Chemical Science最新文献

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Dynamic-Structural-Distortion of Spheroidene Activates a Hidden 3Ag− State Mediating Carotenoid-to-Bacteriochlorophyll Energy Transfer in Light-harvesting 2 球形烯的动态结构扭曲激活了隐藏的3Ag -态介导的类胡萝卜素到细菌叶绿素的能量转移2

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-02-03 DOI: 10.1039/d5sc08508j

Bo Peng, Ming-Qing Chen, Tengfei Ma, Yi-Fan Huang, Peng Wang, Weimin Liu

Carotenoids extend the absorption range of photosynthesis and transfer excitation energy to (Bacterio-)chlorophylls with remarkable efficiency, yet the microscopic mechanism of this process, especially the role of the S_X intermediate remains unresolved. Here, we use femtosecond stimulated Raman spectroscopy, whose high vibrational frequency and temporal resolutions enable direct tracking of excited-state intermediates and their symmetry characteristics. By probing spheroidene in both solution and light-harvesting 2 complex of Rhodobacter sphaeroides, we reveal structural change in S₂ (1B_u⁺) state that form distorted S_X and S₁ (2A_g⁻) intermediates. The S_X state is assigned to optically forbidden 3A_g⁻ configuration rather than the earlier 1B_u⁻ or A_g⁺ proposals, and is identified as an efficient pathway for energy transfer to bacteriochlorophylls. The spheroidene-to-bacteriochlorophyll energy transfer efficiencies are quantified as 32% via S_X state, combine with 50% from the S2 state and 12% from the S₁ state, yielding an overall transfer efficiency of 94%, in excellent agreement with previous reports. We propose that the observed structural distortions of spheroidene dynamically enhance Coulombic coupling with surrounding bacteriochlorophylls, which may underlie the remarkably high efficiency of excitation energy transfer.

类胡萝卜素扩展了光合作用的吸收范围，并以显著的效率将激发能传递给（细菌-）叶绿素，但这一过程的微观机制，特别是SX中间体的作用尚未明确。在这里，我们使用飞秒受激拉曼光谱，其高振动频率和时间分辨率可以直接跟踪激发态中间体及其对称性特征。通过探测球形红杆菌溶液和光收集2配合物中的球状体，我们揭示了S2 （1Bu+）态的结构变化，形成扭曲的SX和S1 （2Ag−）中间体。SX态被分配到光学禁止的3Ag -构型，而不是先前的1Bu -或Ag+构型，并且被确定为能量转移到细菌叶绿素的有效途径。通过SX态，球粒到细菌叶绿素的能量转移效率被量化为32%，再加上50%的S2态和12%的S1态，总转移效率为94%，与之前的报道非常一致。我们认为，观察到的球状体结构扭曲动态地增强了与周围细菌叶绿素的库仑耦合，这可能是激发能转移效率显著提高的基础。

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引用次数: 0

Single-Crystal-Ordered-Mesoporous Metal Nitrides without Intrinsic Raman Signals for Highly Sensitive SERS Detection 无本征拉曼信号的单晶有序介孔金属氮化物用于高灵敏度SERS检测

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-02-03 DOI: 10.1039/d5sc09344a

Linchangqing Yang, Yijing Zong, Meng Yin, Wencai Yi, Jungfang Li, Jie Lin, Qinghong Kong, Guangcheng Xi

The formation of transition metal nitrides (TMNs) necessitates overcoming extremely high reaction barriers, which renders the precise synthesis of TMN materials with tailored structures a significant challenge. Herein, we propose a molten-salt/template strategy for the accurate customization of TMNs featuring a rare single-crystal ordered mesoporous (SCOM) structure. By leveraging this strategy, 5 types of SCOM-structured TMNs—including WN, MoN, TiN, VN, and CoN were synthesized. Hydroxylation of templates and the subsequent formation of SCOM-structured metal oxides were identified as the key factors governing the formation of SCOM-TMNs. Interestingly, these SCOM-structured WN lack the intrinsic Raman signals typically possessed by non-metallic materials, effectively resolving the long-standing issue of background interference in non-metallic surface-enhanced Raman scattering (SERS) substrates. The WN substrate achieves an ultrahigh Raman enhancement factor of up to 7.5×10⁷ and an ultralow detection limit of 1×10⁻¹² M.

过渡金属氮化物（TMNs）的形成需要克服极高的反应障碍，这使得具有定制结构的TMN材料的精确合成成为一项重大挑战。在此，我们提出了一种熔融盐/模板策略，用于精确定制具有罕见单晶有序介孔（SCOM）结构的TMNs。利用这一策略，合成了5种scom结构的tmn，包括WN、MoN、TiN、VN和CoN。模板的羟基化和随后形成的scom结构金属氧化物被认为是控制scom - tmn形成的关键因素。有趣的是，这些scom结构的纳米材料缺乏非金属材料通常具有的本征拉曼信号，有效地解决了非金属表面增强拉曼散射（SERS）衬底中长期存在的背景干扰问题。WN衬底实现了高达7.5×10⁷的超高拉曼增强因子和1×10⁻¹²M的超低检测限。

引用次数: 0

Identifying Phase Transitions in Zeolitic Imidazolate Frameworks: Microscopic Insight from Molecular Simulations 识别沸石咪唑盐框架的相变：分子模拟的微观洞察

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-02-03 DOI: 10.1039/d5sc09468b

Léna Triestram, François-Xavier Coudert

Metal–organic frameworks (MOFs) feature a rich structural diversity, including crystalline, amorphous, and liquid phases of varying topologies. Their structural characterization is often performed either at the local scale (through pair distribution functions, bond angle distributions, etc.) or, for crystalline phases, through topology analysis of the periodic framework — leaving out disordered and amorphous phases. In this work, we develop a computational methodology for the structural characterization of middle-range order in MOFs that is applicable to both crystalline and amorphous phases. We base our method on the statistical analysis of the geometry of the supramolecular framework at the microscopic level, and its evolution during molecular simulation. We analyze the statistics of metal–organic rings, their distribution in size, as well as their geometrical characteristics through mathematical tools derived from polymer physics: radius of gyration, asphericity, and writhe. We show that this advanced characterization can be leveraged for the identification of phases and the detection and analysis of phase transitions.

金属有机骨架（mof）具有丰富的结构多样性，包括不同拓扑结构的结晶、非晶和液相。它们的结构表征通常是在局部尺度上进行的（通过对分布函数、键角分布等），或者对于结晶相，通过周期性框架的拓扑分析进行，忽略无序相和非晶态相。在这项工作中，我们开发了一种适用于晶体和非晶相的mof中阶结构表征的计算方法。我们的方法基于在微观水平上对超分子框架的几何结构及其在分子模拟过程中的演化进行统计分析。我们分析了金属有机环的统计数据，它们在尺寸上的分布，以及它们的几何特征，通过来自聚合物物理学的数学工具：旋转半径，非球面，和扭曲。我们表明，这种先进的表征可以用于相位的识别和相位转变的检测和分析。

引用次数: 0

Pd-Catalyzed Stereospecific Synthesis of Reversed C-Acyl Glycosides: Access to Rare L-Sugars and Higher-Carbon Sugars pd催化立体定向合成逆转c -酰基糖苷：获得稀有l糖和高碳糖

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-02-02 DOI: 10.1039/d5sc08224b

Guoqiang Cheng, Bo Yang, Feng Zhu

Reversed C-acyl glycosides represent a versatile class of nonclassical glycosides with potential in complex carbohydrate synthesis, including L-sugars, higher-carbon sugars, and medicinal chemistry. Conventional strategies for L- and higher-carbon sugars are limited by multi-step protection–deprotection sequences and poor stereocontrol. Herein, we report a general Pd-catalyzed reversed acyl C-glycosylation that efficiently couples configurationally stable reversed glycosyl stannanes with C(sp²)- and C(sp³)-derived thioesters under mild conditions. The reaction proceeds with complete stereoretentive transfer, enabling precise access to both D- and L-type glycosides, including higher-carbon sugar derivatives and C-ferrocenecarbonyl glycosides. The broad substrate scope, excellent functional group tolerance, and predictable stereochemical outcome highlight the robustness and synthetic versatility of this approach. Applications of the resulting reversed C-acyl glycosides as chiral synthons enable D-to-L interconversion, construction of L-sugar analogues, and derivatization toward designer carbohydrate frameworks. Importantly, this transformation enables a distinct D-to-L conversion featuring simultaneous C4 and C5 inversion, unlike conventional methods that modify only C5 configuration. Overall, this protocol establishes a general platform for stereocontrolled construction and diversification of structurally defined nonclassical glycosides, providing a foundation for glycodiversification, complex sugar synthesis, and exploration of biologically relevant C-glycosyl scaffolds.

反相c -酰基糖苷代表了一类多用途的非经典糖苷，在复杂碳水化合物合成中具有潜力，包括l糖、高碳糖和药物化学。L-和高碳糖的传统策略受到多步骤保护-去保护序列和较差的立体控制的限制。在这里，我们报道了一个一般的pd催化的反酰基C-糖基化，在温和的条件下，有效地将构型稳定的反糖基锡烷与C（sp²）-和C（sp³）-衍生的硫酯偶联。反应以完整的立体定向转移进行，可以精确地获得D型和l型糖苷，包括高碳糖衍生物和c -二茂铁羰基糖苷。广泛的底物范围、优异的官能团耐受性和可预测的立体化学结果突出了这种方法的稳健性和合成的多功能性。将得到的逆转c -酰基糖苷用作手性合成物，可以实现D-to-L的相互转化，构建l糖类似物，并衍生为设计碳水化合物框架。重要的是，与仅修改C5配置的传统方法不同，这种转换实现了独特的d - l转换，同时实现了C4和C5的反演。总体而言，该方案为结构定义的非经典糖苷的立体控制构建和多样化建立了一个通用平台，为糖多样化、复合糖合成和探索生物相关的c -糖基支架奠定了基础。

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引用次数: 0

Positioning versatile inorganic cathode materials in the aqueous zinc-ion battery landscape. 定位多功能无机正极材料在水性锌离子电池领域的地位。

IF 7.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-02-02 DOI: 10.1039/d5sc09531j

Kang Guo, Yaokang Lv, Ziyang Song, Lihua Gan, Mingxian Liu

Rechargeable aqueous zinc-ion batteries (AZIBs) have attracted great attention due to their inherent advantages such as high safety, low cost, and environmental friendliness, making them one of the most promising alternatives to traditional lithium-ion batteries. The rational design and continuous optimization of versatile inorganic cathode materials play a crucial role in achieving practical applications. In this review, we first systematically classify inorganic cathode materials and their design strategies, including manganese oxides with rich redox chemistry, vanadium compounds with multiple oxidation states, Prussian blue analogues with open skeleton channels, layered transition metal disulfides with unique interlayer ion storage capabilities, and halogens with reversible multielectron capacity. Furthermore, the structural characteristics, electrochemical performances, and crucial improvement methods of these cathode materials are discussed in detail. Finally, we outline the challenges and the prospects of inorganic cathodes in AZIBs to guide the future development of next-generation energy communities.

可充水锌离子电池（azib）以其高安全性、低成本、环保等固有优势而备受关注，成为传统锂离子电池最有前途的替代品之一。通用无机正极材料的合理设计和不断优化对实现实际应用起着至关重要的作用。本文首先对无机正极材料及其设计策略进行了系统的分类，包括具有丰富氧化还原化学性质的锰氧化物、具有多种氧化态的钒化合物、具有开放骨架通道的普鲁士蓝类似物、具有独特层间离子存储能力的层状过渡金属二硫化物以及具有可逆多电子容量的卤素。此外，还详细讨论了这些阴极材料的结构特点、电化学性能和关键改进方法。最后，我们概述了无机阴极在azib中的挑战和前景，以指导下一代能源社区的未来发展。

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引用次数: 0

Resolving Sequential Electron-Proton Transfer Kinetics for Electrochemical CO2 Reduction at Cu(100)/H2O interface via a Quantum-Classical Framework 用量子-经典框架解析Cu(100)/H2O界面CO2电化学还原的序序电子-质子转移动力学

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-02-02 DOI: 10.1039/d5sc07385e

Yun Yang, Gang Fu

Electron-transfer (ET) and proton-transfer (PT) events occurring at electrochemical interfaces ultimately dictate the efficiency of electrocatalytic energy conversion and chemical synthesis. Despite their significance, a unified theoretical description of ET/PT dynamics has been challenging due to the entangled electronic, nuclear, and solvent degrees of freedom. Herein, we present a quantum-classical multiscale framework integrating constrained density functional theory (CDFT) with machine learning accelerated molecular dynamics (MLMD) to investigate ET and PT during electrochemical CO₂ reduction on Cu(100) in explicit water. Distinct ML potentials are trained for the adiabatic ground state and for two charge-localized diabatic states, enabling efficient configurational sampling while preserving quantum-mechanical fidelity in electronic energies and forces. The derived diabatic free energy surfaces reveal that CO₂ first undergoes inner-sphere ET to yield chemisorbed CO₂^-, followed by PT to form*COOH. Solvent reorganization imposes kinetic constraints on the ET step yet counterintuitively stabilizes the *CO₂^- intermediate through ion-dipole interactions, modulating the vibronic couplings. For PT, solvent relaxation dynamically adjusts the equilibrium donor-acceptor distance, thereby augmenting the Franck-Condon overlap between reactant and product vibronic wavefunctions in excited proton vibrational states, which facilitates nonadiabatic transitions across diabatic surfaces. Rate constants extracted by combining diabatic vibronic PCET theory with generalized Langevin equation-derived Grote-Hynes theory show that the sequential ET-PT pathway outpaces concerted PCET by about 5 orders of magnitude. This methodology establishes a robust paradigm for dissecting ET and PT kinetics at electrochemical interfaces, emphasizing the interplay of quantum nuclear effects, vibronic coupling, and solvent fluctuations.

发生在电化学界面上的电子转移（ET）和质子转移（PT）事件最终决定了电催化能量转换和化学合成的效率。尽管它们具有重要意义，但由于纠缠的电子、核和溶剂自由度，对ET/PT动力学的统一理论描述一直具有挑战性。在此，我们提出了一个量子经典多尺度框架，将约束密度泛函理论（CDFT）与机器学习加速分子动力学（MLMD）相结合，研究了显式水中Cu（100）的电化学CO2还原过程中的ET和PT。对于绝热基态和两个电荷局域的绝热状态，不同的ML势被训练，实现有效的配置采样，同时保持电子能量和力的量子力学保真度。得到的非绝热自由能面表明，CO2首先在球内发生ET反应生成化学吸附的CO2-，然后发生PT反应生成*COOH。溶剂重组对ET步骤施加了动力学约束，但与直觉相反，通过离子-偶极子相互作用，调节了振动耦合，稳定了*CO2-中间体。对于PT，溶剂弛豫动态调节平衡供体-受体距离，从而增加反应物和产物在激发态振动波函数之间的frank - condon重叠，从而促进非绝热表面上的非绝热转变。结合非绝热振动PCET理论和广义Langevin方程推导的Grote-Hynes理论提取的速率常数表明，序贯ET-PT途径比协同PCET约快5个数量级。该方法建立了一个强大的范例，用于解剖电化学界面上的ET和PT动力学，强调量子核效应，振动耦合和溶剂波动的相互作用。

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引用次数: 0

Beyond 800 nm: Recent Progress in High-Performance Near-Infrared Thermally Activated Delayed Fluorescence Based OLEDs 800nm以上：高性能近红外热激活延迟荧光oled的最新进展

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-02-02 DOI: 10.1039/d5sc09087c

Shuo Li, Xiangyu Zhou, Lingjie Xu, Chao Yu, Junteng Liu, Shouke Yan, Zhongjie Ren

Near-infrared (NIR) thermally activated delayed fluorescence (TADF) materials with emission peaks beyond 800 nm have attracted considerable attention owing to their potential applications in bioimaging, optical communication, and night-vision technologies. However, their development remains limited by the energy gap law, which leads to severe non-radiative decay and low external quantum efficiencies. In recent years, researchers have broken through these bottlenecks by employing various molecular design strategies, such as modulating charge-transfer characteristics and reducing the singlet–triplet energy splitting. These efforts have enabled the realization of efficient TADF emission extending into the deep NIR region. In this review, we summarize recent advances in NIR TADF emitters with emission maxima beyond 800 nm, focusing on their molecular design principles, photophysical properties, and device performance, and discuss future perspectives for achieving high-efficiency deep-NIR OLEDs.

近红外（NIR）热激活延迟荧光（TADF）材料由于其在生物成像、光通信和夜视技术中的潜在应用而引起了人们的广泛关注。然而，它们的发展仍然受到能量缺口定律的限制，这导致了严重的非辐射衰变和低的外量子效率。近年来，研究人员通过采用各种分子设计策略，如调制电荷转移特性和减少单重态-三重态能量分裂，突破了这些瓶颈。这些努力已经实现了有效的TADF发射延伸到深近红外区域。在这篇综述中，我们总结了最大发射波长超过800 nm的近红外TADF发射器的最新进展，重点介绍了它们的分子设计原理、光物理性质和器件性能，并讨论了实现高效深近红外oled的未来前景。

引用次数: 0

3D self-assembly of cyclic peptides into multilayered nanosheets 环状肽的三维自组装成多层纳米片

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-02-02 DOI: 10.1039/d5sc09489e

Sandra Díaz, Adrian Sanchez-Fernandez, Juan R Granja, Ignacio Insua, Javier Montenegro

The hierarchical self-assembly of three-dimensional (3D) supramolecular materials presents a significant challenge in molecular design. This process requires monomers with specific packing geometries and orthogonal contacts to enable multidimensional elongation. Here, we describe a new cyclic peptide design that allows hierarchical self-assemblyin all three spatial dimensions to produce nanosheets composed of ordered nanotube layers. The uniformity of the nanosheet aspect ratio and thickness is consistent with the high packing order of the monomers observed in this 3D assembly.

三维（3D）超分子材料的分层自组装是分子设计中的一个重大挑战。该工艺要求单体具有特定的包装几何形状和正交接触，以实现多维延伸。在这里，我们描述了一种新的环状肽设计，允许在所有三个空间维度上分层自组装，以产生由有序纳米管层组成的纳米片。纳米片宽高比和厚度的均匀性与在三维组装中观察到的单体的高堆积顺序一致。

引用次数: 0

Cobalt-mediated structural transition: facilitating rapid synthesis and enhanced performance of pyrochlore materials for efficient water electrolysis. 钴介导的结构转变：促进快速合成和提高高效水电解焦绿盐材料的性能。

IF 7.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-02-02 DOI: 10.1039/d5sc09343k

Yanzong Huang, Tongtong Liu, Qingren Zhang, Yanfei Wang, Zhengping Zhang, Feng Wang

Vacancies, which inevitably exist in all solids, influence numerous atomic behaviors and material properties and play a crucial role in both synthesis processes and application performance. In this study, we present a successful approach utilizing the flexible transition between [CoO₄] and [CoO₆] polyhedra to modulate the oxygen vacancies for further controlling the formation of ruthenate pyrochlores and enhancing the electrocatalytic performance for the oxygen evolution reaction. During the formation of the pyrochlore phase, the incorporation of [CoO₄] tetrahedra introduces an inherent oxygen deficiency, accompanied by the beneficial transformation of [CoO₄] tetrahedra into [CoO₆] octahedra. It kinetically accelerates the diffusive reaction rate constant by 164 times. On the other hand, during the oxygen evolution process by the lattice oxygen mediated mechanism, the flexible transformation between [CoO₆] octahedra and [CoO₄] tetrahedra in pyrochlores can effectively mitigate lattice distortions and suppress the metal-insulator transition induced by atomic rearrangements, thereby significantly enhancing the service life of this multicomponent electrocatalyst in proton and anion exchange membrane water electrolysis applications.

所有固体中都不可避免地存在着空位，空位影响着许多原子行为和材料性能，在合成过程和应用性能中都起着至关重要的作用。在这项研究中，我们提出了一种成功的方法，利用[CoO4]和[CoO6]多面体之间的柔性过渡来调节氧空位，从而进一步控制钌酸盐焦绿石的形成，提高析氧反应的电催化性能。在焦绿盐相的形成过程中，[CoO4]四面体的掺入引入了固有的缺氧，伴随着[CoO4]四面体向[CoO6]八面体的有益转化。它在动力学上使扩散反应速率常数提高了164倍。另一方面，在以晶格氧为媒介的析氧过程中，焦绿石中[CoO6]八面体和[CoO4]四面体之间的柔性转变可以有效地减轻晶格畸变，抑制原子重排引起的金属-绝缘体跃迁，从而显著提高该多组分电催化剂在质子和阴离子交换膜电解中的使用寿命。

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引用次数: 0

Achieving (quasi)-monocoordination in metal complexes with an exceptionally bulky carbene ligand 实现（准）单配位的金属配合物与一个特别大的碳配体

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-02-02 DOI: 10.1039/d5sc09514j

Ludwig Zapf, Eric Rivard

Bulky N-heterocyclic carbenes (NHCs) are powerful tools for controlling the coordination environment and reactivity at inorganic elements. Herein, we report an exceptionally bulky NHC, ^BnITr (^BnITr = [(C₆H₄){NCPh₃}₂C:]), which features a percent buried volume (%V_bur) that exceeds 60%. The steric and electronic properties of ^BnITr were elucidated through a combined experimental and computational study focused on selected silver, gold, and rhodium complexes. The structural impact of the benzylated backbone in ^BnITr leads to the positioning of phenyl rings within the flanking N-trityl (CPh₃, Tr) groups in close proximity to the carbene donor center, enabling the isolation/stabilization of hitherto elusive examples of (quasi)-monocoordinated lithium and gallium(I) cations. Attempts to generate the one-coordinate Pd(0) complex, [^BnITr−Pd], led to an unusual redox-triggered ligand activation/−CPh₃ group migration to palladium.

大体积n -杂环碳烯（NHCs）是控制无机元素配位环境和反应活性的有力工具。在此，我们报告了一个异常庞大的NHC， BnITr (BnITr = [(C6H4){NCPh3}2C:])，其特征是埋藏体积（%Vbur）超过60%。通过对选定的银、金和铑配合物的实验和计算研究，阐明了BnITr的空间和电子性质。BnITr中苯基化主链的结构影响导致苯基环位于靠近碳供体中心的侧翼n -三烷基（CPh3, Tr）基团内，使得迄今为止难以捉摸的（准）单配位锂和镓(I)阳离子的分离/稳定成为可能。试图生成单坐标Pd(0)配合物[BnITr - Pd]，导致了不寻常的氧化还原触发配体激活/ - CPh3基团向钯的迁移。

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引用次数: 0

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