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Photochemical Cyclization of α-Amino Esters to Access 3-Azetidinones α-氨基酯光化学环化制备3-叠氮二酮
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-03 DOI: 10.1039/d5sc09994c
Meemie U Hwang, Achyut R Gogoi, Matthew Scurria, Osvaldo Gutierrez, Karl A Scheidt
A light-driven cyclization of readily available a-amino esters to 3-azetidinones has been developed. This method leverages chromophore activation with the acyl imidazole to generate the triplet diradical species under mild conditions without the need for photosensitizers or transition metals. A selective hydrogen atom transfer event, followed by intramolecular Norrish-Yang radical coupling occurs to yield the N-heterocycle, with facile elimination of the imidazole group to access the 3-azetidinone. Computational calculations reveal the role of the protecting group in favoring the Norrish-Yang cyclization pathway.
已经开发了一种易于获得的A -氨基酯到3-叠氮二酮的光驱动环化。该方法利用与酰基咪唑的发色团活化,在温和的条件下产生三重态二自由基,而不需要光敏剂或过渡金属。一个选择性的氢原子转移事件,随后发生分子内的Norrish-Yang自由基偶联,生成n -杂环,咪唑基很容易消除,得到3-氮杂二酮。计算结果揭示了保护基团在有利于Norrish-Yang环化途径中的作用。
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引用次数: 0
Correction: Stapled histone H3 tails are super-substrates for lysine methyltransferase SETD7 更正:钉定组蛋白H3尾部是赖氨酸甲基转移酶SETD7的超底物
IF 7.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-03 DOI: 10.1039/D6SC90024K
Nurgül Bilgin, Laust Moesgaard, Jacob Kongsted and Jasmin Mecinović

Correction for ‘Stapled histone H3 tails are super-substrates for lysine methyltransferase SETD7’ by Nurgül Bilgin et al., Chem. Sci., 2026, https://doi.org/10.1039/d5sc08094k.

由nurg l Bilgin等人,Chem更正的“钉住的组蛋白H3尾部是赖氨酸甲基转移酶SETD7的超级底物”。科学。, 2026, https://doi.org/10.1039/d5sc08094k。
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引用次数: 0
Chirality-Induced Stereoselective Synthesis of Chiral sp2-Carbon-Conjugated Covalent Organic Frameworks 手性诱导立体选择性合成手性sp2-碳共轭共价有机骨架
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-03 DOI: 10.1039/d5sc09234e
Weijun Weng, Zihan Zhu, Xiaoyan Xu, Jia Guo
A fully conjugated sp2-carbon covalent organic framework (sp2C-COF) possessing global conformational chirality holds great promising for advanced electronic devices. However, the inherent irreversibility of many reactions hinders the chirality-induced synthesis of COFs from achiral building blocks. Herein, we address a chirality-induced linkage exchange strategy to fabricate a vinylene-linked chiral sp2C-COF via an irreversible Aldol reaction. The approach involves the pre-synthesis of a chiral Schiff-base precursor, followed by its acid-catalyzed conversion from imine to vinylene linkages. This chiral precursor induces the orientation of asymmetric vinylene linkages, enabling enantioselective formation of periodic frameworks. Through a self-template mechanism, the layered stacking amplifies the structural handedness and dominates the evolution of branched nanofibers. The resulting chiral sp2C-COF exhibits a high dissymmetry factor in circularly polarized luminescence along with a substantial quantum yield, achieving a superior Figure-of-Merit of up to 0.01. An ultrathin film of the chiral sp2C-COF is fabricated and implemented in an interdigitated capacitive sensor capable of simultaneous quantification and chiral recognition of tryptophan within the 10–40 µM range. This work not only provides a strategic pathway to overcome chiral propagation barriers in irreversible reactions but also contributes an emerging class of chiral two-dimensional carbon materials.
具有全局构象手性的完全共轭sp2-碳共价有机骨架(sp2C-COF)在先进电子器件中具有很大的应用前景。然而,许多反应固有的不可逆性阻碍了手性诱导的由非手性构建块合成COFs。本文提出了一种手性诱导的键交换策略,通过不可逆的Aldol反应制备乙烯连接的手性sp2C-COF。该方法包括手性希夫碱前驱体的预合成,然后将其酸催化从亚胺键转化为乙烯键。这种手性前体诱导不对称乙烯键的取向,使周期框架的对映选择性形成。通过自模板机制,层状堆叠增强了结构的手性,并主导了支化纳米纤维的演化。所得的手性sp2C-COF在圆极化发光中表现出很高的不对称因子,同时具有可观的量子产率,达到了高达0.01的优异品质系数。制备了一种手性sp2C-COF超薄薄膜,并在交叉电容式传感器中实现,该传感器能够在10-40µM范围内同时定量和手性识别色氨酸。这项工作不仅为克服不可逆反应中的手性传播障碍提供了一条战略途径,而且为一类新兴的手性二维碳材料做出了贡献。
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引用次数: 0
“DIVE” into hydrogen storage materials discovery with AI agents 与人工智能代理一起“潜入”发现储氢材料。
IF 7.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-03 DOI: 10.1039/D5SC09921H
Di Zhang, Xue Jia, Hung Ba Tran, Seong Hoon Jang, Linda Zhang, Ryuhei Sato, Yusuke Hashimoto, Toyoto Sato, Kiyoe Konno, Shin-ichi Orimo and Hao Li

Despite the surge of AI in energy materials research, fully autonomous workflows that connect high-precision experimental knowledge to the discovery of credible new energy-related materials remain at an early stage. Here, we develop the Descriptive Interpretation of Visual Expression (DIVE) multi-agent workflow, which systematically reads and organizes experimental data from graphical elements in scientific literature. Applied to solid-state hydrogen storage materials—a class of materials central to future clean-energy technologies—DIVE markedly improves the accuracy and coverage of data extraction compared to the direct extraction method, with gains of 10–15% over commercial models and over 30% relative to open-source models. Building on a curated database of over 30 000 entries from >4000 publications, we establish a rapid inverse-design AI workflow capable of proposing new materials within minutes. This transferable, end-to-end paradigm illustrates how multimodal AI agents can convert literature-embedded scientific knowledge into actionable innovation, offering a scalable pathway for accelerated discovery across chemistry and materials science.

尽管人工智能在能源材料研究中的应用激增,但将高精度实验知识与可靠的新能源相关材料的发现联系起来的完全自主的工作流程仍处于早期阶段。在这里,我们开发了视觉表达的描述性解释(DIVE)多智能体工作流,它系统地读取和组织科学文献中图形元素的实验数据。应用于固态储氢材料——一类未来清洁能源技术的核心材料——与直接提取方法相比,dive显著提高了数据提取的准确性和覆盖范围,比商业模型提高了10-15%,比开源模型提高了30%以上。基于bbbb4000出版物的30,000多个条目的策划数据库,我们建立了一个快速的反向设计AI工作流,能够在几分钟内提出新材料。这种可转移的端到端范式说明了多模式人工智能代理如何将文献嵌入的科学知识转化为可操作的创新,为加速化学和材料科学的发现提供了可扩展的途径。
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引用次数: 0
Subunit fusion unlocks rapid in vitro maturation for slowly activating heterodimeric [FeFe]-hydrogenases 亚基融合解锁体外快速成熟缓慢激活异二聚体[FeFe]-氢化酶
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-03 DOI: 10.1039/d5sc07299a
Martin Helmut Winkler, Jan Jaenecke, Konstantin Bikbaev, Julia Bronold, Shanika Yadav, Ulf-Peter Apfel, James A. Birrell, Ingrid Span, Nicolas Plumere, Christophe Léger, Miriam Malagnini
Hydrogenases offer a sustainable alternative to noble metals for catalyzing H₂-oxidation and H₂-production. The heterodimeric [FeFe]-hydrogenase of Desulfovibrio desulfuricans ATCC 7757 (DdHydAB) is most promising due to its exceptional catalytic activity and high-yield heterologous expression of its apo-form. Scalable production of the holo-form relies on in vitro maturation of the apo-enzyme using a chemically synthesized 2FeH cofactor mimic. However, the unusually slow in vitro maturation of DdHydAB raises mechanistic questions and limits its scalability. Through structural and sequence analysis, we identified the cause of this slow maturation and redesigned the enzyme via subunit fusion, inserting short peptide linkers near the active site. This modification facilitates the rearrangement of a critical locking element after cofactor uptake, increasing the maturation rate by up to 41-fold without compromising catalytic performance. Our findings elucidate a key step in the “plug-lock-lid” mechanism underlying maturation and promote the industrial applicability of DdHydAB.
氢化酶为催化氢氧化和氢生成提供了一种可持续的贵金属替代品。脱硫弧菌ATCC 7757 (DdHydAB)的异二聚体[FeFe]-氢化酶因其特殊的催化活性和载子形式的高产异源表达而最有前途。可扩展的生产全息形式依赖于载脂蛋白酶的体外成熟,使用化学合成的2FeH辅助因子模拟物。然而,DdHydAB异常缓慢的体外成熟引发了机制问题,并限制了其可扩展性。通过结构和序列分析,我们确定了这种缓慢成熟的原因,并通过亚基融合重新设计酶,在活性位点附近插入短肽连接物。这种修饰促进了辅因子摄取后关键锁定元件的重排,在不影响催化性能的情况下,将成熟率提高了41倍。我们的研究结果阐明了“plug-lock-lid”机制成熟的关键步骤,并促进了DdHydAB的工业适用性。
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引用次数: 0
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 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 SX 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 (1Bu+) state that form distorted SX and S1 (2Ag) intermediates. The SX state is assigned to optically forbidden 3Ag configuration rather than the earlier 1Bu or Ag+ 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 SX 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 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。
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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 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。
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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 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
In situ X-ray diffraction investigation of NiS x -formation on Ni-foam using chemical vapor deposition with H2S. H2S化学气相沉积法在泡沫镍上形成NiS x的原位x射线衍射研究。
IF 7.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-02 DOI: 10.1039/d5sc08479b
Soffi Ester Sola Olesen, Magnus Kløve, Anders Bæk Borup, Andreas Dueholm Bertelsen, Marcus Viktor Kragh-Schwarz, Thorbjørn Erik Køppen Christensen, Frederik Holm Gjørup, Mads Ry Vogel Jørgensen, Jacopo Catalano, Anders W Jensen, Bo B Iversen

Nickel foam treated via chemical vapor deposition (CVD) with H2S has demonstrated potential in applications such as supercapacitors and catalysis for alkaline water electrolysis. However, the formation mechanism of the nickel sulfide surface layer remains poorly understood. In this study, in situ powder X-ray diffraction (PXRD) was employed to identify the crystalline phase transformations and the reaction mechanism and assess its kinetics. Ni3S2 formation was investigated under industrially relevant conditions by passing 3% H2S/Ar through Ni foam and tracking the growth of the sulfided layer in relation to thickness and time. The reduced sulfidation rate observed at low flow, extended time, and greater depths indicated strong mass transfer limitations, whereas the pronounced increase between 90 and 170 °C revealed the high activation energy of the sulfidation process. A diffusion-reaction model is proposed to describe the spatial and time evolution of the Ni3S2 layer growth, assuming that H2S diffuses through the newly formed Ni3S2 layer before reacting at the Ni interface. The modelling results indicate that both the reaction and diffusion occur at fast rates and compete in the temperature range of 130-170 °C. Post-synthesis SEM and tomography analysis confirmed improved uniformity in nickel-sulfide layer thickness and extrusion coverage when the process is reaction limited rather than diffusion limited: either at synthesis temperatures below 130 °C or a higher flow rate at 130 °C. On the other hand, higher temperatures promote the formation of large NiS x extrusions. These results provide insight into the effect of the synthesis parameters on the microstructure and the formation of Ni3S2 and NiS x , providing fundamental physico-chemical and transport properties for process optimization and upscaling.

通过化学气相沉积(CVD)和H2S处理泡沫镍,在超级电容器和催化碱性电解等应用中显示出潜力。然而,硫化镍表面层的形成机制仍不清楚。在本研究中,采用原位粉末x射线衍射(PXRD)来鉴定晶体相变和反应机理,并评估其动力学。在工业相关条件下,通过3% H2S/Ar通过Ni泡沫,并跟踪硫化层的生长与厚度和时间的关系,研究了Ni3S2的形成。在低流量、长时间和深度下观察到的硫化速率降低表明了强烈的传质限制,而在90 ~ 170℃之间的显著增加表明了硫化过程的高活化能。假设H2S在Ni界面处发生反应前先扩散穿过新形成的Ni3S2层,提出了一种描述Ni3S2层生长的扩散-反应模型。模拟结果表明,在130 ~ 170℃的温度范围内,反应和扩散都以较快的速度发生。合成后的SEM和断层扫描分析证实,当反应限制而不是扩散限制时,无论是在低于130°C的合成温度下还是在130°C的更高流速下,硫化镍层厚度和挤压覆盖率的均匀性都得到了改善。另一方面,较高的温度促进形成大的NiS x挤压。这些结果揭示了合成参数对Ni3S2和nix的微观结构和形成的影响,为工艺优化和升级提供了基本的物理化学和输运性质。
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引用次数: 0
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