Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102823
Bayu I.Z. Ahmad , Phillip J. Milner
In this issue of Chem, Queen and co-workers introduce cluster dehydroxylation by using rapid heat treatment as a new defect-engineering strategy in zirconium-based frameworks. They thoroughly characterize the oxygen-vacancy nature of the defect, primarily by pair distribution function (PDF) analysis. Dehydrated DUT-67 exhibited double the catalytic activity for glyoxal hydration of the pristine material.
{"title":"Untapped defect-engineering strategy: Cluster dehydroxylation of zirconium-based MOFs","authors":"Bayu I.Z. Ahmad , Phillip J. Milner","doi":"10.1016/j.chempr.2025.102823","DOIUrl":"10.1016/j.chempr.2025.102823","url":null,"abstract":"<div><div>In this issue of <em>Chem</em>, Queen and co-workers introduce cluster dehydroxylation by using rapid heat treatment as a new defect-engineering strategy in zirconium-based frameworks. They thoroughly characterize the oxygen-vacancy nature of the defect, primarily by pair distribution function (PDF) analysis. Dehydrated DUT-67 exhibited double the catalytic activity for glyoxal hydration of the pristine material.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102823"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145403967","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102598
Wenchao Wu , Hao Xu , Yang Xu , Peijie Luo , Qingrui Zeng , Yuntian Chen , Yan Xu , Dongxiao Zhang , Fanyang Mo
Efficient compound separation remains a persistent challenge in synthetic chemistry, with column chromatography serving as a critical purification tool. Traditional methods require extensive expertise and repetitive labor—areas where AI offers significant advantages. This study introduces an AI-driven platform to automate data collection and optimize separation processes. By leveraging deep learning, the system predicts key separation parameters, while transfer learning enables adaptation to diverse column specifications. A novel metric, separation probability , quantifies the likelihood of successful component isolation and has been experimentally validated. The approach enhances precision, reduces manual intervention, and expands the scope of chromatographic applications, offering a more efficient and scalable solution for chemical purification.
{"title":"Intelligent column chromatography prediction model based on automation and machine learning","authors":"Wenchao Wu , Hao Xu , Yang Xu , Peijie Luo , Qingrui Zeng , Yuntian Chen , Yan Xu , Dongxiao Zhang , Fanyang Mo","doi":"10.1016/j.chempr.2025.102598","DOIUrl":"10.1016/j.chempr.2025.102598","url":null,"abstract":"<div><div>Efficient compound separation remains a persistent challenge in synthetic chemistry, with column chromatography serving as a critical purification tool. Traditional methods require extensive expertise and repetitive labor—areas where AI offers significant advantages. This study introduces an AI-driven platform to automate data collection and optimize separation processes. By leveraging deep learning, the system predicts key separation parameters, while transfer learning enables adaptation to diverse column specifications. A novel metric, separation probability <span><math><mfenced><msub><mi>S</mi><mi>p</mi></msub></mfenced></math></span>, quantifies the likelihood of successful component isolation and has been experimentally validated. The approach enhances precision, reduces manual intervention, and expands the scope of chromatographic applications, offering a more efficient and scalable solution for chemical purification.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102598"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165532","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102629
Yufeng Luo , Zijian Zheng
The sulfur redox pathways in lithium-sulfur (Li-S) batteries involve an intricate 16-electron conversion process featuring multiple polysulfide intermediates. These polysulfides show high solubility and reactivity in ether-based electrolytes, leading to complex electrochemical and chemical reaction branches. Unlike the much-discussed electrochemical reactions, chemical reactions associated with polysulfides have been largely overlooked in the literature. Herein, we comprehensively summarize these polysulfide-associated chemical reactions with different components in Li-S batteries and discuss their crucial impacts on electrochemical performance. We also propose several notable scientific challenges from the perspective of chemical reactions in practical Li-S batteries and outline feasible strategies to address them for future research.
{"title":"Chemical reactions in lithium-sulfur batteries","authors":"Yufeng Luo , Zijian Zheng","doi":"10.1016/j.chempr.2025.102629","DOIUrl":"10.1016/j.chempr.2025.102629","url":null,"abstract":"<div><div><span>The sulfur redox pathways in lithium-sulfur (Li-S) batteries involve an intricate 16-electron conversion process featuring multiple polysulfide<span> intermediates. These polysulfides show high solubility and reactivity in ether-based electrolytes, leading to complex electrochemical and chemical reaction branches. Unlike the much-discussed electrochemical reactions, chemical reactions associated with polysulfides have been largely overlooked in the literature. Herein, we comprehensively summarize these polysulfide-associated chemical reactions with different components in Li-S batteries and discuss their crucial impacts on </span></span>electrochemical performance. We also propose several notable scientific challenges from the perspective of chemical reactions in practical Li-S batteries and outline feasible strategies to address them for future research.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102629"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533795","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102815
Sihyeong Yi , Ji Hyae Lee , Seung Bum Park
Optimizing natural products for drug discovery remains vital yet challenging. In this issue of Chem, Oguri and co-workers apply a divergent synthetic strategy to redesign the scaffold of the anticancer drug ecteinascidin 743, generating 14- to 17-membered macrocycles with shifted bridgehead connectivity. These analogs preserve the core pharmacophore, expand structural space, and fine-tune DNA alkylation and anticancer potency, offering new strategies for natural product-inspired therapeutics.
{"title":"Divergent scaffold redesign of ecteinascidin 743 as a gateway to anticancer macrocycles","authors":"Sihyeong Yi , Ji Hyae Lee , Seung Bum Park","doi":"10.1016/j.chempr.2025.102815","DOIUrl":"10.1016/j.chempr.2025.102815","url":null,"abstract":"<div><div>Optimizing natural products for drug discovery remains vital yet challenging. In this issue of <em>Chem</em>, Oguri and co-workers apply a divergent synthetic strategy to redesign the scaffold of the anticancer drug ecteinascidin 743, generating 14- to 17-membered macrocycles with shifted bridgehead connectivity. These analogs preserve the core pharmacophore, expand structural space, and fine-tune DNA alkylation and anticancer potency, offering new strategies for natural product-inspired therapeutics.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102815"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500401","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102826
Alexis Grimaud
Enhancing the selectivity of carbon monoxide reduction toward multi-carbon products poses a significant challenge. Now, writing in Nature Chemistry, Zhang and colleagues demonstrate that high ionic strength significantly improves C–C coupling by decreasing water ordering on the surface of copper catalysts and thus achieves more than 90% Faradaic efficiency toward multi-carbon products.
{"title":"Enhancing multi-carbon product formation by increasing water disordering","authors":"Alexis Grimaud","doi":"10.1016/j.chempr.2025.102826","DOIUrl":"10.1016/j.chempr.2025.102826","url":null,"abstract":"<div><div>Enhancing the selectivity of carbon monoxide reduction toward multi-carbon products poses a significant challenge. Now, writing in <em>Nature Chemistry</em>, Zhang and colleagues demonstrate that high ionic strength significantly improves C–C coupling by decreasing water ordering on the surface of copper catalysts and thus achieves more than 90% Faradaic efficiency toward multi-carbon products.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102826"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145428201","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102553
Scot M. Sutton , Sunil Pulletikurti , Huacan Lin , Ramanarayanan Krishnamurthy , Charles L. Liotta
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.
{"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":"10.1016/j.chempr.2025.102553","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102553"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102644
Woo Jae Jeong , Seoungjun Ha , Woon Ju Song
Metalloproteins have evolved through the selective, strong, and precise interactions between metal ions and polypeptides. The coordination of metal ions to amino acid side chains is therefore a fundamental prerequisite for designing metalloproteins. Here, we present Metal-Installer, a user-friendly in silico tool that proposes probable mutation sites for metal ligation. This tool employs four geometric restraints with defined numerical ranges, derived from the chemically guided curation and in-depth analysis of comprehensive metalloprotein structures, and further refines the candidates using probability maps. To validate its utility and accuracy, we applied Metal-Installer to two unrelated protein scaffolds. We successfully created 13 artificial mononuclear and dinuclear metalloproteins incorporating zinc, manganese, iron, or copper. The X-ray crystal structures, biochemical properties, spectroscopic features, and catalytic activities of these metalloproteins closely match our predictions, demonstrating that Metal-Installer enables the accurate and broadly applicable design of artificial metalloproteins across diverse protein scaffolds, metal elements, ligand combinations, and nuclearities.
{"title":"Accurate computational design of artificial metalloproteins using Metal-Installer","authors":"Woo Jae Jeong , Seoungjun Ha , Woon Ju Song","doi":"10.1016/j.chempr.2025.102644","DOIUrl":"10.1016/j.chempr.2025.102644","url":null,"abstract":"<div><div>Metalloproteins have evolved through the selective, strong, and precise interactions between metal ions and polypeptides. The coordination of metal ions to amino acid side chains is therefore a fundamental prerequisite for designing metalloproteins. Here, we present Metal-Installer, a user-friendly <em>in silico</em> tool that proposes probable mutation sites for metal ligation. This tool employs four geometric restraints with defined numerical ranges, derived from the chemically guided curation and in-depth analysis of comprehensive metalloprotein structures, and further refines the candidates using probability maps. To validate its utility and accuracy, we applied Metal-Installer to two unrelated protein scaffolds. We successfully created 13 artificial mononuclear and dinuclear metalloproteins incorporating zinc, manganese, iron, or copper. The X-ray crystal structures, biochemical properties, spectroscopic features, and catalytic activities of these metalloproteins closely match our predictions, demonstrating that Metal-Installer enables the accurate and broadly applicable design of artificial metalloproteins across diverse protein scaffolds, metal elements, ligand combinations, and nuclearities.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102644"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516261","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}
Pub Date : 2025-11-13DOI: 10.1016/j.chempr.2025.102658
Jonas Spengler , Yvonne Wagenhäuser , Frank Würthner
The discovery of different sp2-carbon allotropes such as fullerenes (0D), carbon nanotubes (1D), and graphene (2D) has tremendously impacted molecular materials research. Starting from simple but highly interesting non-planar hydrocarbon building blocks, the logical extension into three dimensions—curved structures called schwarzites—was theoretically predicted by Mackay and Terrones in 1991 but remains elusive, owing to the tremendous synthetic challenge these structures present. In this perspective, we discuss approaches toward schwarzite carbon materials and present our own vision of how atomically precise schwarzites might be synthesized. Key steps of this approach are the template-mediated preorganization of small molecular cutouts of schwarzites and the subsequent formation of the desired, three-dimensionally conjugated carbon allotrope under suitable conditions for C–C bond formation and reorganization.
{"title":"Schwarzite—The holy grail of carbon allotropes","authors":"Jonas Spengler , Yvonne Wagenhäuser , Frank Würthner","doi":"10.1016/j.chempr.2025.102658","DOIUrl":"10.1016/j.chempr.2025.102658","url":null,"abstract":"<div><div>The discovery of different sp<sup>2</sup>-carbon allotropes such as fullerenes (0D), carbon nanotubes (1D), and graphene (2D) has tremendously impacted molecular materials research. Starting from simple but highly interesting non-planar hydrocarbon building blocks, the logical extension into three dimensions—curved structures called schwarzites—was theoretically predicted by Mackay and Terrones in 1991 but remains elusive, owing to the tremendous synthetic challenge these structures present. In this perspective, we discuss approaches toward schwarzite carbon materials and present our own vision of how atomically precise schwarzites might be synthesized. Key steps of this approach are the template-mediated preorganization of small molecular cutouts of schwarzites and the subsequent formation of the desired, three-dimensionally conjugated carbon allotrope under suitable conditions for C–C bond formation and reorganization.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102658"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144715639","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}
Pub Date : 2025-11-07DOI: 10.1016/j.chempr.2025.102817
Marco Pierau, Mathis J. Karrasch, Paulina Hartmann, Constantin G. Daniliuc, Andrea Hamza, Frank Glorius
Nitrogen-enriched (partially) saturated fused heterocycles have emerged as highly relevant scaffolds for improved pharmaceuticals. Increased solubility, along with fine-tuneable target affinity and specificity, differentiate them from their nitrogen-poor aromatic counterparts. Contrary to their growing demand, applications are severely limited by arduous bottom-up synthesis routes and the lack of a general solution for facile access. Herein, we report an efficient method for the synthesis of chiral (semi-)saturated pyridine-fused heterocycles and their respective N-permutations by enantioselective arene hydrogenation with a newly developed ruthenium catalyst. We obtained versatile and highly valuable product motifs, including pyridine- and piperidine-fused scaffolds with up to four newly formed stereocenters, of which several have not been previously reported. We conducted extensive in silico studies to elucidate a rare inverse-pressure-dependent enantioselectivity and to develop a rational model for predicting the stereochemical outcome. This contribution is expected to accelerate the exploration of new frameworks in drug discovery.
{"title":"Direct access to chiral nitrogen-rich (semi-)saturated heterocycles","authors":"Marco Pierau, Mathis J. Karrasch, Paulina Hartmann, Constantin G. Daniliuc, Andrea Hamza, Frank Glorius","doi":"10.1016/j.chempr.2025.102817","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102817","url":null,"abstract":"Nitrogen-enriched (partially) saturated fused heterocycles have emerged as highly relevant scaffolds for improved pharmaceuticals. Increased solubility, along with fine-tuneable target affinity and specificity, differentiate them from their nitrogen-poor aromatic counterparts. Contrary to their growing demand, applications are severely limited by arduous bottom-up synthesis routes and the lack of a general solution for facile access. Herein, we report an efficient method for the synthesis of chiral (semi-)saturated pyridine-fused heterocycles and their respective N-permutations by enantioselective arene hydrogenation with a newly developed ruthenium catalyst. We obtained versatile and highly valuable product motifs, including pyridine- and piperidine-fused scaffolds with up to four newly formed stereocenters, of which several have not been previously reported. We conducted extensive <em>in silico</em> studies to elucidate a rare inverse-pressure-dependent enantioselectivity and to develop a rational model for predicting the stereochemical outcome. This contribution is expected to accelerate the exploration of new frameworks in drug discovery.","PeriodicalId":268,"journal":{"name":"Chem","volume":"1 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145455209","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}
Pub Date : 2025-11-05DOI: 10.1016/j.chempr.2025.102814
Lei Cui, Wanning Wu, Ethan R. Pezoulas, Jiangtao Jia, Zheng Bian, Jeffrey R. Long, Guangshan Zhu
Implementing marine uranium extraction is crucial for maintaining a continuous supply of fuel for nuclear reactors. Many adsorbents leverage oxime or amidoxime functional groups to bind uranyl ions, but the competitive adsorption of orthovanadate inhibits their practical application. Despite the high affinity of these ligands for binding both uranyl and orthovanadate, the different steric profiles of the two ions could be leveraged for their separation. Here, porous aromatic frameworks (PAFs) functionalized with oxime and amidoxime groups (PAF-1-O and PAF-1-AO) were synthesized and tested for their size-sieving capabilities. In both materials, the narrow pore size and rigid nature of the framework lead to the exclusion of the larger orthovanadate ions, whereas the smaller uranyl ions penetrate the framework and are readily adsorbed by the binding groups. In a binary mixture of uranyl and orthovanadate ions (∼2 mg L−1 each), PAF-1-O and PAF-1-AO both exhibit near-perfect adsorption selectivity for uranyl. In an unmodified sample of seawater, PAF-1-AO reached a uranium-adsorption capacity of 11.5 mg g−1 within 28 days and a record uranium-to-vanadium (U/V) selectivity of 243. The sieving-based selectivity exhibited by these PAF materials offers a promising new prospect for the extraction of uranium from seawater.
实施海洋铀提取对维持核反应堆燃料的持续供应至关重要。许多吸附剂利用肟或偕胺肟官能团结合铀酰离子，但正钒酸盐的竞争性吸附抑制了它们的实际应用。尽管这些配体对铀酰和正钒酸盐都有很高的亲和力，但这两种离子的不同空间分布可以用来分离它们。本文合成了肟基和偕胺肟基（PAF-1-O和PAF-1-AO）功能化的多孔芳香骨架（paf），并对其筛分能力进行了测试。在这两种材料中，狭窄的孔径和框架的刚性导致较大的正钒酸盐离子被排除在外，而较小的铀酰离子穿透框架并容易被结合基团吸附。在铀酰和正钒酸盐离子的二元混合物中（各约2 mg L−1），PAF-1-O和PAF-1-AO对铀酰都表现出近乎完美的吸附选择性。在未经改性的海水样品中，PAF-1-AO在28天内达到11.5 mg g -1的铀吸附量，并且创纪录的铀对钒（U/V）选择性为243。这些PAF材料所表现出的基于筛选的选择性为从海水中提取铀提供了一个有希望的新前景。
{"title":"Highly selective and efficient uranium recovery by size-sieving porous aromatic frameworks with rigidly functionalized windows","authors":"Lei Cui, Wanning Wu, Ethan R. Pezoulas, Jiangtao Jia, Zheng Bian, Jeffrey R. Long, Guangshan Zhu","doi":"10.1016/j.chempr.2025.102814","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102814","url":null,"abstract":"Implementing marine uranium extraction is crucial for maintaining a continuous supply of fuel for nuclear reactors. Many adsorbents leverage oxime or amidoxime functional groups to bind uranyl ions, but the competitive adsorption of orthovanadate inhibits their practical application. Despite the high affinity of these ligands for binding both uranyl and orthovanadate, the different steric profiles of the two ions could be leveraged for their separation. Here, porous aromatic frameworks (PAFs) functionalized with oxime and amidoxime groups (PAF-1-O and PAF-1-AO) were synthesized and tested for their size-sieving capabilities. In both materials, the narrow pore size and rigid nature of the framework lead to the exclusion of the larger orthovanadate ions, whereas the smaller uranyl ions penetrate the framework and are readily adsorbed by the binding groups. In a binary mixture of uranyl and orthovanadate ions (∼2 mg L<sup>−1</sup> each), PAF-1-O and PAF-1-AO both exhibit near-perfect adsorption selectivity for uranyl. In an unmodified sample of seawater, PAF-1-AO reached a uranium-adsorption capacity of 11.5 mg g<sup>−1</sup> within 28 days and a record uranium-to-vanadium (U/V) selectivity of 243. The sieving-based selectivity exhibited by these PAF materials offers a promising new prospect for the extraction of uranium from seawater.","PeriodicalId":268,"journal":{"name":"Chem","volume":"166 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145441721","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}
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