ACS Combinatorial Science最新文献

{"title":"Exceptionally Short Tetracoordinated Carbon–Halogen Bonds in Hexafluorodihalocubanes","authors":"Masafumi Sugiyama,&nbsp;Yuta Uetake*,&nbsp;Nozomu Miyagi,&nbsp;Masaaki Yoshida,&nbsp;Kyoko Nozaki,&nbsp;Takashi Okazoe and Midori Akiyama*,&nbsp;","doi":"10.1021/jacs.4c1273210.1021/jacs.4c12732","DOIUrl":"https://doi.org/10.1021/jacs.4c12732https://doi.org/10.1021/jacs.4c12732","url":null,"abstract":"<p >Molecules that contain bonds whose length significantly deviates from the average are of interest in the context of understanding the nature and limits of the chemical bonds. However, it is difficult to disentangle the individual contributions of the multiple factors that give rise to such bond-length deviations as reports on such molecules remain scarce. In the present study, we have succeeded in synthesizing hexafluorodihalocubanes of the type C₈F₆X₂ (<b>2</b>) (X = Cl (<b>2</b>_<b>Cl</b>), Br (<b>2</b>_<b>Br</b>), I (<b>2</b>_<b>I</b>)), which represent a new series of molecules with unusual C(sp³)–halogen bonds. The C(sp³)–halogen bonds of <b>2</b>_<b>Cl</b>, <b>2</b>_<b>Br</b>, and <b>2</b>_<b>I</b>, determined via single-crystal X-ray diffraction analysis, are approximately 0.07–0.09 Å shorter than typical C(sp³)–halogen bonds. In particular, the carbon–iodine bonds of <b>2</b>_<b>I</b> are the shortest C(sp³)–I bonds reported to date. The solution-state structures and electronic states of the C(sp³)–halogen bonds in these hexafluorodihalocubanes were analyzed by X-ray absorption spectroscopy, which revealed detailed information on the length of these C(sp³)–halogen bonds in solution and the solid state as well as on the electron-deficient nature of <b>2</b>. Detailed theoretical calculations and a comparison with halotrinitromethanes (<b>1</b>), which represent another series of molecules with shortened C(sp³)–halogen bonds, revealed that the factors responsible for the shortening of the C(sp³)–halogen bond vary among the different C(sp³)–halogen bonds, i.e., for C(sp³)–Cl and C(sp³)–Br, the s-character and hyperconjugation effects predominate, whereas for C(sp³)–I, the interatomic Coulombic interaction effect prevails.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30686–30697 30686–30697"},"PeriodicalIF":14.4,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585490","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multifunctionalization of Alkenyl Alcohols via a Sequential Relay Process","authors":"Chong Liu,&nbsp;Ling Wang and Haibo Ge*,&nbsp;","doi":"10.1021/jacs.4c0952210.1021/jacs.4c09522","DOIUrl":"https://doi.org/10.1021/jacs.4c09522https://doi.org/10.1021/jacs.4c09522","url":null,"abstract":"<p >Aryl-substituted aliphatic amines are widely recognized as immensely valuable molecules. Consequently, the development of practical strategies for the construction of these molecules becomes increasingly urgent and critical. Here, we have successfully achieved multifunctionalization reactions of alkenyl alcohols in a sequential relay process, which enables transformation patterns of arylamination, deuterated arylamination, and methylenated arylamination to the easy access of multifarious arylalkylamines. Notably, a novel functionalization mode for carbonyl groups has been developed to facilitate the processes of deuterium incorporation and methylene introduction, thereby providing new means for the diverse transformations of carbonyl groups. This methodology displays a wide tolerance toward functional groups, while also exhibiting good applicability across various skeletal structures of alkenols and amines.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"30733–30740 30733–30740"},"PeriodicalIF":14.4,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609189","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"4hJCHOCH Spin Coupling in a Lewisx Trisaccharide as Evidence of Inter-Residue C–H···O Hydrogen Bonding in Aqueous Solution","authors":"Mi-Kyung Yoon,&nbsp;Pradip Shit,&nbsp;Wenhui Zhang,&nbsp;Reagan J. Meredith,&nbsp;Hannah Kang,&nbsp;Ian Carmichael and Anthony S. Serianni*,&nbsp;","doi":"10.1021/jacs.4c1194810.1021/jacs.4c11948","DOIUrl":"https://doi.org/10.1021/jacs.4c11948https://doi.org/10.1021/jacs.4c11948","url":null,"abstract":"<p >Prior studies of the solution conformation of the Lewis^x (Le^x) trisaccharide, αFuc-(1→3)[βGal-(1→4)]-βGlcNAc, suggest that nonclassical inter-residue C–H···O hydrogen bonding in aqueous solution contributes to the stabilization of its 3D structure and affects its biological properties. Experimental evidence for this hydrogen bond in aqueous solution has been reported in the form of a ^4h<i>J</i>_CHOCH NMR spin-coupling constant between C5′Fuc and H1″Gal measured by 2D NMR methods in unlabeled samples. A methyl glycoside of Le^x (MeβLe^x) was prepared containing selective ¹³C-labeling at C5′Fuc, and the H1″Gal signal was examined in high-field ¹H NMR spectra for evidence of splitting or line-broadening caused by the ¹³C at C5′Fuc. High-resolution ¹H NMR spectra obtained at high field and at different temperatures using different FID processing parameters showed no resolved splitting of the H1″Gal signal or evidence of line-broadening. Spectral simulation showed that this splitting and/or line-broadening would be observable if the reported <i>J-</i>value (∼1.1 Hz) is correct. DFT calculations on MeβLe^x and a carbon analog (O5″Gal replaced by a CH₂ group) gave very small and nearly identical calculated ^4h<i>J</i>_C5′,H1″ values, suggesting that the coupling is essentially zero. DFT calculations also showed that an alternate inter-residue ^3h<i>J</i>_H5′,H1″ is small. Based on NMR analyses and DFT calculations, we found that ^4h<i>J</i>_C5′,H1″ in MeβLe^x has an upper limit of ∼0.4 Hz and that the value could be lower, possibly zero, calling into question its value as experimental proof of persistent nonclassical hydrogen bonding in aqueous solutions of MeβLe^x and related structures.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"31264–31273 31264–31273"},"PeriodicalIF":14.4,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609200","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical Formation of C2+ Products Steered by Bridge-Bonded *CO Confined by *OH Domains","authors":"Haibin Ma,&nbsp;Enric Ibáñez-Alé,&nbsp;Futian You,&nbsp;Núria López* and Boon Siang Yeo*,&nbsp;","doi":"10.1021/jacs.4c0875510.1021/jacs.4c08755","DOIUrl":"https://doi.org/10.1021/jacs.4c08755https://doi.org/10.1021/jacs.4c08755","url":null,"abstract":"<p >During the electrochemical CO₂ reduction reaction (eCO₂RR) on copper catalysts, linear-bonded CO (*CO_L) is commonly regarded as the key intermediate for the CO-CO coupling step, which leads to the formation of multicarbon products. In this work, we unveil the significant role of bridge-bonded *CO (*CO_B) as an active species. By combining <i>in situ</i> Raman spectroscopy, gas and liquid chromatography, and density functional theory (DFT) simulations, we show that adsorbed *OH domains displace *CO_L to *CO_B. The electroreduction of a ¹²CO+¹³CO₂ cofeed demonstrates that *CO_B distinctly favors the production of acetate and 1-propanol, while *CO_L favors ethylene and ethanol formation. This work enhances our understanding of the mechanistic intricacies of eCO₍₂₎RR and suggests new directions for designing operational conditions by modifying the competitive adsorption of surface species, thereby steering the reaction toward specific multicarbon products.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30183–30193 30183–30193"},"PeriodicalIF":14.4,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacs.4c08755","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Organometallic Chemistry Tools for Building Biologically Relevant Nanoscale Systems","authors":"James A. R. Tilden,&nbsp;Evan A. Doud,&nbsp;Hayden R. Montgomery,&nbsp;Heather D. Maynard and Alexander M. Spokoyny*,&nbsp;","doi":"10.1021/jacs.4c0711010.1021/jacs.4c07110","DOIUrl":"https://doi.org/10.1021/jacs.4c07110https://doi.org/10.1021/jacs.4c07110","url":null,"abstract":"<p >The recent emergence of organometallic chemistry for modification of biomolecular nanostructures has begun to rewrite the long-standing assumption among practitioners that small-molecule organometallics are fundamentally incompatible with biological systems. This Perspective sets out to clarify some of the existing misconceptions by focusing on the growing organometallic toolbox for biomolecular modification. Specifically, we highlight key organometallic transformations in constructing complex biologically relevant systems on the nanomolecular scale, and the organometallic synthesis of hybrid nanomaterials composed of classical nanomaterial components combined with biologically relevant species. As research progresses, many of the challenges associated with applying organometallic chemistry in this context are rapidly being reassessed. Looking to the future, the growing utility of organometallic transformations will likely make them more ubiquitous in the construction and modification of biomolecular nanostructures.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"29989–30003 29989–30003"},"PeriodicalIF":14.4,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Protamine-Mediated Tangles Produce Extreme Deoxyribonucleic Acid Compaction","authors":"Vikhyaat Ahlawat,&nbsp;Anshika Dhiman,&nbsp;Hashini Ekanayake Mudiyanselage and Huan-Xiang Zhou*,&nbsp;","doi":"10.1021/jacs.4c1246810.1021/jacs.4c12468","DOIUrl":"https://doi.org/10.1021/jacs.4c12468https://doi.org/10.1021/jacs.4c12468","url":null,"abstract":"<p >In sperm cells, protamine replaces histones to compact DNA 10–20 times more than in somatic cells. To characterize the extreme compaction, we employed confocal microscopy and optical tweezers to determine the conformations and stability of protamine-bound λ-DNA. Confocal images show increasing compaction of λ-DNA at increasing protamine concentration. In the presence of protamine, single λ-DNA molecules form tangles that withstand forces strong enough (∼55 pN) for strand separation and shorten the contour length by up to 40% even at high forces, as well as bends and loops that rupture at 10–40 pN forces. Strand separation nucleates tangles, implicating protamine interactions with DNA bases. Molecular dynamics simulations show that Arg sidechains of protamine each form hydrogen bonds with multiple bases, frequently in the form of a wedge between the two strands of DNA. Protamine may participate in both local and higher-order chromatin organization, leading to extreme compaction and global transcription silencing.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30668–30677 30668–30677"},"PeriodicalIF":14.4,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585991","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cobalt Nitride-Implanted PtCo Intermetallic Nanocatalysts for Ultrahigh Fuel Cell Cathode Performance","authors":"Muhammad Irfansyah Maulana,&nbsp;Tae Hwan Jo,&nbsp;Ha-Young Lee,&nbsp;Chaehyeon Lee,&nbsp;Caleb Gyan-Barimah,&nbsp;Cheol-Hwan Shin,&nbsp;Jeong-Hoon Yu,&nbsp;Kug-Seung Lee,&nbsp;Seoin Back* and Jong-Sung Yu*,&nbsp;","doi":"10.1021/jacs.4c0951410.1021/jacs.4c09514","DOIUrl":"https://doi.org/10.1021/jacs.4c09514https://doi.org/10.1021/jacs.4c09514","url":null,"abstract":"<p >Stable and active oxygen reduction electrocatalysts are essential for practical fuel cells. Herein, we report a novel class of highly ordered platinum-cobalt (Pt-Co) alloys embedded with cobalt nitride. The intermetallic core–shell catalyst demonstrates an initial mass activity of 0.88 A mg_Pt^–1 at 0.9 V with 71% retention after 30,000 potential cycles of an aggressive square-wave accelerated durability test and loses only 9% of its electrochemical surface area, far exceeding the US Department of Energy 2025 targets, with unprecedented stability and only a minimal voltage loss under practical fuel cell operating conditions. We discover that regulating the atomic ordering in the core results in an optimal lattice configuration that accelerates the oxygen reduction kinetics. The presence of cobalt nitride decorated within PtCo superlattices guarantees a larger barrier to Co dissolution, leading to the excellent endurance of the electrocatalysts. This work brings up a transformative structural engineering strategy for rationally designing high-performing Pt-based catalysts with a unique atomic configuration for broad practical uses in energy conversion technology.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"30922–30932 30922–30932"},"PeriodicalIF":14.4,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Carborane-Derived Proton-Coupled Electron Transfer Reagent","authors":"Enric H. Adillon,&nbsp; and ,&nbsp;Jonas C. Peters*,&nbsp;","doi":"10.1021/jacs.4c0900710.1021/jacs.4c09007","DOIUrl":"https://doi.org/10.1021/jacs.4c09007https://doi.org/10.1021/jacs.4c09007","url":null,"abstract":"<p >Reagents capable of concerted proton–electron transfer (CPET) reactions can access reaction pathways with lower reaction barriers compared to stepwise pathways involving electron transfer (ET) and proton transfer (PT). To realize reductive multielectron/proton transformations involving CPET, one approach that has shown recent promise involves coupling a cobaltocene ET site with a protonated arylamine Brønsted acid PT site. This strategy colocalizes the electron/proton in a matter compatible with a CPET step and net reductive electrocatalysis. To probe the generality of such an approach a class of C,C′-diaryl-<i>o</i>-carboranes is herein explored as a conceptual substitute for the cobaltocene subunit, with an arylamine linkage still serving as a colocalized Brønsted base suitable for protonation. The featured <i>o</i>-carborane (Ph<b>Cb</b>Ph^N) can be reduced and protonated to generate an N–H bond with a weak effective bond dissociation free energy (BDFE_eff) of 31 kcal/mol, estimated with measured thermodynamic data. This N–H bond is among the lowest measured element–H bonds for analyzed nonmetal compounds. Distinct solid-state crystal structures of the one- and two-electron reduced forms of diaryl-<i>o</i>-carboranes are disclosed to gain insight into their well-behaved redox characteristics. The singly reduced, protonated form of the diaryl-<i>o</i>-carborane can mediate multi-ET/PT reductions of azoarenes, diphenylfumarate, and nitrotoluene. In contrast to the aforementioned cobaltocene system, available mechanistic data disclosed herein support these reactions occurring by a rate-limiting ET step and not a CPET step. A relevant hydrogen evolution reaction (HER) reaction was also studied, with data pointing to a PT/ET/PT mechanism, where the reduced carborane core is itself highly stable to protonation.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30204–30211 30204–30211"},"PeriodicalIF":14.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacs.4c09007","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585757","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lipidation Engineering in Daptomycin Biosynthesis","authors":"Chang-Hun Ji,&nbsp;Sehong Park,&nbsp;Kunwoo Lee,&nbsp;Hyun-Woo Je and Hahk-Soo Kang*,&nbsp;","doi":"10.1021/jacs.4c1096610.1021/jacs.4c10966","DOIUrl":"https://doi.org/10.1021/jacs.4c10966https://doi.org/10.1021/jacs.4c10966","url":null,"abstract":"<p >Lipopeptides are an important family of natural products, some of which are clinically used as antibiotics to treat multidrug-resistant pathogens. Although the lipid moieties play a crucial role in balancing antibacterial activity and hemolytic toxicity, modifying the lipid moieties has been challenging due to the complexity of the lipidation process in lipopeptide biosynthesis. Here, we show that the lipid profile can be altered by engineering both secondary and primary metabolisms, using daptomycin as an example. First, swapping the fatty acyl AMP ligase (FAAL) gene <i>dptF</i> with foreign FAAL homologs improved the fatty acyl specificity of the lipidation process for decanoic acid. Then, the introduction of <i>Mycobacterium</i> type I fatty acid synthase operon (MvFAS-Ib/MvAcpS) and <i>Cryptosporidium</i> thioesterase (CpTEII) enriched the fatty acid pool with decanoic acid in <i>Streptomyces roseosporus</i>. The engineered fatty acid metabolism eliminates the need for external decanoic acid supplementation by enabling <i>S. roseosporus</i> to biosynthesize decanoic acid. By complete engineering of the lipidation process, we achieved, for the first time, high-purity, natural production of daptomycin. The lipidation engineering approach we demonstrate here lays the foundation for the lipidation control in lipopeptide biosynthesis.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30434–30442 30434–30442"},"PeriodicalIF":14.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585984","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Programmable Plasma-Microdroplet Cascade Reactions for Multicomponent Systems","authors":"Alexander J. Grooms,&nbsp;Isabella M. Marcelo,&nbsp;Robert T. Huttner and Abraham K. Badu-Tawiah*,&nbsp;","doi":"10.1021/jacs.4c0705310.1021/jacs.4c07053","DOIUrl":"https://doi.org/10.1021/jacs.4c07053https://doi.org/10.1021/jacs.4c07053","url":null,"abstract":"<p >The concept of programmable cascade reactions in charged microdroplets is introduced using carbon–carbon (C–C) bond formation via uncatalyzed Michael addition in a three-tier study culminating in programmable Hantzsch multicomponent, multistep reactions. In situ generated reactive oxygen species (ROS) from nonthermal plasma discharge are fused with charged water microdroplets (devoid of ROS) in real time for accelerated chemical reactions. This plasma-microdroplet fusion platform utilizing a coaxial spray configuration enabled product selection while avoiding unwanted side reactions. Hydrogen abstraction via ROS facilitated the formation of enolate anions without strong base use. Reaction enhancement factors &gt;10³ were calculated for plasma-microdroplet fusion versus microdroplet-only reactions. The platform programmability was showcased through (i) uncatalyzed 1,4-Michael addition of α,β-unsaturated carbonyls, (ii) novel C–C bond formation via the use of pro-electrophilic amine and alcohol substrates─activated through collisions in the microdroplet environment to serve as Michael acceptors, and (iii) selective Hantzsch cascade reaction with cross-coupling products, avoiding side reactions including N-alkylation and self-coupling product formation. Milligram quantity product collection is achieved, showcasing plasma-microdroplet fusion as an effective tool for preparative-scale synthesis. Thus, the controlled generation of ROS via plasma discharge during charged water microdroplet evolution establishes a green synthetic method for uncatalyzed C–C bond formation.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 44","pages":"30068–30077 30068–30077"},"PeriodicalIF":14.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585941","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}