Chem最新文献 - Book学术

NHC-catalyzed covalent activation and control of P(V)-stereogenic phosphorus centers via phosphonyl azolium intermediates nhc催化的磷(V)-立体性磷中心的共价活化及磷酰基偶氮中间体的控制

IF 23.5 1区化学

Chem Pub Date : 2025-05-09 DOI: 10.1016/j.chempr.2025.102586

Yanyan Wang, Kuohong Chen, Fengrui Che, Sha Zhao, Pinpin Feng, Qiang Zhao, Donghui Wei, Xingxing Wu, Yonggui Robin Chi

{"title":"NHC-catalyzed covalent activation and control of P(V)-stereogenic phosphorus centers via phosphonyl azolium intermediates","authors":"Yanyan Wang, Kuohong Chen, Fengrui Che, Sha Zhao, Pinpin Feng, Qiang Zhao, Donghui Wei, Xingxing Wu, Yonggui Robin Chi","doi":"10.1016/j.chempr.2025.102586","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102586","url":null,"abstract":"Despite various impressive advancements in the construction of chiral phosphorus centers, enantioselective control of P(V)-stereogenicity with covalent nucleophilic catalysts for direct preparation of chiral phosphorus compounds remains relatively underdeveloped. Here, we disclose a new mode of covalent organocatalysis for enantioselective construction of chiral phosphorus scaffolds via new P–O bond formations. Key steps in our approach involve the addition of an <em>N</em>-heterocyclic carbene (NHC) catalyst to a phosphonate, leading to the formation of a pivotal phosphonyl azolium reactive intermediate that effectively forges the asymmetric P–O bond formation in high selectivity. The resulting phosphonate products bearing a leaving group allow further stereospecific P–O/N coupling, facilitating the phosphonylated functionalization of diverse natural products and bioactive molecules. Unlike classical NHC organocatalysis that focuses on “C”-stereocenters, this study realizes efficient catalyst control over P(V)-stereogenicity through phosphorus-based azolium intermediates for the first time, offering a new platform for covalent bond activation in the synthesis of stereogenic phosphorus compounds.","PeriodicalId":268,"journal":{"name":"Chem","volume":"12372 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143927095","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

A fully light-driven approach to separate carbon dioxide from emission streams 一种完全光驱动的方法，从排放流中分离二氧化碳

IF 23.5 1区化学

Chem Pub Date : 2025-05-09 DOI: 10.1016/j.chempr.2025.102583

Bayu I.Z. Ahmad, Kiser Z. Colley, Andrew J. Musser, Phillip J. Milner

引用次数: 0

Visualization of CO formation at the triple-phase boundary in gas diffusion electrodes for ecCO2RR ecCO2RR气体扩散电极三相边界CO生成的可视化

IF 23.5 1区化学

Chem Pub Date : 2025-05-09 DOI: 10.1016/j.chempr.2025.102582

Sebastian Brosch, Eike Häger, Ole Frank, Patrick Scholz, Wenzel Plischka, Matthias Wessling

{"title":"Visualization of CO formation at the triple-phase boundary in gas diffusion electrodes for ecCO2RR","authors":"Sebastian Brosch, Eike Häger, Ole Frank, Patrick Scholz, Wenzel Plischka, Matthias Wessling","doi":"10.1016/j.chempr.2025.102582","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102582","url":null,"abstract":"Electrochemical CO<sub>2</sub> reduction represents a promising technology for mitigating the impact of greenhouse gas emissions, particularly CO<sub>2</sub>. Gas diffusion electrodes (GDEs) are widely utilized in this process. Although CO<sub>2</sub> reduction has been successfully demonstrated on small scales with various catalysts, the role of the wetting state of the catalyst layer in GDEs remains poorly understood. This factor significantly influences current density and faradaic efficiency. However, two fundamental questions persist: where within the electrode does the desired reaction occur, and what operating state should be targeted for optimizing performance? In this study, we employ a microfluidic electrolyzer to visualize and selectively identify reaction zones producing CO, the desired product. This approach enables the characterization of reactivity across different states of the electrode, revealing the impact of catalyst-layer wetting on product selectivity. Together with our previous research on GDEs, these findings provide a comprehensive understanding of electrochemical CO<sub>2</sub> reduction.","PeriodicalId":268,"journal":{"name":"Chem","volume":"9 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143927094","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

Oxidative three-component on-DNA click reactions using a convenient HILIC-LC-MS analysis method 氧化三组分在dna上的点击反应使用方便的HILIC-LC-MS分析方法

IF 23.5 1区化学

Chem Pub Date : 2025-05-09 DOI: 10.1016/j.chempr.2025.102584

Yun Hu, Hillary J. Dequina, Minxue Huang, Yun Ding, Martha M. Vestling, Jing Chai, Jennifer M. Schomaker

{"title":"Oxidative three-component on-DNA click reactions using a convenient HILIC-LC-MS analysis method","authors":"Yun Hu, Hillary J. Dequina, Minxue Huang, Yun Ding, Martha M. Vestling, Jing Chai, Jennifer M. Schomaker","doi":"10.1016/j.chempr.2025.102584","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102584","url":null,"abstract":"DNA-encoded library (DEL) technology is a transformative tool for drug discovery that enables the rapid synthesis and screening of billions of compounds. New DNA-compatible methods are needed to expand bioactive chemical space; however, oxidative transformations present significant challenges for on-DNA chemistry. Herein, we report a suite of mild on-DNA oxidative three-component click (OTC) reactions, where <em>in situ</em>-generated 1,3-dipoles are trapped by DNA-conjugated alkenes and alkynes. The chemistry furnishes <em>N</em>-heterocycles in good-to-excellent yields, including isoxazolines, isoxazoles, pyrazolines, and pyrazoles of diverse substitution patterns, while preserving the integrity of the DNA barcodes. As traditional ion-pairing reversed-phase liquid chromatography-mass spectrometry (IP-RP LC-MS) could not be used on our shared departmental instrumentation, we developed an MS-friendly hydrophilic interaction chromatography (HILIC) method to facilitate analyses of small DNA-containing fragments. This work provides a practical framework for other academic labs to evaluate new methods for on-DNA chemistries without the need for dedicated instrumentation.","PeriodicalId":268,"journal":{"name":"Chem","volume":"28 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143927097","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

Toward synthetic life—Emergence, growth, creation of offspring, decay, and rescue of fuel-dependent synthetic cells 走向合成生命——依赖燃料的合成细胞的出现、生长、后代的创造、衰变和拯救

IF 23.5 1区化学

Chem Pub Date : 2025-05-09 DOI: 10.1016/j.chempr.2025.102578

Monika Wenisch, Yinqing Li, Marius G. Braun, Lukas Eylert, Fabian Späth, Simone M. Poprawa, Bernhard Rieger, Christopher V. Synatschke, Henrike Niederholtmeyer, Job Boekhoven

{"title":"Toward synthetic life—Emergence, growth, creation of offspring, decay, and rescue of fuel-dependent synthetic cells","authors":"Monika Wenisch, Yinqing Li, Marius G. Braun, Lukas Eylert, Fabian Späth, Simone M. Poprawa, Bernhard Rieger, Christopher V. Synatschke, Henrike Niederholtmeyer, Job Boekhoven","doi":"10.1016/j.chempr.2025.102578","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102578","url":null,"abstract":"The <em>de novo</em> synthesis of life from non-living matter represents a bold scientific challenge, advancing our understanding of life’s minimal requirements and offering revolutionary applications in biotechnology. We explore fuel-dependent synthetic cells based on complex coacervate droplets, which lack membranes and readily take up reactants. Given their fuel-dependent nature, these droplets emerge and grow when fuel is abundant but dissolve under starvation conditions, mimicking the non-equilibrium nature of life. However, their ability to produce offspring—a key requirement for life—has remained elusive. Moreover, their rescue in repetitive fueling-starvation experiments has not been demonstrated. Our work elucidates a mechanism of producing offspring by synthetic cells driven by solid-like speckles in droplets liberated as offspring. By fine-tuning parameters, we control offspring number and survival. Finally, refueling sustains second-generation synthetic cells. This system provides a platform for coupling offspring production with self-replicating molecules, paving the way for synthetic cells capable of Darwinian evolution.","PeriodicalId":268,"journal":{"name":"Chem","volume":"118 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143927098","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

A new breakthrough in ethanol reforming for zero-carbon hydrogen production 零碳制氢乙醇重整的新突破

IF 19.1 1区化学

Chem Pub Date : 2025-05-08 DOI: 10.1016/j.chempr.2025.102554

Ying Sun , Chang Yu , Jieshan Qiu

引用次数: 0

Interfacial water regulation for water-participating electrocatalytic hydrogenation reactions 参与水电催化加氢反应的界面水调节

IF 19.1 1区化学

Chem Pub Date : 2025-05-08 DOI: 10.1016/j.chempr.2025.102533

Yanmei Huang , Ying Gao , Bin Zhang

{"title":"Interfacial water regulation for water-participating electrocatalytic hydrogenation reactions","authors":"Yanmei Huang , Ying Gao , Bin Zhang","doi":"10.1016/j.chempr.2025.102533","DOIUrl":"10.1016/j.chempr.2025.102533","url":null,"abstract":"<div><div>Electrocatalytic hydrogenation of abundant feedstocks to value-added products using water as the hydrogen source offers promising alternatives to traditional methods. At the electrode-electrolyte interface, water molecules not only act as active hydrogen sources but also facilitate mass transport via hydrogen-bond networks. The configuration, orientation, and distribution of interfacial water molecules are directly related to the connectivity of the hydrogen-bond network, thereby directly determining the hydrogenation efficiency. A fundamental understanding of interfacial water dynamics and the development of precise modulation strategies are key to advancing electrochemical hydrogenation. This perspective systematically discusses three dominant strategies—namely, manipulating the local electric field, engineering surface modifications/electrolyte additives, and tuning solvated-cation interactions—to regulate the properties of interfacial water and enhance the corresponding hydrogenation performance. Finally, we highlight critical issues for future research aimed at better controlling interfacial water dynamics to enhance the performance of electrocatalytic hydrogenation and other water-participating reactions.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 5","pages":"Article 102533"},"PeriodicalIF":19.1,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841944","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

Toward aramid polymers by ring-opening polymerization 开环聚合对芳纶聚合物的影响

IF 19.1 1区化学

Chem Pub Date : 2025-05-08 DOI: 10.1016/j.chempr.2025.102588

Colin Bonduelle

引用次数: 0

Using second-sphere recognition for selective metal separation by precipitation 用第二球识别进行沉淀选择性金属分离

IF 19.1 1区化学

Chem Pub Date : 2025-05-08 DOI: 10.1016/j.chempr.2025.102581

Jason B. Love

引用次数: 0

A sustainable cobalt separation with validation by techno-economic analysis and life-cycle assessment 通过技术经济分析和生命周期评估验证的可持续钴分离

IF 19.1 1区化学

Chem Pub Date : 2025-05-08 DOI: 10.1016/j.chempr.2024.10.028

Boyang Zhang , Alexander B. Weberg , Andrew J. Ahn , Marta Guron , Leighton O. Jones , Michael R. Gau , George C. Schatz , Eric J. Schelter

{"title":"A sustainable cobalt separation with validation by techno-economic analysis and life-cycle assessment","authors":"Boyang Zhang , Alexander B. Weberg , Andrew J. Ahn , Marta Guron , Leighton O. Jones , Michael R. Gau , George C. Schatz , Eric J. Schelter","doi":"10.1016/j.chempr.2024.10.028","DOIUrl":"10.1016/j.chempr.2024.10.028","url":null,"abstract":"<div><div>Sustainable, cost-effective cobalt/nickel separations chemistry contributes to the realization of economically competitive lithium-ion battery recycling, as well as primary mining of cobalt and nickel. Such improvements can address supply chain challenges for cobalt, a critical element. Herein, we disclose a simple method for separating Co/Ni by second coordination-sphere molecular recognition. Selective cobalt precipitation is achieved using carbonate ions in an ammonia solution due to the outer-sphere, hydrogen bonding interactions between [Co(NH<sub>3</sub>)<sub>6</sub>]<sup>3+</sup> and CO<sub>3</sub><sup>2−</sup>, evaluated with density functional theory calculations. We demonstrate this method on mixtures of Co/Ni chlorides comprising a 10-fold excess of Ni and provide comparisons with ore-processing systems. High purities (99.4(3)% Co; 98.2(4)% Ni) and recoveries (77(8)% Co; ∼100% Ni) were observed for both Co- and Ni-enriched products using optimized conditions. This method is potentially economically competitive based on initial techno-economic analysis (TEA) and life-cycle assessment (LCA) that also illustrate advantages in terms of sustainability.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 5","pages":"Article 102361"},"PeriodicalIF":19.1,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760253","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