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Simultaneous Control of Dual Axial Chirality: Chiral Phosphoric Acid-Catalyzed Atroposelective Synthesis of Diaryl Ethers 双轴手性的同时控制:手性磷酸催化二芳基醚的atroopselective合成
IF 11.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-21 DOI: 10.31635/ccschem.025.202507266
Pengyang Wang, Xiaoyu Chen, Linlong Dai, Lin Fan, Chang He, Hongda Qiu, Daokai Xiong, Xiaofei Zeng, Wanbin Zhang, Guofu Zhong
Compounds with two axial chiralities are highly valuable yet synthetically challenging targets. We disclose a chiral phosphoric acid (CPA)-catalyzed atroposelective Paal-Knorr reaction that enables the direct construction of chiral diaryl ethers featuring two distinct axial chiralities, including a C-N axis. This operationally simple protocol delivers both diastereomers in high combined yield (up to 91%) and excellent enantiopurities (up to 96% ee and 99% ee, respectively). A proposed CPA-dimer catalytic model accounts for the observed stereoselectivity. The scalability of the process and successful product derivatizations highlight the method‘s practicality and the potential of these diaxially chiral skeletons in catalysis.
具有两个轴向手性的化合物是非常有价值的,但合成上具有挑战性的目标。我们揭示了一个手性磷酸(CPA)催化的atroopselective Paal-Knorr反应,该反应能够直接构建具有两个不同轴向手性的手性二芳醚,包括C-N轴。这种操作简单的方案提供了高综合收率(高达91%)和优异的对映异构体(分别高达96% ee和99% ee)。提出的二聚体催化模型解释了观察到的立体选择性。该工艺的可扩展性和成功的产品衍生化突出了该方法的实用性和这些双轴手性骨架在催化中的潜力。
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引用次数: 0
Implantable Organic Transistors: Architectures, Properties and Applications 可植入有机晶体管:结构、特性和应用
IF 11.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-18 DOI: 10.31635/ccschem.025.202507280
Tao Hai, Shen Zhang, Yunqi Liu, Derong Kong, Dacheng Wei
Organic transistors hold great promise for implantable applications in personalized health monitoring and precise therapy because of their light weight, mechanical compatibility with soft tissues and tunable electrical properties. From single devices to complicated circuits, recent years have witnessed the rapid development of devices with various structures for innovative implantable applications. The types and working mechanisms of organic transistors, as well as the properties necessary for implantable applications are reviewed. The latest advances and representative applications of implantable organic transistors are summarized and analyzed, with a perspective for future development.
有机晶体管由于其重量轻,与软组织的机械兼容性和可调谐的电学特性,在个性化健康监测和精确治疗的植入式应用中具有很大的前景。从单一器件到复杂电路,近年来各种结构的器件快速发展,用于创新的植入式应用。综述了有机晶体管的类型和工作机理,以及可植入应用所需的性能。对可植入有机晶体管的最新进展和代表性应用进行了总结和分析,并对未来的发展进行了展望。
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引用次数: 0
Chiral Copper Clusters as Artificial Light-Harvesting Antennas Enabling Sequential Circularly Polarized Fürster Resonance Energy Transfer 手性铜簇作为人工光收集天线实现顺序圆极化相位<e:1>共振能量转移
IF 11.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-14 DOI: 10.31635/ccschem.025.202507344
Tian-Li Gao, Qi-Xiang Cai, Xiao-Jie Xu, Shuai-Peng Chen, Li-Zhen Wang, Ying-Xue Yuan, Shuang-Quan Zang
The continuous transmission and amplification of chirality is a fascinating feature in natural biological systems. However, achieving sequential transmission of circularly polarized luminescence (CPL) through multistep energy transfer remains a formidable challenge. Here, chiral N-heterocyclic carbene-protected Cu3 clusters (R/S-Cu3) were synthesized as light-harvesting antennas, self-assembling into blue-emitting nanospheres with considerable CPL-active. Coumarin 6 (C-6), a green emitter, was introduced as key relay baton for both chirality and energy transmission. We constructed chiral light-harvesting systems (LHSs) through the co-assembly of R/S-Cu3, C-6, and red-emitting Nile Red (NiR), enabling efficient two-step energy transfer with a maximum efficiency (ΦET, max) of 87.86%. Supramolecular engineering was employed to fabricate nanofiber bundles serving as film-templates, which facilitates sequential CPL transmission from Cu3 to C-6 and subsequently to NiR. The sequential circularly polarized Forster resonance energy transfer (CP-FRET) was verified via CPL spectral comparisons, resulting in distinct amplification of the dissymmetry factor. This work develops metal clusters-driven sequential CPL and energy transmission in chiral LHSs and provides in-depth insights into CPFRET mechanism.
手性的持续传递和扩增是自然生物系统中一个令人着迷的特征。然而,通过多步能量转移实现圆偏振光的顺序传输仍然是一个巨大的挑战。在这里,手性n -杂环碳保护Cu3簇(R/S-Cu3)被合成为光收集天线,自组装成具有相当大的cplo活性的蓝色发射纳米球。香豆素6 (C-6)是一种绿色发射器,作为手性和能量传递的关键接力棒。我们通过R/S-Cu3, C-6和红色尼罗红(NiR)的共组装构建了手性光收集系统(lhs),实现了高效的两步能量传递,最大效率(ΦET, max)为87.86%。采用超分子工程技术制备纳米纤维束作为膜模板,促进CPL从Cu3到C-6依次传输到近红外。通过CPL光谱比较验证了顺序圆极化福斯特共振能量传递(CP-FRET),导致不对称因子明显放大。本研究开发了手性lhs中金属簇驱动的顺序CPL和能量传递,并对CPFRET机制提供了深入的见解。
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引用次数: 0
Molecular Ferroelectric Catalysis 铁电分子催化
IF 11.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-14 DOI: 10.31635/ccschem.026.202607396
Jun-Chao Qi, Lutao Li, Huihui Hu, Xiao-Gang Chen, Chen-Kai Yang, Huan-Huan Chen, Yan Qin, Wei-Qiang Liao, Guifu Zou, Yu-Meng You, Ren-Gen Xiong
Ferroelectric materials with unique spontaneous polarization and ferroelectric domains have drawn growing academic focus as novel catalytic candidates in recent years, owing to their distinctive ability to regulate charge carrier behavior. The spontaneous polarization forms a built-in electric field to promote the separation of charge carriers, and polarization modulation triggered by external stimuli induces the release of free charges from the ferroelectric domain surface, which expedites the progression of redox reactions. In contrast to widely used inorganic ferroelectrics, molecular ferroelectrics hold prominent advantages, such as the low acoustic impedance that facilitates efficient mechanical energy transmission from solvent to catalyst, and the solvent solubility that enables good catalyst recyclability. Such traits make them highly prospective for advancing efficient and sustainable ferroelectric catalysis. This minireview summarizes recent advances in molecular ferroelectric catalysis. The principle of ferroelectric catalysis and the advantages of molecular ferroelectric catalysis are first outlined. The recent progress in molecular ferroelectric catalysis, including catalytic quinoline annulation, olefin difunctionalization, alkane oxidation, alkyne coupling, and hydrogen production, was then presented, which shows much better catalytic performance than that of inorganic counterparts. Finally, the challenges, opportunities, and perspectives within the field are discussed to inspire future research studies into molecular ferroelectric catalysis.
近年来,具有独特的自发极化和铁电畴的铁电材料由于其独特的调节载流子行为的能力而成为新的催化候选材料,引起了越来越多的学术关注。自发极化形成内嵌电场促进载流子分离,外加刺激引发的极化调制诱导铁电畴表面释放自由电荷,加速氧化还原反应的进行。与广泛使用的无机铁电体相比,分子铁电体具有突出的优势,例如低声阻抗,有利于从溶剂到催化剂的有效机械能传递,以及溶剂溶解度,使催化剂具有良好的可回收性。这些特性使它们在推进高效和可持续的铁电催化方面具有很高的前景。本文综述了铁电分子催化的最新进展。首先概述了铁电催化的原理和分子铁电催化的优点。介绍了铁电分子催化的最新进展,包括催化喹啉环化、烯烃双官能化、烷烃氧化、炔烃偶联和制氢等,表明铁电分子催化性能远优于无机铁电分子催化。最后,讨论了该领域的挑战、机遇和前景,以启发未来对分子铁电催化的研究。
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引用次数: 0
Non-Phase-Change Membrane Separation of Liquid Alkanes: Mechanisms, Materials Design, and Emerging Perspectives 液体烷烃的非相变膜分离:机理、材料设计和新兴观点
IF 11.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-14 DOI: 10.31635/ccschem.025.202507261
Luxin Sun, Changhui Dai, Yucheng Guo, Sheng Guo
Liquid alkanes constitute the dominant components of petroleum-derived streams and serve as key intermediates in refining and chemical manufacturing, making their efficient separation a central yet challenging task in chemical processing. However, the separation of liquid alkanes has long relied on thermodynamically driven phase-change operations, such as distillation and rectification, which inherently couple separation efficiency with high energy consumption and limited molecularlevel selectivity. These limitations become particularly pronounced when molecular-level discrimination among structurally similar alkanes is required. In this context, non-phase-change membrane separation provides an alternative pathway by enabling selective transport of liquid alkanes without vapor-liquid transitions. Recent advances in membrane chemistry have demonstrated that separation performance can be regulated through separation mechanisms, polymer architecture design, and solvation-transport coupling. This Mini Review summarizes recent progress in non-phase-change membrane separation of liquid alkanes, with emphasis on underlying separation mechanisms, representative materials design strategies, and emerging perspectives. These insights provide a mechanistic framework for understanding liquid alkane separation beyond conventional phase-change processes and highlight potential opportunities for further advancing efficient hydrocarbon separation, including through the integration of data-driven and artificial-intelligence-assisted approaches.
液态烷烃是石油衍生流的主要组成部分,是炼油和化工生产的关键中间体,使其高效分离成为化学加工的核心但具有挑战性的任务。然而,液态烷烃的分离长期依赖于热力学驱动的相变操作,如蒸馏和精馏,这些操作固有地将分离效率与高能耗和有限的分子水平选择性耦合在一起。当需要在结构相似的烷烃之间进行分子水平的区分时,这些限制变得特别明显。在这种情况下,非相变膜分离提供了一种替代途径,使液体烷烃的选择性运输没有汽液转变。膜化学的最新进展表明,分离性能可以通过分离机制、聚合物结构设计和溶剂-输运耦合来调节。本文综述了近年来液体烷烃非相变膜分离的研究进展,重点介绍了潜在的分离机制、代表性材料设计策略和新兴观点。这些见解为理解液态烷烃分离提供了一个超越传统相变过程的机制框架,并强调了进一步推进高效碳氢化合物分离的潜在机会,包括通过数据驱动和人工智能辅助方法的整合。
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引用次数: 0
Tailoring Electronic and Vibrational Properties in Isostructural Metal Nanoclusters 等结构金属纳米团簇的电子和振动特性
IF 11.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-13 DOI: 10.31635/ccschem.026.202507120
Jie Kong, Qingxi Zhai, Fangming Zhao, Linlin Zeng, Xu Liu, Yan Zhu, Yi Luo, Meng Zhou
Atomic-level doping while preserving structural integrity is a powerful approach for tailoring nanocluster properties. In this study, we investigate Pd-doped Au38 nanoclusters, Pd1Au37 and Pd2Au36, in which Pd atoms are selectively introduced into the central sites of the bi-icosahedral core while preserving the global framework. This isostructural system enables precise modulation of electronic structure and vibrational behavior. Theoretical calculations reveal that Pd substitution significantly redistributes electron and hole densities and narrows the highest occupied molecular orbital–lowest unoccupied molecular orbital gap, in contrast to the parent Au38 nanocluster. Ultrafast transient absorption spectroscopy shows dramatic changes in excited-state dynamics, including a three-orders-of-magnitude increase in lifetime for Pd1Au37 in nitrogenous solvents. Coherent vibrational analyses, corroborated by steady-state Raman spectroscopy, uncovers a distinct evolution of lattice dynamics: while Au38 and Pd2Au36 exhibit single vibrational modes at 0.8 and 1.7 THz respectively, Pd1Au37 uniquely exhibits dual modes, reflecting enhanced coupling and vibrational complexity. The results demonstrate that isostructural doping serves as an effective strategy for tailoring electronic and vibrational properties at the atomic scale.
在保持结构完整性的同时,原子级掺杂是调整纳米团簇性质的有效方法。在这项研究中,我们研究了Pd掺杂的Au38纳米簇Pd1Au37和Pd2Au36,其中Pd原子被选择性地引入到双二十面体核心的中心位置,同时保留了整体框架。该等结构系统能够精确调制电子结构和振动行为。理论计算表明,与母体Au38纳米团簇相比,Pd取代显著地重新分配了电子和空穴密度,缩小了最高已占据分子轨道和最低未占据分子轨道的差距。超快瞬态吸收光谱显示了激发态动力学的巨大变化,包括Pd1Au37在含氮溶剂中的寿命增加了三个数量级。稳态拉曼光谱证实了相干振动分析,揭示了晶格动力学的独特演变:Au38和Pd2Au36分别在0.8和1.7太赫兹下表现为单振动模式,而Pd1Au37独特地表现为双模式,反映了增强的耦合和振动复杂性。结果表明,在原子尺度上,同结构掺杂是一种有效的调整电子和振动特性的策略。
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引用次数: 0
Hydroperoxide-Mediated Photochargeable Molecular Cage for Post-Irradiation Dark Catalysis 辐照后暗催化氢过氧化物介导的光充电分子笼
IF 11.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-13 DOI: 10.31635/ccschem.025.202506995
Jiang-Pei Yuan, Zong-Jie Guan, Wen-Ting Li, Ling Yuan, Hang Xing, Abdullah M. Al-Enizi, Ayman Nafady, He Zheng, Shengqian Ma, Yu Fang
Designing energy-storage materials that mimic the light-dark coupling mechanism of natural photosynthesis represents a key challenge in the field of energy conversion. Current catalysts for photoelectrocatalytic applications, namely semiconductors, metal-organic frameworks (MOFs), and organic photocatalysts, display material-specific inherent limitations. In this study, we developed a series of porous coordination cages (PCCs), designated as <b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"><bold>PCC-X</bold></b> (where X=6, 7, 8), that exhibited extremely rare photochargeable property, which can accelerate a variety of reactions in the post-irradiation dark period. In the irradiation period, PCC activates the C(sp<sup>3</sup>)-H bonds of hydrocarbons, rapidly generating hydroperoxides and stored the energy there, forming <b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"><bold>THF-OOH@PCC-X</bold></b>. With the sulfur atom in the phenothiazine core of the <b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"><bold>PCC-6</bold></b> gradually oxidized to sulfoxide (<b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"><bold>PCC-7</bold></b>) and sulfone (<b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"><bold>PCC-8</bold></b>), the latter exhibited superior oxidation properties, thanks to its highest positive valence band value. In the dark period, <b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"><bold>THF-OOH@PCC-8</bold></b> not only catalyzes the formation of C-S, O-S, S-S, and N-S bonds, but also facilitates the rapid detoxification of a real chemical
设计模拟自然光合作用的光暗耦合机制的储能材料是能量转换领域的一个关键挑战。目前用于光电催化应用的催化剂,即半导体、金属有机框架(MOFs)和有机光催化剂,显示出特定材料的固有局限性。在本研究中,我们开发了一系列多孔配位笼(PCCs),命名为PCCs -X(其中X= 6,7,8),具有极其罕见的光充电特性,可以加速辐照后黑暗期的各种反应。在辐照期间,PCC激活碳氢化合物的C(sp3)-H键,迅速生成氢过氧化物并将能量储存在那里,形成THF-OOH@PCC-X。随着PCC-6吩噻嗪核心的硫原子逐渐氧化为亚砜(PCC-7)和砜(PCC-8),后者由于其正价带值最高而表现出优异的氧化性能。在暗期,THF-OOH@PCC-8不仅催化了C-S、O-S、S-S和N-S键的形成,而且还促进了一种真正的化学武器剂(o -乙基- s -[2-(二异丙基氨基)乙基]甲基膦硫酸盐,VX)的快速解毒。这项工作引入了第一个能够耦合光和暗反应的分子笼,提供了一种通过在异常活跃的物种中有效储存光能来模拟光合作用的新方法。
{"title":"Hydroperoxide-Mediated Photochargeable Molecular Cage for Post-Irradiation Dark Catalysis","authors":"Jiang-Pei Yuan, Zong-Jie Guan, Wen-Ting Li, Ling Yuan, Hang Xing, Abdullah M. Al-Enizi, Ayman Nafady, He Zheng, Shengqian Ma, Yu Fang","doi":"10.31635/ccschem.025.202506995","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506995","url":null,"abstract":"Designing energy-storage materials that mimic the light-dark coupling mechanism of natural photosynthesis represents a key challenge in the field of energy conversion. Current catalysts for photoelectrocatalytic applications, namely semiconductors, metal-organic frameworks (MOFs), and organic photocatalysts, display material-specific inherent limitations. In this study, we developed a series of porous coordination cages (PCCs), designated as &lt;b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"&gt;\u0000&lt;bold&gt;PCC-X&lt;/bold&gt;&lt;/b&gt; (where X=6, 7, 8), that exhibited extremely rare photochargeable property, which can accelerate a variety of reactions in the post-irradiation dark period. In the irradiation period, PCC activates the C(sp&lt;sup&gt;3&lt;/sup&gt;)-H bonds of hydrocarbons, rapidly generating hydroperoxides and stored the energy there, forming &lt;b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"&gt;\u0000&lt;bold&gt;THF-OOH@PCC-X&lt;/bold&gt;&lt;/b&gt;. With the sulfur atom in the phenothiazine core of the &lt;b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"&gt;\u0000&lt;bold&gt;PCC-6&lt;/bold&gt;&lt;/b&gt; gradually oxidized to sulfoxide (&lt;b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"&gt;\u0000&lt;bold&gt;PCC-7&lt;/bold&gt;&lt;/b&gt;) and sulfone (&lt;b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"&gt;\u0000&lt;bold&gt;PCC-8&lt;/bold&gt;&lt;/b&gt;), the latter exhibited superior oxidation properties, thanks to its highest positive valence band value. In the dark period, &lt;b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"&gt;\u0000&lt;bold&gt;THF-OOH@PCC-8&lt;/bold&gt;&lt;/b&gt; not only catalyzes the formation of C-S, O-S, S-S, and N-S bonds, but also facilitates the rapid detoxification of a real chemical","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"100 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461932","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
Elucidating the Sodium Insertion Mechanism of an Organic Electrode Material for Sodium-Ion Batteries 一种钠离子电池用有机电极材料的插钠机理研究
IF 11.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-13 DOI: 10.31635/ccschem.026.202507155
Maximillian G. Stanzione, Oxana V. Magdysyuk, Daniel J. M. Irving, Chinnasamy Murugesan, Nicole L. Kelly, Yingling Liao, Pech Thongkam, Heitor S. Seleghini, Paul S. Wheatley, David B. Cordes, Simon J. Coles, Daniel N. Rainer, Aamod V. Desai, Sharon E. Ashbrook, Julia L. Payne, Russell E. Morris, A. Robert Armstrong
Organic anode materials for sodium-ion batteries are attracting a great deal of interest due to their sustainability and design flexibility. However, the Na+ insertion mechanism is poorly understood, especially for disordered organic anode materials. A lack of understanding restricts optimization efforts and potential commercialization. Herein, we apply a range of characterization techniques, such as three-dimensional electron diffraction, powder X-ray diffraction, Raman spectroscopy, electron paramagnetic resonance spectroscopy, and pair distribution function (PDF) analysis to a model system, sodium naphthalene-2,6-dicarboxylate, to elucidate the Na+ storage mechanism. A combined ab initio random structure search and PDF study was conducted to postulate a structure of sodiated Na2+xNDC (s-NDC). Our work reveals an expansion in the Na+–O storage layer to allow for the accommodation of inserted Na+. Meanwhile, the naphthalene units exist as radical species, promoting a reorientation to accommodate the inserted Na+, as well as facilitating a stabilizing π interaction. Ultimately, our results illustrate the efficacy of using a multi-technique approach to study the sodiation mechanism of an organic anode material and offer insight into the sodiated structure. This approach can inform the strategic molecular design of future organic anode materials.
钠离子电池的有机负极材料由于其可持续性和设计灵活性而引起了人们的极大兴趣。然而,Na+的插入机制,特别是无序有机负极材料的插入机制尚不清楚。缺乏理解限制了优化工作和潜在的商业化。本文采用三维电子衍射、粉末x射线衍射、拉曼光谱、电子顺磁共振光谱和对分布函数(PDF)分析等表征技术对模型体系萘-2,6-二羧酸钠进行了表征,以阐明Na+的储存机制。采用从头算随机结构搜索和PDF相结合的方法,假设了一种介导Na2+xNDC (s-NDC)的结构。我们的工作揭示了Na+ -O存储层的扩展,以允许插入Na+的容纳。同时,萘单元以自由基形式存在,促进了取向的改变以容纳插入的Na+,并促进了π相互作用的稳定。最后,我们的结果说明了使用多技术方法研究有机阳极材料的调解机制的有效性,并提供了对调解结构的见解。这种方法可以为未来有机阳极材料的战略性分子设计提供信息。
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引用次数: 0
Late-Stage Cyclization of Natural Products and Drug Molecules Enabled by C–C Bond Cleavage of Aryl Ketones 芳基酮C-C键裂解导致天然产物和药物分子的后期环化
IF 11.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-12 DOI: 10.31635/ccschem.026.202507090
Xing Wang, Yu-Xi Li, Qing-Ying Zeng, Xin-Ming Yu, Tian-Qi Gao, Huan Liu, Ling-Xia Zhang, Hui Xu, Zhen-Yu Wang, Lefu Lan, Hui-Xiong Dai
We report herein an efficient palladium-catalyzed method for the construction of four- to eight-membered rings, including benzocyclobutene, indole, indene, indanone, naphthalene, phenanthrene, azepine, and azocine cores, on the aryl moiety of unstrained aryl ketones via C–C cleavage as the key step. A variety of cyclization products were synthesized with excellent functional-group tolerance and high regioselectivity, especially for unsymmetrical alkynes. The late-stage diversification of a series of natural products and pharmaceuticals highlights the synthetic utility of this methodology. Furthermore, multiple dehydroabietic acid-based derivatives were successfully constructed, leading to the rapid identification of several molecules with significantly enhanced antimicrobial activity.
本文报道了一种高效的钯催化方法,以C-C裂解为关键步骤,在未张力芳基酮的芳基部分上构建四至八元环,包括苯并环丁烯、吲哚、茚、茚酮、萘、菲、氮平和偶氮嘧啶核心。合成了多种具有良好官能团耐受性和高区域选择性的环化产物,特别是对不对称炔的环化产物。一系列天然产品和药品的后期多样化突出了这种方法的合成效用。此外,我们成功构建了多种脱氢枞酸衍生物,从而快速鉴定了几种具有显著增强抗菌活性的分子。
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引用次数: 0
Controlled Regulation of Cell Membrane Receptor Activation Using Programmable DNA Nano-modulators and Host–Guest Interactions 利用可编程DNA纳米调节剂和主-客体相互作用控制细胞膜受体激活的调控
IF 11.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-12 DOI: 10.31635/ccschem.026.202607341
Qingqing Zou, Bin Du, Jiayu Sun, Xiaohai Yang, Kemin Wang, Qing Wang
Nanoscale distribution of mesenchymal-to-epithelial transition factor (Met) on the cell surface is essential for intracellular signaling and cell behavior. Met oligomerization activates cell behavior, and ligand spacing is crucial to this activation mechanism. However, the optimal spatial distance for Met oligomerization-mediated activation remains unknown, hindering the design of related cellular function modulators. Herein, based on the programmability of aptamers, β-cyclodextrin (β-CD)-mediated DNA nano-modulators with different ligand spacings were designed to dynamically modulate the lateral distance between receptors on cell membranes, studying the effects of ligand distances on Met oligomerization activation. Four HCR-based DNA nano-modulators (S-HCR18/28/44/60) with 18–60 bp spacings were self-assembled via complementary base pairing. The results showed that DNA nano-modulators with 28- and 44- bp spacings were most effective in activating Met. This regulation was also designed to be reversible via competitive displacement of β-CD. For example, reversible Met activation was achieved using adamantane (Ada) to displace S-HCR28 and S-HCR44. Additionally, the four DNA nano-modulators had varying efficacy in repairing acetaminophen-induced liver injury, with S-HCR28 and S-HCR44 being more effective. This work could guide the design of efficient cellular receptor modulators and offer spatial distance insights for cell biology.
细胞表面间充质-上皮转化因子(Met)的纳米级分布对细胞内信号传导和细胞行为至关重要。Met寡聚化激活细胞行为,配体间距对这种激活机制至关重要。然而,Met寡聚化介导激活的最佳空间距离仍然未知,这阻碍了相关细胞功能调节剂的设计。本文基于适配体的可编程性,设计了不同配体间距的β-环糊精(β-CD)介导的DNA纳米调节剂,动态调节细胞膜上受体之间的横向距离,研究了配体间距对Met寡聚化活化的影响。通过互补碱基配对自组装了4个间隔为18 - 60bp的hcr基DNA纳米调节剂(S-HCR18/28/44/60)。结果表明,28- bp和44- bp的DNA纳米调节剂对激活Met最有效。这种调节也被设计为通过β-CD的竞争性位移可逆。例如,使用金刚烷(Ada)取代S-HCR28和S-HCR44实现了可逆的Met活化。此外,四种DNA纳米调节剂在修复对乙酰氨基酚诱导的肝损伤方面具有不同的效果,其中S-HCR28和S-HCR44的效果更好。这项工作可以指导有效的细胞受体调节剂的设计,并为细胞生物学提供空间距离的见解。
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引用次数: 0
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CCS Chemistry
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