Angewandte Chemie International Edition最新文献_第3页

On the Mechanism of Soft Self-assembly from Melt: The ubiquitous Heat Capacity Hump and Spontaneous Melt Chirality 熔体软自组装机理研究：普遍存在的热容驼峰和熔体自发手性

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-02 DOI: 10.1002/anie.202505548

Yi-nan Xue, Xiang-bing Zeng, Bo-wen Wu, Ya-xin Li, Liliana Cseh, Shu-gui Yang, Jie Liu, Gillian Gehring, Feng Liu, Goran Ungar

{"title":"On the Mechanism of Soft Self-assembly from Melt: The ubiquitous Heat Capacity Hump and Spontaneous Melt Chirality","authors":"Yi-nan Xue, Xiang-bing Zeng, Bo-wen Wu, Ya-xin Li, Liliana Cseh, Shu-gui Yang, Jie Liu, Gillian Gehring, Feng Liu, Goran Ungar","doi":"10.1002/anie.202505548","DOIUrl":"https://doi.org/10.1002/anie.202505548","url":null,"abstract":"We investigate two unusual phenomena in self-assembly of anisotropic molecules from isotropic (Iso) melt: a heat-capacity (Cp) maximum, and spontaneous formation of the recently discovered chiral liquid (Iso*). Based on experiments on new non-chiral monomers, dimers and polymers, we construct a statistical theory that shows why many complex mesostructures form in two stages: continuous equilibrium growth of nano-clusters in melt through strong interactions, causing the Cp-maximum, followed by establishment of positional long-range order (LRO) through a weak first-order transition. We also show why many achiral compounds additionally form an intermediate chiral Iso* liquid through what we find is a second-order transition. We propose that the first process is equivalent to “supramolecular polymerization” in solutions, where the lack of inter-cluster interaction rules out LRO. Furthermore, we argue that separation into a broad and a sharp transition is universal in condensed matter where strong interactions by themselves cannot lead to LRO, either because the clusters are 1D or due to strong frustration. Clusters must first grow to critical size when, at Tc, the combined weak interactions reach ~kBTc, prompting LRO formation. A situation similar to that in soft self-assembly is seen in spin ordering in magnetic crystals, but only near 0 K.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"7 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897987","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}

引用次数: 0

Intrinsically Luminescent Nematic Liquid Crystals Enabling High-Brightness Full-Color and White Circularly Polarized Luminescence via Chiral Co-Assembly 本征发光向列液晶通过手性共组装实现高亮度全彩和白圆偏振发光

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-02 DOI: 10.1002/anie.202507802

Zhen-Xing Yu, Xu-Wei Chen, Chuan-Feng Chen, Meng Li

{"title":"Intrinsically Luminescent Nematic Liquid Crystals Enabling High-Brightness Full-Color and White Circularly Polarized Luminescence via Chiral Co-Assembly","authors":"Zhen-Xing Yu, Xu-Wei Chen, Chuan-Feng Chen, Meng Li","doi":"10.1002/anie.202507802","DOIUrl":"https://doi.org/10.1002/anie.202507802","url":null,"abstract":"Circularly polarized luminescence (CPL) materials with simultaneous high dissymmetry factor (glum) and brightness are pivotal for advanced photonic applications but remain challenging due to inherent trade-offs betwwen glum value and photoluminescenc quantum yield (PLQY). Here, we report a supramolecular engineering strategy to construct intrinsically luminescent chiral nematic liquid crystal (N*-LC) films via co-assembly of luminescent liquid crystals (LLCs) and chiral dopant. Firstly, five intrinsic LLCs molecules (2PFQ, 2PFBQ, 2PFB, 2PFSe, 2PFS) were synthesized by combining the biphenyl framework with dioctyl-functionalized fluorene, achieving exceptional nematic phases and high brightness with PLQY up to 99%. Then, Chiral co-assembly of the obtained LLCs with chiral dopants (P/M-THH) followed by rapid thermal quenching yielded Bragg reflection-free N*-LC films exhibiting high-brightness CPL with recorded glum values (up to 0.75) and PLQY (up to 71%). Full-color tunability and white CPL (CIE: 0.33, 0.33) were realized through precise compositional control. The simultaneous optimization of glum and PLQY enables high-brightness CPL with advanced anti-counterfeiting capabilities, opening new avenues for developing high-brighness CPL materials for polarized photonic and optoelectronic applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"89 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897736","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}

引用次数: 0

Why Does the Performance of Nitrogen-Doped Carbon Electrocatalysts Decrease in Acidic Conditions? 氮掺杂碳电催化剂在酸性条件下性能下降的原因？

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-02 DOI: 10.1002/anie.202502702

Kotaro Takeyasu, Kenji Hayashida, Junji Nakamura

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Dinitrogen Activation with Low-Valent Strontium 低价锶的二氮活化

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-02 DOI: 10.1002/anie.202506989

Michael Morasch, Timothy Vilpas, Neha Patel, Johannes Maurer, Stefan Thum, Marcel A. Schmidt, Jens Langer, Sjoerd Harder

{"title":"Dinitrogen Activation with Low-Valent Strontium","authors":"Michael Morasch, Timothy Vilpas, Neha Patel, Johannes Maurer, Stefan Thum, Marcel A. Schmidt, Jens Langer, Sjoerd Harder","doi":"10.1002/anie.202506989","DOIUrl":"https://doi.org/10.1002/anie.202506989","url":null,"abstract":"DFT calculations on b-diketiminate (BDI) complexes with the full series of alkaline-earth (Ae) metals show that (BDI)AeAe(BDI) complexes of the heavier Ae metals (Ca, Sr, Ba) have long weak Ae-Ae bonds that are prone to homolytic bond cleavage. They also show that isolation of (BDI)Sr(m-N2)Sr(BDI) with a side-on bridging N22ˉ dianion should be feasible. Attempts to stabilize such a complex with the superbulky BDI* ligand failed (BDI* = HC[(Me)C=N-DIPeP]2, DIPeP = 2,6-Et2CH-phenyl). A heterobimetallic approach enabled first N2 fixation with a Sr complex stabilized with a bulky bis-amide ligand DIPePNN: DIPePN-Si(Me)2CH2CH2Si(Me)2-NDIPeP. Reduction of (DIPePNN)Sr with K/KI gave (DIPePNN)2Sr2K2(N2) (6-Sr); a similar Ca product was also isolated (6-Ca). Crystal structures reveal a N22ˉ anion with side-on bonding to Ae2+ and end-on coordination to K+. DFT calculations and Atoms-In-Molecules analyses show mainly ionic bonding. Both 6-Ae complexes are synthons for hitherto unknown (BDI*)AeAe(BDI*) (Ae = Ca, Sr) and react by releasing N2 and two electrons. Although surprisingly stable in benzene, the reduction of I2 and H2 is facile. Fast reaction with Teflon led to isolation of crystalline [(DIPePNN)SrKF]2 (7) which is labile and decomposed to KF and (DIPePNN)Sr. Latter reactivity underscores potential use of 6-Ae complexes as very strong, hydrocarbon-soluble reducing agents.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"22 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901797","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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A Shelf-Stable Reagent for Photocatalytic Radical Pentafluorosulfanylation of Styrene Derivatives 一种货架稳定的光催化苯乙烯衍生物自由基五氟磺化试剂

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-02 DOI: 10.1002/anie.202505146

Yi YANG, HAN Lulu, Alexis Taponard, Lhoussain Khrouz, CHRISTOPHE BUCHER, Monnereau Cyrille, MAURICE MEDEBIELLE, Anis Tlili

引用次数: 0

Nitrate Reduction for Deaminative Suzuki-Miyaura Coupling of Anilines 苯胺脱氨Suzuki-Miyaura偶联的硝酸盐还原

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-02 DOI: 10.1002/anie.202504012

Chen-Chen Li, Áron Adorján, Manolis Sofiadis, Tim Schulte, Javier Mateos, Mike Rippegarten, Tobias Ritter

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Effective Hole Utilization for Atomically Dispersed Low-coordination Molybdenum Accelerating Photocatalytic C–H Activation 原子分散低配位钼的有效空穴利用加速光催化C-H活化

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-02 DOI: 10.1002/anie.202507312

Wangxi Liu, Jingwen Jiang, Zhonghua Li, Bin Gao, Changhao Liu, Chen Liu, Weichang Hao, Rongli Fan, Jianming Liu, Tao Yu, Zhigang Zou, Zhaosheng Li

{"title":"Effective Hole Utilization for Atomically Dispersed Low-coordination Molybdenum Accelerating Photocatalytic C–H Activation","authors":"Wangxi Liu, Jingwen Jiang, Zhonghua Li, Bin Gao, Changhao Liu, Chen Liu, Weichang Hao, Rongli Fan, Jianming Liu, Tao Yu, Zhigang Zou, Zhaosheng Li","doi":"10.1002/anie.202507312","DOIUrl":"https://doi.org/10.1002/anie.202507312","url":null,"abstract":"Photocatalytic acceptorless dehydrogenation of alcohols offers a promising strategy to produce the corresponding carbonyl compounds and clean fuel H2. However, the sluggish kinetics of the alkoxy C–H bond cleavage attributes to the inefficiency utilization of photogenerated holes greatly restricts the photocatalytic activity. Here we develop atomically dispersed low-coordination Mo on ultrathin ZnIn2S4 nanosheets, that can greatly accelerate photocatalytic C–H activation. An internal quantum efficiency of 45.2% at 400 nm together with 99% benzaldehyde (BAD) selectivity is achieved using benzyl alcohol (BA) as a model substrate. Extensive experimental characterizations and theoretical calculation reveal that the low-coordination Mo tunes the local atomic configuration of highest occupied molecular orbital to trap holes produced under photoexcitation within picosecond. Moreover, the incorporated site-specific Mo greatly improves the lifetime and diffusion length of photogenerated holes and optimizes the driving force of alkoxy C–H activation, which are responsible for the excellent performance. This work marks a significant stride to enhance the utilization efficiency of holes for promoting photocatalytic C–H activation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"21 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897735","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}

引用次数: 0

Catching Fullerenes: Synthesis of Molecular Nanogloves 捕集富勒烯：分子纳米手套的合成

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-01 DOI: 10.1002/anie.202505083

Saber Mirzaei, Hormoz Khosravi, Xiangquan Hu, M. Saeed Mirzaei, Victor M. Espinoza Castro, Xu Wang, Nicholas A. Figueroa, Tieyan Chang, Ying-Pin Chen, Gabriella Prieto Ríos, Natalia Isabel Gonzalez-Pech, Yu-Sheng Chen, Raul Hernandez Sanchez

{"title":"Catching Fullerenes: Synthesis of Molecular Nanogloves","authors":"Saber Mirzaei, Hormoz Khosravi, Xiangquan Hu, M. Saeed Mirzaei, Victor M. Espinoza Castro, Xu Wang, Nicholas A. Figueroa, Tieyan Chang, Ying-Pin Chen, Gabriella Prieto Ríos, Natalia Isabel Gonzalez-Pech, Yu-Sheng Chen, Raul Hernandez Sanchez","doi":"10.1002/anie.202505083","DOIUrl":"https://doi.org/10.1002/anie.202505083","url":null,"abstract":"Herein, we report the synthesis of a new series of rigid, all meta-phenylene, conjugated deep-cavity molecules, displaying high binding affinity towards buckyballs. A facile synthetic approach with an overall combined yield of approximately 53% in the last two steps has been developed using a templating strategy that combines the general structure of resorcin[4]arene and [12]cyclo-meta-phenylene. These two moieties are covalently linked via four acetal bonds resulting in a glove-like architecture. 1H NMR titration experiments reveal fullerene binding affinities (Ka) exceeding ≥106 M–1. The size complementarity between fullerenes and these scaffolds maximizes CH⋯π and π⋯π interactions and their host:guest adduct resemble a ball in a glove, hence their name as nanogloves. Fullerene recognition is tested by suspending carbon soot in a solution of nanoglove in 1,1,2,2-tetrachloroethane, where more than a dozen fullerenes are observed ranging from C60 to C96.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"24 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893555","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}

引用次数: 0

Machine learning-augmented molecular dynamics simulations (MD) reveal insights into the disconnect between affinity and activation of ZTP riboswitch ligands 机器学习增强分子动力学模拟（MD）揭示了ZTP核开关配体的亲和力和激活之间的脱节

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-01 DOI: 10.1002/anie.202505971

Christopher Fullenkamp, Shams Mehdi, Christopher Jones, Logan Tenney, Patricio Pichling, Peri R. Prestwood, Adrian R. Ferré-D'Amaré, Pratyush Tiwary, John Schneekloth

{"title":"Machine learning-augmented molecular dynamics simulations (MD) reveal insights into the disconnect between affinity and activation of ZTP riboswitch ligands","authors":"Christopher Fullenkamp, Shams Mehdi, Christopher Jones, Logan Tenney, Patricio Pichling, Peri R. Prestwood, Adrian R. Ferré-D'Amaré, Pratyush Tiwary, John Schneekloth","doi":"10.1002/anie.202505971","DOIUrl":"https://doi.org/10.1002/anie.202505971","url":null,"abstract":"The challenge of targeting RNA with small molecules necessitates a better understanding of RNA-ligand interaction mechanisms. However, the dynamic nature of nucleic acids,\u0000their ligand-induced stabilization, and how conformational changes influence gene expression pose significant difficulties for experimental investigation. This work employs a combination of computational and experimental methods to address these challenges. By integrating structure-informed design, crystallography, and machine learning-augmented all atom molecular dynamics simulations (MD) we synthesized, biophysically and biochemically characterized, and studied the dissociation of a library of small molecule activators of the ZTP riboswitch, a ligand-binding RNA motif that regulates bacterial gene expression. We uncovered key interaction mechanisms, revealing valuable insights into the role of ligand binding kinetics on riboswitch activation. Further, we established that ligand on-rates determine activation potency as opposed to binding affinity and elucidated RNA structural differences, which provide mechanistic insights into the interplay of RNA structure on riboswitch activation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"56 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893553","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}

引用次数: 0

Thioamides Adjacent to the Ionizable Amine Headgroup in Ionizable Lipids Reduce the pKa of Lipid Nanoparticles and Enhance mRNA transfection efficiency In Vitro and In Vivo 可电离脂质中邻近可电离胺头基的硫胺降低脂质纳米颗粒的pKa，提高mRNA转染效率

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-01 DOI: 10.1002/anie.202506954

Yong Chen, Emily De Lombaerde, Aimée Bugler-Lamb, Zifu Zhong, Martijn J. Schuijs, Claudia M. Brenis Gomez, Jamie De Baere, Mark Gontsarik, Heleen Lauwers, Kim Deswarte, Bart N. Lambrecht, Niek N. Sanders, Martin Guilliams, Bruno G. de Geest

{"title":"Thioamides Adjacent to the Ionizable Amine Headgroup in Ionizable Lipids Reduce the pKa of Lipid Nanoparticles and Enhance mRNA transfection efficiency In Vitro and In Vivo","authors":"Yong Chen, Emily De Lombaerde, Aimée Bugler-Lamb, Zifu Zhong, Martijn J. Schuijs, Claudia M. Brenis Gomez, Jamie De Baere, Mark Gontsarik, Heleen Lauwers, Kim Deswarte, Bart N. Lambrecht, Niek N. Sanders, Martin Guilliams, Bruno G. de Geest","doi":"10.1002/anie.202506954","DOIUrl":"https://doi.org/10.1002/anie.202506954","url":null,"abstract":"Lipid nanoparticles (LNPs) are currently the most clinically advanced mRNA delivery vectors. However, optimizing LNPs for in vivo applications remains largely empirical. The apparent pKa of LNPs is a predictive factor for in vivo performance, with pKa values between 6 and 7 showing the highest efficacy. Despite this critical role of ionizable lipids in LNPs, the relationship between lipid structure and its influence on LNP pKa remains poorly studied. In this study, we report the design and the synthesis of a novel class of ionizable lipids featuring a thioamide moiety, enabling direct comparison between thioamide-containing (SAM) LNPs and amide-containing (OAM) LNPs. We find that substituting oxygen with sulfur in the amide group significantly decreases the apparent pKa of LNPs, increasing the likelihood of identifying lipids in combinatorial libraries that yield LNPs with a pKa in the desired 6–7 range. The reduction in pKa in LNPs containing SAM lipids, compared with OAM lipids, is attributed to the increased hydrophobicity of the thioamide group. Furthermore, by synthesizing multiple libraries of SAM lipids and varying the ionizable head group, alkyl chains, and linker length, we discovered thioamide lipids with distinct tissue tropism, including lipids that mediate splenic targeting by LNPs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"35 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893557","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}

引用次数: 0