Accounts of Chemical Research最新文献

{"title":"Transforming Highly Oxidized and Reduced Carbon Feedstocks: Strategies for Catalytic CO2 and CH4 Valorization","authors":"Nilay Hazari, Hannah S. Shafaat, Jenny Y. Yang","doi":"10.1021/acs.accounts.4c00664","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00664","url":null,"abstract":"Carbon is a ubiquitous element in society as a critical component of materials, medicines, commodity chemicals, and fuels. A primary reason for the broad utility of carbon-containing compounds is the redox and chemical versatility of carbon. Remarkably, a carbon atom can span 9 oxidation states (+4 to −4), with fuels typically consisting of highly reduced carbon-based compounds (−1 to −4), (1) biological metabolites concentrating carbon in intermediate oxidation states (−1 to 2), (2) and plastics such as polycarbonates featuring some carbon atoms in their highest oxidation state (+4). (3) The anthropogenic use of carbon-containing compounds to generate energy typically relies on combustion, resulting in the accumulation of CO<sub>2</sub>, the most oxidized form of carbon. In contrast, both biotic and abiotic anoxic processes use oxidized forms of carbon as an electron sink, forming CH<sub>4</sub>, the most reduced form of carbon, as the ultimate product. While CO<sub>2</sub> and CH<sub>4</sub> span the extreme ends of the viable oxidation states of carbon, they share two important chemical attributes: (i) they have high global warming potentials and contribute substantially to climate change (4) and (ii) they have thermodynamically strong C–O or C–H bonds, respectively, and the kinetic barriers to convert these abundant gases into other compounds are typically large. As a result, despite their abundance and low cost, neither CO<sub>2</sub> nor CH<sub>4</sub> is currently used as a carbon feedstock at scale. (4) This special issue of <i>Accounts of Chemical Research</i> is centered on research that addresses the global challenge of CO<sub>2</sub> and CH<sub>4</sub> upgrading. Specifically, it focuses on using homogeneous molecular catalysts or enzymes to valorize these under utilized C<sub>1</sub> gases. For CO<sub>2</sub>, these studies are motivated by the opportunity to replace the fossil-fuel-based carbon feedstocks that are currently used in fuels, chemicals, and materials with a nonfossil source, with global ramifications for climate, the environment, and the economy. (5) For CH<sub>4</sub>, these studies are motivated by the opportunity to limit flaring and instead use it to generate chemicals, which will also impact the global climate. (6) <i>Accounts</i> articles that describe research on the development of heterogeneous catalysts for CO<sub>2</sub> reduction, which is a complementary approach to the molecular-based systems described in this special issue, are already available, (7) as well as a collection that focuses on photo- and electrochemical approaches. (8) Chemists have an expansive toolbox for finding systems for the conversion of CO<sub>2</sub> and CH<sub>4</sub>. Biology offers important templates based on billions of years of evolution selecting for the transformation of inert carbon compounds into value-added products. The methods described in this issue include the use of enzymes that activate CH<sub>4</sub> and CO<sub>2</su","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"30 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832615","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}

{"title":"From the Chemistry of Life’s Emergence to the Chemistry of Life","authors":"Claudia Bonfio,  and , Martina Preiner*, ","doi":"10.1021/acs.accounts.4c0073510.1021/acs.accounts.4c00735","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00735https://doi.org/10.1021/acs.accounts.4c00735","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"57 24","pages":"3454 3454"},"PeriodicalIF":16.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842631","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}

{"title":"Enhancing Biocatalysis: Metal-Organic Frameworks as Multifunctional Enzyme Hosts.","authors":"Fanrui Sha, Xiaoliang Wang, Kent O Kirlikovali, Omar K Farha","doi":"10.1021/acs.accounts.4c00622","DOIUrl":"10.1021/acs.accounts.4c00622","url":null,"abstract":"<p><p>ConspectusEnzymes are highly efficient and selective catalysts that operate under mild conditions, making them invaluable for various chemical transformations. However, their limitations, such as instability and high cost, call for advancements in enzyme immobilization and the development of suitable host materials. Metal-organic frameworks (MOFs), characterized by high porosity, crystallinity, and tunability, are promising candidates for enzyme encapsulation. Among these, zirconium-based MOFs (Zr-MOFs) stand out due to their exceptional structural diversity and chemical stability. The physical and chemical properties of Zr-MOFs can be tuned and characterized with atomic precision, and their interactions with enzymes can be analyzed through a range of techniques spanning from chemistry and materials science to biochemistry. This tunable platform provides opportunities to systematically investigate the impact of encapsulation on the stability and activity of enzymes in order to develop design rules for enzyme hosts.In this Account, we discuss experimentally validated concepts for designing MOF hosts based on their structural properties and enzyme encapsulation mechanisms. We present methods to enhance enzyme catalytic performance through encapsulation and strategies for creating multifunctional enzyme@MOF systems via host modifications. We start by highlighting the importance of host structural design that maximizes substrate diffusion and enzyme availability, with particular focus on MOFs containing hierarchical mesoporous structures such as those in the <b>csq</b> topology. We then delve into the encapsulation process and host-guest interactions examined through techniques such as microscopy, calorimetry, and computational methods, which provide guidelines to fine-tune the local pore chemical environment to enhance enzyme stability and catalytic activity. Techniques found in biochemistry, such as isothermal titration calorimetry (ITC) and confocal laser scanning microscopy (CLSM), were developed to investigate enzyme encapsulation mechanisms, revealing high-entropy-driven host-guest affinity. Additionally, we discuss cases in which enzyme@MOF systems demonstrated enhanced catalytic activities and multifunctional capabilities. Encapsulated enzymes have demonstrated improved thermal and chemical stabilities compared to their free counterparts, maintaining activity under conditions that typically lead to denaturation. Additionally, the highly tunable nature of the MOF platforms allows them to support more complex systems such as tandem reactions, enabling applications in biophotocatalysis, bioelectrocatalysis, and targeted therapeutic protein delivery.The versatility of enzyme@MOFs promises extensive applications in both research and industrial processes across fields including biotechnology, pharmaceutical development, and environmental science. We provide an outlook for promising directions for enzyme@MOF research, with the aim of continuin","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"3500-3511"},"PeriodicalIF":16.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142737667","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}

{"title":"Transforming Highly Oxidized and Reduced Carbon Feedstocks: Strategies for Catalytic CO2 and CH4 Valorization","authors":"Nilay Hazari*, Hannah S. Shafaat* and Jenny Y. Yang*, ","doi":"10.1021/acs.accounts.4c0066410.1021/acs.accounts.4c00664","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00664https://doi.org/10.1021/acs.accounts.4c00664","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"57 24","pages":"3451–3453 3451–3453"},"PeriodicalIF":16.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842630","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}

{"title":"From the Chemistry of Life’s Emergence to the Chemistry of Life","authors":"Claudia Bonfio, Martina Preiner","doi":"10.1021/acs.accounts.4c00735","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00735","url":null,"abstract":"Enzymes catalyze cellular chemistry, ultimately enabling life to exist. They are complex and specialized protein catalysts formed by millions of years of evolution. In modern cells, enzymes, and the metabolic reactions accelerated by them, are often localized within highly specialized and organized membrane-bound or membrane-less cellular compartments. In short, catalysis and compartmentalization are intertwined central traits of life and must have been important factors that shaped its emergence. Several questions surround the emergence of both life traits: Did primordial metabolic reaction networks precede the complex protein apparatuses that now enabled them? What catalysts did enable such prebiotic reactions, and how did they later evolve into enzymes? How did prebiotic compartmentalization influence the catalytic processes? Over the years, many hypotheses have been proposed to explain life’s emergence, primarily based on the intrinsic properties of <i>individual</i> molecules (e.g., RNA) or environments (e.g., warm little ponds or hydrothermal vents). With this Special Issue, we chose to explore the role of prebiotic catalysis and its relation to compartmentalization from various at times contrasting viewpoints. Here, we aim to support more <i>holistic</i> approaches that tie together all life’s key features and, in particular, close the gap between abiotic and biotic reactions and scaffolds. An open discussion of different viewpoints is often the basis of novel scientific developments; it also brought this Special Issue to life, connecting us editors across different research fields. We come from different scientific backgrounds, focus on different questions concerning prebiotic chemistry, and have different opinions on life’s emergence. Nevertheless, we always find common ground from which interesting scientific questions, which could be addressed by both of us together, arise. We think this overall spirit is also reflected in this Special Issue, which shows a variety of opinions, approaches, and disciplines that could provide insights and inspiration to uncover how life emerged from nonliving matter. This article has not yet been cited by other publications.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"85 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832304","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}

{"title":"Use of Intramolecular Quinol Redox Couples to Facilitate the Catalytic Transformation of O2 and O2-Derived Species","authors":"Byron H. Farnum, Christian R. Goldsmith","doi":"10.1021/acs.accounts.4c00645","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00645","url":null,"abstract":"The redox reactivity of transition metal centers can be augmented by nearby redox-active inorganic or organic moieties. In some cases, these functional groups can even allow a metal center to participate in reactions that were previously inaccessible to both the metal center and the functional group by themselves. Our research groups have been synthesizing and characterizing coordination complexes with polydentate quinol-containing ligands. Quinol is capable of being reversibly oxidized by either one or two electrons to semiquinone or <i>para</i>-quinone, respectively. Functionally, quinol behaves much differently than phenol, even though the p<i>K</i>_a values of the first O–H bonds are nearly identical.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"64 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142840956","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}

{"title":"Triftosylhydrazone in Single-Atom Skeletal Editing","authors":"Zhaohong Liu, Xiaolong Zhang, Paramasivam Sivaguru, Xihe Bi","doi":"10.1021/acs.accounts.4c00709","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00709","url":null,"abstract":"In the past decade, single-atom skeletal editing, which involves the precise insertion, deletion, or exchange of single atoms in the core skeleton of a molecule, has emerged as a promising synthetic strategy for the rapid construction or diversification of complex molecules without laborious <i>de novo</i> synthetic processes. Among them, carbene-initiated skeletal editing is particularly appealing due to the ready availability and diverse reactivities of carbene species. The initial endeavors to modify the core skeleton of heteroarenes through carbon-atom insertion could date back to 1881, when Ciamician and Denstedt described the conversion of pyrroles to pyridines by trapping haloform-derived free carbene. Despite its potential synthetic value, the general applicability of this one-carbon insertion has seen limited progress due to poor yields and harsh reaction conditions. Significant advances in skeletal editing via carbene insertion were achieved only in the past 3 years by Levin, Ball, Xu, Song, Glorius, and others. The hallmark of these approaches is facile halocyclopropanation followed by regioselective ring opening facilitated by the expulsion of the halide ion. Consequently, only specially designed α-halocarbene precursors, such as haloform derivatives, α-halodiazoacetates, chlorodiazirines, and α-chlorodiazo oxime esters, can be employed to achieve Ciamician–Denstedt-type skeletal editing. This not only limits the types of functional groups installed on the ring expansion products but also prevents their widespread adoption, especially in late-stage contexts. The enduring quest to develop environmentally friendly and versatile carbene precursors, superior functional group compatibility, and potential application in late-stage diversifications and the investigation of mechanistic insights into carbon insertion reactions remain a fundamental objective.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"192 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142825465","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}

{"title":"Lipid Trafficking in Diverse Bacteria","authors":"Jonathan Chiu-Chun Chou, Laura M. K. Dassama","doi":"10.1021/acs.accounts.4c00540","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00540","url":null,"abstract":"Lipids are essential for life and serve as cell envelope components, signaling molecules, and nutrients. For lipids to achieve their required functions, they need to be correctly localized. This requires the action of transporter proteins and an energy source. The current understanding of bacterial lipid transporters is limited to a few classes. Given the diversity of lipid species and the predicted existence of specific lipid transporters, many more transporters await discovery and characterization. These proteins could be prime targets for modulators that control bacterial cell proliferation and pathogenesis.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"30 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142825464","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}

{"title":"Space Exploration of Metal-Organic Frameworks in the Mesopore Regime.","authors":"Gaoli Hu, Qi Liu, Hexiang Deng","doi":"10.1021/acs.accounts.4c00633","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00633","url":null,"abstract":"<p><p>ConspectusThe past decades have witnessed the proliferation of porous materials offering high surface areas and the revolution in gas storage and separation, where metal-organic frameworks (MOFs) stand out as an important family. Alongside the pursuit of higher surface area, the increase in the size of guests, such as nanoparticles and biomolecules, has also led to the demand for larger space defined by the pores and cages within the MOF structure, from the conventional micropore regime (<2 nm) toward the mesopore regime (2-50 nm). Among the essential elements in the design of MOFs, molecular building blocks, their coordination and spatial arrangement, the chemistry for molecular design, and coordination bonds have become relatively mature, offering precise control of the shape and environment of the molecularly defined 3D cages; however, the correlation between the geometrical parameters and the size of polyhedrons describing the cages, concerning the spatial arrangement of building blocks, is much less explored.In this Account, we made efforts to associate actual cage size with the critical geometrical components, vertices, edges, connectivity, rings, and underlying polyhedrons, as well as the combination of components of various types in the design of MOFs. Several trends were found, such as influence from connectivity and expansion efficiency, offering insights into the construction of 3D cages in MOFs. This enables the creation of extremely large mesoporous cages in MOFs with an internal diameter up to 11.4 nm from relatively small building blocks. Furthermore, we discuss a strategy of partial removal or replacement of organic linkers to construct mesoporous cages from readily known topologies.All of the above efforts urged us to ask the following questions: Is there any limit in the sculpting of the 3D space from molecules? How large an area can one chemical bond support? The answer to these questions will deepen the knowledge of efficient utilization of chemical bonds in the sculpting of 3D spaces and guide the design of larger mesopores. Several general geometrical principals emerged: (1) Expansion efficiency and radius are positively correlated with the number of vertices. (2) Increase in the number of vertices and decrease of their connectivity favor the construction and expansion of large cages. (3) The boundary of the 3D space constructed by the chemical bonds is related to the polyhedron type and determined by the energy involved in crystallinity. Such principals are likely to be applicable also in the design of isolated cages in supramolecular chemistry. In addition to the structural design and synthesis, the applications of these mesoporous cages in MOFs are also summarized.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816634","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}

{"title":"Electroreductive Cross-Coupling Reactions: Carboxylation, Deuteration, and Alkylation.","authors":"Pengfei Li, Yanwei Wang, Hanying Zhao, Youai Qiu","doi":"10.1021/acs.accounts.4c00652","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00652","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusElectrochemistry has been used as a tool to drive chemical reactions for more than two centuries. With the help of an electrode and a power source, chemists are provided with a system whose potential can be precisely dialed in. The theoretically infinite redox range renders electrochemistry capable of oxidizing or reducing some of the most tenacious compounds. Indeed, electroreduction offers an alternative to generating highly active intermediates from electrophiles (e.g., halides, alkenes, etc.) in organic synthesis, which can be untouchable with traditional reduction methods. Meanwhile, the reductive coupling reactions are extensively utilized in both industrial and academic settings due to their ability to swiftly, accurately, and effectively construct C-C and C-X bonds, which present innovative approaches for synthesizing complex molecules. Nonetheless, its application is constrained by several inherent limitations: (a) the requirement for stoichiometric quantities of reducing agents, (b) scarce activation strategies for inert substrates with high reduction potentials, (c) incomplete mechanistic elucidation, and (d) challenges in the isolation of intermediates. The merging of electrochemistry and reductive coupling represents an attractive approach to address the above limitations in organic synthesis and has seen increasing use in the synthetic community over the past few years.Since 2020, our group has been dedicated to developing electroreductive cross-coupling reactions using readily available organic substrates with small molecules, such as organic halides, alkenes, arenes, CO&lt;sub&gt;2&lt;/sub&gt;, and D&lt;sub&gt;2&lt;/sub&gt;O, to construct high value-added organic products. Electroreductive chemistry is highly versatile and offers powerful reducing capacity and precise selectivity control, which has allowed us to develop three electrochemical modes in our lab: (1) An economically advantageous electrochemical direct reduction (EDR) strategy that emphasizes efficiency, achieves high atom utilization, and minimizes unnecessary atomic waste. (2) A class of electrochemical organo-mediated reduction (EOMR) methods that are capable of effectively controlling reaction intermediates and reaction pathways. This allows for precise modulation of reaction processes to enhance efficiency and selectivity. (3) The electrochemical metal-catalyzed reduction (EMCR) method that enables selective activation and functionalization of specific chemical bonds or functional groups under mild conditions, thereby reducing the occurrence of side reactions. We commenced our studies by establishing an organic-mediator-promoted electroreductive carboxylation of aryl and alkyl halides. This strategy was then employed for the arylcarboxylation of simple styrenes with aryl halides in a highly selective manner. Meanwhile, under direct electrolysis conditions, the carboxylation of arenes and epoxides with CO&lt;sub&gt;2&lt;/sub&gt; as the carboxyl source was achieved. Moreover, through t","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816626","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}