Jessica Dröden,Christoph Globisch,Eliane Landwehr,Theresa S Braun,Daniel Summerer,Christine Peter,Malte Drescher
Aminoacyl-tRNA synthetases mediate the activation and transfer of amino acids to their cognate tRNA, which constitutes one of the initial events in protein biosynthesis. Even though different mechanisms of action have been proposed for the catalysis of these enzymes, their entire catalytic cycle remains elusive. Here, we used electron paramagnetic resonance spectroscopy in vitro and in cells in combination with molecular dynamics simulations to study the role of amino acid interactions in the catalytic cycle of pyrrolysyl-tRNA synthetases (PylRS), a widely used tool for genetic code expansion. Experiments using the paramagnetic non-canonical amino acid SLK-1 revealed the presence and occupation of secondary amino acid binding sites in PylRS located at the intermonomer interface, distant from the catalytic binding site. Based on our results, we propose a model that assumes an alternating mode of action of the two PylRS monomers for the catalytic cycle of PylRS.
{"title":"Unraveling Synthetase's Mode of Action: The Pyrrolysyl-tRNA Synthetase Dimer Uses Secondary Binding Sites in the Cell.","authors":"Jessica Dröden,Christoph Globisch,Eliane Landwehr,Theresa S Braun,Daniel Summerer,Christine Peter,Malte Drescher","doi":"10.1002/anie.202514065","DOIUrl":"https://doi.org/10.1002/anie.202514065","url":null,"abstract":"Aminoacyl-tRNA synthetases mediate the activation and transfer of amino acids to their cognate tRNA, which constitutes one of the initial events in protein biosynthesis. Even though different mechanisms of action have been proposed for the catalysis of these enzymes, their entire catalytic cycle remains elusive. Here, we used electron paramagnetic resonance spectroscopy in vitro and in cells in combination with molecular dynamics simulations to study the role of amino acid interactions in the catalytic cycle of pyrrolysyl-tRNA synthetases (PylRS), a widely used tool for genetic code expansion. Experiments using the paramagnetic non-canonical amino acid SLK-1 revealed the presence and occupation of secondary amino acid binding sites in PylRS located at the intermonomer interface, distant from the catalytic binding site. Based on our results, we propose a model that assumes an alternating mode of action of the two PylRS monomers for the catalytic cycle of PylRS.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"92 1","pages":"e14065"},"PeriodicalIF":16.6,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502391","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}
Maoshen Sun,Yunxiang Du,Zhengqing Li,Akejiang Aderjiang,Meixuan Xin,Huasong Ai
Histone H3 lysine 9 methylation (H3K9me) is a central epigenetic mark governing heterochromatin formation. Although the H3K9 methyltransferase Clr4 has been extensively characterized using short histone peptide substrates, how it recognizes and coordinates different structural domains to engage physiological substrate nucleosomes remains poorly understood. Here, we employed chemical protein synthesis to generate site-specifically ubiquitinated H3K14Ub histones and nucleosomes, enabling quantitative biochemical and structural investigations. Using a CAET handle-assisted strategy, we obtained homogeneous H3K14Ub nucleosomes and demonstrated that ubiquitination enhances Clr4 activity by ∼350-fold on nucleosomes relative to unmodified substrates. Clr4 domain deletion analyses revealed that, the intrinsically disordered region (IDR) of Clr4 is critical for nucleosome binding and ubiquitin-dependent stimulation. Through site-directed photo-crosslinking, we identified specific IDR residues mediating interactions with nucleosomal surfaces. Furthermore, using an isoUb-based synthetic approach, we generated H3K9NleK14Ub nucleosomes and determined cryo-EM structures of Clr4-nucleosome complexes, unveiling multivalent nucleosome recognition by the IDR via four distinct interfaces: the H2A-H2B acidic patch, the H2A/H2B basic groove, the H2B and H3 elbow regions. Methyltransferase activity assays confirmed that mutations disrupting these interfaces impair Clr4 activity. Our study provides mechanistic insights into the ubiquitin-dependent activation mechanism of Clr4, highlighting the power of chemical biology in deciphering epigenetic regulation.
{"title":"Chemically Synthesized H3K14Ub Unveils Clr4's IDR-Mediated Multivalent Nucleosome Recognition in H3K9 Methylation.","authors":"Maoshen Sun,Yunxiang Du,Zhengqing Li,Akejiang Aderjiang,Meixuan Xin,Huasong Ai","doi":"10.1002/anie.202520817","DOIUrl":"https://doi.org/10.1002/anie.202520817","url":null,"abstract":"Histone H3 lysine 9 methylation (H3K9me) is a central epigenetic mark governing heterochromatin formation. Although the H3K9 methyltransferase Clr4 has been extensively characterized using short histone peptide substrates, how it recognizes and coordinates different structural domains to engage physiological substrate nucleosomes remains poorly understood. Here, we employed chemical protein synthesis to generate site-specifically ubiquitinated H3K14Ub histones and nucleosomes, enabling quantitative biochemical and structural investigations. Using a CAET handle-assisted strategy, we obtained homogeneous H3K14Ub nucleosomes and demonstrated that ubiquitination enhances Clr4 activity by ∼350-fold on nucleosomes relative to unmodified substrates. Clr4 domain deletion analyses revealed that, the intrinsically disordered region (IDR) of Clr4 is critical for nucleosome binding and ubiquitin-dependent stimulation. Through site-directed photo-crosslinking, we identified specific IDR residues mediating interactions with nucleosomal surfaces. Furthermore, using an isoUb-based synthetic approach, we generated H3K9NleK14Ub nucleosomes and determined cryo-EM structures of Clr4-nucleosome complexes, unveiling multivalent nucleosome recognition by the IDR via four distinct interfaces: the H2A-H2B acidic patch, the H2A/H2B basic groove, the H2B and H3 elbow regions. Methyltransferase activity assays confirmed that mutations disrupting these interfaces impair Clr4 activity. Our study provides mechanistic insights into the ubiquitin-dependent activation mechanism of Clr4, highlighting the power of chemical biology in deciphering epigenetic regulation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"219 1","pages":"e20817"},"PeriodicalIF":16.6,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502392","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 advancement of sustainable synthetic methodologies is a central goal of modern chemistry, given the societal importance of green chemical practices. Amide groups and halogen atoms are prevalent in chemical and biological systems, with major relevance to both organic and medicinal chemistry. Consequently, there is strong demand for efficient methods that enable amide bond formation and selective halogenation under mild, resource-efficient conditions. Conventional approaches typically require separate steps, activating reagents, catalysts, or harsh reaction conditions, which limit scalability and sustainability. To address these challenges, we developed a novel electrochemical cascade methodology that unites amide bond formation and electro-induced C─H halogenation in a single, atom-economical, and environmentally benign process. This strategy provides streamlined access to halogenated N-aryl amides, carbamates, and ureas without additives or co-reagents. The method's generality and robustness are demonstrated across more than 145 examples, encompassing complex, functional group-dense scaffolds and pharmaceutically relevant compounds, including successful scale-up reactions.
{"title":"One-Pot Amidation/C─H Halogenation by an Efficient Electrochemical Cascade.","authors":"Sudipta Ponra,Ruzal Sitdikov,Hasil Aman,Alyssio Calis,Gergely Laczkó,Virgile Rouffeteau,Maxime R Vitale,Imre Pápai,Oscar Verho","doi":"10.1002/anie.9028210","DOIUrl":"https://doi.org/10.1002/anie.9028210","url":null,"abstract":"The advancement of sustainable synthetic methodologies is a central goal of modern chemistry, given the societal importance of green chemical practices. Amide groups and halogen atoms are prevalent in chemical and biological systems, with major relevance to both organic and medicinal chemistry. Consequently, there is strong demand for efficient methods that enable amide bond formation and selective halogenation under mild, resource-efficient conditions. Conventional approaches typically require separate steps, activating reagents, catalysts, or harsh reaction conditions, which limit scalability and sustainability. To address these challenges, we developed a novel electrochemical cascade methodology that unites amide bond formation and electro-induced C─H halogenation in a single, atom-economical, and environmentally benign process. This strategy provides streamlined access to halogenated N-aryl amides, carbamates, and ureas without additives or co-reagents. The method's generality and robustness are demonstrated across more than 145 examples, encompassing complex, functional group-dense scaffolds and pharmaceutically relevant compounds, including successful scale-up reactions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"57 1","pages":"e9028210"},"PeriodicalIF":16.6,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502489","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}
Xiaoni Wang,Xiyang Ge,Qi Zhao,Xiaotong Shen,Xiang Li,Jingyi Qin,Jin Ouyang,Na Na
The axial coordination-based nanozymes with asymmetric local electric field (LEF) are promising for efficient reactive oxygen species (ROS)-mediated antitumor treatments, while normally hindered by a limited LEF upon individual coordination to adjacent atoms. Herein, an axial sulfur-bridged Mo─S─Cu nanozymes with asymmetric LEF (A-CuN3S1@MoS2-x) was constructed based on nanoislands (NIs)-based axial ligand-bridging to enhance ferroptosis-pyroptosis therapy. The S bridge between Cu atoms in CuN3/C nanosheets and Mo site in NIs creates a broad and enhanced LEF, which facilitates rapid electron transfer between the nanozyme and substrates, thereby regulating its enzymatic activities. Theoretical calculations reveal that the S-bridge induces asymmetric electron-rich redistribution along the longitudinal axis of Cu─N3, promoting H2O2 heterolysis and O2 desorption to enhance catalase-like and peroxidase-like activities. Simultaneously, Mo sites extract electrons from Cu via the S bridge, augmenting oxidase-like activities and degrade overexpressed glutathione to avoid nontherapeutic ROS consumption. Consequently, A-CuN3S1@MoS2-x induces robust ferroptosis by cytotoxic ROS accumulation and causing severe mitochondria damages, while simultaneously activating pyroptosis within the tumor region without harming normal tissues. This work demonstrates high-efficiency ferroptosis-pyroptosis therapy driven by multi-enzyme catalysis via axial Mo─S─Cu coordination with an expanded asymmetric LEF, offering a novel strategy for non-apoptotic tumor treatment.
{"title":"Axial Sulfur-Bridged Mo-S-Cu Nanozymes With an Asymmetric Local Electric Field Boosting Multi-Enzymatic Activities for Ferroptosis-Pyroptosis Therapy.","authors":"Xiaoni Wang,Xiyang Ge,Qi Zhao,Xiaotong Shen,Xiang Li,Jingyi Qin,Jin Ouyang,Na Na","doi":"10.1002/anie.202523888","DOIUrl":"https://doi.org/10.1002/anie.202523888","url":null,"abstract":"The axial coordination-based nanozymes with asymmetric local electric field (LEF) are promising for efficient reactive oxygen species (ROS)-mediated antitumor treatments, while normally hindered by a limited LEF upon individual coordination to adjacent atoms. Herein, an axial sulfur-bridged Mo─S─Cu nanozymes with asymmetric LEF (A-CuN3S1@MoS2-x) was constructed based on nanoislands (NIs)-based axial ligand-bridging to enhance ferroptosis-pyroptosis therapy. The S bridge between Cu atoms in CuN3/C nanosheets and Mo site in NIs creates a broad and enhanced LEF, which facilitates rapid electron transfer between the nanozyme and substrates, thereby regulating its enzymatic activities. Theoretical calculations reveal that the S-bridge induces asymmetric electron-rich redistribution along the longitudinal axis of Cu─N3, promoting H2O2 heterolysis and O2 desorption to enhance catalase-like and peroxidase-like activities. Simultaneously, Mo sites extract electrons from Cu via the S bridge, augmenting oxidase-like activities and degrade overexpressed glutathione to avoid nontherapeutic ROS consumption. Consequently, A-CuN3S1@MoS2-x induces robust ferroptosis by cytotoxic ROS accumulation and causing severe mitochondria damages, while simultaneously activating pyroptosis within the tumor region without harming normal tissues. This work demonstrates high-efficiency ferroptosis-pyroptosis therapy driven by multi-enzyme catalysis via axial Mo─S─Cu coordination with an expanded asymmetric LEF, offering a novel strategy for non-apoptotic tumor treatment.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"92 1","pages":"e23888"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502377","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}
Caterina Trotta,Jesse Orta,Hendrik C de Heer,Pim G J van Duren,Maxime A Siegler,Gabriel Menendez Rodriguez,Alceo Macchioni,D G H Hetterscheid
The two-electron water oxidation reaction (2e--WOR) and oxygen reduction reaction (2e--ORR) represent sustainable and promising processes for the electrochemical synthesis of hydrogen peroxide (H2O2). The main factor hampering the realization of a paired electrochemical cell for H2O2 production is finding appropriate catalysts for both 2e--ORR and 2e--WOR, able to work under the same experimental conditions. Herein we show that Cu(tmpa)) and Sn-TMPyP are compatible and efficient catalysts for 2e--ORR and 2e--WOR, respectively. They have been used to assemble a paired electrochemical cell for H2O2 production. The latter exhibits a total overpotential of 570 mV, distributed between the two electrodes. During a 3 h bulk electrolysis experiment, the cathodic Faradaic efficiency ranged from 15% to 19% with a H2O2 production rate of 1.6 µmol h- 1 cm- 2. Meanwhile, at the anode, the Faradaic efficiency stabilized between 40% and 50%, yielding a H2O2 production rate of 3.5 µmol h- 1 cm- 2. The remarkable activity of Sn-TMPyP as a catalyst for the 2e--WOR, ranking among the highest reported for molecular catalysts, is ascribed to the selection of a carbonate buffer as the electrolyte, which enhanced catalytic performance by facilitating dissociation of H2O2 from the Sn catalyst. This work establishes a new benchmark for homogeneous dual-electrode H2O2 electrosynthesis.
{"title":"A Homogeneously Catalyzed Paired Electrolytic Cell for Hydrogen Peroxide Production.","authors":"Caterina Trotta,Jesse Orta,Hendrik C de Heer,Pim G J van Duren,Maxime A Siegler,Gabriel Menendez Rodriguez,Alceo Macchioni,D G H Hetterscheid","doi":"10.1002/anie.202524811","DOIUrl":"https://doi.org/10.1002/anie.202524811","url":null,"abstract":"The two-electron water oxidation reaction (2e--WOR) and oxygen reduction reaction (2e--ORR) represent sustainable and promising processes for the electrochemical synthesis of hydrogen peroxide (H2O2). The main factor hampering the realization of a paired electrochemical cell for H2O2 production is finding appropriate catalysts for both 2e--ORR and 2e--WOR, able to work under the same experimental conditions. Herein we show that Cu(tmpa)) and Sn-TMPyP are compatible and efficient catalysts for 2e--ORR and 2e--WOR, respectively. They have been used to assemble a paired electrochemical cell for H2O2 production. The latter exhibits a total overpotential of 570 mV, distributed between the two electrodes. During a 3 h bulk electrolysis experiment, the cathodic Faradaic efficiency ranged from 15% to 19% with a H2O2 production rate of 1.6 µmol h- 1 cm- 2. Meanwhile, at the anode, the Faradaic efficiency stabilized between 40% and 50%, yielding a H2O2 production rate of 3.5 µmol h- 1 cm- 2. The remarkable activity of Sn-TMPyP as a catalyst for the 2e--WOR, ranking among the highest reported for molecular catalysts, is ascribed to the selection of a carbonate buffer as the electrolyte, which enhanced catalytic performance by facilitating dissociation of H2O2 from the Sn catalyst. This work establishes a new benchmark for homogeneous dual-electrode H2O2 electrosynthesis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"270 1","pages":"e24811"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502383","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}
Direct ammonia fuel cells (DAFCs) are promising for decarbonized electricity generation. However, the sluggish ammonia oxidation reaction (AOR) has long been the major roadblock. Although Pt(100) facet features high AOR activity, fabricating ultrasmall (<5 nm) Pt-based nanocubes (NCs) with (100) facet orientation remains a challenge. Here, we develop a Zn-mediated strategy for the synthesis of PtIr─Zn NCs with an ultrasmall size of 4.1 ± 0.5 nm. Systematic investigations reveal that surface-inserted Zn atoms serve as anchors to enhance the specific adsorption of dibenzyl ether, which directs the exclusive (100)-oriented growth into well-defined NCs. The initial nucleation process is not affected, so there are abundant PtIr seeds, which are the key to yielding the sub-5 nm size. Oxophilic Ir atoms serve as the *OH adsorption sites and promote the *NH3 dehydrogenation. Moreover, Zn-induced surface compression lowers the barrier of rate-determining dehydrogenation step by shortening the hydrogen bonds between *NH3 and *OH. Our PtIr─Zn NCs catalyst exhibits both high intrinsic activity and mass activity, delivering an ultralow onset potential of 0.355 V and a peak mass activity of 238.3 mA mgPt+Ir -1. The DAFC employing PtIr─Zn NCs achieves an open-circuit voltage of 0.60 V and a peak power density of 76.0 mW cm-2.
{"title":"Zn-Mediated Synthesis of Sub-5 nm PtIr─Zn Nanocubes for Direct Ammonia Fuel Cells.","authors":"Zhen-Hua Lyu,Xinbo Ma,Tang Tang,Xiaozhi Liu,Zhe Jiang,Xuerui Liu,Ze-Cheng Yao,Libing Zhang,Jiaju Fu,Liang Ding,Zhuo-Qi Shi,Xiaoying Lu,Dong Su,Jin-Song Hu","doi":"10.1002/anie.4198910","DOIUrl":"https://doi.org/10.1002/anie.4198910","url":null,"abstract":"Direct ammonia fuel cells (DAFCs) are promising for decarbonized electricity generation. However, the sluggish ammonia oxidation reaction (AOR) has long been the major roadblock. Although Pt(100) facet features high AOR activity, fabricating ultrasmall (<5 nm) Pt-based nanocubes (NCs) with (100) facet orientation remains a challenge. Here, we develop a Zn-mediated strategy for the synthesis of PtIr─Zn NCs with an ultrasmall size of 4.1 ± 0.5 nm. Systematic investigations reveal that surface-inserted Zn atoms serve as anchors to enhance the specific adsorption of dibenzyl ether, which directs the exclusive (100)-oriented growth into well-defined NCs. The initial nucleation process is not affected, so there are abundant PtIr seeds, which are the key to yielding the sub-5 nm size. Oxophilic Ir atoms serve as the *OH adsorption sites and promote the *NH3 dehydrogenation. Moreover, Zn-induced surface compression lowers the barrier of rate-determining dehydrogenation step by shortening the hydrogen bonds between *NH3 and *OH. Our PtIr─Zn NCs catalyst exhibits both high intrinsic activity and mass activity, delivering an ultralow onset potential of 0.355 V and a peak mass activity of 238.3 mA mgPt+Ir -1. The DAFC employing PtIr─Zn NCs achieves an open-circuit voltage of 0.60 V and a peak power density of 76.0 mW cm-2.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":"e4198910"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495181","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}
<p>K. K. Ghosh, R. Chowdhury, J. P. Gordon, T. V. RajanBabu, “Ligand Effects in Regio- and Enantioselective Cobalt-Catalyzed Intramolecular [4+2]- and [2+2]-Cycloaddition Reactions of Unactivated 1,3-Diene-8-ynes and 1,3-Diene-8-enes”, <i>Angewandte Chemie International Edition</i> 64 (2025): e202515154</p> <p>Because of an inadvertent error in the configurations of the Ph-bearing starting material <b>3b</b> shown in Equation 3, some of the data in Table 2 (entries 10–15) require corrections. The two isomeric <b>3b</b> diene-enes, (2<i>E</i>,4<i>E</i>)-<b>3b</b> and (2<i>Z</i>,4<i>E</i>)-<b>3b</b>, differing in the configuration of the internal double bond, were used in these entries, even though in the original Equation 3, the starting material <b>3b</b> was depicted without any configurational assignments, thus implying a (2<i>E</i>,4<i>E</i>) configuration. The two isomeric compounds were prepared via two routes (Equations 3a and 3b). The (2<i>E</i>,4<i>E</i>)-<b>3b</b> was prepared via Mitsunobu coupling of <i>N</i>-allyl-<i>N</i>-(4-methyl)benzene sulfonamide and (2<i>E</i>,4<i>E</i>)-5-phenyl-penta-2,4-dienol (p. S8 and S14). The (2<i>Z</i>,4<i>E</i>)-<b>3b</b> was prepared via coupling of 4-methyl-<i>N</i>-((2<i>Z</i>,4<i>E</i>)-5-phenylpenta-2,4-dien-1-yl)-benzenesulfonamide and allyl alcohol (p. S4 and S14).</p> <div> <header><span>TABLE 2. </span>Effect of chiral ligands on yield and enantioselectivity of [2 + 2]- and [4 + 2]-cycloaddition reactions of 1,3-diene-enes (2<i>E</i>, 4<i>E</i>)-<b>3b</b>, and (2<i>Z</i>, 4<i>E</i>)-<b>3b</b>.</header> <div tabindex="0"> <table> <thead> <tr> <td colspan="6"><img alt="image" loading="lazy" src="/cms/asset/5b9ff981-d60a-4e25-b97b-c44b920bf6ba/anie71911-gra-0001.png"/></td> </tr> <tr> <th style="top: 292px;">Entry</th> <th style="top: 292px;">Ligand</th> <th style="top: 292px;">Substrate</th> <th style="top: 292px;">Yield</th> <th style="top: 292px;">Product</th> <th style="top: 292px;">er (configuration)</th> </tr> </thead> <tbody> <tr> <td colspan="5">(Entries 1–9): Me/<b>3a</b> (2<i>E</i>,4<i>E</i>) no changes in substrates/ligands/products</td> <td> -</td> </tr> <tr> <td colspan="3">(Entries 10–15): Ph/<b>3b</b> (2<i>Z</i>,4<i>E</i>)</td> <td></td> <td></td> <td></td> </tr> <tr> <td>10</td> <td><b>L1</b></td> <td>(2<i>E</i>,4<i>E</i>)-<b>3b</b></td> <td>74%</td> <td><b>4b</b> (only)</td> <td>99:1 (3a<i>S</i>, 5<i>R</i>, 7a<i>R</i>)</td> </tr> <tr> <td>12</td> <td><b>L3</b></td> <td>(2<i>Z</i>,4<i>E</i>)-<b>3b</b></td> <td>71%</td> <td><b>5b</b></td> <td>95:5 (1<i>S</i>, 5<i>R</i>, 6<i>S</i>)</td> </tr> <tr> <td>13</td> <td><b>L4</b></td> <td>(2<i>E</i>,4<i>E</i>)-<b>3b</b></td> <td>40%</td> <td><b>4b</b> (only)</td> <td>97:3 (3a<i>R</i>, 5<i>S</i>, 7a<i>S</i>)</td> </tr> <tr> <td>14</td> <td><b>L5</b></td> <td>(2<i>Z</i>,4<i>E</i>)-<b>3b</b></td> <td>64%</td> <td><b>5b</b></td> <td>79:21</td> </tr> <tr> <td>15</td> <td><b>L6</b></td> <td>(2<i>Z</i>,4<i>E</i>)-<b>3b</b></td> <td>14%</td> <td>
{"title":"Correction to “Ligand Effects in Regio- and Enantioselective Cobalt-Catalyzed Intramolecular [4 + 2]- and [2 + 2]-Cycloaddition Reactions of Unactivated 1,3-Diene-8-ynes and 1,3-Diene-8-enes”","authors":"","doi":"10.1002/anie.4150982","DOIUrl":"https://doi.org/10.1002/anie.4150982","url":null,"abstract":"<p>K. K. Ghosh, R. Chowdhury, J. P. Gordon, T. V. RajanBabu, “Ligand Effects in Regio- and Enantioselective Cobalt-Catalyzed Intramolecular [4+2]- and [2+2]-Cycloaddition Reactions of Unactivated 1,3-Diene-8-ynes and 1,3-Diene-8-enes”, <i>Angewandte Chemie International Edition</i> 64 (2025): e202515154</p>\u0000<p>Because of an inadvertent error in the configurations of the Ph-bearing starting material <b>3b</b> shown in Equation 3, some of the data in Table 2 (entries 10–15) require corrections. The two isomeric <b>3b</b> diene-enes, (2<i>E</i>,4<i>E</i>)-<b>3b</b> and (2<i>Z</i>,4<i>E</i>)-<b>3b</b>, differing in the configuration of the internal double bond, were used in these entries, even though in the original Equation 3, the starting material <b>3b</b> was depicted without any configurational assignments, thus implying a (2<i>E</i>,4<i>E</i>) configuration. The two isomeric compounds were prepared via two routes (Equations 3a and 3b). The (2<i>E</i>,4<i>E</i>)-<b>3b</b> was prepared via Mitsunobu coupling of <i>N</i>-allyl-<i>N</i>-(4-methyl)benzene sulfonamide and (2<i>E</i>,4<i>E</i>)-5-phenyl-penta-2,4-dienol (p. S8 and S14). The (2<i>Z</i>,4<i>E</i>)-<b>3b</b> was prepared via coupling of 4-methyl-<i>N</i>-((2<i>Z</i>,4<i>E</i>)-5-phenylpenta-2,4-dien-1-yl)-benzenesulfonamide and allyl alcohol (p. S4 and S14).</p>\u0000<div>\u0000<header><span>TABLE 2. </span>Effect of chiral ligands on yield and enantioselectivity of [2 + 2]- and [4 + 2]-cycloaddition reactions of 1,3-diene-enes (2<i>E</i>, 4<i>E</i>)-<b>3b</b>, and (2<i>Z</i>, 4<i>E</i>)-<b>3b</b>.</header>\u0000<div tabindex=\"0\">\u0000<table>\u0000<thead>\u0000<tr>\u0000<td colspan=\"6\"><img alt=\"image\" loading=\"lazy\" src=\"/cms/asset/5b9ff981-d60a-4e25-b97b-c44b920bf6ba/anie71911-gra-0001.png\"/></td>\u0000</tr>\u0000<tr>\u0000<th style=\"top: 292px;\">Entry</th>\u0000<th style=\"top: 292px;\">Ligand</th>\u0000<th style=\"top: 292px;\">Substrate</th>\u0000<th style=\"top: 292px;\">Yield</th>\u0000<th style=\"top: 292px;\">Product</th>\u0000<th style=\"top: 292px;\">er (configuration)</th>\u0000</tr>\u0000</thead>\u0000<tbody>\u0000<tr>\u0000<td colspan=\"5\">(Entries 1–9): Me/<b>3a</b> (2<i>E</i>,4<i>E</i>) no changes in substrates/ligands/products</td>\u0000<td> -</td>\u0000</tr>\u0000<tr>\u0000<td colspan=\"3\">(Entries 10–15): Ph/<b>3b</b> (2<i>Z</i>,4<i>E</i>)</td>\u0000<td></td>\u0000<td></td>\u0000<td></td>\u0000</tr>\u0000<tr>\u0000<td>10</td>\u0000<td><b>L1</b></td>\u0000<td>(2<i>E</i>,4<i>E</i>)-<b>3b</b></td>\u0000<td>74%</td>\u0000<td><b>4b</b> (only)</td>\u0000<td>99:1 (3a<i>S</i>, 5<i>R</i>, 7a<i>R</i>)</td>\u0000</tr>\u0000<tr>\u0000<td>12</td>\u0000<td><b>L3</b></td>\u0000<td>(2<i>Z</i>,4<i>E</i>)-<b>3b</b></td>\u0000<td>71%</td>\u0000<td><b>5b</b></td>\u0000<td>95:5 (1<i>S</i>, 5<i>R</i>, 6<i>S</i>)</td>\u0000</tr>\u0000<tr>\u0000<td>13</td>\u0000<td><b>L4</b></td>\u0000<td>(2<i>E</i>,4<i>E</i>)-<b>3b</b></td>\u0000<td>40%</td>\u0000<td><b>4b</b> (only)</td>\u0000<td>97:3 (3a<i>R</i>, 5<i>S</i>, 7a<i>S</i>)</td>\u0000</tr>\u0000<tr>\u0000<td>14</td>\u0000<td><b>L5</b></td>\u0000<td>(2<i>Z</i>,4<i>E</i>)-<b>3b</b></td>\u0000<td>64%</td>\u0000<td><b>5b</b></td>\u0000<td>79:21</td>\u0000</tr>\u0000<tr>\u0000<td>15</td>\u0000<td><b>L6</b></td>\u0000<td>(2<i>Z</i>,4<i>E</i>)-<b>3b</b></td>\u0000<td>14%</td>\u0000<td>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"8 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496342","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}
Electrochemical activation is a critical step for optimal functioning of Li- and Mn-rich (LMR) cathodes, yet the underlying mechanism for such activation remains elusive. Here, by using scanning/transmission electron microscopy (S/TEM) combined with the associated energy-dispersive x-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS), we decipher the origin of the activation enhanced electrochemical properties. We reveal that activation induces the formation of a spinel-like phase within the C2/m domains of the LMR cathode, where the transition-metal ions partially occupy both the tetrahedral (8a) and octahedral (16c) sites of the Fd 3 ¯ $bar{3}$ m spinel lattice, distinguishing the spinel-like phase from the conventional high-voltage spinel. Systematic varying the cycling voltage reveals a critical activation voltage above which this spinel-like phase forms, while lower voltages preserve the layered bulk structure. As the spinel-like phase is a stable structure for electrochemical cycling, the present findings provide direct mechanistic insight into the voltage-dependent activation process and explain how the C2/m to spinel-like transformation upon activation contributes to the electrochemical performance of LMR cathodes, providing guidance for the rational design of Li-rich cathodes with enhanced cycling durability.
{"title":"Origin of Electrochemical Activation Leading to Enhanced Cycling Stability of Li- and Mn-Rich Cathodes.","authors":"Peng Zuo,Daniel P Abraham,Chongmin Wang","doi":"10.1002/anie.8818196","DOIUrl":"https://doi.org/10.1002/anie.8818196","url":null,"abstract":"Electrochemical activation is a critical step for optimal functioning of Li- and Mn-rich (LMR) cathodes, yet the underlying mechanism for such activation remains elusive. Here, by using scanning/transmission electron microscopy (S/TEM) combined with the associated energy-dispersive x-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS), we decipher the origin of the activation enhanced electrochemical properties. We reveal that activation induces the formation of a spinel-like phase within the C2/m domains of the LMR cathode, where the transition-metal ions partially occupy both the tetrahedral (8a) and octahedral (16c) sites of the Fd 3 ¯ $bar{3}$ m spinel lattice, distinguishing the spinel-like phase from the conventional high-voltage spinel. Systematic varying the cycling voltage reveals a critical activation voltage above which this spinel-like phase forms, while lower voltages preserve the layered bulk structure. As the spinel-like phase is a stable structure for electrochemical cycling, the present findings provide direct mechanistic insight into the voltage-dependent activation process and explain how the C2/m to spinel-like transformation upon activation contributes to the electrochemical performance of LMR cathodes, providing guidance for the rational design of Li-rich cathodes with enhanced cycling durability.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"14 1","pages":"e8818196"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502332","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}
Jorge Pascual,Marion Flatken,Eros Radicchi,Mahmoud Aldamasy,Shuaifeng Hu,Omar E Solis,Silver-Hamill Turren-Cruz,Guixiang Li,Armin Hoell,Susan Schorr,Meng Li,Filippo De Angelis,Artem Musiienko,André Dallmann,Antonio Abate
Narrow-bandgap tin and mixed tin-lead halide perovskites are attracting growing interest for optoelectronic applications, yet the difficult-to-control crystallization process has hindered their development. Although additive engineering has effectively improved film formation, the fundamental origins of their distinct crystallization behavior remain less explored. Here, through direct comparison with Pb counterparts, we investigate the pre-crystallization stages of Sn-based perovskite precursor solutions through complementary structural characterizations. We show that Sn precursors are intrinsically more reactive and sensitive to their chemical environment, exhibiting poorer colloidal stability compared to Pb and a strong inherent tendency to agglomerate. These findings explain their narrower processing window, where small variations in solution chemistry strongly affect nucleation and crystallization dynamics. To fabricate high-quality tin-based perovskite through solution methods, we highlight the importance of controlling the often-overlooked pre-crystallization stages, though, for example, rational solvent and additive designs. Overall, we provide fundamental insights into precursor solution chemistry and establish pre-crystallization engineering as a key strategy for overcoming long-standing limitations in thin-film fabrication, particularly in light of the field's rapid progression toward large-scale, sustainable, and solvent-conscious manufacturing.
{"title":"Unravelling the Intrinsic Reactivity and Colloidal Instability in Tin-Based Halide Perovskite Precursor Solutions.","authors":"Jorge Pascual,Marion Flatken,Eros Radicchi,Mahmoud Aldamasy,Shuaifeng Hu,Omar E Solis,Silver-Hamill Turren-Cruz,Guixiang Li,Armin Hoell,Susan Schorr,Meng Li,Filippo De Angelis,Artem Musiienko,André Dallmann,Antonio Abate","doi":"10.1002/anie.7703450","DOIUrl":"https://doi.org/10.1002/anie.7703450","url":null,"abstract":"Narrow-bandgap tin and mixed tin-lead halide perovskites are attracting growing interest for optoelectronic applications, yet the difficult-to-control crystallization process has hindered their development. Although additive engineering has effectively improved film formation, the fundamental origins of their distinct crystallization behavior remain less explored. Here, through direct comparison with Pb counterparts, we investigate the pre-crystallization stages of Sn-based perovskite precursor solutions through complementary structural characterizations. We show that Sn precursors are intrinsically more reactive and sensitive to their chemical environment, exhibiting poorer colloidal stability compared to Pb and a strong inherent tendency to agglomerate. These findings explain their narrower processing window, where small variations in solution chemistry strongly affect nucleation and crystallization dynamics. To fabricate high-quality tin-based perovskite through solution methods, we highlight the importance of controlling the often-overlooked pre-crystallization stages, though, for example, rational solvent and additive designs. Overall, we provide fundamental insights into precursor solution chemistry and establish pre-crystallization engineering as a key strategy for overcoming long-standing limitations in thin-film fabrication, particularly in light of the field's rapid progression toward large-scale, sustainable, and solvent-conscious manufacturing.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"190 1","pages":"e7703450"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502380","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}
{"title":"Correction to \"Defect-Rich Adhesive Nanozymes as Efficient Antibiotics for Enhanced Bacterial Inhibition\".","authors":"","doi":"10.1002/anie.7386489","DOIUrl":"https://doi.org/10.1002/anie.7386489","url":null,"abstract":"","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":"e7386489"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502485","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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