Chemical ReviewsPub Date : 2026-08-12Epub Date: 2026-07-16DOI: 10.1021/acs.chemrev.6c00255
Pu-Fan Qian, Jia-Heng Hu, Yan-Xuan Wu, Yuan Xu, Keary M. Engle, Bing-Feng Shi
{"title":"Earth-Abundant 3d Transition Metal-Catalyzed Enantioselective C–H Functionalization","authors":"Pu-Fan Qian, Jia-Heng Hu, Yan-Xuan Wu, Yuan Xu, Keary M. Engle, Bing-Feng Shi","doi":"10.1021/acs.chemrev.6c00255","DOIUrl":"10.1021/acs.chemrev.6c00255","url":null,"abstract":"<p>Transition metal-catalyzed enantioselective C–Hfunctionalizationhas emerged as a next-generation synthetic paradigm, offering numerousopportunities for the <em>de novo</em> construction and late-stagemodification of complex molecular architectures. In parallel withwell-established precious metal catalysts, increasing research effortshave shifted toward the use of earth-abundant 3d transition metals,driven by their distinctive intrinsic properties and reactivity profiles.This review summarizes the rapid progress in 3d metal-catalyzed enantioselectiveC–H functionalization up to March 2025, encompassing both inner-sphereand outer-sphere mechanisms. Emphasis is placed on the underlyingchallenges and core strategic solutions that have enabled these developments.To provide a comprehensive perspective, the advancements are categorizedbased on distinct metal/ligand catalytic systems and subcategorizedaccording to the type of C–H functionalization reactions. Keyaspects such as ligand design, reaction development, mechanistic insights,synthetic applications, and current limitations are discussed in detailwhere appropriate.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"126 15","pages":"8768–8852"},"PeriodicalIF":64.2,"publicationDate":"2026-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148467927","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}
Chemical ReviewsPub Date : 2026-08-12Epub Date: 2026-07-24DOI: 10.1021/acs.chemrev.5c00922
Justin A. North, Hannah S. Shafaat
{"title":"Function, Structure, and Regulation of Nitrogen Fixation-like Metalloproteins for Nitrogen, Energy, Carbon, and Sulfur Metabolism","authors":"Justin A. North, Hannah S. Shafaat","doi":"10.1021/acs.chemrev.5c00922","DOIUrl":"10.1021/acs.chemrev.5c00922","url":null,"abstract":"<p>Nitrogenases (N<sub>2</sub>ases) and nitrogen fixation-like(NFL)systems play distinct roles in nitrogen, carbon, sulfur, and energymetabolism based on their fundamental differences in structure andmetallocofactor identity. As new NFL systems have recently been identifiedand characterized, striking parallels and differences compared toN<sub>2</sub>ase structure, catalysis, and regulation have emerged.NFL systems use metallocofactors that span from simple [4Fe-4S] clustersto complex clusters akin to FeMo-co, previously only thought to occurin N<sub>2</sub>ase. This review describes the present state of knowledgeon the function, structure, catalytic mechanisms, and regulation ofNFL systems that perform distinct biological roles across all threedomains of life. Recent advancements in N<sub>2</sub>ase spectroscopictechniques for probing metallocofactor structure and electronic statesguide current and future work on how each NFL system catalyzes itsspecific biological reaction(s). Key knowledge gaps and needed areasof research for uncovering the specific metallocofactors and structuralmotifs that are at the heart of NFL system reaction specificity, alongwith how these systems are regulated, are discussed.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"126 15","pages":"8234–8283"},"PeriodicalIF":64.2,"publicationDate":"2026-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148589156","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}
Chemical ReviewsPub Date : 2026-08-12Epub Date: 2026-07-20DOI: 10.1021/acs.chemrev.5c00990
Anastassia A. Vorobieva, Rituparna Samanta, Toon Van Thillo
{"title":"De Novo Design of Protein Nanopores: From Minimal Peptides to AI-Driven Design","authors":"Anastassia A. Vorobieva, Rituparna Samanta, Toon Van Thillo","doi":"10.1021/acs.chemrev.5c00990","DOIUrl":"10.1021/acs.chemrev.5c00990","url":null,"abstract":"<p>Protein nanoporesoffer a powerful platform for analytical applicationsby directly converting chemical properties into information-rich,single-molecule electrical readouts. However, engineering naturalnanopores for sensing remains challenging due to the limited numberof available scaffolds and evolutionary constraints on their geometriesand chemistries. Recent advances in AI- and data-driven protein designare enabling increasingly complex membrane protein architectures,opening new possibilities for designing synthetic nanopores with tailoredfolds and functions. This review surveys the evolution of de novonanopore design, from minimal sequences to AI-supported approaches,highlights emerging strategies, and outlines key challenges─includingdata scarcity, membrane modeling, and experimental characterization─thatmust be addressed to realize robust, programmable nanopores for next-generationsensing technologies.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"126 15","pages":"8284–8305"},"PeriodicalIF":64.2,"publicationDate":"2026-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148522043","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}
Chemical ReviewsPub Date : 2026-08-12Epub Date: 2026-08-03DOI: 10.1021/acs.chemrev.6c00154
Jaehwan Choi, Seongmin Kim, Junkil Park, Junyoung Choi, Sunggi An, Yousung Jung
{"title":"AI for Accelerated Materials Discovery: From Generative Design to Autonomous Realization","authors":"Jaehwan Choi, Seongmin Kim, Junkil Park, Junyoung Choi, Sunggi An, Yousung Jung","doi":"10.1021/acs.chemrev.6c00154","DOIUrl":"10.1021/acs.chemrev.6c00154","url":null,"abstract":"<p>Artificial intelligence(AI) is fundamentally transforming materialsdiscovery, shifting the paradigm from labor-intensive trial-and-errorapproaches to data-driven, automated workflows. This review examinesemerging AI methodologies for accelerated materials discovery, withparticular emphasis on how computational design, data infrastructure,synthesis planning, and autonomous experimentation can be connectedinto experimentally grounded workflows. We begin by surveying generativemodels for inverse materials design, tracing the evolution from earlyvariational autoencoders and generative adversarial networks to recentdiffusion models, Bayesian flow networks, flow-based architectures,transformer-based methods, and large language model-driven approachesfor the de novo generation of crystalline materials with targetedproperties. We then discuss physics-informed and data-efficient AIstrategies that incorporate domain knowledge to enhance the modelgeneralizability and robustness in low-data regimes. The emergenceof multimodal foundation models, which integrate heterogeneous datamodalities including crystal structures, text, and spectroscopic informationinto unified representations, is examined as a key enabler for crosstask generalization. We further review AI-driven synthesis planningalgorithms and autonomous self-driving laboratories that bridge thepersistent gap between the computational design and experimental realization.Critical infrastructure challenges, including database limitations,FAIR data principles, and knowledge-graph construction, are also addressed.By highlighting both demonstrated capabilities and persistent limitations,this review aims to guide the reliable application of AI toward materialsdiscovery workflows that connect candidate generation, synthesis feasibility,experimental feedback, and data provenance.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"126 15","pages":"8644–8693"},"PeriodicalIF":64.2,"publicationDate":"2026-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148655906","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}
Chemical ReviewsPub Date : 2026-08-12Epub Date: 2026-07-01DOI: 10.1021/acs.chemrev.6c00037
Fan Wang, Nikolaos Samartzis, Tao Wang, Sheng Dai
{"title":"Synthetic Porous Carbons for High-Energy, High-Power Supercapacitors","authors":"Fan Wang, Nikolaos Samartzis, Tao Wang, Sheng Dai","doi":"10.1021/acs.chemrev.6c00037","DOIUrl":"10.1021/acs.chemrev.6c00037","url":null,"abstract":"<p>Porous carbons are premier electrode materials for supercapacitors,yet overcoming the tradeoff between energy and power density remainsa fundamental challenge. Guided by the overarching goal of achievingsimultaneously high energy and high power, significant progress hasbeen made in the design of advanced carbon materials, accompaniedby a deepened mechanistic understanding of electrochemical chargestorage at complex interfaces. This Review provides a comprehensiveand critical overview of key advances in synthetic porous carbons(SPCs) developed by the broader research community, with an emphasison materials derived from well-defined molecular and polymeric precursors.Bottom-up synthetic strategies that enable precise control over thepore structure and surface chemistry are highlighted. We summarizefundamental charge storage mechanisms and discuss how hierarchicalporosity and heteroatom doping can be rationally engineered to balanceenergy and power performance. Emerging synthetic methodologies, machine-learning-guidedmaterials design, and advanced in situ and operando characterizationtechniques are identified as key enablers of predictive and scalablecarbon design. These insights outline pathways toward next-generationsupercapacitors capable of simultaneous fast charging and high-energystorage.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"126 15","pages":"8517–8598"},"PeriodicalIF":64.2,"publicationDate":"2026-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148358414","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}
Chemical ReviewsPub Date : 2026-08-12Epub Date: 2026-07-21DOI: 10.1021/acs.chemrev.6c00021
Huijie Zhang, Nicolas Plumeré
{"title":"Photosystem-Based Biophotoelectrodes for Solar Energy Conversion","authors":"Huijie Zhang, Nicolas Plumeré","doi":"10.1021/acs.chemrev.6c00021","DOIUrl":"10.1021/acs.chemrev.6c00021","url":null,"abstract":"<p>Photosystem-modified electrodes have been developed asalternativesto classical semiconductor-based systems for solar energy conversioninto chemicals or electricity. Photosystems, the photoactive proteinsof natural photosynthesis, offer exceptional light-harvesting efficiencyand large charge separation and are composed entirely of earth-abundantelements. Their main limitations remain their limited robustness anddifficulty of efficiently interfacing them with electrodes. Here,we review the strategies for integrating the three major classes ofphotosystems (photosystem II, photosystem I, and bacterial reactioncenters) into functional devices. We examine electrode architecturessuch as biophotoanodes and biophotocathodes as well as their assemblyinto biased and bias-free biophotoelectrochemical cells using variousprotein immobilization approaches aimed at maximizing photocurrentand energy efficiency. Particular emphasis is placed on understandingelectron-transfer pathways between electrodes and photosystems, includingpotential short-circuiting pathways. Finally, we highlight key characterizationtools and performance metrics that are essential for identifying bottlenecksand guiding optimization.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"126 15","pages":"8456–8486"},"PeriodicalIF":64.2,"publicationDate":"2026-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148539181","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}
Chemical ReviewsPub Date : 2026-08-12Epub Date: 2026-07-30DOI: 10.1021/acs.chemrev.6c00201
Yanjun Yang, Yiping Zhao
{"title":"Surface-Enhanced Raman Spectroscopy for Viral Diagnostics: Principles, Strategies, Clinical Challenges, and Future Directions","authors":"Yanjun Yang, Yiping Zhao","doi":"10.1021/acs.chemrev.6c00201","DOIUrl":"10.1021/acs.chemrev.6c00201","url":null,"abstract":"<p>Viral outbreaks such as SARS-CoV, MERS-CoV, and COVID-19underscorethe urgent need for rapid, sensitive, and scalable diagnostic technologies.Current standard methods, including nucleic acid amplification testsand immunoassays, offer complementary strengths but face limitationsin cost, turnaround time, and early-stage detection. Surface-enhancedRaman spectroscopy (SERS) has emerged as a promising alternative,leveraging plasmonic nanostructures to amplify weak Raman signalsand provide molecular “fingerprints” of viral componentswith single-molecule sensitivity. This review provides a comprehensiveoverview of SERS-based virus detection, highlighting the fundamentalprinciples of Raman enhancement, the role of substrates and hotspots,and analyte-specific challenges. We categorize sensing strategiesinto direct detection of intact viruses and components, affinity-basedapproaches using antibodies, aptamers, or viral receptors, and labeledmethods that amplify specificity and multiplexing. Advances in nanofabrication,receptor engineering, and machine learning have significantly improvedsensitivity, reproducibility, and classification accuracy, with detectionlimits reaching down to a few viral particles per milliliter. Despitethese advances, challenges remain in handling biological complexity,ensuring reproducibility, and translating assays into clinical practice.We conclude by outlining opportunities for integrating SERS with portabledevices, standardized spectral libraries, and artificial intelligence,paving the way toward rapid, robust, and deployable viral diagnosticsfor future pandemic preparedness.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"126 15","pages":"8694–8742"},"PeriodicalIF":64.2,"publicationDate":"2026-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148655907","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}
Chemical ReviewsPub Date : 2026-08-12Epub Date: 2026-07-15DOI: 10.1021/acs.chemrev.5c00939
Alexey S. Ladokhin
{"title":"Conformational Switching on Lipid Interfaces: Lessons from Refolding and Membrane Insertion of Diphtheria Toxin, BCL-2 Apoptotic Regulators and pHLIP","authors":"Alexey S. Ladokhin","doi":"10.1021/acs.chemrev.5c00939","DOIUrl":"10.1021/acs.chemrev.5c00939","url":null,"abstract":"<p>The conformational switching of a protein from its water-solubleconformation to its membrane-inserted conformation is critical formany cellular processes: cellular entry of bacterial toxins via escapefrom the endosome, apoptotic regulation by the Bcl-2 protein familyto preserve or disrupt the outer mitochondrial membrane, and tumortargeting by <em>pH</em>-<em>L</em>ow-<em>I</em>nsertion-<em>P</em> eptide pHLIP. Here, several empiricalmechanisms of conformational switching are described, illustratinghow the formation of membrane-competent conformation and subsequentmembrane insertion can be triggered and modulated by pH and divalentcations, abided by changes in lipid composition of the target membranes.Despite structural similarities of the water-soluble conformationsof the diphtheria toxin translocation (T) domain with that of proapoptoticBAX and antiapoptotic Bcl-xL, their corresponding insertion pathwaysand modes of conformational switching are markedly different. Theconformational switching of the T-domain is initiated by protonationof key histidine residues in solution, while in the Bcl-2 proteinsBAX and Bcl-xL, it occurs in the membrane proximity. Consequently,changes in the composition of the lipid bilayer (<em>e.g</em>., local enrichment in cardiolipin) can affect insertion and functioningof Bcl-2 proteins. Conformational switching of pHLIP occurs on membraneinterfaces via pH-dependent and Ca<sup>2+</sup>-dependent mechanisms,which is strongly influenced by lipid composition.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"126 15","pages":"8436–8455"},"PeriodicalIF":64.2,"publicationDate":"2026-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148441353","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}
Chemical ReviewsPub Date : 2026-08-12Epub Date: 2026-07-20DOI: 10.1021/acs.chemrev.5c01041
Pedro S. F. Mendes, Daniel P. Costa, Jeroen Lauwaert, Joris W. Thybaut
{"title":"Catalyst Design for Sustainable Reactions: A Primer toward Knowledge-Driven Innovation","authors":"Pedro S. F. Mendes, Daniel P. Costa, Jeroen Lauwaert, Joris W. Thybaut","doi":"10.1021/acs.chemrev.5c01041","DOIUrl":"10.1021/acs.chemrev.5c01041","url":null,"abstract":"<p>When aiming at designing performant catalysts for existingor novel(sustainable) reactions, a wide variety of methodologies can be adopted,turning catalyst design into a science on its own. However, fundamentalknowledge and clear guidelines for the application of these methodologiesfor catalyst innovation are lacking, impeding truly efficient andadequate catalyst design, with serendipity still playing too importanta role. This review fills this gap by systematically categorizingand reviewing the most relevant methodologies and providing theirfundamentals. Despite the strong benefit from systematically collecteddata incoming from digital laboratories, the main common drawbackremains how to design catalysts truly “out of the box”?While various methodologies can serve more humble purposes (e.g.,fine-tuning catalyst compositions), truly innovative catalyst designcan only be achieved via a knowledge-driven approach, strongly supportedby kinetic models in combination with suitable catalysis informaticstools.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"126 15","pages":"8306–8357"},"PeriodicalIF":64.2,"publicationDate":"2026-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148522042","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}
Chemical ReviewsPub Date : 2026-08-12Epub Date: 2026-07-24DOI: 10.1021/acs.chemrev.5c00650
Hyein Lee, Dong-Hyun Lee, Jiyu Hyun, Hyun Su Park, Gun-Jae Jeong, Kwang-Ho Jo, Sang-Kyu Lee, Kyoung-Jun Jang, Suk Ho Bhang, Taekyung Yu
{"title":"Development and Prospects of Zirconia 3D Printing for Artificial Prosthesis Applications","authors":"Hyein Lee, Dong-Hyun Lee, Jiyu Hyun, Hyun Su Park, Gun-Jae Jeong, Kwang-Ho Jo, Sang-Kyu Lee, Kyoung-Jun Jang, Suk Ho Bhang, Taekyung Yu","doi":"10.1021/acs.chemrev.5c00650","DOIUrl":"10.1021/acs.chemrev.5c00650","url":null,"abstract":"<p>Artificialprosthetic manufacturing is moving toward patient-specificdesign and production, and zirconia-based three-dimensional printingis emerging as a promising approach because of its mechanical propertiesand biocompatibility. Yet the step from laboratory development toclinical use is still limited by the gap between laboratory-scaleprocess optimization and clinically relevant validation of performance,reproducibility, and long-term reliability. This review provides anapplication-oriented overview of zirconia-based photopolymerizationadditive manufacturing for dental, orthopedic, and scaffold applications,discussing relevant functional requirements alongside key processingparameters, postprocessing steps, and quality-critical variables.We outline major bottlenecks, such as optical scattering and slurryrheology during fabrication, as well as defects and dimensional deviationsintroduced during debinding and sintering, and we discuss recent performance-orientedstrategies, including triply periodic minimal surface (TPMS) architecturesand functionally graded additive manufacturing (FGAM) routes. Finally,we highlight the critical requirements for clinical translation, includingqualification-ready process control, lot-to-lot manufacturing consistency,and robust durability validation under clinically relevant conditions.Taken together, these aspects establish a process–defect–performancerelationship, where photopolymerization parameters govern defect evolutionduring debinding and sintering and, ultimately, determine the mechanicalreliability and clinical performance of zirconia-based prostheses.Addressing these challenges will be essential for bridging the gapbetween laboratory-scale demonstrations and the scalable productionof patient-specific zirconia prostheses.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"126 15","pages":"8203–8233"},"PeriodicalIF":64.2,"publicationDate":"2026-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148589208","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}