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Nitrogen-atom insertion enables skeletal editing of pyrrolidines for tetrahydropyridazine synthesis 氮原子插入使骨架编辑吡咯烷为四氢吡啶合成
IF 19.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-09 DOI: 10.1016/j.chempr.2025.102757
Yuan Liang , Shuang-Feng Song , Siyu Liu , Zhi-Liang Shen , Xiao-Feng Wu
In the July 17 issue of Science, Lu et al. disclose a strategy for converting abundant pyrrolidines into tetrahydropyridazines via a nitrogen-atom insertion process with O-diphenylphosphinyl hydroxylamine as the nitrogen source, providing a powerful platform for the rapid construction of a variety of nitrogen-containing diazacycles and the late-stage derivatization of drug-like molecules.
在7月17日出版的Science杂志上,Lu等人披露了以O-diphenylphosphinyl hydroxylamine为氮源,通过氮原子插入工艺将丰富的吡啶转化为四氢吡啶的策略,为快速构建各种含氮的二氮环和后期衍生化类药物分子提供了强大的平台。
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引用次数: 0
Lighting up dark reactions: An imine network ratchets a coupled equilibrium 点亮暗反应:亚胺网络棘轮耦合平衡
IF 19.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-09 DOI: 10.1016/j.chempr.2025.102783
Merve Temel , Stefano Crespi
In this issue of Chem, Wu and Greenfield demonstrate how a light-fueled information ratchet in a photoswitchable imine pair shifts the composition of free amines to drive a non-photoresponsive transimination out of equilibrium. The ratchet thus establishes a nonequilibrium steady state in homogeneous solution and provides a blueprint for light-controlled reaction cascades.
在本期的《化学》杂志上,Wu和Greenfield展示了光可切换亚胺对中的光燃料信息棘轮如何改变自由胺的组成,从而使非光响应性透射失去平衡。因此,棘轮在均匀溶液中建立了非平衡稳态,并为光控反应级联提供了蓝图。
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引用次数: 0
NHC-catalyzed covalent activation and control of P(V)-stereogenic phosphorus centers via phosphonyl azolium intermediates nhc催化的磷(V)-立体性磷中心的共价活化及磷酰基偶氮中间体的控制
IF 19.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-09 DOI: 10.1016/j.chempr.2025.102586
Yanyan Wang , Kuohong Chen , Fengrui Che , Sha Zhao , Pinpin Feng , Qiang Zhao , Donghui Wei , Xingxing Wu , Yonggui Robin Chi
Despite various impressive advancements in the construction of chiral phosphorus centers, enantioselective control of P(V)-stereogenicity with covalent nucleophilic catalysts for direct preparation of chiral phosphorus compounds remains relatively underdeveloped. Here, we disclose a new mode of covalent organocatalysis for enantioselective construction of chiral phosphorus scaffolds via new P–O bond formations. Key steps in our approach involve the addition of an N-heterocyclic carbene (NHC) catalyst to a phosphonate, leading to the formation of a pivotal phosphonyl azolium reactive intermediate that effectively forges the asymmetric P–O bond formation in high selectivity. The resulting phosphonate products bearing a leaving group allow further stereospecific P–O/N coupling, facilitating the phosphonylated functionalization of diverse natural products and bioactive molecules. Unlike classical NHC organocatalysis that focuses on “C”-stereocenters, this study realizes efficient catalyst control over P(V)-stereogenicity through phosphorus-based azolium intermediates for the first time, offering a new platform for covalent bond activation in the synthesis of stereogenic phosphorus compounds.
尽管在构建手性磷中心方面取得了许多令人印象深刻的进展,但用共价亲核催化剂控制P(V)-立体性直接制备手性磷化合物的对映选择性仍然相对不发达。在这里,我们揭示了一种新的共价有机催化模式,通过新的P-O键形成手性磷支架的对映选择性构建。我们方法的关键步骤包括在膦酸盐上添加n -杂环碳(NHC)催化剂,从而形成关键的膦酰唑反应中间体,有效地形成高选择性的不对称P-O键。由此产生的带有离去基的膦酸盐产物允许进一步的立体特异性P-O /N偶联,促进多种天然产物和生物活性分子的膦化功能化。与传统NHC有机催化主要关注“C”-立体中心不同,本研究首次通过磷基偶氮中间体实现了对P(V)-立体性的有效催化剂控制,为合成立体性磷化合物的共价键激活提供了新的平台。
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引用次数: 0
Unlocking the synthesis of homochiral carborane-fused boraphenanthrenes 解锁同手性碳硼烷-融合硼菲蒽的合成
IF 19.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-09 DOI: 10.1016/j.chempr.2025.102779
Zheng Zhu , Yangjian Quan
Although the asymmetric synthesis of enantioenriched carborane derivatives has been disclosed, the homochiral carborane-fused polyarene remains synthetically elusive. In the September issue of Cell Reports Physical Science, Mu and co-workers report the modular synthesis of various boraphenanthrenes containing carborane blocks. Mechanistic studies show that the key steps are the transfer of axial chirality and an unusual 1,2-boron migration.
虽然不对称合成富集对映体碳硼烷衍生物已经公开,但同手性碳硼烷融合聚芳烃的合成仍然是难以捉摸的。在9月份的《细胞报告-物理科学》杂志上,Mu和他的同事们报道了含有碳硼烷块的各种硼菲蒽的模块化合成。机理研究表明,关键步骤是轴向手性转移和不寻常的1,2-硼迁移。
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引用次数: 0
Harnessing light to drive a non-photoresponsive reaction out of equilibrium 利用光来驱动非光反应,使其失去平衡
IF 19.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-09 DOI: 10.1016/j.chempr.2025.102579
Jiarong Wu (邬佳蓉) , Jake L. Greenfield
Driving non-photoresponsive transformations out of equilibrium with light requires transducing light energy into a different stimulus. Here, we demonstrate this using a dynamic-covalent network of four interconverting imines. In this system, photoirradiation drives a transimination reaction involving photoswitchable imines into a non-equilibrium steady state, altering the composition of both the photochromic imines and free amines. This shift in amine composition subsequently perturbs a coupled transimination reaction that does not directly absorb this wavelength of light. Notably, coupling these two reactions enhances the system’s response; the amines generated in each transimination facilitate the other, amplifying the overall departure from equilibrium beyond what is observed for the reactions in isolation. Operating entirely in solution, this light-fueled cascade provides a blueprint for designing dynamic-covalent systems that harness light energy to control non-photoresponsive transformations, expanding the scope and complexity of light-driven processes in systems chemistry.
驱动非光响应转换与光的平衡需要将光能转换为不同的刺激。在这里,我们使用四个相互转换亚胺的动态共价网络来证明这一点。在该系统中,光照射驱动涉及光致变色亚胺的透射反应进入非平衡稳态,改变了光致变色亚胺和自由胺的组成。胺组成的这种变化随后扰乱了不直接吸收该波长光的耦合透射反应。值得注意的是,将这两种反应结合起来可以增强系统的响应;在每一个过渡中产生的胺促进了另一个,放大了从平衡的整体偏离,超出了在孤立的反应中观察到的。完全在溶液中运行,这种光燃料级联为设计利用光能控制非光响应转换的动态共价系统提供了蓝图,扩大了系统化学中光驱动过程的范围和复杂性。
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引用次数: 0
Visualization of CO formation at the triple-phase boundary in gas diffusion electrodes for ecCO2RR ecCO2RR气体扩散电极三相边界CO生成的可视化
IF 19.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-09 DOI: 10.1016/j.chempr.2025.102582
Sebastian Brosch , Eike Häger , Ole Frank , Patrick Scholz , Wenzel Plischka , Matthias Wessling
Electrochemical CO2 reduction represents a promising technology for mitigating the impact of greenhouse gas emissions, particularly CO2. Gas diffusion electrodes (GDEs) are widely utilized in this process. Although CO2 reduction has been successfully demonstrated on small scales with various catalysts, the role of the wetting state of the catalyst layer in GDEs remains poorly understood. This factor significantly influences current density and faradaic efficiency. However, two fundamental questions persist: where within the electrode does the desired reaction occur, and what operating state should be targeted for optimizing performance? In this study, we employ a microfluidic electrolyzer to visualize and selectively identify reaction zones producing CO, the desired product. This approach enables the characterization of reactivity across different states of the electrode, revealing the impact of catalyst-layer wetting on product selectivity. Together with our previous research on GDEs, these findings provide a comprehensive understanding of electrochemical CO2 reduction.
电化学二氧化碳还原技术是一种很有前途的技术,可以减轻温室气体排放的影响,特别是二氧化碳的排放。气体扩散电极(GDEs)广泛应用于该工艺。尽管各种催化剂已经成功地在小尺度上证明了二氧化碳的还原作用,但人们对催化剂层湿润状态在gde中的作用仍然知之甚少。这一因素显著影响电流密度和法拉第效率。然而,两个基本问题仍然存在:在电极内的什么地方发生所需的反应,以及应该以什么样的工作状态为目标来优化性能?在这项研究中,我们使用微流控电解槽来可视化和选择性地识别产生所需产物CO的反应区域。这种方法能够表征电极不同状态的反应性,揭示催化剂层润湿对产物选择性的影响。结合我们之前对gde的研究,这些发现提供了对电化学CO2还原的全面理解。
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引用次数: 0
Suppressing molecular motions: A pathway to enhanced organic room-temperature phosphorescence 抑制分子运动:增强有机室温磷光的途径
IF 19.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-09 DOI: 10.1016/j.chempr.2025.102654
Chensen Li , Minghui Wu , Zheng Zhao , Jacky W.Y. Lam , Bo Xu , Ben Zhong Tang
Organic room-temperature phosphorescence (RTP) emitters have emerged as a compelling research field with broad applications in optoelectronics, anti-counterfeiting, and biomedical imaging. This interest stems from the efficient utilization of the radiative relaxation of the triplet excited state. An efficient intersystem crossing (ISC) process alone is not sufficient for efficient and long-lived RTP emission. It is also crucial to suppress molecular motion, including rotation, vibration, and translation. By rigidifying molecular structures to suppress these motions, triplet excitons are effectively stabilized, and non-radiative transitions are reduced, presenting a viable strategy for developing a variety of efficient and long-lived RTP materials. This review focuses on the current rational engineering efforts to suppress molecular motion for efficient and long-lived RTP generation, enhancing understanding of the interplay between molecular motion and RTP emission, and emphasizing the critical role of restricting molecular motion in the development of efficient and long-lived RTP materials.
有机室温磷光(RTP)发射器已成为一个引人注目的研究领域,在光电子学,防伪和生物医学成像方面具有广泛的应用。这种兴趣源于对三重态激发态辐射松弛的有效利用。一个有效的系统间交叉(ISC)过程本身并不足以有效和长寿命的RTP排放。抑制分子运动,包括旋转、振动和平移也是至关重要的。通过固化分子结构来抑制这些运动,三重态激子被有效地稳定,非辐射跃迁被减少,为开发各种高效和长寿命的RTP材料提供了可行的策略。本文综述了目前在抑制分子运动以制备高效、长寿命RTP材料方面所做的合理工程努力,加强了对分子运动与RTP发射相互作用的认识,强调了限制分子运动在开发高效、长寿命RTP材料中的关键作用。
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引用次数: 0
Structure-driven medicinal applications of selenium nanoparticles: Challenges and opportunities in clinical translation 结构驱动的纳米硒药物应用:临床转化的挑战和机遇
IF 19.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-09 DOI: 10.1016/j.chempr.2025.102684
Zushuang Xiong , Yanzi Yu , Lizhen He , Tianfeng Chen
Since the bioactivity of nanomedicines is intrinsically governed by their structural configuration, selenium nanoparticles (SeNPs) exhibit structure-dependent therapeutic efficacy in diverse biomedical domains spanning oncology, redox homeostasis regulation, immunomodulation, antimicrobial therapy, and regenerative therapy. However, their inherent dynamic instability and unclear chemical structure pose significant challenges in elucidating their action mechanisms, consequently impeding clinical translation, with current therapeutic applications remaining in their nascent stages. This perspective will delve into the synthetic strategies, structure-activity relationships, and biomedical applications of SeNPs while providing insights into the underlying connection between structure-driven therapeutic optimization and clinical translation.
由于纳米药物的生物活性本质上是由其结构配置决定的,因此硒纳米颗粒(SeNPs)在多种生物医学领域表现出结构依赖的治疗效果,包括肿瘤学、氧化还原稳态调节、免疫调节、抗菌治疗和再生治疗。然而,它们固有的动态不稳定性和不明确的化学结构给阐明其作用机制带来了重大挑战,从而阻碍了临床转化,目前的治疗应用仍处于初级阶段。该视角将深入研究SeNPs的合成策略、结构-活性关系和生物医学应用,同时提供结构驱动的治疗优化与临床转化之间的潜在联系。
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引用次数: 0
A journey from carbolong complexes to in-plane metallo-annulenes 从碳长络合物到面内金属环烯的历程
IF 19.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-09 DOI: 10.1016/j.chempr.2025.102786
Binbin Xu , Dafa Chen , Haiping Xia
Metallaaromatics represent a distinct class of aromatic systems wherein at least one metal atom is structurally integrated into the conjugated π-framework of the aromatic ring structure. Carbolong complexes, one of the primary types, feature one metal center occupying the bridgehead position of at least two fused five-membered rings. This Backstory outlines the development process from carbolong complexes to in-plane metallo-annulenes, metallaaromatics in which the metal occupies the planar annulene cavity, and highlights the interplay between serendipitous discovery and rational design.
金属芳构学代表了一类独特的芳香体系,其中至少有一个金属原子在结构上集成到芳香环结构的共轭π框架中。碳龙配合物是主要类型之一,其特征是一个金属中心占据至少两个熔融五元环的桥头堡位置。本背景故事概述了从碳龙配合物到平面内金属环烯的发展过程,金属占据平面环烯腔的金属力学,并强调了偶然发现和合理设计之间的相互作用。
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引用次数: 0
Electrochemical sequencing of sequence-defined ferrocene-containing oligourethanes 序列定义的含二茂铁低聚脲的电化学测序
IF 19.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-09 DOI: 10.1016/j.chempr.2025.102571
Bipin Pandey , Bharadwaj Muralidharan , Tianmu Ma , Akshi Pant , Matthew Onorato , Kenneth A. Johnson , Ananth Dodabalapur , Praveen Pasupathy , Eric V. Anslyn
The growing demand for data storage has driven research into alternative storage media. Although DNA has proven effective, synthetic sequence-defined polymers (SDPs) offer tailored information-encoding potential. Despite advances in SDP chemodiversity, sequencing methods remain limited, primarily relying on tandem mass spectrometry. To address this, we developed an electrochemical sequencing technique for sequence-defined oligourethanes (SDOs), incorporating four ferrocene-based monomers. Our method combines controlled chain-end degradation with differential pulse voltammetry (DPV) to yield unique voltammograms specific to each sequence. Coupled with kinetic modeling and principal component analysis (PCA), this approach enables accurate sequence identification. We automated this process with a Python program that decodes sequences by comparing experimental DPV data to predicted profiles and thereby successfully demonstrated the encoding and decoding of an 11-character password. The technique expands the toolbox for sequencing SDPs and opens new possibilities for molecular data storage.
对数据存储日益增长的需求推动了对替代存储介质的研究。虽然DNA已被证明是有效的,但合成序列定义聚合物(sdp)提供了定制的信息编码潜力。尽管在SDP化学多样性方面取得了进展,但测序方法仍然有限,主要依赖于串联质谱。为了解决这个问题,我们开发了一种包含四种二茂铁基单体的序列定义低聚氨基甲酸乙酯(sdo)的电化学测序技术。我们的方法结合了控制链端降解和差分脉冲伏安法(DPV)来产生特定于每个序列的独特伏安图。结合动力学建模和主成分分析(PCA),该方法可以实现准确的序列识别。我们使用Python程序自动化了这一过程,该程序通过将实验DPV数据与预测配置文件进行比较来解码序列,从而成功地演示了11个字符密码的编码和解码。该技术扩展了sdp测序工具箱,并为分子数据存储开辟了新的可能性。
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引用次数: 0
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Chem
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