Shults
{"title":"Synthesis of Macrocyclic Peptide-Diterpenoid Conjugates by a Sequential Arylation/Peptide Coupling/Click Macrocyclization Procedure","authors":"Mariia A. Gromova, Y. Kharitonov, T. S. Golubeva, E. Shults","doi":"10.6060/mhc210945s","DOIUrl":"https://doi.org/10.6060/mhc210945s","url":null,"abstract":"","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":"1 1","pages":""},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71167169","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dmitry A. Erzunov, A. Botnar, T. Tikhomirova, V. Maizlish, V. Aleksandriiskii, Igor G. Abramov, Yurii S. Marfin, A. Vashurin
{"title":"Investigation of Catalytic Processes of Thio-Compounds Conversion to Disulfides Using Novel Butyl/Butoxy-Phthalocyaninates of d-Metals","authors":"Dmitry A. Erzunov, A. Botnar, T. Tikhomirova, V. Maizlish, V. Aleksandriiskii, Igor G. Abramov, Yurii S. Marfin, A. Vashurin","doi":"10.6060/mhc214025v","DOIUrl":"https://doi.org/10.6060/mhc214025v","url":null,"abstract":"","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":"49 1","pages":""},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71167518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Precursors for the Synthesis of Macroheterocyclic Compounds. Modeling of the Mechanism for Formation of 2-Amino-5-methyl-1,3,4-thiadiazole by Quantum Chemistry Methods","authors":"Y. Suvorova, V. V. Dunaeva, M. Islyaikin","doi":"10.6060/mhc224061i","DOIUrl":"https://doi.org/10.6060/mhc224061i","url":null,"abstract":"","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":"1 1","pages":""},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71167564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
G. G. Martirosyan, A. A. Hovhannisyan, A. S. Azizyan, G. Hovhannisyan, A. Iretskii
{"title":"Low Temperature Spectroscopic Study of the Sulfides Binding by Dioxygen Adduct of Cobalt Porphyrin","authors":"G. G. Martirosyan, A. A. Hovhannisyan, A. S. Azizyan, G. Hovhannisyan, A. Iretskii","doi":"10.6060/mhc214035m","DOIUrl":"https://doi.org/10.6060/mhc214035m","url":null,"abstract":"","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":"1 1","pages":""},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71167775","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wei Tang, Yuanyuan Qiu, Xiaonan Li, Rodah Soy, J. Mack, T. Nyokong, Xu Liang
Supporting Information for article. Earth-abundant first row transition metal corrole complexes have played an important role in fundamental research due to their unique molecular structures and attractive properties. In comparison to porphyrins, corroles have three inner N-H protons and are ring-contracted with a smaller macrocyclic cavity. First row transition metal corroles have been widely used as effective electrochemical catalysts for small molecule activations, such as hydrogen evolution, oxygen reduction/evolution and CO2 reduction reactions (HERs, ORRs/OERs and CO2 RRs) through homogenous and/or heterogenous prodecures. Several strategies have been used to modulate the catalytic efficiency of synthetic metallocorroles.
{"title":"pH-Dependent Electrochemically Catalyzed Oxygen Reduction Behaviors of o-Substituted Co (III) Corroles Research Data.pdf","authors":"Wei Tang, Yuanyuan Qiu, Xiaonan Li, Rodah Soy, J. Mack, T. Nyokong, Xu Liang","doi":"10.6060/mhc200183l","DOIUrl":"https://doi.org/10.6060/mhc200183l","url":null,"abstract":"Supporting Information for article. \u0000\u0000Earth-abundant first row transition metal corrole\u0000complexes have played an important role in fundamental research due to their\u0000unique molecular structures and attractive properties. In comparison to\u0000porphyrins, corroles have three inner N-H protons and are ring-contracted with\u0000a smaller macrocyclic cavity. First row transition metal corroles have been\u0000widely used as effective electrochemical catalysts for small molecule\u0000activations, such as hydrogen evolution, oxygen reduction/evolution and CO2\u0000reduction reactions (HERs, ORRs/OERs and CO2 RRs) through homogenous and/or\u0000heterogenous prodecures. Several strategies have been used to modulate the\u0000catalytic efficiency of synthetic metallocorroles.","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":"1 1","pages":""},"PeriodicalIF":1.4,"publicationDate":"2020-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43475912","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
O. Dmitrieva, M. O. Koifman, Ulyana M. Derbyshina, N. Chizhova, N. Mamardashvili
Processes of axial coordination of small organic molecules (imidazole, histidine, methyl ethers of p-aminobenzoic acid and valine) with Zn(II)-tetraarylporphyrins with different numbers of chlorine and bromine atoms in pyrrole and phenyl fragments of the macrocycle were studied by the methods of spectrophotometric titration and 1 H NMR spectroscopy. Using quantum chemical calculations, the degree of distortion of the porphyrin macrocycle was determined as halogen atoms were consistently introduced into the macrocycle and the structures of the axial complexes of the studied zinc porphyrinates with ligands of various nature were optimized. The stability constants of the obtained complexes were calculated and a correspondence was found between the experimental, thermodynamic and calculated values of the Zn-L bond energy in the corresponding complexes.
{"title":"The Effect of Selective Halogenation of Tetrapyrrolic Macrocycle on Binding Ability of Zn-Tetraarylporphyrins towards Small Organic Molecules","authors":"O. Dmitrieva, M. O. Koifman, Ulyana M. Derbyshina, N. Chizhova, N. Mamardashvili","doi":"10.6060/mhc191282m","DOIUrl":"https://doi.org/10.6060/mhc191282m","url":null,"abstract":"Processes of axial coordination of small organic molecules (imidazole, histidine, methyl ethers of p-aminobenzoic acid and valine) with Zn(II)-tetraarylporphyrins with different numbers of chlorine and bromine atoms in pyrrole and phenyl fragments of the macrocycle were studied by the methods of spectrophotometric titration and 1 H NMR spectroscopy. Using quantum chemical calculations, the degree of distortion of the porphyrin macrocycle was determined as halogen atoms were consistently introduced into the macrocycle and the structures of the axial complexes of the studied zinc porphyrinates with ligands of various nature were optimized. The stability constants of the obtained complexes were calculated and a correspondence was found between the experimental, thermodynamic and calculated values of the Zn-L bond energy in the corresponding complexes.","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":"1 1","pages":""},"PeriodicalIF":1.4,"publicationDate":"2020-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71165948","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
His parents immigrated to South Africa in 1952 where he completed his school and university education, and earned his PhD degree at the formerly known Potchefstroom University (now the University of the North-West) while working with Professor Jan van den Berg. Thereafter, he worked as post-doc with Professor Gordon M. Harris at SUNY at Buffalo, USA (1972 and 1978) and as an Alexander von Humboldt Fellow (1977) he joined Professor Hartwig Kelm at the Goethe University, Frankfurt am Main, Germany. At the end of 1979 he moved with his family to Frankfurt am Main, where he completed his Habilitation in Physical Chemistry in 1982. After faculty positions at the Private University of Witten-Herdecke (Full Professor in Inorganic Chemistry 1987-1994), and at the Friedrich-Alexander University Erlangen-Nuremberg (Chair of Inorganic and Analytical Chemistry 1994-2010) he retired in 2010, and joined the Faculties of Chemistry of the Jagiellonian University in Krakow and the Nicolaus Copernicus University in Torun, Poland, where he is still working full time and continuing his research actively. He has published 175 research papers, reviews and monographs in refereed journals during the period after his retirement. Rudi is the recipient of many awards and honors in chemistry, including Honorary Doctor of Science, Potchefstroom University, South Africa (1997), Honorary Doctor of Science, University of Kragujevac, Serbia (2006), Honorary Fellow of the Royal Society of South Africa (2007), Federal Cross of Merit (‘Bundesverdienstkreuz’) awarded by the Federal President of Germany (2009), Inorganic Mechanisms Award, Royal Society of Chemistry, London (2009), Honorary Doctor of Science, Jagiellonian University, Krakow, Poland (2010), Honorary Doctor of Science, University of Pretoria, South Africa (2010), Honorary Doctor of Science, Ivanovo State University of Chemistry and Technology, Russia (2012) and Alumni Award – Research Category from the North-West University, South Africa (2017). Despite his numerous achievements he has always been a down to earth person with wise and well balanced personality. In many of his award addresses we found Rudi acclaiming the contributions of others including his co-workers and collaborators.
他的父母于1952年移民到南非，在那里他完成了他的中学和大学教育，并在以前的Potchefstroom大学(现在的西北大学)获得了博士学位，同时与Jan van den Berg教授一起工作。此后，他在美国纽约州立大学布法罗分校跟随Gordon M. Harris教授做博士后(1972年和1978年)，并作为Alexander von Humboldt研究员(1977年)与德国法兰克福歌德大学Hartwig Kelm教授一起工作。1979年底，他随家人搬到美因河畔的法兰克福，并于1982年在那里完成了物理化学的培训。在Witten-Herdecke私立大学(1987-1994年无机化学全职教授)和Erlangen-Nuremberg弗里德里希-亚历山大大学(1994-2010年无机和分析化学系主任)担任教职后，他于2010年退休，加入了克拉科夫雅盖隆大学化学系和波兰托伦尼古拉斯哥白尼大学化学系，他仍然全职工作并积极继续他的研究。退休后，在权威期刊上发表研究论文、评论和专著175篇。Rudi在化学领域获得了许多奖项和荣誉，包括南非Potchefstroom大学荣誉科学博士(1997年)，塞尔维亚克拉古耶瓦茨大学荣誉科学博士(2006年)，南非皇家学会荣誉院士(2007年)，德国联邦总统颁发的联邦功绩十字勋章(“Bundesverdienstkreuz”)(2009年)，伦敦皇家化学学会无机机制奖(2009年)，荣誉科学博士，英国化学学会荣誉化学博士。波兰克拉科夫雅盖隆尼亚大学(2010年)，南非比勒陀利亚大学荣誉科学博士(2010年)，俄罗斯伊万诺沃州立化学技术大学荣誉科学博士(2012年)和南非西北大学校友奖-研究类(2017年)。尽管他取得了许多成就，但他一直是一个脚踏实地的人，具有智慧和平衡的个性。在他的许多获奖致辞中，我们发现鲁迪赞扬了其他人的贡献，包括他的同事和合作者。
{"title":"Rudi van Eldik – Kinetics Extraordinaire","authors":"Debabrata Chatterjee, S. V. Makarov","doi":"10.6060/mhc202011e","DOIUrl":"https://doi.org/10.6060/mhc202011e","url":null,"abstract":"His parents immigrated to South Africa in 1952 where he completed his school and university education, and earned his PhD degree at the formerly known Potchefstroom University (now the University of the North-West) while working with Professor Jan van den Berg. Thereafter, he worked as post-doc with Professor Gordon M. Harris at SUNY at Buffalo, USA (1972 and 1978) and as an Alexander von Humboldt Fellow (1977) he joined Professor Hartwig Kelm at the Goethe University, Frankfurt am Main, Germany. At the end of 1979 he moved with his family to Frankfurt am Main, where he completed his Habilitation in Physical Chemistry in 1982. After faculty positions at the Private University of Witten-Herdecke (Full Professor in Inorganic Chemistry 1987-1994), and at the Friedrich-Alexander University Erlangen-Nuremberg (Chair of Inorganic and Analytical Chemistry 1994-2010) he retired in 2010, and joined the Faculties of Chemistry of the Jagiellonian University in Krakow and the Nicolaus Copernicus University in Torun, Poland, where he is still working full time and continuing his research actively. He has published 175 research papers, reviews and monographs in refereed journals during the period after his retirement. Rudi is the recipient of many awards and honors in chemistry, including Honorary Doctor of Science, Potchefstroom University, South Africa (1997), Honorary Doctor of Science, University of Kragujevac, Serbia (2006), Honorary Fellow of the Royal Society of South Africa (2007), Federal Cross of Merit (‘Bundesverdienstkreuz’) awarded by the Federal President of Germany (2009), Inorganic Mechanisms Award, Royal Society of Chemistry, London (2009), Honorary Doctor of Science, Jagiellonian University, Krakow, Poland (2010), Honorary Doctor of Science, University of Pretoria, South Africa (2010), Honorary Doctor of Science, Ivanovo State University of Chemistry and Technology, Russia (2012) and Alumni Award – Research Category from the North-West University, South Africa (2017). Despite his numerous achievements he has always been a down to earth person with wise and well balanced personality. In many of his award addresses we found Rudi acclaiming the contributions of others including his co-workers and collaborators.","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":"1 1","pages":""},"PeriodicalIF":1.4,"publicationDate":"2020-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71166029","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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