IF 23.5 1区化学

Chem Pub Date : 2024-10-21 DOI: 10.1016/j.chempr.2024.09.030

Libo Zhu, Chang Chen, Tiantian Wu, Xu Yu, Han Tian, Fantao Kong, Ziwei Chang, Wenshu Luo, Xiangzhi Cui, Jianlin Shi

{"title":"Borohydride oxidation-water reduction fuel cells advanced by local hydroxyl enrichment-inhibited borohydride hydrolysis on Cu(0) sites","authors":"Libo Zhu, Chang Chen, Tiantian Wu, Xu Yu, Han Tian, Fantao Kong, Ziwei Chang, Wenshu Luo, Xiangzhi Cui, Jianlin Shi","doi":"10.1016/j.chempr.2024.09.030","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.09.030","url":null,"abstract":"A promising fuel cell using the acidic hydrogen evolution reaction (HER) instead of kinetically sluggish oxygen reduction reaction to couple with the borohydride oxidation reaction (BOR) has been established. This BOR-HER fuel cell (BHFC) has achieved the concurrent electricity generation and hydrogen production. To catalyze HER/BOR, a copper (Cu)-doped cobalt phosphide nanosheet grown on Cu foam (Cu–CoP/CF) was developed, which exhibits significantly inhibited competitive NaBH4 hydrolysis during BOR, along with excellent HER performance and stability over 700 h. Specifically, the Cu(0), in situ formed on the surface of Cu–CoP/CF, plays a decisive role in creating an OH−-enriched local environment, resulting in significantly inhibited borohydride hydrolysis but greatly enhanced BOR selectivity of up to 85%, as well as the reduced thermodynamic barrier of BOR. The assembled BHFC equipped with Cu–CoP/CF is capable of generating a high power density of 114 mW cm−2 and concurrently producing hydrogen at a rate of at least 40 mol h−1 m−2 at cathode.","PeriodicalId":268,"journal":{"name":"Chem","volume":"24 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452039","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}

引用次数: 0

Tetralactam-based anion transporters 基于四内酰胺的阴离子转运体

IF 23.5 1区化学

Chem Pub Date : 2024-10-21 DOI: 10.1016/j.chempr.2024.09.028

Alexander M. Gilchrist, Daniel A. McNaughton, Mohamed Fares, Xin Wu, Bryson A. Hawkins, Stephen J. Butler, David E. Hibbs, Philip A. Gale

引用次数: 0

Engineering a photoenzyme to use red light 利用红光改造光酵素

IF 23.5 1区化学

Chem Pub Date : 2024-10-16 DOI: 10.1016/j.chempr.2024.09.017

Jose M. Carceller, Bhumika Jayee, Claire G. Page, Daniel G. Oblinsky, Gustavo Mondragón-Solórzano, Nithin Chintala, Jingzhe Cao, Zayed Alassad, Zheyu Zhang, Nathaniel White, Danny J. Diaz, Andrew D. Ellington, Gregory D. Scholes, Sijia S. Dong, Todd K. Hyster

{"title":"Engineering a photoenzyme to use red light","authors":"Jose M. Carceller, Bhumika Jayee, Claire G. Page, Daniel G. Oblinsky, Gustavo Mondragón-Solórzano, Nithin Chintala, Jingzhe Cao, Zayed Alassad, Zheyu Zhang, Nathaniel White, Danny J. Diaz, Andrew D. Ellington, Gregory D. Scholes, Sijia S. Dong, Todd K. Hyster","doi":"10.1016/j.chempr.2024.09.017","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.09.017","url":null,"abstract":"Photoenzymatic reactions involving flavin-dependent “ene”-reductases (EREDs) rely on protein-templated charge transfer (CT) complexes between the cofactor and substrate for radical initiation. These complexes typically absorb in the blue region of the electromagnetic spectrum. Here, we engineered an ERED to form CT complexes that absorb red light. Mechanistic studies indicate that red-light activity is due to the growth of a red-absorbing shoulder off the previously identified cyan absorption feature. Molecular dynamics simulations, docking, and excited-state calculations suggest that the cyan feature involves a π→π∗ transition on flavin, whereas the red-light absorption is a π→π∗ transition between flavin and the substrate. Differences in the electronic transition are due to changes in the substrate-binding conformation and allosteric tuning of the electronic structure of the cofactor-substrate complex. Microenvironment tuning of the CT complex for red-light activity is observed with other engineered photoenzymatic reactions, highlighting this effect’s generality.","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142439790","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}

引用次数: 0

Exerting control of self-assembly pathways via morphological switching and patterning in amino-acid-based benzene-1,3,5-tricarboxamide conjugates 通过氨基酸基苯-1,3,5-三甲酰胺共轭物的形态切换和图案化控制自组装途径

IF 23.5 1区化学

Chem Pub Date : 2024-10-16 DOI: 10.1016/j.chempr.2024.09.020

Aramballi J. Savyasachi, Oxana Kotova, Ena T. Luis, Amy D. Lynes, Shaun Mills, Sandra A. Bright, Gavin J. McManus, Matthias E. Möbius, D. Clive Williams, Robert Pal, John J. Boland, Thorfinnur Gunnlaugsson

{"title":"Exerting control of self-assembly pathways via morphological switching and patterning in amino-acid-based benzene-1,3,5-tricarboxamide conjugates","authors":"Aramballi J. Savyasachi, Oxana Kotova, Ena T. Luis, Amy D. Lynes, Shaun Mills, Sandra A. Bright, Gavin J. McManus, Matthias E. Möbius, D. Clive Williams, Robert Pal, John J. Boland, Thorfinnur Gunnlaugsson","doi":"10.1016/j.chempr.2024.09.020","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.09.020","url":null,"abstract":"Small structural changes to benzene-1,3,5-tricarboxamide (BTA) dictate its self-assembly behavior and morphological outcome. Functionalization with an α-amino acid close to the BTA core, which also possesses a terminal terpyridine (tpy) unit, led to a robust gel in the case of glycine, whereas monodisperse, solid microspheres formed in the case of alanine, phenylalanine, and leucine. The self-assembly pathways of the chiral and achiral BTAs are orthogonal and both microspheres and gel fibers independently assemble in the same medium. Further hierarchical self-assembly results upon addition of lanthanide ions (i.e., Eu(III) and Tb(III) that emit at long wavelengths with long excited-state lifetimes) that crosslink the microspheres through coordination, whereas coordination within the gel led to a change in morphology toward microspheres, as well as the formation of hierarchical superstructures. The chirality of the BTA influences helicity of the assembly and the resulting enantiomeric conformation around the lanthanides, evidenced by circularly polarized luminescence.","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142439928","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}

引用次数: 0

Dearomative dimerization of quinolines and their skeletal rearrangement to indoles triggered by single-electron transfer 单电子转移引发的喹啉二聚化及其骨架重排为吲哚的过程

IF 23.5 1区化学

Chem Pub Date : 2024-10-16 DOI: 10.1016/j.chempr.2024.09.016

Eugene Yew Kun Tan, Alireza Dehdari, Amirah S. Mat Lani, Derek A. Pratt, Shunsuke Chiba

{"title":"Dearomative dimerization of quinolines and their skeletal rearrangement to indoles triggered by single-electron transfer","authors":"Eugene Yew Kun Tan, Alireza Dehdari, Amirah S. Mat Lani, Derek A. Pratt, Shunsuke Chiba","doi":"10.1016/j.chempr.2024.09.016","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.09.016","url":null,"abstract":"Dearomatization of two-dimensional planar aromatic feedstocks is an attractive strategy for the introduction of three-dimensional vectors into chemical scaffolds to expand chemical space for drug discovery. Here, we demonstrate the dearomative dimerization and skeletal rearrangement of quinolines under polysulfide anion photocatalysis, in which the additive dictates the reaction courses. In the presence of formate, dearomative dimerization of quinolines is followed by cyclization to form an sp3-rich polyheterocyclic hybrid of a 2,5-methanobenzo[b]azepine and a tetrahydroquinoline in a net-reductive manner. On the other hand, in the presence of triethylamine instead of formate, sequential dimerization and skeletal rearrangement occurs to afford 4-(3-indolylmethyl)quinolines in a redox-neutral manner. These observations enabled the design of a net-reductive skeletal rearrangement of 4-arylquinolines to 3-(arylmethyl)indoles. Detailed mechanistic investigations revealed that this umpolung transformation from electron-deficient quinolines to electron-rich indoles is mediated via a 1,2-aryl migration/ring-contraction sequence, as opposed to the more commonly invoked neophyl-like rearrangement.","PeriodicalId":268,"journal":{"name":"Chem","volume":"18 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142439965","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}

引用次数: 0

The cyclotriborate trianion 环三硼酸盐三阴离子

IF 23.5 1区化学

Chem Pub Date : 2024-10-16 DOI: 10.1016/j.chempr.2024.09.002

Manjur O. Akram, Caleb D. Martin

引用次数: 0

Globally aromatic odd-electron π-magnetic macrocycle 全芳香奇电子π-磁性大环

IF 23.5 1区化学

Chem Pub Date : 2024-10-15 DOI: 10.1016/j.chempr.2024.09.015

Federico Villalobos, Jan Berger, Adam Matěj, Reed Nieman, Ana Sánchez-Grande, Diego Soler, Andrés Pinar Solé, Hans Lischka, Mikuláš Matoušek, Jiri Brabec, Libor Veis, Alba Millan, Carlos Sánchez-Sánchez, Araceli G. Campaña, Juan M. Cuerva, Pavel Jelínek

引用次数: 0

Stimuli-responsive actuation enabled by selective host-guest recognition of urea cage 通过对尿素笼的主客体选择性识别实现刺激响应式驱动

IF 19.1 1区化学

Chem Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.09.013

Zhuo Huang , Xinxing Zhang

引用次数: 0

Anion-derived contact ion pairing as a unifying principle for electrolyte design 阴离子衍生接触离子配对作为电解质设计的统一原则

IF 19.1 1区化学

Chem Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.07.031

Stefan Ilic , Sydney N. Lavan , Justin G. Connell

引用次数: 0

The tension-activated carbon–carbon bond 张力激活的碳-碳键