IF 23.5 1区化学

Chem Pub Date : 2025-04-28 DOI: 10.1016/j.chempr.2025.102556

Xiang Sun, Kai Wu, Paula C.P. Teeuwen, Philipp Pracht, David J. Wales, Jonathan R. Nitschke

{"title":"Proton-driven lithium separation using alkali-templated coordination cages","authors":"Xiang Sun, Kai Wu, Paula C.P. Teeuwen, Philipp Pracht, David J. Wales, Jonathan R. Nitschke","doi":"10.1016/j.chempr.2025.102556","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102556","url":null,"abstract":"The extraction of lithium from natural deposits is energy intensive due to its coexistence with physiochemically similar alkali (Na+ and K+) and alkaline earth (Mg2+ and Ca2+) metal ions. Methods for the direct and specific extraction of lithium from salt mixtures are thus essential to ensure an adequate supply of this metal for the batteries needed to decarbonize the world economy. Here, we present the preparation of alkali-metal-templated coordination cages and their application to lithium extraction. Within the cage framework, protons alter the relative binding affinities of Li+ and similar metal ions: protons associate exclusively with Li+ in close proximity at the cage vertices, repelling other cations as a result of increased electrostatic repulsion, enhanced steric hindrance, and reduced availability of coordinating nitrogen atoms. We developed this proton-driven lithium recognition within coordination cages into a separation cycle capable of extracting Li+ from a mixture of salts that includes Na+, K+, Mg2+, and Ca2+.","PeriodicalId":268,"journal":{"name":"Chem","volume":"147 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143880698","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

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 23.5 1区化学

Chem Pub Date : 2025-04-24 DOI: 10.1016/j.chempr.2025.102581

Jason B. Love

引用次数: 0

Syngas chemistry: Rational design of tandem reaction pathway for directional hydrocarbon synthesis 合成气化学：定向合成烃串联反应途径的合理设计

IF 23.5 1区化学

Chem Pub Date : 2025-04-24 DOI: 10.1016/j.chempr.2025.102552

Junjie Su, Chang Liu, Haibo Zhou, Lin Zhang, Wenqian Jiao, Su Liu, Yangdong Wang, Zaiku Xie

引用次数: 0

Generalized concept of catalysis for chemical reactions: Nanocatalysis in medicine as a paradigm 化学反应催化的广义概念：纳米催化在医学上的范例

IF 23.5 1区化学

Chem Pub Date : 2025-04-24 DOI: 10.1016/j.chempr.2025.102549

Bowen Yang, Jianlin Shi

引用次数: 0

Abiotic aldol reactions of formaldehyde with ketoses and aldoses—Implications for the prebiotic synthesis of sugars by the formose reaction 甲醛与酮糖和醛糖的非生物醛醇反应——通过甲醛反应合成糖的益生元意义

IF 23.5 1区化学

Chem Pub Date : 2025-04-23 DOI: 10.1016/j.chempr.2025.102553

Scot M. Sutton, Sunil Pulletikurti, Huacan Lin, Ramanarayanan Krishnamurthy, Charles L. Liotta

{"title":"Abiotic aldol reactions of formaldehyde with ketoses and aldoses—Implications for the prebiotic synthesis of sugars by the formose reaction","authors":"Scot M. Sutton, Sunil Pulletikurti, Huacan Lin, Ramanarayanan Krishnamurthy, Charles L. Liotta","doi":"10.1016/j.chempr.2025.102553","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102553","url":null,"abstract":"The aldol reactions of formaldehyde is the essence of the formose reaction, considered the leading prebiotic pathway for accessing sugars on the early Earth. However, the formose reaction produces an intractable mixture, and efforts to tame the reaction to selectively and efficiently form aldose sugars have been unsuccessful. We have undertaken an NMR-mechanistic study of the aldol reactions of excess formaldehyde with glycolaldehyde, dihydroxyacetone, erythrulose, and erythrose under mild conditions and show that the reaction pathway is dominated by the formation linear ketoses and eventual accumulation of branched ketoses. Formation of C4 and higher aldo-sugars were not observed, implying that neither carbonyl migrations nor retroaldol reactions are occurring. Our results suggest that (1) controlling the aldol reaction of formaldehyde to selectively produce linear aldoses appears unfeasible; and (2) the concept of the formose reaction as a prebiotic source of ribose on early Earth needs serious reconsideration, and other models/options should be explored.","PeriodicalId":268,"journal":{"name":"Chem","volume":"51 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862586","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

Ligand-enabled override of the memory effect in Rh-catalyzed asymmetric Suzuki reactions 铑催化的不对称铃木反应中配体激活的记忆效应

IF 23.5 1区化学

Chem Pub Date : 2025-04-21 DOI: 10.1016/j.chempr.2025.102550

Ke Liu, David Egea-Arrebola, Ruchuta Ardkhean, Laura Cunningham, Kirsten E. Christensen, Robert S. Paton, Stephen P. Fletcher

{"title":"Ligand-enabled override of the memory effect in Rh-catalyzed asymmetric Suzuki reactions","authors":"Ke Liu, David Egea-Arrebola, Ruchuta Ardkhean, Laura Cunningham, Kirsten E. Christensen, Robert S. Paton, Stephen P. Fletcher","doi":"10.1016/j.chempr.2025.102550","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102550","url":null,"abstract":"Chiral non-racemic allylic species are key building blocks for many carbon-containing molecules, including pharmaceuticals and polymers. Metal-catalyzed asymmetric additions of nucleophiles to allylic species undergo different pathways depending on the metal and nucleophile combination, hindering the development of useful addition reactions with aromatic nucleophiles. We report an asymmetric cross-coupling method between aryl boronic acids and linear allylic phosphates to give branched allylic products. This Suzuki-type reaction overcomes the “memory effect” in Rh catalysis, enabling an overall SN2′ transformation by rate-determining reductive elimination and forming a new stereogenic center adjacent to a terminal vinyl moiety. The method tolerates preexisting stereogenic centers, allowing for synthetic strategies where drugs and natural products are elaborated via diastereoselective allylic arylations. The method is used, as the catalyst-controlled stereochemistry-setting step, in an iterative strategy to give arrays of aryl-substituted contiguous stereogenic centers. This approach will complement existing catalyst-controlled stereoselective methods for forming C–C bonds.","PeriodicalId":268,"journal":{"name":"Chem","volume":"6 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853600","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

Polar π stacking for metal-free near, remote, and ultra-remote C–H coupling with aryliodanes 极性π堆叠与芳基二极管的无金属近程、远程和超远程 C-H 耦合

IF 23.5 1区化学

Chem Pub Date : 2025-04-18 DOI: 10.1016/j.chempr.2025.102546

Jorge D. Martín-Bernardos, Katrin Golob, Wei W. Chen, Orsola A. Luongo, Inés Sedó, Ana B. Cuenca, Alexandr Shafir

{"title":"Polar π stacking for metal-free near, remote, and ultra-remote C–H coupling with aryliodanes","authors":"Jorge D. Martín-Bernardos, Katrin Golob, Wei W. Chen, Orsola A. Luongo, Inés Sedó, Ana B. Cuenca, Alexandr Shafir","doi":"10.1016/j.chempr.2025.102546","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102546","url":null,"abstract":"We introduce a C–H coupling process in which an aromatic C–I position serves as trampoline for targeting various aromatic C–H positions. The reaction is set in motion by an interaction between the λ3-iodane ArI(OAc)2 and the π system of polyunsaturated organosilanes. In particular, the silyl-terminated enynes engage in fully regioselective ortho and para C–H functionalization, with selectivity switch achieved by reversing the order of the substrate’s ene and yne fragments. Density functional theory (DFT) calculations show that the ortho selectivity is governed by a [3,3] sigmatropic rearrangement, while the para coupling occurs through a directional three-point π interaction of the enyne-derived cationic π system, giving rise to an essentially barrierless [5,5] sigmatropic rearrangement. Furthermore, iodane-guided C–H functionalization of 2-iodonaphthalene could be directed to the ultra-remote C6 position through further π extension of the organosilanes partner. The latter reaction represents a nearly unprecedented example of a formal [7,7] sigmatropic rearrangement.","PeriodicalId":268,"journal":{"name":"Chem","volume":"30 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846495","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

Scintillators with aggregation-induced emission 具有聚集诱导发射的闪烁体

IF 23.5 1区化学

Chem Pub Date : 2025-04-18 DOI: 10.1016/j.chempr.2025.102534

Sheng-Yi Yang, Liang Zhang, Fan-Cheng Kong, Yingying Chen, Wei-Jian Li, Fei Wang, Cheng Liu, Xuan He, Xuedong Xiao, Jin Wang, Jianwei Sun, Philip C.Y. Chow, Ryan T.K. Kwok, Jacky W.Y. Lam, Ben Zhong Tang

{"title":"Scintillators with aggregation-induced emission","authors":"Sheng-Yi Yang, Liang Zhang, Fan-Cheng Kong, Yingying Chen, Wei-Jian Li, Fei Wang, Cheng Liu, Xuan He, Xuedong Xiao, Jin Wang, Jianwei Sun, Philip C.Y. Chow, Ryan T.K. Kwok, Jacky W.Y. Lam, Ben Zhong Tang","doi":"10.1016/j.chempr.2025.102534","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102534","url":null,"abstract":"Scintillators are vital components in high-energy radiation detectors and are used in fields like high-energy physics, non-destructive testing, radiochemistry, and medical diagnostics. Scintillators with aggregation-induced emission (AIE), through rational molecular design and preparation techniques, can be endowed with such properties that effectively overcome the inherent defects of existing inorganic and/or organic scintillators, such as high costs and poor mechanical properties in inorganic types and low light yield and aggregation-caused quenching for organic kinds, thus affording novel optoelectronic properties, superior performance, and broader applications. This review classifies AIE scintillators from a molecular perspective, based on their luminescence mechanisms and construction strategies, into fluorescent scintillators, thermally activated delayed fluorescence scintillators, metal cluster scintillators, organic-inorganic hybrid scintillators, and metal-organic framework scintillators. This review starts with analyses of these building strategies and the structure-performance relationships and then describes the applications of AIE scintillators based on their molecular structures and optoelectronic properties.","PeriodicalId":268,"journal":{"name":"Chem","volume":"75 5 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846761","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 Sm(II)-based catalyst for the reduction of dinitrogen, nitrite, and nitrate to ammonia or urea 一种Sm（II）基催化剂，用于将二氮、亚硝酸盐和硝酸盐还原为氨或尿素

IF 23.5 1区化学

Chem Pub Date : 2025-04-18 DOI: 10.1016/j.chempr.2025.102547

Rohan Bhimpuria, Rima Charaf, Ke Ye, Anders Thapper, Harsha Sathyan, Mårten Ahlquist, Leif Hammarström, K. Eszter Borbas

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 23.5 1区化学

Chem Pub Date : 2025-04-17 DOI: 10.1016/j.chempr.2025.102554

Ying Sun, Chang Yu, Jieshan Qiu

引用次数: 0

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