Supramolecular aggregates,formed through the highly directional and reversible noncovalent assembly of building blocks,represent a cornerstone of modern materials science,enabling the creation of complex architectures...Supramolecular aggregates,formed through the highly directional and reversible noncovalent assembly of building blocks,represent a cornerstone of modern materials science,enabling the creation of complex architectures with emergent properties.Among the diverse molecular platforms available,resorcin[4]arene-derived cavitands have emerged as particularly powerful building units due to their intrinsic concave cavity,tunable geometry,and versatile functionalization capacity.This review highlights recent progress in the construction of functional supramolecular aggregates based on resorcin[4]arene cavitands,with a focus on their assembly strategies and wide-ranging applications.The review systematically covers several key types of aggregate systems:porous coordination aggregates(e.g.,metal-organic frameworks[MOFs])with stimuli-responsive properties,dynamic polymeric aggregates exhibiting self-healing behavior,sensing aggregates enabling differential detection,and therapeutic aggregates for combination therapy.These systems are unified by their exploitation of cavitands'unique host-vip chemistry and their ability to form well-defined superstructures through various noncovalent interactions.We emphasize how the precise manipulation of cavitand structure directs the assembly process and dictates the functional output of the resulting aggregates.Finally,we outline current challenges and future opportunities in this field,highlighting the potential of cavitand-based aggregates to enable next-generation technologies in sensing,catalysis,biomedicine,and energy materials.This review is expected to provide valuable insights and inspiration for researchers working in supramolecular chemistry and aggregate science.The construction of supramolecular aggregates triggered by macrocycles has become a thriving area of supramolecular chemistry.In this context,resorcinarene cavitands,a class of macrocyclic receptors with intrinsic cavities,have been drawn into the limelight because of their advantages,such as the concave-shaped structure,adjustable cavity size,favorable host-vip behavior,and ease of functionalization.They can induce organic and inorganic molecules to self-assemble into supramolecular aggregates through various bonding modes,including hydrophobic interactions,metal-ligand coordination,van der Waals forces,hydrogen bonding,electrostatic interactions,π-πstacking,and amphiphilic interactions.This minireview focuses on some representative resorcinarene cavitand-based assembly aggregates,including microporous MOFs,supramolecular polymers,sensor arrays,and multifunctional nanodrugs.Each section highlights recent advancements,structural characteristics,and functional applications of these aggregate systems.This review will provide useful information for researchers working on not only cavitand chemistry but also the chemistry of other macrocyclic hosts,and it will inspire new discoveries in the field of supramolecular assemblies and systems containing macrocyclic hosts.展开更多
N-oxides,characterized by a highly polar N^(+)-O−bond,have recently demonstrated rapidly growing applications in biomedicineand material science due to their high solubility and redox activity.However,the chemical and...N-oxides,characterized by a highly polar N^(+)-O−bond,have recently demonstrated rapidly growing applications in biomedicineand material science due to their high solubility and redox activity.However,the chemical and physical properties of the N-oxide have not been fully studied,limiting its advanced applications.Herein,we report the unprecedented observation thatN-oxide could undergo structure-dependent aggregation.This observation is initiated by the appearance of dimers and trimersof a model compound,(4-piperidinophenyl)methanol N-oxide,in mass spectrometry.More convincingly,when it is conjugatedwith tetraphenylethylene(TPE)derivatives via the benzyloxy group,4-piperidinobenzyl N-oxide promotes the aggregation andfluorescence emission of the resulting conjugate,though it is highly polar.This observation of aggregation is further confirmedby the morphology study via scanning electron microscopy.Interestingly,no aggregation is observed when N-oxide is conjugateddirectly to TPE,indicating that N-oxide-induced aggregation is structure-dependent.Based on these fundamental observations andstudies,we develop a novel heme-targeting probe that can specifically and sensitively detect the level of total heme in the plasmafrom hemolytic mice to distinguish hemolysis.Altogether,these findings will advance our understanding of structure-dependentaggregation of the N-oxide and help to bring new insights into its application in biomedicine and material science.展开更多
Copper is one of the most abundant and less toxic transition metals in nature,which exhibits rich oxidation states and versatile catalytic activity using O2 as an oxidant.To date,enormous efforts in crystallographic a...Copper is one of the most abundant and less toxic transition metals in nature,which exhibits rich oxidation states and versatile catalytic activity using O2 as an oxidant.To date,enormous efforts in crystallographic and spectroscopic analyses have explicitly disclosed the pivotal role of polynuclear copper aggregates in the biological and organocatalytic redox processes.Notably,most biological Cu-O active sites often have unsymmetrical coordination environments for each copper ion,which finally account for the differentiated redox properties and biological functions.Inspired by the structural biology advances,numerous synthetic model complexes as enzyme mimics and organocatalytic active species have been established to identify enzymatic reaction intermediates and clarify the catalytic mechanisms.However,those synthetic models often show identical or similar coordination environments for individual copper ions because of the extensive application of synthetically accessible symmetrical ligands.In this Perspective,we endeavor to summarize the composition and structural details of Cu-O active species in several important copper-containing enzymes and pay special attention to the coordination environments of individual copper ions therein.Mechanistic studies on the biased functions of individual copper centers and the cooperative effect among them have been comprehensively surveyed.Recent progress of the synthetic Cu-O model complexes with unsymmetrical coordination environments,including the distinctive bi-cluster[alkynyl-copper-oxygen]aggregate,is discussed in detail to clarify the distinctive structure-property relationship of nonequivalent copper ions.We hope that this Perspective reiterates the unsymmetrical structural features of polynuclear copper aggregates in copper-catalytic systems and highlights the unique effect of coordination unequivalence in redox process,and provides new inspiration for the rational design of novel multimetallic catalysts.展开更多
Ischemic stroke inflicts severe neurological damage by disrupting the neurovascular unit.While promising,mesenchymal stem cell(MSC)therapies are hampered by poor posttransplantation survival and nonspecific secretomes...Ischemic stroke inflicts severe neurological damage by disrupting the neurovascular unit.While promising,mesenchymal stem cell(MSC)therapies are hampered by poor posttransplantation survival and nonspecific secretomes.Here,we introduce a bioengineering strategy that employs cadherin-functionalized interfaces to generate cohesive multicellular MSC aggregates(Cad-MAs).Priming MSCs with recombinant N-cadherin and VE-cadherin stimulated endogenous cadherin expression and facilitated the self-assembly of stable spheroids with reinforced intercellular adherens junctions.Cad-MAs exhibited increased resistance to inflammatory stress and anoikis,and secreted a reparative profile enriched in neurotrophic and angiogenic factors,as well as exosomes carrying therapeutic miRNAs such as miR-21-5p and miR-126-3p.The in vitro analyses indicate that cadherin-empowered assembly yields MSC aggregates in which structural stability is coupled with a pro-survival,pro-regenerative phenotype.Furthermore,in a mouse stroke model,systemically delivered Cad-MAs significantly outperformed conventional dissociated MSCs,promoting functional recovery,reducing infarct volume,and improving cerebral perfusion alongside evidence of enhanced angiogenesis and preservation of blood-brain barrier integrity markers.This approach,termed functional aggregation-induced emergence(F-AIE),provides a versatile framework for engineering integrated cellular therapeutics with tailored functional outputs for regenerative applications.展开更多
X.Li,J.Gao,L.Gao,et al.,“Self-Aggregation-Induced Polymerization for Constructing Multifunctional Dynamic Zwitterionic Hydrogels,”Aggregate 6(2025):e70227.There was a graphical error in the chemical structures prese...X.Li,J.Gao,L.Gao,et al.,“Self-Aggregation-Induced Polymerization for Constructing Multifunctional Dynamic Zwitterionic Hydrogels,”Aggregate 6(2025):e70227.There was a graphical error in the chemical structures presented in Figure 1b and the Graphical Abstract.Figure 1b and the Graphical Abstract have been corrected to reflect the accurate chemical structure.展开更多
Electrochemiluminescence(ECL)populates the luminescent excited states through electrochemical reactions.It is challenging to mediate the ECL behaviors of molecular nanoaggregates because both the photophysical and ele...Electrochemiluminescence(ECL)populates the luminescent excited states through electrochemical reactions.It is challenging to mediate the ECL behaviors of molecular nanoaggregates because both the photophysical and electrochemical properties usually deteriorate in aggregate states.In this work,we demonstrate an unprecedented supramolecular strategy that simultaneously modulates both the photophysical and electrochemical factors governing ECL.The ECL performance of rubrene(RUB)nanoaggregates can be significantly enhanced through the incorporation of hole-transporting molecules as both redox and photophysical mediators.A balanced state,inhibiting the singlet fission(SF)and retaining the triplet-triplet annihilation(TTA),was achieved for RUB,which not only reduced the quenching of luminescent singlet state excitons but also well utilized the electrochemically generated triplet state excitons.The redox-mediating properties of hole-transporting molecules toward co-reactant not only promote the formation of excitons but also reduce the luminescent potential.The RUB nanoaggregates showed significantly enhanced photoluminescence quantum efficiency(2.3-fold)and ECL intensity(50-fold)in aqueous conditions and were demonstrated as promising ECL imaging probes.This work opens up a new avenue for the preparation of ECL nano-emitters with high-brightness in aqueous conditions.展开更多
In November 2025,the Chinese Academy of Sciences(CAS)announced the newly elected members.In this profile column,we introduce six foreign CAS members of the Chemistry Discipline.Congratulations to all the elected acade...In November 2025,the Chinese Academy of Sciences(CAS)announced the newly elected members.In this profile column,we introduce six foreign CAS members of the Chemistry Discipline.Congratulations to all the elected academicians!展开更多
Metal-organic frameworks(MOFs)have long been highly regarded for their crystalline order,structural modularity,and precisely defined porosity.Metal nodes and organic linkers form ordered lattices with defined pores,en...Metal-organic frameworks(MOFs)have long been highly regarded for their crystalline order,structural modularity,and precisely defined porosity.Metal nodes and organic linkers form ordered lattices with defined pores,enabling predictable adsorp-tion and transport processes.Traditionally,research on MOFs has primarily focused on established fields such as molecular adsorption and heterogeneous catalysis[1,2]展开更多
How time flies-Aggregate has turned 5!What began as a blank page has now grown into a first chapter filled with achievement and promise.In just 5 years,Aggregate has built its academic rep-utation from the ground up a...How time flies-Aggregate has turned 5!What began as a blank page has now grown into a first chapter filled with achievement and promise.In just 5 years,Aggregate has built its academic rep-utation from the ground up and achieved remarkable milestones,including strong journal metrics,broad database indexing,a well-established readership,and steady growth in both publication vol-ume and scholarly impact(Figure 1).As outlined in my previous editorial charting the future direction of the journal[1],we will continue to prioritize the publication of high-quality research,expand our global influence,and strengthen connections with researchers worldwide,with the ultimate goal of establishing Aggregate as the flagship journal in aggregate science.To realize this vision,resting on our laurels is not an option;instead,we must pursue proactive reforms and provide improved publishing services to better serve the scientific community.展开更多
Peptide-and drug-protected gold nanoclusters(Au NCs)with atomic precision have attracted research attention in the last few years owing to their ultrasmall size(<2 nm),well-defined structures,tunable photoluminesce...Peptide-and drug-protected gold nanoclusters(Au NCs)with atomic precision have attracted research attention in the last few years owing to their ultrasmall size(<2 nm),well-defined structures,tunable photoluminescence from the visible to near-infrared range,water solubility,and good biocompatibility.These features,combined with low toxicity and efficient renal clearance,make such Au NCs promising candidates for biomedical use,including diagnosis,therapy,and theranostic.The incorporation of peptides or drugs into Au NCs enhances the stability,targeting specificity,cellular uptake,and prolonged circulation,enabling precise modulation of biological responses.Despite notable advances in achieving atomic precision employing complex ligands such as peptides or drugs,the synthetic methods of this new class of NCs remain a challenge.Careful control of molar ratio(Au:peptide/drug),reducing agent,temperature,and reaction time is required,because these factors directly influence the cluster size,optical properties,and in vivo performance.In this review,we highlight different synthetic approaches of atomically precise peptide-and drug-protected Au NCs,emphasizing the role of rational ligand design and reaction conditions,as well as the challenges associated with structural determination.We further discuss the optical and photoluminescence properties of peptide-protected Au NCs-the mostly explored features for biomedical applications.Finally,we conclude by outlining the current challenges,opportunities for scale-up synthesis,and future design perspectives for these emerging nanomaterials.展开更多
In November 2025,the Chinese Academy of Sciences(CAS)announced the newly elected members.In this Profile column,we introduce 10 Chinese members in the Chemistry Division of the CAS.Congratulations to all the elected a...In November 2025,the Chinese Academy of Sciences(CAS)announced the newly elected members.In this Profile column,we introduce 10 Chinese members in the Chemistry Division of the CAS.Congratulations to all the elected academicians!展开更多
Collagen fibrillogenesis underlies the structural and mechanical properties of the extracellular matrix in connective and other tissues,yet its molecular mechanism remains poorly understood.Here,we show that a europi...Collagen fibrillogenesis underlies the structural and mechanical properties of the extracellular matrix in connective and other tissues,yet its molecular mechanism remains poorly understood.Here,we show that a europium(Ⅲ)dipicolinate complex(EuDPA)acts as a luminescent reporter of collagen aggregation.We combine Raman microscopy,circularly polarized luminescence(CPL),and molecular dynamics(MD)simulations to study this process.While Raman imaging directly visualizes the EuDPA-enhanced fibrillar architecture,CPL reveals enantioselective EuDPA-collagen interactions that accompany the fibrillogenesis.MD simulations indicate the presence of stabilizing interactions between hydroxyproline residues and the dipicolinate ligand.The results pave the way to monitoring of protein aggregation in general,and are relevant to fibrotic pathologies and biomimetic materials design.展开更多
There is an urgent need to develop innovative therapeutic strategies for hepatocellular carcinoma(HCC)treatment with severe hypoxia.Covalent organic frameworks(COFs)hold promise for photodynamic therapy(PDT),yet their...There is an urgent need to develop innovative therapeutic strategies for hepatocellular carcinoma(HCC)treatment with severe hypoxia.Covalent organic frameworks(COFs)hold promise for photodynamic therapy(PDT),yet their antitumor efficacy is limited by the hypoxia intolerance of type II PDT.Herein,we report a COF-based nanoplatform grafted with type I photosensitizer(Enbs-Ar-NH2)and co-loaded with lenvatinib(Len)and curcumin(Cur),enabling concurrent type I PDT and chemotherapy(CT).The platform is conjugated with galactose(GalNAc)and RGD peptides,denoted as LC@GR-COF-E,which achieves dual-targeting toward hepatocytes via ASGPR recognition and tumor-associated endothelia binding.In vitro results demonstrate that the combination of Len and Cur effectively suppresses tumor cell proliferation.Importantly,LC@GR-COF-E can be activated to eradicate hypoxic tumor cells via oxygen-independent type I PDT under NIR irradiation.LC@GR-COF-E/NIR exhibits potent anti-metastatic effects,particularly against HCC cancer stem cell-like cells(C5WN1),by downregulating MMP-2 and MMP-9 and modulating epithelial-mesenchymal transition(EMT)-related protein expression(N-cadherin).In a subcutaneous C5WN1 hypoxic tumor-bearing mouse model,the platform achieves a tumor inhibition rate of 95.5%±1.7%,offering a powerful strategy to overcome HCC hypoxia barriers.Our work pioneers a COF-based type I PDT platform for precise therapy against hypoxic HCC.展开更多
Circularly polarized luminescence(CPL)materials,which exhibit their unique chiroptical properties,display great potential for applications in optoelectronics and bioimaging.However,it remains a significant challenge t...Circularly polarized luminescence(CPL)materials,which exhibit their unique chiroptical properties,display great potential for applications in optoelectronics and bioimaging.However,it remains a significant challenge to synthesize CPL materials with high dissymmetry factors(g_(lum))and photoluminescence quantum yields(PLQY)simultaneously.Herein,we report a deep-eutectic-solvent(DES)-assisted self-assembly protocol integrated with an active-learning(AL)framework that enables the targeted fabrication of G-quadruplex(G4)supramolecular gels with high g_(lum)and PLQY.AL pinpointed the optimal synthesis parameters in just four iterations,dramatically accelerating material development.The top-performing gel achieved a g_(lum)of 0.29,setting a new benchmark for nucleoside/nucleotide-based CPL materials.The maximum PLQY reached 10.64%,which represents a substantial level of performance.Furthermore,by integrating SHapley Additive exPlanations(SHAP),we elucidated the relationship between reaction parameters and target properties.Building on this result,we also demonstrated multicolor fluorescence resonance energy transfer(FRET)by incorporating dyes,successfully developing a series of multicolor CPL-active materials.This work not only provides new insights into the design of bio-based chiral CPL materials but also highlights the promising role of artificial intelligence in advancing material development.展开更多
Like-charge pairing is a physical manifestation of the unique solvation properties of certain ion pairs in water.Water's high dielectric constant and related charge screening capability significantly influence the...Like-charge pairing is a physical manifestation of the unique solvation properties of certain ion pairs in water.Water's high dielectric constant and related charge screening capability significantly influence the interaction between like-charged ions,with the possibility to transform it-in exceptional cases when noncovalent interactions are involved-from repulsion to attraction.Guanidinium cations(Gdm^(+))represent a quintessential example of such like-charge pairing due to their specific geometry and electronic structure.In this work,we present experimental validation and quantification of Gdm^(+)-Gdm contact ion pairing in water utilizing nuclear magnetic resonance(NMR)spectroscopy complemented by molecular dynamics(MD)simulations and density functional theory(DFT)calculations.The observed Gdm^(+)-Gdm^(+)interaction is attractive albeit weak-about 0.5 kJ·mol^(-1)-which aligns with theoretical estimation from MD simulations.We contrast the behavior of Gdm^(+) with that of NH_(4)^(+) cations,which exhibit no contact ion pairing in water.DFT calculations predict that the NMR chemical shift of Gdm^(+) dimers is different than that of monomers,in agreement with NMR titration curves that display a nonlinear Langmuir-like behavior.Additionally,we conducted cryo-electron microscopy-to our knowledge,for the first time-on concentrated oligoarginines R9,which,unlike nona-lysines K9,exhibit aggregation in water.These results point to like charge pairing of the guanidinium side chain groups,as corroborated also by MD simulations and free energy calculations.展开更多
Rotational dynamics in molecular crystals influence not only internal structures but also bulk properties such as photophysical behavior.In this work,we present novel crystalline chiral binuclear N-heterocyclic carben...Rotational dynamics in molecular crystals influence not only internal structures but also bulk properties such as photophysical behavior.In this work,we present novel crystalline chiral binuclear N-heterocyclic carbene(NHC)Au(I)complexes,1-R and 1-S,which display a distinct axially chiral conformation with C_(2)-symmetry,derived from non-equivalent orientations of phenyl groups on the NHC ligands.These phenyl moieties undergo two distinct types of rapid rotational motion,as revealed by variable-temperature solid-state^(2)H NMR studies.Such dynamic motions promote structural symmetrization within the crystal,shifting from C_(2)-symmetry toward a more D_(2)-like symmetry.This symmetry evolution significantly affects the chiroptical properties of the crystals.Both experimental measurements and TD-DFT calculations confirm that such motion modulates chiroptical properties,leading to temperature-dependent changes in emission intensity and the luminescence dissymmetry factor(g_(lum)).These results highlight dynamic molecular rotation as a powerful tool for tuning symmetry and chiroptical responses in crystalline materials,offering new design principles for solid-state chiral systems.展开更多
Metal nanoclusters(MNCs),comprising several to hundreds of metal atoms,have attracted significant research interest owing to their distinctive physicochemical properties.Reticular frameworks(RFs)with ordered porous st...Metal nanoclusters(MNCs),comprising several to hundreds of metal atoms,have attracted significant research interest owing to their distinctive physicochemical properties.Reticular frameworks(RFs)with ordered porous structures,including metalorganic frameworks(MOFs),covalent organic frameworks(COFs),hydrogen-bonded organic frameworks(HOFs),and supramolecular organic frameworks(SOFs),possess a variety of unique properties due to their high crystallinity,high porosity,large surface area,and adjustable structure.The integration of MNCs with RFs endows the resulting composites with desirable features(e.g.,enhanced and tunable optical properties,improved catalytic and photophysical activities,selective molecular recognition),which facilitates a broad spectrum of biomedical applications and advancing the development of integrated theranostic nanoplatforms.This review summarizes recent advances in the synthesis and biomedical applications of various MNCs/RFs composites.We systematically categorize and evaluate key strategies for incorporating MNCs into four types of RFs(MOFs,COFs,HOFs,and SOFs)while discussing the advantages and limitations of each approach.The biomedical applications of these composites are comprehensively reviewed,encompassing biosensing,bioimaging,antitumor therapy,and antibacterial treatments.Finally,the review addresses current challenges and outlines future research directions,with the aim of guiding the rational design of novel MNCs/RFs composites,enabling precise control over their structures and functions toward advanced biomedical applications.展开更多
Organic room-temperature phosphorescent(RTP)materials,characterized by their prolonged emission durations,cost-effectiveness and environmental sustainability,present substantial potential for utilization in optoelectr...Organic room-temperature phosphorescent(RTP)materials,characterized by their prolonged emission durations,cost-effectiveness and environmental sustainability,present substantial potential for utilization in optoelectronic devices and information encryption,thereby garnering considerable research attention.Nevertheless,the intrinsically weak spin-orbit coupling(SOC)in organic molecules hampers efficient intersystem crossing(ISC)between singlet and triplet states,thereby shortening the lifetime(τ)of RTP.Achieving room-temperature phosphorescence in organic molecules hinges on overcoming two fundamental challenges:promoting efficient ISC between singlet and triplet states and suppressing non-radiative decay through rigid microenvironmental confinement.This review summarizes recent advances in pure organic RTP from the perspective of multicomponent systems,highlighting emerging strategies for modulating exciton dynamics and rigidifying the local environment of emissive molecules.Approaches such as supramolecular self-assembly,vip-host doping,eutectic formation and exciplex engineering are discussed as effective means to suppress non-radiative deactivation and realize ultralong RTP(emission lifetime of over 100 ms).The underlying design principles and representative applications of these systems are delineated,and future directions for constructing high-performance pure organic RTP materials are outlined.Our goal is to foster interdisciplinary collaboration and innovation to fully exploit the potential of RTP materials in organic optoelectronics and biomedicine.This review aims to delineate a coherent research trajectory and offer forward-looking insights into emerging opportunities in this rapidly evolving field.By promoting cross-disciplinary dialogue to catalyze new ideas and applications that harness the unique photophysical characteristics of RTP materials for transformative technological advancements.展开更多
As environmental concerns and the transition to a carbon-neutral society gain importance,proton exchange membrane fuel cells(PEMFCs)using hydrogen as a fuel have attracted significant attention as eco-friendly energy ...As environmental concerns and the transition to a carbon-neutral society gain importance,proton exchange membrane fuel cells(PEMFCs)using hydrogen as a fuel have attracted significant attention as eco-friendly energy technology.Although Pt is the primary catalyst for PEMFC anodes,its high cost and limited availability pose major barriers to commercialization.To address these challenges,non-Pt catalysts,alloy catalysts,and core-shell structured catalysts have been extensively studied;nevertheless,performance degradation and structural instability remain significant issues.In this study,we design Pt-lean Pt1 Co4 alloy nanoparticles encapsulated with an ultrathin carbon shell derived from the carbon sources of the metal precursor ligands.Notably,after synthesizing the carbon-incorporated alloy nanoparticles,heat treatment under a carbon monoxide(CO)atmosphere induces selective surface segregation of Pt atoms due to their strong CO binding affinity,occurring before the carbonization temperature is reached for carbon shell formation,resulting in a Pt-enriched surface structure.The carbon shell imparts a nano-confinement effect that effectively suppresses particle growth and aggregation during heat treatment,thereby significantly enhancing electrochemical stability.Remarkably,despite a 55%reduction in Pt content,the combination of surface segregation and near-surface alloying allows the Pt-lean alloy catalyst to maintain hydrogen oxidation reaction activity comparable to a bare Pt catalyst while providing superior durability.Owing to this dual function of heat treatment,the design of the Pt-lean alloy catalyst structure offers a promising strategy for developing highly efficient and cost-effective anode catalysts for PEMFCs.展开更多
The aggregation of superatoms,serving as stable building blocks,can be understood in terms of classical chemical bonding concepts,thereby enabling a rational design of molecular materials despite their different sizes...The aggregation of superatoms,serving as stable building blocks,can be understood in terms of classical chemical bonding concepts,thereby enabling a rational design of molecular materials despite their different sizes,shapes,and compositions.From this perspective,the interaction between superatomic electronic shells from different building blocks is analogous to that between atomic orbitals,yielding cluster based supermolecular counterparts of prototypical molecules.The resulting intercluster bonding modes,including single,multiple,and hybrid bonds,are found in linear,cyclic,and three-dimensional aggregates.Moreover,the notion of concentric bonding in multilayered clusters is explored,highlighting electronic interactions across nested structural layers.These insights advance the understanding of electronic structure,bonding variability,and aggregation in ligand-protected coinage metal clusters,providing a robust foundation for the rational design of superatomic materials with tailored electronic,catalytic,and optical functionalities.This framework bridges classical chemical bonding and emerging nanoscale architectures,promoting the development of cluster-based functional materials with novel properties.展开更多
基金supported by the National Natural Science Foundation of China(22322107,22301174,and 22571190)the Shanghai Scientific and Technological Committee(22010500300).
文摘Supramolecular aggregates,formed through the highly directional and reversible noncovalent assembly of building blocks,represent a cornerstone of modern materials science,enabling the creation of complex architectures with emergent properties.Among the diverse molecular platforms available,resorcin[4]arene-derived cavitands have emerged as particularly powerful building units due to their intrinsic concave cavity,tunable geometry,and versatile functionalization capacity.This review highlights recent progress in the construction of functional supramolecular aggregates based on resorcin[4]arene cavitands,with a focus on their assembly strategies and wide-ranging applications.The review systematically covers several key types of aggregate systems:porous coordination aggregates(e.g.,metal-organic frameworks[MOFs])with stimuli-responsive properties,dynamic polymeric aggregates exhibiting self-healing behavior,sensing aggregates enabling differential detection,and therapeutic aggregates for combination therapy.These systems are unified by their exploitation of cavitands'unique host-vip chemistry and their ability to form well-defined superstructures through various noncovalent interactions.We emphasize how the precise manipulation of cavitand structure directs the assembly process and dictates the functional output of the resulting aggregates.Finally,we outline current challenges and future opportunities in this field,highlighting the potential of cavitand-based aggregates to enable next-generation technologies in sensing,catalysis,biomedicine,and energy materials.This review is expected to provide valuable insights and inspiration for researchers working in supramolecular chemistry and aggregate science.The construction of supramolecular aggregates triggered by macrocycles has become a thriving area of supramolecular chemistry.In this context,resorcinarene cavitands,a class of macrocyclic receptors with intrinsic cavities,have been drawn into the limelight because of their advantages,such as the concave-shaped structure,adjustable cavity size,favorable host-vip behavior,and ease of functionalization.They can induce organic and inorganic molecules to self-assemble into supramolecular aggregates through various bonding modes,including hydrophobic interactions,metal-ligand coordination,van der Waals forces,hydrogen bonding,electrostatic interactions,π-πstacking,and amphiphilic interactions.This minireview focuses on some representative resorcinarene cavitand-based assembly aggregates,including microporous MOFs,supramolecular polymers,sensor arrays,and multifunctional nanodrugs.Each section highlights recent advancements,structural characteristics,and functional applications of these aggregate systems.This review will provide useful information for researchers working on not only cavitand chemistry but also the chemistry of other macrocyclic hosts,and it will inspire new discoveries in the field of supramolecular assemblies and systems containing macrocyclic hosts.
基金supported by the National Key Research and Development Program of China(no.2025YFC3408704)the Jining Municipal Key R&D Program(no.2023YXNS171).
文摘N-oxides,characterized by a highly polar N^(+)-O−bond,have recently demonstrated rapidly growing applications in biomedicineand material science due to their high solubility and redox activity.However,the chemical and physical properties of the N-oxide have not been fully studied,limiting its advanced applications.Herein,we report the unprecedented observation thatN-oxide could undergo structure-dependent aggregation.This observation is initiated by the appearance of dimers and trimersof a model compound,(4-piperidinophenyl)methanol N-oxide,in mass spectrometry.More convincingly,when it is conjugatedwith tetraphenylethylene(TPE)derivatives via the benzyloxy group,4-piperidinobenzyl N-oxide promotes the aggregation andfluorescence emission of the resulting conjugate,though it is highly polar.This observation of aggregation is further confirmedby the morphology study via scanning electron microscopy.Interestingly,no aggregation is observed when N-oxide is conjugateddirectly to TPE,indicating that N-oxide-induced aggregation is structure-dependent.Based on these fundamental observations andstudies,we develop a novel heme-targeting probe that can specifically and sensitively detect the level of total heme in the plasmafrom hemolytic mice to distinguish hemolysis.Altogether,these findings will advance our understanding of structure-dependentaggregation of the N-oxide and help to bring new insights into its application in biomedicine and material science.
基金the National Natural Science Foundation of China(22401242 for S.Z.,and 22025105 and 22350002 for L.Z.)Natural Science Foundation of Jiangsu Province(SBK2024043314,24KJB150033 and JSSCBS0365 for S.Z.),Xuzhou Medical University“Gaofeng project”for S.Z.
文摘Copper is one of the most abundant and less toxic transition metals in nature,which exhibits rich oxidation states and versatile catalytic activity using O2 as an oxidant.To date,enormous efforts in crystallographic and spectroscopic analyses have explicitly disclosed the pivotal role of polynuclear copper aggregates in the biological and organocatalytic redox processes.Notably,most biological Cu-O active sites often have unsymmetrical coordination environments for each copper ion,which finally account for the differentiated redox properties and biological functions.Inspired by the structural biology advances,numerous synthetic model complexes as enzyme mimics and organocatalytic active species have been established to identify enzymatic reaction intermediates and clarify the catalytic mechanisms.However,those synthetic models often show identical or similar coordination environments for individual copper ions because of the extensive application of synthetically accessible symmetrical ligands.In this Perspective,we endeavor to summarize the composition and structural details of Cu-O active species in several important copper-containing enzymes and pay special attention to the coordination environments of individual copper ions therein.Mechanistic studies on the biased functions of individual copper centers and the cooperative effect among them have been comprehensively surveyed.Recent progress of the synthetic Cu-O model complexes with unsymmetrical coordination environments,including the distinctive bi-cluster[alkynyl-copper-oxygen]aggregate,is discussed in detail to clarify the distinctive structure-property relationship of nonequivalent copper ions.We hope that this Perspective reiterates the unsymmetrical structural features of polynuclear copper aggregates in copper-catalytic systems and highlights the unique effect of coordination unequivalence in redox process,and provides new inspiration for the rational design of novel multimetallic catalysts.
基金financial support from the Ministry of Science and Technology of the People’s Republic of China(No.2020YFA0710802)National Natural Science Foundation of China(Nos.32371419,32071364,82171320)the Tianjin Municipal Science and Technology Bureau(No.24JCZDJC00530).
文摘Ischemic stroke inflicts severe neurological damage by disrupting the neurovascular unit.While promising,mesenchymal stem cell(MSC)therapies are hampered by poor posttransplantation survival and nonspecific secretomes.Here,we introduce a bioengineering strategy that employs cadherin-functionalized interfaces to generate cohesive multicellular MSC aggregates(Cad-MAs).Priming MSCs with recombinant N-cadherin and VE-cadherin stimulated endogenous cadherin expression and facilitated the self-assembly of stable spheroids with reinforced intercellular adherens junctions.Cad-MAs exhibited increased resistance to inflammatory stress and anoikis,and secreted a reparative profile enriched in neurotrophic and angiogenic factors,as well as exosomes carrying therapeutic miRNAs such as miR-21-5p and miR-126-3p.The in vitro analyses indicate that cadherin-empowered assembly yields MSC aggregates in which structural stability is coupled with a pro-survival,pro-regenerative phenotype.Furthermore,in a mouse stroke model,systemically delivered Cad-MAs significantly outperformed conventional dissociated MSCs,promoting functional recovery,reducing infarct volume,and improving cerebral perfusion alongside evidence of enhanced angiogenesis and preservation of blood-brain barrier integrity markers.This approach,termed functional aggregation-induced emergence(F-AIE),provides a versatile framework for engineering integrated cellular therapeutics with tailored functional outputs for regenerative applications.
文摘X.Li,J.Gao,L.Gao,et al.,“Self-Aggregation-Induced Polymerization for Constructing Multifunctional Dynamic Zwitterionic Hydrogels,”Aggregate 6(2025):e70227.There was a graphical error in the chemical structures presented in Figure 1b and the Graphical Abstract.Figure 1b and the Graphical Abstract have been corrected to reflect the accurate chemical structure.
基金supported by the National Natural Science Foundation of China(22374059 and 22274062).
文摘Electrochemiluminescence(ECL)populates the luminescent excited states through electrochemical reactions.It is challenging to mediate the ECL behaviors of molecular nanoaggregates because both the photophysical and electrochemical properties usually deteriorate in aggregate states.In this work,we demonstrate an unprecedented supramolecular strategy that simultaneously modulates both the photophysical and electrochemical factors governing ECL.The ECL performance of rubrene(RUB)nanoaggregates can be significantly enhanced through the incorporation of hole-transporting molecules as both redox and photophysical mediators.A balanced state,inhibiting the singlet fission(SF)and retaining the triplet-triplet annihilation(TTA),was achieved for RUB,which not only reduced the quenching of luminescent singlet state excitons but also well utilized the electrochemically generated triplet state excitons.The redox-mediating properties of hole-transporting molecules toward co-reactant not only promote the formation of excitons but also reduce the luminescent potential.The RUB nanoaggregates showed significantly enhanced photoluminescence quantum efficiency(2.3-fold)and ECL intensity(50-fold)in aqueous conditions and were demonstrated as promising ECL imaging probes.This work opens up a new avenue for the preparation of ECL nano-emitters with high-brightness in aqueous conditions.
文摘In November 2025,the Chinese Academy of Sciences(CAS)announced the newly elected members.In this profile column,we introduce six foreign CAS members of the Chemistry Discipline.Congratulations to all the elected academicians!
文摘Metal-organic frameworks(MOFs)have long been highly regarded for their crystalline order,structural modularity,and precisely defined porosity.Metal nodes and organic linkers form ordered lattices with defined pores,enabling predictable adsorp-tion and transport processes.Traditionally,research on MOFs has primarily focused on established fields such as molecular adsorption and heterogeneous catalysis[1,2]
文摘How time flies-Aggregate has turned 5!What began as a blank page has now grown into a first chapter filled with achievement and promise.In just 5 years,Aggregate has built its academic rep-utation from the ground up and achieved remarkable milestones,including strong journal metrics,broad database indexing,a well-established readership,and steady growth in both publication vol-ume and scholarly impact(Figure 1).As outlined in my previous editorial charting the future direction of the journal[1],we will continue to prioritize the publication of high-quality research,expand our global influence,and strengthen connections with researchers worldwide,with the ultimate goal of establishing Aggregate as the flagship journal in aggregate science.To realize this vision,resting on our laurels is not an option;instead,we must pursue proactive reforms and provide improved publishing services to better serve the scientific community.
基金RGM is grateful to CNPq for the PDE fellowship(200437/2025-9),MTM acknowledges CNPq research scholarship(314470/2023-9)FAPESP fundings(2022/01825-22025/063196).
文摘Peptide-and drug-protected gold nanoclusters(Au NCs)with atomic precision have attracted research attention in the last few years owing to their ultrasmall size(<2 nm),well-defined structures,tunable photoluminescence from the visible to near-infrared range,water solubility,and good biocompatibility.These features,combined with low toxicity and efficient renal clearance,make such Au NCs promising candidates for biomedical use,including diagnosis,therapy,and theranostic.The incorporation of peptides or drugs into Au NCs enhances the stability,targeting specificity,cellular uptake,and prolonged circulation,enabling precise modulation of biological responses.Despite notable advances in achieving atomic precision employing complex ligands such as peptides or drugs,the synthetic methods of this new class of NCs remain a challenge.Careful control of molar ratio(Au:peptide/drug),reducing agent,temperature,and reaction time is required,because these factors directly influence the cluster size,optical properties,and in vivo performance.In this review,we highlight different synthetic approaches of atomically precise peptide-and drug-protected Au NCs,emphasizing the role of rational ligand design and reaction conditions,as well as the challenges associated with structural determination.We further discuss the optical and photoluminescence properties of peptide-protected Au NCs-the mostly explored features for biomedical applications.Finally,we conclude by outlining the current challenges,opportunities for scale-up synthesis,and future design perspectives for these emerging nanomaterials.
文摘In November 2025,the Chinese Academy of Sciences(CAS)announced the newly elected members.In this Profile column,we introduce 10 Chinese members in the Chemistry Division of the CAS.Congratulations to all the elected academicians!
基金supported by the Czech Science Foundation(23-05378S to TW and 2515726S to PB)the Ministry of Education,Youth and Sports of the Czech Republic through the e-INFRA CZ(ID:90140).
文摘Collagen fibrillogenesis underlies the structural and mechanical properties of the extracellular matrix in connective and other tissues,yet its molecular mechanism remains poorly understood.Here,we show that a europium(Ⅲ)dipicolinate complex(EuDPA)acts as a luminescent reporter of collagen aggregation.We combine Raman microscopy,circularly polarized luminescence(CPL),and molecular dynamics(MD)simulations to study this process.While Raman imaging directly visualizes the EuDPA-enhanced fibrillar architecture,CPL reveals enantioselective EuDPA-collagen interactions that accompany the fibrillogenesis.MD simulations indicate the presence of stabilizing interactions between hydroxyproline residues and the dipicolinate ligand.The results pave the way to monitoring of protein aggregation in general,and are relevant to fibrotic pathologies and biomimetic materials design.
基金supported by the National Key R&D Program of China(2024YFA0918300,China)the National Natural Science Foundation of China(22478153,22177041,22408066,China)the Natural Science Foundation of Jiangsu Province(BK20202002,China).
文摘There is an urgent need to develop innovative therapeutic strategies for hepatocellular carcinoma(HCC)treatment with severe hypoxia.Covalent organic frameworks(COFs)hold promise for photodynamic therapy(PDT),yet their antitumor efficacy is limited by the hypoxia intolerance of type II PDT.Herein,we report a COF-based nanoplatform grafted with type I photosensitizer(Enbs-Ar-NH2)and co-loaded with lenvatinib(Len)and curcumin(Cur),enabling concurrent type I PDT and chemotherapy(CT).The platform is conjugated with galactose(GalNAc)and RGD peptides,denoted as LC@GR-COF-E,which achieves dual-targeting toward hepatocytes via ASGPR recognition and tumor-associated endothelia binding.In vitro results demonstrate that the combination of Len and Cur effectively suppresses tumor cell proliferation.Importantly,LC@GR-COF-E can be activated to eradicate hypoxic tumor cells via oxygen-independent type I PDT under NIR irradiation.LC@GR-COF-E/NIR exhibits potent anti-metastatic effects,particularly against HCC cancer stem cell-like cells(C5WN1),by downregulating MMP-2 and MMP-9 and modulating epithelial-mesenchymal transition(EMT)-related protein expression(N-cadherin).In a subcutaneous C5WN1 hypoxic tumor-bearing mouse model,the platform achieves a tumor inhibition rate of 95.5%±1.7%,offering a powerful strategy to overcome HCC hypoxia barriers.Our work pioneers a COF-based type I PDT platform for precise therapy against hypoxic HCC.
基金supported by the Program for Advanced Materials-National Science and Technology Major Project(Grant Numbers:2025ZD0620100,2025ZD0619502)Distinguished Professor of Shanghai Universities(Oriental Scholars),Tracking Plan(GZ2022009)+2 种基金the National Natural Science Foundation of China(22177067)the Shanghai Rising-Star Program(20QA1403400)and the Shanghai Sailing Program(24YF2712500).
文摘Circularly polarized luminescence(CPL)materials,which exhibit their unique chiroptical properties,display great potential for applications in optoelectronics and bioimaging.However,it remains a significant challenge to synthesize CPL materials with high dissymmetry factors(g_(lum))and photoluminescence quantum yields(PLQY)simultaneously.Herein,we report a deep-eutectic-solvent(DES)-assisted self-assembly protocol integrated with an active-learning(AL)framework that enables the targeted fabrication of G-quadruplex(G4)supramolecular gels with high g_(lum)and PLQY.AL pinpointed the optimal synthesis parameters in just four iterations,dramatically accelerating material development.The top-performing gel achieved a g_(lum)of 0.29,setting a new benchmark for nucleoside/nucleotide-based CPL materials.The maximum PLQY reached 10.64%,which represents a substantial level of performance.Furthermore,by integrating SHapley Additive exPlanations(SHAP),we elucidated the relationship between reaction parameters and target properties.Building on this result,we also demonstrated multicolor fluorescence resonance energy transfer(FRET)by incorporating dyes,successfully developing a series of multicolor CPL-active materials.This work not only provides new insights into the design of bio-based chiral CPL materials but also highlights the promising role of artificial intelligence in advancing material development.
基金support from the project“National Institute of Virology and Bacteriology(Program EXCELES,ID Project No.LX22NPO5103)Funded by the European Union-Next Generation EU".D.B.also acknowledges VSB-Technical University of Ostrava,IT4Innovations National Supercomputing Center,Czech Republic,for awarding this project access to the LUMI supercomputer,owned by the EuroHPC Joint Undertaking,hosted by CSC(Finland)and the LUMI consortium through the Ministry of Education,Youth and Sports of the Czech Republic through the e-INFRA CZ(Grant ID:90254)+4 种基金project OPEN-35-3.M.V.and J.H.acknowledge the Czech Science Foundation for support via grant number 25-16117S and the project"The Energy Conversion and Storage"funded as project No.CZ.02.01.01/00/22_008/0004617 by Programme Johannes Amos Comeniuscall Excellent Research.M.V.also acknowledges support by the Ministry of Education,Youth and Sports of the Czech Republic through the e-INFRA CZ(ID:90254)Project OPEN-30-53.P.J.acknowledges support from the European Research Council via an ERC Advanced Grant no.101095957The authors would like to acknowledge the contribution of COST Action CA21169,supported by COST(European Cooperation in Science and Technology).
文摘Like-charge pairing is a physical manifestation of the unique solvation properties of certain ion pairs in water.Water's high dielectric constant and related charge screening capability significantly influence the interaction between like-charged ions,with the possibility to transform it-in exceptional cases when noncovalent interactions are involved-from repulsion to attraction.Guanidinium cations(Gdm^(+))represent a quintessential example of such like-charge pairing due to their specific geometry and electronic structure.In this work,we present experimental validation and quantification of Gdm^(+)-Gdm contact ion pairing in water utilizing nuclear magnetic resonance(NMR)spectroscopy complemented by molecular dynamics(MD)simulations and density functional theory(DFT)calculations.The observed Gdm^(+)-Gdm^(+)interaction is attractive albeit weak-about 0.5 kJ·mol^(-1)-which aligns with theoretical estimation from MD simulations.We contrast the behavior of Gdm^(+) with that of NH_(4)^(+) cations,which exhibit no contact ion pairing in water.DFT calculations predict that the NMR chemical shift of Gdm^(+) dimers is different than that of monomers,in agreement with NMR titration curves that display a nonlinear Langmuir-like behavior.Additionally,we conducted cryo-electron microscopy-to our knowledge,for the first time-on concentrated oligoarginines R9,which,unlike nona-lysines K9,exhibit aggregation in water.These results point to like charge pairing of the guanidinium side chain groups,as corroborated also by MD simulations and free energy calculations.
基金supported by the Japan Society for the Pro-motion of Science(JSPS)via KAKENHI grants JP20H04666,JP21K14637,JP22K18333,JP22H00318 and JP25K23603by the JST via CREST grant JPMJCR19R1+1 种基金by FOREST grant JPMJFR232Cby the Institute for Chemical Reaction Design and Discovery(ICReDD)established by the World Premier International Research Initiative(WPI),MEXT,Japan.
文摘Rotational dynamics in molecular crystals influence not only internal structures but also bulk properties such as photophysical behavior.In this work,we present novel crystalline chiral binuclear N-heterocyclic carbene(NHC)Au(I)complexes,1-R and 1-S,which display a distinct axially chiral conformation with C_(2)-symmetry,derived from non-equivalent orientations of phenyl groups on the NHC ligands.These phenyl moieties undergo two distinct types of rapid rotational motion,as revealed by variable-temperature solid-state^(2)H NMR studies.Such dynamic motions promote structural symmetrization within the crystal,shifting from C_(2)-symmetry toward a more D_(2)-like symmetry.This symmetry evolution significantly affects the chiroptical properties of the crystals.Both experimental measurements and TD-DFT calculations confirm that such motion modulates chiroptical properties,leading to temperature-dependent changes in emission intensity and the luminescence dissymmetry factor(g_(lum)).These results highlight dynamic molecular rotation as a powerful tool for tuning symmetry and chiroptical responses in crystalline materials,offering new design principles for solid-state chiral systems.
基金supported by the National Natural Science Foundation of China(Nos.U213010103,22274131).
文摘Metal nanoclusters(MNCs),comprising several to hundreds of metal atoms,have attracted significant research interest owing to their distinctive physicochemical properties.Reticular frameworks(RFs)with ordered porous structures,including metalorganic frameworks(MOFs),covalent organic frameworks(COFs),hydrogen-bonded organic frameworks(HOFs),and supramolecular organic frameworks(SOFs),possess a variety of unique properties due to their high crystallinity,high porosity,large surface area,and adjustable structure.The integration of MNCs with RFs endows the resulting composites with desirable features(e.g.,enhanced and tunable optical properties,improved catalytic and photophysical activities,selective molecular recognition),which facilitates a broad spectrum of biomedical applications and advancing the development of integrated theranostic nanoplatforms.This review summarizes recent advances in the synthesis and biomedical applications of various MNCs/RFs composites.We systematically categorize and evaluate key strategies for incorporating MNCs into four types of RFs(MOFs,COFs,HOFs,and SOFs)while discussing the advantages and limitations of each approach.The biomedical applications of these composites are comprehensively reviewed,encompassing biosensing,bioimaging,antitumor therapy,and antibacterial treatments.Finally,the review addresses current challenges and outlines future research directions,with the aim of guiding the rational design of novel MNCs/RFs composites,enabling precise control over their structures and functions toward advanced biomedical applications.
基金supported by the National Natural Science Foundation of China(Nos.22261028,22465022)the Education Department of Jiangxi Province Foundation of China(Nos.GJJ2201905,GJJ2401811).
文摘Organic room-temperature phosphorescent(RTP)materials,characterized by their prolonged emission durations,cost-effectiveness and environmental sustainability,present substantial potential for utilization in optoelectronic devices and information encryption,thereby garnering considerable research attention.Nevertheless,the intrinsically weak spin-orbit coupling(SOC)in organic molecules hampers efficient intersystem crossing(ISC)between singlet and triplet states,thereby shortening the lifetime(τ)of RTP.Achieving room-temperature phosphorescence in organic molecules hinges on overcoming two fundamental challenges:promoting efficient ISC between singlet and triplet states and suppressing non-radiative decay through rigid microenvironmental confinement.This review summarizes recent advances in pure organic RTP from the perspective of multicomponent systems,highlighting emerging strategies for modulating exciton dynamics and rigidifying the local environment of emissive molecules.Approaches such as supramolecular self-assembly,vip-host doping,eutectic formation and exciplex engineering are discussed as effective means to suppress non-radiative deactivation and realize ultralong RTP(emission lifetime of over 100 ms).The underlying design principles and representative applications of these systems are delineated,and future directions for constructing high-performance pure organic RTP materials are outlined.Our goal is to foster interdisciplinary collaboration and innovation to fully exploit the potential of RTP materials in organic optoelectronics and biomedicine.This review aims to delineate a coherent research trajectory and offer forward-looking insights into emerging opportunities in this rapidly evolving field.By promoting cross-disciplinary dialogue to catalyze new ideas and applications that harness the unique photophysical characteristics of RTP materials for transformative technological advancements.
基金supported by the Technology Innovation Program(Nos.20020400,RS-2024-00423147)funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea)by a National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIP)(No.RS-2021-NR059501).
文摘As environmental concerns and the transition to a carbon-neutral society gain importance,proton exchange membrane fuel cells(PEMFCs)using hydrogen as a fuel have attracted significant attention as eco-friendly energy technology.Although Pt is the primary catalyst for PEMFC anodes,its high cost and limited availability pose major barriers to commercialization.To address these challenges,non-Pt catalysts,alloy catalysts,and core-shell structured catalysts have been extensively studied;nevertheless,performance degradation and structural instability remain significant issues.In this study,we design Pt-lean Pt1 Co4 alloy nanoparticles encapsulated with an ultrathin carbon shell derived from the carbon sources of the metal precursor ligands.Notably,after synthesizing the carbon-incorporated alloy nanoparticles,heat treatment under a carbon monoxide(CO)atmosphere induces selective surface segregation of Pt atoms due to their strong CO binding affinity,occurring before the carbonization temperature is reached for carbon shell formation,resulting in a Pt-enriched surface structure.The carbon shell imparts a nano-confinement effect that effectively suppresses particle growth and aggregation during heat treatment,thereby significantly enhancing electrochemical stability.Remarkably,despite a 55%reduction in Pt content,the combination of surface segregation and near-surface alloying allows the Pt-lean alloy catalyst to maintain hydrogen oxidation reaction activity comparable to a bare Pt catalyst while providing superior durability.Owing to this dual function of heat treatment,the design of the Pt-lean alloy catalyst structure offers a promising strategy for developing highly efficient and cost-effective anode catalysts for PEMFCs.
文摘The aggregation of superatoms,serving as stable building blocks,can be understood in terms of classical chemical bonding concepts,thereby enabling a rational design of molecular materials despite their different sizes,shapes,and compositions.From this perspective,the interaction between superatomic electronic shells from different building blocks is analogous to that between atomic orbitals,yielding cluster based supermolecular counterparts of prototypical molecules.The resulting intercluster bonding modes,including single,multiple,and hybrid bonds,are found in linear,cyclic,and three-dimensional aggregates.Moreover,the notion of concentric bonding in multilayered clusters is explored,highlighting electronic interactions across nested structural layers.These insights advance the understanding of electronic structure,bonding variability,and aggregation in ligand-protected coinage metal clusters,providing a robust foundation for the rational design of superatomic materials with tailored electronic,catalytic,and optical functionalities.This framework bridges classical chemical bonding and emerging nanoscale architectures,promoting the development of cluster-based functional materials with novel properties.
