Accounts of Chemical Research最新文献

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Hunting for the Intermolecular Diels-Alderase. 寻找分子间二醛酸酯酶
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2024-07-12 DOI: 10.1021/acs.accounts.4c00315
Lei Gao, Qi Ding, Xiaoguang Lei
{"title":"Hunting for the Intermolecular Diels-Alderase.","authors":"Lei Gao, Qi Ding, Xiaoguang Lei","doi":"10.1021/acs.accounts.4c00315","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00315","url":null,"abstract":"<p><p>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 <i>endo</i>-selective Diels-Alderase and is then functionally characterized as a standalone intermolecular Diels-Alderase with a concerted but asynchronous mechanism. We also discover the <i>exo</i>-selective intermolecular Diels-Alderases in <i>Morus</i> plants. Both the <i>endo</i>- and <i>exo</i>-selective Diels-Alderases feature a broad substrate scope, but their mechanisms for controlling the <i>endo</i>/<i>exo</i> 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 <i>Morus</i> plants, particularly highlighting the importance of biomimetic synthesis and chemical proteomics in ","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588889","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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
Accounts of Chemical Research Pub Date : 2024-07-12 DOI: 10.1021/acs.accounts.4c00256
Anna Gonzàlez-Rosell, Stacy M Copp
{"title":"An Atom-Precise Understanding of DNA-Stabilized Silver Nanoclusters.","authors":"Anna Gonzàlez-Rosell, Stacy M Copp","doi":"10.1021/acs.accounts.4c00256","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00256","url":null,"abstract":"<p><p>ConspectusDNA-stabilized silver nanoclusters (Ag<sub>N</sub>-DNAs) are sequence-encoded fluorophores. Like other noble metal nanoclusters, the optical properties of Ag<sub>N</sub>-DNAs are dictated by their atomically precise sizes and shapes. What makes Ag<sub>N</sub>-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 Ag<sub>N</sub>-DNAs with diverse emission colors and other intriguing photophysical properties. Ag<sub>N</sub>-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 Ag<sub>N</sub>-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 Ag<sub>N</sub>-DNAs in order to design Ag<sub>N</sub>-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 Ag<sub>N</sub>-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 Ag<sub>N</sub>-DNAs, together with combinatorial experiments and machine learning-guided design. A combined approach is essential due to the major challenge of growing suitable Ag<sub>N</sub>-DNA crystals for diffraction and to the labor-intensive nature of preparing and solving the molecular formulas of atomically precise Ag<sub>N</sub>-DNAs by mass spectrometry. These approaches alone are not feasibly scaled to explore the large sequence space of DNA oligomer templates for Ag<sub>N</sub>-DNAs.This account describes recent fundamental advances in Ag<sub>N</sub>-DNA science that have been enabled by high throughput synthesis and fluorimetry together with detailed analytical studies of purified Ag<sub>N</sub>-DNAs. First, short introductions to nanocluster chemistry and Ag<sub>N</sub>-DNA basics are presented. Then, we review recent large-scale studies that have screened thousands of DNA templates for Ag<sub>N</sub>-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 Ag<sub>N</sub>-DNAs enabled the first <i>ab initio</i> calculations of Ag<sub>N</sub>-DNA electronic structure and present new approaches to stabilize these emitters in biologically relevant conditions. Near-infrared (NIR) emissive Ag<sub>N</sub>-DNAs are also found to exhibit diverse structures and prope","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588890","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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
Accounts of Chemical Research Pub Date : 2024-07-11 DOI: 10.1021/acs.accounts.4c00251
Weichun Huang, Yuming Yang, Han Zhang
{"title":"Surface Engineering of Two-Dimensional Black Phosphorus for Advanced Nanophotonics.","authors":"Weichun Huang, Yuming Yang, Han Zhang","doi":"10.1021/acs.accounts.4c00251","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00251","url":null,"abstract":"<p><p>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 <i>in vivo</i>. 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","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588854","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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
Accounts of Chemical Research Pub Date : 2024-07-11 DOI: 10.1021/acs.accounts.4c00232
Federico Rossi, Sandra Ristori, Ali Abou-Hassan
{"title":"Multiscale Approach for Tuning Communication among Chemical Oscillators Confined in Biomimetic Microcompartments.","authors":"Federico Rossi, Sandra Ristori, Ali Abou-Hassan","doi":"10.1021/acs.accounts.4c00232","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00232","url":null,"abstract":"<p><p>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 ","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588888","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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
Accounts of Chemical Research 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
{"title":"How Droplets Can Accelerate Reactions─Coacervate Protocells as Catalytic Microcompartments.","authors":"Iris B A Smokers, Brent S Visser, Annemiek D Slootbeek, Wilhelm T S Huck, Evan Spruijt","doi":"10.1021/acs.accounts.4c00114","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00114","url":null,"abstract":"<p><p>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.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141537174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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
Accounts of Chemical Research Pub Date : 2024-07-04 DOI: 10.1021/acs.accounts.4c00206
Adrian Moreno, Mika H Sipponen
{"title":"Overcoming Challenges of Lignin Nanoparticles: Expanding Opportunities for Scalable and Multifunctional Nanomaterials.","authors":"Adrian Moreno, Mika H Sipponen","doi":"10.1021/acs.accounts.4c00206","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00206","url":null,"abstract":"<p><p>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.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532877","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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
Accounts of Chemical Research Pub Date : 2024-07-04 DOI: 10.1021/acs.accounts.4c00305
Yang Lu, Paolo Samorì, Xinliang Feng
{"title":"Rational Construction of Two-Dimensional Conjugated Metal-Organic Frameworks (2D c-MOFs) for Electronics and Beyond.","authors":"Yang Lu, Paolo Samorì, Xinliang Feng","doi":"10.1021/acs.accounts.4c00305","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00305","url":null,"abstract":"<p><p>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 <i>sp</i><sup>2</sup> 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","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141496305","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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
Accounts of Chemical Research Pub Date : 2024-07-03 DOI: 10.1021/acs.accounts.4c00309
Wenhao Xu, Tao Xu
{"title":"Dual Nickel- and Photoredox-Catalyzed Asymmetric Reductive Cross-Couplings: Just a Change of the Reduction System?","authors":"Wenhao Xu, Tao Xu","doi":"10.1021/acs.accounts.4c00309","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00309","url":null,"abstract":"<p><p>ConspectusIn recent years, nickel-catalyzed asymmetric coupling reactions have emerged as efficient methods for constructing chiral C(sp<sup>3</sup>) 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(sp<sup>3</sup>)-C(sp<sup>2</sup>) 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(sp<sup>3</sup>)-C(sp) bond formation, asymmetric alkynylations of α-bromophosphonates and α-trifluoromethyl alkyl bromides have been presented herein. Regarding C(sp<sup>3</sup>)-C(sp<sup>3</sup>) 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","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141496306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Recent Advances in Halogen-Metal Exchange Reactions. 卤素金属交换反应的最新进展。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2024-07-02 DOI: 10.1021/acs.accounts.4c00242
Baosheng Wei, Yi-Hung Chen, Paul Knochel
{"title":"Recent Advances in Halogen-Metal Exchange Reactions.","authors":"Baosheng Wei, Yi-Hung Chen, Paul Knochel","doi":"10.1021/acs.accounts.4c00242","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00242","url":null,"abstract":"<p><p>ConspectusThe halogen-metal exchange reaction is a very powerful method for preparing functionalized organometallic reagents in the fields of organic and organometallic chemistry. Since its inception, significant interest has been directed toward the on-demand development of new halogen-metal exchange reactions, primarily through the upgrading of exchange reagents. The enduring quest for optimal reactivity, superior functional group compatibility, and innovative synthetic applications of exchange reagents remains a fundamental objective. In the past several years, the emergence of some significant discoveries in halogen-metal exchange reactions has proclaimed a renaissance to this field. This Account outlines the latest advances within the domain contributed by the Knochel group, including the main points as follows.The stereoretentive I/Li exchange on stereodefined secondary alkyl iodides was developed for the synthesis of nonstabilized chiral secondary alkyllithium reagents. This provided a straightforward method to access chiral organolithium reagents, which can be trapped by various electrophiles or transmetalated with other metals such as copper, zinc, and magnesium, thus enabling the stereoselective synthesis of a series of functionalized compounds and natural products.Faster halogen-magnesium and halogen-zinc exchanges in toluene were realized using a novel kind of exchange reagent complexed with lithium alkoxide. These highly efficient exchange reactions are much faster than traditional ones and performed in an industrially friendly solvent. These advantages are of great value in practical synthesis, paving the way for new developments in this evolving area.Halogen-lanthanide exchanges and their novel applications in organic synthesis were established. These new exchanges introduced the lanthanide metals into halogen-metal exchange reactions for the first time, thereby opening new avenues in synthetic chemistry. Building on these achievements, a comparative analysis of the exchange reaction rates by kinetic study has quantified the relationship between the electronegativity of metals and the rates of halogen-metal exchanges.Br/Na exchange in continuous flow was achieved using a hexane-soluble exchange reagent, 2-ethylhexylsodium. This approach effectively circumvented the poor solubility of the organosodium reagent, which has proven to be of significant practical value and greatly enhanced the synthetic utility of the organosodium reagent in organic synthesis.These remarkable breakthroughs as mentioned above are fueled mainly by upgrading the exchange reagents, resulting in the development of new halogen-metal exchange reactions and innovative applications in organic synthesis. Given the importance of halogen-metal exchanges in synthetic chemistry, the pursuit of other types of exchange reactions, particularly those involving new metals, will be in continuous demand. This Account provides a timely summary of recent progress and will","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489853","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Advancing Ion Separation: Covalent-Organic-Framework Membranes for Sustainable Energy and Water Applications. 推进离子分离:用于可持续能源和水应用的共价-有机框架膜。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2024-07-01 DOI: 10.1021/acs.accounts.4c00268
Weipeng Xian, Di Wu, Zhuozhi Lai, Sai Wang, Qi Sun
{"title":"Advancing Ion Separation: Covalent-Organic-Framework Membranes for Sustainable Energy and Water Applications.","authors":"Weipeng Xian, Di Wu, Zhuozhi Lai, Sai Wang, Qi Sun","doi":"10.1021/acs.accounts.4c00268","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00268","url":null,"abstract":"<p><p>ConspectusMembranes are pivotal in a myriad of energy production processes and modern separation techniques. They are essential in devices for energy generation, facilities for extracting energy elements, and plants for wastewater treatment, each of which hinges on effective ion separation. While biological ion channels show exceptional permeability and selectivity, designing synthetic membranes with defined pore architecture and chemistry on the (sub)nanometer scale has been challenging. Consequently, a typical trade-off emerges: highly permeable membranes often sacrifice selectivity and vice versa. To tackle this dilemma, a comprehensive understanding and modeling of synthetic membranes across various scales is imperative. This lays the foundation for establishing design criteria for advanced membrane materials. Key attributes for such materials encompass appropriately sized pores, a narrow pore size distribution, and finely tuned interactions between desired permeants and the membrane. The advent of covalent-organic-framework (COF) membranes offers promising solutions to the challenges faced by conventional membranes in selective ion separation within the water-energy nexus. COFs are molecular Legos, facilitating the precise integration of small organic structs into extended, porous, crystalline architectures through covalent linkage. This unique molecular architecture allows for precise control over pore sizes, shapes, and distributions within the membrane. Additionally, COFs offer the flexibility to modify their pore spaces with distinct functionalities. This adaptability not only enhances their permeability but also facilitates tailored interactions with specific ions. As a result, COF membranes are positioned as prime candidates to achieve both superior permeability and selectivity in ion separation processes.In this Account, we delineate our endeavors aimed at leveraging the distinctive attributes of COFs to augment ion separation processes, tackling fundamental inquiries while identifying avenues for further exploration. Our strategies for fabricating COF membranes with enhanced ion selectivity encompass the following: (1) crafting (sub)nanoscale ion channels to enhance permselectivity, thereby amplifying energy production; (2) implementing a multivariate (MTV) synthesis method to control charge density within nanochannels, optimizing ion transport efficiency; (3) modifying the pore environment within confined mass transfer channels to establish distinct pathways for ion transport. For each strategy, we expound on its chemical foundations and offer illustrative examples that underscore fundamental principles. Our efforts have culminated in the creation of groundbreaking membrane materials that surpass traditional counterparts, propelling advancements in sustainable energy conversion, waste heat utilization, energy element extraction, and pollutant removal. These innovations are poised to redefine energy systems and industrial waste","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475369","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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