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Structurally Asymmetric Nonplanar π-Conjugated Naphthoquinone Derivatives Modified from Natural Lawsone for High-Stability Aqueous Redox Flow Batteries. 高稳定性水氧化还原液流电池用天然Lawsone修饰的非对称非平面π共轭萘醌衍生物
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-12 DOI: 10.1002/anie.202519793
Pengbo Zhang,Sheng Wen,Yongkang Chen,Yuzhu Liu,Jie Wei,Zuoao Wu,Guochun Ding,Xinmei Song,Tengfei Dai,Zhihu You,Qingbo Guo,Peng Liu,Jianwen Guo,Zuoxiu Tie,Zhong Jin
Aqueous organic redox flow batteries (AORFBs) have attracted growing interest for grid-scale energy storage by reducing reliance on scarce mineral resources used in transition metal-based systems. Natural naphthoquinone derivatives, while environmentally friendly and abundant, suffer from poor solubility and electrochemical instability, hindering their practical use in AORFBs. To address these challenges, we report the functionalization of a naturally abundant dye, lawsone (i.e., 2-HNQ), through non-planar π-conjugation extension and asymmetric intramolecular charge distribution, yielding a non-planar π-conjugated polar naphthoquinone derivative (namely BANQ) with enhanced water solubility and redox reversibility. Computational simulations and spectroscopic analysis confirmed that the introduction of benzoic acid group imparts a polar π-conjugation extended structure with asymmetric charge distribution. This structural modification efficiently enhances aqueous solubility and suppresses degradation pathways, such as Michael addition and irreversible keto-enol tautomerism. Compared with 2-HNQ precursor, BANQ exhibits lower sensitivity to nucleophilic and electrophilic attacks. The BANQ anolyte exhibited a very low-capacity decay rate of merely 0.00018% per cycle (or 0.045% per day), representing a two-order-of-magnitude reduction compared to that of 2-HNQ (0.032% per cycle or 8.22% per day). This study highlights the potential of modifying natural-derived products with rationally designed conjugated electron structure for green and sustainable energy storage solutions.
水性有机氧化还原液流电池(aorfb)通过减少对过渡金属基系统中使用的稀缺矿产资源的依赖,在电网规模储能方面引起了越来越多的兴趣。天然萘醌衍生物虽然环境友好且储量丰富,但其溶解度差,电化学不稳定,阻碍了其在aorfb中的实际应用。为了解决这些挑战,我们报道了天然丰富的染料lawsone(即2-HNQ)通过非平面π共轭延伸和不对称分子内电荷分布的功能化,得到了具有增强水溶性和氧化还原可逆性的非平面π共轭极性萘醌衍生物(即BANQ)。计算模拟和光谱分析证实,苯甲酸基团的引入赋予了具有不对称电荷分布的极性π共轭扩展结构。这种结构修饰有效地提高了水溶性,抑制了降解途径,如迈克尔加成和不可逆酮烯醇互变异构。与2-HNQ前体相比,BANQ对亲核和亲电攻击的敏感性较低。BANQ阳极电解质表现出非常低的容量衰减率,每循环仅为0.00018%(或每天0.045%),与2-HNQ(每循环0.032%或每天8.22%)相比,降低了两个数量级。这项研究强调了通过合理设计共轭电子结构来修饰天然衍生产品的潜力,以实现绿色和可持续的储能解决方案。
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引用次数: 0
N-Heterocyclic Carbene Monolayers on Nickel, Iron, and Steel by a Radical-to-Carbene Strategy. 镍,铁和钢上的n -杂环卡宾单分子膜的自由基-卡宾策略。
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-12 DOI: 10.1002/anie.202518099
Christian Gutheil,Alessia Petti,Julius Gemen,Nils H Rendel,Saeed Amirjalayer,Herbert Feld,Björn Braunschweig,Frank Glorius
N-Heterocyclic carbenes (NHCs) have recently emerged as the next-generation surface ligands with improved stability and molecular flexibility. Despite these premises, research on NHC-enriched flat surfaces is mainly limited to noble metals, while formation of free NHCs often requires the use of vacuum, bases, or strictly air- and moisture-free conditions. We hereby report an unprecedented radical-to-carbene-based approach for fabricating NHC monolayers on earth-abundant and naturally oxidized metal surfaces of nickel, iron, and stainless steel. Following an open-cell electrografting approach, 2-azolyl radicals are firstly formed and immobilized on the metal to then rearrange into NHC monolayers apparently composed of flat-lying NHCs, as corroborated by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), sum-frequency generation (SFG), and cyclic voltammetry (CV) measurements. Density functional theory (DFT) calculations highlighted the role of metal adatoms in facilitating the radical-to-carbene transition. A surface stability test was conducted to assess the tolerance of the NHC-enriched surfaces toward physical, chemical, and electrochemical stress. Ultimately, this work expands the application field of carbenes-on-surfaces to cost-effective and widely used materials, while offering an agile and, until now, mechanistically unknown approach to their generation.
n -杂环碳烯(NHCs)是近年来出现的新一代表面配体,具有更好的稳定性和分子柔韧性。尽管有这些前提,但对富含nhc的平面的研究主要局限于贵金属,而游离nhc的形成通常需要使用真空、碱基或严格的无空气和无湿条件。我们在此报告了一种前所未有的基于自由基到碳烯的方法,用于在地球上丰富的自然氧化金属表面(镍、铁和不锈钢)上制造NHC单层。在开孔电接枝方法下,2-偶氮基自由基首先形成并固定在金属上,然后重新排列成NHC单层,显然由平坦的NHC组成,x射线光电子能谱(XPS)、飞行时间二次离子质谱(ToF-SIMS)、和频生成(SFG)和循环伏安法(CV)测量证实了这一点。密度泛函理论(DFT)计算强调了金属配原子在促进自由基到碳过渡中的作用。进行了表面稳定性测试,以评估富含nhc的表面对物理、化学和电化学应力的耐受性。最终,这项工作将表面碳化合物的应用领域扩展到具有成本效益和广泛使用的材料上,同时为它们的生成提供了一种灵活的、迄今为止尚不为人知的机械方法。
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引用次数: 0
Yb-Doped Cu-Based Catalyst Boosting Electrochemical CO2-to-C2+ Reduction Across pH Range at Ampere-Level Current Density. yb掺杂cu基催化剂在安培电流密度下促进pH范围内co2到c2 +的电化学还原。
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-12 DOI: 10.1002/anie.202510755
Ao Feng,Nan Fang,Xiao-Tian Yuan,Kun-Lin Li,Xuantao Deng,Jia-Feng Du,Zhi-Ming Zhang,Si-Ying Li,De-Yin Wu,Jin-Yu Ye,Qi-Zheng Zheng,Zhi-You Zhou,Shi-Gang Sun
Efficient electrochemical conversion of CO2 to multi-carbon (C2+) products remains significant challenges, particularly under broad pH ranges and high-current-density conditions. Herein, we report ampere-level CO2-to-C2+ electroreduction with exceptional efficiency across a wide pH range using ytterbium-doped CuOx catalysts. The catalyst achieves Faradaic efficiency of 87 ± 2%, 77 ± 1%, and 78 ± 1% under alkaline, neutral, and acidic conditions, respectively. Electrochemical in situ infrared spectroscopy and Raman spectroscopy reveal that Yb-stabilizing Cu+ species and enriching *CO on Cu terrace sites are two critical factors for enhancing C─C coupling. This work not only develops a highly efficient electrocatalysts for sustainable C2+ production, but also establishes a doping strategy for stabilizing active sites and optimizing *CO adsorption configurations.
将二氧化碳有效地电化学转化为多碳(C2+)产物仍然是一个重大挑战,特别是在宽pH范围和高电流密度条件下。在这里,我们报告了使用掺镱CuOx催化剂在宽pH范围内具有卓越效率的安培级co2到c2 +电还原。该催化剂在碱性、中性和酸性条件下的法拉第效率分别为87±2%、77±1%和78±1%。电化学原位红外光谱和拉曼光谱分析表明,Cu阶地上Cu+的yb稳定和CO的富集是增强C─C耦合的两个关键因素。这项工作不仅开发了一种高效的可持续生产C2+的电催化剂,而且建立了稳定活性位点和优化*CO吸附构型的掺杂策略。
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引用次数: 0
Multilayer Sulfide-Electrolyte Engineering Stabilizes Interfaces for Long-Cycling, Wide-Temperature Lithium-Organic Solid-State Batteries. 多层硫化物-电解质工程稳定长循环,宽温度锂有机固态电池的界面。
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-12 DOI: 10.1002/anie.202524363
Wenwen Deng,Ying Zhou,Xuyong Feng,Qingqing Ma,Longfei Li,Yuhang Guo,Weiwei Huang,Lingyun Zhu,Linghao Deng,Yonggang Wang
Interfacial instability remains a key barrier for sulfide electrolyte-based all-solid-state lithium-organic batteries (ASSLOBs). While prior efforts have mainly focused on improving chemical compatibility between active materials and electrolytes, the role of mechanical stress in interfacial degradation has been largely overlooked. Here, we report dibenzo[b,i]thianthrene-5,7,12,14-tetraone (DTT) as a conductive organic cathode integrated with a Li6PS5Cl (LPSC)-Li10GeP2S12 (LGPS)-Li6PS5Cl trilayer electrolyte and a lithium metal anode. Linear sweep voltammetry (LSV), operando pressure monitoring, and in situ electrochemical impedance spectroscopy coupled with distribution of relaxation times (EIS-DRT) reveal that the trilayer design effectively mitigates stress accumulation and suppresses interfacial degradation, while cross-sectional backscattered scanning electron microscopy (BSEM) and energy-dispersive X-ray spectroscopy (EDS) confirm superior structural integrity. Benefiting from this architecture, the ASSLOB delivers 296 mAh g-1 (0.1C) with remarkable long-term stability (90.2% retention after 4800 cycles at 2 C, 60 °C), together with excellent low-temperature and high-loading performance, representing the best results reported for ASSOLBs using lithium anode. Our work establishes electrolyte architecture engineering as a versatile strategy to achieve high-rate, durable, and temperature-resilient solid-state batteries.
界面不稳定性仍然是硫化物电解质基全固态有机锂电池(asslob)的关键障碍。虽然先前的努力主要集中在改善活性材料和电解质之间的化学相容性,但机械应力在界面降解中的作用在很大程度上被忽视了。在这里,我们报道了二苯并[b,i]噻吩-5,7,12,14-四酮(DTT)作为导电有机阴极与Li6PS5Cl (LPSC)-Li10GeP2S12 (LGPS)-Li6PS5Cl三层电解质和锂金属阳极集成。线性扫描伏安法(LSV)、操作压力监测、结合弛豫时间分布的原位电化学阻抗谱(EIS-DRT)显示,三层设计有效地减轻了应力积累,抑制了界面退化,而截面背散射扫描电子显微镜(BSEM)和能量色散x射线光谱(EDS)证实了优越的结构完整性。得益于这种结构,ASSLOB提供296 mAh g-1 (0.1C),具有卓越的长期稳定性(在2℃,60℃下4800次循环后保持90.2%),以及出色的低温和高负载性能,代表了使用锂阳极的ASSLOB的最佳结果。我们的工作建立了电解质结构工程作为实现高速率,耐用和温度弹性固态电池的通用策略。
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引用次数: 0
Biomimetic NaK Channel Membrane Enabled by a Crown Ether‐Coordinated Metal–Organic Framework 冠醚-配位金属-有机骨架激活的仿生NaK通道膜
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-10 DOI: 10.1002/anie.202521527
Chen Zhao, Na Li, Sijia Shi, Jue Hou, Li Gao, Benny D. Freeman, Huanting Wang, Huacheng Zhang
Biological NaK channels integrate exquisite ion selectivity with dynamic gating to regulate life processes, yet achieving such multifunctionality in synthetic channels has remained a formidable challenge. Here, we present a metal–organic framework (MOF) channel membrane that combines two complementary ion‐conduction motifs: carboxyl groups from UiO‐66‐COOH and carboxybenzo‐15‐crown‐5 (15C5‐COOH), assembled in a one‐step coordination strategy. This hybrid architecture recapitulates essential NaK channel functions, offering both ultrahigh ion selectivity and controllable gating. The membrane enables highly selective conduction of monovalent cations while effectively excluding Mg 2+ , yielding M + /Mg 2+ selectivity above 10 2 . Under mixed‐ion conditions, it achieves unprecedented Na⁺/K⁺ selectivity exceeding 10 3 , far surpassing reported artificial ion channels. Remarkably, Mg 2+ ions dynamically gate Na⁺ and K⁺ transport with sustainable on–off ratios around 30. These outstanding performances arise from the synergistic interplay of crown ether and carboxyl groups confined within subnanometer MOF pores. This work establishes a versatile strategy for designing multifunctional artificial ion channels, opening avenues toward advanced ionic devices for artificial cells and biomedical technologies.
生物NaK通道结合了精细的离子选择性和动态门控来调节生命过程,但在合成通道中实现这种多功能性仍然是一个巨大的挑战。在这里,我们提出了一种金属有机框架(MOF)通道膜,它结合了两个互补的离子传导基序:来自UiO‐66‐COOH的羧基和来自羧基苯并‐15‐冠‐5 (15C5‐COOH)的羧基,以一步配位策略组装。这种混合结构概括了基本的NaK通道功能,提供超高离子选择性和可控门控。该膜能够高度选择性地传导单价阳离子,同时有效地排除Mg 2+,产生M + /Mg 2+的选择性高于10 2。在混合离子条件下,它实现了前所未有的Na + /K +选择性,超过了103,远远超过了报道的人工离子通道。值得注意的是,mg2 +离子动态地阻断了Na +和K +的传输,其通断比在30左右。这些优异的性能来自于亚纳米MOF孔中的冠醚和羧基的协同作用。这项工作为设计多功能人工离子通道建立了一种通用策略,为人工细胞和生物医学技术的先进离子装置开辟了道路。
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引用次数: 0
Dual‐Induced Confined Synthesis of Metastable γ‐MnO 2 Nanoclusters in Metal–Organic Frameworks for Highly Efficient Ozone Decomposition 在金属-有机框架中双诱导受限合成亚稳γ - mno2纳米团簇用于高效臭氧分解
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-10 DOI: 10.1002/anie.5562966
Yuning Lou, Wen‐Xiong Shi, Yuejiang Han, Qiu‐Ping Zhao, Tianshuo Li, Lin Liu, Zhi‐Ming Zhang, Zhengbo Han
Ultrafine metal oxide nanoclusters (UMONs) exhibit remarkable catalytic potential due to their high specific surface area; however, achieving precise control over both the size and crystal phase of UMONs remains a significant challenge. Herein, we developed a dual‐induced confined synthesis strategy that couples hydrophobic gating with thermally triggered phase transformation to precisely confine UMONs within the pores of a metal–organic framework (MOF). 13 UMONs@MOF composites were successfully synthesized with the metal cations in UMONs spanning different regions of the periodic table. Notably, sub‐3 nm metastable γ‐MnO 2 was stabilized and confined within MIL‐101(Fe) for the first time. The optimized 15% γ‐MnO 2 @MIL‐101(Fe) showed a durable 100% O 3 removal efficiency for over 100 h. This performance was maintained in a continuous air flow containing 40 ppm O 3 at a high gas hourly space velocity of 1.7 × 10 5 h −1 over a wide humidity range of 10%–90%. Mechanistic studies reveal that its superior catalytic activity originates from the synergistic effect between the confined γ‐MnO 2 active sites and the Fe 3 O clusters in the MIL‐101(Fe). This work provides a universal approach for the precise control of the size and crystal phase of UMONs, paving the way for designing high‐performance catalysts.
超细金属氧化物纳米团簇(UMONs)由于其高比表面积而表现出显著的催化潜力;然而,实现对umon尺寸和晶相的精确控制仍然是一个重大挑战。在此,我们开发了一种双诱导受限合成策略,将疏水门控与热触发相变耦合在一起,以精确地将umon限制在金属有机框架(MOF)的孔隙中。本文成功地合成了13个UMONs@MOF复合材料,其中金属阳离子在umon中跨越元素周期表的不同区域。值得注意的是,亚3nm亚稳态γ - mno2首次被稳定并限制在MIL - 101(Fe)中。优化后的15% γ - mno2 @MIL - 101(Fe)在超过100小时的时间内表现出100%的O 3去除效率。在含40 ppm O 3的连续气流中,在高气体每小时空间速度为1.7 × 10 5 h−1、10%-90%的宽湿度范围内,这种性能保持不变。机理研究表明,其优越的催化活性源于MIL - 101(Fe)中受限的γ - mno2活性位点与Fe - 3o簇之间的协同作用。这项工作为精确控制umon的尺寸和晶相提供了一种通用的方法,为设计高性能催化剂铺平了道路。
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引用次数: 0
A Novel Acetylcholine Nanosensor for Single Vesicle Storage and Sub‐Quantal Exocytosis in Living Neurons and Organoids 一种新型乙酰胆碱纳米传感器,用于活体神经元和类器官的单囊泡储存和亚量子胞吐
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-10 DOI: 10.1002/anie.202520854
Wanying Zhu, Yufan Zhang, Hanwen Yu, Da Wang, Xinyue Zhang, Xiaowen Du, Shanshan Wu, Bingzhi Li, Yizhou Zhang, Hongliang Xin, Xing Guo, Yan Liu
Acetylcholine (ACh) is a critical neurotransmitter that regulates diverse physiological functions, such as cognition and muscle contraction, through synaptic transmission. However, in situ quantitative chemical analysis of single‐vesicle storage and release dynamics at single‐cell level remains a major technical challenge, hindering mechanistic understanding of cholinergic synaptic plasticity across physiological and pathological states. To address this, we developed an Ti 3 C 2 T x MXene/enzyme‐functionalized (M@E@CF) nanosensor, enabling real‐time monitoring of vesicular ACh storage and exocytotic release in primary cholinergic neurons and human spinal cord organoids. Our findings reveal a sub‐quantal release mode in both mouse and human‐derived neurons. To further elucidate the regulatory principles of exocytosis kinetics, we classified single‐vesicle exocytosis patterns based on signal peak shapes using a 1D convolutional neural network (1D‐CNN) deep learning model, uncovering significant differences in the number of released molecules and kinetic parameters across modes. Critically, in Down syndrome models, we observed significantly reduced single vesicle ACh storage and release alongside an elevated release fraction, concurrent with shortened fusion pore durations during exocytosis. Thus, the M@E@CF nanosensor platform establishes a versatile tool for spatiotemporal investigation of neurotransmitter storage and release dynamics, providing a critical technical foundation for exploring physiological functions and pathological mechanisms of the cholinergic system.
乙酰胆碱(Acetylcholine, ACh)是一种重要的神经递质,通过突触传递调节多种生理功能,如认知和肌肉收缩。然而,单细胞水平单囊泡储存和释放动力学的原位定量化学分析仍然是一个主要的技术挑战,阻碍了对生理和病理状态下胆碱能突触可塑性的机制理解。为了解决这个问题,我们开发了一种Ti 3c2txmxene /酶功能化(M@E@CF)纳米传感器,能够实时监测初级胆碱能神经元和人脊髓类器官中囊泡ACh的储存和胞外释放。我们的研究结果揭示了在小鼠和人类来源的神经元中都存在亚量子释放模式。为了进一步阐明胞吐动力学的调控原理,我们使用一维卷积神经网络(1D - CNN)深度学习模型,基于信号峰值形状对单囊胞吐模式进行分类,揭示了不同模式下释放分子数量和动力学参数的显著差异。关键的是,在唐氏综合征模型中,我们观察到单囊泡乙酰胆碱的储存和释放显著减少,释放分数升高,同时胞吐过程中融合孔持续时间缩短。因此,M@E@CF纳米传感器平台为神经递质储存和释放动力学的时空研究建立了一个多功能工具,为探索胆碱能系统的生理功能和病理机制提供了关键的技术基础。
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引用次数: 0
Decoupling Adsorption of Key Intermediates Enabled by Asymmetric 3d-5d-Orbital Hybridization: Durable High-Performance AEM Water Electrolysis and Zn–Air Batteries 非对称3d-5d轨道杂化使关键中间体解耦吸附:持久高性能AEM水电解和锌-空气电池
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-10 DOI: 10.1002/anie.202524805
Xin-Yi Zhang, Hang Yin, Han-Hao Liu, Ying-Di Ge, Cong-Cong Dang, Shuo-Hang Zheng, Zhen-Yi Gu, Jun-Ming Cao, Jin-Zhi Guo, Xing-Long Wu
Decoupling key intermediates’ adsorption via asymmetric 3d-5d-orbital hybridization overcomes the intrinsic scaling relation bottleneck, enabling rational design of high-performance, durable multifunctional electrocatalysts for anion exchange membrane water electrolyzers (AEMWEs) and Zn–air batteries (ZABs). Here, we reveal that asymmetric 3d-5d-orbital hybridization, engineered through the synergy of lattice strain and defect structures in a nitrogen-doped carbon-supported PtCo alloy (PtCo@NPC), effectively decouples these adsorption energies of key intermediates. PtCo@NPC demonstrates exceptional multifunctional electrocatalytic performance for the hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction in alkaline media. Density functional theory calculations suggest that electronic structure modulation tunes the adsorption characteristics of intermediates, while X-ray absorption fine structure spectroscopy confirms the corresponding changes in the electronic states of surface Pt and Co atoms. When deployed in devices, PtCo@NPC enables AEMWEs to operate stably for 522 h at 1000 mA cm−2 with a voltage decay rate of only 0.103 mV h−1 and empowers ZABs to achieve a long cycle life of over 2520 cycles at 5.0 mA cm−2. This study highlights electronic-structure modulation as a powerful strategy for advanced energy technologies.
通过不对称3d-5d轨道杂化实现关键中间体的解耦吸附,克服了固有的结垢关系瓶颈,实现了阴离子交换膜水电解槽(AEMWEs)和锌空气电池(ZABs)高性能、耐用多功能电催化剂的合理设计。在这里,我们揭示了不对称的3d-5d轨道杂化,通过氮掺杂碳负载PtCo合金(PtCo@NPC)的晶格应变和缺陷结构的协同作用,有效地解耦了这些关键中间体的吸附能。PtCo@NPC在碱性介质中对析氢反应、析氧反应和氧还原反应表现出优异的多功能电催化性能。密度泛函理论计算表明,电子结构调制调节了中间体的吸附特性,而x射线吸收精细结构光谱证实了表面Pt和Co原子电子态的相应变化。当部署在器件中时,PtCo@NPC使AEMWEs能够在1000 mA cm - 2下稳定运行522小时,电压衰减率仅为0.103 mV h - 1,并使ZABs能够在5.0 mA cm - 2下实现超过2520个周期的长循环寿命。这项研究强调了电子结构调制作为先进能源技术的有力策略。
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引用次数: 0
Energy‐Transfer‐Enabled Skeletal Rearrangement of Cyclic Ketones into Strained Cyclopropane‐Fused Medium Rings 能量转移使环酮骨架重排成应变环丙烷融合介质环
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-10 DOI: 10.1002/anie.202522620
Yingru Xu, Zehui Wang, Jianjian Huang, Tengfei Pang, Miao Jiang, Fangrui Zhong, Guojiao Wu
Cyclopropane‐fused medium rings (CFMR) are attractive structural motifs that combine high strain with unique three dimensionality, however their efficient and modular synthesis remains a formidable challenge. Herein, we present a general photocatalytic skeletal editing strategy that enables a direct topological leap—a single‐step reorganization that simultaneously alters both ring size and fusion topology—from readily available five‐ to eight‐membered cyclic ketones into diverse seven‐ to ten‐membered cyclopropane‐fused medium rings. This transformation proceeds through a novel energy‐transfer‐induced, diradical‐mediated 1,4‐carbonyl migration, orchestrating a “ring expansion–collapse” cascade to forge the strained bicyclic frameworks straightforward, which is supported by DFT calculations. This strategy features broad substrate scope, excellent functional‐group compatibility, and high efficiency, enabling the late‐stage diversification of complex molecules and exploration of CFMR chemical space that was previously inaccessible. Moreover, integration of this strategy with further skeletal modification enables rapid construction of versatile [n.3.0] bicycles.
环丙烷熔合介质环(CFMR)是一种结合了高应变和独特三维特性的极具吸引力的结构基元,但其高效和模块化合成仍然是一个巨大的挑战。在此,我们提出了一种通用的光催化骨架编辑策略,该策略可以实现直接的拓扑飞跃-同时改变环尺寸和融合拓扑的单步重组-从现成的五到八元环酮到各种七到十元环丙烷融合介质环。这种转变是通过一种新的能量转移诱导的,双自由基介导的1,4羰基迁移进行的,协调了一个“环膨胀-坍塌”级联,形成了张力双环框架,这是由DFT计算支持的。该策略具有广泛的底物范围、优异的官能团相容性和高效率,使复杂分子的后期多样化和CFMR化学空间的探索成为可能。此外,将这种策略与进一步的骨骼修改相结合,可以快速构建多功能自行车。
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引用次数: 0
Synergistic Action of Crystallophore and Imaging-Crystallophore Enhances the Production and Imaging of Protein Crystals 晶体载体和成像载体的协同作用增强了蛋白质晶体的生成和成像
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-10 DOI: 10.1002/anie.202525011
Margaux Roux, Amandine Roux, Thomas Boukéké-Lespulier, François Riobé, Christian Chapelle, Nicolas Foos, Elise Dumont, Eric Girard, Natacha Gillet, Olivier Maury
The synthesis and photophysical characterization of a new family of terbium(III) complexes called Imaging-crystallophore, substituted by π-conjugated antennas, is reported. Previous crystallophore variants (such as Tb-Xo4) have shown very interesting nucleating properties to obtain high-quality protein crystals. In addition, the Imaging-crystallophore emits in the green and accumulates in the protein crystals, enabling very easy crystal detection using fluorescence microscopy under one-photon but also under two-photon excitations. X-ray diffraction crystallography and molecular dynamics simulations demonstrate that the binding site of the Imaging-crystallophore in hen-egg white lysozyme (HEWL) is similar to that of the Tb-Xo4 but present additional hydrophobic interactions with the conjugated antennas. However, its nucleating properties are not as effective as those of Tb-Xo4. Finally, we emphasize the synergy between the two generations of crystallophore by preparing and analyzing the properties of the mix (10/0.2) corresponding to a mixture of Tb-Xo4 and Imaging-crystallophore. By combining the best of nucleating and imaging properties, we can easily obtain and detect high-quality protein crystals
本文报道了一类被π共轭天线取代的新型铽(III)配合物的合成及其光物理性质。以前的晶体载体变体(如Tb-Xo4)已经显示出非常有趣的成核特性,可以获得高质量的蛋白质晶体。此外,成像晶体发出绿色并在蛋白质晶体中积累,使得在单光子和双光子激发下使用荧光显微镜进行晶体检测非常容易。x射线衍射晶体学和分子动力学模拟表明,蛋清溶菌酶(HEWL)中成像晶体的结合位点与Tb-Xo4相似,但与共轭天线存在额外的疏水相互作用。然而,其成核性能不如Tb-Xo4有效。最后,我们通过制备和分析Tb-Xo4和成像晶体的混合物(10/0.2)的性质来强调两代晶体之间的协同作用。通过结合成核和成像特性,我们可以轻松地获得和检测高质量的蛋白质晶体
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引用次数: 0
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Angewandte Chemie International Edition
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