{"title":"Enhancing CO<sub>2</sub> Electroreduction to Ethylene in Acidic Solution by Optimizing Cation Configuration on the Cu Surface.","authors":"Yaoyu Yin, Zhongnan Ling, Shiqiang Liu, Jiapeng Jiao, Yiyong Wang, Yaguang Peng, Xing Tong, Meng Zhou, Rongjuan Feng, Xueqing Xing, Yi Xu, Qinggong Zhu, Xiaofu Sun, Mingchuan Luo, Xinchen Kang, Buxing Han","doi":"10.1021/jacs.5c06402","DOIUrl":"https://doi.org/10.1021/jacs.5c06402","url":null,"abstract":"<p><p>The electroreduction of CO<sub>2</sub> to C<sub>2</sub>H<sub>4</sub> offers a promising avenue for advancing carbon neutrality and promoting sustainable chemical manufacturing. In acidic environments, while long-term operational stability and CO<sub>2</sub> utilization efficiency are enhanced, the formation of C-C bonds is hindered due to the weak adsorption of *CO intermediates and the competing hydrogen evolution reaction (HER). Theoretical studies suggest that K<sup>+</sup> cations with reduced bound water content can strengthen the adsorption of the critical *CO intermediate, and that elevated K<sup>+</sup> concentrations on the Cu electrode surface significantly facilitate CO<sub>2</sub> electroreduction to C<sub>2</sub>H<sub>4</sub>. In this work, a catalyst termed Cu<sub>TEA</sub> was developed by strategically modifying the Nafion ionomer distribution within the catalyst layer. This structural adjustment effectively lowers the bound water associated with K<sup>+</sup> cations and concurrently elevates the surface concentration of K<sup>+</sup> on the Cu electrode, thereby promoting C-C coupling for C<sub>2</sub>H<sub>4</sub> formation while suppressing HER. Consequently, Cu<sub>TEA</sub> achieves a Faradaic efficiency of 70.2% for C<sub>2</sub>H<sub>4</sub> production, accompanied by a high partial current density of 561.6 mA cm<sup>-2</sup> in an acidic electrolyte (pH = 1).</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144606854","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Austin D Ready, Varun Tej Raviprolu, Tyler A Kerr, Joseph W Treacy, Mei L Matsumoto, Prairie E Hammer, Ellen M Sletten, K N Houk, Alexander M Spokoyny
{"title":"Carboranes without Cage Carbons: <i>closo</i>-Dodecaborate Mimics of Neutral <i>closo</i>-Carboranes.","authors":"Austin D Ready, Varun Tej Raviprolu, Tyler A Kerr, Joseph W Treacy, Mei L Matsumoto, Prairie E Hammer, Ellen M Sletten, K N Houk, Alexander M Spokoyny","doi":"10.1021/jacs.5c05637","DOIUrl":"https://doi.org/10.1021/jacs.5c05637","url":null,"abstract":"<p><p>Substituted two-dimensional aromatic systems, such as arenes, exhibit well-established reactivity patterns at specific sites, largely due to the pronounced electronic directing effects of attached substituents. In contrast, the regioselectivity of three-dimensional aromatic molecules as a function of substituents remains less understood and documented. In this work, we demonstrate that a series of <i>closo</i>-dodecaborate ([B<sub>12</sub>H<sub>12</sub>]<sup>2-</sup>) cluster isomers containing two -NMe<sub>3</sub><sup>+</sup> moieties exhibit unprecedented regioselective reactivity at boron vertices farthest from the charged substituents. Through a combination of theoretical and experimental studies, we reveal that these boron clusters display near-perfect regioselectivity with multiple electrophiles, ultimately enabling vertex differentiation chemistry within these systems. This observed phenomenon closely parallels the reactivity patterns typically associated with icosahedral <i>closo</i>-carboranes, where a carbon-based vertex induces a strong electronic dipole, leading to pronounced vertex-specific reactivity differences at boron sites. Our findings suggest that these modified <i>closo</i>-dodecaborates serve as electronic analogs of neutral <i>closo</i>-carboranes, achieving similar electronic directing effects without the need for cage-based carbon atoms. Instead, exopolyhedral substituents alone govern the regioselective behavior, expanding the potential for tailored functionalization in boron cluster chemistry.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144606849","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jasleen K Bindra, Daniel Malinowski, Bernardo Salcido-Santacruz, Guiying He, Matthew Y Sfeir, Luis M Campos, Jens Niklas, Oleg G Poluektov
{"title":"Elucidating Quintet-State Dynamics in Singlet Fission Oligomers and Polymers with Tetracene Pendants.","authors":"Jasleen K Bindra, Daniel Malinowski, Bernardo Salcido-Santacruz, Guiying He, Matthew Y Sfeir, Luis M Campos, Jens Niklas, Oleg G Poluektov","doi":"10.1021/jacs.5c07136","DOIUrl":"https://doi.org/10.1021/jacs.5c07136","url":null,"abstract":"<p><p>To unlock the potential of molecular engineering for practical quantum sensing and computing, it is essential to create and control pure magnetic states in molecular systems. Singlet fission (SF) in organic materials offers a promising approach by generating pairs of triplet excited states from photoexcited singlets. In this work, we investigate SF in a polymer with strategically positioned tetracene pendant groups along a polynorbornene backbone and its oligomeric counterparts, facilitating intrapolymer through-space coupling. Using continuous-wave and pulsed time-resolved electron paramagnetic resonance (EPR) spectroscopy, we elucidate the spin dynamics and identify key intermediates, including the quintet state, that emerge during SF. Our findings reveal that exciton translational motion along the pendant groups enhances the dissociation of triplet pairs, with oligomer length playing a critical role in modulating spin state interconversion and exciton transport. Our results provide key insights into the SF mechanism in polymeric materials and highlight the role of oligomer length in modulating spin state interconversion and exciton transport. This work advances our understanding of SF in polymers, paving the way for their application in quantum information science and energy conversion technologies.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144606852","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"(Hetero)anilines from Dinitrogen Via Nucleophilic Aromatic Substitution at Tungsten Nitrido Complexes.","authors":"Lukas Eberle, Joachim Ballmann","doi":"10.1021/jacs.5c06407","DOIUrl":"https://doi.org/10.1021/jacs.5c06407","url":null,"abstract":"<p><p>A protocol for the arylation of both N atoms in dinitrogen is presented. This protocol relies on the use of tungsten pincer complexes to split N<sub>2</sub> and generate tungsten nitrides, which were shown to undergo nucleophilic aromatic substitution (S<sub>N</sub>Ar) reactions with electron-deficient aryl chlorides. Starting from (<sup>15</sup>N)<sub>2</sub>, this two-step process was exploited for the preparation of different <sup>15</sup>N-labeled aryl amines.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144612042","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lin Yang, Youqi Chu, Yitian Feng, Yongbiao Mu, Lingfeng Zou, Chao Li, Chaozhu Huang, Huicun Gu, Chi Li, Qing Zhang, Lin Zeng
{"title":"Breaking Voltage Limitations: Triethyl Phosphate-Engineered PVDF-Based Electrolytes with Dual-Interphase Stabilization for 4.7 V-Class Quasi-solid-state Lithium Metal Batteries.","authors":"Lin Yang, Youqi Chu, Yitian Feng, Yongbiao Mu, Lingfeng Zou, Chao Li, Chaozhu Huang, Huicun Gu, Chi Li, Qing Zhang, Lin Zeng","doi":"10.1021/jacs.5c08493","DOIUrl":"https://doi.org/10.1021/jacs.5c08493","url":null,"abstract":"<p><p>The advancement of high-voltage solid-state electrolytes constitutes a pivotal challenge for realizing practical solid-state lithium metal batteries (SSLMBs). This work overcomes intrinsic voltage constraints in conventional dimethylformamide-processed poly(vinylidene fluoride) quasi-solid-state polymer electrolytes (SPEs) through molecular engineering of triethyl phosphate (TEP) as a high-band-gap solvent. First-principles calculations demonstrate TEP's exceptional frontier orbital configuration, featuring a 9.4 eV HOMO-LUMO gap, thus expanding the electrochemical window to 4.8 V, an enhancement of 0.5 V compared to DMF-based systems (4.3 V). Leveraging this design, the optimized SPEs enable the stable operation of Li||NCM811 cells at ultrahigh voltages up to 4.7 V. Remarkably, these cells exhibit excellent long-term cycling stability, capacity retentions of 88.2% (1800 cycles at 4.2 V) and 86.8% (900 cycles at 4.5 V) are achieved. Even under the ultrahigh voltage of 4.7 V, the batteries maintain remarkable cycling stability, successfully completing 500 cycles and showcasing exceptional performance. Multiscale analysis reveals dual interfacial stabilization mechanisms: a TEP-derived Li<sub>3</sub>PO<sub>4</sub>-rich cathode interphase suppressing structural degradation coupled with a 25 nm crystalline Li<sub>2</sub>O-dominated anode interphase inhibiting dendrites. This molecular design paradigm establishes a pathway toward 4.7 V-class SSLMBs through interfacial architecture stabilization.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144612043","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Deesha D Malik, Shilpa Bhatia, Maike N Lundahl, Haley N Bautel, Dylan M Rogers, Werner Kaminsky, Julie A Kovacs
{"title":"Intramolecular Oxo Atom Migration to the <i>cis</i> Thiolate Sulfur of an Fe-Oxo Intermediate.","authors":"Deesha D Malik, Shilpa Bhatia, Maike N Lundahl, Haley N Bautel, Dylan M Rogers, Werner Kaminsky, Julie A Kovacs","doi":"10.1021/jacs.5c04340","DOIUrl":"https://doi.org/10.1021/jacs.5c04340","url":null,"abstract":"<p><p>Herein, we show for the first time that thiolate ligands can play an important role in promoting 2e- oxo atom transfer with nonheme iron. We examine the mechanism of oxo atom transfer to a <i>cis</i> thiolate sulfur for two structurally related iron complexes using low-temperature kinetics, spectroscopic, and computational methods. Intermediate oxo atom donor adducts, FeOIAr, are spectroscopically characterized and shown to have electronic spectral, EPR, and Mössbauer parameters, and kinetic barriers dependent on the nature of the oxo atom donor. More stable adducts containing pyridine N-oxide (PNO) were crystallographically characterized and computationally optimized to establish optimum functionals and basis sets. Oxo atom transfer is shown both experimentally and computationally to involve a stepwise, as opposed to a concerted, mechanism. A new metastable intermediate is observed by low-temperature Mössbauer and ⊥-mode EPR after the Fe-O<sub><i>x</i></sub>IPh intermediate and prior to the final sulfenate Fe-OSR product. The DFT calculated minimum energy pathway is shown to contain a local minimum between the Fe-O<sub>2</sub>IPh adduct and Fe-S(R)O product. The DFT optimized geometric and electronic structure of this intermediate is shown to be consistent with an <i>S</i> = 1 Fe(IV)═O that is antiferromagnetically coupled to an <i>S</i> = 1/2 radical delocalized over the two cis thiolate-sulfurs, analogous to the electronic configuration of P450 Cmpd I. Radical character on the thiolate sulfur adjacent to the oxo is shown to facilitate trapping of the high-valent Fe-oxo as a η<sup>2</sup>-SO-Fe sulfenate complex.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144612048","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Seungcheol Han, Yeosan Lee, Jaeyoon Seo, Junseok Lee, Seung Hwan Cho
{"title":"[1,3]-Hydride Shift in α-Boryl Cations: Strategic Design of Fluorine-Triggered Cyclopropanation.","authors":"Seungcheol Han, Yeosan Lee, Jaeyoon Seo, Junseok Lee, Seung Hwan Cho","doi":"10.1021/jacs.5c08276","DOIUrl":"https://doi.org/10.1021/jacs.5c08276","url":null,"abstract":"<p><p>Hydride shift represents an important process in carbocation chemistry, yet controlled access to the [1,3]-hydride shift has remained elusive despite its potential synthetic utility. Here, we report direct observation and synthetic demonstration of the [1,3]-hydride shift using α-fluoro-diborylalkanes. Initial [1,2]-fluoride migration generates an α-boryl cation that selectively undergoes a [1,3]-hydride shift via a three-center two-electron interaction, enabling efficient synthesis of cyclopropyl boronic esters. Deuterium labeling experiments and computational studies reveal the key electronic factors governing this unusual selectivity. The methodology provides both mechanistic insights into longer-range hydride shifts and a practical platform for accessing diverse molecular architectures through versatile transformations of the resulting cyclopropyl boronic esters.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144606843","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zi-Wang Wei, Phillip Daniel-Ivad, Li Zhang, Katherine S Ryan
{"title":"Structure and Mechanism of the Azomycin Biosynthetic Enzyme RohQ That Catalyzes a Spontaneous Cyclodehydration.","authors":"Zi-Wang Wei, Phillip Daniel-Ivad, Li Zhang, Katherine S Ryan","doi":"10.1021/jacs.5c04341","DOIUrl":"https://doi.org/10.1021/jacs.5c04341","url":null,"abstract":"<p><p>RohQ from the azomycin biosynthetic pathway catalyzes a spontaneous cyclodehydration to form 2-aminoimidazole. Here we report the structure and mechanism of RohQ and use a serendipitously bound imidazole to pinpoint active site residues. We propose that catalysis occurs at the dimeric interface using two key aspartic acid residues for proton transfer steps to accelerate 3 × 10<sup>4</sup>-fold intramolecular cyclization of a guanidino group and aldehyde, releasing water. Our work expands our understanding of <i>de novo</i> emerged enzymes and provides the first structural and mechanistic view of a yet-unexplored protein family.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144612049","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Biomimetic Sandwich-Structured Tubular Ion Pump Arrays for Lithium Metal Batteries.","authors":"Shang-Qi Li, Zhenzhen Wang, Xiaoyang Zheng, Mao-Lin Guo, Jia-Ning Yang, Yong Li, Zhefei Sun, Xue-Yan Wu, Chaofei Guo, Han Tian, Hui Zong, Liang Gao, Yao-Wen Zhang, Jing-Zhe Wan, Jia-Xi Xu, Qiaobao Zhang, Kai-Xue Wang, Jie-Sheng Chen","doi":"10.1021/jacs.5c08237","DOIUrl":"https://doi.org/10.1021/jacs.5c08237","url":null,"abstract":"<p><p>Controlling the rapid, uniform deposition and efficient, stable stripping of Li is crucial for achieving durable high-energy-density Li-metal batteries. Herein, unique biomimetic sandwich-structured tubular ion pump arrays achieved by sandwiching ZnSe nanoparticle tubes between ultrathin N-doped graphene-like layers and vertically aligning on N-doped graphene-Ni foam (NG@ZnSe@NG) are reported, working as a highly efficient and robust Li host for homogeneous and stable Li plating/stripping. After complete lithiation, such a biomimetic tubular ion pump featuring symmetric inner and outer layers with high ion-electron transport rates and a key self-accelerating middle layer is generated, accelerating uniform Li deposition into the interior and efficient stripping of Li from the cavity. Furthermore, the formation process and unique operating mechanism of the ion pump are elucidated in detail across multiple scales using <i>in situ</i> X-ray diffraction (XRD) analyses, <i>in situ</i> transmission electron microscopy (TEM) observations, and theoretical calculations. An ultrahigh Coulombic efficiency of 99.2% over 1100 cycles in asymmetric cells and an ultralong lifespan of 4970 h in symmetric cells are achieved. When assembled with LiFePO<sub>4</sub> and O<sub>2</sub> cathodes into coin cells, exceptional electrochemical performance is exhibited. Remarkably, under harsh conditions, the NG@ZnSe@NG@Li||NCM83 pouch cell maintains 85.4% capacity retention after 130 cycles at 0.5 C (2.5 mA cm<sup>-2</sup>), demonstrating excellent stability and reliability in industrial applications.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144606847","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jinhyeong Jang, Yuzi Liu, David J Gosztola, Ivan Kuzmenko, Jens Niklas, Oleg G Poluektov, Byeongdu Lee, Elena A Rozhkova
{"title":"Photosynthetic Biohybrid System for Enhanced Abiotic N<sub>2</sub>-to-NH<sub>3</sub> Conversion under Ambient Conditions.","authors":"Jinhyeong Jang, Yuzi Liu, David J Gosztola, Ivan Kuzmenko, Jens Niklas, Oleg G Poluektov, Byeongdu Lee, Elena A Rozhkova","doi":"10.1021/jacs.5c08453","DOIUrl":"https://doi.org/10.1021/jacs.5c08453","url":null,"abstract":"<p><p>Photosynthetic biohybrid systems (PBSs) offer an eco-friendly approach to transforming solar energy into value-added products by integrating biological entities with inorganic semiconductors. However, the chemical conversion capacity of most PBSs has inherent limitations, as whole-cell bacteria and isolated enzymes require fine-tuning of environmental conditions. Here, we report a new PBS developed by introducing free-standing ceria nanoparticles into the purple membrane (PM) of <i>Halobacterium salinarum</i> archaea, which can unidirectionally transfer charge carriers in response to incident photons, even after separation from living archaea at various conditions. Our microscopy, spectroscopy, and synchrotron X-ray scattering analyses confirm that the electrostatic assembly between ceria and PM creates seamless interfacial contact, thereby enhancing the photocatalytic capacity of ceria. Although the conversion of dinitrogen (N<sub>2</sub>) to ammonia (NH<sub>3</sub>) is thermodynamically challenging due to the triple bond in N<sub>2</sub> and a series of charge-transfer reactions, our PM-ceria (PMC) hybrid nanoparticle efficiently produces NH<sub>3</sub> by reducing N<sub>2</sub> using solar energy even under atmospheric pressure and room temperature while simultaneously converting glycerol into value-added derivatives. Additionally, our PMC nanoparticle involves neither toxic/precious metals nor bioengineering processes to achieve enhanced photocatalytic N<sub>2</sub>-to-NH<sub>3</sub> conversion. This study sheds light on the new aspect of PBSs by employing PM to potentially resolve the global energy and environmental challenges posed by the conventional Haber-Bosch process.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144606861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}