Accounts of Chemical Research最新文献

{"title":"Construction and Function of Low-Symmetry Metallo-Supramolecules.","authors":"Junjuan Shi,Ming Wang","doi":"10.1021/acs.accounts.5c00209","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00209","url":null,"abstract":"ConspectusNatural systems often exhibit high-symmetry structures, which are vital in biological processes. Inspired by nature, chemists have focused on designing high-symmetry metallo-supramolecular architectures due to the high predictability and controllability for self-assembly. In contrast, low-symmetry structures are ubiquitous and also play a key role in living systems. Mimicking natural low-symmetry structures has proven challenging; substantial efforts have been devoted to developing low-symmetry metallo-supramolecules. However, there are still significant challenges in both construction and function of low-symmetry metallo-supramolecules: (1) unexpected structures with similar thermodynamic stability will be generated, resulting in uncontrollable self-assembly; (2) functionalized low-symmetry supramolecular systems are limited by uncontrollable self-assembly. To address the key challenges, we developed various strategies to control the assembly process and explore the functionalities. In this Account, we summarize the recent research progress achieved by our efforts in preparing low-symmetry metallo-supramolecules and exploring their functionalities. First, the efficient approaches are discussed: (1) precise configurational control by subtly modulating ligands, (2) ligand and metal-ion selectivities enabled by selective self-complementary coordination motifs, and (3) enhancing the steric effect to control coordination modes. Second, the functionality of multidecker structures with well-organized homo/hetero-chromophoric arrangements will be introduced. Finally, a low-symmetry functionalized prismatic system with high universality was developed, which realized a high photoluminescence quantum yield, tunable luminescence, mechanically interlocked structures, and selective encapsulation of low-symmetry guests.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"33 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144136682","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":"Catalytic 1,2-Radical Acyloxy Migration: A Strategy to Access Novel Chemical Space and Reaction Profiles","authors":"Gaoyuan Zhao,&nbsp;Upasana Mukherjee,&nbsp;Wang Yao and Ming-Yu Ngai*,&nbsp;","doi":"10.1021/acs.accounts.5c0020510.1021/acs.accounts.5c00205","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00205https://doi.org/10.1021/acs.accounts.5c00205","url":null,"abstract":"<p >Radical migration represents a powerful strategy for reaction discovery and development in organic synthesis, offering access to unprecedented functional molecules and chemical space. In this Account, we describe our contributions to the field, particularly focusing on 1,2-radical acyloxy migration (RAM), a process involving the transposition of a radical and an acyloxy group. We highlight its application in carbohydrate modification and allyl carboxylate trifunctionalization, demonstrating how this reactivity enables the streamlined synthesis of novel glycomimetics and facilitates selective 1,2,3-trifunctionalization of allyl carboxylates. These advances establish 1,2-RAM as a versatile platform for catalytic radical transformations, unlocking new opportunities in reaction development and functional molecule design.</p><p >Our approach leverages excited-state palladium and ground-state nickel catalysis to modify carbohydrates, specifically at the C2 position. This strategy enables C2-deoxy-hydrogenation, deuteration, iodination, alkenylation, allylation, ketonylation, and arylation reactions, providing direct access to unprecedented glycomimetics. These transformations streamline the synthesis of structurally diverse glycomimetics, facilitating the discovery and development of carbohydrate-based functional molecules. Furthermore, the mild reaction conditions and high functional group tolerance of these catalytic systems make them particularly attractive for late-stage functionalization, broadening their applicability in complex molecule synthesis.</p><p >Beyond carbohydrates, we have extended 1,2-RAM reactivity to achieve unprecedented 1,2,3-trifunctionalization of allyl carboxylates. By employing excited-state phosphine catalysis, we demonstrate a 1,3-carbobromination reaction accompanied by an acyloxy shift. This proof-of-concept study lays the foundation for developing a broader range of 1,2,3-trifunctionalization reactions, effectively transforming allyl carboxylates into substituted isopropyl carboxylate donors. This advancement expands the synthetic utility of allyl carboxylates, enabling the rapid construction of structurally diverse molecular scaffolds.</p><p >In summary, the 1,2-RAM reactivity opens a new avenue for reaction discovery and development, granting access to new functional molecules and chemical space. The mild conditions, broad functional group compatibility, and unique reactivity of this approach make it a valuable tool for chemical synthesis. We anticipate that merging 1,2-RAM with other catalytic platforms will further advance bond disconnection strategies, provide access to new functional molecules, and expand the frontiers of chemical synthesis.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 11","pages":"1815–1829 1815–1829"},"PeriodicalIF":16.4,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144194117","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":"Physical Origin and Periodicity of the Highest Oxidation States in Heavy-Element Chemistry.","authors":"Lian-Wei Ye, Han-Shi Hu, W H Eugen Schwarz, Jun Li","doi":"10.1021/acs.accounts.5c00233","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00233","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusThe exploitation of combustion of materials stands as a cornerstone of early human development. A theoretical framework for this field began to take shape only around 1700 and finally achieved a sound foundation through the electronic quantum-chemical oxidation concepts of the 20th century. Eventually, a decade ago the IUPAC defined the essential rules for a unique definition of atomic oxidation states (OS) or OS numbers in molecules and extended structures. In specific cases, however, these rules need be tailored to specific chemical observations, including amazing experiences with the heaviest elements. We review our findings and updated interpretations, particularly with regard to previously unexpected trends in the highest oxidation states (HOS) of heavy atomic compounds.The HOS is a qualitative integer parameter for characterizing the chemistry of an element. It is determined by three basic factors: (i) by the number &lt;i&gt;g&lt;/i&gt; of loosely bound electrons in the atom's valence shell, usually related to its group number &lt;i&gt;G&lt;/i&gt; in the periodic table (&lt;i&gt;g = G&lt;/i&gt; mod 10, with mod meaning &lt;i&gt;g&lt;/i&gt; = 2 to 8 for &lt;i&gt;G&lt;/i&gt; = 12-18); (ii) by the fraction of these &lt;i&gt;g&lt;/i&gt; electrons that can be chemically activated and may fall below &lt;i&gt;g&lt;/i&gt; toward the end of a series; and (iii) by the local and long-range \"environmental\" conditions (mainly the interaction strengths of the ligands), which range from those in normal life, laboratories and industry, to more extreme conditions such as deep inside the Earth, outside in cosmic space, or in special laboratories.In recent years, our group has systematically investigated the regularity of the HOS over the periodic table, in particular the electronic structures of compounds of various d- (transition metals) and f-block elements (lanthanides and actinides), applying both density-functional approximations and more advanced quantum-chemical methods. Details of the HOS values in the border ranges of feasibility, depending on thermodynamic environment and ligand-interaction capabilities, are conceptually analyzed, incorporating also discoveries of other researchers. The patterns of the HOS from the light s- and sp- to the heavy d- and f-block elements are elucidated, showing systematic deviations from simple textbook rules. The particularly large and small Core-Valence (CV) orbital-energy gaps at, respectively, the upper-right and lower-left corners of the periodic table interrupt the regular trends of the HOS of the sp-block elements, causing HOS &lt; &lt;i&gt;g&lt;/i&gt; (as for O or Pt) or HOS &gt; &lt;i&gt;g&lt;/i&gt; (as for Cs or Ra). On the other hand, the d-transition metals (TM) and also the actinide 5f-series (An) in the middle of the periodic table show a more uniform variation of the HOS with one common maximum at 8(±1), while the lanthanide 4f-series (Ln) shows two lower HOS maxima, due to their peculiarly small 4f-orbital radii and varying energies.Our report is intended both as a summary of knowledge, as a distil","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144126109","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":"ASKCOS: Open-Source, Data-Driven Synthesis Planning","authors":"Zhengkai Tu,&nbsp;Sourabh J. Choure,&nbsp;Mun Hong Fong,&nbsp;Jihye Roh,&nbsp;Itai Levin,&nbsp;Kevin Yu,&nbsp;Joonyoung F. Joung,&nbsp;Nathan Morgan,&nbsp;Shih-Cheng Li,&nbsp;Xiaoqi Sun,&nbsp;Huiqian Lin,&nbsp;Mark Murnin,&nbsp;Jordan P. Liles,&nbsp;Thomas J. Struble,&nbsp;Michael E. Fortunato,&nbsp;Mengjie Liu,&nbsp;William H. Green,&nbsp;Klavs F. Jensen and Connor W. Coley*,&nbsp;","doi":"10.1021/acs.accounts.5c0015510.1021/acs.accounts.5c00155","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00155https://doi.org/10.1021/acs.accounts.5c00155","url":null,"abstract":"<p >The advancement of machine learning and the availability of large-scale reaction datasets have accelerated the development of data-driven models for computer-aided synthesis planning (CASP) in the past decade. In this Account, we describe the range of data-driven methods and models that have been incorporated into the newest version of ASKCOS, an open-source software suite for synthesis planning that we have been developing since 2016. This ongoing effort has been driven by the importance of bridging the gap between research and development, making research advances available through a freely available practical tool. ASKCOS integrates modules for retrosynthetic planning, modules for complementary capabilities of condition prediction and reaction product prediction, and several supplementary modules and utilities with various roles in synthesis planning. For retrosynthetic planning, we have developed an Interactive Path Planner (IPP) for user-guided search as well as a Tree Builder for automatic planning with two well-known tree search algorithms, Monte Carlo Tree Search (MCTS) and Retro*. Four one-step retrosynthesis models covering template-based and template-free strategies form the basis of retrosynthetic predictions and can be used simultaneously to combine their advantages and propose diverse suggestions. Strategies for assessing the feasibility of proposed reaction steps and evaluating the full pathways are built on top of several pioneering efforts that we have made in the subtasks of reaction condition recommendation, pathway scoring and clustering, and the prediction of reaction outcomes including the major product, impurities, site selectivity, and regioselectivity. In addition, we have also developed auxiliary capabilities in ASKCOS based on our past and ongoing work for solubility prediction and quantum mechanical descriptor prediction, which can provide more insight into the suitability of proposed reaction solvents or the hypothetical selectivity of desired transformations. For each of these capabilities, we highlight its relevance in the context of synthesis planning and present a comprehensive overview of how it is built on top of not only our work but also of other recent advancements in the field. We also describe in detail how chemists can easily interact with these capabilities via user-friendly interfaces. ASKCOS has assisted hundreds of medicinal, synthetic, and process chemists in their day-to-day tasks by complementing expert decision making and route ideation. It is our belief that CASP tools are an important part of modern chemistry research and offer ever-increasing utility and accessibility.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 11","pages":"1764–1775 1764–1775"},"PeriodicalIF":16.4,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144194323","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":"Decoding the Penicillin-Binding Proteins with Activity-Based Probes.","authors":"Erin E Carlson,Nicholas Sparks,Shivani Diwakar","doi":"10.1021/acs.accounts.5c00113","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00113","url":null,"abstract":"ConspectusThe bacterial cell wall is a complex structure that is primarily composed of peptidoglycan (PG), which provides protection from the environment and structural rigidity for the cell. As such, PG plays an important role in bacterial survival, which has made its biosynthesis a crucial target for antibiotic development for many decades. Despite long-standing efforts to inhibit PG construction, much remains unknown about the enzymes required for PG biosynthesis or how PG composition and architecture are altered to enable adaptation to environmental stressors. This knowledge will be crucial in the identification of new ways to interfere with PG construction that could overcome widespread resistance to cell wall-targeting antibacterial agents.All bacterial species possess a suite of penicillin-binding proteins (PBPs), which are critical actors in PG construction and remodeling, as well as the main targets of β-lactam antibiotics. While the importance of the PBPs is well-known, the field lacks a complete understanding of PBP activity regulation, localization, and critical protein-protein interactions during the growth and division process. Bacteria possess between 4 and 16 PBP homologues with only one or several being genetically essential in each cell. A key outstanding question about these proteins is why bacteria expend the energy required to maintain this relatively large number of related proteins when so few are required to maintain life. The Carlson lab focuses on the development of chemical tools to address this fundamental question. In particular, we have generated a suite of chemical probes to selectively target one or a small number of PBP homologues in their catalytically active state. These activity-based probes (ABPs) have and will continue to enable a deeper understanding of the traits that differentiate the PBPs over the bacterial lifespan.In this account, we discuss the development of selective chemical tools to study the PBPs. Key to our success has been assessment of the PBP inhibition profiles of an expansive set of commercially available β-lactams in both Gram-positive and Gram-negative bacteria. This work has directly identified molecules that can be used in chemical genetic studies and provided scaffolds for the generation of PBP-selective ABPs. We also discovered a novel β-lactone scaffold that is exquisitely selective for PBPs over other protein classes and targets a different subclass of these proteins than related β-lactams. Using these probes, we have explored PG biosynthesis in Streptococcus pneumoniae, Escherichia coli and Bacillus subtilis yielding new insights about their cell wall construction and remodeling processes, as well as specialized activities under stress.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"135 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144103665","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":"Decoding the Penicillin-Binding Proteins with Activity-Based Probes","authors":"Erin E. Carlson*,&nbsp;Nicholas Sparks and Shivani Diwakar,&nbsp;","doi":"10.1021/acs.accounts.5c0011310.1021/acs.accounts.5c00113","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00113https://doi.org/10.1021/acs.accounts.5c00113","url":null,"abstract":"<p >The bacterial cell wall is a complex structure that is primarily composed of peptidoglycan (PG), which provides protection from the environment and structural rigidity for the cell. As such, PG plays an important role in bacterial survival, which has made its biosynthesis a crucial target for antibiotic development for many decades. Despite long-standing efforts to inhibit PG construction, much remains unknown about the enzymes required for PG biosynthesis or how PG composition and architecture are altered to enable adaptation to environmental stressors. This knowledge will be crucial in the identification of new ways to interfere with PG construction that could overcome widespread resistance to cell wall-targeting antibacterial agents.</p><p >All bacterial species possess a suite of penicillin-binding proteins (PBPs), which are critical actors in PG construction and remodeling, as well as the main targets of β-lactam antibiotics. While the importance of the PBPs is well-known, the field lacks a complete understanding of PBP activity regulation, localization, and critical protein–protein interactions during the growth and division process. Bacteria possess between 4 and 16 PBP homologues with only one or several being genetically essential in each cell. A key outstanding question about these proteins is why bacteria expend the energy required to maintain this relatively large number of related proteins when so few are required to maintain life. The Carlson lab focuses on the development of chemical tools to address this fundamental question. In particular, we have generated a suite of chemical probes to selectively target one or a small number of PBP homologues in their catalytically active state. These activity-based probes (ABPs) have and will continue to enable a deeper understanding of the traits that differentiate the PBPs over the bacterial lifespan.</p><p >In this account, we discuss the development of selective chemical tools to study the PBPs. Key to our success has been assessment of the PBP inhibition profiles of an expansive set of commercially available β-lactams in both Gram-positive and Gram-negative bacteria. This work has directly identified molecules that can be used in chemical genetic studies and provided scaffolds for the generation of PBP-selective ABPs. We also discovered a novel β-lactone scaffold that is exquisitely selective for PBPs over other protein classes and targets a different subclass of these proteins than related β-lactams. Using these probes, we have explored PG biosynthesis in <i>Streptococcus pneumoniae</i>, <i>Escherichia coli</i> and <i>Bacillus subtilis</i> yielding new insights about their cell wall construction and remodeling processes, as well as specialized activities under stress.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 11","pages":"1754–1763 1754–1763"},"PeriodicalIF":16.4,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144194419","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":"Rational Design of Layered Oxide Materials for Batteries","authors":"Qidi Wang*,&nbsp;Chenglong Zhao and Marnix Wagemaker,&nbsp;","doi":"10.1021/acs.accounts.5c0007410.1021/acs.accounts.5c00074","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00074https://doi.org/10.1021/acs.accounts.5c00074","url":null,"abstract":"<p >Layered transition metal (TM) compounds are pivotal in the development of rechargeable battery technologies for efficient energy storage. The history of these materials dates back to the 1970s, when the concept of intercalation chemistry was introduced into the battery. This process involves the insertion of alkali-metal ions between the layers of a host material (e.g., TiS₂) without causing significant structural disruption. This breakthrough laid the foundation for Li-ion batteries, with materials like LiCoO₂ becoming key to their commercial success, thanks to their high energy density and good stability. However, despite these advantages, challenges remain in the broader application of these materials in batteries. Issues such as lattice strain, cation migration, and structural collapse result in rapid capacity degradation and a reduction in battery lifespan. Moreover, the performance of batteries is often constrained by the properties of the available materials, particularly in layered oxide materials. This has driven the exploration of materials with diverse compositions. The relationship between composition and structural chemistry is crucial for determining reversible capacity, redox activity, and phase transitions, yet predicting this remains a significant challenge, especially for complex compositions.</p><p >In this Account, we outline our efforts to explore rational principles for optimal battery materials that offer a higher performance. The core of this is the concept of ionic potential, a parameter that measures the strength of the electrostatic interaction between ions. It is defined as the ratio of an ion’s charge to its ionic radius, offering a quantitative way to evaluate interactions between cations and anions in crystal structures. By building on this concept, we introduce the cationic potential, which is emerging as a crystallographic tool that captures critical interactions within layered oxide materials. This approach provides insights into structural organization, enabling the prediction of P2- and O3-type stacking arrangements in layered oxides. A key advantage of using the cationic potential is its ability to guide the rational design of electrode materials with improved performance. For example, introducing P-type structural motifs into the material framework can significantly enhance ion mobility, mitigating detrimental phase transitions that often compromise battery efficiency and longevity. Furthermore, ionic potential serves as a representative parameter to quantitatively describe the properties of various TM compositions, providing a straightforward calculation method for designing multielement systems. We anticipate that this Account will provide fundamental insights and contribute to significant advancements in the design of layered materials, not only for battery applications but also for broader fields that require control of the material properties.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 11","pages":"1742–1753 1742–1753"},"PeriodicalIF":16.4,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.accounts.5c00074","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144194343","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Advancing Light-Driven Reactions with Surface-Modified Optical Fibers.","authors":"Zhe Zhao, Han Fu, Li Ling, Paul Westerhoff","doi":"10.1021/acs.accounts.5c00022","DOIUrl":"10.1021/acs.accounts.5c00022","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusThe challenge of optimizing decentralized water, wastewater, and reuse treatment systems calls for innovative, efficient technologies. One advancement involves surface-modified side-emitting optical fibers (SEOFs), which enhance biochemical and chemical light-driven reactions. SEOFs are thin glass or polymeric optical fibers with functionalized surfaces that can be used individually or bundled together. They can be attached to various light sources, such as light-emitting diodes (LEDs) or lasers, which launch ultraviolet (UV) or visible light into the fibers. This light is then emitted along the fiber's surface, creating irradiance similar to a glow stick. The resulting SEOFs uniquely deliver light energy to complex environments while maximizing photon utilization and minimizing energy loss, addressing long-standing inefficiencies in photolysis and photocatalysis systems. SEOFs generate and leverage refracted light and evanescent waves to achieve continuous irradiation of their cladding, wherein photocatalysts are embedded. This method contrasts with traditional slurry-based systems, where light energy is often scattered or absorbed before reaching the reaction sites. Such scattering typically reduces quantum yields and reaction kinetics. In contrast, SEOFs create a controlled light delivery system that enhances reaction efficiency and adaptability to diverse applications.Important chemical and physical concepts are explored when scaling up SEOFs for three potential engineered applications. The selection of polymer materials and nanoparticle compositions is crucial for optimizing SEOFs as waveguides for visible to UV-C wavelengths and for embedding surface-accessible photocatalysts within porous polymer coatings on SEOF surfaces. Additionally, understanding how light propagates within SEOFs and emits along their exterior surface and length is essential for influencing the quantum yields of chemical products and enhancing biochemical sensitivity to low UV-C exposure. UV-C SEOFs are employed for germicidal disinfection, inactivating biofilms and pathogens in water systems. By overcoming UV light attenuation issues in traditional methods, SEOFs facilitate uniform distribution of UV-C energy, disrupting biofilm formation at early stages. SEOFs enhance UV-A and visible-light photocatalytic degradation of pollutants. Embedding photocatalysts in porous polymer cladding enables simultaneous improvements in reaction kinetics and quantum yields. SEOFs enable decentralized light-driven production of clean energy resources such as hydrogen, hydrogen peroxide, and formic acid, offering sustainable alternatives for off-grid systems.The design principles of SEOFs emphasize scalability, flexibility, and efficiency. Recent innovations in polymer chemistry, nanoparticle coatings, and surface roughness engineering have further optimized light delivery and side-emission. Tailoring the refractive index and nanoparticle distribution on fiber surfaces e","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"1596-1606"},"PeriodicalIF":16.4,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143950692","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":"Fundamental Principles in Catalysis from Mechanistic Studies of Oxidative Decarboxylative Coupling Reactions.","authors":"Jessica M Hoover","doi":"10.1021/acs.accounts.5c00142","DOIUrl":"10.1021/acs.accounts.5c00142","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusOxidative decarboxylative coupling (ODC) reactions have been recognized as powerful alternatives to traditional cross-coupling reactions due to the ability to generate (hetero)biaryl structures from simple and readily available carboxylic acid precursors. These reactions, however, are underdeveloped due to the requirement for &lt;i&gt;ortho&lt;/i&gt;-nitrobenzoate coupling partners and silver salts as oxidants. Our research program has focused on the development of new catalytic ODC reactions, as well as mechanistic studies of these reactions to uncover the origin of these synthetic limitations. As the framework for these studies, we explored two key ODC reactions developed in our group: (1) a Ni-catalyzed decarboxylative arylation reaction that relies on silver as the oxidant and (2) a Cu-catalyzed decarboxylative thiolation reaction capable of operating under aerobic conditions. Our findings, disclosed in this Account, have uncovered the importance of the &lt;i&gt;ortho&lt;/i&gt;-substituent and revealed that Ag-based oxidants are also responsible for mediating the decarboxylation and transmetalation steps.Systematic exploration of the decarboxylation of a series of well-defined Ag-benzoate complexes allowed us to probe the importance of the &lt;i&gt;ortho&lt;/i&gt;-nitro group in the decarboxylation step. Kinetic measurements of a large series of differently substituted benzoates were found to correlate with the field effect (&lt;i&gt;F&lt;/i&gt;) of the &lt;i&gt;ortho&lt;/i&gt;-substituent, revealing this feature to be responsible for the enhanced reactivity of these favored benzoates.Our studies of the Ni-catalyzed decarboxylative arylation reaction uncovered an unexpected redox transmetalation step in this system. Synthesis and isolation of the proposed nickelacycle and Ag-aryl intermediates enabled direct study of the fundamental coupling steps. Catalytic and stoichiometric reactions of these complexes, paired with DFT calculations, supported a redox transmetalation step in which the Ag-aryl intermediate transfers the aryl ligand from Ag&lt;sup&gt;I&lt;/sup&gt; to Ni&lt;sup&gt;II&lt;/sup&gt; with concomitant oxidation to generate a Ni&lt;sup&gt;III&lt;/sup&gt;-bis(aryl) intermediate.Finally, detailed mechanistic studies of our Cu-catalyzed decarboxylative thiolation reaction demonstrated how this catalyst system is able to use O&lt;sub&gt;2&lt;/sub&gt; as the terminal oxidant. Kinetic studies paired with the synthesis and reactivity of well-defined copper intermediates revealed decarboxylation from a Cu&lt;sup&gt;I&lt;/sup&gt;-benzoate resting state, despite the oxidizing reaction conditions which could support higher oxidation state intermediates. We also identified the intermediacy of diphenyl disulfide (PhSSPh) formed from the thiophenol (PhSH) coupling partner under the aerobic Cu-catalyzed conditions. The reaction of PhSSPh with the catalyst proceeds via oxidative transfer of the PhS fragment to Cu&lt;sup&gt;I&lt;/sup&gt; that is analogous to that of the redox transmetalation observed in Ni-catalyzed decarboxylative arylation.These studies combined","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"1670-1682"},"PeriodicalIF":16.4,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143950711","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":"Rational Design of Layered Oxide Materials for Batteries","authors":"Qidi Wang, Chenglong Zhao, Marnix Wagemaker","doi":"10.1021/acs.accounts.5c00074","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00074","url":null,"abstract":"Layered transition metal (TM) compounds are pivotal in the development of rechargeable battery technologies for efficient energy storage. The history of these materials dates back to the 1970s, when the concept of intercalation chemistry was introduced into the battery. This process involves the insertion of alkali-metal ions between the layers of a host material (e.g., TiS₂) without causing significant structural disruption. This breakthrough laid the foundation for Li-ion batteries, with materials like LiCoO₂ becoming key to their commercial success, thanks to their high energy density and good stability. However, despite these advantages, challenges remain in the broader application of these materials in batteries. Issues such as lattice strain, cation migration, and structural collapse result in rapid capacity degradation and a reduction in battery lifespan. Moreover, the performance of batteries is often constrained by the properties of the available materials, particularly in layered oxide materials. This has driven the exploration of materials with diverse compositions. The relationship between composition and structural chemistry is crucial for determining reversible capacity, redox activity, and phase transitions, yet predicting this remains a significant challenge, especially for complex compositions.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"28 5 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144096963","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}