Accounts of Chemical Research最新文献

{"title":"Plasmonic Scattering Interferometric Microscopy: Decoding the Dynamic Interfacial Chemistry of Single Nanoparticles.","authors":"Gang Wu, Jun-Hao Wan, Chen Qian, Xian-Wei Liu","doi":"10.1021/acs.accounts.5c00294","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00294","url":null,"abstract":"<p><p>ConspectusThe ability to detect and image nanomaterials at interfaces is crucial for a wide range of applications, from the engineering and characterization of nanocomposites to enabling label-free detection for biomedical diagnostics and therapy. Light microscopy, which relies on the optical properties of nanomaterials, has significantly contributed to this goal due to its adequate temporal and spatial resolutions and compatibility with diverse application scenarios. However, the optical intensity readout of these label-free optical imaging techniques inherently limits their selectivity. Consequently, visualizing dynamic interfacial changes over a single particle with high spatiotemporal resolution under mild solution reaction conditions remains a challenge.In this Account, we highlight the recent progress in plasmonic scattering interferometric microscopy (PSIM), a technique developed to address these challenges. We begin with the fundamental principles of plasmonics and light scattering relevant to PSIM, demonstrating its ability to optically identify and measure various nanoparticles. Significant improvements in imaging quality were achieved through the development of a high-resolution plasmonic scattering interferometric microscope (HR-PSIM). These advances have enabled the real-time observation of compositional transformations in single nanoparticles, offering new insights into their electrocatalytic activity and reaction kinetics at the single-particle level. Leveraging the high-resolution capacity of HR-PSIM for visualizing chemical reactions, we explored electrochemical processes in real-time with remarkable spatial resolution. In addition, we introduce novel algorithmic tools for noise reduction and automation, designed to eliminate background interference and reconstruct high-quality, high-resolution images. The integration of deep learning into PSIM has further advanced the technique, enabling the precise localization and identification of nanoparticles with enhanced robustness across varying spatiotemporal conditions. This Account concludes with an outlook on the future development of PSIM, discussing current limitations and the potential for further enhancements. We envision that the continued refinement of PSIM will open new avenues for studying surface chemistry and nanoscale reactions, leading to significant breakthroughs in nanoscience research and a broad range of practical applications.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":17.7,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144935597","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":"Overcoming the Hydration and Solvation Problem in Ion Recognition and Binding: The Biomimetic Approach","authors":"Pavel Anzenbacher Jr.*,&nbsp;Anjusha Prakash,&nbsp;Sandra M. George,&nbsp;Austin R. Sartori,&nbsp;Mikhail Zamkov and Alexander N. Tarnovsky,&nbsp;","doi":"10.1021/acs.accounts.5c00472","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00472","url":null,"abstract":"&lt;p &gt;Artificial receptors for cations and anions utilizing noncovalent binding, transport, sequestration, or sensing in aqueous media must address enthalpic factors such as electrostatic attraction, hydrogen bonding, van der Waals forces, and London dispersion forces. The entropic component also significantly contributes to the free energy of association, especially in polar environments like water, where binding may be entropy-driven due to the release of ordered solvent molecules from the solvation sphere, increasing system entropy and resulting in a negative free Gibbs energy. Over the years, chemists have focused on enthalpic criteria, such as size complementarity and functional group interactions, for designing artificial receptors. However, designing for the entropic component, particularly solvation/desolvation, remains challenging and often depends on fortunate circumstances.&lt;/p&gt;&lt;p &gt;As shown by X-ray crystallography, enzymes and proteins can strip solvating water molecules from the ions. Inspired by phosphate-binding enzymes and transporters, we examined polymers comprising amide bonds, such as polyamides and polyurethanes, to mimic protein backbones. These hydrophilic polymers can be engineered to absorb specific amounts of water (10–100% or even more). We aimed to use hydrophilic polymers to remove water molecules from hydrated ions, rendering them “naked” ions, thus enabling better recognition by receptors based on enthalpic factors. To test this, we used copolymers with amide and urethane–amide moieties with different ratios of poly(ethylene oxide) and poly(butylene oxide) to control water uptake between 10% and 100%, along with embedded fluorescent sensors. We found that polymers with 30–50% water uptake showed the highest fluorescence response, while uptake below 20% resulted in small changes in fluorescence and 60–100% led to diminished responses. Low water uptake caused reduced ion co-transport, while high uptake formed large water pools within the polymers, isolating solvated ions from receptors. The optimal water uptake of 30–50% produced (semi)naked ions and a water–organic matrix similar to that of DMSO–water environments. Just like proteins, the structure impacts the recognition and internalization of anions, such as phosphate or sulfate; here too, the monomer composition and synthetic sequence greatly influence material responses to anions, with lipophilic ones eliciting lower responses. The data analysis of fluorescence responses enables the generation of sensor arrays for both cations and anions in water, buffers, saliva, urine, or blood plasma, both qualitative and quantitative analyses, for single analytes or as analyte mixtures. Overall, this biomimetic approach focused on the recovery of the enthalpic factor (by diminishing the impact of solvation and entropy) has proven remarkably successful in creating sensors and adsorbents for charged species in aqueous media and water and is expected to find applications in optica","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 17","pages":"2792–2803"},"PeriodicalIF":17.7,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924769","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 Molecules to Modules: Pathways toward Scalable Electrochemical CO₂ Reduction.","authors":"Gong Zhang, Shuying Li, Xiaowei Du, Yangning Zhang, Tuo Wang, Peng Zhang, Jinlong Gong","doi":"10.1021/acs.accounts.5c00416","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00416","url":null,"abstract":"<p><p>ConspectusAchieving carbon neutrality requires the development of robust carbon capture, utilization, and storage (CCUS) technologies. Among the various carbon utilization pathways, the electrochemical carbon dioxide (CO₂) reduction reaction (CO₂R) presents a compelling approach, enabling the direct conversion of CO₂ and water into valuable fuels and chemical feedstocks using renewable electricity. While recent breakthroughs in mechanistic insights, catalyst materials, and reactor designs have been achieved, significant challenges remain in translating promising lab-scale results into techno-economically viable technologies. Key challenges hindering this transition include (1) a lack of rational screening and scalable fabrication methods for high-performance electrocatalysts and corresponding electrode assemblies; (2) a shortage of understanding how the transport phenomena within the electrodes and electrolyzers affect the microenvironment of reactions; and (3) a deficiency in designing principles for electrolyzers and stacks capable of large-scale production. All these points originate from the knowledge mismatch of the CO₂R between the microscopic perspective and the systematic point of view. Therefore, bridging the gap between fundamental knowledge of the reaction at the molecular level and process engineering for scale-up at the module level is crucial to accelerating the application of CO₂R.This Account describes chemistry and engineering methodologies, highlighting progress from our group and the broader field, aimed at inspiring a pathway toward large-scale CO₂R. Addressing the need for screening highly active catalysts, we leverage descriptor-based neural networks to rationally construct alloys and single-atom active sites to exhibit tailored reactivity. We then focus on translating these molecular concepts into durable, high-performance catalyst layers integrated into gas diffusion electrodes (GDEs) through advanced coating and fabrication techniques. These approaches are crucial for managing interfacial contact resistances and distributed Ohmic losses. Moreover, they enable precise control over interfacial gas-liquid equilibria within the porous electrode architecture. To tackle challenges of gas-flow pressure drop and Joule heating during scale-up, we have proposed device design requirements for conducting CO₂ electrolysis at elevated pressure and temperature. Additionally, an outlook for a CO₂R technology roadmap is discussed. Ultimately, this Account underscores how integrating fundamental molecular insights with rigorous process design provides a powerful roadmap toward industrial CO₂R technology.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":17.7,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144935608","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":"Divergent Synthesis of Kopsia and Structurally Related Monoterpenoid Indole Alkaloids: A Non-biomimetic Strategy","authors":"Hui Wang,&nbsp; and ,&nbsp;Zhiqiang Ma*,&nbsp;","doi":"10.1021/acs.accounts.5c00461","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00461","url":null,"abstract":"<p >Monoterpenoid indole alkaloids constitute one of the largest natural product families, with over 3000 members reported to date. <i>Kopsia</i>, a genus of about 30 species, is notable for its rich alkaloid diversity. These plants produce unique monoterpenoid indole alkaloids with intriguing structures and bioactive properties, making them a key focus in synthetic chemistry research over the years. Between 2015 and 2022, a new class of compounds belonging to the genus <i>Kopsia</i> was isolated, including arboridinine, arborisidine, arboduridine, and arbornamine. Interestingly, a structurally related alkaloid named alstrostine G, which resembles the pentacyclic system of arbornamine, was isolated from <i>Alstonia rostrata</i> in 2017. These five alkaloids feature complex polycyclic skeletons and dense stereocenters, drawing significant attention from the synthesis community upon their isolation. Biogenetically, these four <i>Kopsia</i> alkaloids are derived from subincanadine E containing a medium-sized ring, which undergoes distinct pathways to yield the four alkaloids with distinct frameworks. Alstrostine G was proposed to be derived from stemmadenine, which resembles subincanadine E. Enzymes enable their biosynthesis with precise regio-, stereo-, and enantioselectivity. From a laboratory synthesis perspective, however, mimicking this biosynthetic pathway without the help of enzymes can be quite challenging. These facts suggest the need to devise an alternative synthetic strategy for the divergent synthesis of this class of monoterpenoid indole alkaloids. Besides our work, about nine impressive total syntheses or synthetic studies have been reported by seven research groups. However, prior studies mainly focused on an individual natural product, such as arboridinine, arborisidine, arbornamine, or alstratine A. Our group has achieved the collective total synthesis of all five alkaloids by a divergent and non-biomimetic strategy.</p><p >In this Account, we summarize our recent endeavors on the divergent total synthesis of these five monoterpenoid indole alkaloids via a non-biomimetic strategy. In-depth structural analysis of the five alkaloids revealed their hidden topological connection. We consequently classified them into two categories: (1) arboridinine, arborisidine, and arboduridine with caged frameworks, which share a common tricyclic A/B/D ring system, and (2) arbornamine and alstrostine G, which feature a 1,1-disubstituted tetrahydro-β-carboline (THBC) core. For the first category, we initially reported a divergent racemic synthesis of skeletally distinct arboridinine and arborisidine. This strategy features a Michael and Mannich cascade process to efficiently assemble the common tricyclic A/B/D ring core, followed by site-selective late-stage diversification to access the unique tetracyclic frameworks of arboridinine and arborisidine. Subsequently, we constructed the enantioenriched tricyclic A/B/D ring system via an enantioselective ","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 17","pages":"2781–2791"},"PeriodicalIF":17.7,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924815","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":"Mainstream and Sidestream Modeling in Oxygen Evolution Electrocatalysis","authors":"Federico Calle-Vallejo*,&nbsp;","doi":"10.1021/acs.accounts.5c00439","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00439","url":null,"abstract":"<p >The oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are key in numerous electrochemical technologies, such as water electrolyzers, CO₂ electrolyzers, low-temperature fuel cells, regenerative fuel cells and some metal-air batteries. The OER and ORR tend to be sluggish and catalyzed by scarce and expensive materials, the durability of which is often insufficient. For two decades, computational methods have been regarded as a cost-effective means to explain experimental observations, test hypothesis, and design new materials for these two reactions.</p><p >Currently, the most widely used computational model is based on the free energies of the intermediates (*O, *OH, *OOH) and the scaling relations among them. Since the publication of two seminal papers in 2011, the scaling relation between the adsorption energies of *OOH and *OH was assigned all the responsibility for the experimental inefficiencies of OER and ORR electrocatalysts. This triggered a research paradigm based on breaking such scaling relation that still lasts until this day (see the diagram next to this text). After noting in 2018 that breaking the scaling relation between *OOH and *OH does not necessarily entail an improvement of the OER overpotential, my group moved away from the mainstream and has since been devising alternative descriptors and methods to enhance OER electrocatalysts and bifunctional OER/ORR electrocatalysts.</p><p >In this Account, I will describe when and why we introduced the concepts of electrochemical symmetry, delta-epsilon optimization, bifunctional volcano plot, and error awareness, among others, aiming to provide quantitative tools for the computational design and optimization of electrocatalysts.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 17","pages":"2749–2759"},"PeriodicalIF":17.7,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00439","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924774","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":"Nanocatalytic Antioxidation: A General Chemical Approach for Alleviating Oxidative Stress in Diseases","authors":"Bowen Yang*,&nbsp; and ,&nbsp;Jianlin Shi*,&nbsp;","doi":"10.1021/acs.accounts.5c00408","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00408","url":null,"abstract":"&lt;p &gt;The overexpression of reactive oxygen species (ROS) is one of the major causes of various human diseases, including cardiovascular diseases, neurodegenerative diseases, and multiple inflammations, by initiating local oxidative stress at specific sites. The excessive ROS not only leads to oxidative injury of normal functional cells but also activates immune cells to aggravate inflammation. Therefore, scavenging excessive ROS is a feasible strategy for treating these diseases. Although many molecular drugs (such as &lt;i&gt;N&lt;/i&gt;-acetylcysteine and coenzyme Q10) have been approved for antioxidative therapies, from the perspective of chemical reaction, these antioxidant molecules can only act as reactants to react with ROS, leading to a nonsustainable antioxidative effect, largely compromising therapeutic outcome.&lt;/p&gt;&lt;p &gt;Our research team has proposed the concept of “nanocatalytic medicine”, which aims to use nanoparticles to trigger catalytic reactions in pathological sites, regulating the concentrations of ROS efficiently and sustainably for disease treatments. Till now, most efforts have been focusing on the development of pro-oxidative nanocatalysts to catalyze ROS generation for tumor therapy, which induces oxidative damage of cancer cells, while the antioxidative nanocatalysts for treating other oxidative stress-related diseases have been less reported, and the chemical strategy of nanocatalytic antioxidation has rarely been discussed specifically, which is in contrast to the conventional nanocatalytic pro-oxidation approach for tumor therapy.&lt;/p&gt;&lt;p &gt;During the last several years, our laboratory has developed various catalytic antioxidative nanosystems to trigger nanocatalytic antioxidation reactions for treating multiple diseases, including ischemic cardiomyopathy, diabetic cardiomyopathy, aortic dissection, alcoholic liver injury, inflammatory bowel disease, psoriasis, atopic dermatitis, rheumatoid arthritis, etc. From the perspective of chemical reaction, these nanosystems act as catalysts in antioxidation reactions and therefore will not be consumed but can lead to a sustainable and highly efficient antioxidative effect. Such a strategy not only largely elevates therapeutic efficacy but also reduces the doses of therapeutic agents required for administration. Moreover, the established catalytic antioxidation reactions may modulate the immune microenvironments at pathological sites, resulting in favorable therapeutic outcomes. In this Account, we will discuss the recent advances in our laboratory in the design and fabrication of antioxidative nanocatalysts for various disease treatments, highlighting nanocatalytic antioxidation as a general chemical strategy for alleviating oxidative stress in diseases. The material chemistry of these catalytic antioxidative nanosystems will be elucidated, which underlies elevated therapeutic outcome. It is expected that such a chemical strategy of nanocatalytic antioxidation will make a significant contri","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 17","pages":"2708–2723"},"PeriodicalIF":17.7,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924775","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":"Late Metal Sandwich Catalysts for Olefin Polymerization","authors":"Joseph T. Medina,&nbsp;Quan H. Tran,&nbsp;Girish G. Ramachandru,&nbsp;Maurice Brookhart* and Olafs Daugulis*,&nbsp;","doi":"10.1021/acs.accounts.5c00440","DOIUrl":"10.1021/acs.accounts.5c00440","url":null,"abstract":"&lt;p &gt;Polyolefins are by far the most ubiquitous industrially produced polymers and are primarily produced by early transition metal catalysts. These catalysts are not functional group tolerant, and copolymerization of ethylene and polar vinyl monomers is quite challenging. Furthermore, early metal catalysts convert ethylene to linear polyethylene, and introduction of branches requires addition of comonomers. In this Account, we describe our efforts in designing and implementing new Pd(II) and Ni(II) olefin polymerization catalysts based on mechanistic understanding of the chain growth process. The original hindered nickel- and palladium-aryl-substituted diimine complexes were discovered in 1995. The key to the success of these now “classic” systems in generating high polymers rather than dimers or oligomers was realizing that incorporation of ortho-disubstituted aryl groups partially blocks the axial sites of the metal and thus retards the rate of chain transfer relative to propagation. Two key features of these late metal catalysts distinguish them from early metal complexes. First, they tolerate certain functional groups, which allows copolymerization of olefins with polar comonomers. Second, they can form a branched polymer from ethylene without the need to add α-olefin comonomers. Importantly, for nickel catalysts, branching levels can be modulated by changing reaction conditions, such as temperature and monomer pressure.&lt;/p&gt;&lt;p &gt;Based on molecular modeling, we speculated that 8-(arylnaphthyl) substitution in α-diimine catalysts should result in sandwich-type structures and thus exhibit much more efficient blocking of the axial sites relative to the classical ortho-disubstituted aryl diimines. This analysis proved to be quite fruitful. In this Account we describe the synthesis of palladium and nickel sandwich catalysts, mechanistic investigations of their catalytic behavior, and their use in building new polymer structures. The enhanced axial shielding by the two capping aryl groups in these catalysts results in exceptionally slow rates of chain transfer and, consequently, formation of extremely high molecular weight polymers with very narrow molecular weight distributions, features characteristic of living polymerizations. This behavior, coupled with the ability (particularly for nickel) to control polymer branching densities and thus mechanical properties through pressure and temperature variations permits generation of ultrahigh molecular weight polyethylenes (&lt;i&gt;M&lt;/i&gt;&lt;sub&gt;n&lt;/sub&gt;’s over 10&lt;sup&gt;7&lt;/sup&gt; Da) with branches ranging from 9 to 100 per 1000 carbons and &lt;i&gt;T&lt;/i&gt;&lt;sub&gt;m&lt;/sub&gt; values from 17 to 132 °C. Furthermore, the living nature of the polymerization and the variation of branching with pressure has permitted the synthesis of diblock and multiblock polymers with narrow dispersities and complete control of molecular weights as well as specification of hard and soft segment lengths. Such structures are receiving extensive attention a","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 17","pages":"2770–2780"},"PeriodicalIF":17.7,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144870114","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":"Direct Optical Processing of Electrochromic Materials for Non-emissive Displays","authors":"Chang Gu,&nbsp;Guojian Yang,&nbsp;Sean Xiao-An Zhang and Yu-Mo Zhang*,&nbsp;","doi":"10.1021/acs.accounts.5c00433","DOIUrl":"10.1021/acs.accounts.5c00433","url":null,"abstract":"<p >The rapid evolution of human–machine interaction frameworks and global digitization initiatives has imposed heightened requirements for intelligent display systems. Electrochromic (EC) non-emissive displays, which dynamically modulate optical properties (e.g., color, absorption, transmittance) via electrochemically driven redox processes, represent a significant advancement in next-generation display architectures. These systems inherently have advantages including ultralow power consumption, sunlight-readable contrast, eye comfort, optical transparency, and mechanical flexibility. Nevertheless, their practical implementation remains constrained by undesirable spatial resolution and EC performances.</p><p >The direct optical processing strategy has emerged as a paradigm-shifting approach, facilitating photochemical modification of EC functional materials through noncontact photoirradiation protocols. This strategy demonstrates unparalleled capabilities in resolution control and scalable manufacturing throughput. Furthermore, on-demand precision engineering of EC materials via in situ photoactivated cross-linking, bond cleavage, and polymerization enables systematic optimization of electro-optical responsiveness and multidimensional functional integration. These features position direct optical processing as a foundational methodology for high-precision display fabrication, directly addressing EC resolution and performance bottlenecks.</p><p >In this Account, we present a comprehensive overview of our recent advances in direct optical processing protocols for EC material systems in non-emissive display applications. By correlating material structural characteristics with photochemical mechanisms, we analyze three systematic processing approaches: matrix-engineered lithography, covalent-engineered lithography, and surface-engineered lithography. Then we introduce corresponding single-pixel addressing capabilities based on passive or active matrix driving modes. The discussion subsequently evaluates the positive enhancement of EC performance in electro-optical modulation dynamics and durability enabled by direct optical processing while elucidating the mechanistic relationship between optical processing parameters and device functionality. Additionally, extended applications in ultra-fine displays, flexible wearable electronics, optical communications, and integrated multifunctional applications are outlined. This Account concludes with a forward-looking roadmap for commercialization, highlighting synergistic opportunities between EC material innovations and advanced direct optical processing platforms to accelerate the realization of EC non-emissive display technologies.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 17","pages":"2737–2748"},"PeriodicalIF":17.7,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881627","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":"Multi-Catalytic-Field Assisted Conversion of Low-Concentration CO2 in Steel Byproduct Gas for Synergistic Steel-Chemical Production","authors":"Qiannan Li,&nbsp;, ,&nbsp;Guangsheng Wei*,&nbsp;, ,&nbsp;Jian Qi*,&nbsp;, ,&nbsp;Kun Zhao*,&nbsp;, and ,&nbsp;Baochen Han*,&nbsp;","doi":"10.1021/acs.accounts.5c00348","DOIUrl":"10.1021/acs.accounts.5c00348","url":null,"abstract":"&lt;p &gt;The iron and steel industry, as a major global CO&lt;sub&gt;2&lt;/sub&gt; emitter, urgently requires technological breakthroughs in its carbon neutrality pathway. Existing emission reduction technologies such as carbon capture, utilization and storage are economically insufficient, while the full utilization of byproduct gas may lead to energy shortages in steel enterprises. Steel byproduct gases (e.g., converter gas) have complex composition, and traditional combustion results in high emissions. In this context, the proposed low concentration CO&lt;sub&gt;2&lt;/sub&gt; (LCC) system demonstrates dual advantages: (1) enhancing the calorific value of the byproduct gas to meet the demands of high-energy steelmaking processes and (2) achieving the recovery of high-purity CO&lt;sub&gt;2&lt;/sub&gt; postcombustion, thereby facilitating the carbon neutrality pathway with minimized separation energy consumption. However, components such as CO and N&lt;sub&gt;2&lt;/sub&gt; in the gas lead to competitive adsorption, low catalytic selectivity, and complex reaction pathways, necessitating breakthroughs in catalytic mechanisms and process innovation.&lt;/p&gt;&lt;p &gt;This Account based on the research accumulation of the authors’ team in the field of CO&lt;sub&gt;2&lt;/sub&gt; catalytic reduction and iron and steel metallurgy systematically reviews the key scientific issues and technological advancements in the catalytic conversion of LCC, using converter gas as a typical case. First, addressing the challenge of selective CO&lt;sub&gt;2&lt;/sub&gt; adsorption, the competitive mechanisms of different adsorption models in complex gas environments were explored. Second, in terms of activation and reaction pathway regulation, the influence patterns of gases such as CO and N&lt;sub&gt;2&lt;/sub&gt; on the CO&lt;sub&gt;2&lt;/sub&gt; reduction reaction are analyzed. Furthermore, through in-depth analysis, new principles and processes for CO&lt;sub&gt;2&lt;/sub&gt; adsorption in novel scenarios, catalyst matching, and directional design, material surface reconstruction under industrial environmental conditions is considered. Finally, we integrate the LCC reduction technology into the synergistic steel-chemical production technology route, focusing on elucidating the scientific design principles of meso-macro bridging in the engineering application process, providing a reference for the treatment of various industrial flue gases and tail gases.&lt;/p&gt;&lt;p &gt;The LCC catalytic reduction technology aids steel industry carbon emission reduction through “source conversion-end utilization”, but its industrialization requires collaborative innovation in theory and engineering. Future efforts should focus on the catalytic surface and interface mechanisms under complex gaseous conditions, develop highly efficient and stable catalysts, and design an integrated intelligent system of “catalysis-calorific value-chemical” to promote the near-zero carbon transformation in the steel industry. This technology not only supports carbon neutrality in the steel industry but also provides interdisciplinary ","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 20","pages":"3111–3122"},"PeriodicalIF":17.7,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144870115","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":"Crystalline Porous Frameworks via Hierarchical Dynamic Covalent Assembly","authors":"Yanqing Ge,&nbsp;, ,&nbsp;Shaofeng Huang,&nbsp;, ,&nbsp;Zhehao Yuan,&nbsp;, and ,&nbsp;Wei Zhang*,&nbsp;","doi":"10.1021/acs.accounts.5c00393","DOIUrl":"10.1021/acs.accounts.5c00393","url":null,"abstract":"<p >Crystalline porous frameworks, such as covalent organic frameworks (COFs), metal–organic frameworks (MOFs), and hydrogen-bonded organic frameworks (HOFs), have demonstrated exceptional potential in diverse applications, including gas adsorption/separation, catalysis, sensing, electronic devices, etc. However, the building blocks for constructing ordered frameworks are typically limited to multisubstituted aromatic small molecules, and uncontrolled interpenetration has remained a long-standing challenge in the field. Shape-persistent macrocycles and molecular cages have garnered significant attention in supramolecular chemistry and materials science due to their unique structures and novel properties. Using such preporous shape-persistent 2D macrocycles or 3D cages as building blocks to construct extended networks is particularly appealing. This <i>macrocycle-to-framework/cage-to-framework</i> hierarchical assembly approach not only mitigates the issue of interpenetration but also enables the integration of diverse properties in an emergent fashion. Since our demonstration of the first organic cage framework (OCF) in 2011 and the first macrocycle-based ionic COFs (ICOFs) in 2015, substantial advancements have been made over the past decade. In this Account, we will summarize our contributions to the development of crystalline porous frameworks, consisting of shape-persistent macrocycles and molecular cages as preporous building blocks, via hierarchical dynamic covalent assembly. We will begin by reviewing representative design strategies and the synthesis of shape-persistent macrocycles and molecular cages from small molecule-based primary building blocks, emphasizing the critical role of dynamic covalent chemistry (DCvC). Next, we will discuss the further assembly of preporous macrocycle/cage-based secondary building blocks into extended frameworks, followed by an overview of their properties and applications. Finally, we will highlight the current challenges and future directions for this hierarchical assembly approach in the synthesis of crystalline porous frameworks. This Account offers valuable insights into the design and synthesis of functional porous frameworks, contributing to the advancement of this important field.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 19","pages":"2970–2984"},"PeriodicalIF":17.7,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144870113","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}