Journal of the American Chemical Society最新文献

{"title":"A Copper–Zinc Cyanamide Solid-Solution Catalyst with Tailored Surface Electrostatic Potentials Promotes Asymmetric N-Intermediate Adsorption in Nitrite Electroreduction","authors":"Jiacheng Jayden Wang, Huong T. D. Bui, Xunlu Wang, Zhuoran Lv, Huashuai Hu, Shuyi Kong, Zhiqiang Wang, Lijia Liu, Wei Chen, Hui Bi, Minghui Yang, Tore Brinck, Jiacheng Wang, Fuqiang Huang","doi":"10.1021/jacs.5c00837","DOIUrl":"https://doi.org/10.1021/jacs.5c00837","url":null,"abstract":"The electrocatalytic nitrite reduction (NO₂RR) converts nitrogen-containing pollutants to high-value ammonia (NH₃) under ambient conditions. However, its multiple intermediates and multielectron coupled proton transfer process lead to low activity and NH₃ selectivity for the existing electrocatalysts. Herein, we synthesize a solid-solution copper–zinc cyanamide (Cu_0.8Zn_0.2NCN) with localized structure distortion and tailored surface electrostatic potential, allowing for the asymmetric binding of NO₂^–. It exhibits outstanding NO₂RR performance with a Faradaic efficiency of ∼100% and an NH₃ yield of 22 mg h^–1 cm^–2, among the best for such a process. Theoretical calculations and in situ spectroscopic measurements demonstrate that Cu–Zn sites coordinated with linear polarized [NCN]^2– could transform symmetric [Cu–O–N–O–Cu] in CuNCN-NO₂^– to a [Cu–N–O–Zn] asymmetric configuration in Cu_0.8Zn_0.2NCN-NO₂^–, thus enhancing adsorption and bond cleavage. A paired electro-refinery with the Cu_0.8Zn_0.2NCN cathode reaches 2000 mA cm^–2 at 2.36 V and remains fully operational at industrial-level 400 mA cm^–2 for >140 h with a NH₃ production rate of ∼30 mg_NH3 h^–1 cm^–2. Our work opens a new avenue of tailoring surface electrostatic potentials using a solid-solution strategy for advanced electrocatalysis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"177 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435609","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":"The Local-Scale Origin of Ferroic Properties in BiVO₄.","authors":"Bryce G Mullens, Frederick P Marlton, Helen E A Brand, Helen E Maynard-Casely, Michelle Everett, Matthew G Tucker, Emily R Van Auken, Alicia M Manjon-Sanz, Gianguido Baldinozzi, Simon M Vornholt, Karena W Chapman, Brendan J Kennedy","doi":"10.1021/jacs.4c18032","DOIUrl":"https://doi.org/10.1021/jacs.4c18032","url":null,"abstract":"<p><p>Earth-abundant metal oxides are excellent candidates for photocatalytic applications due to their low cost and high stability in aqueous solutions. Materials that contain a combination of metal cations with an <i>s</i>² electron lone pair and a <i>d</i>⁰ electronic configuration, such as BiVO₄, possess favorable band gaps. BiVO₄ has also been reported to possess noncentrosymmetric polar properties, such as flexoelectricity, piezo-photocatalysis, and an anomalous photovoltaic effect, despite its centrosymmetric crystal structure. Here, it is shown how centrosymmetric materials possessing <i>s</i>² and <i>d</i>⁰ cations can display \"hidden\" local-scale features, often ignored by conventional crystallography, that influence their physical properties. Anomalous peak shapes are observed in the high-resolution synchrotron X-ray powder diffraction of BiVO₄, and temperature-dependent local-scale distortions are revealed using neutron total scattering methods. Together, these suggest the polar properties of BiVO₄ are related to local-scale distortions induced by the Bi³⁺ 6<i>s</i>² electron lone pairs. This demonstrates the possibility of engineering specific interatomic distances between lone pair-bearing cations and the anion sublattice, creating new opportunities for photocatalytic and polar materials from compounds with long-range centrosymmetric structures.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447331","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":"Engineering Helical Chirality in Metal-Coordinated Cyclodextrin Nanochannels","authors":"Zhiyuan Jiang, Zhi Chen, Xiujun Yu, Shuai Lu, Wenmin Xu, Bo Yu, Charlotte L. Stern, Shu-Yi Li, Yue Zhao, Xinzhi Liu, Yeqiang Han, Shuqi Chen, Kang Cai, Dengke Shen, Kaikai Ma, Xiaopeng Li, Aspen X.-Y. Chen","doi":"10.1021/jacs.4c14123","DOIUrl":"https://doi.org/10.1021/jacs.4c14123","url":null,"abstract":"Helicates are a defining element of DNAs and proteins, with functions that are critical to a variety of biological processes. Cyclodextrins are promising candidates for forging multiple-stranded helicates with well-defined helicity, but a lack of available tools has precluded the construction of artificial helical nanochannels with a controllable geometry and helicity from these widely available chiral building blocks. Herein, we disclose a family of Ag₆L₂ helical nanochannels that can be readily assembled from α-cyclodextrin-derived ligands through coordination between pyridinyl groups and Ag⁺ cations. We discovered that the nanochannels exhibit either an <i>M</i> or a <i>P</i> helicity when the Ag⁺ cations adopt a tetrahedral coordination geometry while losing most of their helicity when the Ag⁺ cations are linearly coordinated. Both the geometry and helicity of the nanochannels can be precisely controlled by simply changing the number of methyl groups at the <i>ortho</i> positions of the pyridinyl ligands. The tetracoordinated Ag⁺ cations interconnect the helical nanochannels into an infinite two-dimensional coordinative network characterized by hexagonal tessellation. Theoretical calculations, which reveal lower energies of the helical conformations observed in crystals compared with those of their inverted counterparts, support the experimental results.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"49 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435604","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":"From Magic Size to Atomic Precision: Facile Synthesis of a CdTe Semiconductor Nanocluster.","authors":"Saryvoudh A Mech, Joshua O Gibson, Fuyan Ma, Lukasz M Dobrzycki, Chenjie Zeng","doi":"10.1021/jacs.4c16188","DOIUrl":"https://doi.org/10.1021/jacs.4c16188","url":null,"abstract":"<p><p>Facile synthesis of atomically precise semiconductor nanoclusters remains an important challenge, especially for those with heavier chalcogens. Combining coordination and colloidal methods, we developed a simple approach for synthesizing an atomically precise CdTe nanocluster with high purity and stability. Specifically, a precise cadmium-thiolate compound, [Cd₄(SR)₉]_n, was reacted with a facile phosphine telluride (TePR₃) precursor to produce a CdTe magic-sized cluster with a distinct absorption peak at 377 nm and a narrow linewidth of 20 nm. X-ray crystallography reveals the cluster is Cd₃₂Te₁₄(SR)₃₆(PR₃)₄, a homologue of Cd₃₂S₁₄ and Cd₃₂Se₁₄ reported about three decades ago, thus filling the missing link in this family. The cluster features a zincblende core in a truncated tetrahedron shape. While the core is achiral, chirality emerges from the rotational stacking of surface ligands. The left and right enantiomers self-assemble into a highly ordered, atomically coherent cubic superlattice, leading to a rare racemic crystal coined as \"kryptoracemate.\" This method provides an accessible platform for further atomic engineering of CdTe and related nanoclusters toward their target applications.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447294","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":"Arylsulfonothioates: Thiol-Activated Donors of Hydropersulfides which are Excreted to Maintain Cellular Redox Homeostasis or Retained to Counter Oxidative Stress","authors":"Vinayak S. Khodade, Qi Liu, Chengximeng Zhang, Gizem Keceli, Nazareno Paolocci, John P. Toscano","doi":"10.1021/jacs.4c17661","DOIUrl":"https://doi.org/10.1021/jacs.4c17661","url":null,"abstract":"Despite their biological significance, the study of hydropersulfides (RSSH) is often limited due to their inherent instability. Here, we introduce arylsulfonothioates as thiol-activated RSSH donors and provide insight into cellular reactive sulfur species homeostasis. These precursors persulfidate physiologically relevant thiols (RSH) to form the corresponding RSSH. Real-time monitoring of hydrogen sulfide (H₂S) generation via membrane inlet mass spectrometry (MIMS) was employed to follow RSSH production, revealing that electron-donating aryl substituents marginally slow RSSH release rates, whereas electron-withdrawing substituents slightly accelerate release. Furthermore, arylsulfonothioates with strong electron-withdrawing substituents offer superior protection against doxorubicin (DOX)-induced cardiotoxicity. Experiments using H9c2 cardiomyocytes affirmed the cell-permeability of arylsulfonothioates and their ability to increase intracellular RSSH levels and protein persulfidation levels. Notably, we observe the excretion of RSSH into the extracellular medium. Further investigations revealed the involvement of the cystine/glutamate antiporter SLC7A11, as cotreatment with its inhibitor, sulfasalazine, significantly reduce extracellular RSSH release. H9c2 cells exhibit tolerance to arylsulfonothioate <b>1g</b> with an electron-withdrawing 4-cyano group at 1 mM; however, inhibition of the cystine antiporter results in a minor decrease in cell viability. Under oxidative stress conditions induced by DOX or hydrogen peroxide (H₂O₂), cotreatment with <b>1g</b> diminishes the excretion of RSSH and confers cytoprotection against DOX or H₂O₂-mediated toxicity. Our findings show adaptive cellular responses to RSSH levels, demonstrating excretion under elevated conditions to maintain redox homeostasis and intracellular retention as a protective response during oxidative stress.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"57 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435607","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":"Fluorogenic Platform for Real-Time Imaging of Subcellular Payload Release in Antibody-Drug Conjugates.","authors":"Ferran Nadal-Bufi, Paulin L Salomon, Fabio de Moliner, Kathy A Sarris, Zhi Wang, Rachel D Wills, Violeta L Marin, Xiaona Shi, Kuo Zhou, Zhongyuan Wang, Zhou Xu, Michael J McPherson, Christopher C Marvin, Adrian D Hobson, Marc Vendrell","doi":"10.1021/jacs.4c16842","DOIUrl":"https://doi.org/10.1021/jacs.4c16842","url":null,"abstract":"<p><p>Antibody-drug conjugates (ADCs) represent promising therapeutic constructs to enhance the selective delivery of drugs to target cells; however, attaining precise control over the timing and location of payload release remains challenging due to the complex intracellular processes that define ADC internalization, trafficking, and linker cleavage. In this study, we present novel real-time fluorogenic probes to monitor both subcellular dynamics of ADC trafficking and payload release. We optimized a tandem molecular design of sequential pH- and enzyme-activatable naphthalimide fluorophores to (1) track their subcellular localization along the endolysosomal pathway and (2) monitor linker cleavage with OFF-to-ON fluorescence switches. Live-cell imaging microscopy revealed that fluorogenic ADCs can traffic to the lysosomes and yet require residence time in these subcellular compartments for efficient linker cleavage. Notably, the compact size of fluorogenic naphthalimides did not impair the recognition of target cell surface reporters or the kinetics of payload release. This modular platform is applicable to many ADCs and holds promise to inform their rational design for optimal release profiles and therapeutic efficacy.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447291","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":"Tuning the Crystallinity of a Metal–Organic Coordination Network at the Liquid–Solid Interface","authors":"Antonino Cucinotta, Samuel Eyley, Jack A. Davies, Wim Thielemans, Kunal S. Mali, Steven De Feyter","doi":"10.1021/jacs.4c17152","DOIUrl":"https://doi.org/10.1021/jacs.4c17152","url":null,"abstract":"Single layered metal–organic coordination networks (MOCNs) are gaining attention thanks to their unique electronic and magnetic properties. The presence of coordinatively unsaturated metal sites within their structures provides additional binding locations for substrates in catalytic processes. Consequently, MOCNs fabricated on solid surfaces are emerging as promising candidates for use in solution-based heterogeneous applications. The bottom-up synthesis of such surface-supported MOCNs requires a rigorous design by utilizing two-dimensional (2D) crystal engineering. However, a comprehensive description of the factors governing their synthesis at the liquid–solid interface is still missing, resulting in only a few reported examples. In this work, we use scanning tunneling microscopy (STM) at the liquid–solid interface to reveal the effect of the choice of solvent, concentration, and temperature on the structure of a surface-supported MOCN constituted by a tritopic ligand containing pyridyl moieties and <i>trans</i>-protected Pd(II) cations. A quantitative analysis of the network’s crystallinity is presented. Furthermore, the impact of the synthetic pathway is investigated and a qualitative description of the growth mechanism is provided. Finally, the porosity of the extended honeycomb network is examined by studying the adsorption of guest molecules in its pores.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"85 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435606","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":"Tailoring Lewis Acidity of Metal Oxides on Nickel to Boost Electrocatalytic Hydrogen Evolution in Neutral Electrolyte.","authors":"Lin-Lin Wang, Xiao-Ran Wang, Hong-Juan Wang, Chong Zhang, Jing-Jing Li, Guo-Jin Feng, Xuan-Xuan Cheng, Xue-Rong Qin, Zi-You Yu, Tong-Bu Lu","doi":"10.1021/jacs.4c16596","DOIUrl":"https://doi.org/10.1021/jacs.4c16596","url":null,"abstract":"<p><p>Neutral-pH water splitting for hydrogen production features a benign environment that could alleviate catalyst and electrolyzer corrosion but calls for the corresponding high-efficiency and earth-abundant hydrogen evolution reaction (HER) catalysts. Herein, we first designed a series of metal oxides decorated on Ni as the model catalysts and found a volcano-shaped relationship between the Lewis acidity of Ni/metal oxides and HER activity in neutral media. The Ni/ZnO with the optimum Lewis acidity could balance water dissociation and hydroxyl desorption, thereby greatly boosting the HER. On the basis of this finding, we further in situ grew the Ni/ZnO heterostructure on a three-dimensional conductive support. The resulting catalyst requires overpotentials of merely 34 and 194 mV to deliver the current densities of 10 and 200 mA cm^-2, respectively, and can stably operate at these current densities for 2000 h in 1 M phosphate buffer solution (pH 7), representing the most active and durable HER catalyst in neutral electrolyte reported thus far. Our work provides an effective design scheme for low-cost and high-performance neutral HER catalysts.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447322","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":"A Route toward the On-Surface Synthesis of Organic Ferromagnetic Quantum Spin Chains.","authors":"Fabian Paschke, Ricardo Ortiz, Shantanu Mishra, Manuel Vilas-Varela, Florian Albrecht, Diego Peña, Manuel Melle-Franco, Leo Gross","doi":"10.1021/jacs.4c18123","DOIUrl":"https://doi.org/10.1021/jacs.4c18123","url":null,"abstract":"<p><p>Engineering sublattice imbalance is an intuitive way to induce high-spin ground states in bipartite polycyclic conjugated hydrocarbons (PCHs). Such molecules can be employed as building blocks of quantum spin chains, which are outstanding platforms to study fundamental models in quantum magnetism. This is exemplified by recent reports on the bottom-up synthesis of antiferromagnetic spin chains that provided insights into paradigmatic quantum phenomena such as fractionalization. In contrast to antiferromagnetism, demonstration of ferromagnetic coupling between PCHs has been scarce. Previous attempts in this direction were limited by the formation of nonbenzenoid rings leading to spin quenching or the use of spacer motifs that weaken the magnitude of ferromagnetic exchange. Here, we demonstrate the on-surface synthesis of short ferromagnetic spin chains based on dibenzotriangulene, a triplet PCH. Our synthetic strategy centers on the concept of achieving a direct (without spacer motifs) majority-minority sublattice coupling between adjacent molecules. This leads to a global sublattice imbalance in spin chains scaling with the chain length and therefore a ferromagnetic ground state with a strong intermolecular ferromagnetic exchange. Through scanning probe measurements and quantum chemical calculations, we analyze the electronic and magnetic properties of ferromagnetic dimers and trimers of dibenzotriangulene and confirm their quintet and septet ground states, respectively, with an intermolecular ferromagnetic exchange of 7 meV. Furthermore, we elucidate the role of sublattice coupling on magnetism through complementary experiments on antiferromagnetic dibenzotriangulene dimers with majority-majority and minority-minority sublattice couplings. We expect our study to provide impetus for the design of organic ferromagnetic materials.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447407","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":"Dynamic Deprotonation Enhancement Triggered by Accelerated Electrochemical Delithiation Reconstruction during Acidic Water Oxidation.","authors":"Sheng Zhao, Sung-Fu Hung, Yue Wang, Shaoxiong Li, Juan Yang, Wen-Jing Zeng, Ying Zhang, Hao-Hsiang Chang, Han-Yi Chen, Feng Hu, Linlin Li, Shengjie Peng","doi":"10.1021/jacs.5c00493","DOIUrl":"https://doi.org/10.1021/jacs.5c00493","url":null,"abstract":"<p><p>The structure-dependent transition in reaction pathways during acidic oxygen evolution (OER) is pivotal due to the active site oxidation accompanied by the coordination environment changes. In this work, charge-polarized Ir-O-Co units are constructed in alkali metal cobalt oxides (LiCoO₂, and Na_0.74CoO₂) to modify the lower Hubbard band. Benefiting from the accelerated delithiation reconstruction induced by the altered band structure, typical Ir-LiCoO₂ produces high-valent Ir sites with unsaturated coordination through the charge compensation during OER. Oxygen atoms shared by trimetallic sites exhibit strong Bro̷nsted acidity, promoting proton migration for unsaturated Ir sites and dynamically enhancing deprotonation. Furthermore, the stable coordination environment, along with electron donation from Co sites, significantly improves the stability of Ir sites. The unique electrochemical activation results in a low overpotential of 190 mV at 10 mA cm^-2 during acidic OER and delivers exceptional stability at 1 A cm^-2 for 150 h with a slight voltage degradation in a proton exchange membrane electrolyzer. This work provides in-depth insights into the relationship between catalyst reconstruction and reaction mechanisms.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447280","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}