He Xia, Wenjuan Zhou, Dezheng Li, Fan Peng, Chao Wang, Liyang Yu, Jingyi Du, Yang Zheng, Yuanhua Sang, Yu Zhang, Lin Han, Hong Liu, Aijun Hao, Jichuan Qiu
{"title":"Engineering Neural Stem Cells with Micropatches for Improved Therapy of Traumatic Brain Injury.","authors":"He Xia, Wenjuan Zhou, Dezheng Li, Fan Peng, Chao Wang, Liyang Yu, Jingyi Du, Yang Zheng, Yuanhua Sang, Yu Zhang, Lin Han, Hong Liu, Aijun Hao, Jichuan Qiu","doi":"10.1002/anie.202512804","DOIUrl":"10.1002/anie.202512804","url":null,"abstract":"<p><p>Transplantation of neural stem cells (NSCs) holds promise for repairing traumatic brain injury (TBI) but their therapeutic performance is hindered due to the low efficient differentiation into neurons. Direct injection of differentiation modulators to the lesion site has limited improvement to neuronal differentiation as they tend to diffuse or be degraded. In the present study, we report a simple and versatile strategy to engineer the NSCs with a micropatch to improve their therapeutic performance in TBI treatment. The micropatches are fabricated through microcontact printing technique and can adhere to the membrane with negligible detachment or internalization within 14 days after surface modification. The micropatches on the cell membrane can move together with stem cells and sustainedly release retinoic acid, a neuronal differentiation modulator, to regulate the surrounding microenvironment of NSCs, improving their neuronal differentiation rate from 28.0% to 54.2%. The micropatch-engineered NSCs can be implanted into the injured brain tissue through a minimally invasive microinjection approach and show outperformance in repairing damaged neural tissue of TBI mice compared to normal stem cells. Overall, this work highlights a new pathway to engineer stem cells and holds great potential in nerve regeneration and neurodegenerative disease treatment.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202512804"},"PeriodicalIF":0.0,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144562596","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}
{"title":"Suppressing Halide Segregation of Wide Bandgap Perovskite by Interface Molecular Coordination for High-Performance All-Perovskite Tandem Solar Cells.","authors":"Wenzhuo Li, Gaoqi Liu, Xin Wen, Xianyuan Jiang, Haobo Wu, Mingyu Ma, Wei Zhou, Hao Liang, Qilin Zhou, Yunlong Liu, Ruiqi Xu, Wenjing Wang, Zhenhuang Su, Wenjia Zhou, Xingyu Gao, Zhijun Ning","doi":"10.1002/anie.202511743","DOIUrl":"10.1002/anie.202511743","url":null,"abstract":"<p><p>Hole transporting layers made by self-assembled molecules (SAMs) are emerging as promising hole transporting materials (HTMs) for perovskite-based tandem solar cells, owing to their reduced parasitic absorption and effective carrier extraction. However, perovskite films grown on HTM substrates typically exhibit a high defect density, which adversely affects device performance. In this study, we investigated the film growth kinetics of wide-bandgap perovskite on monolayer material substrates and uncovered a halide phase segregation in the initial nucleation stage during crystal growth kinetics at the interface, which brings small grain sizes and significant lattice strain within the perovskite film. To address this issue, we introduced a biphosphate-substituted molecule on the HTM surface to coordinate with PbBr<sub>2</sub> that suppresses halide phase segregation, leading to improved crystallographic orientation and a reduction in defect density. As a result, the wide-bandgap (1.77 eV) perovskite solar cells (PSCs) achieved a power conversion efficiency (PCE) of 19.5% with an open-circuit voltage of 1.35 V, while tandem devices reached an impressive efficiency of 28.65%.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202511743"},"PeriodicalIF":0.0,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144562599","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}
Cyprien Muller, Maciej Piejko, Sinan Bascil, Joseph Moran
{"title":"The Diels-Alder Reaction as a Mechanistic Probe for Vibrational Strong Coupling.","authors":"Cyprien Muller, Maciej Piejko, Sinan Bascil, Joseph Moran","doi":"10.1002/anie.202509391","DOIUrl":"10.1002/anie.202509391","url":null,"abstract":"<p><p>Vibrational Strong Coupling (VSC) has recently been reported to alter reaction kinetics. Hypotheses on how it does this have been proposed, but open questions remain regarding the importance of the polarity of the reaction mechanism and of intramolecular vibrational redistribution (IVR), among other factors. We propose the Diels-Alder (DA) reaction as a probe to study chemistry under VSC, owing to the high diversity of its reaction partners. Herein, fixed-width cavities and UV-vis spectroscopy were used to determine the rate constants for the reactions of the diene 1,3-diphenylisobenzofuran (DPIBF) with various dienophiles under different coupling conditions. We investigated the effect of coupling six different solvents and of cooperative coupling of the dienophile through the solvent. Secondly, as the DA reaction can be catalyzed by hydrogen bonding, we investigated how the reaction was influenced by coupling alcohol solvents. Finally, we explored the direct coupling of vibrational modes of the dienophiles, including the stretching mode of the reactive C═C bond. In all cases, no substantial changes to the reaction rate constants were observed among the diverse coupling scenarios explored. This work initiates the use of the DA reaction as a mechanistic platform to understand how VSC changes chemistry and invites further experimental and theoretical studies.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202509391"},"PeriodicalIF":0.0,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144562600","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}
Subhashis Jana, Alex J Eddins, Yogesh M Gangarde, P Andrew Karplus, Ryan A Mehl
{"title":"Tuning Encodable Tetrazine Chemistry for Site-Specific Protein Bioorthogonal Ligations.","authors":"Subhashis Jana, Alex J Eddins, Yogesh M Gangarde, P Andrew Karplus, Ryan A Mehl","doi":"10.1002/anie.202508922","DOIUrl":"10.1002/anie.202508922","url":null,"abstract":"<p><p>Using genetic code expansion (GCE) to encode bioorthogonal chemistry has emerged as a promising method for protein labeling, both in vitro and within cells. Here, we demonstrate that tetrazine (Tet) amino acids incorporated into proteins are highly tunable and have extraordinary potential for fast and quantitative bioorthogonal ligations. We describe the synthesis and characterization of reaction rates for 29 Tet amino acids (20 of which are new) and compare their encoding ability into proteins using evolved tRNA/RS pairs. For these systems, we characterized on-protein Tet stability, reaction rates, and ligation extents as the utility of a bioorthogonal labeling group depends on its stability and reactivity when encoded into proteins. By integrating data on encoding efficiency, selectivity, on-protein stability, and in-cell labeling for Tet tRNA/RS pairs, we developed the smallest, fastest, and most stable Tet to date. This was achieved by introducing fluorine substituents to Tet4, resulting in reaction rates at the 10⁶ M⁻¹s⁻¹ level while minimizing degradation. This study expands the toolbox of bioorthogonal reagents for Tet-sTCO-based, site-specific protein labeling and demonstrates that the Tet is a uniquely tunable, highly reactive, and encodable bioorthogonal functional group. These findings provide a foundation to further explore Tet encoding and reactivity.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202508922"},"PeriodicalIF":0.0,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144562601","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}
{"title":"Access to Chiral Cyclic β-Enaminones via Enantioselective Imine Condensation.","authors":"Yaru Gao, Zhi-Keng Lin, Mingjin Liu, Jiameng Deng, Tao Zhang, Bin-Miao Yang, Yu Zhao","doi":"10.1002/anie.202512405","DOIUrl":"10.1002/anie.202512405","url":null,"abstract":"<p><p>We report herein an unprecedented catalytic enantioselective synthesis of cyclic β-enaminones from simple meso-1,3-diketones via chiral phosphoric acid-catalyzed desymmetrization through imine condensation. This transformation provides efficient access to a broad array of cyclic β-enaminones and acridinones bearing a remote β-stereogenic center, delivering products in excellent yields and enantioselectivities under mild conditions with a straightforward protocol. Furthermore, the resulting β-enaminones can undergo one-step derivatizations to furnish diverse enantioenriched carbo- and heterocycles, highlighting their high potential for applications in medicinal chemistry.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202512405"},"PeriodicalIF":0.0,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144556472","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}
Emily Xi Tan, Jaslyn Ru Ting Chen, Desmond Wei Cheng Pang, Nguan Soon Tan, In Yee Phang, Xing Yi Ling
{"title":"Transfer Learning-Assisted SERS: Predicting Molecular Identity and Concentration in Mixtures Using Pure Compound Spectra.","authors":"Emily Xi Tan, Jaslyn Ru Ting Chen, Desmond Wei Cheng Pang, Nguan Soon Tan, In Yee Phang, Xing Yi Ling","doi":"10.1002/anie.202508717","DOIUrl":"10.1002/anie.202508717","url":null,"abstract":"<p><p>Identifying and quantifying compounds in unknown mixtures represents the ultimate goal of surface-enhanced Raman scattering (SERS) spectroscopy but remains a significant challenge in real-world applications. Existing machine learning-driven SERS methods are limited by their reliance on prior knowledge of mixture composition, while time-consuming experimental testing of all possibilities is not feasible. We integrate the molecular specificity of SERS with an adaptive transfer learning (TL) strategy to sequentially identify and quantify carnitine components in 11 unknown binary, ternary, and quaternary multicarnitine mixtures, achieving 100% identification accuracy and a mean quantitation error of only 3%. All models are trained solely on pure compound spectral data, enabling scalable, qualitative, and quantitative analysis of complex, unseen multiplex spectra-without requiring costly and time-consuming training data collection for every possible mixture. This predictive transfer learning-driven approach marks a transformative leap for practical SERS applications, allowing accurate analysis of complex mixtures without prior knowledge of components or ratios.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202508717"},"PeriodicalIF":0.0,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144556473","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}
Congcong Jin, Yang Li, Jin Seong Kim, Jong-Hoon Lim, Hongbo Huang, Chong-An Chen, Jihyun Lee, Yejin Heo, Bingbing Zhang, Joon Ik Jang, Kang Min Ok
{"title":"Exceptional Second Harmonic Generation in Ultraviolet Nonlinear Optical Oxyfluoroniobate Crystals via Structural Fingerprint Optimization of Polar Chains.","authors":"Congcong Jin, Yang Li, Jin Seong Kim, Jong-Hoon Lim, Hongbo Huang, Chong-An Chen, Jihyun Lee, Yejin Heo, Bingbing Zhang, Joon Ik Jang, Kang Min Ok","doi":"10.1002/anie.202512618","DOIUrl":"10.1002/anie.202512618","url":null,"abstract":"<p><p>Partial fluorination of oxides has positioned oxyfluorides as a promising class of nonlinear optical (NLO) materials owing to their balanced optical properties. However, effectively arranging optical chromophores to achieve strong optical nonlinearity remains challenging. In this study, we explore the structural chemistry of <sup>1</sup>[NbOF<sub>4</sub>]<sub>∞</sub> chain-based oxyfluoroniobates and establish a molecular geometric framework to quantify key structural fingerprint factors, namely, the ∠(O─Nb─O') bond angle, χ[F,Nb,Nb',F'] torsion angle, chain alignment, and distortion of [NbO<sub>2</sub>F<sub>4</sub>] nodes. Theoretical calculations confirm that these factors critically influence second harmonic generation (SHG) activity. By integrating π-conjugated biuret (C<sub>2</sub>H<sub>5</sub>N<sub>3</sub>O<sub>2</sub>) molecules with optimally aligned <sup>1</sup>[NbOF<sub>4</sub>]<sub>∞</sub> chains, we synthesized (H<sub>3</sub>O)(Biu)<sub>2</sub>(NbOF<sub>4</sub>) (Biu = biuret), a crystal exhibiting a record-breaking SHG response, reaching 10.8 times that of KH<sub>2</sub>PO<sub>4</sub>, among transition metal (TM) oxyfluorides. Its moderate birefringence (Δn = 0.062 @1064 nm) and wide band gap (E<sub>g</sub> = 4.50 eV) further support its potential as a high-performance ultraviolet (UV) NLO material. These results highlight the power of structural fingerprint optimization in fully activating polar chains and offer a new strategy for designing next-generation UV NLO crystals with enhanced SHG performance.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202512618"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144546804","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}
Zhenlin Wang, Haiyan Duan, Wenqiang Qu, Donglin Han, Xingchi Li, Li Zhu, Xuan Jiang, Danhong Cheng, Yongjie Shen, Ming Xie, Emiliano Cortes, Dengsong Zhang
{"title":"Sulfur Mediated Interfacial Proton-Directed Transfer Boosts Electrocatalytic Nitric Oxide Reduction to Ammonia over Dual-Site Catalysts.","authors":"Zhenlin Wang, Haiyan Duan, Wenqiang Qu, Donglin Han, Xingchi Li, Li Zhu, Xuan Jiang, Danhong Cheng, Yongjie Shen, Ming Xie, Emiliano Cortes, Dengsong Zhang","doi":"10.1002/anie.202511398","DOIUrl":"10.1002/anie.202511398","url":null,"abstract":"<p><p>Electrocatalytic nitric oxide reduction reaction (NORR) for ammonia (NH<sub>3</sub>) synthesis represents a sustainable strategy that simultaneously realizes the nitrogen cycle and resource integration. The key issue hindering the NORR efficiency is accelerating proton (*H) transfer to facilitate NO hydrogenation while inhibiting the hydrogen evolution reaction (HER). Herein, we demonstrate an interface-engineered sulfur-mediated Cu@Co electrocatalyst (S-Cu@Co/C) that boosts NORR performance through dual modulation of electronic structure and proton transfer on active sites. A comprehensive program of experimental and theoretical calculations was employed to discover that sulfur incorporation induces electron redistribution in the Cu-Co interface, creating electron-rich sulfur and electron-deficient metals. This electronic configuration synergistically enhances NO adsorption on Cu sites and promotes water dissociation on Co sites. More critically, sulfur could direct the rapid transfer of *H from Co to Cu sites, thereby accelerating the NO hydrogenation and suppressing HER. Consequently, S-Cu@Co/C achieves an NH<sub>3</sub> yield rate of 655.3 µmol h<sup>-1</sup> cm<sup>-2</sup> in a flow cell and a Faradaic efficiency of 92.4% in an H-cell. Remarkably, the catalyst could maintain continuous electrolysis tests and steady NH<sub>3</sub> yield up to 100 h. This work provides innovative insights into the fabrication of efficient electrocatalysts via heteroatom-mediated interfacial engineering strategies.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202511398"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144546811","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}
Xiaozhen Huang, Taiyu Wang, Wenjie Chen, Zhengye Wang, Zhiye Lin, Di Wang, Xiaofeng Li, Diwei Zhang, Shidong Cai, Xiafeng He, Jie Gao, Dong Wei, Hongfang Du, Youchao Wei, Yue Wang, Mingwei An, Yang Wang
{"title":"Bottom-Up Regulation of Perovskite Growth and Energetics via Oligoether Functionalized Self-Assembling Molecules for High-Performance Solar Cells.","authors":"Xiaozhen Huang, Taiyu Wang, Wenjie Chen, Zhengye Wang, Zhiye Lin, Di Wang, Xiaofeng Li, Diwei Zhang, Shidong Cai, Xiafeng He, Jie Gao, Dong Wei, Hongfang Du, Youchao Wei, Yue Wang, Mingwei An, Yang Wang","doi":"10.1002/anie.202507513","DOIUrl":"10.1002/anie.202507513","url":null,"abstract":"<p><p>Self-assembling molecules (SAMs) are widely used as interfacial layers to optimize the surface properties of nickel oxides (NiO<sub>x</sub>) in inverted perovskite solar cells (PSCs). However, less attention is paid to the effect of SAMs on the regulation of perovskite growth and energetics. Here, based on the donor-acceptor molecular backbone, an oligoether chain is introduced with different chain lengths to endow two novel SAMs, namely, EPA and MEPA, with good capability of bottom-up regulation of perovskite formation and energetics. Compared to the model SAM MPA, EPA and MEPA can render NiO<sub>x</sub> with better coverage and conductivity. Moreover, the oligoether chain-containing SAMs are able to assist the formation of perovskite film with ordered growth, high crystallization, and importantly well-matched energy level alignment at the top surface, especially for MEPA. Consequently, a remarkably high efficiency of 25.50% is realized for NiO<sub>x</sub>/MEPA-based PSCs along with good device stability, which can maintain 90% of the initial efficiency under ISOS-L-1 conditions over 1260 h.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202507513"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144546803","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}
{"title":"Predicting A-Element Substitution and MXene Formation in Reactions Between MAX Phases and Molten Salts.","authors":"Jonas Björk, Johanna Rosen","doi":"10.1002/anie.202506622","DOIUrl":"10.1002/anie.202506622","url":null,"abstract":"<p><p>Selective etching has emerged as a key method for synthesizing 2D materials, with the conversion of MAX phases to MXenes being by far the most widely studied and reported example. While traditional methods rely on etching in primarily acidic aqueous media, molten salts offer an intriguing alternative. However, the current understanding of MAX phase reactivity in molten salts is limited, restricting our ability to predict reaction outcomes. In this study, we present a computational framework that uses process-specific phase diagrams to model A-element substitution and MXene formation, as well as competing side reactions. Applying this approach to Ti3AlC2, V2AlC and Ti2AlN in ZnCl2 molten salt we reveal distinct reaction behaviors despite identical redox potentials of key processes. Our findings underscore the limitations of predicting reactions based solely on redox potentials and show that our model can capture key trends in MXene synthesis. Beyond MXenes, our methodology lays the groundwork for identifying new 2D materials accessible through molten salt etching.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202506622"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144546808","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}