{"title":"Mechanism and stereoselectivity in metal and enzyme catalyzed carbene insertion into X-H and C(sp<sup>2</sup>)-H bonds.","authors":"Reena Balhara, Ritwika Chatterjee, Garima Jindal","doi":"10.1039/d4cs00742e","DOIUrl":"https://doi.org/10.1039/d4cs00742e","url":null,"abstract":"<p><p>Constructing highly proficient C-X (X = O, N, S, <i>etc.</i>) and C-C bonds by leveraging TMs (transition metals) (Fe, Cu, Pd, Rh, Au, <i>etc.</i>) and enzymes to catalyze carbene insertion into X-H/C(sp<sup>2</sup>)-H is a highly versatile strategy. This is primarily achieved through the <i>in situ</i> generation of metal carbenes from the interaction of TMs with diazo compounds. Over the last few decades, significant advancements have been made, encompassing a wide array of X-H bond insertions using various TMs. These reactions typically favor a stepwise ionic pathway where the nucleophilic attack on the metal carbene leads to the generation of a metal ylide species. This intermediate marks a critical juncture in the reaction cascade, presenting multiple avenues for proton transfer to yield the X-H inserted product. The mechanism of C(sp<sup>2</sup>)-H insertion reactions closely resembles those of X-H insertion reactions and thus have been included here. A major development in carbene insertion reactions has been the use of engineered enzymes as catalysts. Since the seminal report of a non-natural \"carbene transferase\" by Arnold in 2013, \"P411\", several heme-based enzymes have been reported in the literature to catalyze various abiological carbene insertion reactions into C(sp<sup>2</sup>)-H, N-H and S-H bonds. These enzymes possess an extraordinary ability to regulate the orientation and conformations of reactive intermediates, facilitating stereoselective carbene transfers. However, the absence of a suitable stereochemical model has impeded the development of asymmetric reactions employing a lone chiral catalyst, including enzymes. There is a pressing need to investigate alternative mechanisms and models to enhance our comprehension of stereoselectivity in these processes, which will be crucial for advancing the fields of asymmetric synthesis and biocatalysis. The current review aims to provide details on the mechanistic aspects of the asymmetric X-H and C(sp<sup>2</sup>)-H insertion reactions catalyzed by Fe, Cu, Pd, Rh, Au, and enzymes, focusing on the detailed mechanism and stereochemical model. The review is divided into sections focusing on a specific X-H/C(sp<sup>2</sup>)-H bond type catalyzed by different TMs and enzymes.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":40.4,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398741","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}
Laura Collado, Alejandro H. Pizarro, Mariam Barawi, Miguel García-Tecedor, Marta Liras, Víctor A. de la Peña O'Shea
{"title":"Light-driven nitrogen fixation routes for green ammonia production","authors":"Laura Collado, Alejandro H. Pizarro, Mariam Barawi, Miguel García-Tecedor, Marta Liras, Víctor A. de la Peña O'Shea","doi":"10.1039/d3cs01075a","DOIUrl":"https://doi.org/10.1039/d3cs01075a","url":null,"abstract":"The global goal for decarbonization of the energy sector and the chemical industry could become a reality by a massive increase in renewable-based technologies. For this clean energy transition, the versatile green ammonia may play a key role in the future as a fossil-free fertilizer, long-term energy storage medium, chemical feedstock, and clean burning fuel for transportation and decentralized power generation. The high energy-intensive industrial ammonia production has triggered researchers to look for a step change in new synthetic approaches powered by renewable energies. This review provides a comprehensive comparison of light-mediated N<small><sub>2</sub></small> fixation technologies for green ammonia production, including photocatalytic, photoelectrocatalytic, PV-electrocatalytic and photothermocatalytic routes. Since these approaches are still at laboratory scale, we examine the most recent developments and discuss the open challenges for future improvements. Last, we offer a technoeconomic comparison of current and emerging ammonia production technologies, highlighting costs, barriers, recommendations, and potential opportunities for the real development of the next generation of green ammonia solutions.","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142397838","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 the potential: machine learning applications in electrocatalyst design for electrochemical hydrogen energy transformation","authors":"Rui Ding, Junhong Chen, Yuxin Chen, Jianguo Liu, Yoshio Bando, Xuebin Wang","doi":"10.1039/d4cs00844h","DOIUrl":"https://doi.org/10.1039/d4cs00844h","url":null,"abstract":"Machine learning (ML) is rapidly emerging as a pivotal tool in the hydrogen energy industry for the creation and optimization of electrocatalysts, which enhance key electrochemical reactions like the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER), the hydrogen oxidation reaction (HOR), and the oxygen reduction reaction (ORR). This comprehensive review demonstrates how cutting-edge ML techniques are being leveraged in electrocatalyst design to overcome the time-consuming limitations of traditional approaches. ML methods, using experimental data from high-throughput experiments and computational data from simulations such as density functional theory (DFT), readily identify complex correlations between electrocatalyst performance and key material descriptors. Leveraging its unparalleled speed and accuracy, ML has facilitated the discovery of novel candidates and the improvement of known products through its pattern recognition capabilities. This review aims to provide a tailored breakdown of ML applications in a format that is readily accessible to materials scientists. Hence, we comprehensively organize ML-driven research by commonly studied material types for different electrochemical reactions to illustrate how ML adeptly navigates the complex landscape of descriptors for these scenarios. We further highlight ML's critical role in the future discovery and development of electrocatalysts for hydrogen energy transformation. Potential challenges and gaps to fill within this focused domain are also discussed. As a practical guide, we hope this work will bridge the gap between communities and encourage novel paradigms in electrocatalysis research, aiming for more effective and sustainable energy solutions.","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385498","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}
Geon-Tae Park, Nam-Yung Park, Hoon-Hee Ryu, H. Hohyun Sun, Jang-Yeon Hwang, Yang-Kook Sun
{"title":"Nano-rods in Ni-rich layered cathodes for practical batteries","authors":"Geon-Tae Park, Nam-Yung Park, Hoon-Hee Ryu, H. Hohyun Sun, Jang-Yeon Hwang, Yang-Kook Sun","doi":"10.1039/d3cs01110k","DOIUrl":"https://doi.org/10.1039/d3cs01110k","url":null,"abstract":"Lithium transition metal oxide layers, Li[Ni<small><sub>1−<em>x</em>−<em>y</em></sub></small>Co<small><sub><em>x</em></sub></small>(Mn and/or Al)<small><sub><em>y</em></sub></small>]O<small><sub>2</sub></small>, are widely used and mass-produced for current rechargeable battery cathodes. Development of cathode materials has focused on increasing the Ni content by simply controlling the chemical composition, but as the Ni content has almost reached its limit, a new breakthrough is required. In this regard, microstructural modification is rapidly emerging as a prospective approach, namely in the production of nano-rod layered cathode materials. A comprehensive review of the physicochemical properties and electrochemical performances of cathodes bearing the nano-rod microstructure is provided herein. A detailed discussion is regarding the structural stability of the cathode, which should be maximized to suppress microcrack formation, the main cause of capacity fading in Ni-rich cathode materials. In addition, the morphological features required to achieve optimal performance are examined. Following a discussion of the initial nano-rod cathodes, which were based on compositional concentration gradients, the preparation of nano-rod cathodes without the inclusion of a concentration gradient is reviewed, highlighting the importance of the precursor. Subsequently, the challenges and advances associated with the nano-rod structure are discussed, including considerations for synthesizing nano-rod cathodes and surface shielding of the nano-rod structure. It goes on to cover nano-rod cathode materials for next-generation batteries (<em>e.g.</em>, all-solid-state, lithium-metal, and sodium-ion batteries), inspiring the battery community and other materials scientists looking for clues to the solution of the challenges that they encounter.","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385500","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}
Chao Xie, Wei Chen, Yanyong Wang, Yahui Yang, Shuangyin Wang
{"title":"Dynamic evolution processes in electrocatalysis: structure evolution, characterization and regulation.","authors":"Chao Xie, Wei Chen, Yanyong Wang, Yahui Yang, Shuangyin Wang","doi":"10.1039/d3cs00756a","DOIUrl":"https://doi.org/10.1039/d3cs00756a","url":null,"abstract":"<p><p>Reactions on electrocatalytic interfaces often involve multiple processes, including the diffusion, adsorption, and conversion of reaction species and the interaction between reactants and electrocatalysts. Generally, these processes are constantly changing rather than being in a steady state. Recently, dynamic evolution processes on electrocatalytic interfaces have attracted increasing attention owing to their significant roles in catalytic reaction kinetics. In this review, we aim to provide insights into the dynamic evolution processes in electrocatalysis to emphasize the importance of unsteady-state processes in electrocatalysis. Specifically, the dynamic structure evolution of electrocatalysts, methods for the characterization of the dynamic evolution and the strategies for the regulation of the dynamic evolution for improving electrocatalytic performance are summarized. Finally, the conclusion and outlook on the research on dynamic evolution processes in electrocatalysis are presented. It is hoped that this review will provide a deeper understanding of dynamic evolution in electrocatalysis, and studies of electrocatalytic reaction processes and kinetics on the unsteady-state microscopic spatial and temporal scales will be given more attention.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":40.4,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386446","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":"Light/X-ray/ultrasound activated delayed photon emission of organic molecular probes for optical imaging: mechanisms, design strategies, and biomedical applications","authors":"Rui Qu, Xiqun Jiang, Xu Zhen","doi":"10.1039/d4cs00599f","DOIUrl":"https://doi.org/10.1039/d4cs00599f","url":null,"abstract":"Conventional optical imaging, particularly fluorescence imaging, often encounters significant background noise due to tissue autofluorescence under real-time light excitation. To address this issue, a novel optical imaging strategy that captures optical signals after light excitation has been developed. This approach relies on molecular probes designed to store photoenergy and release it gradually as photons, resulting in delayed photon emission that minimizes background noise during signal acquisition. These molecular probes undergo various photophysical processes to facilitate delayed photon emission, including (1) charge separation and recombination, (2) generation, stabilization, and conversion of the triplet excitons, and (3) generation and decomposition of chemical traps. Another challenge in optical imaging is the limited tissue penetration depth of light, which severely restricts the efficiency of energy delivery, leading to a reduced penetration depth for delayed photon emission. In contrast, X-ray and ultrasound serve as deep-tissue energy sources that facilitate the conversion of high-energy photons or mechanical waves into the potential energy of excitons or the chemical energy of intermediates. This review highlights recent advancements in organic molecular probes designed for delayed photon emission using various energy sources. We discuss distinct mechanisms, and molecular design strategies, and offer insights into the future development of organic molecular probes for enhanced delayed photon emission.","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385501","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":"Designed functions of oxide/hydroxide nanosheets <i>via</i> elemental replacement/doping.","authors":"Kanji Saito, Masashi Morita, Tomohiko Okada, Rattanawadee Ploy Wijitwongwan, Makoto Ogawa","doi":"10.1039/d4cs00339j","DOIUrl":"https://doi.org/10.1039/d4cs00339j","url":null,"abstract":"<p><p>Partial replacement of one structural element in a solid with another of a similar size was conducted to impart functionality to the solids and modify their properties. This phenomenon is found in nature in coloured gemstones and clay minerals and is used in materials chemistry and physics, endowing materials with useful properties that can be controlled by incorporated heteroelements and their amounts. Depending on the area of research (or expected functions), the replacement is referred to as \"isomorphous substitution\", \"doping\", <i>etc.</i> Herein, elemental replacement in two-dimensional (2D) oxides and hydroxides (nanosheets or layered materials) is summarised with emphasis on the uniqueness of their preparation, characterisation and application compared with those of the corresponding bulk materials. Among the 2D materials (graphene, metallenes, transition metal chalcogenides, metal phosphate/phosphonates, MXenes, <i>etc.</i>), 2D oxides and hydroxides are characterised by their presence in nature, facile synthesis and storage under ambient conditions, and possible structural variation from atomic-level nanosheets to thicker nanosheets composed of multilayered structures. The heteroelements to be doped were selected depending on the target application objectively; however, there are structural and synthetic limitations in the doping of heteroelements. In the case of layered double hydroxides (single layer) and layered alkali silicates (from single layer to multiple layers), including layered clay minerals (2 : 1 layer), the replacement (commonly called isomorphous substitution) is discussed to understand/design characteristics such as catalytic, adsorptive (including ion exchange), and swelling properties. Due to the variation in their main components, the design of layered transition metal oxide/hydroxide materials <i>via</i> isomorphous substitution is more versatile; in this case, tuning their band structure, doping both holes and electrons, and creating impurity levels are examined by the elemental replacement of the main components. As typical examples, material design for the photocatalytic function of an ion-exchangeable layered titanate (lepidocrocite-type titanate) and a perovskite niobate (KCa<sub>2</sub>Nb<sub>3</sub>O<sub>10</sub>) is discussed, where elemental replacement is effective in designing their multiple functions.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":40.4,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142379529","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":"Reactive oxygen species-mediated organic long-persistent luminophores light up biomedicine: from two-component separated nano-systems to integrated uni-luminophores.","authors":"Zhe Li, Hongwen Liu, Xiao-Bing Zhang","doi":"10.1039/d4cs00443d","DOIUrl":"https://doi.org/10.1039/d4cs00443d","url":null,"abstract":"<p><p>Organic luminophores have been widely utilized in cells and <i>in vivo</i> fluorescence imaging but face extreme challenges, including a low signal-to-noise ratio (SNR) and even false signals, due to non-negligible background signals derived from real-time excitation lasers. To overcome these challenges, in the last decade, functionalized organic long-persistent luminophores have gained much attention. Such luminophores could not only overcome the biological toxicity of inorganic long-persistent luminescent materials (metabolic toxicity and leakage risk of inorganic heavy metals), but also continue to emit long-persistent luminescence after removing the excitation source, thus effectively improving imaging quality. More importantly, organic long-persistent luminophores have good structure tailorability for the construction of activable probes, which is favorable for biosensing. Recently, the development of reactive oxygen species (ROS)-mediated long-persistent (ROSLP) luminophores (especially organic small-molecule ROSLP luminophores) is still in the rising stage. Notably, ROSLP luminophores for <i>in vivo</i> imaging have experienced from two-component separated nano-systems to integrated uni-luminophores, which obtained gradually better designability and biocompatibility. In this review, we summarize the progress and challenges of organic long-persistent luminophores, focusing on their development history, long-persistent luminescence working mechanisms, and biomedical applications. We hope that these insights will help scientists further develop functionalized organic long-persistent luminophores for the biomedical field.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":40.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370274","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}
Benjamin Vermeeren, Sofie Van Praet, Wouter Arts, Thomas Narmon, Yingtuan Zhang, Cheng Zhou, Hans P Steenackers, Bert F Sels
{"title":"From sugars to aliphatic amines: as sweet as it sounds? Production and applications of bio-based aliphatic amines.","authors":"Benjamin Vermeeren, Sofie Van Praet, Wouter Arts, Thomas Narmon, Yingtuan Zhang, Cheng Zhou, Hans P Steenackers, Bert F Sels","doi":"10.1039/d4cs00244j","DOIUrl":"https://doi.org/10.1039/d4cs00244j","url":null,"abstract":"<p><p>Aliphatic amines encompass a diverse group of amines that include alkylamines, alkyl polyamines, alkanolamines and aliphatic heterocyclic amines. Their structural diversity and distinctive characteristics position them as indispensable components across multiple industrial domains, ranging from chemistry and technology to agriculture and medicine. Currently, the industrial production of aliphatic amines is facing pressing sustainability, health and safety issues which all arise due to the strong dependency on fossil feedstock. Interestingly, these issues can be fundamentally resolved by shifting toward biomass as the feedstock. In this regard, cellulose and hemicellulose, the carbohydrate fraction of lignocellulose, emerge as promising feedstock for the production of aliphatic amines as they are available in abundance, safe to use and their aliphatic backbone is susceptible to chemical transformations. Consequently, the academic interest in bio-based aliphatic amines <i>via</i> the catalytic reductive amination of (hemi)cellulose-derived substrates has systematically increased over the past years. From an industrial perspective, however, the production of bio-based aliphatic amines will only be the middle part of a larger, ideally circular, value chain. This value chain additionally includes, as the first part, the refinery of the biomass feedstock to suitable substrates and, as the final part, the implementation of these aliphatic amines in various applications. Each part of the bio-based aliphatic amine value chain will be covered in this Review. Applying a holistic perspective enables one to acknowledge the requirements and limitations of each part and to efficiently spot and potentially bridge knowledge gaps between the different parts.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":40.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370272","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}
Zhixing Lin, Hai Liu, Joseph J Richardson, Wanjun Xu, Jingqu Chen, Jiajing Zhou, Frank Caruso
{"title":"Metal-phenolic network composites: from fundamentals to applications.","authors":"Zhixing Lin, Hai Liu, Joseph J Richardson, Wanjun Xu, Jingqu Chen, Jiajing Zhou, Frank Caruso","doi":"10.1039/d3cs00273j","DOIUrl":"https://doi.org/10.1039/d3cs00273j","url":null,"abstract":"<p><p>Composites with tailored compositions and functions have attracted widespread scientific and industrial interest. Metal-phenolic networks (MPNs), which are composed of phenolic ligands and metal ions, are amorphous adhesive coordination polymers that have been combined with various functional components to create composites with potential in chemistry, biology, and materials science. This review aims to provide a comprehensive summary of both fundamental knowledge and advancements in the field of MPN composites. The advantages of amorphous MPNs, over crystalline metal-organic frameworks, for fabricating composites are highlighted, including their mild synthesis, diverse interactions, and numerous intrinsic functionalities. The formation mechanisms and state-of-the-art synthesis strategies of MPN composites are summarized to guide their rational design. Subsequently, a detailed overview of the chemical interactions and structure-property relationships of composites based on different functional components (<i>e.g.</i>, small molecules, polymers, biomacromolecules) is provided. Finally, perspectives are offered on the current challenges and future directions of MPN composites. This tutorial review is expected to serve as a fundamental guide for researchers in the field of metal-organic materials and to provide insights and avenues to enhance the performance of existing functional materials in applications across diverse fields.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":40.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370273","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}