Stella A. Fors, Richard J. Monsky, Emily R. Mahoney, Christian A. Malapit, William R. Dichtel
Efficient, scalable, and well-understood methods for degrading per- and polyfluoroalkyl substances (PFAS) are essential for limiting their numerous negative human health and environmental effects. Electrochemical methods are promising for PFAS degradation but are currently not yet well developed for use in non-aqueous conditions relevant for PFAS sorbent regeneration without resorting to specialized electrode materials. Herein, we report the mediated electrochemical conversion of perfluoroalkyl sulfonates to carboxylates using commercial Pt electrodes in acetonitrile. Perfluorooctane sulfonate (PFOS) was converted primarily to perfluorooctanoic acid (PFOA) alongside several shorter-chain carboxylates through a proposed radical desulfonation and hydroxide coupling process explored in a detailed mechanistic study. Following the near-complete conversion of PFOS to perfluoroalkyl carboxylates, all species are mineralized to fluoride and non-fluorinated carbon byproducts using established low-temperature DMSO/NaOH conditions. HPLC-MS, ion chromatography, and quantitative nuclear magnetic resonance (NMR) methods determined a significant loss in fluorine and carbon balance after electrochemistry, which we attribute to the production of volatile byproducts. This degradation approach provides new insights into PFAS degradation mechanisms under highly oxidative, non-aqueous conditions and highlights the potential for organic electrochemistry to address environmental challenges by promoting controlled and selective destruction pathways for common organic pollutants.
{"title":"Electrochemical Degradation of Perfluoroalkyl Sulfonates via Sulfonate to Carboxylate Conversion","authors":"Stella A. Fors, Richard J. Monsky, Emily R. Mahoney, Christian A. Malapit, William R. Dichtel","doi":"10.1002/anie.202525896","DOIUrl":"https://doi.org/10.1002/anie.202525896","url":null,"abstract":"Efficient, scalable, and well-understood methods for degrading per- and polyfluoroalkyl substances (PFAS) are essential for limiting their numerous negative human health and environmental effects. Electrochemical methods are promising for PFAS degradation but are currently not yet well developed for use in non-aqueous conditions relevant for PFAS sorbent regeneration without resorting to specialized electrode materials. Herein, we report the mediated electrochemical conversion of perfluoroalkyl sulfonates to carboxylates using commercial Pt electrodes in acetonitrile. Perfluorooctane sulfonate (PFOS) was converted primarily to perfluorooctanoic acid (PFOA) alongside several shorter-chain carboxylates through a proposed radical desulfonation and hydroxide coupling process explored in a detailed mechanistic study. Following the near-complete conversion of PFOS to perfluoroalkyl carboxylates, all species are mineralized to fluoride and non-fluorinated carbon byproducts using established low-temperature DMSO/NaOH conditions. HPLC-MS, ion chromatography, and quantitative nuclear magnetic resonance (NMR) methods determined a significant loss in fluorine and carbon balance after electrochemistry, which we attribute to the production of volatile byproducts. This degradation approach provides new insights into PFAS degradation mechanisms under highly oxidative, non-aqueous conditions and highlights the potential for organic electrochemistry to address environmental challenges by promoting controlled and selective destruction pathways for common organic pollutants.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"57 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920601","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}
Catalytic alkene cyclization initiated by carbon electrophiles represents an emerging strategy for constructing valuable and challenging molecular architectures. However, due to reactivity issues, the realization of such reactions with tertiary carbon electrophiles remains a formidable challenge. Herein, we report an efficient Brønsted acid-catalyzed system that overcomes this limitation. Using 1-adamantanols as precursors of tertiary carbocation electrophiles, and through TfOH catalysis, alkenes tethered with carboxyl, sulfonamide, and hydroxyl groups, including those with relatively low reactivity such as alkyl-substituted and terminal alkenes, can be converted into a variety of adamantylated heterocycles in hexafluoroisopropanol with good yields via 1,2-addition or formal 1,1-addition, with high regio- and stereoselectivity. The products serve as versatile synthetic building blocks and can be readily transformed into valuable adamantyl-containing compounds, including derivatives with anti-influenza A activity. Density functional theory (DFT) calculations and control experiments indicate that the moderate electrophilicity of the adamantyl carbocation and the hyperconjugative effect of the adamantyl group in stabilizing carbocations form the basis for achieving the electrophilic cyclization. Additionally, they also reveal that different nucleophilic groups can influence the progression of the reaction. These findings provide references for the design of new electrophilic reactions.
{"title":"Catalytic 1,2- and 1,1-Carbocyclization of Alkenes Employing Adamantanols as Tertiary Carbocation Precursors","authors":"Hongtai Huang, Wangzhen Qiu, Lihao Liao, Xiaodan Zhao","doi":"10.1002/anie.202524449","DOIUrl":"https://doi.org/10.1002/anie.202524449","url":null,"abstract":"Catalytic alkene cyclization initiated by carbon electrophiles represents an emerging strategy for constructing valuable and challenging molecular architectures. However, due to reactivity issues, the realization of such reactions with tertiary carbon electrophiles remains a formidable challenge. Herein, we report an efficient Brønsted acid-catalyzed system that overcomes this limitation. Using 1-adamantanols as precursors of tertiary carbocation electrophiles, and through TfOH catalysis, alkenes tethered with carboxyl, sulfonamide, and hydroxyl groups, including those with relatively low reactivity such as alkyl-substituted and terminal alkenes, can be converted into a variety of adamantylated heterocycles in hexafluoroisopropanol with good yields via 1,2-addition or formal 1,1-addition, with high regio- and stereoselectivity. The products serve as versatile synthetic building blocks and can be readily transformed into valuable adamantyl-containing compounds, including derivatives with anti-influenza A activity. Density functional theory (DFT) calculations and control experiments indicate that the moderate electrophilicity of the adamantyl carbocation and the hyperconjugative effect of the adamantyl group in stabilizing carbocations form the basis for achieving the electrophilic cyclization. Additionally, they also reveal that different nucleophilic groups can influence the progression of the reaction. These findings provide references for the design of new electrophilic reactions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"157 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920602","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}
Tinghao Yun, Kexing Cai, Zhijie Jiang, Jun Zhao, Lei Li, Sihong Du, Xuzhou Yan
Silicon/carbon (Si/C) composite anodes are among the most promising candidates for high-energy-density lithium-ion batteries but suffer from severe volume fluctuation and interfacial degradation during cycling. Herein, we report a water-processable covalent-and-supramolecular polymeric binders (CSPBs) that synergistically dissipate mechanical stress and promote Li+ transport to stabilize the Si/C anode interface. The CSPBs integrate poly(acrylic acid) (PAA), amine-terminated eight-arm poly(ethylene glycol) (8arm-PEG-NH2), and benzo-21-crown-7/secondary ammonium host–guest complexes through amidation during electrode fabrication. The covalent linkages impart strong structural integrity, while the reversible supramolecular interactions act as sacrificial bonds to dissipate stress arising from Si volume expansion. Additionally, oxygen-rich PEG chains form continuous Li+ conduction pathways, enabling efficient ion transport. As a result, the CSPB-2-based Si/C anode delivers a high specific capacity of 582.0 mAh g−1 after 265 cycles at 1C, with superior rate capability than the electrodes based on PAA or solely covalently cross-linked binders (CCBs). Kinetic analysis reveals an enhanced Li+ diffusion coefficient, confirming the improved ionic conductivity of the binder system. This work demonstrates a new strategy for integrating covalent anchoring and dynamic supramolecular adaptability within a sustainable, water-processable polymeric binder system, paving the way for the design of durable and high-performance silicon-based anodes.
硅/碳（Si/C）复合阳极是高能量密度锂离子电池最有前途的候选材料之一，但在循环过程中存在严重的体积波动和界面退化问题。在此，我们报告了一种可水处理的共价和超分子聚合物粘合剂（CSPBs），它可以协同消散机械应力并促进Li+传输以稳定Si/C阳极界面。CSPBs在电极制备过程中通过酰胺化集成了聚丙烯酸（PAA）、胺端八臂聚乙二醇（8臂- peg - nh2）和苯并-21-冠-7/仲铵主客体配合物。共价键具有很强的结构完整性，而可逆的超分子相互作用作为牺牲键来消散硅体积膨胀引起的应力。此外，富氧PEG链形成连续的Li+传导途径，实现高效的离子传输。因此，基于cspb -2的Si/C阳极在1C下循环265次后提供了582.0 mAh g - 1的高比容量，比基于PAA或单独共价交联粘合剂（CCBs）的电极具有更高的倍率能力。动力学分析表明Li+扩散系数增强，证实了粘结剂体系离子电导率的提高。这项工作展示了一种将共价锚定和动态超分子适应性整合到可持续的、可水处理的聚合物粘合剂体系中的新策略，为设计耐用和高性能的硅基阳极铺平了道路。
{"title":"Water-Processable Covalent-and-Supramolecular Polymeric Binders for Silicon/Carbon Anodes with High Interfacial Stability in Lithium-Ion Batteries","authors":"Tinghao Yun, Kexing Cai, Zhijie Jiang, Jun Zhao, Lei Li, Sihong Du, Xuzhou Yan","doi":"10.1002/anie.202525354","DOIUrl":"https://doi.org/10.1002/anie.202525354","url":null,"abstract":"Silicon/carbon (Si/C) composite anodes are among the most promising candidates for high-energy-density lithium-ion batteries but suffer from severe volume fluctuation and interfacial degradation during cycling. Herein, we report a water-processable covalent-and-supramolecular polymeric binders (CSPBs) that synergistically dissipate mechanical stress and promote Li<sup>+</sup> transport to stabilize the Si/C anode interface. The CSPBs integrate poly(acrylic acid) (PAA), amine-terminated eight-arm poly(ethylene glycol) (8arm-PEG-NH<sub>2</sub>), and benzo-21-crown-7/secondary ammonium host–guest complexes through amidation during electrode fabrication. The covalent linkages impart strong structural integrity, while the reversible supramolecular interactions act as sacrificial bonds to dissipate stress arising from Si volume expansion. Additionally, oxygen-rich PEG chains form continuous Li<sup>+</sup> conduction pathways, enabling efficient ion transport. As a result, the CSPB-<b>2</b>-based Si/C anode delivers a high specific capacity of 582.0 mAh g<sup>−1</sup> after 265 cycles at 1C, with superior rate capability than the electrodes based on PAA or solely covalently cross-linked binders (CCBs). Kinetic analysis reveals an enhanced Li<sup>+</sup> diffusion coefficient, confirming the improved ionic conductivity of the binder system. This work demonstrates a new strategy for integrating covalent anchoring and dynamic supramolecular adaptability within a sustainable, water-processable polymeric binder system, paving the way for the design of durable and high-performance silicon-based anodes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"51 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920606","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}
Helicobacter pylori infection represents a major global health challenge, characterized by high prevalence, significant association with gastric cancer, and rising antibiotic resistance. Carbohydrate-based vaccines targeting the O-antigen of lipopolysaccharide (LPS) present a promising alternative to conventional antimicrobial therapies. To explore the immunogenicity of LPS O-antigen from clinical isolate H. pylori SS1, we report an integrated chemoenzymatic strategy for the first synthesis of its octadecasaccharide O-antigen and related fragments for antigenicity evaluation. Our strategy features modular chemical synthesis of a decasaccharide precursor containing a high-carbon sugar (D,D-Hep) residue, a unique oligomeric β1,2-linked ribofuranosyl tetrasaccharide motif and a switchable glucosamine (GlcNH2) residue through stereoconvergent [6 + 4] assembly, followed by protecting-group-controlled enzymatic elongation to precisely install hybrid Lewis antigen moiety (Ley-Lex) in a site-specific fucosylation manner to afford the target octadecasaccharide bearing five challenging 1,2-cis-glycosidic linkages. Chemical stereoselective construction of 1,2-cis-glucosidic and 1,2-cis-fucosidic linkages was accomplished by reagent-controlled glycosylation and 4-O-acyl remote participation, respectively. Enzymatic site-specific installation of the remaining three 1,2-cis-fucosidic linkages was achieved using two robust fucosyltransferases and a strategically designed GlcNH2 residue. Glycan microarray-based screening of the synthetic O-antigen and its subunits with H. pylori-infected patient sera identified an undecasaccharide as a simpler and key epitope for vaccine development.
幽门螺杆菌感染是一项主要的全球健康挑战，其特点是患病率高，与胃癌有显著关联，并且抗生素耐药性不断上升。针对脂多糖（LPS） o抗原的碳水化合物疫苗是传统抗菌疗法的一个有希望的替代方案。为了探索临床分离幽门螺杆菌SS1 LPS o抗原的免疫原性，我们报道了一种综合的化学酶策略，首次合成了其十八糖o抗原和相关片段，用于抗原性评价。我们的策略是通过立体聚合[6 + 4]组装，模块化化学合成含有高碳糖（D,D- hep）残基、独特的寡聚β1,2-连接核呋喃基四糖基基和可切换氨基（GlcNH2）残基的十糖前体。然后是保护基团控制的酶延伸，以位点特异性聚焦方式精确安装杂交Lewis抗原片段（Ley-Lex），以使目标十八糖具有5个具有挑战性的1,2-顺式糖苷键。1,2-顺式糖苷键和1,2-顺式聚焦键的化学立体选择性构建分别通过试剂控制的糖基化和4- o -酰基远程参与完成。剩余的三个1,2-顺式聚焦键的酶位点特异性安装是通过两个强大的聚焦转移酶和一个战略性设计的GlcNH2残基实现的。基于糖微阵列的筛选合成o抗原及其亚基与幽门螺杆菌感染患者的血清鉴定出一种非糖糖作为疫苗开发的更简单和关键的表位。
{"title":"Chemoenzymatic Synthesis and Antigenicity Evaluation of an O-Antigen Octadecasaccharide from Helicobacter pylori","authors":"Wei Liu, Wei Zhang, Zhuojia Xu, Wenkai Liu, Jiajia Wang, Xia Li, Jian Gao, Tiehai Li","doi":"10.1002/anie.202523768","DOIUrl":"https://doi.org/10.1002/anie.202523768","url":null,"abstract":"<i>Helicobacter pylori</i> infection represents a major global health challenge, characterized by high prevalence, significant association with gastric cancer, and rising antibiotic resistance. Carbohydrate-based vaccines targeting the O-antigen of lipopolysaccharide (LPS) present a promising alternative to conventional antimicrobial therapies. To explore the immunogenicity of LPS O-antigen from clinical isolate <i>H. pylori</i> SS1, we report an integrated chemoenzymatic strategy for the first synthesis of its octadecasaccharide O-antigen and related fragments for antigenicity evaluation. Our strategy features modular chemical synthesis of a decasaccharide precursor containing a high-carbon sugar (D,D-Hep) residue, a unique oligomeric β1,2-linked ribofuranosyl tetrasaccharide motif and a switchable glucosamine (GlcNH<sub>2</sub>) residue through stereoconvergent [6 + 4] assembly, followed by protecting-group-controlled enzymatic elongation to precisely install hybrid Lewis antigen moiety (Le<i><sup>y</sup></i>-Le<i><sup>x</sup></i>) in a site-specific fucosylation manner to afford the target octadecasaccharide bearing five challenging 1,2-<i>cis</i>-glycosidic linkages. Chemical stereoselective construction of 1,2-<i>cis</i>-glucosidic and 1,2-<i>cis</i>-fucosidic linkages was accomplished by reagent-controlled glycosylation and 4-<i>O</i>-acyl remote participation, respectively. Enzymatic site-specific installation of the remaining three 1,2-<i>cis</i>-fucosidic linkages was achieved using two robust fucosyltransferases and a strategically designed GlcNH<sub>2</sub> residue. Glycan microarray-based screening of the synthetic O-antigen and its subunits with <i>H. pylori</i>-infected patient sera identified an undecasaccharide as a simpler and key epitope for vaccine development.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"44 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920611","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}
Cyclative C(sp3)–H functionalization of unactivated C─H bonds with heteroatoms is a straightforward way to construct saturated aza- and oxo-heterocycles, which continues to display ever-increasing prevalence in drug design. Building upon our recently reported copper catalysis that used simple N-methoxyamides as radical precursors, we report a method to access diverse aza- and oxo-heterocycles, including cyclic sulfonamides, cyclic ethers, and lactones of different ring sizes. By placing a heteroatom in the N-methoxyamide substrate, the carbon radical formed at the γ-position from the intramolecular H-abstraction by the amidyl radical could be trapped with the pendant heteroatom, leading to a redox-neutral Cu-catalyzed cyclative γ-C(sp3)–H functionalization. The syntheses of a wide range of saturated aza- and oxo-heterocycles demonstrate the versatility of this method.
{"title":"Redox-Neutral Cu-Catalyzed Cyclative γ-C–H Functionalization Enroute to Aza- and Oxo-heterocycles","authors":"Zi-Jun Zhang, Shupeng Zhou, Jin-Quan Yu","doi":"10.1002/anie.202521635","DOIUrl":"https://doi.org/10.1002/anie.202521635","url":null,"abstract":"Cyclative C(sp<sup>3</sup>)–H functionalization of unactivated C─H bonds with heteroatoms is a straightforward way to construct saturated aza- and oxo-heterocycles, which continues to display ever-increasing prevalence in drug design. Building upon our recently reported copper catalysis that used simple <i>N</i>-methoxyamides as radical precursors, we report a method to access diverse aza- and oxo-heterocycles, including cyclic sulfonamides, cyclic ethers, and lactones of different ring sizes. By placing a heteroatom in the <i>N</i>-methoxyamide substrate, the carbon radical formed at the γ-position from the intramolecular H-abstraction by the amidyl radical could be trapped with the pendant heteroatom, leading to a redox-neutral Cu-catalyzed cyclative γ-C(sp<sup>3</sup>)–H functionalization. The syntheses of a wide range of saturated aza- and oxo-heterocycles demonstrate the versatility of this method.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920612","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}
Zijie Luo, Kaustubh R. Bhuskute, Yuxue Cao, Jie Tang, Amandeep Kaur
The plasma membrane exhibits diverse substructures, such as pseudopodia, membrane nanotubes, and migrasomes, that are essential for cellular communication and cargo transport. Imaging these fine structures remains challenging due to their nanoscale dimensions and limitations of existing fluorescent probes. Here, we report the development of two rhodamine-based probes, RSD1 and RSD2, incorporating anionic membrane-anchoring groups and pyrrolidine auxochromes to enable wash-free, serum-compatible, long-term plasma membrane imaging. RSD2, in particular, demonstrates superior fluorogenicity, brightness, and photoswitching properties, facilitating high-resolution imaging in both live and fixed cells. It selectively labels membrane substructures across diverse cell types and maintains membrane specificity in the presence of serum. RSD2 is compatible with advanced microscopy techniques including confocal microscopy, instant structured illumination microscopy (iSIM), and direct stochastic optical reconstruction microscopy (dSTORM), achieving up to 40 nm resolution. Using two-color dSTORM, we visualize silica nanoparticle trafficking via membrane nanotubes and gondola-like bulges in neuronal cells, marking the first such observation. RSD2 also enables imaging of migrasomes and retraction fibers, revealing dynamic membrane-mediated transport processes. This probe offers a robust and versatile platform for investigating membrane architecture and function, with broad applicability in cell biology, nanomedicine, and super-resolution imaging.
{"title":"Fluorogenic Rhodamine Probes Enable High-Resolution Visualization of Plasma Membrane Nanostructures","authors":"Zijie Luo, Kaustubh R. Bhuskute, Yuxue Cao, Jie Tang, Amandeep Kaur","doi":"10.1002/anie.202519056","DOIUrl":"https://doi.org/10.1002/anie.202519056","url":null,"abstract":"The plasma membrane exhibits diverse substructures, such as pseudopodia, membrane nanotubes, and migrasomes, that are essential for cellular communication and cargo transport. Imaging these fine structures remains challenging due to their nanoscale dimensions and limitations of existing fluorescent probes. Here, we report the development of two rhodamine-based probes, <b>RSD1</b> and <b>RSD2</b>, incorporating anionic membrane-anchoring groups and pyrrolidine auxochromes to enable wash-free, serum-compatible, long-term plasma membrane imaging. <b>RSD2</b>, in particular, demonstrates superior fluorogenicity, brightness, and photoswitching properties, facilitating high-resolution imaging in both live and fixed cells. It selectively labels membrane substructures across diverse cell types and maintains membrane specificity in the presence of serum. <b>RSD2</b> is compatible with advanced microscopy techniques including confocal microscopy, instant structured illumination microscopy (iSIM), and direct stochastic optical reconstruction microscopy (dSTORM), achieving up to 40 nm resolution. Using two-color dSTORM, we visualize silica nanoparticle trafficking via membrane nanotubes and gondola-like bulges in neuronal cells, marking the first such observation. <b>RSD2</b> also enables imaging of migrasomes and retraction fibers, revealing dynamic membrane-mediated transport processes. This probe offers a robust and versatile platform for investigating membrane architecture and function, with broad applicability in cell biology, nanomedicine, and super-resolution imaging.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"27 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145919891","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}
Xiongli Liu, Zhiyuan Zhang, Shuo Zhang, Lin Li, Junhua Wang, Feng Shui, Mao Yi, Zifeng You, Shan Wang, Yilian Liu, Qiao Zhao, Baiyan Li, Xian-He Bu
Capturing radioactive molecular iodine (I2) from nuclear waste under industrial conditions remains a considerable challenge. Herein, we developed for the first time a pore space multiple-layer functionalization (PSMLF) strategy, which enables directionally distribute functional sites across the multi-layer regions of large pore space, thereby enhancing the I2 adsorption ability by optimizing pore space utilization. Utilizing this approach, the optimized adsorbent PAF-1-NTM achieves a record-high I2 uptake of 88.58 wt% under simulated industrial conditions (150 °C and 150 ppmv I2), a 108-fold improvement over its parent material, PAF-1. This performance significantly surpasses that of industrial Ag@MOR and all previously benchmarked adsorbents under the same conditions. Furthermore, adsorption kinetic of PAF-1-NTM (k1 = 0.025 min−1) are significantly higher than those of all other porous adsorbents reported to date. These results thus establish PAF-1-NTM as a new benchmark for high-temperature I2 adsorbents. Mechanism investigation reveals a new insight that the I2 adsorption capacity is positively correlated with the pore space utilization rate. Our work not only develops a promising adsorbent for industrial radioactive I2 capture but also establishes a general design principle for creating high-temperature I2 adsorbents suitable for practical applications.
{"title":"Pore Space Multi-Layer Functionalization Boosting Industrial Radioactive Iodine Capture with Record Capacity and Exceptional Kinetics","authors":"Xiongli Liu, Zhiyuan Zhang, Shuo Zhang, Lin Li, Junhua Wang, Feng Shui, Mao Yi, Zifeng You, Shan Wang, Yilian Liu, Qiao Zhao, Baiyan Li, Xian-He Bu","doi":"10.1002/anie.202521492","DOIUrl":"https://doi.org/10.1002/anie.202521492","url":null,"abstract":"Capturing radioactive molecular iodine (I<sub>2</sub>) from nuclear waste under industrial conditions remains a considerable challenge. Herein, we developed for the first time a pore space multiple-layer functionalization (PSMLF) strategy, which enables directionally distribute functional sites across the multi-layer regions of large pore space, thereby enhancing the I<sub>2</sub> adsorption ability by optimizing pore space utilization. Utilizing this approach, the optimized adsorbent PAF-1-NTM achieves a record-high I<sub>2</sub> uptake of 88.58 wt% under simulated industrial conditions (150 °C and 150 ppmv I<sub>2</sub>), a 108-fold improvement over its parent material, PAF-1. This performance significantly surpasses that of industrial Ag@MOR and all previously benchmarked adsorbents under the same conditions. Furthermore, adsorption kinetic of PAF-1-NTM (<i>k</i><sub>1</sub> = 0.025 min<sup>−1</sup>) are significantly higher than those of all other porous adsorbents reported to date. These results thus establish PAF-1-NTM as a new benchmark for high-temperature I<sub>2</sub> adsorbents. Mechanism investigation reveals a new insight that the I<sub>2</sub> adsorption capacity is positively correlated with the pore space utilization rate. Our work not only develops a promising adsorbent for industrial radioactive I<sub>2</sub> capture but also establishes a general design principle for creating high-temperature I<sub>2</sub> adsorbents suitable for practical applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"2 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920605","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}
Maxime Hourtoule,Piotr Skumial,Sven Trienes,Hasret Can Gülen,Jian Zhang,Lutz Ackermann
Due to their intensive use in every aspect of our everyday life, plastics are accumulating in the environment, hence representing a major societal challenge. The accumulation of plastic waste in the oceans is expected to reach 40 billion tons by 2050. Thus, efficient methods for chemical plastic waste recycling continue to be in high demand toward a future circular economy. Herein, we report a powerful and user-friendly strategy merging inexpensive and earth-abundant iron catalysis, light irradiation and electricity to recycle polystyrene and styrene-containing copolymers into value-added benzoyl products with up to 73% yield. The robustness of this approach using iron-electrocatalysis under light irradiation was further demonstrated using postconsumer waste, also viable on multigram scale. Cathodic formation of molecular hydrogen through the hydrogen evolution reaction (HER) offers an outstanding potential for a decentralized green hydrogen economy through a societally useful anodic oxidative transformation.
{"title":"Synergistic Effects of Electricity and Light for Efficient Iron-Catalyzed Recycling of Polystyrene Waste.","authors":"Maxime Hourtoule,Piotr Skumial,Sven Trienes,Hasret Can Gülen,Jian Zhang,Lutz Ackermann","doi":"10.1002/anie.202519237","DOIUrl":"https://doi.org/10.1002/anie.202519237","url":null,"abstract":"Due to their intensive use in every aspect of our everyday life, plastics are accumulating in the environment, hence representing a major societal challenge. The accumulation of plastic waste in the oceans is expected to reach 40 billion tons by 2050. Thus, efficient methods for chemical plastic waste recycling continue to be in high demand toward a future circular economy. Herein, we report a powerful and user-friendly strategy merging inexpensive and earth-abundant iron catalysis, light irradiation and electricity to recycle polystyrene and styrene-containing copolymers into value-added benzoyl products with up to 73% yield. The robustness of this approach using iron-electrocatalysis under light irradiation was further demonstrated using postconsumer waste, also viable on multigram scale. Cathodic formation of molecular hydrogen through the hydrogen evolution reaction (HER) offers an outstanding potential for a decentralized green hydrogen economy through a societally useful anodic oxidative transformation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"23 1","pages":"e19237"},"PeriodicalIF":16.6,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145907786","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}
Covalent organic frameworks (COFs) incorporating photoredox-active motifs show great promise as heterogeneous catalysts, yet their applications have been largely confined to one-step transformations. In this work, we design and synthesize a series of three-dimensional (3D) COFs with different π-extended dihydrophenazine cores to achieve superior photocatalytic performance. These 3D COFs exhibit excellent crystallinity, high surface areas, and remarkable chemical stability. More importantly, they can work as highly efficient and recyclable catalysts for photocatalytic tandem polymerization reactions using styrene and fluoroalkyl anhydrides as substrates, yielding fluoroalkylated polystyrene polymers with narrow dispersity. These COFs constitute the first examples as tandem photocatalysts toward polymerization reactions. Moreover, optimal energy level alignment and enhanced photophysical properties are identified as key factors contributing to their high efficacy. This work not only provides a viable design strategy for multifunctional COF catalysts, but also expands their utility in complex synthetic sequences involving tandem catalytic processes.
{"title":"Energy Level Engineering of Dihydrophenazine-Based Covalent Organic Frameworks Through π-Expansion of Cores Toward Tandem Photocatalytic Polymerization.","authors":"Sheng Niu,Zhenyang Hu,Xiaoyi Xu,Hongzheng Chen,Alex K-Y Jen,Ning Huang","doi":"10.1002/anie.202523520","DOIUrl":"https://doi.org/10.1002/anie.202523520","url":null,"abstract":"Covalent organic frameworks (COFs) incorporating photoredox-active motifs show great promise as heterogeneous catalysts, yet their applications have been largely confined to one-step transformations. In this work, we design and synthesize a series of three-dimensional (3D) COFs with different π-extended dihydrophenazine cores to achieve superior photocatalytic performance. These 3D COFs exhibit excellent crystallinity, high surface areas, and remarkable chemical stability. More importantly, they can work as highly efficient and recyclable catalysts for photocatalytic tandem polymerization reactions using styrene and fluoroalkyl anhydrides as substrates, yielding fluoroalkylated polystyrene polymers with narrow dispersity. These COFs constitute the first examples as tandem photocatalysts toward polymerization reactions. Moreover, optimal energy level alignment and enhanced photophysical properties are identified as key factors contributing to their high efficacy. This work not only provides a viable design strategy for multifunctional COF catalysts, but also expands their utility in complex synthetic sequences involving tandem catalytic processes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"183 1","pages":"e23520"},"PeriodicalIF":16.6,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145907891","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}
Upcycling of waste plastics into commodity chemicals such as amino acids represents a promising route toward achieving negative carbon emissions and enabling a circular carbon economy. However, existing thermocatalytic methods typically require harsh conditions. While photocatalytic upcycling operates under mild conditions, its dependence on a high-temperature hydrolysis step for plastic pretreatment undermines its overall practicality. Here we report a bio-photocatalytic hybrid system that converts polylactic acid (PLA) plastics into alanine under ambient conditions. The integrated system begins with enzymatic depolymerization of PLA to lactic acid (LA) with 92% conversion at 55°C and pH 10, catalyzed by an engineered peptidase derived from the Micromonospora sp. strain. Without any purification, the resulting hydrolysate is fed directly to the photosynthesis system, where the LA monomers are converted to alanine over a Ni/ZnIn2S4 catalyst using ammonia as a nitrogen source. This photocatalytic process, which proceeds via an oxygen-centered radical intermediate pathway, achieves an alanine production rate of 61.91 mmol g-1 h-1 and an overall yield of 60%. Life cycle assessment demonstrates that our tandem bio-photoconversion system substantially reduces the carbon footprint compared to single-step thermocatalytic and photocatalytic systems. This work thus establishes a sustainable route for valued chemicals production from low-cost feedstocks.
{"title":"Solar-Biohybrid Upcycling of Polylactic Acid Plastics to Alanine.","authors":"Mengmeng Du,Haolan Tao,Xuyun Guo,Bin Xie,Mingzhu Han,Yingxin Ma,Valeria Nicolosi,Weiliang Dong,Min Jiang,Cheng Lian,Jie Zhou,Bocheng Qiu","doi":"10.1002/anie.202523771","DOIUrl":"https://doi.org/10.1002/anie.202523771","url":null,"abstract":"Upcycling of waste plastics into commodity chemicals such as amino acids represents a promising route toward achieving negative carbon emissions and enabling a circular carbon economy. However, existing thermocatalytic methods typically require harsh conditions. While photocatalytic upcycling operates under mild conditions, its dependence on a high-temperature hydrolysis step for plastic pretreatment undermines its overall practicality. Here we report a bio-photocatalytic hybrid system that converts polylactic acid (PLA) plastics into alanine under ambient conditions. The integrated system begins with enzymatic depolymerization of PLA to lactic acid (LA) with 92% conversion at 55°C and pH 10, catalyzed by an engineered peptidase derived from the Micromonospora sp. strain. Without any purification, the resulting hydrolysate is fed directly to the photosynthesis system, where the LA monomers are converted to alanine over a Ni/ZnIn2S4 catalyst using ammonia as a nitrogen source. This photocatalytic process, which proceeds via an oxygen-centered radical intermediate pathway, achieves an alanine production rate of 61.91 mmol g-1 h-1 and an overall yield of 60%. Life cycle assessment demonstrates that our tandem bio-photoconversion system substantially reduces the carbon footprint compared to single-step thermocatalytic and photocatalytic systems. This work thus establishes a sustainable route for valued chemicals production from low-cost feedstocks.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":"e23771"},"PeriodicalIF":16.6,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145907785","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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