Angewandte Chemie (International ed. in English)最新文献_第6页

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-16 DOI: 10.1002/anie.202514533

Larissa K S von Krbek

引用次数: 0

Design of Tough 3D Printable Elastomers with Human-in-the-Loop Reinforcement Learning. 基于人在环强化学习的强韧3D可打印弹性体设计。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-13 DOI: 10.1002/anie.202513147

Johann L Rapp, Dylan M Anstine, Filipp Gusev, Filipp Nikitin, Kelly H Yun, Meredith A Borden, Vittal Bhat, Olexandr Isayev, Frank A Leibfarth

{"title":"Design of Tough 3D Printable Elastomers with Human-in-the-Loop Reinforcement Learning.","authors":"Johann L Rapp, Dylan M Anstine, Filipp Gusev, Filipp Nikitin, Kelly H Yun, Meredith A Borden, Vittal Bhat, Olexandr Isayev, Frank A Leibfarth","doi":"10.1002/anie.202513147","DOIUrl":"10.1002/anie.202513147","url":null,"abstract":"The development of high-performance elastomers for additive manufacturing requires overcoming complex property trade-offs that challenge conventional material discovery pipelines. Here, a human-in-the-loop reinforcement learning (RL) approach is used to discover polyurethane elastomers that overcome pervasive stress-strain property tradeoffs. Starting with a diverse training set of 92 formulations, a coupled multi-component reward system was identified that guides RL agents toward materials with both high strength and extensibility. Through three rounds of iterative optimization combining RL predictions with human chemical intuition, we identified elastomers with more than double the average toughness compared to the initial training set. The final exploitation round, aided by solubility prescreening, predicted twelve materials exhibiting both high strength (>10 MPa) and high strain at break (>200%). Analysis of the high-performing materials revealed structure-property insights, including the benefits of high molar mass urethane oligomers, a high density of urethane functional groups, and incorporation of rigid low molecular weight diols and unsymmetric diisocyanates. These findings demonstrate that machine-guided, human-augmented design is a powerful strategy for accelerating polymer discovery in applications where data is scarce and expensive to acquire, with broad applicability to multi-objective materials optimization.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202513147"},"PeriodicalIF":0.0,"publicationDate":"2025-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144629295","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Revealing Parallel Inter- and Intra-Ligand Charge Transfer Dynamics in [Ru(L)₂(dppz)]²⁺ Molecular Lightswitch with N K-Edge X-Ray Absorption Spectroscopy. 用N - k边x射线吸收光谱揭示[Ru(L)2(dppz)]2+分子光开关中平行配体间和配体内电荷转移动力学。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-10 DOI: 10.1002/anie.202509496

Elizabeth S Ryland, Xinzheng Yang, Douglas Garratt, Wade C Henke, Abdullah Kahraman, Maxwell Taub, Michael Sachs, Elisa Biasin, Christina Y Hampton, David J Hoffman, Giacomo Coslovich, Kristjan Kunnus, Georgi L Dakovski, Michael W Mara, Lin X Chen, Karen L Mulfort, Xiaosong Li, Amy A Cordones

{"title":"Revealing Parallel Inter- and Intra-Ligand Charge Transfer Dynamics in [Ru(L)2(dppz)]2+ Molecular Lightswitch with N K-Edge X-Ray Absorption Spectroscopy.","authors":"Elizabeth S Ryland, Xinzheng Yang, Douglas Garratt, Wade C Henke, Abdullah Kahraman, Maxwell Taub, Michael Sachs, Elisa Biasin, Christina Y Hampton, David J Hoffman, Giacomo Coslovich, Kristjan Kunnus, Georgi L Dakovski, Michael W Mara, Lin X Chen, Karen L Mulfort, Xiaosong Li, Amy A Cordones","doi":"10.1002/anie.202509496","DOIUrl":"10.1002/anie.202509496","url":null,"abstract":"In photoactive metal complexes the localization of photoexcited charges dictates the site of chemical reactivity, but few studies measure the charge redistribution in these systems with spatial precision. Herein, we track the inter- and intra-ligand charge transfer processes that underpin light-driven charge separation in the well-studied \"molecular lightswitch\" [Ru(bpy)2dppz]2+ (aqueous [RutheniumII(2,2'-bipyridine)2(dipyrido[3,2-a:2',3'-c]phenazine)]2+[Cl-]2) by probing the electronic structure of ligand nitrogen atoms in real-time using ultrafast X-ray absorption spectroscopy and first principles calculations. We confirm the localization of excited electron density on the phenazine N atoms of dppz and we newly identify two parallel electron transfer pathways to populate this state. Sub-70 fs electron transfer to the phenazine portion of dppz is observed and attributed to intra-ligand electron transfer following Ru-to-dppz metal-to-ligand charge transfer (MLCT) excitation. This fast charge transfer was not reported in prior ultrafast studies. The slower (ca. 2 ps) charge transfer reported extensively in time-resolved optical absorption and emission studies is reassigned here to inter-ligand electron \"hopping\" between nearly isoenergetic ligand moieties following Ru-to-bpy MLCT excitation. The results demonstrate much faster charge separation than previously identified in this well-studied system, highlighting how extended azaacene ligand motifs promote the competitive charge transfer processes needed to drive light-driven electron transfer chemistry.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202509496"},"PeriodicalIF":0.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144610917","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Metalloenzyme-Catalyzed Asymmetric Transfer Hydrogenation for the Synthesis of Chiral Amines. 金属酶催化不对称转移加氢合成手性胺。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-09 DOI: 10.1002/anie.202511298

Dong Cui, Xiaochen Cai, Xinyu Duan, Yuchen Chu, Bingyi Li, Zhiguo Wang, Feng Cheng, Jian Xu

引用次数: 0

Antisolvent-Bathing Strategy with Ultra-Wide Processing Window for Making High-efficiency Perovskite Solar Cells in Ambient Air. 超宽加工窗口的抗溶剂浴策略在环境空气中制造高效钙钛矿太阳能电池。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-09 DOI: 10.1002/anie.202506418

Lixiu Zhang, Chuantian Zuo, Mei Zhang, Ruihao Chen, Xiangyu Chen, Ke Jin, Feng Hao, Keyou Yan, Zuo Xiao, Congcong Wu, Jingjing Chang, Yong Ding, Liming Ding

{"title":"Antisolvent-Bathing Strategy with Ultra-Wide Processing Window for Making High-efficiency Perovskite Solar Cells in Ambient Air.","authors":"Lixiu Zhang, Chuantian Zuo, Mei Zhang, Ruihao Chen, Xiangyu Chen, Ke Jin, Feng Hao, Keyou Yan, Zuo Xiao, Congcong Wu, Jingjing Chang, Yong Ding, Liming Ding","doi":"10.1002/anie.202506418","DOIUrl":"10.1002/anie.202506418","url":null,"abstract":"Most record-efficiency perovskite solar cells rely on spin-coating with antisolvent dripping, which is fundamentally incompatible with roll-to-roll (R2R) manufacturing. The crystallization kinetics of dynamic wet film during spin coating differs widely from the static wet film during R2R fabrication, which makes the existing crystallization control strategies become inapplicable while upscaling. The crystallization regulation of static wet film remains a critical challenge, particularly under ambient conditions. In this study, we employed the antisolvent-bathing method that can efficiently regulate the crystallization process of static wet films made by drop coating. Through systematic investigation of solvent-antisolvent interdiffusion kinetics and in-situ crystallization monitoring via time-resolved UV-Vis spectroscopy, we identify alkyl chlorides (particularly chloroform) as optimal bathing agents. The champion device made by CF bathing achieved an efficiency of 24.49% under ambient conditions (RH 30%-50%), representing the highest efficiency for perovskite solar cells made by the antisolvent bathing method. The device showed negligible decay after 2256 h storage in N2 atmosphere. The method demonstrates exceptional environmental resilience to humidity and solvent accumulation, accompanied by an ultra-wide processing window (10 s-10 min bathing duration, >2 min post-bathing delay tolerance).","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202506418"},"PeriodicalIF":0.0,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144602721","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Near-Infrared Emissive Molecular Carbons Based on Quadruple [n]Helicenes. 基于四[n]螺旋烯的近红外发射分子碳。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202507891

Yilun Zhao, Zixin Liu, Xu Wen, Kai Chen, Guogang Liu, Zhaohui Wang, Wei Jiang

{"title":"Near-Infrared Emissive Molecular Carbons Based on Quadruple [n]Helicenes.","authors":"Yilun Zhao, Zixin Liu, Xu Wen, Kai Chen, Guogang Liu, Zhaohui Wang, Wei Jiang","doi":"10.1002/anie.202507891","DOIUrl":"10.1002/anie.202507891","url":null,"abstract":"We present a molecular design strategy that combines structural multiplicity and π-extension on a quaterrylene diimide scaffold to construct efficient near-infrared (NIR) circularly polarized luminescence (CPL) emitters. Through a carefully controlled synthesis involving sequential regioselective Suzuki coupling followed by Sholl-type oxidative cyclization, we successfully obtained two novel quadruple [n]helicenes (QnH). Comprehensive experimental characterization and theoretical calculations demonstrated their distinct configurational preferences: Q5H exclusively adopted the meso (P,P,M,M) configuration, while Q6H produced only the (P,P,P,P)/(M,M,M,M) enantiomeric pair. Single-crystal X-ray diffraction unambiguously confirmed the unique \"four-bladed propeller\" structure of (P,P,M,M)-Q5H. Both compounds demonstrated intense NIR fluorescence emission with photoluminescence quantum yields (ΦPL) of 47% for Q5H and 37% for Q6H. The chiral (P,P,P,P)/(M,M,M,M)-Q6H enantiomers showed exceptional chiroptical properties, including intense Cotton effects reached 719 M-1 cm-1 at 410 nm, a high absorption dissymmetry factor |gabs| of 0.035, and prominent CPL activity across 600-800 nm with a CPL brightness (BCPL) of 93 M-1 cm-1.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202507891"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586151","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Atomic-Level Design of Acid-Base Pairs in Oxides for Selective Catalytic Reduction of Nitrogen Oxides with Ammonia. 氨选择性催化还原氮氧化物中酸碱对的原子水平设计。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202509362

Guoquan Liu, He Zhang, Pengfei Wang, Chao Gao, Zechao Zhuang, Dingsheng Wang, Sihui Zhan

{"title":"Atomic-Level Design of Acid-Base Pairs in Oxides for Selective Catalytic Reduction of Nitrogen Oxides with Ammonia.","authors":"Guoquan Liu, He Zhang, Pengfei Wang, Chao Gao, Zechao Zhuang, Dingsheng Wang, Sihui Zhan","doi":"10.1002/anie.202509362","DOIUrl":"10.1002/anie.202509362","url":null,"abstract":"Selective catalytic reduction of nitrogen oxides (NOx) with NH3 (NH3-SCR) poses considerable potential in the abatement of NOx emissions. However, the efficient adsorption and speedy reaction of reactants following the specific mechanism in a favorable way is still a challenge for enhancing catalysis. Herein, we propose the strategy aimed at adjusting electronic properties of Ce-Ov-W acid-base pairs through constructing oxygen vacancies on Ce/WOx, thereby fostering SCR activity. Experimental and theoretical results reveal that Ce-Ov-W acid-base pairs not only provide more Ce3+ sites for promoting the reactivity of adsorbed NO, but also accelerate the reaction between NH3 and gaseous NO owing to the generation of W5+ species with superior surface acidity, which enhance Langmuir-Hinshelwood and Eley-Rideal mechanisms, respectively. Consequently, the designed catalysts achieve over 90% NOx conversion above 250 °C and exhibit higher activity than normal Ce/WO3 and V/W-TiO2 commercial catalysts, with anti-poisoning of SO2 and H2O under harsh working conditions, expecting to provide the guidance for promoting de-NOx industrial application.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202509362"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586133","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Donor Engineering for High Performance n-Type OECT Materials with Exceptional Operational Stability. 具有优异运行稳定性的高性能n型OECT材料的供体工程。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202513182

Riqing Ding, Xiage Zhang, Yidan Luan, Meishan Peng, Wantao Chen, Sijing Wang, Shengyao Su, Shunyang Lu, Sang Young Jeong, Han Young Woo, Xugang Guo, Kui Feng, Zi-Hao Guo

{"title":"Donor Engineering for High Performance n-Type OECT Materials with Exceptional Operational Stability.","authors":"Riqing Ding, Xiage Zhang, Yidan Luan, Meishan Peng, Wantao Chen, Sijing Wang, Shengyao Su, Shunyang Lu, Sang Young Jeong, Han Young Woo, Xugang Guo, Kui Feng, Zi-Hao Guo","doi":"10.1002/anie.202513182","DOIUrl":"10.1002/anie.202513182","url":null,"abstract":"Donor-acceptor (D-A) conjugated polymeric mixed ionic-electronic conductors (PMIECs) have been widely used in organic electrochemical transistors (OECTs) due to their structural diversity and the tunability of their frontier molecular orbital (FMO) energy levels. However, the slower development of n-type materials compared to p-type ones limits their potential in advanced technological applications. In this study, we design and synthesize a novel thiophene-based donor building block, 2,3-di(thiophen-2-yl)fumaronitrile (DTFMCN), for D-A conjugated n-type PMIECs through donor engineering strategies. DTFMCN can be easily synthesized from commercially available starting materials via a simple one-step process. The DTFMCN-based D-A conjugated polymers, S-DTFMCN and B-DTFMCN, exhibit extremely low-lying lowest unoccupied molecular orbital (LUMO) energy levels and show typical n-type characteristics. OECT devices based on these polymers demonstrate ultra-low threshold voltages (6 and 40 mV) and high µC* values of 13.49 and 13.57 F cm-1 V-1 s-1, respectively. More importantly, these devices exhibit exceptionally high operational stability; the current retention rate after 168 minutes of operation is 96%, making them one of the most stable n-type OECT devices reported to date. This study highlights the effectiveness of DTFMCN in improving the operational stability of n-type OECT devices, offering promising potential for applications in bioelectronics.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202513182"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586138","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

When Bigger is Better: Lanthanum Complexes of Bis(phenoxy-amidine) FAlen Ligands as Unique Catalysts for the Isoselective Ring-Opening Polymerization of Racemic β-Lactones. 越大越好：双（苯氧基氨基）FAlen配体镧配合物作为外消旋β-内酯等选择开环聚合的独特催化剂。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202509587

Thanh-Tu Bui, Jérôme Bayardon, Cédric Balan, Thierry Roisnel, Raluca Malacea-Kabbara, Pierre Le Gendre, Evgueni Kirillov, Jean-François Carpentier

{"title":"When Bigger is Better: Lanthanum Complexes of Bis(phenoxy-amidine) FAlen Ligands as Unique Catalysts for the Isoselective Ring-Opening Polymerization of Racemic β-Lactones.","authors":"Thanh-Tu Bui, Jérôme Bayardon, Cédric Balan, Thierry Roisnel, Raluca Malacea-Kabbara, Pierre Le Gendre, Evgueni Kirillov, Jean-François Carpentier","doi":"10.1002/anie.202509587","DOIUrl":"10.1002/anie.202509587","url":null,"abstract":"Discrete yttrium and lanthanum complexes supported by new bis(phenoxy-amidine) ligands have been prepared in high yields. Some of these so-called FAlen ligands, when coordinated onto the large La3+ in contrast to the small Y3+, can adopt an η3 coordination mode of both amidine moieties. These La-FAlen complexes, either previously isolated or conveniently prepared in situ, act as highly efficient ROP catalysts of simple and functional β-propiolactones rac-BLR (R = Me, CH2OiPr, CH2OSitBuMe2) under mild conditions, returning the corresponding linear polymers PBLR with high control over the molecular weights and narrow dispersities. More uniquely, when substituents with appropriate bulkiness are installed on the phenoxy and amidine moieties, the polymers all feature high isotacticity (Pm up to 0.93). High activity and isoselectivity are maintained, no matter the nature and polarity of the solvent used.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202509587"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586162","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Molecular Scale Interfacial Water Management Switching Reaction Pathway of Carbon Dioxide Electroreduction. 二氧化碳电还原的分子尺度界面水管理切换反应途径。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202508801

Zongying Li, Rongzhen Chen, Wangxin Ge, Kunchi Xie, Yating Wang, Ling Zhang, Zhen Song, Fengwang Li, Yuhang Li, Chunzhong Li

{"title":"Molecular Scale Interfacial Water Management Switching Reaction Pathway of Carbon Dioxide Electroreduction.","authors":"Zongying Li, Rongzhen Chen, Wangxin Ge, Kunchi Xie, Yating Wang, Ling Zhang, Zhen Song, Fengwang Li, Yuhang Li, Chunzhong Li","doi":"10.1002/anie.202508801","DOIUrl":"10.1002/anie.202508801","url":null,"abstract":"The electrochemical carbon dioxide reduction reaction (eCO2RR) involves numerous intermediates and simultaneous interactions between these intermediates and water (H2O) molecules. Although extensive research has focused on stabilizing the carbon-related intermediates, limited attention has been paid to investigating the local regulations of H2O molecules at molecular level. Considering the electrocatalytic interface, H2O is critical during CO2RR process, as H2O molecules are directly involved in CO2 reduction process or indirectly modify the solid-liquid interfacial structure, thereby impacting the reaction process. In this study, we use a model copper-based catalyst, containing palladium and indium dopants that have different hydrogen and oxygen adsorption capabilities, to investigate the influence of H2O molecules on CO2 electroreduction selectivity. We find, by enhancing the participation of isolated H2O molecules, instead of asymmetric H-bonded H2O or ice-like H2O, in the local electrocatalytic microenvironment during CO2 reduction process, that the cathodic products remarkably change from 95% C1 FE to 70% C2 FE. We unveil, via in-situ ATR-SEIRAS measurement, that the H2O microenvironment regulation can promote the formation of key intermediates, thus tuning the CO2 reduction pathways.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202508801"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586150","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0