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Recent progress in energy-saving hydrogen production by coupling with value-added anodic reactions 通过与增值阳极反应耦合实现节能制氢的最新进展

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.08.009

Replacement of the oxygen evolution reaction (OER) by energetically more favorable electrooxidation reactions opens up an innovative pathway for energy-saving hydrogen (H₂) production. In particular, the electrooxidation of biomass molecules, plastic wastes, and organic compounds has attracted escalating interest in recent years, owing to its potential for simultaneous H₂ production at the cathode and value-added chemical and fuel generation at the anode. This review article does not aim to provide a comprehensive overview of these reactions but rather to highlight the key advancements in the strategies of reaction design, activity enhancement, and selectivity regulation based on the features and challenges in each type of reaction. Through this review of key advancements, we offer mechanistic insights that guide the design of more efficient coupling systems. Lastly, the challenges and future prospects in this field are discussed.

以能量上更有利的电氧化反应取代氧进化反应（OER），为节能制氢（H2）开辟了一条创新之路。近年来，生物质分子、塑料废料和有机化合物的电氧化反应尤其引起了越来越多的关注，因为它具有在阴极同时生产氢气、在阳极同时生产增值化学品和燃料的潜力。这篇综述文章的目的不是全面概述这些反应，而是根据每种反应的特点和挑战，重点介绍在反应设计、活性增强和选择性调节策略方面的主要进展。通过对主要进展的回顾，我们提出了指导设计更高效偶联体系的机理见解。最后，我们还讨论了这一领域的挑战和未来前景。

引用次数: 0

Modifying commodity-relevant unsaturated polymers via Co-catalyzed MHAT 通过共催化 MHAT 改性与商品相关的不饱和聚合物

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.05.021

The past 2 decades have witnessed the rapid development of CoSalen-catalyzed hydrofunctionalization reactions, mostly on terminal and conjugation-activated olefins. However, the use of 1,2-dialkyl-substituted alkenes continues to pose challenges. In this study, we revisit this substrate class in the context of Carreira-type hydrofunctionalization reactions and introduce a simple yet effective modification (over a 250-fold-increase in turnover number [TON]). Near-quantitative yields can be achieved at a low catalyst loading, typically 0.05 mol %. The key lies in inhibiting the degradation of the salen backbone using molecular sieves. This protocol facilitates a study on the metal hydride hydrogen atom transfer (MHAT) regioselectivity of this type of alkene. We found that allylic electron-negative groups and hyperconjugation have profound effects, yielding regioisomeric ratios ranging from 6.5:1 to < 1:20. The high TONs, mild conditions, and versatility of this method further enable its application in the post-polymerization modification of several olefin-rich, commodity-relevant polymers, demonstrating the rich potential of MHAT hydrofunctionalization in macromolecular settings.

在过去的二十年里，CoSalen 催化的加氢官能化反应得到了快速发展，主要用于末端和共轭活化的烯烃。然而，1,2-二烷基取代烯烃的使用仍然面临挑战。在本研究中，我们在 Carreira 型氢官能化反应的背景下重新审视了这一类底物，并介绍了一种简单而有效的改性方法（转化率 [TON] 增加 250 倍以上）。催化剂负载量较低时（通常为 0.05 摩尔%）即可获得接近定量的产量。关键在于利用分子筛抑制沙林骨架的降解。这种方法有助于研究这类烯烃的金属氢化物氢原子转移（MHAT）的区域选择性。我们发现，烯丙基负电子基团和超共轭作用具有深远的影响，可产生从 6.5:1 到 1:20 的区域异构比。这种方法的高通量系数、温和的条件和多功能性使其能够进一步应用于几种富含烯烃、与商品相关的聚合物的聚合后改性，证明了 MHAT 氢功能化在大分子环境中的巨大潜力。

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引用次数: 0

A light-driven chloride anion transporter 光驱动的氯阴离子转运体

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.09.012

Recent advances in artificial transmembrane transporters that may address the limitations of natural ion channels include a photoswitchable Cl⁻ anion pump developed by Aprahamian et al., reported in Science,¹ utilizing hydrazone units for active transport against the concentration gradient. This molecular transporter leverages light-induced isomerization to control anion grabbing and releasing, showing significant potential for drug discovery and molecular machinery.

人工跨膜转运体的最新进展可能解决了天然离子通道的局限性，其中包括 Aprahamian 等人开发的一种光开关 Cl- 阴离子泵（发表于《科学》1），该泵利用腙单元进行活性转运，对抗浓度梯度。这种分子转运体利用光诱导的异构化来控制阴离子的抓取和释放，在药物发现和分子机械方面显示出巨大的潜力。

引用次数: 0

Transition metal-free difunctionalization of unactivated alkenes: Arylation/azidation, arylation/chlorination, and arylation/cyanation 未活化烯烃的无过渡金属双官能化：芳基化/唑化、芳基化/氯化和芳基化/氰化

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.07.036

Arylethylamines represent a privileged scaffold in pharmaceutical compounds and form the backbone of many medical drugs, including those used for treating neurological diseases and pain. Their biomedical significance has inspired new synthetic methods that rely on transition metal-catalyzed aminoarylation reaction to an alkene, often in conjunction with a photoredox catalyst or a photosensitizer and guided by a directing or stabilizing group. Here, we introduce a simple and effective method for the azidoarylation of unactivated alkenes under transition metal-free conditions. Visible- or near-UV-light irradiation of readily available triarylbismuth dichlorides generates an aryl radical that selectively adds to the alkene, and the resulting homobenzyl radical is intercepted by an amine equivalent. This method offers a broad substrate scope and also enables the arylchlorination and arylcyanation of unactivated alkenes.

芳基乙胺是药物化合物中的一种特殊支架，是许多医疗药物（包括用于治疗神经系统疾病和疼痛的药物）的骨架。它们的生物医学意义激发了新的合成方法，这些方法依赖于过渡金属催化的烯烃氨基芳基化反应，通常与光氧化催化剂或光敏剂一起进行，并由定向或稳定基团引导。在此，我们介绍一种在无过渡金属条件下对未活化烯烃进行叠氮芳基化的简单而有效的方法。用可见光或近紫外光照射现成的三芳基二氯化铋，会产生一个芳基自由基，选择性地与烯烃发生加成反应，生成的均苄基自由基会被等效的胺截获。这种方法提供了广泛的底物范围，还可以对未活化的烯烃进行芳基氯化和芳基氰化。

引用次数: 0

Hierarchical porous covalent organic framework nanosheets with adjustable large mesopores 具有可调大介孔的分层多孔共价有机框架纳米片

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.05.022

Synchronous manipulation of meso-structure and architecture of covalent organic frameworks (COFs) is vital for customized applications but still remains challenging. Here, we develop a polymerization-induced co-assembly approach to construct hierarchical porous COF-based nanosheets with adjustable large mesopores (7–40 nm), intrinsic micropores (∼1.2 nm), ultra-thin thickness (∼24 nm), and a crystalline wall. Furthermore, density functional theory calculations and adsorption experiments indicated that the complementarity of the two-dimensional architecture and intrinsic micropores of COFs can effectively confine iodine molecules. Meanwhile, the exposed nitrogen-containing active sites created by the unique mesoporous structure can strongly anchor iodine species, thereby greatly inhibiting their dissolution and shuttling. Therefore, as a cathode for zinc-iodine battery, they delivered an outstanding rate capability (191.2 mAh g⁻¹ at 0.5 A g⁻¹) and stable long-term cyclability (154.8 mAh g⁻¹ at 3 A g⁻¹ after 20,000 cycles). This approach sheds light on the precise fabrication of crystalline porous materials for diverse applications.

同步操纵共价有机框架（COFs）的中层结构和体系结构对定制应用至关重要，但仍然具有挑战性。在这里，我们开发了一种聚合诱导的共组装方法，以构建具有可调节的大中孔（7-40 nm）、本征微孔（∼1.2 nm）、超薄厚度（∼24 nm）和晶壁的分层多孔 COF 基纳米片。此外，密度泛函理论计算和吸附实验表明，COFs 的二维结构和固有微孔的互补性可有效禁锢碘分子。同时，独特的介孔结构所形成的外露含氮活性位点可以强力锚定碘物种，从而极大地抑制其溶解和穿梭。因此，作为锌碘电池的阴极，它们具有出色的速率能力（0.5 A g-1 时为 191.2 mAh g-1）和稳定的长期循环能力（20,000 次循环后，3 A g-1 时为 154.8 mAh g-1）。这种方法为精确制造晶体多孔材料的各种应用提供了启示。

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引用次数: 0

Terpenoid-based high-performance polyester with tacticity-independent crystallinity and chemical circularity 萜类高性能聚酯，具有与触觉无关的结晶性和化学循环性

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.05.024

The development of chemically circular, bio-based polymers is an urgently needed solution to combat the plastic waste crisis. However, the most prominent, commercially implemented bio-based aliphatic polyester, poly(lactic acid) (PLA), is brittle, therefore largely limiting its broad applications. Herein, we introduce a class of aliphatic polyesters produced through the ring-opening polymerization (ROP) of (1R,5S)-8,8-dimethyl-3-oxabicyclo[3.2.1]octan-2-one (D-CamL) and the racemic mixture (rac-CamL), which exhibit superior material properties relative to PLA. A metal-based or organic catalyst was used for the modulation of polymer tacticity. Notably, regardless of tacticity, poly(CamL) exhibits intrinsic crystallinity, resulting in polyesters with high yield stress (24–39 MPa), high Young’s modulus (1.36–2.00 GPa), tunable fracture strains (6%–218%), and high melting temperatures (161°C–225°C). Importantly, poly(CamL) can be chemically recycled to monomer in high yield, and virgin-quality poly(CamL) is obtained after repolymerization. Overall, poly(CamL) represents a new class of bio-derived and chemically circular high-performance polyesters.

开发化学循环型生物基聚合物是应对塑料废弃物危机急需的解决方案。然而，最著名的商业化生物基脂肪族聚酯--聚乳酸（PLA）却很脆，因此在很大程度上限制了它的广泛应用。在本文中，我们介绍了通过 (1R,5S)-8,8-二甲基-3-氧杂双环[3.2.1]辛烷-2-酮（D-CamL）和外消旋混合物（rac-CamL）的开环聚合（ROP）生产的一类脂肪族聚酯，与聚乳酸相比，这种聚酯表现出更优越的材料特性。金属催化剂或有机催化剂可用于调节聚合物的触变性。值得注意的是，无论触变性如何，聚（CamL）都表现出固有的结晶性，因此聚酯具有高屈服应力（24-39 兆帕）、高杨氏模量（1.36-2.00 GPa）、可调断裂应变（6%-218%）和高熔化温度（161°C-225°C）。重要的是，聚（CamL）可以通过化学方法高产率地回收为单体，并在重新聚合后获得原生质量的聚（CamL）。总之，聚（CamL）是一类新型的生物衍生和化学循环高性能聚酯。

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引用次数: 0

Chiral stacks of a curved nanographene 弯曲纳米石墨的手性叠层

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.07.008

Despite enormous advances in the edge extension chemistry of nanographenes, examples of peri-annulations and the knowledge of their effect on molecular properties remain scarce. Here, we show the synthesis of a curved C₆₀S₅ nanographene comprising quintuple [5]thiahelicenes arranged in a C₅-symmetric fashion on the zigzag edge (L-region) of a bowl-shaped corannulene core. The synthesis is achieved with the help of Stille coupling, alkynyl thiolation, sulfide/aryne cyclization, and direct arylation reactions. The prepared bowl-helix chiral structure absorbs and emits in the visible and near-IR regions. It assembles into persistent molecular bilayer graphene stacks in solution, solid state, and gas phase. The concave cavities of the supramolecular dimers can recognize the convex surfaces of fullerene C₆₀ through shape complementarity and π-π stacking interactions in the solid state. A properties comparison with ortho-annulated analogs and archetypical nanographenes indicates the superiority of peri-annulations in the design of molecular graphenes.

尽管在纳米石墨烯的边缘延伸化学方面取得了巨大进步，但围嵌合的实例及其对分子特性影响的知识仍然很少。在这里，我们展示了一种弯曲的 C60S5 纳米石墨烯的合成方法，它由五倍 [5]thiahelicenes 组成，以 C5 对称的方式排列在碗形茱萸核的人字形边缘（L 区域）上。该合成是通过斯蒂尔偶联、炔基硫代、硫化物/芳基环化和直接芳基化反应实现的。所制备的碗状螺旋手性结构在可见光和近红外区域吸收和发光。它能在溶液、固态和气相中组装成持久的分子双层石墨烯堆栈。在固态下，超分子二聚体的凹腔可以通过形状互补和π-π堆叠相互作用识别富勒烯 C60 的凸面。与正嵌段类似物和原型纳米石墨烯的性质比较表明，围嵌段在设计分子石墨烯方面具有优越性。

引用次数: 0

Ribosomal peptides with polycyclic isoprenoid moieties 具有多环异戊二烯分子的核糖体肽

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.07.026

Isoprenoid modifications of proteins and peptides serve fundamental biological functions and are of therapeutic interest. While C₁₅ (farnesyl) and C₂₀ (geranylgeranyl) moieties are prevalent among proteins, known ribosomal peptide prenylations involve shorter-chain units not exceeding farnesyl in size. To our knowledge, cyclized terpene moieties have not been reported from either biomolecule class. Here, we used targeted genome mining and heterologous pathway reconstitution to identify ribosomally synthesized and post-translationally modified peptides (RiPPs) with elaborate, cyclized geranylgeranyl modifications. The installing maturases commonly feature fused prenyltransferase-terpene cyclase architectures. We characterized two bifunctional maturases with distinct prenyltransferase folds and identified the terminal product of a cyanobacterial proteusin as an exceptionally complex pseudosteroid-annelated polycyclic peptide. Bioassays suggest modest anti-cyanobacterial activity with the modification being crucial for activity. Genome data predict cyclic isoprenoid units for various RiPP families, including proteusin, Nif11, and lasso peptides, and thus the broader natural and biotechnological compatibility of the maturase system.

蛋白质和肽的异戊烯基修饰具有基本的生物学功能和治疗意义。虽然 C15（法呢基）和 C20（香叶基）分子在蛋白质中很普遍，但已知的核糖体肽前炔基化涉及的短链单位大小不超过法呢基。据我们所知，这两类生物大分子中都没有环化萜烯分子的报道。在这里，我们利用有针对性的基因组挖掘和异源途径重组来鉴定核糖体合成和翻译后修饰肽（RiPPs），这些肽具有精细的环化香叶基萜烯修饰。安装的成熟酶通常具有融合的前酰基转移酶-萜烯环化酶结构。我们对两种具有不同前炔基转移酶折叠的双功能成熟酶进行了鉴定，并发现蓝藻蛋白苷的末端产物是一种异常复杂的假甾醇-通道化多环肽。生物测定表明，这种酶具有适度的抗蓝藻活性，而修饰是其活性的关键。基因组数据预测了各种 RiPP 家族的环状异戊二烯单元，包括蛋白肽、Nif11 和拉索肽，从而使成熟酶系统具有更广泛的自然和生物技术兼容性。

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引用次数: 0

On the road to isolable geminal carbodications 通往可分离的宝石碳化物之路

IF 23.5 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.09.008

Yiwei Gong, Jan Langwald, Florian F. Mulks

Recent advances in the isolation of masked gem-carbodications have shown that such species may be more accessible than we thought. This perspective article summarizes the milestones of the last 140 years of research and aims to point the way toward the isolation of species containing true four-valence-electron carbon. Currently, strong mesomeric donation or coordination by donor ligands is used to stabilize such dications. Achieving true localization of both charges on a single atom will require smart combinations of inductive donation, hyperconjugation, and steric hindrance.

最近在分离掩蔽宝石碳化物方面取得的进展表明，这类物种可能比我们想象的更容易获得。这篇观点性文章总结了过去 140 年研究的里程碑，旨在为分离含有真正四价电子碳的物种指明方向。目前，供体配体的强中间体捐赠或配位被用来稳定此类阳离子。要在单个原子上实现两种电荷的真正定位，需要巧妙地结合感应捐献、超共轭和立体阻碍。

引用次数: 0

Kinetic sieving separation of a gating macrocyclic crystal for purification of propylene 用于提纯丙烯的门控大环晶体的动力学筛分分离技术

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.06.007

Finding an energy-efficient alternative to cryogenic distillation for the room temperature, pressure-swing-adsorptive separation of propylene/propane (C₃H₆/C₃H₈) is challenging due to their physiochemical similarity. Herein, we report a gating macrocyclic crystal facilely prepared by the recrystallization of a macrocyclic arene (i.e., naphthyl-hexnutarene), which exhibits outstanding separation capabilities for C₃H₆/C₃H₈, with a remarkable kinetic selectivity of 76.7 and fast C₃H₆ adsorption kinetics with a diffusional time constant of 0.1727 min⁻¹. The achievement is attributed to the transient motions of a gating methoxy group on the macrocycle that extend toward the contracted pore apertures, effectively amplifying the subtle distinction in guest transport. Furthermore, this crystal demonstrates great potential in actual pressure swing adsorption processes, showcasing energy-saving and efficient regeneration, as evidenced by a low heat of adsorption of 15.4 kJ mol⁻¹ for C₃H₆ and full recovery of adsorption capacity through dynamic vacuum at room temperature, together with merited exclusions of co-present C₂H₆/C₂H₄/CH₄/CO₂/N₂ for C₃H₆ purification.

由于丙烯/丙烷（C3H6/C3H8）具有相似的物理化学性质，因此寻找一种替代低温蒸馏的高能效室温压力摆动吸附分离技术具有挑战性。在此，我们报告了一种通过重结晶大环芳烃（即萘六烯）而方便制备的门控大环晶体，该晶体对 C3H6/C3H8 具有出色的分离能力，其动力学选择性高达 76.7，对 C3H6 的吸附动力学速度极快，扩散时间常数为 0.1727 min-1。这一成果归功于大循环上的门控甲氧基向收缩孔径延伸的瞬态运动，有效地放大了客体传输中的微妙差异。此外，这种晶体在实际变压吸附过程中表现出巨大的潜力，展示了节能和高效的再生能力，这体现在它对 C3H6 的吸附热低至 15.4 kJ mol-1，并且在室温下通过动态真空完全恢复了吸附能力，同时还排除了共存的 C2H6/C2H4/CH4/CO2/N2，有利于 C3H6 的提纯。

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