Chi Li, Yong Chen, Yuheng Li, Zhewei Zhang, Jing Yang, Yao Wang, Lijie Gong, Zhen Yuan, Lusheng Liang, Siyi Liu, Yongxin Zhu, Chongyan Lian, Mustafa Haider, Tie Guo, Xiaohua Xu, Dongdong Li, Enbing Bi, Peng Gao
A novel bidentate-anchored superwetting aromatic self-assembled monolayer is employed as a hole-selective layer (HSL) in inverted wide-bandgap PSCs. The reversely substituted carbazole approach is crucial in promoting the formation of a robust HSL, improving hole extraction efficiency. The optimized wide-bandgap PSCs attain a power conversion efficiency (PCE) of 22.83%, and the fabricated P/S-TSCs achieve an impressive efficiency of 32.19% (certified 31.54%) while maintaining excellent photostability.
{"title":"Achieving 32% Efficiency in Perovskite/Silicon Tandem Solar Cells with Bidentate-Anchored Superwetting Self-Assembled Molecular Layers","authors":"Chi Li, Yong Chen, Yuheng Li, Zhewei Zhang, Jing Yang, Yao Wang, Lijie Gong, Zhen Yuan, Lusheng Liang, Siyi Liu, Yongxin Zhu, Chongyan Lian, Mustafa Haider, Tie Guo, Xiaohua Xu, Dongdong Li, Enbing Bi, Peng Gao","doi":"10.1002/anie.202502730","DOIUrl":"https://doi.org/10.1002/anie.202502730","url":null,"abstract":"A novel bidentate-anchored superwetting aromatic self-assembled monolayer is employed as a hole-selective layer (HSL) in inverted wide-bandgap PSCs. The reversely substituted carbazole approach is crucial in promoting the formation of a robust HSL, improving hole extraction efficiency. The optimized wide-bandgap PSCs attain a power conversion efficiency (PCE) of 22.83%, and the fabricated P/S-TSCs achieve an impressive efficiency of 32.19% (certified 31.54%) while maintaining excellent photostability.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"31 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758556","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}
Topological chemical reactions in confined environments offer unique opportunities for constructing dynamically tunable crystalline materials and architecturally defined polymers. However, their potential within functional supramolecular systems and chiral materials remains largely untapped. In this work, we introduce, for the first time, a borate esterification reaction to achieve dynamic modulation of supramolecular chirality and chiroptical properties under aggregation conditions. Pyrene‐phenylalanine derivatives, following functionalization with phenylboronic acid groups, co‐assemble with catechol‐functionalized pyrene derivatives. This co‐assembly undergoes spontaneous and highly efficient borate esterification under ambient conditions, inducing nanoscale morphological evolution and an inversion of supramolecular chirality. Both experimental results and DFT‐based computations reveal that the supramolecular chirality inversion is primarily driven by a transition from π–π stacking to CH–π interactions between pyrene moieties. This co‐assembly‐borate esterification process represents a powerful integration of non‐covalent assembly and covalent chemistry, providing a versatile platform for the design of soft materials and chiral functional systems. Moreover, the introduction of alizarin derivatives containing catechol motifs enables the transfer of circularly polarized luminescence (CPL), resulting in tunable emission shifts from blue and cyan to red. This work broadens the functional scope of chiral luminescent materials and opens new avenues for their application.
{"title":"Dynamic Borate Esterification for Evolved Supramolecular Chirality and Chiral Optics","authors":"Zhuoer Wang, Changyu Chu, Aiyou Hao, Pengyao Xing","doi":"10.1002/anie.202504617","DOIUrl":"https://doi.org/10.1002/anie.202504617","url":null,"abstract":"Topological chemical reactions in confined environments offer unique opportunities for constructing dynamically tunable crystalline materials and architecturally defined polymers. However, their potential within functional supramolecular systems and chiral materials remains largely untapped. In this work, we introduce, for the first time, a borate esterification reaction to achieve dynamic modulation of supramolecular chirality and chiroptical properties under aggregation conditions. Pyrene‐phenylalanine derivatives, following functionalization with phenylboronic acid groups, co‐assemble with catechol‐functionalized pyrene derivatives. This co‐assembly undergoes spontaneous and highly efficient borate esterification under ambient conditions, inducing nanoscale morphological evolution and an inversion of supramolecular chirality. Both experimental results and DFT‐based computations reveal that the supramolecular chirality inversion is primarily driven by a transition from π–π stacking to CH–π interactions between pyrene moieties. This co‐assembly‐borate esterification process represents a powerful integration of non‐covalent assembly and covalent chemistry, providing a versatile platform for the design of soft materials and chiral functional systems. Moreover, the introduction of alizarin derivatives containing catechol motifs enables the transfer of circularly polarized luminescence (CPL), resulting in tunable emission shifts from blue and cyan to red. This work broadens the functional scope of chiral luminescent materials and opens new avenues for their application.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"5 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143757829","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}
Currently, electrolyte design for sodium‐based batteries is largely inherited from their lithium‐based counterparts, which often present critical challenges that hinder forging new perspectives and thus further improvements. This work delves into the key properties of representative sodium and lithium‐based electrolytes, encompassing prevailing salt anions. It aims to evaluate the impact of cation chemistry, including their nature and the degree of interactions with counter anions, thereby bridging the gap in effectively transferring the know‐how accumulated in lithium batteries to sodium‐based batteries. The results demonstrate that the unique impact of salt anions on the properties of metal‐ion conducting electrolytes is tightly correlated with the nature of metal cations. By synchronizing the anionic structures with the critical feature of sodium cations, the solvating dynamics and transport properties, chemical stability, aluminum corrosion behavior, and other key properties of the electrolytes could be finely tuned to fit the specific requirements of advanced sodium‐based batteries. This work gives an in‐depth insight into the chemical and physical features of sodium‐based electrolytes, with a potential avenue to accelerate the deployment of high‐performance sodium batteries and simultaneously inspire and guide the design of other electrolytes for emerging mono‐ and multi‐valent cations‐based rechargeable batteries.
{"title":"Electrolyte Chemistry Development for Sodium‐Based Batteries: A Blueprint from Lithium or a Step Towards Originality?","authors":"Ziyu Song, Zhirong Xing, Jiaxun Yang, Jiayi Chen, Weican Hu, Pu Li, Wenfang Feng, Gebrekidan Gebresilassie Eshetu, Egbert Figgemeier, Stefano Passerini, Michel Armand, Zhibin Zhou, Heng Zhang","doi":"10.1002/anie.202424543","DOIUrl":"https://doi.org/10.1002/anie.202424543","url":null,"abstract":"Currently, electrolyte design for sodium‐based batteries is largely inherited from their lithium‐based counterparts, which often present critical challenges that hinder forging new perspectives and thus further improvements. This work delves into the key properties of representative sodium and lithium‐based electrolytes, encompassing prevailing salt anions. It aims to evaluate the impact of cation chemistry, including their nature and the degree of interactions with counter anions, thereby bridging the gap in effectively transferring the know‐how accumulated in lithium batteries to sodium‐based batteries. The results demonstrate that the unique impact of salt anions on the properties of metal‐ion conducting electrolytes is tightly correlated with the nature of metal cations. By synchronizing the anionic structures with the critical feature of sodium cations, the solvating dynamics and transport properties, chemical stability, aluminum corrosion behavior, and other key properties of the electrolytes could be finely tuned to fit the specific requirements of advanced sodium‐based batteries. This work gives an in‐depth insight into the chemical and physical features of sodium‐based electrolytes, with a potential avenue to accelerate the deployment of high‐performance sodium batteries and simultaneously inspire and guide the design of other electrolytes for emerging mono‐ and multi‐valent cations‐based rechargeable batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"235 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143757811","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}
Yi An, Ru Zhou, Ningjin Zhang, Aocheng Chen, Junfei Xing, Shu Zhang, Quan Li
Traditional fluorophores often face aggregation‐caused quenching (ACQ), limiting their efficacy in high‐concentration applications. We demonstrate that a combined effect of anion and mechanical bond can significantly increase fluorescence intensity, up to 14‐fold and a quantum yield of 97.0%. A large number of crystal analysis reveal that this enhancement is primarily driven by non‐classical hydrogen bonds, which stabilizes the structure and restricts molecular motion. The versatility of this synergistic effect opens new avenues for applications, including circularly polarized luminescence (CPL) facilitated by chiral anions, and the development of a novel fluorescence switchable rotaxane shuttle that operates without charge transfer.
{"title":"Non‐Classical Hydrogen Bond Based Efficient Solid‐State Organic Emitters Enabled by a Synergistic Anion and Mechanical Bond Effect","authors":"Yi An, Ru Zhou, Ningjin Zhang, Aocheng Chen, Junfei Xing, Shu Zhang, Quan Li","doi":"10.1002/anie.202505774","DOIUrl":"https://doi.org/10.1002/anie.202505774","url":null,"abstract":"Traditional fluorophores often face aggregation‐caused quenching (ACQ), limiting their efficacy in high‐concentration applications. We demonstrate that a combined effect of anion and mechanical bond can significantly increase fluorescence intensity, up to 14‐fold and a quantum yield of 97.0%. A large number of crystal analysis reveal that this enhancement is primarily driven by non‐classical hydrogen bonds, which stabilizes the structure and restricts molecular motion. The versatility of this synergistic effect opens new avenues for applications, including circularly polarized luminescence (CPL) facilitated by chiral anions, and the development of a novel fluorescence switchable rotaxane shuttle that operates without charge transfer.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"32 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143757819","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}
Qiwen Sun, Jin Wang, Linke Fu, Yao Ye, Xiaoxia Chang, Bingjun Xu
Gas diffusion electrodes (GDEs) are widely used in electrochemical CO and CO2 reduction reactions (CO(2)RR) in flow cells due to their ability to alleviate mass transport limitations of gaseous reactants. The flow cell configuration makes uniform distribution of reactants, intermediates, products, and speciation within the catalyst layer (CL) unlikely. In this work, a first‐of‐its‐kind in situ characterization technique capable of probing the cross section of the CL with confocal Raman spectroscopy was developed to investigate the speciation distribution across the Cu CL in CO(2)RR with a spatial resolution of ~4 μm. In both CORR in alkaline medium and CO2RR in acidic electrolyte, the active region of CL was identified as that with the presence of the Raman band for adsorbed CO (COad). The strong correlation of COad and CO32‐ bands provides the first spectroscopic evidence that CO2RR only occurs in an alkaline microenvironment.
{"title":"Probing Inside the Catalyst Layer on Gas Diffusion Electrodes in Electrochemical Reduction of CO and CO2","authors":"Qiwen Sun, Jin Wang, Linke Fu, Yao Ye, Xiaoxia Chang, Bingjun Xu","doi":"10.1002/anie.202504715","DOIUrl":"https://doi.org/10.1002/anie.202504715","url":null,"abstract":"Gas diffusion electrodes (GDEs) are widely used in electrochemical CO and CO2 reduction reactions (CO(2)RR) in flow cells due to their ability to alleviate mass transport limitations of gaseous reactants. The flow cell configuration makes uniform distribution of reactants, intermediates, products, and speciation within the catalyst layer (CL) unlikely. In this work, a first‐of‐its‐kind in situ characterization technique capable of probing the cross section of the CL with confocal Raman spectroscopy was developed to investigate the speciation distribution across the Cu CL in CO(2)RR with a spatial resolution of ~4 μm. In both CORR in alkaline medium and CO2RR in acidic electrolyte, the active region of CL was identified as that with the presence of the Raman band for adsorbed CO (COad). The strong correlation of COad and CO32‐ bands provides the first spectroscopic evidence that CO2RR only occurs in an alkaline microenvironment.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"12 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143757810","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}
Zongnan Li, Yongbiao Mu, Kunxi Lü, Guojian Kang, Ting Yang, Shuping Huang, Mingdeng Wei, Lin Zeng, Yafeng Li
Within the family of halide solid electrolytes (SEs), Li2ZrCl6 demonstrates high oxidative stability, cost‐effectiveness, and mechanical deformability, positioning it as a promising candidate for SEs. However, the application of Li2ZrCl6 as a SEs was hindered by its low ionic conductivity at room temperature. Current strategies to enhance the ionic conductivity of Li2ZrCl6 primarily are focused on single cation or anion sublattice‐engineering, each with distinct advantages and limitations. Here, we propose a novel cation and anion‐sublattice‐engineering strategy, termed CASE, to increase the amorphous content and thus enhance ionic conductivity. The incorporation of Cu2+ and O2‐ induces distinctive structural modifications within Li2ZrCl6. This structure corroborated through analytic data of X‐ray absorption spectroscopy, the neutron diffraction, and ab initio molecular dynamics. Consequently, the amorphous Li2.1Zr0.95Cu0.05Cl4.4O0.8 achieves an enhanced ionic conductivity of 2.05 mS cm‐1 at 25 °C. Furthermore, all‐solid‐state lithium batteries utilizing the amorphous Li2.1Zr0.95Cu0.05Cl4.4O0.8 as an electrolyte and LiNi0.83Co0.11Mn0.06O2 as a cathode exhibit a superior long‐term cycling stability retaining 90.3% of capacity after 1000 cycles at 2 C under room temperature, which are much higher than those of Zr‐based halide electrolytes in publications. Such a result might stimulate the development of more amorphous structures with high ionic conductivity in the CASE strategy.
{"title":"Cation‐Anion‐Engineering Modified Oxychloride Zr‐Based Lithium Superionic Conductors for All‐Solid‐State Lithium Batteries","authors":"Zongnan Li, Yongbiao Mu, Kunxi Lü, Guojian Kang, Ting Yang, Shuping Huang, Mingdeng Wei, Lin Zeng, Yafeng Li","doi":"10.1002/anie.202501749","DOIUrl":"https://doi.org/10.1002/anie.202501749","url":null,"abstract":"Within the family of halide solid electrolytes (SEs), Li2ZrCl6 demonstrates high oxidative stability, cost‐effectiveness, and mechanical deformability, positioning it as a promising candidate for SEs. However, the application of Li2ZrCl6 as a SEs was hindered by its low ionic conductivity at room temperature. Current strategies to enhance the ionic conductivity of Li2ZrCl6 primarily are focused on single cation or anion sublattice‐engineering, each with distinct advantages and limitations. Here, we propose a novel cation and anion‐sublattice‐engineering strategy, termed CASE, to increase the amorphous content and thus enhance ionic conductivity. The incorporation of Cu2+ and O2‐ induces distinctive structural modifications within Li2ZrCl6. This structure corroborated through analytic data of X‐ray absorption spectroscopy, the neutron diffraction, and ab initio molecular dynamics. Consequently, the amorphous Li2.1Zr0.95Cu0.05Cl4.4O0.8 achieves an enhanced ionic conductivity of 2.05 mS cm‐1 at 25 °C. Furthermore, all‐solid‐state lithium batteries utilizing the amorphous Li2.1Zr0.95Cu0.05Cl4.4O0.8 as an electrolyte and LiNi0.83Co0.11Mn0.06O2 as a cathode exhibit a superior long‐term cycling stability retaining 90.3% of capacity after 1000 cycles at 2 C under room temperature, which are much higher than those of Zr‐based halide electrolytes in publications. Such a result might stimulate the development of more amorphous structures with high ionic conductivity in the CASE strategy.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"26 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745095","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}
Haijing Liu, Ping Li, Kaicai Fan, Fenghong Lu, Qi Sun, Qi Zhang, Bin Li, Yajie Shu, Lingbo Zong, Lei Wang
Single atom catalysts embracing metal‐nitrogen (MNx) moieties show promising performance for oxygen reduction reaction (ORR). The modification on spatially confined microenvironments, which won copious attention with respect to achieving efficient catalysts, are auspicious but yet to be inspected for MNx moieties from modulating the energetics and kinetics of ORR. Here, Fe single atoms (SAs) are immobilized in microporous hard carbon (Fe‐SAs/MPC), in which the microporous structure with crumpled graphene sheets serves confined microenvironment for catalysis. Fe‐SAs/MPC holds a remarkable half‐wave potential of 0.927 V and excellent stability for ORR. Theoretical studies unveil that hydrogen bonding between the intermediate of O* and micropore interior surfaces substantially promotes its protonation and accelerates overall ORR kinetics. Both the aqueous and quasi‐solid‐state zinc‐air batteries driven by Fe‐SAs/MPC air cathode show excellent stability with small charging/discharging voltage gaps. Importantly, when used as the air cathode for industrial chlor‐alkali process, the applied voltage of Fe‐SAs/MPC‐based flow cell to reach 300 mA cm−2 is 1.57 V, which is 210 mV smaller than Pt/C‐based one. These findings provide in‐depth insights into the confined microenvironment of MNx moieties for boosted electrochemical performance, and pave the pathways for future catalyst development satisfying the requirement of industrial applications.
{"title":"Microporous Hard Carbon Support Provokes Exceptional Performance of Single Atom Electrocatalysts for Advanced Air Cathodes","authors":"Haijing Liu, Ping Li, Kaicai Fan, Fenghong Lu, Qi Sun, Qi Zhang, Bin Li, Yajie Shu, Lingbo Zong, Lei Wang","doi":"10.1002/anie.202501307","DOIUrl":"https://doi.org/10.1002/anie.202501307","url":null,"abstract":"Single atom catalysts embracing metal‐nitrogen (MNx) moieties show promising performance for oxygen reduction reaction (ORR). The modification on spatially confined microenvironments, which won copious attention with respect to achieving efficient catalysts, are auspicious but yet to be inspected for MNx moieties from modulating the energetics and kinetics of ORR. Here, Fe single atoms (SAs) are immobilized in microporous hard carbon (Fe‐SAs/MPC), in which the microporous structure with crumpled graphene sheets serves confined microenvironment for catalysis. Fe‐SAs/MPC holds a remarkable half‐wave potential of 0.927 V and excellent stability for ORR. Theoretical studies unveil that hydrogen bonding between the intermediate of O* and micropore interior surfaces substantially promotes its protonation and accelerates overall ORR kinetics. Both the aqueous and quasi‐solid‐state zinc‐air batteries driven by Fe‐SAs/MPC air cathode show excellent stability with small charging/discharging voltage gaps. Importantly, when used as the air cathode for industrial chlor‐alkali process, the applied voltage of Fe‐SAs/MPC‐based flow cell to reach 300 mA cm−2 is 1.57 V, which is 210 mV smaller than Pt/C‐based one. These findings provide in‐depth insights into the confined microenvironment of MNx moieties for boosted electrochemical performance, and pave the pathways for future catalyst development satisfying the requirement of industrial applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"183 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745098","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}
Ning Xu, Qinglong Qiao, Chao Wang, Wei Zhou, Pengjun Bao, Jin Li, Shaowei Wu, Xiaogang Liu, Zhaochao Xu
Fluorophore‐ligand conjugates play a pivotal role in cellular imaging, providing high target specificity. However, simultaneously achieving conjugates with high brightness and ligand‐targeting diversity presents significant challenges. Traditional strategies often require complex, multi‐step modifications for fluorophore enhancement and ligand conjugation. Here, we present an azetidinecarboxamide strategy that addresses these challenges by integrating brightness enhancement and ligand conjugation capabilities within a single molecular framework. The azetidinecarboxamide core suppresses twisted intramolecular charge transfer (TICT), thereby enhancing fluorescence quantum yield. Its carbonyl group provides a versatile site for conjugating a wide range of targeting ligands, enabling the rapid development of diverse and tunable fluorophore‐ligand conjugates. This streamlined approach reduces synthetic complexity, accelerates probe development, and is compatible with a wide variety of fluorophores, such as coumarin, naphthalimide, NBD, rhodol, rhodamine, and silicon‐rhodamine, facilitating the creation of high‐performance, multifunctional probes for advanced cellular imaging.
{"title":"Bright and Versatile Azetidinecarboxamide‐Based Fluorophore‐Ligand Conjugates for High‐Resolution Cell Imaging","authors":"Ning Xu, Qinglong Qiao, Chao Wang, Wei Zhou, Pengjun Bao, Jin Li, Shaowei Wu, Xiaogang Liu, Zhaochao Xu","doi":"10.1002/anie.202505579","DOIUrl":"https://doi.org/10.1002/anie.202505579","url":null,"abstract":"Fluorophore‐ligand conjugates play a pivotal role in cellular imaging, providing high target specificity. However, simultaneously achieving conjugates with high brightness and ligand‐targeting diversity presents significant challenges. Traditional strategies often require complex, multi‐step modifications for fluorophore enhancement and ligand conjugation. Here, we present an azetidinecarboxamide strategy that addresses these challenges by integrating brightness enhancement and ligand conjugation capabilities within a single molecular framework. The azetidinecarboxamide core suppresses twisted intramolecular charge transfer (TICT), thereby enhancing fluorescence quantum yield. Its carbonyl group provides a versatile site for conjugating a wide range of targeting ligands, enabling the rapid development of diverse and tunable fluorophore‐ligand conjugates. This streamlined approach reduces synthetic complexity, accelerates probe development, and is compatible with a wide variety of fluorophores, such as coumarin, naphthalimide, NBD, rhodol, rhodamine, and silicon‐rhodamine, facilitating the creation of high‐performance, multifunctional probes for advanced cellular imaging.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"88 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745116","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}
Min Zeng, William Parsons, Yixuan Chen, David K. Chalmers, Sebastien Perrier
Polymer‐conjugated peptides are attractive building blocks for the construction of new nanomaterials. However, the ability to control the self‐assembly of these materials remains a major limitation to their wider utilization. Herein, we report a facile strategy to fine‐tune the assembly of water‐soluble hydrophilic polymer‐conjugated cyclic peptides by incorporating a defined, short hydrocarbon linker between the polymer and peptide. This addition creates a well‐defined hydrophobic ‘inner shell’ that suppresses water from disrupting the organized peptide hydrogen bond network. Our approach is demonstrated using a series of cyclic peptide‐linker‐PDMA conjugates which were evaluated by asymmetric flow field flow fractionation, small angle neutron scattering and transmission electron microscopy. Molecular dynamics simulations were also used to show how the polymer and the peptide stacks interact and illustrate the impact of this hydrophobic inner shell approach. This strategy provides a modular approach to fine control the nanotube self‐assembling behavior. We expect that this technique will improve the versatility of peptide nanotubes for the engineering of advanced nanomaterials.
{"title":"Hydrophobicity‐Controlled Self‐Assembly of Supramolecular Peptide Nanotubes in Water","authors":"Min Zeng, William Parsons, Yixuan Chen, David K. Chalmers, Sebastien Perrier","doi":"10.1002/anie.202423828","DOIUrl":"https://doi.org/10.1002/anie.202423828","url":null,"abstract":"Polymer‐conjugated peptides are attractive building blocks for the construction of new nanomaterials. However, the ability to control the self‐assembly of these materials remains a major limitation to their wider utilization. Herein, we report a facile strategy to fine‐tune the assembly of water‐soluble hydrophilic polymer‐conjugated cyclic peptides by incorporating a defined, short hydrocarbon linker between the polymer and peptide. This addition creates a well‐defined hydrophobic ‘inner shell’ that suppresses water from disrupting the organized peptide hydrogen bond network. Our approach is demonstrated using a series of cyclic peptide‐linker‐PDMA conjugates which were evaluated by asymmetric flow field flow fractionation, small angle neutron scattering and transmission electron microscopy. Molecular dynamics simulations were also used to show how the polymer and the peptide stacks interact and illustrate the impact of this hydrophobic inner shell approach. This strategy provides a modular approach to fine control the nanotube self‐assembling behavior. We expect that this technique will improve the versatility of peptide nanotubes for the engineering of advanced nanomaterials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"47 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745115","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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