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Sequence-defined main-chain photoswitching macromolecules with odd-even-effect-controlled properties 具有奇偶效应控制特性的序列定义主链光开关大分子

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.10.008

Linh Duy Thai , Jochen A. Kammerer , Dmitri Golberg , Hatice Mutlu , Christopher Barner-Kowollik

The installation of stimuli-responsive moieties into their main chain maximizes the stimuli response of polymers. Yet, facile and orthogonal synthesis of such complex macromolecules is a daunting challenge, especially for achieving absolute chain-end-group fidelity, monodispersity, and the formation of block copolymers (BCPs). We harness metal-free hydroxyl-yne click and deprotection chemistry to realize monodisperse, sequence-defined oligomers and BCPs featuring α-bisimines as main-chain photoswitches and orthogonally incorporate functional terminal groups (olefins, acrylates, and non-activated alkynes). We reveal the significant influence of the sequence on solution and solid-state material properties, which manifests as a strong odd-even effect on the hydrodynamic volume, glass transition temperature, and BCP domain spacing. The odd-even effect originates from the distinct symmetries of the sequences resulting from our precise synthetic strategy. Thus, our sequence-defined, orthogonal synthesis strategy with near absolute chain-end-group fidelity and wide functional group compatibility paves the way toward complex polymeric materials with precise properties, topology, composition, and main-chain functionalities.

在聚合物主链中加入刺激响应分子可最大限度地提高聚合物的刺激响应。然而，这种复杂大分子的简便正交合成是一项艰巨的挑战，尤其是在实现绝对的链端基团保真度、单分散性和形成嵌段共聚物（BCP）方面。我们利用无金属羟基-炔单击和脱保护化学来实现单分散、序列确定的低聚物和 BCP，其特点是以α-二亚胺作为主链光开关，并正交加入功能性末端基团（烯烃、丙烯酸酯和非活化炔）。我们揭示了序列对溶液和固态材料特性的重大影响，表现为对流体力学体积、玻璃化转变温度和 BCP 域间距的强烈奇偶效应。奇偶效应源于我们精确的合成策略所产生的序列的独特对称性。因此，我们的序列定义正交合成策略具有近乎绝对的链端组保真度和广泛的官能团兼容性，为实现具有精确性质、拓扑结构、组成和主链功能的复杂聚合物材料铺平了道路。

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引用次数: 0

Ordered [2]catenanes in covalent organic frameworks: From molecules to materials 共价有机框架中的有序[2]链烷：从分子到材料

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.10.024

Ruozhou Huang , Yuping Wang

In a recent issue of Chem, an innovative approach for the synthesis of crystalline [2]catenane-containing covalent organic frameworks was developed. This breakthrough elucidates how the dynamics of microscopic, interlocked components influence material properties, thereby advancing the design of two-dimensional materials with sophisticated topological features.

在最近一期的《化学》（Chem）杂志上，研究了一种合成含[2]链烷的结晶共价有机骨架的创新方法。这一突破阐明了微观、互锁组分的动力学如何影响材料性能，从而推进了具有复杂拓扑特征的二维材料的设计。

引用次数: 0

2D covalent organic framework via catenation 通过催化反应实现二维共价有机框架

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.09.006

Thirumurugan Prakasam , Sudhir Kumar Sharma , Florent Ravaux , Farah Benyettou , Matteo Lusi , Varghese Sabu , Philippe Bazin , Thomas Delclos , Ramesh Jagannathan , Jamie Whelan , Mohamad El-Roz , Mark A. Olson , Mahmoud Abdellatief , Obieda S. Mudraj , Felipe Gándara , Ali Trabolsi

Molecular-level structural modification is a well-established approach to impart advanced functionality to materials that continues to be the focus of research and development in both academic and industrial laboratories. Here, we report the synthesis of an ordered two-dimensional (2D) poly[2]catenate from the simultaneous self-assembly of two organic ligands and a metal salt by the formation of catenate links using metal coordination and imine condensation reactions. Subsequent chemical reduction of the imine bonds generated the corresponding demetallized poly[2]catenane, which was found to have greater non-rigid-body-like character than the poly[2]catenate as a result of the increased internal dynamics of the mechanical bonds and resulted in an 8-fold increase in elasticity. This synthetic approach allowed for the efficient incorporation of mechanically interlocked molecules (MIMs) within a 2D ordered structure and demonstrated their importance in improving the physical properties of materials by accessing molecular degrees of freedom that cannot be achieved by other means.

分子级结构修饰是赋予材料高级功能的一种行之有效的方法，一直是学术界和工业界实验室的研发重点。在此，我们报告了利用金属配位和亚胺缩合反应形成的烯酸链节，通过两种有机配体和一种金属盐的同时自组装合成有序二维（2D）聚[2]烯酸酯的过程。随后对亚胺键进行化学还原，生成了相应的脱金属聚[2]卡烯酸酯，由于机械键的内部动态增加，这种聚[2]卡烯酸酯比聚[2]卡烯酸酯具有更强的非刚性体特性，并使弹性增加了 8 倍。这种合成方法可以在二维有序结构中有效地加入机械互锁分子（MIMs），并通过获得其他方法无法实现的分子自由度，证明了它们在改善材料物理性质方面的重要性。

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引用次数: 0

Anion-coordination- and π-π-stacking-interaction-driven assembly of a complex Frank-Kasper structure 阴离子配位和π-π堆积相互作用驱动的复杂弗兰克-卡斯帕结构组装

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.11.009

Zhu Zhuo , Zi-Ang Nan , Wen-Zheng Fu , Wei Wang , Guo-Ling Li , Ming-Yan Wu , Maochun Hong , You-Gui Huang

Constructing artificial sophisticated architectures from simple small-molecular subunits by cooperative interactions remains one of the most formidable challenges. Herein, we report a complex supramolecular structure, {{[CoL(SCN)]₂₀}{[CoL(SCN)]₂₄}₃(SO₄)₂₃(HSO₄)₄₆}·246(CH₃CN) (1), that arises from the assembly of [CoL(SCN)]⁺ with SO₄²⁻ and HSO₄⁻ (L = tris(2-benzimidazolylmethyl)amine) under solvothermal condition. The crystallization of compound 1 is driven by the cooperation of the π-π stacking interactions between [CoL(SCN)]⁺ cations and the hydrogen bonds between [CoL(SCN)]⁺ and SO₄²⁻ and HSO₄⁻. [CoL(SCN)]⁺ cations self-associate through intermolecular π-π stacking interactions to create two π-stacked polyhedral 5¹²-{[CoL(SCN)]₂₀} dodecahedra and 5¹²6²-{[CoL(SCN)]₂₄} tetrakaidekahedra. These two π-stacked polyhedral subunits coexist in the same lattice in a 1:3 ratio and coordinate with SO₄²⁻ and HSO₄⁻, resulting in a complex Frank-Kasper (FK) A15 structure. This research demonstrates that small-molecular scaffolds can assemble into sophisticated architectures and creates exciting perspectives for constructing sophisticated clathrate structures from simple small molecules.

从简单的小分子亚基通过协同作用构建人工精密结构，仍然是最艰巨的挑战之一。在此，我们报告了一种复杂的超分子结构，{{[CoL(SCN)]20}{[CoL(SCN)]24}3(SO4)23(HSO4)46}-246(CH3CN) (1)，它是由[CoL(SCN)]+与 SO42- 和 HSO4-（L = 三(2-苯并咪唑基甲基)胺）在溶热条件下组装而成。化合物 1 的结晶是由 [CoL(SCN)]+ 阳离子之间的 π-π 堆叠相互作用以及 [CoL(SCN)]+ 与 SO42- 和 HSO4- 之间的氢键协同作用驱动的。[CoL(SCN)]+ 阳离子通过分子间的π-π堆叠作用自结合，形成两个π堆叠多面体 512-{[CoL(SCN)]20}十二面体和 51262-{[CoL(SCN)]24}四开二面体。这两个π堆叠多面体亚基以 1:3 的比例共存于同一晶格中，并与 SO42- 和 HSO4- 配合，形成复杂的弗兰克-卡斯帕（FK）A15 结构。这项研究表明，小分子支架可以组装成复杂的结构，并为利用简单的小分子构建复杂的凝块结构开辟了令人兴奋的前景。

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引用次数: 0

Single-site nanozyme with exposed unsaturated Cu-O2 sites for tumor therapy by coordinating innate immunity and vasculature normalization 带有暴露的不饱和 Cu-O2 位点的单位点纳米酶，通过协调先天免疫和血管正常化治疗肿瘤

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.08.020

Yang Liu , Huan Zhao , Rui Niu , Bin Zhang , Boon Teck Garrick Lim , Shuyan Song , Yinghui Wang , Hongjie Zhang , Yanli Zhao

The low immunogenicity of tumors, coupled with abnormal and dysfunctional tumor vasculature, hinders the infiltration and function of effector T cells and suppresses the efficacy of immunotherapy. Herein, we developed a defective-copper-based metal-organic framework single-site nanozyme (F@D-CHTP SN) with co-loaded MSA-2 (stimulator of interferon genes [STING] agonist) and fruquintinib (vascular endothelial growth factor receptor [VEGFR] inhibitor). The conjugated organic ligands and highly exposed unsaturated Cu-O₂ single-atom sites endow F@D-CHTP SN with excellent reactive oxygen species generation activity, which can disrupt the cellular redox balance, impair mitochondrial function, and ultimately induce cuproptosis and ferroptosis, enhancing tumor immunogenicity. Meanwhile, intratumoral STING activation and VEGFR blockade synergistically promote tumor vasculature normalization, further reshaping the immunosuppressive microenvironment and enhancing T cell infiltration to achieve effective tumor suppression. Our work demonstrates the feasibility and significant synergistic effects of initiating cascade-enhancing immunity by combining cuproptosis and ferroptosis with STING activation and tumor vasculature normalization.

肿瘤的免疫原性低，加上肿瘤血管异常和功能失调，阻碍了效应T细胞的浸润和功能，抑制了免疫疗法的疗效。在此，我们开发了一种缺陷铜基金属有机框架单位纳米酶（F@D-CHTP SN），其中共载了MSA-2（干扰素基因刺激剂[STING]激动剂）和fruquintinib（血管内皮生长因子受体[VEGFR]抑制剂）。共轭有机配体和高度暴露的不饱和 Cu-O2 单原子位点赋予 F@D-CHTP SN 极佳的活性氧生成活性，可破坏细胞氧化还原平衡，损害线粒体功能，最终诱导铜氧化酶和铁氧化酶，增强肿瘤免疫原性。同时，瘤内 STING 激活和血管内皮生长因子受体阻断协同促进肿瘤血管正常化，进一步重塑免疫抑制微环境，增强 T 细胞浸润，从而达到有效抑制肿瘤的目的。我们的工作证明了将杯突症和铁突症与 STING 激活和肿瘤血管正常化相结合，启动级联增强免疫的可行性和显著的协同效应。

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引用次数: 0

Exerting control of self-assembly pathways via morphological switching and patterning in amino-acid-based benzene-1,3,5-tricarboxamide conjugates 通过氨基酸基苯-1,3,5-三甲酰胺共轭物的形态切换和图案化控制自组装途径

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.09.020

Aramballi J. Savyasachi , Oxana Kotova , Ena T. Luis , Amy D. Lynes , Shaun Mills , Sandra A. Bright , Gavin J. McManus , Matthias E. Möbius , D. Clive Williams , Robert Pal , John J. Boland , Thorfinnur Gunnlaugsson

Small structural changes to benzene-1,3,5-tricarboxamide (BTA) dictate its self-assembly behavior and morphological outcome. Functionalization with an α-amino acid close to the BTA core, which also possesses a terminal terpyridine (tpy) unit, led to a robust gel in the case of glycine, whereas monodisperse, solid microspheres formed in the case of alanine, phenylalanine, and leucine. The self-assembly pathways of the chiral and achiral BTAs are orthogonal and both microspheres and gel fibers independently assemble in the same medium. Further hierarchical self-assembly results upon addition of lanthanide ions (i.e., Eu(III) and Tb(III) that emit at long wavelengths with long excited-state lifetimes) that crosslink the microspheres through coordination, whereas coordination within the gel led to a change in morphology toward microspheres, as well as the formation of hierarchical superstructures. The chirality of the BTA influences helicity of the assembly and the resulting enantiomeric conformation around the lanthanides, evidenced by circularly polarized luminescence.

苯-1,3,5-三甲酰胺（BTA）的微小结构变化决定了其自组装行为和形态结果。用靠近 BTA 核心的 α- 氨基酸进行官能化（BTA 核心还具有一个末端的terpyridine (typy)单元）会导致甘氨酸形成坚固的凝胶，而丙氨酸、苯丙氨酸和亮氨酸则会形成单分散的固体微球。手性和非手性 BTA 的自组装途径是正交的，微球和凝胶纤维在同一介质中独立组装。加入镧系离子（即 Eu（III）和 Tb（III），它们的发射波长长、激发态寿命长）后，微球通过配位交联，而凝胶中的配位导致形态向微球转变，并形成分层超结构，从而进一步实现分层自组装。BTA 的手性影响了组装的螺旋性以及由此产生的围绕镧系元素的对映体构象，这一点可以通过圆偏振发光得到证明。

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引用次数: 0

Hydrogen-bond catalysis in biomass valorization 生物质增值中的氢键催化

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.11.002

Yingchuan Zhang , George W. Huber , Zhengxiao Guo

As a biomimetic concept of enzymatic catalysis, hydrogen-bond catalysis (HBC) leverages H-bond-inducing atomic sites or functional groups in catalysts to regulate substrate binding and transition states so as to enable highly efficient and (stereo)selective organic reactions. However, it has rarely been employed in catalytic biomass valorization toward renewable fuels and value-added chemicals until recently. This perspective aims to highlight the opportunities offered by HBC to promote effective transformations of biomass-derived oxygenates. The concept and characterization approaches of HBC strategies are first introduced, followed by a critical overview of HBC-involved reactions, catalyst structures, and dynamic interfaces between biomass substrates and catalysts. Particular attention is paid to binding configurations and adsorption energetics for which engineered H-bonds can tune bond cleavage/formation and promote desirable reaction pathways in association with intrinsic catalytic sites (e.g., Lewis/Brønsted acid sites, metal active sites, and photogenerated charges) and therefore enable biomass valorization in more efficient and sustainable manners.

氢键催化（HBC）是酶催化的一种仿生概念，利用催化剂中诱导氢键的原子位点或官能团调节底物结合和过渡状态，从而实现高效（立体）选择性有机反应。然而，直到最近，它很少被用于可再生燃料和增值化学品的催化生物质增值。这一观点旨在强调HBC提供的机会，以促进生物质衍生氧合物的有效转化。首先介绍了HBC策略的概念和表征方法，然后概述了HBC相关的反应、催化剂结构以及生物质基质和催化剂之间的动态界面。特别关注结合构型和吸附能量学，其中工程氢键可以调节键的切割/形成，并促进与内在催化位点（例如Lewis/Brønsted酸位点、金属活性位点和光生电荷）相关的理想反应途径，从而使生物质以更有效和可持续的方式增值。

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引用次数: 0

Producing economically viable renewable diesel by upgrading organic solid waste with natural gas

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2025.102459

Ali Omidkar, Avinash Alagumalai, Razieh Es’haghian, Hua Song

引用次数: 0

Rolling-circle-amplification-based DNA-enzyme nanostructure for immobilization and functionalization of enzymes 用于酶固定化和功能化的基于滚动圈扩增技术的 DNA 酶纳米结构

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.10.002

Dongsheng Mao , Wenxing Li , Xueliang Liu , Jingqi Chen , Dali Wei , Lei Luo , Qianqin Yuan , Yu Yang , Xiaoli Zhu , Weihong Tan

Enzymes with ingenious structures and diverse functions are crucial for biomedical applications but face challenges like instability, limited targetability, and delivery complexity. We developed core-shell DNA-enzyme conjugates using rolling circle amplification (RCA), creating RCA-based DNA-enzyme nanostructure (RCA-DEN) for efficient enzyme immobilization and functionalization. RCA-DEN, characterized by densely packed nucleic acids and negligible disruption of enzyme activity, increases the stability of enzymes and nucleic acids while reducing technical difficulties, making it a versatile platform for diverse biomedical applications. This approach facilitates the modular customization of enzymes and the incorporation of functionalities such as aptamers and DNAzymes. The efficacy of RCA-DEN has been demonstrated in several areas, including selective catalysis, cascade catalysis, dynamic monitoring of intracellular chemical processes, and synergistic therapeutic interventions against tumors. Overall, this work provides a new perspective on enzyme immobilization and functionalization, paving the way for broader biomedical applications of enzymes.

具有巧妙结构和多样化功能的酶对生物医学应用至关重要，但也面临着不稳定性、靶向性有限和传递复杂性等挑战。我们利用滚动圆扩增（RCA）技术开发了核壳DNA-酶共轭物，形成了基于RCA的DNA-酶纳米结构（RCA-DEN），实现了酶的高效固定和功能化。RCA-DEN 的特点是核酸密集包装，对酶活性的干扰微乎其微，在增加酶和核酸稳定性的同时降低了技术难度，使其成为一个可用于多种生物医学应用的多功能平台。这种方法有利于对酶进行模块化定制，并加入适配体和 DNA 酶等功能。RCA-DEN 的功效已在多个领域得到证实，包括选择性催化、级联催化、细胞内化学过程的动态监测以及针对肿瘤的协同治疗干预。总之，这项工作为酶的固定化和功能化提供了一个新的视角，为酶更广泛的生物医学应用铺平了道路。

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引用次数: 0

Exploring enzymatic degradation, reinforcement, recycling, and upcycling of poly(ester)-poly(urethane) with movable crosslinks 探索具有可移动交联的聚（酯）-聚（氨基甲酸乙酯）的酶降解、加固、回收和再循环

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.09.026

Jiaxiong Liu , Ryohei Ikura , Kenji Yamaoka , Akihide Sugawara , Yuya Takahashi , Bunsho Kure , Naomi Takenaka , Junsu Park , Hiroshi Uyama , Yoshinori Takashima

Enzymes are highly efficient, chemoselective, and sustainable biocatalysts, standing out as eco-friendly tools to advance the circular plastics economy. Herein, we explored enzymatic reactions of poly(ε-caprolactone)-poly(urethane) (PCL-PUs) in organic solvent under different reaction conditions using Novozym 435 (immobilized lipase) as the enzyme. PCL-PUs with triacetylated γ-cyclodextrin (TAcγCD)-based movable crosslinks (PCL-γCD-PU) not only exhibited excellent mechanical properties due to effective energy dissipation, but also efficient enzymatic degradation that was optimized for increases in TAcγCD content. Under reaction time control, molecular weight and mechanical properties of PCL-γCD-PU were enhanced by a novel enzymatic reinforcement strategy. Without sorting, the degraded products are versatile resources that can be enzymatically closed-loop recycled by switching reaction concentration or enzymatically upcycled into value-added polymers by mixing with selective substrates. The facile polymer structure design combined with enzymatic reactions is expected to provide a broad approach for toughening various polymeric materials and advancing their development as sustainable resources.

酶是一种高效、化学选择性和可持续的生物催化剂，是推动循环塑料经济的环保工具。在此，我们以 Novozym 435（固定化脂肪酶）为酶，探索了在不同反应条件下有机溶剂中聚（ε-己内酯）-聚（氨基甲酸乙酯）（PCL-PUs）的酶促反应。具有基于三乙酰化γ-环糊精（TAcγCD）的可移动交联的 PCL-PU（PCL-γCD-PU）不仅由于有效的能量耗散而表现出优异的机械性能，而且随着 TAcγCD 含量的增加，酶降解效果也得到了优化。在反应时间控制下，新型酶强化策略提高了 PCL-γCD-PU 的分子量和机械性能。降解产物无需分拣，是一种多功能资源，可通过转换反应浓度进行酶法闭环循环，或通过与选择性基质混合进行酶法升级循环，转化为高附加值聚合物。简便的聚合物结构设计与酶促反应相结合，有望为各种聚合物材料的增韧提供广泛的方法，并推动其作为可持续资源的发展。

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引用次数: 0

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