The pyridine contracted to form the pyrrole ring. This transformation belongs to a unique class of reactions with the fundamental characteristic of the cleavage of the aromatic structure. By investigating the unusual coordination chemistry of N-confused pyriporphyrin with silver and gold ions, we observed this process and obtained several complexes that exhibited remarkable reactivity. This includes the reversible cleavage of C-O bonds and the selective demetallation of the outer metal ion.
{"title":"Pyridine Into Pyrrole Transformation Induced Within the Confinement of the Macrocycle.","authors":"Paulina Krzyszowska,Agata Burska-Jabłońska,Mateusz Oberski,Michał J Białek,Lechosław Latos-Grażyński,Karolina Hurej","doi":"10.1002/anie.202525506","DOIUrl":"https://doi.org/10.1002/anie.202525506","url":null,"abstract":"The pyridine contracted to form the pyrrole ring. This transformation belongs to a unique class of reactions with the fundamental characteristic of the cleavage of the aromatic structure. By investigating the unusual coordination chemistry of N-confused pyriporphyrin with silver and gold ions, we observed this process and obtained several complexes that exhibited remarkable reactivity. This includes the reversible cleavage of C-O bonds and the selective demetallation of the outer metal ion.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"36 1","pages":"e25506"},"PeriodicalIF":16.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089198","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}
Enzyme therapeutics require both catalytic activity and efficient cytosolic delivery-yet protective encapsulation typically compromises enzymatic function, while achieving cellular uptake without lysosomal degradation remains challenging. We address this with a rationally designed supramolecular adhesive photoinitiator (GuCD⊃BP-SH) that unifies surface adhesion, radical initiation, and membrane translocation within a single host-guest architecture. Guanidinium (Gu+) motifs on a cyclodextrin scaffold (GuCD) enable non-covalent adhesion to protein surfaces at carboxylate-rich regions; the cyclodextrin cavity hosts a thiol-benzophenone guest (BP-SH) whose photoactivation (365 nm, 60 mW cm-2 for 30 min) initiates localized grafting-from polymerization, constructing a semi-permeable polymer jacket. Applied to β-galactosidase, this yields sub-100 nm multi-enzyme nanoassemblies (containing ∼10 enzymes per particle) retaining ∼30% catalytic activity with exceptional proteolytic resistance: 86% activity retained versus 25% for unprotected enzyme after Proteinase K challenge. The incorporated Gu+ motifs enable efficient, energy-independent cytosolic delivery via membrane translocation, with 91% of cells showing catalytic activity compared to 5% with non-jacketed enzyme. This modular strategy confers protection and cell-penetrating capability onto native biomacromolecules while maintaining catalytic function, eliminating the need for enzyme release-a persistent bottleneck in therapeutic delivery.
{"title":"Adhesive Photoinitiator Constructs Polymer Jackets on Enzymes: Direct, Release-Free Cytosolic Delivery.","authors":"Shuran He,Soumen Ghosh,Kou Okuro","doi":"10.1002/anie.202524301","DOIUrl":"https://doi.org/10.1002/anie.202524301","url":null,"abstract":"Enzyme therapeutics require both catalytic activity and efficient cytosolic delivery-yet protective encapsulation typically compromises enzymatic function, while achieving cellular uptake without lysosomal degradation remains challenging. We address this with a rationally designed supramolecular adhesive photoinitiator (GuCD⊃BP-SH) that unifies surface adhesion, radical initiation, and membrane translocation within a single host-guest architecture. Guanidinium (Gu+) motifs on a cyclodextrin scaffold (GuCD) enable non-covalent adhesion to protein surfaces at carboxylate-rich regions; the cyclodextrin cavity hosts a thiol-benzophenone guest (BP-SH) whose photoactivation (365 nm, 60 mW cm-2 for 30 min) initiates localized grafting-from polymerization, constructing a semi-permeable polymer jacket. Applied to β-galactosidase, this yields sub-100 nm multi-enzyme nanoassemblies (containing ∼10 enzymes per particle) retaining ∼30% catalytic activity with exceptional proteolytic resistance: 86% activity retained versus 25% for unprotected enzyme after Proteinase K challenge. The incorporated Gu+ motifs enable efficient, energy-independent cytosolic delivery via membrane translocation, with 91% of cells showing catalytic activity compared to 5% with non-jacketed enzyme. This modular strategy confers protection and cell-penetrating capability onto native biomacromolecules while maintaining catalytic function, eliminating the need for enzyme release-a persistent bottleneck in therapeutic delivery.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"180 1","pages":"e24301"},"PeriodicalIF":16.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073363","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}
Lithium-sulfur (Li-S) batteries hold great potential as high-energy-density energy storage devices, yet their practical application is hindered by rapid cycling failure caused by parasitic reactions between lithium polysulfides (LiPSs) and lithium metal anodes. Inspired by lithium bond chemistry, we herein propose a weak cation interaction strategy as a new molecular design principle to intrinsically mitigate the parasitic reactivity of LiPSs and endow long-cycling Li-S batteries operating at 500 Wh kg-1 level. Specifically, molecular-level interaction regulation is introduced by employing ammonium cation (NH4 +) with weaker polarizing power than Li+ to interact with LiPSs, thereby attenuating their electrophilicity, elevating their lowest unoccupied molecular orbital energy levels, and suppressing the detrimental parasitic reactions with lithium metal anodes. This regulation strategy markedly prolongs the lifespan of Li-S coin cells from 53 to 149 cycles under harsh conditions of using 4.2 mg cm-2-loading sulfur cathodes and 50 µm-thick lithium anodes. More importantly, an 8 Ah-level Li-S pouch cell achieves a high initial energy density of 502 Wh kg-1 and stable 16 cycles. This work establishes a new weak cation interaction regulation strategy following lithium bond chemistry, offering a generalizable route toward long-cycling and high-energy-density Li-S batteries.
{"title":"Regulating Lithium Bond to Reduce Polysulfide Parasitic Reactivity for High-Stability Lithium Metal Anode.","authors":"Zheng Li,Bo-Quan Li,Li-Li Chen,Yu-Chen Gao,Chen-Xi Bi,Meng Zhao,Xiang Chen,Xi-Yao Li,Qiang Zhang","doi":"10.1002/anie.202522034","DOIUrl":"https://doi.org/10.1002/anie.202522034","url":null,"abstract":"Lithium-sulfur (Li-S) batteries hold great potential as high-energy-density energy storage devices, yet their practical application is hindered by rapid cycling failure caused by parasitic reactions between lithium polysulfides (LiPSs) and lithium metal anodes. Inspired by lithium bond chemistry, we herein propose a weak cation interaction strategy as a new molecular design principle to intrinsically mitigate the parasitic reactivity of LiPSs and endow long-cycling Li-S batteries operating at 500 Wh kg-1 level. Specifically, molecular-level interaction regulation is introduced by employing ammonium cation (NH4 +) with weaker polarizing power than Li+ to interact with LiPSs, thereby attenuating their electrophilicity, elevating their lowest unoccupied molecular orbital energy levels, and suppressing the detrimental parasitic reactions with lithium metal anodes. This regulation strategy markedly prolongs the lifespan of Li-S coin cells from 53 to 149 cycles under harsh conditions of using 4.2 mg cm-2-loading sulfur cathodes and 50 µm-thick lithium anodes. More importantly, an 8 Ah-level Li-S pouch cell achieves a high initial energy density of 502 Wh kg-1 and stable 16 cycles. This work establishes a new weak cation interaction regulation strategy following lithium bond chemistry, offering a generalizable route toward long-cycling and high-energy-density Li-S batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"81 1","pages":"e22034"},"PeriodicalIF":16.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089200","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 \"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}
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