ACS Catalysis 最新文献

{"title":"CuZnOx Active Sites Anchored on the Silanols of Hollow Silicalite-1 Zeolite Enhance CO2 Hydrogenation to Methanol","authors":"Xianglong Meng, Chunzheng Wang, Soryong Chae, Yanjiao Wang, Chao Wu, Shibo Xi, Enrico Catizzone, Girolamo Giordano, Hailing Guo, Svetlana Mintova","doi":"10.1021/acscatal.4c07257","DOIUrl":"https://doi.org/10.1021/acscatal.4c07257","url":null,"abstract":"The confinement effect of zeolites has proven to be an effective method for enhancing the catalyst stability and activity. Herein, we employed an in situ defect-capture strategy to encapsulate CuZnO_<i>x</i> species within the cavities of hollow silicalite-1 (H-S-1) zeolite. Initially, alkali etching of silicalite-1 crystals generated unsaturated silicon species, which then captured metal oxides (i.e., CuO and ZnO) on the zeolite surface. These metal oxides, carried by unsaturated silicon, subsequently migrated into the zeolite cavities of the hollow S-1 crystals, while a pure silicon shell was formed on the external surface of zeolite. The metal species were anchored on the silanol sites, leading to the reconstruction of ultrasmall bimetallic nanoparticles (∼ 2.2 nm) and preventing their aggregation. The resulting catalyst, CuO-ZnO_<i>x</i>@H-S-1, exhibited high metal dispersion (37.1%) with loadings of 5.8 wt % Cu and 5.0 wt % Zn. In the CO₂ hydrogenation to methanol reaction at 240 °C and 3 MPa, this catalyst maintained an 85% selectivity toward methanol with a CO₂ conversion rate of 9.6%, achieving a methanol yield per unit mass of Cu of 1.6 g_MeOH g_Cu^–1 h^–1. Moreover, the CuO-ZnO_<i>x</i>@H-S-1 catalyst demonstrated high stability without deactivation over 200 h. In situ infrared spectroscopy confirmed that methanol formation followed the formate reaction pathway, with highly dispersed Cu and ZnO_<i>x</i> increasing the abundance of the active CuZnO_<i>x</i> interface, thereby promoting the rapid conversion of HCOO* to H₃CO* intermediates. This study presents an approach for preparing high-loading, bimetallic catalysts within zeolites, offering an effective strategy for stabilizing metals under harsh reaction conditions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"86 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654002","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":"Modular Chemoenzymatic Cascade for Highly Diastereo- and Enantioselective Synthesis of 1,3-Disubstituted Tetrahydroisoquinolines","authors":"Honghui Zhang, Yan Zhang, Changtong Zhu, Zhiwei Deng, Luyun Ji, Dejing Yin, Changmei Liu, Zhengshan Luo, Zhenbo Yuan, Yijian Rao","doi":"10.1021/acscatal.5c01322","DOIUrl":"https://doi.org/10.1021/acscatal.5c01322","url":null,"abstract":"1,3-Disubstituted tetrahydroisoquinolines (THIQs) are widespread structural skeletons among alkaloid natural products with diverse biological activities. The lack of their unambiguous biosynthetic pathways to produce these structures has, however, impeded their efficient production through environmentally friendly biosynthesis. Herein, a modular chemoenzymatic cascade has been developed to circumvent this limitation for the synthesis of various 1,3-disubstituted THIQs bearing two stereo carbon centers with high diastereo- and enantioselectivities after the semirational design of the imine reductase <i>Sn</i>IR. More importantly, the preparative stereodivergent synthesis of both <i>cis</i>- and <i>trans</i>-1,3-disubstituted THIQs is achieved through the plug-and-play strategy. Therefore, this work highlights the promising potential of modular chemoenzymatic strategies for the preparation of a series of value-added products and derivatives through synthetic biology.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"56 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654003","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":"FADS-Based Directed Evolution of a Robust Bst DNA Polymerase Adapting High-Temperature Loop-Mediated Isothermal Amplification (HT-LAMP)","authors":"Xiao Li, Qiongwei Tang, Jingjie Jiang, Yuepeng Shang, Zelin Lu, Mingli Chen, Jiajia He, Feng Liu, Sisi Zhu, Zengping Zhang, Hui Han, Xixi Yu, Qiuxian Li, Yuansong Xiu, Yuhong Yang, Ping Gui, Xuefeng Wang, Feng Lu, Wei Jing, Langping Xu, Yanna Lin, Xinglong Wang, Shu Quan, Xiang Liu, Huancai Yin, Fuqiang Ma","doi":"10.1021/acscatal.4c07614","DOIUrl":"https://doi.org/10.1021/acscatal.4c07614","url":null,"abstract":"Bst DNA polymerase is a key enzyme used in both molecular diagnosis and scientific research. Employing the fluorescence-activated droplet sorting (FADS) technique, we successfully evolved a suboptimal wild-type Bst DNA polymerase into practically valuable mutants through directed evolution. The mutants exhibited significantly improved thermostability and strand displacement capability, enabling much better loop-mediated isothermal amplification (LAMP) performance, with a faster reaction speed (reduced from 40 to 10 min) and a highly stable solid reagent that remained stable for 2 months at 50 °C. Moreover, these robust mutants facilitated high-temperature LAMP assays at 70 °C, thereby eliminating the common issue of false positives in LAMP assays. To better understand the molecular mechanism behind the strand displacement capability, we proposed the strand displacement index (SDI) as a parameter to quantify this property. We also proposed the “hydrophobic blade” hypothesis, providing insights into the mechanism underlying enhanced strand displacement capability. This work serves as a successful example of molecular engineering and LAMP applications of the Bst DNA polymerase.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"11 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640007","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":"Origin of Electrocatalytic Selectivity during the Oxygen Reduction Reaction on Au(111)","authors":"Elias Diesen, Alexandra M. Dudzinski, Karsten Reuter, Vanessa J. Bukas","doi":"10.1021/acscatal.4c04413","DOIUrl":"https://doi.org/10.1021/acscatal.4c04413","url":null,"abstract":"A puzzling observation during the oxygen reduction reaction (ORR) on weak-binding electrodes such as Au is the preference to form hydrogen peroxide (H₂O₂) instead of the thermodynamically favored water product. This selectivity cannot be explained on the basis of thermodynamic reaction models that simply assume a series of proton-coupled electron transfers (PCETs). Here, we use ab initio molecular dynamics along with umbrella sampling to obtain free energy profiles for competing key ORR steps on Au(111). Our comparison includes not only PCETs but also “chemical” reaction steps that do not include an explicit faradaic charge transfer, such as desorption or surface dissociation. This allows one to explore favorable reaction paths while varying the capacitive charging to represent realistic ORR potentials. Our results show that all reaction steps competing with H₂O₂ formation have sizable kinetic barriers and are thus prohibited, even though they may be thermodynamically favored. We find that this situation does not change under more reducing conditions and specifically determines the “nobleness” of Au as playing a decisive role in preventing O–O bond scission. It is thus not the applied potential but the underlying chemistry that drives the ORR selectivity. Our study overall further highlights the kinetic competition between PCET and non-PCET steps that cannot be resolved via simple Bro̷nsted–Evans–Polanyi scaling relations.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"183 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654000","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":"Surface Structure-Dependent Mechanistic Modulation of the Selective Oxidative Dehydrogenation of Ethane with CO2 over Iron Oxide Catalysts","authors":"Li Kang, Feigang Zhao, Jingyang Zhang, Tiantian Xiao, Shengping Wang, Xinbin Ma","doi":"10.1021/acscatal.4c08099","DOIUrl":"https://doi.org/10.1021/acscatal.4c08099","url":null,"abstract":"The selective oxidative dehydrogenation of ethane with CO₂ (CO₂–ODHE) catalyzed by iron oxide (FeO_<i>x</i>) provides a CO₂-utilizing route for ethylene production, simultaneously utilizing greenhouse gases and enabling the efficient conversion of light alkanes. However, the diverse phases formed by FeO_<i>x</i> catalysts under the reaction conditions expose surface structures with distinct Fe and O atom arrangements, complicating the identification of reactive active sites. In this study, we demonstrate the pivotal role of surface structures of FeO_<i>x</i> catalysts in governing the ethylene formation activity and selectivity. Among various phases, Fe₃O₄ with octahedrally coordinated Fe terminations (Fe₃O₄–B2) is characterized by frustrated Lewis pair (FLP) and low oxygen vacancy formation energy, which synergistically promote ethane activation and facilitate the CO₂-mediated regeneration of active sites via the Mars-van Krevelen mechanism. Additionally, the coordination geometry of surface Fe atoms optimizes the interaction between the Fe 4s orbitals and the π* orbitals of the ethyl group (C₂H₅), stabilizing C₂H₅ adsorption. This electronic stabilization is complemented by spatial confinement imposed by FLP, effectively suppressing C₂H₅ migration and inhibiting the formation of CH₃CH intermediates in the dry reforming of ethane, thereby enhancing the ethylene selectivity. The synergistic role of electronic and geometric effects of the Fe₃O₄–B2 surface structure remarkably enhances ethylene selectivity while maintaining high catalytic activity. These findings provide mechanistic insights into the structure–activity–selectivity relationships of FeO_<i>x</i> catalysts and offer a solid theoretical foundation for designing advanced catalysts for efficient, CO₂-integrated hydrocarbon conversion.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"12 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640420","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":"Z-Selective Semihydrogenation of Alkynes Catalyzed by a Co(I)PCNHCP Pincer Complex: A Simple, Fast, and Practical Methodology","authors":"Tofayel Sheikh Mohammad, Pavel Sakharov, Sakthi Raje, Graham de Ruiter","doi":"10.1021/acscatal.5c00792","DOIUrl":"https://doi.org/10.1021/acscatal.5c00792","url":null,"abstract":"The stereoselective synthesis of alkenes from their corresponding internal alkynes is a highly desirable and atom-economical reaction that is typically performed via transfer hydrogenation. Very few practical methods have been developed that allow for the direct hydrogenation of alkynes under mild reaction conditions and with high stereoselectivities. Here, we demonstrated that a well-defined cobalt catalyst [(PC_NHCP)Co(N₂)][BAr₄^F] (<b>1</b>) catalyzes the semihydrogenation of alkynes under mild conditions (25 °C; 1 bar H₂) and with high stereoselectivities (&gt;99:1). The reaction does not require any additives, is fast (&lt;60 min), and is compatible with a variety of functional groups that include aldehydes, ketones, esters, and alcohols. Even natural products can be used with our hydrogenation protocol highlighting its versatility. Our mechanistic studies indicate the presence of a transient Co(III)-dihydride that is responsible for the hydrogenation of the herein reported internal and terminal alkynes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"55 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640419","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":"Influence of the Mn Promoter on the Composition and Activity of the Adsorbed Phase in the Carbon Paths of the CO Hydrogenation Reaction on 20 wt % Co/MnOx-Al2O3: An Operando-SSITKA and Transient Kinetic Study","authors":"Michalis A. Vasiliades, Denzil Moodley, Renier Crous, Jana Potgieter, Thys Botha, Angelos M. Efstathiou","doi":"10.1021/acscatal.4c07921","DOIUrl":"https://doi.org/10.1021/acscatal.4c07921","url":null,"abstract":"Herein, we explored the influence of the Mn/Co molar ratio (0.011–0.268) on the composition and activity of the adsorbed phase established during CO hydrogenation at 230 °C (P_T = 1.2 bar) over a 20 wt % Co/MnO_<i>x</i>-Al₂O₃ industrially relevant catalyst as a function of time-on-stream, TOS (2–50 h). Correlations between surface coverages of active and inactive carbonaceous species, site activity (k, s^–1) for methanation and chain growth, and the Mn/Co molar ratio for optimum performance were derived. ¹³CO-SSITKA revealed that the Mn/Co molar ratio and TOS significantly influenced the dynamic net rate of CO chemisorption and that of −CH_<i>x</i> formation, θ_CO, θ_CHx, TOF_CH4, and k (s^–1) of methanation and chain growth kinetic parameters in a diverse way. An optimum Mn/Co ratio of 0.111 was found for chain growth (C₂–C₅ hydrocarbons) and which was related to the dependence of θ_CO and θ_CHx on the Mn/Co ratio. Dynamic hydrogen chemisorption at 100 °C and H₂-TPD studies indicated the increase of θ_H and alteration of H-chemisorption site distribution with increasing Mn/Co ratio. <i>Operando</i> DRIFTS-mass spectrometry transient hydrogenation of two linear type adsorbed CO-s revealed the influence of Mn/Co ratio on their relative hydrogenation activity (k), highlighting the importance of the population of CO chemisorption sites of lower hydrogenation activity toward methane. Structural and topological information for the presence of the MnO_<i>x</i> promoter in Co/γ-Al₂O₃ was obtained via HRTEM/EDX (RGB mapping). Highly dispersed MnO_<i>x</i> clusters were formed on the cobalt surface for low Mn/Co ratios (ca. 0.011), while for higher Mn/Co ratios both MnO_<i>x</i> particles surrounded the Co particles (10–12 nm) and Mn chemically interacted with the Co surface (e.g., Co-MnO clusters and agglomerates). It is proposed that optimum chain growth is the result of a balance between unpromoted and Mn-promoted cobalt surface regions for the present 20 wt % Co/MnO_<i>x</i>-Al₂O₃ catalytic system. This work paved the way for deriving reliable correlations between important kinetic parameters of CO hydrogenation that control the chain growth in FTS for Mn-based and other promoted Co-based FTS catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"54 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635467","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":"Coupling Plastic Upgrading and Photocatalysis: Catalytic Mechanisms and Design Principles","authors":"Zongyang Ya, Shengbo Zhang, Dong Xu, Hua Wang, Mei Li","doi":"10.1021/acscatal.5c00139","DOIUrl":"https://doi.org/10.1021/acscatal.5c00139","url":null,"abstract":"Converting plastic wastes into valuable chemicals and fuels provides an attractive alternative solution. However, current catalytic technologies often require rigorous conditions such as high temperature, high pressure, and caustic bases, resulting in high energy costs and secondary environmental contamination. Recently, integrating plastic upgrading with photocatalysis into one reaction system has been proven to be an effective approach that can sufficiently utilize photogenerated electrons and holes to achieve sustainable economic development. In this review, we summarize current advances in coupling plastic upgrading and photocatalysis by focusing on the catalyst selection, design principles of these integrated systems, including photoreforming H₂ evolution, photocoupling CO₂ reduction, and photo-oxidation, and the underlying catalytic mechanisms, including holes and reactive oxygen species mechanisms. We also assess the economic feasibility and environmental impact of these integrated technologies based on techno-economic analysis and life cycle assessment. The ongoing challenges and future research directions in this field are critically discussed. We believe that this review will inspire more creativity in designing such win–win coupled photoredox reaction systems.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"8 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640005","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":"Unlocking Isonitrile Insertion with N-Centered Radicals: A General Synthetic Strategy toward Quinazolinone Alkaloids by Synergistic Photo/Copper Catalysis","authors":"Xiaoyu Guo, Hui Wang, Zhongyan Hu, Yu Zhao, Jinhuan Dong, Kangbao Zhong, Yu Lan, Xianxiu Xu","doi":"10.1021/acscatal.5c00608","DOIUrl":"https://doi.org/10.1021/acscatal.5c00608","url":null,"abstract":"Significant progress has been achieved in radical isonitrile insertion reactions, yet the reactivity of isonitriles toward <i>N</i>-centered radicals remains underexplored. Herein, we report an efficient method that enables isonitrile insertion into <i>N</i>-centered radicals, facilitated by a synergistic photocatalyst/copper catalytic system. This insertion triggers a highly efficient cascade cyclization that constitutes a flexible strategy for synthesizing alkaloids with a fused quinolizinone scaffold. Alkaloids, including luotonin A, rutaecarpine, and 2-methoxy-13-methylrutaecarpine, along with 37 natural product-like molecules, were synthesized by this method in a single step, starting from readily synthesizable <i>ortho</i>-isocyano-<i>N</i>-tosylbenzamides as <i>N</i>-radical precursors. Mechanistic investigations, encompassing photophysical, electrochemical, Einstein–Podolsky–Rosen studies, and density functional theory calculations, imply that arylisonitrile-Cu(I) complexes serve as effective reductants, quenching the excited iridium photocatalyst via single-electron transfer at the onset of the reaction. Crucially, the Cu(I)/Cu(II)/Cu(III) catalytic cycle plays a key role in sustaining the photocatalytic process and driving the radical cascade cyclization.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"55 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635465","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":"Cooperative Ligand-Enabled Facile Synthesis of γ-C(sp3)–H Alkenylated Aliphatic Amides: A Comprehensive Protocol to Free N–H Tolerance","authors":"Suparna Dutta, Nikunj Kumar, Minhajul Islam, Wajid Ali, Puneet Gupta, Debabrata Maiti","doi":"10.1021/acscatal.4c07905","DOIUrl":"https://doi.org/10.1021/acscatal.4c07905","url":null,"abstract":"Site-selective distal C(<i>sp³</i>)–H functionalization of aliphatic amides is one of the longstanding challenges in synthetic methodology. Herein, we report a palladium-catalyzed <i>γ</i>-C(<i>sp³</i>)–H alkenylation of native aliphatic amide, exploiting a cooperative ligand approach to harness the weak coordinating ability of the amide functional group. Apart from tertiary amides, the protocol developed by us is also suitable for secondary, primary, and relatively unbiased <i>β</i>-C–H bond-containing amides, which remain unexplored till date. Theoretical calculations revealed that the combination of ligands is crucial for the reaction. Monoprotected amino acid (MPAA) ligand is essential for the concerted metalation–deprotonation (CMD) step of the C–H activation, occurring <i>via</i> a distinctive [5,6]-palladacyclic transition state. Meanwhile, the pyridone ligand plays a key role in forming the catalyst resting state, promoting <i>β</i>-hydride elimination, and facilitating product release. Both experimental and computational mechanistic studies confirm that C–H activation is the rate-limiting step in this process, providing crucial insights into the factors governing regioselective functionalization at the distant <i>γ</i>-site.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"136 3 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143627384","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}