{"title":"Correction to \"Dual-Targeting Biomimetic Semiconducting Polymer Nanocomposites for Amplified Theranostics of Bone Metastasis\".","authors":"","doi":"10.1002/anie.3182300","DOIUrl":"https://doi.org/10.1002/anie.3182300","url":null,"abstract":"","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"6 1","pages":"e3182300"},"PeriodicalIF":16.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073257","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}
Florent J Dubray,Yu-Hsun Wang,Mikalai A Artsiusheuski,Jiawei Guo,Rene Verel,Ambarish Kulkarni,Jeroen A van Bokhoven,Vitaly L Sushkevich
Given the sustained demand for alkylated aromatics and the strained olefin market, there is an urgent need to develop efficient one-step processes for the direct alkylation of aromatics using alkanes instead of olefins. Such technologies offer greater energy efficiency and sustainability by eliminating the need for separate, energy-intensive alkane dehydrogenation steps. In this work, we report a dual chemical looping / catalytic process that couples alkane dehydrogenation with aromatic alkylation over a copper-containing mordenite yielding up to 25% of alkylated aromatics with >97% selectivity per cycle. In situ MAS NMR and FTIR spectroscopies combined with DFT calculations showed that the alkylation of benzene with alkanes proceeds via a π-bounded Cu(I)-olefin intermediate, which subsequently interacts with benzene, catalyzed by Brønsted acid sites, leading to alkylated products that readily desorb from the active material into the gas phase. DFT calculations show that alkylation mediated solely by Cu(I) has prohibitively high barriers (>1.8 eV), whereas a bi-functional pathway involving both Cu(I) and Brønsted acid sites can proceed with significantly lower barrier (0.8 eV) through a concerted C-C bond formation and proton transfer step.
{"title":"Dual Chemical Looping/Catalytic Process for Alkylation of Benzene With Ethane and Propane Yielding Ethylbenzene and Cumene Over Copper-Containing Mordenite.","authors":"Florent J Dubray,Yu-Hsun Wang,Mikalai A Artsiusheuski,Jiawei Guo,Rene Verel,Ambarish Kulkarni,Jeroen A van Bokhoven,Vitaly L Sushkevich","doi":"10.1002/anie.202523668","DOIUrl":"https://doi.org/10.1002/anie.202523668","url":null,"abstract":"Given the sustained demand for alkylated aromatics and the strained olefin market, there is an urgent need to develop efficient one-step processes for the direct alkylation of aromatics using alkanes instead of olefins. Such technologies offer greater energy efficiency and sustainability by eliminating the need for separate, energy-intensive alkane dehydrogenation steps. In this work, we report a dual chemical looping / catalytic process that couples alkane dehydrogenation with aromatic alkylation over a copper-containing mordenite yielding up to 25% of alkylated aromatics with >97% selectivity per cycle. In situ MAS NMR and FTIR spectroscopies combined with DFT calculations showed that the alkylation of benzene with alkanes proceeds via a π-bounded Cu(I)-olefin intermediate, which subsequently interacts with benzene, catalyzed by Brønsted acid sites, leading to alkylated products that readily desorb from the active material into the gas phase. DFT calculations show that alkylation mediated solely by Cu(I) has prohibitively high barriers (>1.8 eV), whereas a bi-functional pathway involving both Cu(I) and Brønsted acid sites can proceed with significantly lower barrier (0.8 eV) through a concerted C-C bond formation and proton transfer step.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":"e23668"},"PeriodicalIF":16.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073360","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}
Rational engineering of the local microenvironment in catalytic host materials is pivotal for high-performance zinc-iodine batteries, as it governs iodine species adsorption, accelerates redox kinetics, and suppresses polyiodides shuttling. Herein, we propose a local polarity engineering strategy by incorporating unsaturated Cu-N3 sites into carbon matrix to construct polarized microenvironments and promote iodine redox chemistry. Combined theoretical and experimental analyses reveal that the unsaturated coordination of Cu atoms induces intrinsic local polarity, which enhances charge redistribution, lowers the activation barrier of the I2/I- redox reaction, and strengthens electronic coupling with polyiodide intermediates. In situ UV-vis and Raman spectroscopies corroborate that the Cu-N3 sites effectively immobilize polyiodides, thus mitigating the shuttle effect. As cathode host, the Cu-N3 sites-rich carbon electrode achieves high discharge capacity of 232.2 mAh g-1 at 0.2 A g-1 and exceptional long-term stability with 94.02% capacity retention after 50,000 cycles at 10 A g-1. More importantly, benefiting from its superior catalytic activity toward iodine redox reaction, the Cu-N3 sites-rich carbon enables solar cells to achieve a remarkable power conversion efficiency of 9.14%. This work elucidates a novel design principle for regulating local polarity to propel iodine electrochemistry, offering new insights into the development of advanced iodine-based energy devices.
合理设计催化宿主材料中的局部微环境对高性能锌碘电池至关重要，因为它控制碘物质的吸附，加速氧化还原动力学，抑制多碘化物的穿梭。在此，我们提出了一种局部极性工程策略，将不饱和Cu-N3位点加入碳基质中，构建极化微环境，促进碘氧化还原化学。理论与实验相结合的分析表明，Cu原子的不饱和配位诱导了本质局域极性，增强了电荷再分配，降低了I2/I-氧化还原反应的激活势垒，增强了与多碘化物中间体的电子耦合。原位紫外-可见和拉曼光谱证实，Cu-N3位点有效地固定了多碘化物，从而减轻了穿梭效应。作为阴极主体，富Cu-N3位碳电极在0.2 A g-1下具有232.2 mAh g-1的高放电容量，在10 A g-1下经过5万次循环后具有94.02%的长期稳定性。更重要的是，得益于其对碘氧化还原反应的优异催化活性，富Cu-N3位碳使太阳能电池的功率转换效率达到了9.14%。这项工作阐明了一种新的设计原理来调节局部极性以推动碘电化学，为先进的碘基能源装置的发展提供了新的见解。
{"title":"Local Polarity Engineering via Unsaturated Cu-N3 Sites for Enhanced Iodine Redox Chemistry in Zinc-Iodine Batteries.","authors":"Yangjun Ma,Xiangtong Meng,Xiaoying Wang,Yadong Du,Jun Qi,Hongqi Zou,Jiachun Li,Zhanhao Jiang,Jieshan Qiu","doi":"10.1002/anie.202525573","DOIUrl":"https://doi.org/10.1002/anie.202525573","url":null,"abstract":"Rational engineering of the local microenvironment in catalytic host materials is pivotal for high-performance zinc-iodine batteries, as it governs iodine species adsorption, accelerates redox kinetics, and suppresses polyiodides shuttling. Herein, we propose a local polarity engineering strategy by incorporating unsaturated Cu-N3 sites into carbon matrix to construct polarized microenvironments and promote iodine redox chemistry. Combined theoretical and experimental analyses reveal that the unsaturated coordination of Cu atoms induces intrinsic local polarity, which enhances charge redistribution, lowers the activation barrier of the I2/I- redox reaction, and strengthens electronic coupling with polyiodide intermediates. In situ UV-vis and Raman spectroscopies corroborate that the Cu-N3 sites effectively immobilize polyiodides, thus mitigating the shuttle effect. As cathode host, the Cu-N3 sites-rich carbon electrode achieves high discharge capacity of 232.2 mAh g-1 at 0.2 A g-1 and exceptional long-term stability with 94.02% capacity retention after 50,000 cycles at 10 A g-1. More importantly, benefiting from its superior catalytic activity toward iodine redox reaction, the Cu-N3 sites-rich carbon enables solar cells to achieve a remarkable power conversion efficiency of 9.14%. This work elucidates a novel design principle for regulating local polarity to propel iodine electrochemistry, offering new insights into the development of advanced iodine-based energy devices.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"36 1","pages":"e25573"},"PeriodicalIF":16.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073365","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}
Huadong Suo,Zhonghui Chen,Chaozhong Liu,Xinhua Yan,Shanshan Xu,Zixu Sun,Hua Kun Liu,Shi Xue Dou,Bo Song
Hard carbons, despite their cost-efficient production and precursor availability, face critical electrochemical performance constraints from excessive defects, limited closed-pore structures, and poor interfacial stability. Herein, a multi-scale structural regulation strategy is proposed to tailor both micro- and nanoscale architectures of polymer-derived hard carbons for efficient sodium storage under both ambient and subzero conditions. The pitch-modulated carbonization directs the self-assembly of polyphosphazene (PZS) precursors into monodisperse microparticles while in situ forming nanoscale short-range-ordered graphitic domains. The resulting hard carbons integrate enhanced bulk conductivity, abundant closed pores, and defect-tailored low-surface-area microparticles, collectively enabling an inorganic-rich solid electrolyte interphase (SEI), fast Na+ transport, and suppressed side reactions. The optimized sample delivers a remarkable reversible capacity (413.7 mAh g-1 at 0.05 A g-1) with high initial Columbic efficiency (ICE) (87.1%) and excellent rate capability. More notably, it demonstrates high reversible capacity and exceptional cycling stability at -20°C, achieving a remarkable capacity retention of 98.8% after 3000 cycles and highlighting its practical viability under extreme conditions. The sodium storage mechanisms and accelerated kinetics are revealed through various in situ characterizations and computational techniques, providing deep insights into microstructure tailoring of hard carbons for high-performance sodium-ion batteries (SIBs).
尽管硬碳具有成本效益和前驱体可用性，但由于缺陷过多、闭孔结构有限和界面稳定性差，硬碳面临着关键的电化学性能限制。本文提出了一种多尺度结构调节策略，以定制聚合物衍生硬碳的微纳米尺度结构，以在环境和零下条件下有效地储存钠。沥青调制碳化使聚磷腈（PZS）前驱体自组装成单分散的微颗粒，同时在原位形成纳米尺度的近程有序石墨畴。由此产生的硬碳整合了增强的整体导电性，丰富的封闭孔隙和缺陷定制的低表面积微粒，共同实现了富无机固体电解质界面（SEI），快速Na+传输和抑制副反应。优化后的样品具有显著的可逆容量（413.7 mAh g-1, 0.05 a g-1），具有高初始哥伦比亚效率（ICE）（87.1%）和优异的倍率能力。更值得注意的是，它在-20°C下表现出高可逆容量和卓越的循环稳定性，在3000次循环后实现了98.8%的显着容量保持，并突出了其在极端条件下的实际可行性。通过各种原位表征和计算技术揭示了钠的储存机制和加速动力学，为高性能钠离子电池（SIBs）硬碳的微观结构定制提供了深入的见解。
{"title":"Multi-Scale Architecture Regulation of Hard Carbons for High-Efficiency Sodium Storage Across Ambient and Subzero Conditions.","authors":"Huadong Suo,Zhonghui Chen,Chaozhong Liu,Xinhua Yan,Shanshan Xu,Zixu Sun,Hua Kun Liu,Shi Xue Dou,Bo Song","doi":"10.1002/anie.202525761","DOIUrl":"https://doi.org/10.1002/anie.202525761","url":null,"abstract":"Hard carbons, despite their cost-efficient production and precursor availability, face critical electrochemical performance constraints from excessive defects, limited closed-pore structures, and poor interfacial stability. Herein, a multi-scale structural regulation strategy is proposed to tailor both micro- and nanoscale architectures of polymer-derived hard carbons for efficient sodium storage under both ambient and subzero conditions. The pitch-modulated carbonization directs the self-assembly of polyphosphazene (PZS) precursors into monodisperse microparticles while in situ forming nanoscale short-range-ordered graphitic domains. The resulting hard carbons integrate enhanced bulk conductivity, abundant closed pores, and defect-tailored low-surface-area microparticles, collectively enabling an inorganic-rich solid electrolyte interphase (SEI), fast Na+ transport, and suppressed side reactions. The optimized sample delivers a remarkable reversible capacity (413.7 mAh g-1 at 0.05 A g-1) with high initial Columbic efficiency (ICE) (87.1%) and excellent rate capability. More notably, it demonstrates high reversible capacity and exceptional cycling stability at -20°C, achieving a remarkable capacity retention of 98.8% after 3000 cycles and highlighting its practical viability under extreme conditions. The sodium storage mechanisms and accelerated kinetics are revealed through various in situ characterizations and computational techniques, providing deep insights into microstructure tailoring of hard carbons for high-performance sodium-ion batteries (SIBs).","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"282 1","pages":"e25761"},"PeriodicalIF":16.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089057","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}
Sören Lehmkuhl, Simon Fleischer, Jing Yang, Eduard Y. Chekmenev, Thomas Theis, Stephan Appelt, Jan G. Korvink, Mazin Jouda
Conventional Magnetic Resonance Imaging (MRI) relies on high‐power Radio‐Frequency (RF) pulses to excite nuclear spins and in turn generate NMR signals. These pulses require large high‐power RF‐amplifiers and cause heat deposition in the tissue, which must be minimized for safety, presenting a growing problem when moving toward ever‐higher field MRI. An alternative to RF‐pulse excitation is self‐excitation of nuclear spins using Radiofrequency Amplification by Stimulated Emission of Radiation (RASER), where the nuclear spins undergo spontaneous transition, without RF excitation, from an over‐populated state to a ground state. Here, the feasibility of recording rapid proton RASER MRI images of pyrazine at low concentration (120 mM) with large matrix (128x128 pixels) in as little as 78 ms is demonstrated at 500 MHz (11.7 T). We also recorded a time‐series of images using a single bolus hyperpolarized pyrazine highlighting the feasibility of dynamic tracking. The demonstrated approach allows recording MRI scans without transmit‐receive electronics of the MRI scanner, which is highly desirable for portable MRI as well as the emerging field of hyperpolarized MRI using, e.g., HP protons, 129 Xe gas or HP 13 C labeled biomolecules as molecular tracers and imaging agents.
{"title":"Rapid RASER MRI","authors":"Sören Lehmkuhl, Simon Fleischer, Jing Yang, Eduard Y. Chekmenev, Thomas Theis, Stephan Appelt, Jan G. Korvink, Mazin Jouda","doi":"10.1002/anie.202525699","DOIUrl":"https://doi.org/10.1002/anie.202525699","url":null,"abstract":"Conventional Magnetic Resonance Imaging (MRI) relies on high‐power Radio‐Frequency (RF) pulses to excite nuclear spins and in turn generate NMR signals. These pulses require large high‐power RF‐amplifiers and cause heat deposition in the tissue, which must be minimized for safety, presenting a growing problem when moving toward ever‐higher field MRI. An alternative to RF‐pulse excitation is self‐excitation of nuclear spins using Radiofrequency Amplification by Stimulated Emission of Radiation (RASER), where the nuclear spins undergo spontaneous transition, without RF excitation, from an over‐populated state to a ground state. Here, the feasibility of recording rapid proton RASER MRI images of pyrazine at low concentration (120 mM) with large matrix (128x128 pixels) in as little as 78 ms is demonstrated at 500 MHz (11.7 T). We also recorded a time‐series of images using a single bolus hyperpolarized pyrazine highlighting the feasibility of dynamic tracking. The demonstrated approach allows recording MRI scans without transmit‐receive electronics of the MRI scanner, which is highly desirable for portable MRI as well as the emerging field of hyperpolarized MRI using, e.g., HP protons, <jats:sup>129</jats:sup> Xe gas or HP <jats:sup>13</jats:sup> C labeled biomolecules as molecular tracers and imaging agents.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"10 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146071460","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}
Zihao Gao, Qiaomei Chen, Meng Duan, Ziheng Lu, Jiachen Wu, Chengyi Xiao, Christopher R. McNeill, Weiwei Li
Organic solar cells (OSCs) face a trade‐off between power conversion efficiency (PCE) and mechanical robustness: high toughness requires low‐crystallinity amorphous polymers, which impair photovoltaic performance. Herein, we propose a strategy combining random copolymerization and hydrogen‐bonding modulation to resolve this conflict. First, the incorporation of an ester‐substituted thiophene yields PM6‐H, exhibiting improved toughness (high crack‐onset strain, COS ) but lower PCE. Subsequently, introducing ─OH and ─OOCNHC 6 H 13 groups at the terminals of alkyl chains forms PM6‐OH and PM6‐UR. The hydrogen bonding serves dual functions: acting as dynamic cross‐linking sites to further enhance mechanical properties while restoring optimal lamellar stacking for efficient charge transport. As a result, these copolymers simultaneously achieve a COS exceeding 46%, a high PCE of up to 20.4%, and superior storage, thermal, and light stability (with T80 being twice that of the PM6 benchmark). Flexible OSCs fabricated using these donor polymers deliver a PCE of 18.22% while maintaining outstanding flexibility, with ∼90% PCE retention after 2200 bending cycles (vs. 78% for controls). This work demonstrates that copolymerization with controlled hydrogen‐bonding interactions overcomes the efficiency‐robustness trade‐off in OSCs through precise structural modulation, paving the way for high‐performance, mechanically durable, and stable OSCs suitable for practical applications.
{"title":"Resolving the Efficiency–Mechanical Trade‐off in Organic Solar Cells: 20.4% Enabled by Hydrogen‐Bonding Engineering","authors":"Zihao Gao, Qiaomei Chen, Meng Duan, Ziheng Lu, Jiachen Wu, Chengyi Xiao, Christopher R. McNeill, Weiwei Li","doi":"10.1002/anie.202524211","DOIUrl":"https://doi.org/10.1002/anie.202524211","url":null,"abstract":"Organic solar cells (OSCs) face a trade‐off between power conversion efficiency (PCE) and mechanical robustness: high toughness requires low‐crystallinity amorphous polymers, which impair photovoltaic performance. Herein, we propose a strategy combining random copolymerization and hydrogen‐bonding modulation to resolve this conflict. First, the incorporation of an ester‐substituted thiophene yields PM6‐H, exhibiting improved toughness (high crack‐onset strain, <jats:italic>COS</jats:italic> ) but lower PCE. Subsequently, introducing ─OH and ─OOCNHC <jats:sub>6</jats:sub> H <jats:sub>13</jats:sub> groups at the terminals of alkyl chains forms PM6‐OH and PM6‐UR. The hydrogen bonding serves dual functions: acting as dynamic cross‐linking sites to further enhance mechanical properties while restoring optimal lamellar stacking for efficient charge transport. As a result, these copolymers simultaneously achieve a <jats:italic>COS</jats:italic> exceeding 46%, a high PCE of up to 20.4%, and superior storage, thermal, and light stability (with <jats:italic>T</jats:italic> <jats:sub>80</jats:sub> being twice that of the PM6 benchmark). Flexible OSCs fabricated using these donor polymers deliver a PCE of 18.22% while maintaining outstanding flexibility, with ∼90% PCE retention after 2200 bending cycles (vs. 78% for controls). This work demonstrates that copolymerization with controlled hydrogen‐bonding interactions overcomes the efficiency‐robustness trade‐off in OSCs through precise structural modulation, paving the way for high‐performance, mechanically durable, and stable OSCs suitable for practical applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"7 1","pages":"e24211"},"PeriodicalIF":16.6,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070685","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}
PROteolysis TArgeting Chimeras (PROTACs) represents a promising therapeutic modality with the potential to revolutionize targeted protein degradation. However, challenges such as low bioavailability and off‐target effects significantly limit their clinical efficacy. Herein, we introduce a Split‐Deliver‐Click nanoplatform that enables tumor‐specific protein degradation through “AND” logic‐gated, in‐cell bioorthogonal clicking of PROTACs, inspired by the ternary structure of PROTACs and logic‐gated stimulus‐sensitive drug delivery. First, PROTACs were split with click‐reactive ligands, enabling their direct use in cellular assays for efficient PROTAC screening. Next, a delivery system was developed, utilizing an “AND” logic gate mechanism triggered by tumor‐overexpressed enzymes legumain and cathepsin B to separately activate and release the split PROTAC precursors. Finally, this approach permitted in‐cell click chemistry to generate PROTAC (Click‐PROTAC), achieving efficient and specific protein degradation. This Split‐Deliver‐Click strategy facilitated the in situ generation of PROTACs for precise protein degradation.
{"title":"Split‐Deliver‐Click: Tumor‐Specific Protein Degradation via “AND” Logic‐Gated In‐Cell Bioorthogonal Clicking of PROTACs","authors":"He Dong, Cilong Chu, Ihsan Ullah, Qing Xu, Zhenhai Pan, Youyong Yuan","doi":"10.1002/anie.202520774","DOIUrl":"https://doi.org/10.1002/anie.202520774","url":null,"abstract":"PROteolysis TArgeting Chimeras (PROTACs) represents a promising therapeutic modality with the potential to revolutionize targeted protein degradation. However, challenges such as low bioavailability and off‐target effects significantly limit their clinical efficacy. Herein, we introduce a Split‐Deliver‐Click nanoplatform that enables tumor‐specific protein degradation through “AND” logic‐gated, in‐cell bioorthogonal clicking of PROTACs, inspired by the ternary structure of PROTACs and logic‐gated stimulus‐sensitive drug delivery. First, PROTACs were split with click‐reactive ligands, enabling their direct use in cellular assays for efficient PROTAC screening. Next, a delivery system was developed, utilizing an “AND” logic gate mechanism triggered by tumor‐overexpressed enzymes legumain and cathepsin B to separately activate and release the split PROTAC precursors. Finally, this approach permitted in‐cell click chemistry to generate PROTAC (Click‐PROTAC), achieving efficient and specific protein degradation. This Split‐Deliver‐Click strategy facilitated the in situ generation of PROTACs for precise protein degradation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"43 1","pages":"e20774"},"PeriodicalIF":16.6,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070684","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}
Equilibrium-limited endothermic reactions play a crucial role in the transition toward a more sustainable chemical industry, but are typically plagued by the need for high operation temperatures (>500°C). Here, we show that the temperature gradients generated by the selective and localized heating of catalyst materials in a colder reactor environment shift the equilibrium of thermodynamically-limited endothermic reactions and improve their performance. In particular, the reverse water gas shift reaction and magnetic induction are selected as the model reaction and selective catalyst heating method, respectively. Magnetically induced catalysis using standard Cu-Al spinel-derived catalyst functionalized with carbon-coated iron nanoparticles enables high CO yield (up to 62%) at mild catalyst and reactor temperatures (estimated at 300°C and determined as 25-123°C, respectively). We demonstrate that the catalyst temperature and not the reactor temperature governs the equilibrium product composition of the rWGS, and that the temperature gradient promotes the in situ removal of water to shift the gas phase thermodynamic equilibrium. These two points synergistically result in a CO yield that would require a reactor temperature of 650°C in a conventionally heated gas phase reaction.
{"title":"Low-Temperature Reverse Water-Gas Shift Enabled by Magnetically Induced Catalysis.","authors":"Junhui Hu,Lise Marie Lacroix,Jacob Johny,Sourav Ghosh,Elisabeth Hannah Wolf,Jeongmin Ji,Sheng-Hsiang Lin,Manisha Durai,Alin Benice Schöne,Walid Hetaba,Holger Ruland,Walter Leitner,Alexis Bordet","doi":"10.1002/anie.202523576","DOIUrl":"https://doi.org/10.1002/anie.202523576","url":null,"abstract":"Equilibrium-limited endothermic reactions play a crucial role in the transition toward a more sustainable chemical industry, but are typically plagued by the need for high operation temperatures (>500°C). Here, we show that the temperature gradients generated by the selective and localized heating of catalyst materials in a colder reactor environment shift the equilibrium of thermodynamically-limited endothermic reactions and improve their performance. In particular, the reverse water gas shift reaction and magnetic induction are selected as the model reaction and selective catalyst heating method, respectively. Magnetically induced catalysis using standard Cu-Al spinel-derived catalyst functionalized with carbon-coated iron nanoparticles enables high CO yield (up to 62%) at mild catalyst and reactor temperatures (estimated at 300°C and determined as 25-123°C, respectively). We demonstrate that the catalyst temperature and not the reactor temperature governs the equilibrium product composition of the rWGS, and that the temperature gradient promotes the in situ removal of water to shift the gas phase thermodynamic equilibrium. These two points synergistically result in a CO yield that would require a reactor temperature of 650°C in a conventionally heated gas phase reaction.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"30 1","pages":"e23576"},"PeriodicalIF":16.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056885","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}
Zhen Wang,Fengrui Xiang,Xingyu Liao,Qingsong Wu,Jinbiao Jiao,Angzhi Bi,Siyang Liu,Dan Wang,Minyan Wang,Zijian Guo,Jie P Li
Reactions that excel in small-molecule settings typically require metal loadings far exceeding the number of protein reaction sites (often ≥10-fold) once transplanted into proteinaceous media-conditions that are not truly "catalytic." Here, we show that biologically inert metal-ligand complexes based on bathocuproine disulfonic acid disodium salt (BCS) overcome this barrier and enable ligand-accelerated catalysis (LAC) on proteins under substoichiometric conditions. For example, Ni-BCS effects complete deprotection of green fluorescent protein bearing Nε-propargyloxycarbonyl-L-lysine (GFP-ProcLys) at 5 mol% catalyst with an observed turnover number (TON) ≈ 20, surpassing all previously reported metal-catalyzed depropargylation reactions. Mechanistic studies indicate that an in situ Ni-H intermediate mediates multiple transformations on proteins, including reductive deuteration of terminal alkenes/alkynes and efficient decaging across diverse amino acid side chains. Likewise, Cu-BCS enables copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) on proteins at 10 mol% with low residual copper and no protein oxidation, in sharp contrast to the benchmark Cu-BTTAA (tris((1-tert-butyl-1H-1,2,3-triazol-4-yl)methyl)amine) system. These outcomes stem from a screening strategy that prioritized metal-ligand stability, eliminating metal complexes susceptible to protein sequestration and selecting strongly coordinating, physiologically inert pairs. The resulting rational ligand-design framework for protein-level transition-metal catalysis expands the frontier of protein chemistry and paves the way to translate advanced small-molecule LAC strategies onto protein substrates for posttranslational mutagenesis.
{"title":"Inert Complexes Unlock Ligand-Accelerated Transition-Metal Catalysis on Proteins.","authors":"Zhen Wang,Fengrui Xiang,Xingyu Liao,Qingsong Wu,Jinbiao Jiao,Angzhi Bi,Siyang Liu,Dan Wang,Minyan Wang,Zijian Guo,Jie P Li","doi":"10.1002/anie.202522057","DOIUrl":"https://doi.org/10.1002/anie.202522057","url":null,"abstract":"Reactions that excel in small-molecule settings typically require metal loadings far exceeding the number of protein reaction sites (often ≥10-fold) once transplanted into proteinaceous media-conditions that are not truly \"catalytic.\" Here, we show that biologically inert metal-ligand complexes based on bathocuproine disulfonic acid disodium salt (BCS) overcome this barrier and enable ligand-accelerated catalysis (LAC) on proteins under substoichiometric conditions. For example, Ni-BCS effects complete deprotection of green fluorescent protein bearing Nε-propargyloxycarbonyl-L-lysine (GFP-ProcLys) at 5 mol% catalyst with an observed turnover number (TON) ≈ 20, surpassing all previously reported metal-catalyzed depropargylation reactions. Mechanistic studies indicate that an in situ Ni-H intermediate mediates multiple transformations on proteins, including reductive deuteration of terminal alkenes/alkynes and efficient decaging across diverse amino acid side chains. Likewise, Cu-BCS enables copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) on proteins at 10 mol% with low residual copper and no protein oxidation, in sharp contrast to the benchmark Cu-BTTAA (tris((1-tert-butyl-1H-1,2,3-triazol-4-yl)methyl)amine) system. These outcomes stem from a screening strategy that prioritized metal-ligand stability, eliminating metal complexes susceptible to protein sequestration and selecting strongly coordinating, physiologically inert pairs. The resulting rational ligand-design framework for protein-level transition-metal catalysis expands the frontier of protein chemistry and paves the way to translate advanced small-molecule LAC strategies onto protein substrates for posttranslational mutagenesis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"272 1","pages":"e22057"},"PeriodicalIF":16.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070041","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}
Conventional small-molecule hole-transporting materials (SM-HTMs), although morphologically robust, typically suffer from limited hole mobility, interfacial energy misalignment, and inefficient charge extraction, which collectively hinder power conversion efficiencies (PCEs) above 25% in inverted perovskite solar cells (PSCs). Herein, breaking from conventional design paradigm, novel spatial molecular engineering was targeted proposed for SM-HTMs to overcome inherent limitations while reinforcing advantages. By spatially exposing the functional heterocyclic core to release its full potential, the tailored WH13 dramatically enhances the perovskite/HTM interfacial interactions, promotes crystallization, and facilitates hole extraction. More importantly, the resultant planar-steric architecture enables long-range π-stacking order while supporting nanocrystal-level film-formation, thereby achieving an optimal balance between charge transport dynamics and morphological features. Consequently, WH13-based inverted PSCs achieve a champion PCE of 26.6% (certified 26.24%) with exceptional operational stability (>99%, ISOS-L-1 500 h), representing the highest efficiency reported to date for SM-HTM-based PSCs. This spatial molecular engineering strategy establishes a generalizable design paradigm for next-generation HTMs, opening a promising pathway toward high-performance, operationally stable, and commercially viable PSCs.
传统的小分子空穴传输材料（SM-HTMs）虽然形态稳定，但通常存在空穴迁移率有限、界面能错位和电荷提取效率低下等问题，这些问题共同阻碍了倒置钙钛矿太阳能电池（PSCs）的功率转换效率（pce）达到25%以上。本文突破传统设计范式，针对sm - htm提出了一种新的空间分子工程设计方法，以克服其固有的局限性，增强其优势。通过在空间上暴露功能杂环核心以释放其全部潜力，定制的WH13显着增强了钙钛矿/HTM界面相互作用，促进了结晶，并有利于孔提取。更重要的是，由此产生的平面立体结构在支持纳米级成膜的同时，实现了远距离π堆积顺序，从而实现了电荷输运动力学和形态特征之间的最佳平衡。因此，基于wh13的倒置PSCs实现了26.6%（认证26.24%）的冠军PCE，具有出色的运行稳定性（bbb99 %， iso - l -1 500小时），代表了迄今为止基于sm - html的PSCs的最高效率。这种空间分子工程策略为下一代HTMs建立了一种通用的设计范式，为高性能、操作稳定和商业可行的psc开辟了一条有希望的途径。
{"title":"Spatial Molecular Engineering of Hole Semiconductors Enables Record Efficiency and Durability in Inverted Perovskite Solar Cells.","authors":"Zongyuan Yang,Chenzhe Xu,Zhe Wang,Zhihui Wang,Zhaolong Ma,Mengyuan Li,Rui Kong,Hui Cheng,Xin Xiong,Suhao Yan,Xueping Zong,Lixin Xiao,Mao Liang","doi":"10.1002/anie.202523665","DOIUrl":"https://doi.org/10.1002/anie.202523665","url":null,"abstract":"Conventional small-molecule hole-transporting materials (SM-HTMs), although morphologically robust, typically suffer from limited hole mobility, interfacial energy misalignment, and inefficient charge extraction, which collectively hinder power conversion efficiencies (PCEs) above 25% in inverted perovskite solar cells (PSCs). Herein, breaking from conventional design paradigm, novel spatial molecular engineering was targeted proposed for SM-HTMs to overcome inherent limitations while reinforcing advantages. By spatially exposing the functional heterocyclic core to release its full potential, the tailored WH13 dramatically enhances the perovskite/HTM interfacial interactions, promotes crystallization, and facilitates hole extraction. More importantly, the resultant planar-steric architecture enables long-range π-stacking order while supporting nanocrystal-level film-formation, thereby achieving an optimal balance between charge transport dynamics and morphological features. Consequently, WH13-based inverted PSCs achieve a champion PCE of 26.6% (certified 26.24%) with exceptional operational stability (>99%, ISOS-L-1 500 h), representing the highest efficiency reported to date for SM-HTM-based PSCs. This spatial molecular engineering strategy establishes a generalizable design paradigm for next-generation HTMs, opening a promising pathway toward high-performance, operationally stable, and commercially viable PSCs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"42 1","pages":"e23665"},"PeriodicalIF":16.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056855","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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