{"title":"Leveraging Ligand Desymmetrization to Enrich Structural Diversity of Zirconium Metal–Organic Frameworks for Toxic Chemical Adsorption","authors":"Yongwei Chen, Haomiao Xie, Xingjie Wang, Fanrui Sha, Kent Kirlikovali, Xiaoliang Wang, Zi-Ming Ye, Xianhui Tang, Chenghui Zhang, Gregory Peterson, Zhibo Li, Omar Farha","doi":"10.1002/anie.202417664","DOIUrl":"https://doi.org/10.1002/anie.202417664","url":null,"abstract":"The discovery of metal–organic frameworks (MOFs) with novel structures provides significant opportunities for developing porous solids with new properties and enriching the structural diversity of functional materials for various applications. The rational design of building units with specific geometric conformations is essential to direct the construction of MOFs with unique properties. Herein, we leverage a ligand desymmetrization approach to construct a series of new MOFs. A flexible tetratopic carboxylate ligand with a tetrahedral geometry was designed and assembled with a Zr6 cluster, generating four Zr‐based MOF structures: NU‐2600, NU‐2700, NU‐2800, and NU‐1802, in which the ligand configurations and Zr6 cluster connectivities can be controlled by varying solvents and modulators during synthesis. Except for NU‐1802, these represent entirely new topologies. Notably, NU‐1802 exhibits structural flexibility, with up to a 74% reduction in the unit cell volume as confirmed by single‐crystal X‐ray diffraction studies. Given their microporous structures, we studied the adsorption behaviors of n‐hexane and 2‐chloroethyl ethyl sulfide to explore the structure‐property relationships of these MOFs. Overall, this work highlights ligand desymmetrization as a powerful method to enrich MOF structural diversity and access complex MOFs with non‐default topologies suitable for applications such as toxic gas capture.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"42 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Vivek C Wakchaure, Maria Mercedes Lorenzo-García, Francesco Fasano, Martina Crosta, Nicolas Biot, Pradip Kumar Mondal, Nicola Demitri, Benjamin Ward, Davide Bonifazi
{"title":"Escape from Flatland: Stereoselective Synthesis of Hexa-aryl Borazines and their sp²-Based 3D Architectures","authors":"Vivek C Wakchaure, Maria Mercedes Lorenzo-García, Francesco Fasano, Martina Crosta, Nicolas Biot, Pradip Kumar Mondal, Nicola Demitri, Benjamin Ward, Davide Bonifazi","doi":"10.1002/anie.202416700","DOIUrl":"https://doi.org/10.1002/anie.202416700","url":null,"abstract":"Borazine and its derivatives can be considered critical doping units for engineering hybrid C(sp2)-based molecules with tailored optoelectronic properties. Herein, we report the first synthesis of hexaarylborazines that, bearing ortho-substituted aryl moieties, extend three-dimensionally. Using a one-pot protocol, we first form an electrophilic chloroborazole and then react it with an aryl lithium (ArLi). By selecting the appropriate ortho-substituent, we can guide the ArLi to add to the BN-core in a specific way, ultimately controlling the stereochemical outcome of the three-substitution reaction. Rationalization of the stereochemical model through computational analysis allowed us to show that when aryl lithium nucleophiles bearing rigid long-range ortho-substituents are used, i.e., stiff substituents. The ortho-substituent shields its side of the electrophilic B3N3 core, biasing the incoming ArLi to add anti at each addition step, forming the final tri-aryl borazine exclusively as cc-isomer. Leveraging this stereoselective approach, prototypical multichromophoric borazine derivatives were prepared, and we showcased how the stereochemical arrangement of these chromophores distinctly influences their redox behavior. This methodology paves the way for previously inaccessible borazines to serve as privileged precursors to transcend the conventional bidimensionality associated with graphenoid systems and pioneer the construction of new forms of three-dimensional C(sp2)-based architectures.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"196 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599999","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"CRISPRepi: a multi-omic atlas for CRISPR-based epigenome editing","authors":"Leisheng Shi, Shasha Li, Rongyi Zhu, Chenyang Lu, Xintian Xu, Changzhi Li, Xinyue Huang, Xiaolu Zhao, Fengbiao Mao, Kailong Li","doi":"10.1093/nar/gkae1039","DOIUrl":"https://doi.org/10.1093/nar/gkae1039","url":null,"abstract":"CRISPR-based epigenome editing integrates the precision of CRISPR with the capability of epigenetic mark rewriting, offering a tunable and reversible gene regulation strategy without altering the DNA sequences. Various epigenome editing systems have been developed and applied in different organisms and cell types; however, the detailed information is discrete, making it challenging to evaluate the precision of different editing systems and design the optimal sgRNAs for further functional studies. Herein, we developed CRISPRepi (http://crisprepi.maolab.org/ or http://crisprepi.lilab-pkuhsc.org/), a pioneering platform that consolidates extensive sequencing data from 671 meticulously curated RNA-seq, ChIP-seq, Bisulfite-seq and ATAC-seq datasets in 87 cell types manipulated by 74 epigenome editing systems. In total, we have curated 5962 sgRNAs associated with 283 target genes from 2277 samples across six species. CRISPRepi incorporates tools for analyzing editing outcomes and assessing off-target effects by analyzing gene expression changes pre- and post-editing, along with the details of multi-omic epigenetic landscapes. Moreover, CRISPRepi supports the investigation of editing potentials for newly designed sgRNA sequences in a cell/tissue-specific context. By providing a user-friendly interface for searching and selecting optimal editing designs across multiple organisms, CRISPRepi serves as an integrated resource for researchers to evaluate editing efficiency and off-target effects among diverse CRISPR-based epigenome editing systems.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"25 1","pages":""},"PeriodicalIF":14.9,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600996","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuntao Yang, Himansu Kumar, Yuhan Xie, Zhao Li, Rongbin Li, Wenbo Chen, Chiamaka S Diala, Meer A Ali, Yi Xu, Albon Wu, Sayed-Rzgar Hosseini, Erfei Bi, Hongyu Zhao, Pora Kim, W Jim Zheng
{"title":"ASpdb: an integrative knowledgebase of human protein isoforms from experimental and AI-predicted structures","authors":"Yuntao Yang, Himansu Kumar, Yuhan Xie, Zhao Li, Rongbin Li, Wenbo Chen, Chiamaka S Diala, Meer A Ali, Yi Xu, Albon Wu, Sayed-Rzgar Hosseini, Erfei Bi, Hongyu Zhao, Pora Kim, W Jim Zheng","doi":"10.1093/nar/gkae1018","DOIUrl":"https://doi.org/10.1093/nar/gkae1018","url":null,"abstract":"Alternative splicing is a crucial cellular process in eukaryotes, enabling the generation of multiple protein isoforms with diverse functions from a single gene. To better understand the impact of alternative splicing on protein structures, protein–protein interaction and human diseases, we developed ASpdb (https://biodataai.uth.edu/ASpdb/), a comprehensive database integrating experimentally determined structures and AlphaFold 2-predicted models for human protein isoforms. ASpdb includes over 3400 canonical isoforms, each represented by both experimentally resolved and predicted structures, and >7200 alternative isoforms with AlphaFold 2 predictions. In addition to detailed splicing events, 3D structures, sequence variations and functional annotations, ASpdb uniquely offers comparative analyses and visualization of structural alterations among isoforms. This resource is invaluable for advancing research in alternative splicing, structural biology and disease mechanisms.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"11 1","pages":""},"PeriodicalIF":14.9,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601437","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"NIR-II Fluorescence/Photoacoustic Dual Ratiometric Probes with Unique Recognition Site for Quantitatively Visualizing H2S2 in Vivo","authors":"Bangping Hu, Qinian Liu, Yulan Jiang, Yujie Huang, Huiquan Ji, Jiqi Zhang, Xia Wang, Xing-Can Shen, Hua Chen","doi":"10.1002/anie.202418378","DOIUrl":"https://doi.org/10.1002/anie.202418378","url":null,"abstract":"Hydrogen persulfide (H2S2) plays a significant role in redox biology and signal transduction; therefore, quantitative visualization of H2S2 in the deep tissue of living organisms is essential for obtaining reliable information about relevant pathophysiological processes directly. However, currently reported H2S2 probes are unsuitable for this purpose because of their poor selectivity for many polysulfide species or their short wavelength, which hinders precise imaging in deep tissues. Herein, for the first time, we report a unique H2S2-mediated dithiole formation reaction. Based on this reaction, we construct the first NIR-II fluorescence (FL) and photoacoustic (PA) dual-ratiometric probe (NIR-II-H2S2) for quantitatively visualizing H2S2 in vivo. This probe shows dual-ratiometric NIR-II fluorescence (I840/I1000, 107-fold) and photoacoustic (PA800/PA900, 6.5-fold) responses towards Na2S2 species with high specificity, excellent sensitivity (1.8 nM), improved water solubility, and deep-tissue penetration. More importantly, using NIR-II dual-ratiometric FL/PA imaging, we successfully demonstrated that the probe could be used to accurately quantify the fluctuating H2S2 levels in the liver-injury mouse models induced by lipopolysaccharides or metformin drugs. Overall, this study not only presents a promising tool for H2S2-related pathological research, but also provides a unique recognition site that may be generalized for designing more useful H2S2 imaging agents in the future.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"15 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601735","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lanting Qian, Yangyang Huang, Cameron Dean, Ivan Kochetkov, Baltej Singh, Linda Nazar
{"title":"Engineering Stable Decomposition Products on Cathode Surfaces to Enable High Voltage All-Solid-State Batteries","authors":"Lanting Qian, Yangyang Huang, Cameron Dean, Ivan Kochetkov, Baltej Singh, Linda Nazar","doi":"10.1002/anie.202413591","DOIUrl":"https://doi.org/10.1002/anie.202413591","url":null,"abstract":"Sulfide solid electrolytes such as Li6PS5Cl hold high promise for solid state batteries due to their high ionic conductivity; however, their oxidation potential of ~2.5 V is not compatible with high voltage Ni-rich cathodes such as LiNixCoyMn1−x−yO2 (x≥0.8). Here, we devise an effective, conformal and thin coating on the cathode active material guided by density functional theory, which suppresses the oxidative decomposition of Li6PS5Cl as shown by experiment. The nanometric coating on nickel-rich NMC85 enabled capacity retention of 82% after 200 cycles (2.8-4.3 V vs Li+/Li) using Li6PS5Cl as the solid electrolyte. In comparison, cells with an uncoated CAM only displayed 56% capacity retention. The coated-NCM85 cells also demonstrate much better rate performance and higher capacity. The enhanced performance is due to the formation of a stable amorphous cathode-electrolyte interphase accruing from the decomposition products of the LiPO2F2 precursor (as predicted by DFT), which protect the sulfide electrolyte from oxidation. The coating fabricated in this cost-effective process showed superior performance to state-of-the-art coatings such as LiNbO3. This work highlights the importance of rationally designing stable coating materials based on their potential decomposition products and confirms the suitability of a low-cost and conformal coating to enable sulfide electrolyte-based all-solid-state batteries.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"10 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599980","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"MolluscDB 2.0: a comprehensive functional and evolutionary genomics database for over 1400 molluscan species","authors":"Funyun Liu, Bingcheng Cai, Shanshan Lian, Xinyao Chang, Dongsheng Chen, Zhongqi Pu, Lisui Bao, Jing Wang, Jia Lv, Hongkun Zheng, Zhenmin Bao, Lingling Zhang, Shi Wang, Yuli Li","doi":"10.1093/nar/gkae1026","DOIUrl":"https://doi.org/10.1093/nar/gkae1026","url":null,"abstract":"Mollusca represents the second-largest animal phylum but remains less explored genomically. The increase in high-quality genomes and diverse functional genomic data holds great promise for advancing our understanding of molluscan biology and evolution. To address the opportunities and challenges facing the molluscan research community in managing vast multi-omics resources, we developed MolluscDB 2.0 (http://mgbase.qnlm.ac), which integrates extensive functional genomic data and offers user-friendly tools for multilevel integrative and comparative analyses. MolluscDB 2.0 covers 1450 species across all eight molluscan classes and compiles ∼4200 datasets, making it the most comprehensive multi-omics resource for molluscs to date. MolluscDB 2.0 expands the layers of multi-omics data, including genomes, bulk transcriptomes, single-cell transcriptomes, proteomes, epigenomes and metagenomes. MolluscDB 2.0 also more than doubles the number of functional modules and analytical tools, updating 14 original modules and introducing 20 new, specialized modules. Overall, MolluscDB 2.0 provides highly valuable, open-access multi-omics platform for the molluscan research community, expediting scientific discoveries and deepening our understanding of molluscan biology and evolution.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"18 1","pages":""},"PeriodicalIF":14.9,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600997","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Maria Cerezo, Elliot Sollis, Yue Ji, Elizabeth Lewis, Ala Abid, Karatuğ Ozan Bircan, Peggy Hall, James Hayhurst, Sajo John, Abayomi Mosaku, Santhi Ramachandran, Amy Foreman, Arwa Ibrahim, James McLaughlin, Zoë Pendlington, Ray Stefancsik, Samuel A Lambert, Aoife McMahon, Joannella Morales, Thomas Keane, Michael Inouye, Helen Parkinson, Laura W Harris
{"title":"The NHGRI-EBI GWAS Catalog: standards for reusability, sustainability and diversity","authors":"Maria Cerezo, Elliot Sollis, Yue Ji, Elizabeth Lewis, Ala Abid, Karatuğ Ozan Bircan, Peggy Hall, James Hayhurst, Sajo John, Abayomi Mosaku, Santhi Ramachandran, Amy Foreman, Arwa Ibrahim, James McLaughlin, Zoë Pendlington, Ray Stefancsik, Samuel A Lambert, Aoife McMahon, Joannella Morales, Thomas Keane, Michael Inouye, Helen Parkinson, Laura W Harris","doi":"10.1093/nar/gkae1070","DOIUrl":"https://doi.org/10.1093/nar/gkae1070","url":null,"abstract":"The NHGRI-EBI GWAS Catalog serves as a vital resource for the genetic research community, providing access to the most comprehensive database of human GWAS results. Currently, it contains close to 7 000 publications for >15 000 traits, from which more than 625 000 lead associations have been curated. Additionally, 85 000 full genome-wide summary statistics datasets—containing association data for all variants in the analysis—are available for downstream analyses such as meta-analysis, fine-mapping, Mendelian randomisation or development of polygenic risk scores. As a centralised repository for GWAS results, the GWAS Catalog sets and implements standards for data submission and harmonisation, and encourages the use of consistent descriptors for traits, samples and methodologies. We share processes and vocabulary with the PGS Catalog, improving interoperability for a growing user group. Here, we describe the latest changes in data content, improvements in our user interface, and the implementation of the GWAS-SSF standard format for summary statistics. We address the challenges of handling the rapid increase in large-scale molecular quantitative trait GWAS and the need for sensitivity in the use of population and cohort descriptors while maintaining data interoperability and reusability.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"529 1","pages":""},"PeriodicalIF":14.9,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600999","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bin Wu, Haibing Meng, Xingbao Chen, Ying Guo, Li Jiang, Xiaofeng Shi, Jiexin Zhu, Juncai Long, Wenliang Gao, Feng Zeng, Wenjie Jiang, Yongfa Zhu, Dingsheng Wang, Liqiang Mai
{"title":"Structural Modulation of Nanographenes Enabled by Defects, Size and Doping for Oxygen Reduction Reaction","authors":"Bin Wu, Haibing Meng, Xingbao Chen, Ying Guo, Li Jiang, Xiaofeng Shi, Jiexin Zhu, Juncai Long, Wenliang Gao, Feng Zeng, Wenjie Jiang, Yongfa Zhu, Dingsheng Wang, Liqiang Mai","doi":"10.1002/anie.202415071","DOIUrl":"https://doi.org/10.1002/anie.202415071","url":null,"abstract":"Nanographenes are among the fastest-growing materials used for the oxygen reduction reaction (ORR) thanks to their low cost, environmental friendliness, excellent electrical conductivity, and scalable synthesis. The perspective of replacing precious metal-based electrocatalysts with functionalized graphene is highly desirable for reducing costs in energy conversion and storage systems. Generally, the enhanced ORR activity of the nanographenes is typically deemed to originate from the heteroatom doping effect, size effect, defects effect, and/or their synergistic effect. All these factors can efficiently modify the charge distribution on the sp2-conjugated carbon framework, bringing about optimized intermediate adsorption and accelerated electron transfer steps during ORR. In this review, the fundamental chemical and physical properties of nanographenes are first discussed about ORR applications. Afterward, the role of doping, size, defects, and their combined influence in boosting nanographenes’ ORR performance is introduced. Finally, significant challenges and essential perspectives of nanographenes as advanced ORR electrocatalysts are highlighted.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"9 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601740","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Regioselective and Homochiral Supramolecular Polymerization of Nanotadpole Aggremers of Poly(phenylacetylene) Derivatives","authors":"Xinhua Wan, Hua Zeng, Peiyao Yu, Jie Zhang","doi":"10.1002/anie.202417792","DOIUrl":"https://doi.org/10.1002/anie.202417792","url":null,"abstract":"Biological homochirality is a signature of life. Supramolecular polymerization is effective to achieve high hierarchical homochirality in nature, but has not been well‐explored. Herein, we report regioselective and homochiral supramolecular polymerization of chiral nanotadpole aggregates made of either synthetic helical poly(phenylacetylene)s or chirality‐amplified co‐assembly of chiral and achiral poly(phenylacetylene)s. The twisted nanotadpole aggregates with high screw‐sense preference polymerized as monomers (aggremers) into supramolecular chains in a head‐to‐tail regioselective and stepwise manner. Supramolecular copolymerization of enantiomeric aggremers favored formation of homochiral hierarchical supramolecular structures as visualized by TEM. Chiral hexagonal columnar mesophase of aggremers was responsive for the stereoselectivity. The work opens a gate to controllably and effectively construct functional chiral supramolecular materials and deepens the understanding of hierarchical biological homochirality.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"19 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599594","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}