Chinese Chemical Letters最新文献_第4页

Recent advances in carbon dots imaging at the subcellular level: Synthesis strategies, properties, and organelle imaging 亚细胞水平碳点成像的最新进展：合成策略、性质和细胞器成像

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-10-14 DOI: 10.1016/j.cclet.2025.111957

Xinjuan He , Zishuo Wang , Boyang Wang , Yongqiang Zhang , Xiaokai Xu , Huijuan Cai , Siyu Lu

Carbon dots (CDs), a class of emerging fluorescent nanomaterials, have garnered notable attention in the biomedical field owing to their outstanding photoluminescence properties, excellent biocompatibility, and ease of synthesis and functionalization. Recently, numerous CDs have been developed that allow precise subcellular localization through surface modifications or covalent conjugation with targeting ligands such as peptides, small molecules, Golgi-specific agents, and cell membrane-specific agents. This review begins with an overview of the synthesis strategies of CDs, highlighting their exceptional optical properties, stability, biocompatibility, and significance for subcellular imaging. The mechanisms by which CDs target specific organelles, including the nucleus, mitochondrion, lysosomes, Golgi apparatus, and cell membrane, are discussed. These mechanisms include specific targeting molecules, pH-sensitive targeting, charge-driven interactions, and hydrophobic and hydrophilic dynamics. Furthermore, we summarize their applications in subcellular imaging, such as the long-term dynamic monitoring of organelles, sensing, reactive oxygen species scavenging, and therapy. By presenting a comprehensive review of CDs in subcellular imaging, we aim to pave the way for further development of CDs in bioimaging and related biomedical applications.

碳点（CDs）是一类新兴的荧光纳米材料，因其优异的光致发光性能、良好的生物相容性以及易于合成和功能化而在生物医学领域受到广泛关注。最近，已经开发了许多cd，通过表面修饰或与靶向配体（如肽、小分子、高尔基特异性药物和细胞膜特异性药物）的共价偶联，可以实现精确的亚细胞定位。本文首先综述了CDs的合成策略，重点介绍了它们卓越的光学特性、稳定性、生物相容性和对亚细胞成像的意义。讨论了CDs靶向特定细胞器的机制，包括细胞核、线粒体、溶酶体、高尔基体和细胞膜。这些机制包括特异性靶向分子、ph敏感靶向、电荷驱动相互作用以及疏水和亲水动力学。此外，我们总结了它们在亚细胞成像中的应用，如细胞器的长期动态监测、传感、活性氧清除和治疗。通过对亚细胞成像中cd的全面综述，我们旨在为cd在生物成像和相关生物医学应用中的进一步发展铺平道路。

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引用次数: 0

Host-guest interaction mediated low-shrinkage photosensitive positioning adhesive 主客体相互作用介导的低收缩光敏定位胶

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-10-13 DOI: 10.1016/j.cclet.2025.111949

Zhao Liu , Junjian Xie , Xiaoming Ren , Muhammad Tahir , Shixin Fa , Qiuyu Zhang

As a common electronic adhesive, ultraviolet (UV) curing polyurethane acrylate adhesive has both flexibility and wear resistance of polyurethane, excellent weather resistance and optical properties of acrylate. Despite the extensive applications, it is still difficult to solve the problems caused by the shrinkage of adhesive. Here, a new type of photosensitive adhesive for bonding electronic components based on supramolecular interaction was designed and synthesized. The supramolecular interaction of cyclodextrin and adamantane moieties introduced into the adhesive polymer entitles the viscosity of the adhesive to rise rapidly during use, thereby preventing adhesive loss and dislocation of electronic components. UV light could further cure the adhesive and position the electronic components. The adhesive shrunk <2 % when cured by UV light, so it can be used for electronic packaging and high-resolution, defect-free lithography.

紫外线固化聚氨酯丙烯酸酯胶粘剂是一种常用的电子胶粘剂，它既具有聚氨酯的柔韧性和耐磨性，又具有丙烯酸酯优异的耐候性和光学性能。尽管得到了广泛的应用，但由于胶粘剂的收缩引起的问题仍然难以解决。本文设计并合成了一种基于超分子相互作用的新型电子元件光敏胶粘剂。在胶粘剂聚合物中引入环糊精和金刚烷基团的超分子相互作用，使胶粘剂的粘度在使用过程中迅速上升，从而防止了胶粘剂的损失和电子元件的错位。紫外线可以进一步固化胶粘剂和定位电子元件。该胶粘剂经紫外光固化后可收缩<；2 %，因此可用于电子封装和高分辨率，无缺陷光刻。

引用次数: 0

Enhanced structural coloration and thermal management via hydrophobic force-driven colloidal photonic crystals 通过疏水性力驱动的胶体光子晶体增强结构着色和热管理

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-10-12 DOI: 10.1016/j.cclet.2025.111947

Xiaoqing Yu , Jie Ren , Nianxiang Zhang , Zirong Li , Kebing Chen , Jiazhuang Guo , Su Chen , Guoxing Li , Chang Liu

Developing passive cooling materials with dual functionality of high-performance thermal management and aesthetic appeal remains a critical challenge for sustainable development. Here, we present a hydrophobic force-driven assembly strategy to construct crack-free colloidal photonic crystals (CPCs) for colored passive daytime cooling (PDC) textiles. Monodispersed poly(styrene-hydroxypropyl acrylate-hexafluorobutyl methacrylate) (P(St-HPA-HFBMA)) colloidal particles with low surface energy (9 mN/m) and high monodispersity (PDI < 0.05) are synthesized via soap-free emulsion polymerization. The hexafluorobutyl terminal groups (C₃F₆) enable robust hydrophobicity (water contact angle: 124°), facilitating crack-free CPC assembly through hydrophobic driving force. By integrating the CPCs with SiO₂ aerogel-embedded polyethylene oxide (PEO/SiO₂ aerogel) fiber scaffold based on microfluidic spinning technology, a colored hybrid composite film is fabricated, achieving 0.76 solar reflectance and 0.84 thermal emissivity in the atmospheric window (8-13 μm). Outdoor evaluations demonstrate a sub-ambient cooling temperature of 4.1 °C under 732 W/m² solar intensity, reaching the desirable level of PDC materials. The hybrid composite film also exhibits angle-independent structural colors, mechanical robustness (tensile strength: 1.86 MPa), and scalable manufacturability. This work provides a paradigm for multifunctional PDC systems combining aesthetic versatility with sustainable cooling performance.

开发具有高性能热管理和美观双重功能的被动冷却材料仍然是可持续发展的关键挑战。在这里，我们提出了一种疏水力驱动的组装策略，以构建用于彩色被动日间冷却（PDC）纺织品的无裂纹胶体光子晶体（cpc）。采用无皂乳液聚合法制备了低表面能（9 mN/m）、高单分散性（PDI < 0.05）的单分散聚（苯乙烯-丙烯酸羟丙基-甲基丙烯酸六氟丁酯）(P（St-HPA-HFBMA）胶体颗粒。六氟丁基末端基团（C3F6）具有强大的疏水性（水接触角：124°），通过疏水驱动力促进无裂纹CPC组装。基于微流控纺丝技术，将聚苯乙烯与SiO2气凝胶包埋聚乙烯氧化物（PEO/SiO2气凝胶）纤维支架相结合，制备了彩色杂化复合膜，在大气窗口（8 ~ 13 μm）内太阳反射率为0.76，热发射率为0.84。室外评估表明，在732 W/m²太阳强度下，亚环境冷却温度为4.1°C，达到了PDC材料的理想水平。混合复合薄膜还具有与角度无关的结构颜色、机械坚固性（抗拉强度：1.86 MPa）和可扩展制造性。这项工作为多功能PDC系统提供了一个范例，将美观的多功能性与可持续的冷却性能相结合。

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引用次数: 0

Ion-cluster-optimized microphase separation in shape-memory polydisulfides for enhanced mechanical performance 形状记忆聚二硫化物中离子簇优化微相分离增强机械性能

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-10-12 DOI: 10.1016/j.cclet.2025.111946

Chengyuan Yu , Huiyao Lin , Le Li , Ruirui Gu , Qi Zhang , Chenyu Shi , Chenchen Zhang , Fei Tong

Developing advanced polymeric materials with enhanced mechanical properties and functionalities has been a long-standing goal in materials science. Recently, supramolecular polymeric materials (SPMs) have drawn increased attention due to their unique properties and potential applications in self-healing, shape memory, sensors, and flexible electronics. Here, we develop an ionic cluster-optimized microphase separation strategy to enhance the toughening and energy dissipation capabilities of polydisulfide-based supramolecular polymers. The mechanical properties, including Young's modulus and toughness, are significantly improved by integrating the quadruple H-bonding 2-ureido-4-pyrimidone (UPy) induced microphase separation with iron(III)-to-carboxylate ionic clusters. By combining established chemical approaches with adjustable polymer phase ratios, it is revealed that the synergistic effect of these factors expands the interchain spacing, facilitates the formation of microphase domains, and enhances the tolerance of polythioctic acid-based polymers to external mechanical and thermal stimuli, meeting the practical requirements for industrial plastic applications. Moreover, the UPy-functionalized polymers incorporating iron carboxylate clusters exhibit good one-way shape memory behavior with practical applicability at a relatively low recovery temperature. Our work demonstrates a novel strategy for constructing industrially viable shape memory dynamic SPMs and paves the way for future innovations in developing SPMs.

开发具有增强机械性能和功能的先进聚合物材料一直是材料科学的长期目标。近年来，超分子高分子材料（SPMs）因其独特的性能和在自修复、形状记忆、传感器和柔性电子等领域的潜在应用而受到越来越多的关注。在这里，我们开发了一种离子簇优化的微相分离策略，以增强聚二硫基超分子聚合物的增韧和能量耗散能力。通过与铁(III)-羧酸离子团簇整合四氢键2-脲-4-嘧啶（UPy）诱导的微相分离，显著提高了材料的杨氏模量和韧性等力学性能。通过将已建立的化学方法与可调节的聚合物相比相结合，揭示了这些因素的协同效应扩大了链间间距，促进了微相域的形成，增强了聚硫辛酸基聚合物对外部机械和热刺激的耐受性，满足了工业塑料应用的实际要求。此外，含有羧酸铁簇的upy功能化聚合物具有良好的单向形状记忆行为，在相对较低的恢复温度下具有实际适用性。我们的工作展示了构建工业上可行的形状记忆动态spm的新策略，并为未来发展spm的创新铺平了道路。

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引用次数: 0

Polymer modification effects in nanocarrier-loaded dissolving microneedles: Implications for transdermal drug delivery 载纳米载体溶解微针中的聚合物修饰效应：对经皮给药的影响

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-10-11 DOI: 10.1016/j.cclet.2025.111944

Yuhuan Wu , Hoiian Ieong , Wenhao Wang , Chuanbin Wu , Anqi Lu , Xin Pan , Zhengwei Huang

Polymer surface modification constitutes a pivotal strategy for enhancing the efficacy of nanomedicine delivery, where intentional modifications (e.g., PEGylation, hyaluronic acid coating) are designed to optimize nanocarrier performance. However, conventional approaches remain constrained by the impermeable stratum corneum in transdermal applications. Dissolving microneedles (DMNs) circumvent this barrier by creating transient microchannels, thereby offering an innovative route for cutaneous nanocarriers administration. Nevertheless, the DMN polymeric matrix may unintentionally alter the physicochemical attributes of loaded nanocarriers via non-covalent interactions, giving rise to a distinct “polymer modification effect” (PME) that differs from purposeful surface engineering. Such unintended interfacial phenomena can modulate nanocarrier characteristics and, consequently, dictate their in vivo fate, including release kinetics, biodistribution, clearance, cellular uptake, and other interactions with the biological system. Herein, we review documented cases of DMN polymer-nanocarrier modifications, elucidate the underlying mechanisms and implications of PME, and propose rational strategies for its precise regulation. This conceptual framework is expected to guide the rational design of next-generation nanocarrier-loaded DMN delivery systems.

聚合物表面修饰是提高纳米药物递送效率的关键策略，其中有意修饰（例如聚乙二醇化，透明质酸涂层）旨在优化纳米载体的性能。然而，在透皮应用中，传统的方法仍然受到不渗透角质层的限制。溶解微针（DMNs）通过创建瞬时微通道绕过这一屏障，从而为皮肤纳米载体的给药提供了一种创新途径。然而，DMN聚合物基质可能会通过非共价相互作用无意中改变负载纳米载体的物理化学属性，从而产生不同于有目的的表面工程的独特的“聚合物修饰效应”（PME）。这种意想不到的界面现象可以调节纳米载体的特性，从而决定它们在体内的命运，包括释放动力学、生物分布、清除、细胞摄取以及与生物系统的其他相互作用。在此，我们回顾了DMN聚合物-纳米载体修饰的文献案例，阐明了PME的潜在机制和意义，并提出了精确调控的合理策略。这一概念框架有望指导下一代纳米载流子DMN递送系统的合理设计。

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引用次数: 0

Batch and continuous-flow asymmetric synthesis of d-pantothenic acid precursor enabled by immobilized ketoreductase mutant 固定化酮还原酶突变体批量连续不对称合成d-泛酸前体

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-10-11 DOI: 10.1016/j.cclet.2025.111945

Pan Hu , Xiaofan Wu , Yi An , Xianjing Zheng , Liang Gao , Yuan Tao , Yajiao Zhang , Zedu Huang , Fener Chen

We report an immobilized enzyme-catalyzed batch and continuous-flow synthesis of optically pure ethyl (R)-pantothenate ((R)-PaOEt), the direct precursor of d-pantothenic acid. Firstly, a ketoreductase mutant designated as M2, carrying two-point mutations of F97L and M242F relative to the wild-type SSCR, was constructed by site-directed mutagenesis, exhibited simultaneously improved activity toward ethyl 2′-ketopantothenate (K-PaOEt) and isopropanol, and could effectively catalyze the stereoselective reduction of K-PaOEt to (R)-PaOEt by using isopropanol as the sacrificial co-substrate to regenerate NADPH. After screening six commercially available carriers, an amino resin LXTE-700 was identified as the best solid support for the immobilization of M2 via the glutaraldehyde activation method. Upon optimization of the immobilization process and reaction conditions, the fabricated immobilized enzyme M2@amino resin demonstrated excellent recyclability and reusability, with the complete conversion of K-PaOEt to (R)-PaOEt being still realized after 12 cycles of reuse. Finally, M2@amino resin-catalyzed synthesis of (R)-PaOEt was successfully implemented in continuous-flow, accomplishing a 6.3 times higher space-time yield than that with the batch synthesis (529.2 versus 84 g L^-1 d^-1). Our developed flow biocatalysis system also features an outstanding operational stability, as evidenced by the 100 % conversion rate achieved after 15 consecutive days of operation.

我们报道了固定化酶催化分批和连续流合成光纯乙基(R)-泛酸酯（(R)-PaOEt）， d-泛酸的直接前体。首先，通过定点诱变构建了一个携带F97L和M242F位点突变的酮还原酶突变体M2，该突变体对2′-酮酸乙酯（K-PaOEt）和异丙醇的活性同时提高，并能通过异丙醇作为牺牲共底物再生NADPH，有效地催化K-PaOEt立体选择性还原为(R)-PaOEt。在筛选了6种市售载体后，通过戊二醛活化法确定了LXTE-700为固定M2的最佳固体载体。通过对固定化工艺和反应条件的优化，制备的固定化酶M2@amino树脂具有良好的可回收性和可重复使用性，在重复使用12次后仍可实现K-PaOEt完全转化为(R)-PaOEt。最终，M2@amino树脂催化合成(R)-PaOEt在连续流中成功实现，实现了比间歇合成高6.3倍的时空产率（529.2 vs 84 g L-1 d-1）。我们开发的流动生物催化系统还具有出色的运行稳定性，连续15天运行后转化率达到100% %。

{"title":"Batch and continuous-flow asymmetric synthesis of d-pantothenic acid precursor enabled by immobilized ketoreductase mutant","authors":"Pan Hu , Xiaofan Wu , Yi An , Xianjing Zheng , Liang Gao , Yuan Tao , Yajiao Zhang , Zedu Huang , Fener Chen","doi":"10.1016/j.cclet.2025.111945","DOIUrl":"10.1016/j.cclet.2025.111945","url":null,"abstract":"<div><div>We report an immobilized enzyme-catalyzed batch and continuous-flow synthesis of optically pure ethyl (<em>R</em>)-pantothenate ((<em>R</em>)-PaOEt), the direct precursor of <span>d</span>-pantothenic acid. Firstly, a ketoreductase mutant designated as M2, carrying two-point mutations of F97L and M242F relative to the wild-type SSCR, was constructed by site-directed mutagenesis, exhibited simultaneously improved activity toward ethyl 2′-ketopantothenate (K-PaOEt) and isopropanol, and could effectively catalyze the stereoselective reduction of K-PaOEt to (<em>R</em>)-PaOEt by using isopropanol as the sacrificial co-substrate to regenerate NADPH. After screening six commercially available carriers, an amino resin LXTE-700 was identified as the best solid support for the immobilization of M2 <em>via</em> the glutaraldehyde activation method. Upon optimization of the immobilization process and reaction conditions, the fabricated immobilized enzyme M2@amino resin demonstrated excellent recyclability and reusability, with the complete conversion of K-PaOEt to (<em>R</em>)-PaOEt being still realized after 12 cycles of reuse. Finally, M2@amino resin-catalyzed synthesis of (<em>R</em>)-PaOEt was successfully implemented in continuous-flow, accomplishing a 6.3 times higher space-time yield than that with the batch synthesis (529.2 <em>versus</em> 84 g L<sup>-1</sup> d<sup>-1</sup>). Our developed flow biocatalysis system also features an outstanding operational stability, as evidenced by the 100 % conversion rate achieved after 15 consecutive days of operation.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"37 2","pages":"Article 111945"},"PeriodicalIF":8.9,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145578513","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

Electrochemical selenylation of tyrosine oligopeptides to benzo[b]furan-functionalized peptides 酪氨酸寡肽电化学硒化制备苯并[b]呋喃功能化肽

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-10-01 DOI: 10.1016/j.cclet.2025.111928

Xinwei Hu , Yong Zeng , Jiongdong Ma , Han Diao , Fei-Xiao Chen , Mu Chen , Shou-Kun Zhang , Chengzhi Jin , Shao-Fei Ni , Zhixiong Ruan

Benzo[b]furans are significant scaffolds in drug molecules and are prevalent structural components in natural products. Chemically encoded non-natural peptidomimetics have a substantial impact on pharmaceuticals by offering enhanced stability, improved cell permeability, and resistance to enzymatic degradation. Consequently, a strategy for the sustainable assembly of benzo[b]furan/benzopyran-functionalized peptides through the electrochemical late-stage modification of alkyne-modified tyrosine oligopeptides is proposed. This approach facilitates the multifunctional integration of non-native tyrosine-derived substrates, as well as their subsequent functionalization. Notably, the resulting peptides exhibit favorable properties regarding biocompatibility and cellular uptake.

苯并[b]呋喃是药物分子的重要支架，也是天然产物中普遍存在的结构成分。化学编码的非天然肽模拟物通过提供增强的稳定性、改善的细胞渗透性和对酶降解的抵抗力，对药物产生了实质性的影响。因此，提出了一种通过炔修饰酪氨酸寡肽的电化学后期修饰来实现苯并[b]呋喃/苯并吡喃功能化肽的可持续组装策略。这种方法促进了非天然酪氨酸衍生底物的多功能整合，以及它们随后的功能化。值得注意的是，所得肽在生物相容性和细胞摄取方面表现出良好的特性。

引用次数: 0

Rational design of n-type organic thermoelectric materials: Insights from CnBTBT–FmTCNQ charge-transfer complexes n型有机热电材料的合理设计：来自CnBTBT-FmTCNQ电荷转移复合物的见解

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-10-01 DOI: 10.1016/j.cclet.2025.111933

Hongchao Wang , Wei Hao , Haowei Wu , Qianyu Ding , Yu Wei , Hu Zhao , Shuzhou Li , Hanying Li , Jia Zhu

Charge-transfer complexes (CTCs) have emerged as promising n-type organic thermoelectric (TE) materials due to their inherent high electrical conductivity and tunable transport polarities. In this study, we performed a comprehensive first-principles investigation on the TE properties of nine CTCs comprised of 2,7-dialkyl[1]benzothieno[3,2-b][1]benzothiophenes (C_nBTBT, n = 4, 8, 12) as donors and fluorinated derivatives of tetracyanoquinodimethane (F_mTCNQ, m = 0, 2, 4) as acceptors, aiming to identify high-performance n-type organic TE materials and elucidate the underlying structure–property relationships. Our calculation results, based on the Boltzmann transport equation and deformation potential theory, reveal that the length of the alkyl side chains and the number of fluorine substitutions significantly impact their electronic structures and TE properties. Notably, the C_nBTBT–F_mTCNQ CTCs with shorter alkyl chains and more fluorine substitution demonstrate superior n-type characteristics, particularly C₄BTBT–F₄TCNQ, which achieves an excellent power factor of 671 μW cm^-1 K^-2 at an optimal charge carrier concentration. Our findings not only clarify the critical role of molecular engineering in CTC-based TE materials but also provide valuable guidance for developing high-efficiency organic TE materials with versatile practical applications.

电荷转移配合物（ctc）由于其固有的高导电性和可调的输运极性而成为有前途的n型有机热电（TE）材料。在本研究中，我们对以2,7-二烷基[1]苯并噻吩[3,2-b][1]苯并噻吩（CnBTBT, n = 4,8,12）为给体，以四氰喹二甲烷的氟化衍生物（FmTCNQ, m = 0,2,4）为受体组成的九种ctc的TE性质进行了全面的第一性原理研究，旨在鉴定高性能n型有机TE材料并阐明其潜在的结构-性质关系。我们基于玻尔兹曼输运方程和变形势理论的计算结果表明，烷基侧链的长度和氟取代的数量显著影响它们的电子结构和TE性能。值得注意的是，具有较短烷基链和较多氟取代的CnBTBT-FmTCNQ ctc具有较好的n型特性，特别是C4BTBT-F4TCNQ在最佳载流子浓度下的功率因数为671 μW cm-1 K-2。我们的研究结果不仅阐明了分子工程在ctc基TE材料中的关键作用，而且为开发具有多种实际应用的高效有机TE材料提供了有价值的指导。

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引用次数: 0

Oligomeric α-diimine nickel catalysts for enhanced ethylene polymerization 低聚α-二亚胺镍催化剂促进乙烯聚合

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-30 DOI: 10.1016/j.cclet.2025.111930

Jingfeng Yue , Zhenxin Tang , Yuxing Zhang , Zhongbao Jian

Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science. Multi-nuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mono-nuclear catalysts, but which substantially involve multi-step, tedious, and difficult synthesis. Herein, this study reports an intriguing approach to construct multi-nuclear catalysts for the milestone α-diimine nickel catalysts using an oligomeric strategy. A polymerizable norbornene unit is incorporated into the α-diimine ligand backbone, leading to the formation of the monomeric nickel catalyst Ni₁ and its corresponding oligomeric nickel catalysts (Ni₃ and Ni₅) with varying degrees of polymerization (DP = 3 and 5). Notably, the oligomeric catalyst Ni₅ was facilely scaled up (50 g-level), showed enhanced thermal stability, exhibited 4.6 times higher activity, and yielded polyethylene elastomer with a 379 % increased molecular weight in ethylene polymerization, compared to the monomeric catalyst Ni₁. Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent. The kilogram-scale polyethylene, produced using Ni₅ in a 20 L reactor, presented a highly branched all-hydrocarbon structure, which demonstrated typical elastic properties (tensile strength: 4 MPa, elastic recovery: SR = 72 %) along with great processability (MFI = 3.0 g/10 min), insulating characteristics (volume resistivity = 2 × 10¹⁶ Ω/m), and hydrophobicity (water vapor permeability: 0.03 g/m²/day), suggesting potentially practical applications.

催化剂是烯烃聚合反应的关键，在催化科学中无处不在。多核金属催化剂在催化反应中表现出比单核催化剂更强的性能，但单核催化剂的合成过程多步、繁琐、困难。在此，本研究报告了一个有趣的方法来构建多核催化剂里程碑α-二亚胺镍催化剂使用低聚物策略。α-二亚胺配体主链中加入了一个可聚合的降冰片烯单元，形成了聚合度不同的单体镍催化剂Ni1及其对应的低聚镍催化剂Ni3和Ni5 （DP = 3和5）。值得注意的是，与单体催化剂Ni1相比，低聚催化剂Ni5可以很容易地放大（50 g级），表现出更强的热稳定性，表现出4.6倍的活性，并且在乙烯聚合中产生的聚乙烯弹性体的分子量增加了379 %。发现低聚物催化剂的催化性能增强依赖于dp。在20千克尺度聚乙烯,生产使用Ni5 L反应器,提出一个高度支all-hydrocarbon结构,这展示了典型的弹性性能(抗拉强度:4 MPa,弹性回复:SR = 72 %)以及伟大的加工性能(MFI = 3.0  g / 10分钟),绝缘特性(体积电阻率 = 2 × 1016Ω/ m),和疏水性(水蒸气渗透率:0.03 g / m2 /日),表明潜在的实际应用。

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引用次数: 0

Efficient large-current conversion of CO2 to C2H5OH via a *CO-*OCH2 coupling pathway on alkanethiol-modified Cu2O array electrode 在烷硫醇修饰的Cu2O阵列电极上，通过*CO-*OCH2偶联途径实现CO2到C2H5OH的高效大电流转化

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-30 DOI: 10.1016/j.cclet.2025.111926

Min Zhang , Weimin Wang , Jun Li , Xun Zhu , Qian Fu

Developing advanced electrocatalysts to convert CO₂ into liquid fuels such as C₂H₅OH is critical for utilizing intermittent renewable energy. The formation of C₂H₅OH, however, is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts. In this work, an alkanethiol-modified Cu₂O nanowire array (OTT-Cu₂O) was constructed with asymmetric Cu sites consisting of paired Cu–O and Cu–S motifs to overcome previous limitations of C₂H₅OH electrosynthesis via CO₂RR pathway. This catalyst achieves a high Faradaic efficiency of 45 % for CO₂-to-C₂H₅OH conversion at 300 mA/cm², representing a more than two-fold enhancement over the Cu₂O electrode. Mechanistic investigations reveal that the Cu–S site exhibits distinct C-binding capability that stabilizes key intermediates (*OCH₂ and *CO), in contrast to the O-affinitive Cu–O site. The asymmetric S–Cu–O configuration promotes thermodynamically favorable asymmetric C–C coupling between *CO and *OCH₂, forming the critical CO–OCH₂ intermediate and facilitating C₂H₅OH production, as opposed to symmetric O–Cu–O sites that mainly generate HCOOH. This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO₂ reduction to C₂H₅OH and provides fundamental insight into the reaction mechanism.

开发先进的电催化剂将二氧化碳转化为液体燃料，如C2H5OH，对于利用间歇性可再生能源至关重要。然而，与铜基电催化剂的其他碳氢化合物产物相比，C2H5OH的形成通常不太有利。为了克服以往通过CO2RR途径电合成C2H5OH的局限性，利用由Cu - O和Cu - s基序组成的不对称Cu位点构建了烷硫醇修饰的Cu₂O纳米线阵列（ot -Cu₂O）。该催化剂在300 mA/cm2下实现了45 %的co2到c2h5oh转化的高法拉第效率，比Cu2O电极提高了两倍以上。机制研究表明，与o亲和的Cu-O位点相比，Cu-S位点具有明显的c结合能力，可以稳定关键中间体（*OCH2和*CO）。不对称的S-Cu-O结构促进了*CO和*OCH2之间的不对称C-C耦合，形成了关键的CO - OCH2中间体，促进了C2H5OH的生成，而不对称的O-Cu-O位点主要生成HCOOH。本研究为设计高选择性CO 2还原为C2H5OH的多活性位点催化剂提供了有效的策略，并为反应机理提供了基本的见解。

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引用次数: 0