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In Situ Synthesis and Assembly of Functional Materials and Devices in Living Systems. 生物系统中功能材料和设备的原位合成与组装。
IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-15 DOI: 10.1021/acs.accounts.4c00049
Wenbo Wang, Chanan D Sessler, Xiao Wang, Jia Liu

ConspectusIntegrating functional materials and devices with living systems enables novel methods for recording, manipulating, or augmenting organisms not accessible by traditional chemical, optical, or genetic approaches. (The term "device" refers to the fundamental components of complex electronic systems, such as transistors, capacitors, conductors, and electrodes.) Typically, these advanced materials and devices are synthesized, either through chemical or physical reactions, outside the biological systems (ex situ) before they are integrated. This is due in part to the more limited repertoire of biocompatible chemical transformations available for assembling functional materials in vivo. Given that most of the assembled bulk materials are impermeable to cell membranes and cannot go through the blood-brain barrier (BBB), the external synthesis poses challenges when trying to interface these materials and devices with cells precisely and in a timely manner and at the micro- and nanoscale─a crucial requirement for modulating cellular functions. In contrast to presynthesis in a separate location, in situ assembly, wherein small molecules or building blocks are directly assembled into functional materials within a biological system at the desired site of action, has offered a potential solution for spatiotemporal and genetic control of material synthesis and assembly.In this Account, we highlight recent advances in spatially and temporally targeted functional material synthesis and assembly in living cells, tissues and animals and provide perspective on how they may enable novel probing, modulation, or augmentation of fundamental biology. We discuss several strategies, starting from the traditional nontargeted methods to targeted assembly of functional materials and devices based on the endogenous markers of the biological system. We then focus on genetically targeted assembly of functional materials, which employs enzymatic catalysis centers expressed in living systems to assemble functional materials in specific molecular-defined cell types. We introduce the recent efforts of our group to modulate membrane capacitance and neuron excitability using in situ synthesized electrically functional polymers in a genetically targetable manner. These advances demonstrate the promise of in situ synthesis and assembly of functional materials and devices, including the optogenetic polymerization developed by our lab, to interface with cells in a cellular- or subcellular-specific manner by incorporating genetic and/or optical control over material assembly. Finally, we discuss remaining challenges, areas for improvement, potential applications to other biological systems, and novel methods for the in situ synthesis of functional materials that could be elevated by incorporating genetic or material design strategies. As researchers expand the toolkit of biocompatible in situ functional material synthetic techniques, we anticipate that these advancements c

内容提要将功能材料和器件与生命系统结合起来,可实现传统化学、光学或遗传方法无法实现的记录、操纵或增强生物体的新方法。(器件 "一词是指复杂电子系统的基本组件,如晶体管、电容器、导体和电极)。通常情况下,这些先进的材料和设备是在生物系统之外(原位)通过化学或物理反应合成的,然后再进行整合。这部分是由于可用于在体内组装功能材料的生物相容性化学反应种类较为有限。鉴于大多数组装好的块状材料对细胞膜无渗透性,无法通过血脑屏障(BBB),因此当试图将这些材料和设备与细胞精确、及时地连接在一起时,外部合成带来了挑战,而微米和纳米尺度是调节细胞功能的关键要求。在本报告中,我们将重点介绍在活细胞、组织和动物中以空间和时间为目标的功能材料合成和组装的最新进展,并就这些进展如何实现对基础生物学的新颖探测、调控或增强提出看法。我们讨论了几种策略,从传统的非靶向方法到基于生物系统内源标记的功能材料和设备的靶向组装。然后,我们将重点放在基因定向组装功能材料上,即利用在活体系统中表达的酶催化中心,在特定分子定义的细胞类型中组装功能材料。我们将介绍本研究小组最近在利用原位合成的电功能聚合物以基因靶向方式调节膜电容和神经元兴奋性方面所做的努力。这些进展展示了原位合成和组装功能材料和设备的前景,包括我们实验室开发的光遗传聚合技术,通过对材料组装的遗传和/或光学控制,以细胞或亚细胞特异性方式与细胞连接。最后,我们讨论了仍然存在的挑战、有待改进的领域、在其他生物系统中的潜在应用,以及通过纳入基因或材料设计策略来提升功能材料原位合成的新方法。随着研究人员扩大生物兼容原位功能材料合成技术的工具包,我们预计这些进展有可能为探索生物系统和开发治疗方案提供有价值的工具。
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引用次数: 0
Protocell Effects on RNA Folding, Function, and Evolution. 原生细胞对 RNA 折叠、功能和进化的影响
IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-15 DOI: 10.1021/acs.accounts.4c00174
Ranajay Saha, Jongseok A Choi, Irene A Chen

ConspectusCreating a living system from nonliving matter is a great challenge in chemistry and biophysics. The early history of life can provide inspiration from the idea of the prebiotic "RNA World" established by ribozymes, in which all genetic and catalytic activities were executed by RNA. Such a system could be much simpler than the interdependent central dogma characterizing life today. At the same time, cooperative systems require a mechanism such as cellular compartmentalization in order to survive and evolve. Minimal cells might therefore consist of simple vesicles enclosing a prebiotic RNA metabolism.The internal volume of a vesicle is a distinctive environment due to its closed boundary, which alters diffusion and available volume for macromolecules and changes effective molecular concentrations, among other considerations. These physical effects are mechanistically distinct from chemical interactions, such as electrostatic repulsion, that might also occur between the membrane boundary and encapsulated contents. Both indirect and direct interactions between the membrane and RNA can give rise to nonintuitive, "emergent" behaviors in the model protocell system. We have been examining how encapsulation inside membrane vesicles would affect the folding and activity of entrapped RNA.Using biophysical techniques such as FRET, we characterized ribozyme folding and activity inside vesicles. Encapsulation inside model protocells generally promoted RNA folding, consistent with an excluded volume effect, independently of chemical interactions. This energetic stabilization translated into increased ribozyme activity in two different systems that were studied (hairpin ribozyme and self-aminoacylating RNAs). A particularly intriguing finding was that encapsulation could rescue the activity of mutant ribozymes, suggesting that encapsulation could affect not only folding and activity but also evolution. To study this further, we developed a high-throughput sequencing assay to measure the aminoacylation kinetics of many thousands of ribozyme variants in parallel. The results revealed an unexpected tendency for encapsulation to improve the better ribozyme variants more than worse variants. During evolution, this effect would create a tilted playing field, so to speak, that would give additional fitness gains to already-high-activity variants. According to Fisher's Fundamental Theorem of Natural Selection, the increased variance in fitness should manifest as faster evolutionary adaptation. This prediction was borne out experimentally during in vitro evolution, where we observed that the initially diverse ribozyme population converged more quickly to the most active sequences when they were encapsulated inside vesicles.The studies in this Account have expanded our understanding of emergent protocell behavior, by showing how simply entrapping an RNA inside a vesicle, which could occur spontaneously during vesicle formation, might profoundly affect the

Conspectus从非生物物质中创造一个生命系统是化学和生物物理学的巨大挑战。生命的早期历史可以从核糖酶建立的前生物 "RNA 世界 "的想法中得到启发,在这个世界中,所有的遗传和催化活动都是由 RNA 执行的。这样的系统可能比当今生命所特有的相互依存的中心教条要简单得多。同时,合作系统需要一种机制,如细胞分隔,才能生存和进化。因此,最小的细胞可能由简单的囊泡组成,囊泡内封闭着一种前生物 RNA 新陈代谢。囊泡的内部容积是一个独特的环境,因为其封闭的边界改变了大分子的扩散和可用容积,并改变了有效的分子浓度等因素。这些物理效应在机理上有别于静电排斥等化学作用,后者也可能发生在膜边界和封装内容物之间。膜与 RNA 之间的间接和直接相互作用会在原电池模型系统中产生非直观的 "突发 "行为。我们一直在研究膜囊泡内的封装会如何影响夹带的 RNA 的折叠和活性。我们利用 FRET 等生物物理技术,描述了囊泡内核糖核酸酶折叠和活性的特征。在模型原细胞内的封装通常会促进核糖核酸的折叠,这与排除体积效应一致,与化学相互作用无关。在研究的两个不同系统(发夹核糖核酸酶和自氨基酸酰化核糖核酸)中,这种能量稳定化转化为核糖核酸酶活性的提高。一个特别有趣的发现是,封装可以挽救突变核糖酶的活性,这表明封装不仅会影响折叠和活性,还会影响进化。为了进一步研究这个问题,我们开发了一种高通量测序方法,以平行测定数千个核糖酶变体的氨基酰化动力学。结果表明,与较差的变体相比,封装有一种意想不到的趋势,即较好的核糖酶变体会得到更多的改善。可以说,在进化过程中,这种效应会形成一种倾斜的竞争环境,使已经具有较高活性的变体获得额外的适应性收益。根据费雪的自然选择基本定理,适应性差异的增加应表现为更快的进化适应。这一预测在体外进化过程中得到了实验证实。我们观察到,当核糖酶被包裹在囊泡内时,最初多样化的核糖酶群体会更快地向最活跃的序列靠拢。本实验的研究拓展了我们对突发性原细胞行为的理解,展示了在囊泡形成过程中可能自发发生的简单地将RNA包裹在囊泡内的行为是如何深刻影响RNA的进化格局的。由于复制和选择的指数动态变化,即使是活动和功能的微小变化也可能导致重大的进化后果。通过仔细研究最小但却出奇复杂的原细胞的细节,我们也许有一天会追踪到一条从封装 RNA 到生命系统的途径。
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引用次数: 0
Hunting for the Intermolecular Diels-Alderase. 寻找分子间二醛酸酯酶
IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1021/acs.accounts.4c00315
Lei Gao, Qi Ding, Xiaoguang Lei

ConspectusThe Diels-Alder reaction is well known as a concerted [4 + 2] cycloaddition governed by the Woodward-Hoffmann rules. Since Prof. Otto Diels and his student Kurt Alder initially reported the intermolecular [4 + 2] cycloaddition between cyclopentadiene and quinone in 1928, it has been recognized as one of the most powerful chemical transformations to build C-C bonds and construct cyclic structures. This named reaction has been widely used in synthesizing natural products and drug molecules. Driven by the synthetic importance of the Diels-Alder reaction, identifying the enzyme that stereoselectively catalyzes the Diels-Alder reaction has become an intriguing research area in natural product biosynthesis and biocatalysis. With significant progress in sequencing and bioinformatics, dozens of Diels-Alderases have been characterized in microbial natural product biosynthesis. However, few are evolutionally dedicated to catalyzing an intermolecular Diels-Alder reaction with a concerted mechanism.This Account summarizes our endeavors to hunt for the naturally occurring intermolecular Diels-Alderase from plants. Our research journey started from the biomimetic syntheses of D-A-type terpenoids and flavonoids, showing that plants use both nonenzymatic and enzymatic intermolecular [4 + 2] cycloadditions to create complex molecules. Inspired by the biomimetic syntheses, we identify an intermolecular Diels-Alderase hidden in the biosynthetic pathway of mulberry Diels-Alder-type cycloadducts using a biosynthetic intermediate probe-based target identification strategy. This enzyme, MaDA, is an endo-selective Diels-Alderase and is then functionally characterized as a standalone intermolecular Diels-Alderase with a concerted but asynchronous mechanism. We also discover the exo-selective intermolecular Diels-Alderases in Morus plants. Both the endo- and exo-selective Diels-Alderases feature a broad substrate scope, but their mechanisms for controlling the endo/exo pathway are different. These unique intermolecular Diels-Alderases phylogenetically form a subgroup of FAD-dependent enzymes that can be found only in moraceous plants, explaining why this type of [4 + 2] cycloadduct is unique to moraceous plants. Further studies of the evolutionary mechanism reveal that an FAD-dependent oxidocyclase could acquire the Diels-Alderase activity via four critical amino acid mutations and then gradually lose its original oxidative activity to become a standalone Diels-Alderase during the natural evolution. Based on these insights, we designed new Diels-Alderases and achieved the diversity-oriented chemoenzymatic synthesis of D-A products using either naturally occurring or engineered Diels-Alderases.Overall, this Account describes our decade-long efforts to discover the intermolecular Diels-Alderases in Morus plants, particularly highlighting the importance of biomimetic synthesis and chemical proteomics in

产品简介 Diels-Alder 反应是众所周知的受 Woodward-Hoffmann 规则支配的协同 [4 + 2] 环加成反应。自 Otto Diels 教授和他的学生 Kurt Alder 于 1928 年首次报道环戊二烯和醌之间的分子间 [4 + 2] 环加成反应以来,该反应已被公认为是建立 C-C 键和构建环状结构的最强有力的化学转化之一。这一被命名为 "环化 "的反应被广泛用于合成天然产品和药物分子。由于 Diels-Alder 反应在合成方面的重要作用,确定立体选择性催化 Diels-Alder 反应的酶已成为天然产物生物合成和生物催化领域一个引人入胜的研究领域。随着测序和生物信息学的长足进步,在微生物天然产物的生物合成过程中,已有数十种 Diels-Alder 酶得到了表征。本报告总结了我们从植物中寻找天然分子间 Diels-Alder 酶的努力。我们的研究历程始于 D-A 型萜类化合物和黄酮类化合物的仿生合成,结果表明植物利用非酶和酶促分子间[4 + 2]环加成反应生成复杂分子。受仿生合成的启发,我们采用基于生物合成中间体探针的目标鉴定策略,鉴定出了隐藏在桑树 Diels-Alder 型环加成产物生物合成途径中的分子间 Diels-Ald 酶。这种酶(MaDA)是一种内选择性 Diels-Alderase,然后在功能上被表征为一种具有协同但不同步机制的独立分子间 Diels-Alderase 。我们还在桑科植物中发现了外选择性分子间 Diels-Alder 酶。分子内和分子外选择性 Diels-Alderase 的底物范围都很广,但它们控制分子内/分子外途径的机制却各不相同。这些独特的分子间 Diels-Alderase 在系统发育上形成了一个依赖 FAD 的酶亚群,该亚群只存在于腐生植物中,这也解释了为什么这种 [4 + 2] 环加成物是腐生植物所特有的。对进化机制的进一步研究发现,依赖于 FAD 的氧化环化酶可以通过四个关键氨基酸的突变获得 Diels-Alderase 活性,然后在自然进化过程中逐渐失去原有的氧化活性,成为一个独立的 Diels-Alderase 。基于这些认识,我们设计了新的Diels-Alderases,并利用天然存在的或工程化的Diels-Alderases实现了D-A产物的多样性化学合成。总之,本报告描述了我们长达十年之久发现桑科植物分子间Diels-Alderases的努力,特别强调了生物模拟合成和化学蛋白质组学在发现植物中新的分子间Diels-Alderases方面的重要性。同时,本报告还涵盖了分子间 Diels-Alderases 的进化和催化机理研究,为如何发现和设计新的 Diels-Alderases 作为有机合成的强大生物催化剂提供了新的见解。
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引用次数: 0
An Atom-Precise Understanding of DNA-Stabilized Silver Nanoclusters. 从原子角度精确理解 DNA 稳定银纳米簇。
IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1021/acs.accounts.4c00256
Anna Gonzàlez-Rosell, Stacy M Copp

ConspectusDNA-stabilized silver nanoclusters (AgN-DNAs) are sequence-encoded fluorophores. Like other noble metal nanoclusters, the optical properties of AgN-DNAs are dictated by their atomically precise sizes and shapes. What makes AgN-DNAs unique is that nanocluster size and shape are controlled by nucleobase sequence of the templating DNA oligomer. By choice of DNA sequence, it is possible to synthesize a wide range of AgN-DNAs with diverse emission colors and other intriguing photophysical properties. AgN-DNAs hold significant potential as "programmable" emitters for biological imaging due to their combination of small molecular-like sizes, bright and sequence-tuned fluorescence, low toxicities, and cost-effective synthesis. In particular, the potential to extend AgN-DNAs into the second near-infrared region (NIR-II) is promising for deep tissue imaging, which is a major area of interest for advancing biomedical imaging. Achieving this goal requires a deep understanding of the structure-property relationships that govern AgN-DNAs in order to design AgN-DNA emitters with sizes and geometries that support NIR-II emission.In recent years, major advances have been made in understanding the structure and composition of AgN-DNAs, enabling new insights into the correlation of nanocluster structure and photophysical properties. These advances have hinged on combined innovations in mass characterization and crystallography of compositionally pure AgN-DNAs, together with combinatorial experiments and machine learning-guided design. A combined approach is essential due to the major challenge of growing suitable AgN-DNA crystals for diffraction and to the labor-intensive nature of preparing and solving the molecular formulas of atomically precise AgN-DNAs by mass spectrometry. These approaches alone are not feasibly scaled to explore the large sequence space of DNA oligomer templates for AgN-DNAs.This account describes recent fundamental advances in AgN-DNA science that have been enabled by high throughput synthesis and fluorimetry together with detailed analytical studies of purified AgN-DNAs. First, short introductions to nanocluster chemistry and AgN-DNA basics are presented. Then, we review recent large-scale studies that have screened thousands of DNA templates for AgN-DNAs, leading to discovery of distinct classes of these emitters with unique cluster core compositions and ligand chemistries. In particular, the discovery of a new class of chloride-stabilized AgN-DNAs enabled the first ab initio calculations of AgN-DNA electronic structure and present new approaches to stabilize these emitters in biologically relevant conditions. Near-infrared (NIR) emissive AgN-DNAs are also found to exhibit diverse structures and prope

ConspectusDNA 稳定银纳米团簇(AgN-DNAs)是一种序列编码荧光团。与其他贵金属纳米团簇一样,AgN-DNA 的光学特性由其原子级精确尺寸和形状决定。AgN-DNA 的独特之处在于,纳米团簇的大小和形状受模板 DNA 寡聚体核碱基序列的控制。通过选择 DNA 序列,可以合成出多种具有不同发射颜色和其他有趣光物理性质的 AgN-DNA。AgN-DNA 具有类似分子的小尺寸、明亮且序列可调的荧光、低毒性和低成本合成等特点,因此具有作为生物成像 "可编程 "发射体的巨大潜力。特别是,将 AgN-DNA 扩展到第二个近红外区域(NIR-II)的潜力有望用于深部组织成像,而这正是推进生物医学成像的一个主要关注领域。要实现这一目标,需要深入了解 AgN-DNA 的结构-性质关系,以便设计出尺寸和几何形状均支持 NIR-II 发射的 AgN-DNA 发射器。近年来,人们在了解 AgN-DNA 的结构和组成方面取得了重大进展,从而对纳米簇结构和光物理特性的相关性有了新的认识。这些进展有赖于对成分纯净的 AgN-DNA 进行质量表征和晶体学方面的综合创新,以及组合实验和机器学习指导设计。由于生长适合衍射的 AgN-DNA 晶体是一项重大挑战,而且通过质谱法制备和求解原子精确的 AgN-DNA 的分子式也是一项劳动密集型工作,因此必须采用综合方法。本文介绍了 AgN-DNA 科学的最新基本进展,这些进展得益于高通量合成和荧光测定法,以及对纯化 AgN-DNA 的详细分析研究。首先,我们简要介绍了纳米簇化学和 AgN-DNA 基础知识。然后,我们回顾了最近进行的大规模研究,这些研究筛选了成千上万的 AgN-DNA DNA 模板,从而发现了这些具有独特簇核组成和配体化学性质的不同类别的发射器。特别是发现了一类新的氯化物稳定 AgN-DNA,首次实现了 AgN-DNA 电子结构的 ab initio 计算,并提出了在生物相关条件下稳定这些发射体的新方法。我们还发现近红外(NIR)发射型 AgN-DNA 具有多种结构和特性。最后,我们重点介绍了最近用于靶向荧光成像的近红外 AgN-DNA 的原理验证。未来,我们将继续努力将 AgN-DNAs 推向组织透明度窗口,在近红外-II 组织透明度窗口进行荧光成像。
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引用次数: 0
Surface Engineering of Two-Dimensional Black Phosphorus for Advanced Nanophotonics. 用于先进纳米光子学的二维黑磷表面工程。
IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-11 DOI: 10.1021/acs.accounts.4c00251
Weichun Huang, Yuming Yang, Han Zhang

ConspectusEverything in the world has two sides. We should correctly understand its two sides to pursue the positive side and get rid of the negative side. Recently, two-dimensional (2D) black phosphorus (BP) has received a tremendous amount of attention and has been applied for broad applications in optoelectronics, transistors, logic devices, and biomedicines due to its intrinsic properties, e.g., thickness-dependent bandgap, high mobility, highly anisotropic charge transport, and excellent biodegradability and biocompatibility. On one hand, rapid degradation of 2D BP under ambient conditions becomes a vital bottleneck that largely hampers its practical applications in optical and optoelectronic devices and photocatalysis. On the other hand, just because of its ambient instability, 2D BP as a novel kind of nanomedicine in a cancer drug delivery system can not only satisfy effective cancer therapy but also enable its safe biodegradation in vivo. Until now, a variety of surface functionality types and approaches have been employed to rationally modify 2D BP to meet the growing requirements of advanced nanophotonics.In this Account, we describe our research on surface engineering of 2D BP in two opposite ways: (i) stabilizing 2D BP by various approaches for advanced nanophotonic devices with both remarkable photoresponse behavior and environmentally structural stability and (ii) making full use of biodegradation, biocompatibility, and biological activity (e.g., photothermal therapy, photodynamic therapy, and bioimaging) of 2D BP for the construction of high-performance delivery nanoplatforms for biophotonic applications. We highlight the targeted aims of the surface-engineered 2D BP for advanced nanophotonics, including photonic devices (optics, optoelectronics, and photocatalysis) and photoinduced cancer therapy, by means of various surface functionalities, such as heteroatom incorporation, polymer functionalization, coating, heterostructure design, etc. From the viewpoint of potential applications, the fundamental properties of surface-engineered 2D BP and recent advances in surface-engineered 2D BP-based nanophotonic devices are briefly discussed. For the photonic devices, surface-engineered 2D BP can not only effectively improve environmentally structural stability but also simultaneously maintain photoresponse performance, enabling 2D BP-based devices for a wide range of practical applications. In terms of the photoinduced cancer therapy, surface-engineered 2D BP is more appropriate for the treatment of cancer due to negligible toxicity and excellent biodegradation and biocompatibility. We also provide our perspectives on future opportunities and challenges in this important and fast-growing field. It is envisioned that this Account can attract more attention in this area and inspire more scientists in a variety of research communities to accelerate the development of 2D BP for more widespread high-performance nanophotonic applic

观点世界上任何事物都有两面性。我们应该正确认识其两面性,追求积极的一面,摆脱消极的一面。近年来,二维(2D)黑磷(BP)因其与厚度相关的带隙、高迁移率、高度各向异性的电荷传输以及优异的生物降解性和生物相容性等固有特性,受到了广泛关注,并在光电子、晶体管、逻辑器件和生物医药等领域得到了广泛应用。一方面,二维 BP 在环境条件下的快速降解成为一个重要瓶颈,在很大程度上阻碍了其在光学和光电设备以及光催化领域的实际应用。另一方面,正因为二维 BP 在环境中的不稳定性,将其作为一种新型纳米药物应用于癌症给药系统中,不仅能满足有效的癌症治疗,还能实现其在体内的安全生物降解。迄今为止,人们采用了多种表面功能类型和方法对二维 BP 进行合理改性,以满足日益增长的先进纳米光子学的要求。在本报告中,我们从两个相反的方面介绍了我们对二维 BP 表面工程的研究:(i) 通过各种方法稳定二维 BP,使其具有显著的光响应行为和环境结构稳定性的先进纳米光子器件;(ii) 充分利用生物降解、生物相容性和生物活性(如光热疗法、光动力疗法、光子治疗等)、(ii) 充分利用二维 BP 的生物降解性、生物相容性和生物活性(如光热疗法、光动力疗法和生物成像),构建用于生物光子应用的高性能传输纳米平台。我们强调了通过各种表面功能(如杂原子结合、聚合物功能化、涂层、异质结构设计等)将表面工程化的二维 BP 用于先进纳米光子学的目标,包括光子器件(光学、光电子学和光催化)和光诱导癌症治疗。从潜在应用的角度,简要讨论了表面工程二维 BP 的基本特性以及基于表面工程二维 BP 的纳米光子器件的最新进展。对于光子器件而言,表面工程化二维 BP 不仅能有效改善环境结构稳定性,还能同时保持光响应性能,从而使基于二维 BP 的器件具有广泛的实际应用前景。在光诱导癌症治疗方面,表面工程二维 BP 的毒性可忽略不计,且具有良好的生物降解性和生物相容性,因此更适合用于癌症治疗。我们还对这一重要且快速发展的领域未来的机遇和挑战进行了展望。我们希望该开户绑定手机领体验金能吸引更多的人关注这一领域,并激励更多研究界的科学家加快二维 BP 的开发,以实现更广泛的高性能纳米光子应用。
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引用次数: 0
Multiscale Approach for Tuning Communication among Chemical Oscillators Confined in Biomimetic Microcompartments. 仿生微室中化学振荡器间通信的多尺度调谐方法
IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-11 DOI: 10.1021/acs.accounts.4c00232
Federico Rossi, Sandra Ristori, Ali Abou-Hassan

ConspectusInspired by the biological world, new cross-border disciplines and technologies have emerged. Relevant examples include systems chemistry, which offers a bottom-up approach toward chemical complexity, and bio/chemical information and communication technology (bio/chemical ICT), which explores the conditions for propagating signals among individual microreactors separated by selectively permeable membranes. To fabricate specific arrays of microreactors, microfluidics has been demonstrated as an excellent method. In particular, droplet-based microfluidics is a powerful tool for encapsulating biological entities and chemical reagents in artificial microenvironments, mostly water-in-oil microdroplets. In these systems, the interfaces are liquid-liquid, and their physicochemical properties are key factors for tuning the coupling between molecular diffusion. Simple and double emulsions, where aqueous domains are in equilibrium with oil domains through boundary layers of amphiphilic molecules, are organized assemblies with high interfacial-area-to-volume ratios. These membranes can be engineered to obtain different surface charges, single- or multilayer stacking, and a variable degree of defects in molecular packing. Emulsions find application in many fields, including the food industry, pharmaceutics, and cosmetics. Furthermore, micro- and nanoemulsions can be used to model the propagation of chemical species through long distances, which is not only vital for cell signaling but also significant in molecular computing. Here we present in-depth research on the faceted world of solutions confined in restricted environments. In particular, we focused on the multiscale aspects of structure and dynamics from molecular to micro and macro levels. The Belousov-Zhabotinsky chemical reaction, known for its robustness and well-documented oscillatory behavior, was selected to represent a generic signal emitter/receiver confined within microenvironments separated by liquid-liquid interfaces. In this pulse generator, the temporal and spatial progressions are governed by periodic fluctuations in the concentration of chemical species, which act as activatory or inhibitory messengers over long distances. When organized into "colonies" or arrays, these micro-oscillators exhibit emergent dynamical behaviors at the population level. These behaviors can be finely tuned by manipulating the geometrical distribution of the oscillators and the properties of the interfaces at the nanoscale. By carefully selecting the membrane composition, it is possible to drive the system toward either in-phase, antiphase, or mixed synchronization regimes among individual oscillators, depending on messenger molecules. This relatively simple lab-scale model replicates some of the communication strategies commonly found in biological systems, particularly those based on the passive diffusion of chemical and electrical signals. It can help shed light on fundamental life processes

受生物世界的启发,新的跨界学科和技术应运而生。相关的例子包括系统化学和生物/化学信息与通信技术(生物/化学 ICT),前者提供了一种自下而上的方法来研究化学的复杂性,后者则探索了在被选择性渗透膜隔开的单个微反应器之间传播信号的条件。微流控技术已被证明是制造特定微反应器阵列的绝佳方法。尤其是基于液滴的微流控技术,是将生物实体和化学试剂封装在人工微环境(主要是油包水微滴)中的有力工具。在这些系统中,界面是液-液界面,其物理化学特性是调整分子扩散耦合的关键因素。简单乳液和双乳液中,水域通过两亲性分子的边界层与油域处于平衡状态,是具有高界面面积-体积比的有组织集合体。可以对这些膜进行设计,以获得不同的表面电荷、单层或多层堆叠以及不同程度的分子堆积缺陷。乳液在许多领域都有应用,包括食品工业、制药和化妆品。此外,微乳液和纳米乳液还可用于模拟化学物种的远距离传播,这不仅对细胞信号的传递至关重要,而且对分子计算也意义重大。在此,我们将深入研究封闭在受限环境中的溶液世界。我们尤其关注从分子到微观和宏观层面的结构和动力学的多尺度方面。贝洛索夫-扎博金斯基化学反应以其稳健性和有据可查的振荡行为而闻名,我们选择了它来代表被液-液界面分隔的微环境中的通用信号发射器/接收器。在这种脉冲发生器中,时间和空间上的进展受化学物质浓度周期性波动的支配,这些化学物质在长距离上充当激活或抑制信使。当这些微振荡器组织成 "群落 "或阵列时,就会在群体水平上表现出突发性动态行为。通过操纵振荡器的几何分布和纳米级界面的特性,可以对这些行为进行微调。通过仔细选择膜的组成,就有可能根据信使分子的不同驱动系统走向单个振荡器之间的同相、反相或混合同步状态。这个相对简单的实验室规模模型复制了生物系统中常见的一些通信策略,特别是那些基于化学和电信号被动扩散的通信策略。它有助于揭示基本生命过程,并激发分子计算和智能材料的新应用。
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引用次数: 0
How Droplets Can Accelerate Reactions─Coacervate Protocells as Catalytic Microcompartments. 液滴如何加速反应--作为催化微区的凝聚原胞
IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-05 DOI: 10.1021/acs.accounts.4c00114
Iris B A Smokers, Brent S Visser, Annemiek D Slootbeek, Wilhelm T S Huck, Evan Spruijt

ConspectusCoacervates are droplets formed by liquid-liquid phase separation (LLPS) and are often used as model protocells-primitive cell-like compartments that could have aided the emergence of life. Their continued presence as membraneless organelles in modern cells gives further credit to their relevance. The local physicochemical environment inside coacervates is distinctly different from the surrounding dilute solution and offers an interesting microenvironment for prebiotic reactions. Coacervates can selectively take up reactants and enhance their effective concentration, stabilize products, destabilize reactants and lower transition states, and can therefore play a similar role as micellar catalysts in providing rate enhancement and selectivity in reaction outcome. Rate enhancement and selectivity must have been essential for the origins of life by enabling chemical reactions to occur at appreciable rates and overcoming competition from hydrolysis.In this Accounts, we dissect the mechanisms by which coacervate protocells can accelerate reactions and provide selectivity. These mechanisms can similarly be exploited by membraneless organelles to control cellular processes. First, coacervates can affect the local concentration of reactants and accelerate reactions by copartitioning of reactants or exclusion of a product or inhibitor. Second, the local environment inside the coacervate can change the energy landscape for reactions taking place inside the droplets. The coacervate is more apolar than the surrounding solution and often rich in charged moieties, which can affect the stability of reactants, transition states and products. The crowded nature of the droplets can favor complexation of large molecules such as ribozymes. Their locally different proton and water activity can facilitate reactions involving a (de)protonation step, condensation reactions and reactions that are sensitive to hydrolysis. Not only the coacervate core, but also the surface can accelerate reactions and provides an interesting site for chemical reactions with gradients in pH, water activity and charge. The coacervate is often rich in catalytic amino acids and can localize catalysts like divalent metal ions, leading to further rate enhancement inside the droplets. Lastly, these coacervate properties can favor certain reaction pathways, and thereby give selectivity over the reaction outcome.These mechanisms are further illustrated with a case study on ribozyme reactions inside coacervates, for which there is a fine balance between concentration and reactivity that can be tuned by the coacervate composition. Furthermore, coacervates can both catalyze ribozyme reactions and provide product selectivity, demonstrating that coacervates could have functioned as enzyme-like catalytic microcompartments at the origins of life.

Conspectus液态悬浮体是通过液-液相分离(LLPS)形成的液滴,经常被用作原细胞模型--可能有助于生命出现的原始细胞样区室。它们作为无膜细胞器继续存在于现代细胞中,这进一步证明了它们的相关性。凝聚体内部的局部物理化学环境与周围的稀溶液截然不同,为预生物反应提供了一个有趣的微环境。凝聚态可选择性地吸收反应物并提高其有效浓度,稳定生成物,破坏反应物和较低过渡态的稳定性,因此可在提供反应结果的速率增强和选择性方面发挥与胶束催化剂类似的作用。通过使化学反应以可观的速率进行并克服水解竞争,速率增强和选择性对于生命的起源肯定是至关重要的。在本报告中,我们剖析了凝聚态原胞加速反应和提供选择性的机制。无膜细胞器同样可以利用这些机制来控制细胞过程。首先,凝聚态原胞可以影响反应物的局部浓度,并通过反应物的共分配或产物或抑制剂的排斥来加速反应。其次,凝聚态有机物内部的局部环境可以改变液滴内部反应的能量分布。与周围的溶液相比,凝聚态具有更强的极性,通常富含带电分子,这会影响反应物、过渡态和产物的稳定性。液滴的拥挤特性有利于核糖酶等大分子的复合。它们局部不同的质子和水活性可促进涉及(去)质子化步骤的反应、缩合反应和对水解敏感的反应。不仅是凝聚态内核,凝聚态表面也能加速反应,并为 pH 值、水活性和电荷梯度的化学反应提供一个有趣的场所。共蒸物通常富含催化氨基酸,可将二价金属离子等催化剂定位,从而进一步提高液滴内部的速率。最后,辅水合物的这些特性可有利于某些反应途径,从而使反应结果具有选择性。辅水合物内核糖酶反应的案例研究进一步说明了这些机理,其中浓度和反应活性之间的微妙平衡可通过辅水合物的成分进行调整。此外,共渗物既能催化核糖酶反应,又能提供产物选择性,这表明共渗物在生命起源时就能发挥类似酶催化微孔的功能。
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引用次数: 0
Overcoming Challenges of Lignin Nanoparticles: Expanding Opportunities for Scalable and Multifunctional Nanomaterials. 克服木质素纳米颗粒的挑战:拓展可扩展多功能纳米材料的机遇。
IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-04 DOI: 10.1021/acs.accounts.4c00206
Adrian Moreno, Mika H Sipponen

ConspectusThe increasing demand for polymeric materials derived from petroleum resources, along with rising concerns about climate change and global plastic pollution, has driven the development of biobased polymeric materials. Lignin, which is the second most abundant biomacromolecule after cellulose, represents a promising renewable raw material source for the preparation of advanced materials. The lucrative properties of lignin include its high carbon content (>60 atom %), high thermal stability, biodegradability, antioxidant activity, absorbance of ultraviolet radiation, and slower biodegradability compared to other wood components. Moreover, the advent of lignin nanoparticles (LNPs) over the last ten years has circumvented many well-known shortcomings of technical lignins, such as heterogeneity and poor compatibility with polymers, thereby unlocking the great potential of lignin for the development of advanced functional materials.LNPs stand out owing to their well-defined spherical shape and excellent colloidal stability, which is due to the electrostatic repulsion forces of carboxylic acid and phenolic hydroxyl groups enriched on their surface. These forces prevent their aggregation in aqueous dispersions (pH 3-9) and provide a high surface area to mass ratio that has been exploited to adsorb positively charged compounds such as enzymes or polymers. Consequently, it is not surprising that LNPs have become a prominent player in applied research in areas such as biocatalysis and polymeric composites, among others. However, like all ventures of life, LNPs also face certain challenges that limit their potential end-uses. Solvent instability remains the most challenging aspect due to the tendency of these particles to dissolve or aggregate in organic solvents and basic or acidic pH, thus limiting the window for their chemical functionalization and applications. In addition, the need for organic solvent during their preparation, the poor miscibility with hydrophobic polymeric matrices, and the nascent phase regarding their use in smart materials have been identified as important challenges that need to be addressed.In this Account, we recapitulate our efforts over the past years to overcome the main limitations mentioned above. We begin with a brief introduction to the fundamentals of LNPs and a detailed discussion of their associated challenges. We then highlight our work on: (i) Preparation of lignin-based nanocomposites with improved properties through a controlled dispersion of LNPs within a hydrophobic polymeric matrix, (ii) Stabilization of LNPs via covalent (intraparticle cross-linking) and noncovalent (hydration barrier) approaches, (iii) The development of an organic-solvent-free method for the production of LNPs, and (iv) The development of LNPs toward smart materials with high lignin content. Finally, we also offer our perspectives on this rapidly growing field.

展望人们对从石油资源中提炼的聚合材料的需求日益增长,同时对气候变化和全球塑料污染的担忧也日益加剧,这推动了生物基聚合材料的发展。木质素是仅次于纤维素的第二大生物大分子,是制备先进材料的一种前景广阔的可再生原料来源。木质素具有高碳含量(大于 60 原子%)、高热稳定性、生物可降解性、抗氧化活性、紫外线辐射吸收能力以及比其他木材成分更慢的生物降解性等有利特性。此外,近十年来木质素纳米颗粒(LNPs)的出现克服了技术木质素的许多众所周知的缺点,如异质性和与聚合物的兼容性差,从而释放了木质素在开发先进功能材料方面的巨大潜力。木质素纳米颗粒之所以脱颖而出,是因为其表面富含的羧酸和酚羟基的静电斥力使其具有明确的球形和出色的胶体稳定性。这些力量阻止了它们在水分散液(pH 值为 3-9)中的聚集,并提供了高表面积质量比,可用于吸附带正电荷的化合物,如酶或聚合物。因此,LNPs 在生物催化和聚合物复合材料等领域的应用研究中大显身手也就不足为奇了。然而,与所有生命企业一样,LNPs 也面临着某些挑战,限制了其潜在的最终用途。溶剂不稳定性仍然是最具挑战性的方面,因为这些微粒在有机溶剂和碱性或酸性 pH 值下容易溶解或聚集,从而限制了其化学功能化和应用的窗口。此外,在制备过程中需要使用有机溶剂、与疏水性聚合物基质的混溶性差以及在智能材料中的应用尚处于初级阶段等问题也被认为是亟待解决的重要挑战。我们首先简要介绍了 LNPs 的基本原理,并详细讨论了与之相关的挑战。然后,我们将重点介绍我们在以下方面所做的工作(i) 通过控制 LNPs 在疏水性聚合物基质中的分散,制备性能更好的木质素基纳米复合材料;(ii) 通过共价(颗粒内交联)和非共价(水合阻隔)方法稳定 LNPs;(iii) 开发生产 LNPs 的无有机溶剂方法;(iv) 将 LNPs 发展为高木质素含量的智能材料。最后,我们还对这一快速发展的领域提出了自己的看法。
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引用次数: 0
Rational Construction of Two-Dimensional Conjugated Metal-Organic Frameworks (2D c-MOFs) for Electronics and Beyond. 合理构建二维共轭金属有机框架 (2D c-MOFs),用于电子及其他领域。
IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-04 DOI: 10.1021/acs.accounts.4c00305
Yang Lu, Paolo Samorì, Xinliang Feng

ConspectusTwo-dimensional conjugated metal-organic frameworks (2D c-MOFs) have emerged as a novel class of multifunctional materials, attracting increasing attention due to their highly customizable chemistry yielding programmable and unprecedented structures and properties. In particular, over the past decade, the synergistic relationship between the conductivity and porosity of 2D c-MOFs has paved the way toward their widespread applications. Despite their promising potential, the majority of 2D c-MOFs have yet to achieve atomically precise crystal structures, hindering the full understanding and control over their electronic structure and intrinsic charge transport characteristics. When modulating the charge transport properties of two-dimensional layered framework materials, decoupling the charge transport processes within and in between layers is of paramount importance, yet it represents a significant challenge. Unfortunately, 2D c-MOFs systems developed so far have failed to address such a major research target, which can be achieved solely by manipulating charge transport properties in 2D c-MOFs. 2D c-MOFs offer a significant advantage over organic radical molecules and covalent organic frameworks: polymerization through oxidative coordination is a viable route to form "spin-concentrated assemblies". However, the role of these spin centers in charge transport processes is still poorly understood, and the intrinsic dynamics and properties of these spins have seldom been investigated. Consequently, overcoming these challenges is essential to unlock the full potential of 2D c-MOFs in electronics and other related fields, as a new type of quantum materials.In this Account, we summarize and discuss our group's efforts to achieve full control at the atomic level over the structure of 2D c-MOFs and their applications in electronics and spintronics, thereby providing distinct evidence on 2D c-MOFs as a promising platform for exploring novel quantum phenomena. First, we unravel the key role played by the rational design of the ligands to decrease the boundary defects, achieve atomically precise large single crystals, and investigate the intrinsic charge transport properties of 2D c-MOFs. The advantages and disadvantages of the current structural elucidation strategies will be discussed. Second, the fundamental challenge in 2D c-MOF charge transport studies is to decouple the in-plane and interlayer charge transport pathways and achieve precise tuning of the charge transport properties in 2D c-MOFs. To address this challenge, we propose a design concept for the second-generation conjugated ligands, termed "programmable conjugated ligands", to replace the current first-generation ligands which lack modifiability as they mainly consist of sp2 hybridization atoms. Our efforts also extend to controlling the spin dynamics properties of 2D c-MOFs as "spin concentrated assemblies" using a bottom-up strategy.We hope this Account pro

Conspectus二维共轭金属有机框架(2D c-MOFs)已成为一类新型多功能材料,由于其高度可定制的化学性质可产生可编程的、前所未有的结构和性能,因而吸引了越来越多的关注。特别是在过去十年中,二维 c-MOFs 的导电性和多孔性之间的协同关系为其广泛应用铺平了道路。尽管二维 c-MOFs 潜力巨大,但大多数二维 c-MOFs 尚未实现原子精确晶体结构,这阻碍了对其电子结构和内在电荷传输特性的全面了解和控制。在调节二维层状框架材料的电荷传输特性时,解耦层内和层间的电荷传输过程至关重要,但这也是一项重大挑战。遗憾的是,迄今为止开发的二维 c-MOFs 系统都未能实现这一重大研究目标,而这完全可以通过操纵二维 c-MOFs 中的电荷传输特性来实现。与有机自由基分子和共价有机框架相比,二维 c-MOFs 具有显著的优势:通过氧化配位聚合是形成 "自旋中心集合体 "的可行途径。然而,人们对这些自旋中心在电荷传输过程中的作用仍然知之甚少,也很少研究这些自旋的内在动力学和特性。因此,要充分挖掘二维 c-MOFs 作为一种新型量子材料在电子学和其他相关领域的潜力,克服这些挑战至关重要。在本报告中,我们总结并讨论了本研究小组为在原子水平上实现对二维 c-MOFs 结构的完全控制及其在电子学和自旋电子学中的应用所做的努力,从而为二维 c-MOFs 作为探索新型量子现象的前景广阔的平台提供了独特的证据。首先,我们揭示了配体的合理设计在减少边界缺陷、实现原子精度的大单晶以及研究二维 c-MOFs 的内在电荷传输特性方面所起的关键作用。我们将讨论当前结构阐释策略的优缺点。其次,二维 c-MOF 电荷传输研究的基本挑战是解耦平面内和层间电荷传输途径,实现二维 c-MOF 电荷传输特性的精确调谐。为了应对这一挑战,我们提出了第二代共轭配体的设计理念,即 "可编程共轭配体",以取代目前主要由 sp2 杂化原子组成、缺乏可调控性的第一代配体。我们希望本开户绑定手机领体验金能为克服二维 c-MOFs 在电子学和自旋电子学方面的主要挑战提供启发性的基础见解和实用策略。通过合理设计二维平面内的结构调制和层间相互作用,我们致力于在提高这一蓬勃发展的材料家族的功能复杂性方面迈出重要的一步,从而为它们在电子学中的实际应用开辟清晰的前景,最终目标是激励二维 c-MOFs 的进一步发展,充分释放它们作为新兴量子材料的潜力。
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引用次数: 0
Dual Nickel- and Photoredox-Catalyzed Asymmetric Reductive Cross-Couplings: Just a Change of the Reduction System? 镍和光氧化催化的双重不对称还原交叉耦合:仅仅是还原体系的改变?
IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-03 DOI: 10.1021/acs.accounts.4c00309
Wenhao Xu, Tao Xu

ConspectusIn recent years, nickel-catalyzed asymmetric coupling reactions have emerged as efficient methods for constructing chiral C(sp3) carbon centers. Numerous novel approaches have been reported to rapidly construct chiral carbon-carbon bonds through nickel-catalyzed asymmetric couplings between electrophiles and nucleophiles or asymmetric reductive cross-couplings of two different electrophiles. Building upon these advances, our group has been devoted to interrogating dual nickel- and photoredox-catalyzed asymmetric reductive cross-coupling reactions.In our endeavors over the past few years, we have successfully developed several dual Ni-/photoredox-catalyzed asymmetric reductive cross-coupling reactions involving organohalides. While some probably think that this system is just a change of the reduction system from traditional metal reductants to a photocatalysis system, a question that we also pondered at the beginning of our studies, both the achievable reaction types and mechanisms suggest a different conclusion: that this dual catalysis system has its own advantages in the chiral carbon-carbon bond formation. Even in certain asymmetric reactions where the photocatalysis regime functions only as a reducing system, the robust reducing capability of photocatalysts can effectively accelerate the regeneration of low-valent nickel species, thus expanding the selectable scope of chiral ligands. More importantly, in many transformations, besides reducing nickel catalysts, the photocatalysis system can also undertake the responsibility of alkyl radical formation, thereby establishing two coordinated, yet independent catalytic cycles. This catalytic mode has been proven to play a crucial role in achieving diverse asymmetric coupling reactions with great challenges.In this Account, we elucidate our understanding of this system based on our experience and findings. In the Introduction, we provide an overview of the main distinctions between this system and traditional Ni-catalyzed asymmetric reductive cross-couplings with metal reductants and the potential opportunities arising from these differences. Subsequently, we outline various chiral carbon-carbon bond-forming types obtained by this dual Ni/photoredox catalysis system and their mechanisms. In terms of chiral C(sp3)-C(sp2) bond formation, extensive discussion focuses on the asymmetric arylations of α-chloroboronates, α-trifluoromethyl alkyl bromides, α-bromophosphonates, and so on. In the realm of chiral C(sp3)-C(sp) bond formation, asymmetric alkynylations of α-bromophosphonates and α-trifluoromethyl alkyl bromides have been presented herein. Regarding C(sp3)-C(sp3) bond formation, we take the asymmetric alkylation of α-chloroboronates as a compelling example to illustrate the great efficiency of this dual catalysis system. This summary would enable a better grasp of the advantages of this dual catalysis system and clar

摘要 近年来,镍催化的不对称偶联反应已成为构建手性 C(sp3)碳中心的有效方法。通过镍催化的亲电体和亲核体之间的不对称偶联反应或两种不同亲电体的不对称还原交叉偶联反应,快速构建手性碳-碳键的新方法层出不穷。在这些进展的基础上,我们的研究小组一直致力于研究镍和光氧催化的双重不对称还原交叉偶联反应。在过去几年的努力中,我们成功地开发了几个涉及有机卤化物的镍/光氧催化的双重不对称还原交叉偶联反应。虽然有些人可能认为这种体系只是将还原体系从传统的金属还原剂改为光催化体系(我们在研究初期也曾思考过这个问题),但从可实现的反应类型和机理来看,我们得出了不同的结论:这种双重催化体系在手性碳-碳键形成方面有其自身的优势。即使在某些不对称反应中,光催化体系仅起到还原体系的作用,光催化剂强大的还原能力也能有效加速低价镍的再生,从而扩大手性配体的可选择性范围。更重要的是,在许多转化过程中,除了还原镍催化剂外,光催化系统还可以承担烷基自由基形成的责任,从而建立两个协调而独立的催化循环。这种催化模式已被证明在实现各种不对称偶联反应中发挥了至关重要的作用,具有极大的挑战性。在本篇开户绑定手机领体验金中,我们将根据自己的经验和发现,阐明我们对该系统的理解。在导言中,我们概述了该体系与传统的镍催化金属还原剂不对称还原交叉耦合反应之间的主要区别,以及这些区别带来的潜在机遇。随后,我们概述了通过这种镍/光氧化物双催化体系获得的各种手性碳-碳键形成类型及其机理。在手性 C(sp3)-C(sp2)键形成方面,我们重点讨论了 α-氯硼酸盐、α-三氟甲基烷基溴、α-溴膦酸盐等的不对称芳基化反应。在手性 C(sp3)-C(sp)键形成领域,本文介绍了 α-溴膦酸盐和 α-三氟甲基烷基溴的不对称炔化反应。关于 C(sp3)-C(sp3)键的形成,我们以 α-氯硼酸盐的不对称烷基化为例,说明了这种双重催化系统的巨大效率。这一总结将有助于更好地掌握这种双催化系统的优势,并阐明光催化机制如何促进对映选择性转化。我们预计,该开户绑定手机领体验金将提供有价值的见解,并有助于开发该领域的新方法。
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Accounts of Chemical Research
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