Systemic delivery of messenger RNA (mRNA) to non-hepatocytes using lipid nanoparticles (LNPs) remains challenging. Inspired by anion coordination chemistry, here we report the rational chemical design of thiourea-functionalized ionizable lipids (TUILs) for delivering mRNA potently and specifically to the secondary lymphoid organs (SLOs). The leading TUIL, namely 4A3-LNSC8, features an impressive thiourea-based linker capable of binding with various halide anions (F−, Cl−, I−) through hydrogen-bonding interaction, enabling precise regulation of LNP organotropism in vivo. When administered systemically, the representative Cl-4A3-LNSC8 LNPs exclusively redirected mRNA delivery from the liver to SLOs, yielding a 65-fold and 29-fold increase in splenic mRNA expression compared to DLin-MC3-DMA and SM102 LNPs with the addition of anionic lipid (18PA). Notably, upon intravenous injection of 0.2 mg kg−1 Cre mRNA, Cl-4A3-LNSC8 LNPs demonstrated strong tropism for splenic macrophages with high gene editing efficiency up to 65.7%, outperforming the current state-of-the-art spleen-targeted LNPs. Moreover, by leveraging iodine's CT contrast properties, I-4A3-LNSC8 LNPs mediated efficient theranostic mRNA delivery to lymph nodes, allowing early detection of lymphatic metastasis via dual-modal CT and bioluminescence imaging. This work provides new insights into the development of cell-specific ionizable lipids, advancing future applications of macrophage-targeted therapies.
{"title":"Thiourea-Functionalized Ionizable Lipids Enable Systemic mRNA Delivery to Secondary Lymphoid Organs and Dual-Modal Lymphatic Metastasis Imaging","authors":"Zhaoming Chen, Jieyu Yang, Bingbing Zheng, Yuexia Yang, Xinyu Qiu, Hao Zhou, Rui Wang, Hu Xiong","doi":"10.1002/anie.202523579","DOIUrl":"https://doi.org/10.1002/anie.202523579","url":null,"abstract":"Systemic delivery of messenger RNA (mRNA) to non-hepatocytes using lipid nanoparticles (LNPs) remains challenging. Inspired by anion coordination chemistry, here we report the rational chemical design of thiourea-functionalized ionizable lipids (TUILs) for delivering mRNA potently and specifically to the secondary lymphoid organs (SLOs). The leading TUIL, namely 4A3-LNSC8, features an impressive thiourea-based linker capable of binding with various halide anions (F<sup>−</sup>, Cl<sup>−</sup>, I<sup>−</sup>) through hydrogen-bonding interaction, enabling precise regulation of LNP organotropism in vivo. When administered systemically, the representative Cl-4A3-LNSC8 LNPs exclusively redirected mRNA delivery from the liver to SLOs, yielding a 65-fold and 29-fold increase in splenic mRNA expression compared to DLin-MC3-DMA and SM102 LNPs with the addition of anionic lipid (18PA). Notably, upon intravenous injection of 0.2 mg kg<sup>−1</sup> Cre mRNA, Cl-4A3-LNSC8 LNPs demonstrated strong tropism for splenic macrophages with high gene editing efficiency up to 65.7%, outperforming the current state-of-the-art spleen-targeted LNPs. Moreover, by leveraging iodine's CT contrast properties, I-4A3-LNSC8 LNPs mediated efficient theranostic mRNA delivery to lymph nodes, allowing early detection of lymphatic metastasis via dual-modal CT and bioluminescence imaging. This work provides new insights into the development of cell-specific ionizable lipids, advancing future applications of macrophage-targeted therapies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"18 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938032","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}
Youwen Rong, Chuanchuan Yan, Xiaotong Li, Jing Liu, Xiaozhi Su, Guohui Zhang, Dunfeng Gao, Guoxiong Wang, Xinhe Bao
Bicarbonate electrolysis coupling upstream CO2 capture with electrochemical conversion of captured CO2 presents an energy-efficient alternative to existing CO2 electrolysis route. Yet, its practical application is impeded by unsatisfactory reaction rate and energy efficiency. Here, we have improved the bicarbonate electrolysis performance through manipulating reaction microenvironments by introducing ionomers into cobalt phthalocyanine (CoPc) electrodes. The Nafion-incorporated CoPc electrode exhibits a maximum CO partial current density of 410 mA cm−2 at a low cell voltage of 3.09 V in a cation exchange membrane-based zero-gap electrolyzer. Electrode structure characterization and finite element simulation results indicate that the proton conductivity of the Nafion ionomer increases the local concentration of in situ generated CO2 around CoPc catalyst, resulting in impressive CO production performance. A closed-loop demonstration using the Nafion-incorporated CoPc electrode and a simulated flue gas underscores the great promise of the bicarbonate-mediated integrated CO2 capture and electrolysis process.
碳酸氢盐电解耦合上游CO2捕集与捕获CO2的电化学转化是现有CO2电解途径的一种节能替代方案。然而，其实际应用受到反应速率和能量效率不理想的制约。在这里，我们通过在酞菁钴（CoPc）电极中引入离聚体来操纵反应微环境，从而提高了碳酸氢盐的电解性能。在基于阳离子交换膜的零间隙电解槽中，在3.09 V的低电池电压下，加入了nafion的CoPc电极显示出410 mA cm−2的最大CO分电流密度。电极结构表征和有限元模拟结果表明，Nafion离子单体的质子导电性增加了CoPc催化剂周围原位生成的CO2的局部浓度，从而产生了令人印象深刻的CO生产性能。使用nation集成的CoPc电极和模拟烟气的闭环演示强调了碳酸氢盐介导的综合CO2捕获和电解工艺的巨大前景。
{"title":"Ionomer-Driven Reaction Microenvironment Control in Bicarbonate-Mediated Integrated CO2 Capture and Electrolysis","authors":"Youwen Rong, Chuanchuan Yan, Xiaotong Li, Jing Liu, Xiaozhi Su, Guohui Zhang, Dunfeng Gao, Guoxiong Wang, Xinhe Bao","doi":"10.1002/anie.202523118","DOIUrl":"https://doi.org/10.1002/anie.202523118","url":null,"abstract":"Bicarbonate electrolysis coupling upstream CO<sub>2</sub> capture with electrochemical conversion of captured CO<sub>2</sub> presents an energy-efficient alternative to existing CO<sub>2</sub> electrolysis route. Yet, its practical application is impeded by unsatisfactory reaction rate and energy efficiency. Here, we have improved the bicarbonate electrolysis performance through manipulating reaction microenvironments by introducing ionomers into cobalt phthalocyanine (CoPc) electrodes. The Nafion-incorporated CoPc electrode exhibits a maximum CO partial current density of 410 mA cm<sup>−2</sup> at a low cell voltage of 3.09 V in a cation exchange membrane-based zero-gap electrolyzer. Electrode structure characterization and finite element simulation results indicate that the proton conductivity of the Nafion ionomer increases the local concentration of in situ generated CO<sub>2</sub> around CoPc catalyst, resulting in impressive CO production performance. A closed-loop demonstration using the Nafion-incorporated CoPc electrode and a simulated flue gas underscores the great promise of the bicarbonate-mediated integrated CO<sub>2</sub> capture and electrolysis process.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"3 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938030","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}
The selective oxidation of sulfides to sulfoxides represents a fundamental transformation in synthetic and pharmaceutical chemistry, yet most catalytic systems require harsh conditions or long reaction times. Herein, we report a silver–porphyrin single-atom-site catalyst (Ag-TMPP; TMPPH2 = tetrakis(4-methylphenyl)porphyrin) that enables ultrafast photooxidation of sulfides under mild conditions. Ag-TMPP is readily obtained by a simple solution-phase self-assembly of AgNO3 and TMPPH2, affording a well-ordered three-dimensional framework stabilized by C─H···π interactions. The catalyst achieves nearly quantitative conversion of methyl phenyl sulfide to sulfoxide within 15 min, delivering a turnover frequency of 3112 h−1—among the highest reported for heterogeneous metal-based systems. It exhibits excellent recyclability and broad substrate tolerance, efficiently oxidizing both aryl and alkyl sulfides. Mechanistic investigations supported by electron paramagnetic resonance (EPR) spectroscopy and density functional theory (DFT) calculations reveal that the exceptional performance originates from the highly selective generation of singlet oxygen (1O2), whereas other metalloporphyrins (M = Cu, Co, Zn etc.) favor competing reactive oxygen species. This study provides an accessible and efficient strategy for harnessing 1O2 in photooxidation catalysis.
{"title":"Selective Singlet Oxygen Generation over a Silver–Porphyrin Single-Atom-Site Catalyst for Ultrafast Sulfide Photooxidation","authors":"Mengyuan Tu, Chen Wang, Xue Wang, Ling Chen, Ruru Qian, Qianli Zhang, Haizhu Yu, Manzhou Zhu","doi":"10.1002/anie.202523736","DOIUrl":"https://doi.org/10.1002/anie.202523736","url":null,"abstract":"The selective oxidation of sulfides to sulfoxides represents a fundamental transformation in synthetic and pharmaceutical chemistry, yet most catalytic systems require harsh conditions or long reaction times. Herein, we report a silver–porphyrin single-atom-site catalyst (Ag-TMPP; TMPPH<sub>2</sub> = tetrakis(4-methylphenyl)porphyrin) that enables ultrafast photooxidation of sulfides under mild conditions. Ag-TMPP is readily obtained by a simple solution-phase self-assembly of AgNO<sub>3</sub> and TMPPH<sub>2</sub>, affording a well-ordered three-dimensional framework stabilized by C─H···π interactions. The catalyst achieves nearly quantitative conversion of methyl phenyl sulfide to sulfoxide within 15 min, delivering a turnover frequency of 3112 h<sup>−1</sup>—among the highest reported for heterogeneous metal-based systems. It exhibits excellent recyclability and broad substrate tolerance, efficiently oxidizing both aryl and alkyl sulfides. Mechanistic investigations supported by electron paramagnetic resonance (EPR) spectroscopy and density functional theory (DFT) calculations reveal that the exceptional performance originates from the highly selective generation of singlet oxygen (<sup>1</sup>O<sub>2</sub>), whereas other metalloporphyrins (M = Cu, Co, Zn <i>etc</i>.) favor competing reactive oxygen species. This study provides an accessible and efficient strategy for harnessing <sup>1</sup>O<sub>2</sub> in photooxidation catalysis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"15 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938031","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}
Ningning Liu, Linus Bjarne Dittmer, Melina Maag, Elena Michel, Frank Rominger, Matthias Rudolph, Andreas Dreuw, A. Stephen K. Hashmi
Doyle–Kirmse rearrangement reactions are widely recognized as versatile and powerful synthetic tools, promoting the simultaneous generation of C─C and C─S bonds. While notable progress has been attained, Doyle–Kirmse rearrangement reactions involving cyanocarbenes have rarely been reported owing to the limited strategies available for the preparation of cyanocarbene precursors and its inherently restricted reactivity. Herein, we report photochemical Doyle–Kirmse rearrangement reactions of alkynyl triazenes via intermediate cyanocarbenes under metal- and additive-free conditions, leading to valuable α-mercapto-nitriles in generally moderate-to-good yields. In contrast to existing methods that utilize alternative cyanocarbene precurors, this approach delivers the possibility to access highly substituted stereogenic carbon centers and it offers a safer alternative by avoiding hazardous reagents. The reactions proceed under mild conditions, and demonstrate broad substrate compatibility. In addition, upscaling of the reaction was successfully demonstrated. Besides the use of allylsulfides, propargyl as well as allenylsulfides were also feasible substrates demonstrating the great synthetic potential of the transformation.
{"title":"Alkynyltriazenes in Photochemical Metal-Free Doyle–Kirmse Rearrangements","authors":"Ningning Liu, Linus Bjarne Dittmer, Melina Maag, Elena Michel, Frank Rominger, Matthias Rudolph, Andreas Dreuw, A. Stephen K. Hashmi","doi":"10.1002/anie.202521012","DOIUrl":"https://doi.org/10.1002/anie.202521012","url":null,"abstract":"Doyle–Kirmse rearrangement reactions are widely recognized as versatile and powerful synthetic tools, promoting the simultaneous generation of C─C and C─S bonds. While notable progress has been attained, Doyle–Kirmse rearrangement reactions involving cyanocarbenes have rarely been reported owing to the limited strategies available for the preparation of cyanocarbene precursors and its inherently restricted reactivity. Herein, we report photochemical Doyle–Kirmse rearrangement reactions of alkynyl triazenes via intermediate cyanocarbenes under metal- and additive-free conditions, leading to valuable α-mercapto-nitriles in generally moderate-to-good yields. In contrast to existing methods that utilize alternative cyanocarbene precurors, this approach delivers the possibility to access highly substituted stereogenic carbon centers and it offers a safer alternative by avoiding hazardous reagents. The reactions proceed under mild conditions, and demonstrate broad substrate compatibility. In addition, upscaling of the reaction was successfully demonstrated. Besides the use of allylsulfides, propargyl as well as allenylsulfides were also feasible substrates demonstrating the great synthetic potential of the transformation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"24 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938058","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}
Riccardo Parolin, Toby J. Blundell, Allegra Franchino
Gold catalysis provides access to a remarkable array of complex carbon scaffolds, but the use of silver salts to activate gold(I) chloride precatalysts can be problematic due to Ag(I) light sensitivity, hygroscopicity, redox activity, and interference with the desired catalysis. Although H‐bond donors are a promising alternative to silver salts, they still suffer from much lower activity and narrower applicability, as Au–Cl cleavage remains rate limiting. To address these limitations, we have rationally designed a self‐activating phosphine Au(I) chloride complex that incorporates a supramolecular chloride receptor in the form of an anthracene bisurea quintuple H‐bond donor. In the absence of any additive, this complex promotes multiple intra‐ and intermolecular reactions, with a catalytic activity rivalling traditional inorganic chloride scavengers. Mechanistic studies for the model reaction show that the exceptional chloride binding ability of the anthracene bisurea unlocks access to a zwitterionic catalyst resting state where the Au─Cl bond has been cleaved, thus significantly reducing barriers for catalysis. The principles uncovered in this work show how supramolecular anion recognition moieties impact catalyst speciation and enhance performance, enabling for the first time H‐bond donors to compete with inorganic chloride scavengers in terms of activity and generality.
{"title":"Anthracene Bisurea as a Supramolecular Chloride Receptor for Additive‐Free, Broad‐Scope Gold(I) Catalysis","authors":"Riccardo Parolin, Toby J. Blundell, Allegra Franchino","doi":"10.1002/anie.202523431","DOIUrl":"https://doi.org/10.1002/anie.202523431","url":null,"abstract":"Gold catalysis provides access to a remarkable array of complex carbon scaffolds, but the use of silver salts to activate gold(I) chloride precatalysts can be problematic due to Ag(I) light sensitivity, hygroscopicity, redox activity, and interference with the desired catalysis. Although H‐bond donors are a promising alternative to silver salts, they still suffer from much lower activity and narrower applicability, as Au–Cl cleavage remains rate limiting. To address these limitations, we have rationally designed a self‐activating phosphine Au(I) chloride complex that incorporates a supramolecular chloride receptor in the form of an anthracene bisurea quintuple H‐bond donor. In the absence of any additive, this complex promotes multiple intra‐ and intermolecular reactions, with a catalytic activity rivalling traditional inorganic chloride scavengers. Mechanistic studies for the model reaction show that the exceptional chloride binding ability of the anthracene bisurea unlocks access to a zwitterionic catalyst resting state where the Au─Cl bond has been cleaved, thus significantly reducing barriers for catalysis. The principles uncovered in this work show how supramolecular anion recognition moieties impact catalyst speciation and enhance performance, enabling for the first time H‐bond donors to compete with inorganic chloride scavengers in terms of activity and generality.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"9 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145947373","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}
J. Tian, B. Li, F. Zhang, Z. Yao, W. Song, Y. Tang, Y. Ping, * B. Liu. * Activatable Type I Photosensitizer with Quenched Photosensitization Pre and Post Photodynamic Therapy. Angew. Chem. Int. Ed. 2023, 62, e202307288.
In the Supporting Information, Section 16 (“In vivo anti-tumor effect and biosafety”), the image corresponding to the TPFN-AzoCF3 NPs group at day 5 was incorrect. This image has now been removed and replaced with the correct one.
{"title":"Correction to “Activatable Type I Photosensitizer with Quenched Photosensitization Pre and Post Photodynamic Therapy”","authors":"","doi":"10.1002/anie.4736588","DOIUrl":"https://doi.org/10.1002/anie.4736588","url":null,"abstract":"<p>J. Tian, B. Li, F. Zhang, Z. Yao, W. Song, Y. Tang, Y. Ping, * B. Liu. * Activatable Type I Photosensitizer with Quenched Photosensitization Pre and Post Photodynamic Therapy. <i>Angew. Chem. Int. Ed</i>. <b>2023</b>, <i>62</i>, e202307288.</p>\u0000<p>In the Supporting Information, Section 16 (“In vivo anti-tumor effect and biosafety”), the image corresponding to the TPFN-AzoCF<sub>3</sub> NPs group at day 5 was incorrect. This image has now been removed and replaced with the correct one.</p>\u0000<p>We apologize for this error.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"84 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938034","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}
Sara Catalini, Matteo Rutsch, Andrea Lapini, Barbara Rossi, Mariangela Di Donato, Brenda Bracco, Marco Paolantoni, Yang Yao
Water under nanoscale confinement is central to biological function, catalysis, and soft materials, yet how geometry dictates its structure and dynamics remains unresolved. Here, we establish a direct link between interfacial curvature and confined water behavior using an archaeal-inspired phytantriol-water lipidic mesophase platform. By systematically tuning curvature across lamellar, double-gyroid cubic, and reverse micellar phases, and integrating structural, thermodynamic, and ultrafast spectroscopies, we show that geometry controls the dimensionality and mobility of the hydrogen-bond network. Planar interfaces enforce 2D networks that slow down interfacial water through spatial constrain, whereas curved bicontinuous and micellar topologies promote 3D networks with accelerated reorientation. These findings reveal a geometric principle for governing water dynamics in soft nanoconfinement, providing molecular level design rules for confined transport and reactivity in membranes and functional materials.
{"title":"Geometry Controls Confined Water Dynamics in Lipidic Mesophases","authors":"Sara Catalini, Matteo Rutsch, Andrea Lapini, Barbara Rossi, Mariangela Di Donato, Brenda Bracco, Marco Paolantoni, Yang Yao","doi":"10.1002/anie.202522757","DOIUrl":"https://doi.org/10.1002/anie.202522757","url":null,"abstract":"Water under nanoscale confinement is central to biological function, catalysis, and soft materials, yet how geometry dictates its structure and dynamics remains unresolved. Here, we establish a direct link between interfacial curvature and confined water behavior using an archaeal-inspired phytantriol-water lipidic mesophase platform. By systematically tuning curvature across lamellar, double-gyroid cubic, and reverse micellar phases, and integrating structural, thermodynamic, and ultrafast spectroscopies, we show that geometry controls the dimensionality and mobility of the hydrogen-bond network. Planar interfaces enforce 2D networks that slow down interfacial water through spatial constrain, whereas curved bicontinuous and micellar topologies promote 3D networks with accelerated reorientation. These findings reveal a geometric principle for governing water dynamics in soft nanoconfinement, providing molecular level design rules for confined transport and reactivity in membranes and functional materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"47 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938073","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}
The development of efficient, stable, and low-coat plasmonic catalysts for CO2 hydrogenation via the reverse water-gas shift (RWGS) reaction remains a significant challenge. Conventional Cu-based plasmonic catalysts suffer from poor stability due to the valence state fluctuation, nanoparticle sintering, and CO poisoning. Herein, we report a low-cost CuNi bimetallic plasmonic catalyst (CuNi/Al2O3) that address these bottlenecks, achieving a remarkable CO production rate of 4813 µmol/g/h under light irradiation at a relatively low temperature (300 °C), outperforming conventional Cu-based and noble metal catalysts. Systematic experimental and theoretical studies reveal that Ni incorporation enhances catalytic activity and stability by reducing activation energy, maintaining surface valence stability and suppressing nanoparticle sintering. In situ characterization further confirms that light not only drives the CO2 hydrogenation via the localized surface plasmon resonance (LSPR) effect of Cu but also synergizes with Ni to suppress CO poisoning and promote surface reducibility, ensuring long-term stability. This work provides a rational design strategy for low-cost, stable Cu-based plasmonic catalysts and deepens the mechanistic understanding of alloy-mediated plasmonic CO2 conversion, offering insights for advancing solar-driven CO2 valorization.
{"title":"Overcoming Copper Instability via Nickel Alloying for Efficient Plasmon-Catalytic CO2 Hydrogenation","authors":"Yaqin Wang, Feng Xue, Wanqing Zhang, Dongxu Cao, Meixi Zhang, Zhuogen Li, Chao Zhan, Qin Kuang, Zhaoxiong Xie","doi":"10.1002/anie.202521576","DOIUrl":"https://doi.org/10.1002/anie.202521576","url":null,"abstract":"The development of efficient, stable, and low-coat plasmonic catalysts for CO<sub>2</sub> hydrogenation via the reverse water-gas shift (RWGS) reaction remains a significant challenge. Conventional Cu-based plasmonic catalysts suffer from poor stability due to the valence state fluctuation, nanoparticle sintering, and CO poisoning. Herein, we report a low-cost CuNi bimetallic plasmonic catalyst (CuNi/Al<sub>2</sub>O<sub>3</sub>) that address these bottlenecks, achieving a remarkable CO production rate of 4813 µmol/g/h under light irradiation at a relatively low temperature (300 °C), outperforming conventional Cu-based and noble metal catalysts. Systematic experimental and theoretical studies reveal that Ni incorporation enhances catalytic activity and stability by reducing activation energy, maintaining surface valence stability and suppressing nanoparticle sintering. In situ characterization further confirms that light not only drives the CO<sub>2</sub> hydrogenation via the localized surface plasmon resonance (LSPR) effect of Cu but also synergizes with Ni to suppress CO poisoning and promote surface reducibility, ensuring long-term stability. This work provides a rational design strategy for low-cost, stable Cu-based plasmonic catalysts and deepens the mechanistic understanding of alloy-mediated plasmonic CO<sub>2</sub> conversion, offering insights for advancing solar-driven CO<sub>2</sub> valorization.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"125 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938075","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}
Helicenes are chiral π-conjugated molecules whose properties strongly depend on their lengths. Systematic studies of these compounds have been limited by synthetic challenges. Here we report a concise two-step strategy (defined as the helicene-forming sequence from aminohelicene precursors) to access a homologous series of tetraaza[7]–[15]helicenes. Optical spectra converge beyond [11]H, defining a conjugation ceiling, while chiroptical responses amplify sharply, yielding |glum| up to 0.028. Fluorescence quantum yields show a nonmonotonic dependence, with [7]H and [15]H maintaining both high ΦF (0.39 and 0.36) and large |glum|, resulting in outstanding, albeit semi-quantitative, CPL performance, with figures of merit reaching 0.010 and CPL brightness values of approximately 490. TD-DFT calculations attribute this amplification to the delayed alignment of electric and magnetic transition dipoles, while 1H NMR shifts of inner protons provide an independent probe of structural reorganization within the helical cavity. Additionally, experiment and theory have consistently identified [11]H as the critical helicene length at which the framework undergoes a qualitative transition. Notably, the [15]helicene constitutes the longest helicene ever resolved into its enantiomers, underscoring the synthetic power of this modular approach. Importantly, our synthetic route is effective for constructing higher-order helicenes, offering a generalizable platform for length-controlled, heteroatom-containing helicenes. These findings establish long tetraazahelicenes as a rare platform where through-bond conjugation and through-space orbital coupling act cooperatively to govern photophysical and chiroptical properties.
{"title":"Tetraaza[7]–[15]helicenes Synthesized by Two-Step Strategy: Length-Controlled Chiral π-Systems Exhibiting Amplified Circularly Polarized Luminescence","authors":"Takashi Otani, Yuchen Wu, Kohei Ueda, Yuki Ikeda, Yuna Tada, Natsuna Kinoshita, Takanori Shibata","doi":"10.1002/anie.202524463","DOIUrl":"https://doi.org/10.1002/anie.202524463","url":null,"abstract":"Helicenes are chiral π-conjugated molecules whose properties strongly depend on their lengths. Systematic studies of these compounds have been limited by synthetic challenges. Here we report a concise two-step strategy (defined as the helicene-forming sequence from aminohelicene precursors) to access a homologous series of tetraaza[7]–[15]helicenes. Optical spectra converge beyond [11]H, defining a conjugation ceiling, while chiroptical responses amplify sharply, yielding |<i>g</i><sub>lum</sub>| up to 0.028. Fluorescence quantum yields show a nonmonotonic dependence, with [7]H and [15]H maintaining both high <i>Φ</i><sub>F</sub> (0.39 and 0.36) and large |<i>g</i><sub>lum</sub>|, resulting in outstanding, albeit semi-quantitative, CPL performance, with figures of merit reaching 0.010 and CPL brightness values of approximately 490. TD-DFT calculations attribute this amplification to the delayed alignment of electric and magnetic transition dipoles, while <sup>1</sup>H NMR shifts of inner protons provide an independent probe of structural reorganization within the helical cavity. Additionally, experiment and theory have consistently identified [11]H as the critical helicene length at which the framework undergoes a qualitative transition. Notably, the [15]helicene constitutes the longest helicene ever resolved into its enantiomers, underscoring the synthetic power of this modular approach. Importantly, our synthetic route is effective for constructing higher-order helicenes, offering a generalizable platform for length-controlled, heteroatom-containing helicenes. These findings establish long tetraazahelicenes as a rare platform where through-bond conjugation and through-space orbital coupling act cooperatively to govern photophysical and chiroptical properties.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920597","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}
Among more than four thousand monoterpene indole alkaloids (MIAs) isolated to date, only a few feature a 2,2,3-trisubstituted indoline moiety. (+)-Melonine and (+)-N4-oxy melonine possess a highly rearranged carbon framework, presumably arising from cyclization of a rearranged iminium ion of quebrachamine precursor. We report herein the first enantioselective total synthesis of (+)-melonine and (+)-N4-oxy melonine featuring: a) a highly enantioselective CBS reduction followed by a stereospecific Johnson-Claisen rearrangement for the synthesis of enantioenriched β-substituted γ,δ-unsaturated ester; b) Bower's bis-cyclizative diamination of alkene, enabling the conversion of a functionalized cycloheptene to the tetracyclic core of the natural products; and c) an AlMe3-mediated lactamization that concurrently achieves desymmetrization at the C20 prochiral center.
{"title":"Total Synthesis of (+)-Melonine and (+)-N4-Oxy Melonine Enabled by an Intramolecular Alkene Diamination Reaction","authors":"Vincent Goëlo, Qian Wang, Jieping Zhu","doi":"10.1002/anie.8101956","DOIUrl":"https://doi.org/10.1002/anie.8101956","url":null,"abstract":"Among more than four thousand monoterpene indole alkaloids (MIAs) isolated to date, only a few feature a 2,2,3-trisubstituted indoline moiety. (+)-Melonine and (+)-<i>N<sub>4</sub></i>-oxy melonine possess a highly rearranged carbon framework, presumably arising from cyclization of a rearranged iminium ion of quebrachamine precursor. We report herein the first enantioselective total synthesis of (+)-melonine and (+)-<i>N<sub>4</sub></i>-oxy melonine featuring: a) a highly enantioselective CBS reduction followed by a stereospecific Johnson-Claisen rearrangement for the synthesis of enantioenriched <i>β</i>-substituted <i>γ</i>,<i>δ</i>-unsaturated ester; b) Bower's bis-cyclizative diamination of alkene, enabling the conversion of a functionalized cycloheptene to the tetracyclic core of the natural products; and c) an AlMe<sub>3</sub>-mediated lactamization that concurrently achieves desymmetrization at the C20 prochiral center.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"9 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920604","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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