Chemical Reviews最新文献

Leveraging the intrinsic π-acidic character of gold complexes,gold has found widespread application in organic synthesis. Despitethe extensive use of gold as a π-bond activator, its applicationin redox catalysis for achieving cross-coupling reactions has historicallylagged behind. The primary obstacle in advancing gold redox catalysisis the inherent high redox potential of the Au(I)/Au(III) couple,arising from the pronounced relativistic effect. The instability ofAu(III) complexes due to facile reduction to gold nanoparticles presentsan additional challenge. Over the years, extensive efforts were madeto overcome these limitations which led to the identification of severalstrategies to achieve gold redox catalysis. These strategies primarilyrely on the use of external oxidants, photocatalyst/light, aryldiazoniumsalts, hemilabile ligands, electricity and dinuclear gold-complexesto facilitate Au(I)/Au(III) catalysis. Banking on these strategies,gold redox catalysis has emerged as a promising technique for varioustransformations such as cross-coupling reactions, C-H functionalizationreactions and difunctionalization of C-C multiple bonds. Interestingly,the high electronegativity and π-acid character of gold complexesoffer unique reactivities and selectivities compared to commonly usedtransition metals for cross-coupling reactions. Clearly, the fieldof Au(I)/Au(III) catalysis has significantly expanded the utilityof gold in organic synthesis and its applications in biological andmaterials science. This review summarizes an up-to-date developmentin this field since its inception, with a particular emphasis on mechanisticaspects, while outlining the key opportunities and future directions.

Ionotronics encompasses a broad range of phenomena anddevicesbased either on the electron-controlled manipulation of ions in electrolyticmedia or on the use of ionic behavior to control electronic functionality.Although the term itself is relatively recent, the scientific foundationsof ionotronics span more than a century of research. Owing to theirpromising applications in areas ranging from energy storage and harvestingto robotic actuation, nanofiltration, water desalination, sensing,and neuromorphic computation, ionotronic systems have recently attractedrapidly growing attention, particularly in the context of low-dimensionalelectrodes. These advanced architectures can profoundly modify theelectrode–electrolyte interface, where ion transport and interfacialphenomena play a central role. Such systems exhibit distinctive physicsarising either from nanoscale confinement, which restricts the electrolyteto only a few layers of ions or solvent molecules, or from low-dimensionalelectronic effects imposed by confining materials such as graphene,carbon nanotubes, and MXenes. This Focus Review aims to provide acomprehensive yet accessible overview of the fundamental phenomenagoverning low-dimensional ionotronic systems, with particular emphasison the underlying physics that determines their performance and enablesemerging applications.

Scientists have increasingly recognized the significanceof incorporatingcatalyst surface structure dynamics into catalyst design, exploitingsurface structure dynamics to improve catalytic activity, selectivity,and stability. Exploring surface structure dynamics of heterogeneouscatalysis, electrocatalysis and photocatalysis at atomic scale isessential for uncovering molecular mechanisms of catalytic reactionsperformed on surfaces of operational catalysts. It is crucial forpredictively designing catalysts with better catalytic activity, selectivityand durability through bridging the information gap between structuresof pristine catalysts and surfaces of operational catalysts. In thisreview we systematically investigated the surface structure dynamicsof single-crystal monometallic model catalysts, single-crystal bimetallicmodel catalysts, monometallic metal nanoparticles, bimetallic nanoparticles,oxide nanoparticles, single-atom catalysts, catalysts of metal atomsencapsulated in microporous materials, catalysts of metal/supportinterfaces, electrocatalysts, and photocatalysts. We performed criticalanalyses to the mechanisms governing surface structure dynamics atan atomic scale, deposited profound structural mechanisms in thisarticle about how catalyst surface structures evolve under catalyticconditions, and found the guidance predicting surface structure dynamics.We summed up the insights of surface structure dynamics and discussedhow these insights of surface structure dynamics can be leveragedto design novel catalysts and promote catalytic performances. Challengesin the studies of surface structure dynamics were discussed and promisingnew directions were proposed.

Protein aggregationis a pathological process associated with severalhuman diseases termed proteinopathies, including neurodegenerativeand metabolic disorders such as Alzheimer’s disease, Parkinson’sdisease, type II diabetes, amyotrophic lateral sclerosis, and Huntington’sdisease. In these conditions, specific proteins misfold and accumulateinto insoluble aggregates, disrupting normal cellular function andcontributing to disease progression. Many studies have investigatedthe molecular mechanisms that underlie the aggregation pathways, thestructure of aggregates, such as oligomeric intermediates and fibrils,and their cellular toxicity. Studies have also investigated the effectsof cofactors like metals, lipids, other amyloid proteins, and smallmolecules. Recent research has increasingly emphasized the criticalroles of metal ions such as copper (Cu), zinc (Zn), iron (Fe), andmanganese (Mn) in amyloid aggregation and toxicity. Alterations inmetal ion transport, binding, or redox activity have been linked tothe onset and progression of several amyloid-associated diseases.These metal ions can interact directly with amyloidogenic proteins,influencing their structural conformation, aggregation kinetics, andpropensity to form toxic oligomers. This review aims to advance ourunderstanding of how the regulation of metal ions within cells andtheir dysfunction contribute to the accumulation of harmful proteins,which is a key factor in proteinopathies. By examining the interactionsbetween metal ions and key amyloidogenic proteins─includingamyloid-β (Aβ), α-synuclein, tau, superoxide dismutase1 (SOD1), human islet amyloid polypeptide (hIAPP), and insulin─wehighlight both common and unique pathways through which metal ionsinfluence protein aggregation. Additionally, this review exploresthe impact of metal ions on protein clearance mechanisms, such asautophagy and the ubiquitin–proteasome system, as well as emergingtheranostic strategies. These include metal chelation therapies, metal-basedimaging agents, and multifunctional compounds designed to restoremetal balance while preventing aggregation and toxicity. By integratingbiochemical, cellular, and therapeutic insights, this review contributesto a deeper understanding of the metallobiology of proteinopathiesand supports the development of novel diagnostic and treatment approachestargeting metal–protein interactions.

Microsampleseparation in lab-on-a-chip systems is a rapidly evolvingresearch area addressing challenges across biomedical, chemical, andenvironmental sciences. Enabled by advances in micro- and nanofabrication,microfluidic platforms allow high-throughput separation and purificationof complex microsamples through tailored channel structures and externaldriving forces, offering high-throughput, efficient, and integratedalternatives to conventional separation methods. Importantly, researchprogress in the laboratory is swiftly transitioning to address practicalchallenges. As our manuscript specifically focuses on the types andapplications of microfluidic separation technologies, it is highlyvaluable for startups and other commercial entities looking to enterthe separation technology market, as well as for end-user companies.The manuscript commences with a discussion on the development andconstruction processes of microfluidic separation, and then dive intoa detailed analysis of the principles and classifications of separationtechnologies integrating a range of external fields forces. Anothersection focuses on emerging applications of microsample separationtechnologies, highlighting successfully commercialized microfluidicseparation platforms while discussing the challenges currently hinderingfurther commercialization of these technologies. Finally, we provideperspectives on the future direction of this technology, includingthe challenges and opportunities that arise with the development ofartificial intelligence technologies in its applications.

High-energy X-ray and γ-ray detection underpinsmedical imaging,security screening, industrial nondestructive evaluation, and scientificinstrumentation, creating strong demand for semiconductor absorbersthat deliver high detection performance while remaining scalable andcost-effective. Metal halide perovskite single crystals (HPSCs) haveemerged as a potentially disruptive, low-cost alternative: they canbe grown from inexpensive precursors using energy-efficient, low-temperaturesolution processes, and they combine high effective atomic numberswith favorable mobility–lifetime products that can approachor exceed commercial benchmarks. Relative to polycrystalline films,the absence of grain boundaries, ultralow defect densities, and efficientcharge transport in HPSCs enable improved optoelectronic responseand enhanced operational stability in detector architectures. Despiterapid progress in headline device metrics, the field has often emphasizedempirical optimization over mechanistic understanding, leaving keyrelationships between intrinsic crystal quality, defect formationand kinetics, and long-term stability insufficiently resolved. Inparallel, inconsistent reporting of crystal quality and nonstandardperformance protocols complicate cross-study comparisons and impedetranslation to useful applications. This Review provides an integratedframework that connects detector physics, materials science, crystalgrowth, and device engineering to rationalize reported advances andto guide future development.

This review aims to integrate advancementsin the rational designof Cu nanoclusters (NCs) from the past decade. Atomically preciseCu NCs have emerged as promising materials for highly active catalysis,due to their low cost and high efficiency as well as well-definedstructures. The absolute monodispersity of Cu NCs provides directinsights into fundamental catalytic research, including the identificationof active sites, the establishment of structure–activity relationshipsat atomic level, the modulation of metal-kernel structures and ligandsfor selectivity, and the exploration of catalytic mechanisms. In thisreview, we summarize strategies for developing Cu NC catalysts, includingligand engineering, oxidation state modulation, heteroatom doping,and theoretical prediction. Subsequently, we sum up the fast-growingadvances of Cu NCs catalysts in terms of catalytic activities, identificationof active sites and fundamental mechanisms. The catalytic applicationsmainly involve electrocatalysis, photocatalysis, and organic transformations.Finally, we provide comprehensive commentaries on the challenges andfuture perspectives in rational design of Cu NCs and its commercializationas catalysts.

Controlling the energeticlandscape of metal halide perovskitesolar cells is crucial for optimizing device efficiency and stability,as well as enabling new architectures beyond conventional layereddesigns. While band alignment criteria are key determinants of performancein organic photovoltaic devices, they are often insufficient for perovskitesdue to their high charge carrier density, mobile ions, and soft latticestructure. A deep understanding of the electronic structure of theperovskite and the contacting layers remains an active area of researchand requires expertise in the characterization techniques. In thisreview, we analyze how interfacial energetics influence charge extraction,the formation of energy barriers, interfacial recombination, and ionmigration, highlighting the unique challenges posed by the soft ioniclattice of metal halide perovskites. To this end, we provide a comprehensiveoverview of experimental techniques for probing energetic alignment,emphasizing their operating principles, limitations, and emergingin situ variants. Building on these insights, we discuss strategiesfor controlling the interfacial energetics of perovskite solar cells,ranging from interfacial layers and dipolar modifiers to electricaldoping. Finally, we explore the device architectures that eliminatethe need for charge-selective layers. Together, these insights establisha framework for understanding and engineering the energetic landscapeof metal halide perovskite-based devices, linking fundamental semiconductorphysics with practical strategies for future perovskite technologies.

A simple, scientific method to prepare supported metalnanoparticleswas proposed almost 50 years ago, which utilizes the protonation–deprotonationchemistry of the nascent hydroxyl groups that populate typical supportsurfaces. In aqueous solution, these can be protonated and so positivelycharged in the pH range below the point of zero charge (PZC) of thesupport, and deprotonated and negatively charged above the supportPZC. An oppositely charged metal complex in the impregnating solutionwill experience a strong electrostatic attraction to the surface andwill be firmly anchored during drying. The metal nanoparticles producedafter thermochemical conversion of the dried precursor are typicallysmall (<2 nm) and tightly sized. In this review, the past 50 yearsof literature reporting this method have been summarized and critiqued.Electrostatic adsorption has been applied for 1) the preparation ofsingle metal nanoparticles on a wide variety of supports, includingsingle-atom catalysts, 2) well alloyed bimetallic and dilute limitnanoparticles, and 3) selective metal deposition over composite supports.The method has been extended to 4) incipient wetness impregnationand, most recently, to 5) formed catalyst supports. The limitations,troubleshooting, and future directions of this method are discussed.

The engineering of nanoparticles and their assemblieshas traditionallyfocused on creating highly periodic systems with properties that matchpredictions of well-defined scientific models. This review surveysrecent efforts to expand the engineering of nanoparticles and theirassemblies into the realm of high complexity, which can entail disorderor combinations of order and disorder. This review is structured,for clarity of reading, to cover three aspects of complexity: in individualnanoparticles, in assembly structures, and in assembly manufacturingstrategies, with the awareness that these three aspects are intertwined,leading to a huge parameter space to manufacture new functional materials.This review charts a roadmap for harnessing nonperiodic, multiscale,and even polydisperse yet economically desirable nanoparticle architecturesto achieve transformative properties, especially the balance of propertiesimportant in different technological applications such as strength,transparency, and recyclability, at large scale, low cost, and highmodularity, to address critical challenges across materials scienceand technology.