Malay Krishna Mahato, Kavya S Mony, Harsh Baliyan, Subha Biswas, Anoop Thomas
{"title":"Exploring Excited State Proton Transfer in Thin Films Under Vibrational Strong Coupling.","authors":"Malay Krishna Mahato, Kavya S Mony, Harsh Baliyan, Subha Biswas, Anoop Thomas","doi":"10.1002/anie.202424247","DOIUrl":"10.1002/anie.202424247","url":null,"abstract":"<p><p>Molecular structure, solvent/matrix, the surrounding environment, and molecular vibrations can influence the excited-state proton transfer (ESPT) process. Theoretical studies predict that light-matter strong coupling can modify the energy barrier for proton transfer reactions. Here, we experimentally explore the role of vibrational strong coupling (VSC) on the ESPT using the weak photoacid, 7-hydroxy-1-naphthalenesulfonate (N8S) as the probe. The ESPT in N8S can occur through a solvent/matrix bridge connecting the proton-donating and accepting units. To check the role of VSC, we embedded N8S in a poly(vinyl alcohol) (PVA) matrix and strongly coupled the ─OH stretching vibrational modes of PVA. The steady-state and time-resolved emission analysis reveal that the quantum yield of RO<sup>-</sup> emission and the ESPT rate constant enhance by a factor of two under VSC, compared to the noncavity, half-cavity, and off-resonance films. Our findings indicate that VSC can be a tool to control the proton transfer processes, opening avenues for developing physically tunable photoacid-based sensors.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202424247"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144546806","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":"Regulate the Singlet-Triplet Energy Gap by Spatially Separating HOMO and LUMO for High Performance Organic Photovoltaic Acceptors.","authors":"Guangkun Song, Tengfei He, Ruohan Wang, Yanni Ouyang, Nakul Jain, Saisai Liu, Bin Kan, Yujie Shang, Jiaqi Li, Xingkai Wang, Zhaoyang Yao, Xiangjian Wan, Chenxi Li, Wei Ma, Yan Zhao, Guankui Long, Chunfeng Zhang, Feng Gao, Yongsheng Chen","doi":"10.1002/anie.202506357","DOIUrl":"10.1002/anie.202506357","url":null,"abstract":"<p><p>Reducing the single-triplet energy gap (∆E<sub>ST</sub>) for organic photovoltaic (OPV) molecules has been proposed to be able to reduce the nonradiative recombination by tuning the low-lying triplet state (T<sub>1</sub>) and/or the excited state (S<sub>1</sub>), thus reducing the energy loss (E<sub>loss</sub>) and increasing the open-circuit voltage in their devices. However, how to design the non-fullerene acceptor (NFA) with small ∆E<sub>ST</sub> and high performance is challenging. Aiming to address this issue, YDF, YTF, and YTF-H were synthesized. Among them, a device based on YDF with partially spatially separated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) exhibits a much higher power conversion efficiency (PCE) of 20.04%, which is one of the most efficient efficiencies for binary systems. For YTF and YTF-H, their completely spatially separated HOMO and LUMO indeed lead to a much reduced ∆E<sub>ST</sub> caused by the low-lying S<sub>1</sub> state, together with excellent charge mobility and light absorption, required for higher performance OPV. But their low S<sub>1</sub> state causes several non-radiative recombinations due to strong S<sub>1</sub>-S<sub>0</sub> coupling (PCE < 1.5%). These results indicate that future designs to have high performance molecules with small ∆E<sub>ST</sub> should avoid the sharp decrease in S<sub>1</sub>, and the ideal scenario would be to elevate the T<sub>1</sub> state, thereby mitigating the energy gap law.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202506357"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144546809","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":"Multipoint Coordinative Capture of Olefinic Substrates Utilizing Metal-Carbon Bonds by Macrocyclic Complex.","authors":"Kohtaro Sugawara, Kenichiro Omoto, Takashi Nakamura","doi":"10.1002/anie.202505734","DOIUrl":"10.1002/anie.202505734","url":null,"abstract":"<p><p>Terpenoids and unsaturated fatty acids containing C=C double bonds are biologically and synthetically important compounds. The transformation of these substrates catalyzed by proteins relies on precise molecular capture. However, achieving precise molecular recognition of C=C double bonds using synthetically designed hosts remains a significant challenge. We now report a macrocyclic palladium tetranuclear complex that functions as a synthetic receptor featuring coordination sites within its inner cavity. This receptor selectively binds specific double bonds of unsaturated hydrocarbon substrates. Squalene (C30H50), a linear triterpene with chemically similar six isoprenoid units, was captured by the macrocyclic complex through the coordination of four out of the six C=C double bonds, leading to a unique host-guest complex with a folded-squalene structure. Furthermore, the macrocyclic complex exhibited stronger binding affinity for methyl linolenate compared to methyl oleate or methyl linoleate through multipoint coordinative capture. This unprecedented approach to multipoint coordination of specific unsaturated bonds contrasts sharply with biological and traditional artificial receptors, which typically rely on intermolecular interactions such as hydrogen bonding or hydrophobic effects. By achieving precise capture and folding of flexible olefinic substrates, this study establishes a new paradigm for the design of artificial host molecules and a novel platform for enzyme-like reaction vessels.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202505734"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144532704","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}
Johannes Broichhagen, Michael Trumpp, Blaise Gatin-Fraudet, Kjell Bruckmann, Wiktor Burdzinski, Kilian Roßmann, Joshua Levitz, Petra Knaus, Jerome Jatzlau
{"title":"Developing HaloTag and SNAP-Tag Chemical Inducers of Dimerization to Probe Receptor Oligomerization and Downstream Signaling.","authors":"Johannes Broichhagen, Michael Trumpp, Blaise Gatin-Fraudet, Kjell Bruckmann, Wiktor Burdzinski, Kilian Roßmann, Joshua Levitz, Petra Knaus, Jerome Jatzlau","doi":"10.1002/anie.202506830","DOIUrl":"10.1002/anie.202506830","url":null,"abstract":"<p><p>Controlling protein-protein interactions is critical for dissecting signaling pathways, especially those initiated by ligand-receptor interactions which alter receptor oligomerization and drive downstream signaling cascades. Traditional methods for driving protein-protein complexes are using antibodies that face limitations in terms of stoichiometry, geometric rigidity, and antibody specificity. Chemical Inducers of Dimerization (CIDs) for fusion proteins such as HaloTag (Halo) and SNAP-Tags (SNAP) offer precise and covalent control of protein proximities, overcoming limitations of antibody-dependent methods. In this study, we expand the toolkit of Halo and SNAP CIDs with (1) benzylguanine (BG) and HaloTag ligand (HTL) crosslinkers featuring varying polyethylene glycol linker lengths and update this kit with (2) a FRET-based dimerizing sensor to induce and verify protein proximity. Here we establish our CIDs on extracellularly Halo- and SNAP-tagged TGFβ, BMP, neurotrophic factor and metabotropic glutamate receptors, thereby elucidating the signaling potential of ligand-independent dimerization in a heteromeric fashion.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202506830"},"PeriodicalIF":0.0,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144532697","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}
Hao-Cheng Yang, Yi-Zhou Chen, Kai Li, Xin-Yu Guo, Qi-Rui Jiang, Seth B Darling, Zhi-Kang Xu
{"title":"Janus Superiority of Membranes in Chemical Engineering and Beyond.","authors":"Hao-Cheng Yang, Yi-Zhou Chen, Kai Li, Xin-Yu Guo, Qi-Rui Jiang, Seth B Darling, Zhi-Kang Xu","doi":"10.1002/anie.202509503","DOIUrl":"10.1002/anie.202509503","url":null,"abstract":"<p><p>Janus configurations, characterized by their inherent asymmetry, enable directional mass transfer in membrane materials that drive novel and energy-efficient chemical processes. This Janus superiority spans applications from nanoscale molecular and ionic transport to macro-scale separation systems with asymmetric spatial architectures. This review provides an analysis of the material foundations including design principles, structure regulation, and scalability challenges underlying Janus membranes. We explore the physics that governs their unique behavior and examine their diverse applications across chemical engineering, including phase transfer, and molecular or ionic transport. Through a multiscale perspective, we provide a comprehensive understanding of the impact of Janus superiority in advancing chemical engineering technologies. Finally, we discuss the hurdles in translating theoretical advances into practical applications and propose promising avenues for future research to harness the full potential of Janus membranes and systems in addressing global challenges related to energy, sustainability, and beyond.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202509503"},"PeriodicalIF":0.0,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144532700","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":"Asymmetric, Corner-Sharing CuO<sub>5</sub> and CuO<sub>6</sub> Motifs in Cu-Based Metallic Perovskite Oxides Boosting Asymmetric C─C Coupling for CO<sub>2</sub> Electroreduction to C<sub>2</sub>.","authors":"Yu Zhang, Hongyan Zhao, Junjie Zhu, Zitao Chen, Xiangjian Liu, Zhenbao Zhang, Lei Shi, Xuezeng Tian, Heqing Jiang, Yongfa Zhu, Jiawei Zhu","doi":"10.1002/anie.202511546","DOIUrl":"10.1002/anie.202511546","url":null,"abstract":"<p><p>Cu-based perovskite oxides feature significant potential for CO<sub>2</sub> electroreduction (CO<sub>2</sub>RR) but encounter insufficient C<sub>2+</sub> selectivity primarily due to the inherent symmetric charge distribution at Cu sites hindering asymmetric C─C coupling. Here we report a unique type of Cu-based metallic perovskite oxides with asymmetric, corner-sharing CuO<sub>5</sub> and CuO<sub>6</sub> motifs to boost asymmetric C─C coupling for efficient CO<sub>2</sub>-to-C<sub>2+</sub> conversion. For the proof-of-concept catalyst of La<sub>0.8</sub>Ba<sub>0.2</sub>CuO<sub>3-δ</sub>, their ordered, corner-sharing CuO<sub>5</sub> pyramids and CuO<sub>6</sub> octahedra feature localized charge density redistribution, creating abundant asymmetric Cu─Cu dual sites with distinct electronic structures and also strengthening Cu─O covalency. In CO<sub>2</sub>RR (in both alkaline and acidic media), La<sub>0.8</sub>Ba<sub>0.2</sub>CuO<sub>3-δ</sub> greatly promotes C<sub>2+</sub> formation while producing negligible CH<sub>4</sub>, showing a Faradaic efficiency ratio (C<sub>2+</sub> to CH<sub>4</sub>) of up to 180. Moreover, La<sub>0.8</sub>Ba<sub>0.2</sub>CuO<sub>3-δ</sub>, achieving a remarkable C<sub>2+</sub> Faradaic efficiency of 85.0% at 400 mA cm<sup>-2</sup>, together with well-boosted stability, outperforms previously reported Cu-based-perovskite catalysts. Our experiments and theoretical calculations attribute the superb performance mainly to the following factors: the asymmetric CuO<sub>5</sub>─CuO<sub>6</sub> sites promoting differentiated *CO adsorption/hydrogenation to favor asymmetric *CO─*CHO coupling; the strengthened Cu─O covalency stabilizing the Cu sites. Extending this strategy to two additional pairs of Cu-based perovskite oxides generates similarly successful results.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202511546"},"PeriodicalIF":0.0,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144532694","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}
Ying Wu, Qian Wang, Kang Zhu, Liting Zheng, Qingqing Li, Wei Huang, Yang Du, Lanlan Chen, Jibin Song, Huanghao Yang
{"title":"Quantitative Tracking of Apoptotic Caspase-3 In Vivo for Early Evaluation of Radiation Therapy Efficacy.","authors":"Ying Wu, Qian Wang, Kang Zhu, Liting Zheng, Qingqing Li, Wei Huang, Yang Du, Lanlan Chen, Jibin Song, Huanghao Yang","doi":"10.1002/anie.202502811","DOIUrl":"10.1002/anie.202502811","url":null,"abstract":"<p><p>Traditional responsive fluorescent probes are predominantly restricted to qualitative biomarker detection, incapable of delivering real-time quantitative analysis or spatial mapping of protease activity in vivo, which is essential for elucidating disease progression. To overcome this, a ratiometric second near-infrared region (NIR-II) fluorescent (FL) probe (DCNP@IR-806) was developed by conjugating caspase-3-specific peptide substrates and sensitizer molecules (IR-806) to lanthanide-doped down-conversion nanoparticles (DCNP). DCNP@IR-806 achieves single-channel emission at 1550 nm under dual excitation, facilitating self-calibrated quantification and real-time monitoring of activated caspase-3 in vivo. Radiotherapy induces tumor cell apoptosis, thereby activating caspase-3, which subsequently triggers a ratiometric NIR-II FL signal change of DCNP@IR-806. The ratiometric signal demonstrates a linear correlation with caspase-3 concentration, achieving a detection limit of 9.96 U mL<sup>-1</sup>. Then, an early efficacy assessment system capable of predicting radiotherapy outcomes within 12 h post-treatment was constructed, markedly expediting evaluation compared to traditional methods that require weeks. This rapid, precise, and user-friendly assessment facilitates timely optimization of therapeutic regimens to enhance efficacy while minimizing side effects. This platform represents a significant advancement in precision oncology by transitioning from qualitative imaging to in situ quantitative biomarker tracking.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202502811"},"PeriodicalIF":0.0,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144532708","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}
Marcos Martínez-Fernández, Yannic Hartmann, Bernd M Schmidt
{"title":"Porous Organic Cages as Building Blocks for Framework Materials.","authors":"Marcos Martínez-Fernández, Yannic Hartmann, Bernd M Schmidt","doi":"10.1002/anie.202509618","DOIUrl":"10.1002/anie.202509618","url":null,"abstract":"<p><p>Confined nanospaces play a fundamental role in nature, inspiring synthetic analogues that emulate biological precision and efficiency. Among these, porous crystalline materials such as covalent organic frameworks (COFs), metal-organic frameworks (MOFs), and molecular cage compounds have emerged as powerful platforms for catalysis, separation, and energy storage. Recent developments highlight the potential of porous organic cages (POCs) as modular building blocks for the construction of advanced materials. In this Minireview, their integration into extended frameworks, such as Cage-COFs and Cage-MOFs, is described, as they allow precise control over porosity and enhance chemical robustness. These hybrids merge the structural regularity of COFs with the discrete functionality of cages, enabling the design of lightweight, hierarchically organised materials. In addition, polymer-containing Cage-POPs and supramolecular frameworks are discussed. Collectively, these developments position POCs as versatile synthons for next-generation porous materials, unlocking pathways toward functional, adaptive, and recyclable architectures.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202509618"},"PeriodicalIF":0.0,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144532707","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":"Vacancy-Defect Single-Atom Catalysts for Tandem CO<sub>2</sub> Electroreduction and Carbonylation Reactions from Flue Gas.","authors":"Qiu-Ping Zhao, Wen-Xiong Shi, Bo Wang, Zuo-Shu Sun, Shuang Yao, Tong-Bu Lu, Zhi-Ming Zhang","doi":"10.1002/anie.202510693","DOIUrl":"10.1002/anie.202510693","url":null,"abstract":"<p><p>Tandem CO<sub>2</sub> reduction with carbonylation reactions represents a promising approach to convert greenhouse gases into valuable chemicals. Herein, we propose a universal \"N/O mixed pre-coordination pyrolysis\" strategy to construct vacancy-defect single atom catalysts (Ni<sub>1</sub>-, Mn<sub>1</sub>-, Fe<sub>1</sub>-, Co<sub>1</sub>-, and Cu<sub>1</sub>-NC) with M-N<sub>3</sub> coordination microenvironment. This vacancy-defect endows Ni<sub>1</sub>-NC with excellent performance for CO<sub>2</sub> electroreduction, achieving a CO faradaic efficiency exceeding 90% across a wide range of current densities up to 300 mA cm<sup>-2</sup>. The generated CO was directly fed to carbonylation reactions, producing organic chemicals with yields of up to 91.7% and leading to produce 1.13 g of benzophenone in a single run. For the first time, the membrane separation CO<sub>2</sub> system was integrated with tandem catalytic system, enabling direct utilization of flue gas for benzophenone synthesis with a 76.6% yield. This work offers a sustainable, eco-friendly method for CO<sub>2</sub> separation and utilization by feeding industrial waste gas to carbonylation reactions.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202510693"},"PeriodicalIF":0.0,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144532714","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":"Correction to \"Supramolecularly Engineered Reporters with Superoxide Anion Triggered Chemiluminescence for Early Diagnosis and Efficient Amelioration of Acute Kidney Injury\".","authors":"","doi":"10.1002/anie.202513504","DOIUrl":"10.1002/anie.202513504","url":null,"abstract":"","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202513504"},"PeriodicalIF":0.0,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144532696","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}