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Synthesis of single-crystalline sp2-carbon-linked covalent organic frameworks through imine-to-olefin transformation 通过亚胺-烯烃转化合成sp2-碳键单晶共价有机骨架
IF 21.8 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-06 DOI: 10.1038/s41557-024-01690-y
Shengxu Li, Shunqi Xu, En Lin, Tonghai Wang, Haoyong Yang, Junyi Han, Yuxiang Zhao, Qunji Xue, Paolo Samorì, Zhenjie Zhang, Tao Zhang

sp2-carbon-linked covalent organic frameworks (sp2c-COFs) are crystalline porous polymers with repeat organic units linked by sp2 carbons, and have attracted increasing interest due to their robust skeleton and tunable semiconducting properties. Single-crystalline sp2c-COFs with well-defined structures can represent an ideal platform for investigating fundamental physics properties and device performance. However, the robust olefin bonds inhibit the reversible-reaction-based crystal self-correction, thus yielding polycrystalline or amorphous polymers. Here we report an imine-to-olefin transformation strategy to form single-crystal sp2c-COFs. The isolated single crystals display rectangular nanotube-like domains with sizes up to approximately 24 μm × 0.8 μm × 0.8 μm, and permanent pore distribution around 1.1 nm. The highly conjugated olefin linkage endows the crystals with enhanced electronic connectivity which determines a remarkable room-temperature metal-free ferromagnetism (8.6 × 10−3 emu g−1). Our protocol is robust and generally applicable for the synthesis of single-crystalline sp2c-COFs for future spin-electron devices.

sp2碳连接共价有机框架(sp2c-COFs)是由sp2碳连接的重复有机单元的结晶多孔聚合物,由于其坚固的骨架和可调的半导体特性而引起了越来越多的关注。具有明确结构的单晶sp2c-COFs可以代表研究基本物理性质和器件性能的理想平台。然而,坚固的烯烃键抑制了基于可逆反应的晶体自校正,从而产生多晶或非晶聚合物。在这里,我们报道了一种亚胺-烯烃转化策略,以形成单晶sp2c-COFs。分离得到的单晶显示出尺寸约为24 μm × 0.8 μm × 0.8 μm的矩形纳米管状畴,永久孔分布在1.1 nm左右。高度共轭的烯烃键使晶体具有增强的电子连通性,这决定了晶体具有显著的室温无金属铁磁性(8.6 × 10−3 emu g−1)。我们的方案是稳健的,普遍适用于单晶sp2c-COFs的合成,用于未来的自旋电子器件。
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引用次数: 0
Uniform single-crystal mesoporous metal–organic frameworks 均匀单晶介孔金属有机骨架
IF 21.8 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-06 DOI: 10.1038/s41557-024-01693-9
Zirui Lv, Runfeng Lin, Yi Yang, Kun Lan, Chin-Te Hung, Pengfei Zhang, Jinxiu Wang, Wanhai Zhou, Zaiwang Zhao, Zhongyao Wang, Jiawen Zou, Taoyang Wang, Tiancong Zhao, Yifei Xu, Dongliang Chao, Weimin Tan, Bo Yan, Qiaowei Li, Dongyuan Zhao, Xiaomin Li

The synthesis of mesoporous metal–organic frameworks (meso-MOFs) is desirable as these materials can be used in various applications. However, owing to the imbalance in structural tension at the micro-scale (MOF crystallization) and the meso-scales (assembly of micelles with MOF subunits), the formation of single-crystal meso-MOFs is challenging. Here we report the preparation of uniform single-crystal meso-MOF nanoparticles with ordered mesopore channels in microporous frameworks with definite arrangements, through a cooperative assembly method co-mediated by strong and weak acids. These nanoparticles feature a truncated octahedron shape with variable size and well-defined two-dimensional hexagonally structured (p6mm) columnar mesopores. Notably, the match between the crystallization kinetics of MOFs and the assembly kinetics of micelles is critical for forming the single-crystal meso-MOFs. On the basis of this strategy, we have constructed a library of meso-MOFs with tunable large pore sizes, controllable mesophases, various morphologies and multivariate components.

介孔金属有机骨架(meso-MOFs)的合成是理想的,因为这些材料可以用于各种用途。然而,由于结构张力在微观尺度(MOF结晶)和中观尺度(MOF亚基与胶束的组装)上的不平衡,单晶MOF的形成是具有挑战性的。在这里,我们报道了通过强酸和弱酸的协同组装方法,在微孔框架中制备具有有序介孔通道的均匀单晶介孔纳米颗粒。这些纳米颗粒具有截断的八面体形状,具有可变尺寸和定义良好的二维六边形结构(p6mm)柱状介孔。值得注意的是,mof的结晶动力学和胶束组装动力学之间的匹配对于形成单晶介观mof至关重要。基于这一策略,我们构建了一个具有可调大孔径、可控制中间相、多种形态和多元组分的介观mof库。
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引用次数: 0
Intellectual frameworks to understand complex biochemical systems at the origin of life 理解生命起源时复杂生化系统的知识框架
IF 19.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-06 DOI: 10.1038/s41557-024-01698-4
Burckhard Seelig, Irene A. Chen
Understanding the emergence of complex biochemical systems, such as protein translation, is a great challenge. Although synthetic approaches can provide insight into the potential early stages of life, they do not address the equally important question of why the complex systems of life would have evolved. In particular, the intricacies of the mechanisms governing the transfer of information from nucleic acid sequences to proteins make it difficult to imagine how coded protein synthesis could have emerged from a prebiotic soup. Here we discuss the use of intellectual frameworks in studying the emergence of life. We discuss how one such framework, namely the RNA world theory, has spurred research, and provide an overview of its limitations. We suggest that the emergence of coded protein synthesis could be broken into experimentally tractable problems by treating it as a molecular bricolage—a complex system integrating many different parts, each of which originally evolved for uses unrelated to its modern function—to promote a concrete understanding of its origin. It has been challenging to rationalize the emergence of complex biochemical systems because many parts with different functions needed to come together. This Perspective proposes a molecular bricolage—an evolutionary tinkering involving parts that initially evolved for unrelated functions—to provide an intellectual framework to study the origin of protein translation.
理解复杂生化系统的出现,如蛋白质翻译,是一个巨大的挑战。尽管综合方法可以让我们深入了解生命的潜在早期阶段,但它们并没有解决同样重要的问题,即复杂的生命系统为什么会进化。特别是,控制信息从核酸序列转移到蛋白质的复杂机制使得很难想象编码蛋白质合成是如何从益生元汤中出现的。在这里,我们讨论在研究生命的出现中使用智力框架。我们讨论了一个这样的框架,即RNA世界理论,是如何推动研究的,并概述了它的局限性。我们认为编码蛋白质合成的出现可以被分解成实验上易于处理的问题,通过将其视为一个分子拼凑物——一个由许多不同部分组成的复杂系统,每个部分最初都是为了与其现代功能无关的用途而进化的——来促进对其起源的具体理解。
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引用次数: 0
A trimetallic bismuth(I)-based allyl cation 一种三金属铋基烯丙基阳离子
IF 21.8 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-06 DOI: 10.1038/s41557-024-01691-x
Davide Spinnato, Nils Nöthling, Markus Leutzsch, Maurice van Gastel, Lucas Wagner, Frank Neese, Josep Cornella

The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis and unique electronic structure fundamentals. In this work, we describe the synthesis and characterization of a highly reduced bismuth salt featuring a cationic core based on three contiguous Bi(I) centres. The triatomic bismuth-based core exhibits an electronic configuration that mimics the canonical description of the archetypical carbon-based π-allyl cation. Structural, spectroscopic and theoretical analyses validate the unique π-delocalization between the bismuth’s highly diffused 6p orbitals, resulting in a bonding situation in which the three bismuth atoms are interconnected by two bonds, formally possessing a 1.5 bond order each. This electronic situation defines this complex as the heaviest and stable π-allyl cation of the periodic table. Furthermore, we demonstrate that the newly synthesized complex is able to act as a synthon for the transfer of a Bi(I) cation to forge other low-valent organobismuth complexes.

低价铋化合物的化学研究最近在催化和独特的电子结构基础方面开启了新的概念。在这项工作中,我们描述了一种高度还原的铋盐的合成和表征,该盐具有基于三个连续Bi(I)中心的阳离子核心。铋基三原子核的电子构型模仿了典型碳基π-烯丙基阳离子的典型描述。结构、光谱和理论分析验证了铋高度扩散的6p轨道之间独特的π离域,导致三个铋原子通过两个键相互连接的成键情况,每个键的形式顺序为1.5。这种电子状态定义了这个配合物是元素周期表中最重和最稳定的π-烯丙基阳离子。此外,我们证明了新合成的配合物能够作为Bi(I)阳离子转移的合成物来形成其他低价有机铋配合物。
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引用次数: 0
Synthesis of tertiary alkyl amines via photoinduced copper-catalysed nucleophilic substitution 光诱导铜催化亲核取代合成叔烷基胺
IF 21.8 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-03 DOI: 10.1038/s41557-024-01692-w
Hyungdo Cho, Xiaoyu Tong, Giuseppe Zuccarello, Robert L. Anderson, Gregory C. Fu

In view of the high propensity of tertiary alkyl amines to be bioactive, the development of new methods for their synthesis is an important challenge. Transition-metal catalysis has the potential to greatly expand the scope of nucleophilic substitution reactions of alkyl electrophiles; unfortunately, in the case of alkyl amines as nucleophiles, only one success has been described so far: the selective mono-alkylation of primary amines to form secondary amines. Here, using photoinduced copper catalysis, we report the synthesis of tertiary alkyl amines from secondary amines and unactivated alkyl electrophiles, two readily available coupling partners. Utilizing an array of tools, we have analysed the mechanism of this process; specifically, we have structurally characterized the three principal copper-based intermediates that are detected during catalysis and provided support for the key steps of the proposed catalytic cycle, including the coupling of a copper(II)–amine intermediate with an alkyl radical to form a C–N bond.

鉴于叔烷基胺具有较高的生物活性,开发新的合成方法是一项重要的挑战。过渡金属催化具有极大扩展烷基亲电试剂亲核取代反应范围的潜力;不幸的是,在烷基胺作为亲核试剂的情况下,迄今为止只有一个成功的描述:伯胺的选择性单烷基化形成仲胺。在这里,我们报道了利用光诱导铜催化,从仲胺和未活化的烷基亲电试剂这两个容易获得的偶联伙伴合成叔烷基胺。利用一系列工具,我们分析了这一过程的机制;具体来说,我们对催化过程中检测到的三个主要铜基中间体进行了结构表征,并为所提出的催化循环的关键步骤提供了支持,包括铜(II) -胺中间体与烷基自由基的偶联形成C-N键。
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引用次数: 0
Stereoselective amino alcohol synthesis via chemoselective electrocatalytic radical cross-couplings 通过化学选择性电催化自由基交叉偶联合成立体选择性氨基醇
IF 19.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-03 DOI: 10.1038/s41557-024-01695-7
Jiawei Sun, Shuanghu Wang, Kaid C. Harper, Yu Kawamata, Phil S. Baran
Amino alcohols are vital in natural products, pharmaceuticals and agrochemicals, and as key building blocks for various applications. Traditional synthesis methods often rely on polar bond retrosynthetic analysis, requiring extensive protecting group manipulations that complicate direct access. Here we show a streamlined approach using a serine-derived chiral carboxylic acid in stereoselective electrocatalytic decarboxylative transformations, enabling efficient access to enantiopure amino alcohols. Unlike conventional strategies, this radical method is both modular and general, offering stereoselective and chemoselective synthesis of diverse substituted amino alcohols. For example, aryl, alkenyl, alkyl and acyl fragments can be coupled efficiently with the serine-derived chiral acid under electrocatalytic decarboxylative conditions. We demonstrate its utility through the rapid synthesis of medicinally important compounds, as well as useful building blocks, highlighting its ability to simplify complex synthetic pathways through entirely different bond disconnections. This electrocatalytic method is robust and scalable, as demonstrated in a 72-gram-scale flow reaction. Amino alcohols are essential in pharmaceuticals, agrochemicals and other applications. Now, using a serine-derived chiral carboxylic acid, an electrocatalytic decarboxylative transformation enables efficient and stereoselective access to diverse amino alcohols. This method is scalable, modular and could offer rapid synthesis of medicinal compounds and key building blocks.
氨基醇在天然产品、药品和农用化学品中至关重要,是各种应用的关键组成部分。传统的合成方法通常依赖于极性键反合成分析,需要大量的保护基团操作,使直接获取复杂化。在这里,我们展示了一种流线型的方法,使用丝氨酸衍生的手性羧酸进行立体选择性电催化脱羧转化,从而有效地获得对映纯氨基醇。与传统的策略不同,这种激进的方法是模块化和通用的,提供立体选择性和化学选择性合成不同的取代氨基醇。例如,芳基、烯基、烷基和酰基片段可以在电催化脱羧条件下与丝氨酸衍生的手性酸有效偶联。我们通过快速合成具有重要医学意义的化合物以及有用的构建块来证明它的实用性,突出了它通过完全不同的键断开简化复杂合成途径的能力。这种电催化方法是稳健的和可扩展的,正如在72克规模的流动反应中所证明的那样。
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引用次数: 0
Four-electron reduction of benzene by a samarium(ii)-alkyl without the addition of external reducing agents 在不添加外部还原剂的情况下,烷基钐对苯的四电子还原
IF 19.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-03 DOI: 10.1038/s41557-024-01688-6
Georgia M. Richardson, Thayalan Rajeshkumar, Finlay M. Burke, Scott A. Cameron, Brooke D. Nicholls, Joanne E. Harvey, Robert A. Keyzers, Tane Butler, Simon Granville, Lujia Liu, Julien Langley, Li F. Lim, Nicholas Cox, Nicholas F. Chilton, Jamie Hicks, Nathaniel J. L. K. Davis, Laurent Maron, Mathew D. Anker
Benzene reduction by molecular complexes remains an important synthetic challenge, requiring harsh reaction conditions involving group I metals. Reductions of benzene, to date, typically result in a loss of aromaticity, although the benzene tetra-anion, a 10π-electron system, has been calculated to be stable and aromatic. Due to the lack of sufficiently potent reductants, four-electron reduction of benzene usually requires the use of group I metals. Here we demonstrate the four-electron reduction of benzene and some of its derivatives using a samarium(ii) alkyl reagent, with no requirement for group I metals. Whereas organosamarium(ii) typically reacts through one-electron processes, the compounds reported here feature a rare two-electron process. Combined experimental and computational results implicate a transient samarium(i) intermediate involved in this reduction process, which ultimately provides the benzene tetra-anion. The remarkably strong reducing power of this samarium(ii) alkyl implies a rich reactivity, providing scope for its application as a reducing agent. Benzene reduction by molecular complexes remains a considerable synthetic challenge, and typically requires harsh reaction conditions involving group I metals. Now it has been shown that a highly polar organometallic samarium alkyl complex enables the reduction of benzene to its tetra-anion without the need for a group I metal.
通过分子络合物还原苯仍然是一个重要的合成挑战,需要涉及I族金属的苛刻反应条件。迄今为止,苯的还原通常会导致芳香性的损失,尽管苯四阴离子,一个10π电子系统,已经计算出是稳定的和芳香的。由于缺乏足够有效的还原剂,苯的四电子还原通常需要使用I族金属。在这里,我们展示了四电子还原苯和它的一些衍生物使用钐(ii)烷基试剂,不需要I族金属。虽然有机钐(ii)通常通过单电子过程反应,但本文报道的化合物具有罕见的双电子过程。结合实验和计算结果表明,瞬态钐(i)中间体参与了这一还原过程,最终提供了苯四阴离子。烷基钐具有很强的还原性,具有丰富的反应活性,为其作为还原剂的应用提供了广阔的空间。
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引用次数: 0
Cytoskeleton-functionalized synthetic cells with life-like mechanical features and regulated membrane dynamicity 细胞骨架功能化的合成细胞,具有类似生命的机械特征和可调节的膜动力学
IF 21.8 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-03 DOI: 10.1038/s41557-024-01697-5
Sebastian Novosedlik, Felix Reichel, Thijs van Veldhuisen, Yudong Li, Hanglong Wu, Henk Janssen, Jochen Guck, Jan van Hest

The cytoskeleton is a crucial determinant of mammalian cell structure and function, providing mechanical resilience, supporting the cell membrane and orchestrating essential processes such as cell division and motility. Because of its fundamental role in living cells, developing a reconstituted or artificial cytoskeleton is of major interest. Here we present an approach to construct an artificial cytoskeleton that imparts mechanical support and regulates membrane dynamics. Our system involves amylose-based coacervates stabilized by a terpolymer membrane, with a cytoskeleton formed from polydiacetylene fibrils. The fibrils bundle due to interactions with the positively charged amylose derivative, forming micrometre-sized structures mimicking a cytoskeleton. Given the intricate interplay between cellular structure and function, the design and integration of this artificial cytoskeleton represent a crucial advancement, paving the way for the development of artificial cell platforms exhibiting enhanced life-like behaviour.

细胞骨架是哺乳动物细胞结构和功能的关键决定因素,提供机械弹性,支持细胞膜并协调细胞分裂和运动等基本过程。由于其在活细胞中的基本作用,开发重建或人工细胞骨架是主要的兴趣。在这里,我们提出了一种方法来构建一个人工细胞骨架,赋予机械支持和调节膜动力学。我们的系统包括由三元共聚物膜稳定的淀粉基凝聚体,以及由聚二乙炔原纤维形成的细胞骨架。原纤维束由于与带正电荷的直链淀粉衍生物相互作用,形成微米大小的结构,模拟细胞骨架。考虑到细胞结构和功能之间错综复杂的相互作用,这种人造细胞骨架的设计和集成代表了一个关键的进步,为开发具有增强的类生命行为的人造细胞平台铺平了道路。
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引用次数: 0
In situ nonlinear optical spectroscopy for probing buried oxide–water interfaces 原位非线性光谱学探测埋藏的氧化-水界面
IF 21.8 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-02 DOI: 10.1038/s41557-024-01709-4
Oxide–water interfaces are ubiquitous in nature and technological processes, but their characterization is difficult. Now, an in situ nonlinear optical spectroscopy approach enables the characterization of such buried interfaces. Aided by ab initio molecular dynamic simulations, unexpected reaction pathways are revealed for the silicon dioxide–water interface.
氧化-水界面在自然界和工艺过程中无处不在,但它们的表征是困难的。现在,一种原位非线性光谱学方法使这种埋藏界面的表征成为可能。借助从头算分子动力学模拟,揭示了二氧化硅-水界面意想不到的反应途径。
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引用次数: 0
Adaptive metal ion transport and metalloregulation-driven differentiation in pluripotent synthetic cells 多能合成细胞中适应性金属离子转运和金属调控驱动的分化
IF 19.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-23 DOI: 10.1038/s41557-024-01682-y
Sayuri L. Higashi, Yanjun Zheng, Taniya Chakraborty, Azadeh Alavizargar, Andreas Heuer, Seraphine V. Wegner
Pluripotent cells can yield different cell types determined by the specific sequence of differentiation signals that they encounter as the cell activates or deactivates functions and retains memory of previous inputs. Here, we achieved pluripotency in synthetic cells by incorporating three dormant apo-metalloenzymes such that they could differentiate towards distinct fates, depending on the sequence of specific metal ion transport with ionophores. In the first differentiation step, we selectively transported one of three extracellular metal ion cofactors into pluripotent giant unilamellar vesicles (GUVs), which resulted in elevation of intracellular pH, hydrogen peroxide production or GUV lysis. Previously added ionophores suppress transport with subsequent ionophores owing to interactions among them in the membrane, as corroborated by atomistic simulations. Consequently, the addition of a second ionophore elicits a dampened response in the multipotent GUV and a third ionophore results in no further response, reminiscent of a terminally differentiated GUV. The pluripotent GUV can differentiate into five final fates, depending on the sequence in which the three ionophores are added. The sequence of specific differentiation signals determines the fate of a pluripotent cell. Here pluripotency was introduced into synthetic cells by loading them with three dormant apo-metalloenzymes, which were activated through selective metal ion transport by one of three ionophores. Depending on the sequence of metal ion intake, the synthetic cells differentiated towards five distinct fates.
多能细胞可以产生不同的细胞类型,这取决于它们在细胞激活或禁用功能并保留先前输入的记忆时遇到的特定分化信号序列。在这里,我们通过结合三种休眠的载脂蛋白金属酶,在合成细胞中实现了多能性,这样它们就可以根据特定金属离子与离子载体运输的顺序,向不同的命运分化。在分化的第一步,我们选择性地将三种细胞外金属离子辅助因子中的一种转运到多能巨型单层囊泡(GUVs)中,导致细胞内pH升高,过氧化氢产生或GUV裂解。先前添加的离子载体由于在膜中相互作用而抑制与后续离子载体的运输,正如原子模拟所证实的那样。因此,在多能GUV中添加第二个电离层会导致反应减弱,而第三个电离层则不会导致进一步的反应,这让人联想到一个终末分化的GUV。多能GUV可以分化为五种最终命运,这取决于三个离子载体的添加顺序。
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引用次数: 0
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