White-Emitting Gold Nanocluster Assembly with Dynamic Color Tuning.

We report that constructed Au nanoclusters (NCs) can afford amazing white emission synergistically dictated by the Au(0)-dominated core-state fluorescence and Au(I)-governed surface-state phosphorescence, with record-high absolute quantum yields of 42.1% and 53.6% in the aqueous solution and powder state, respectively. Moreover, the dynamic color tuning is achieved in a wide warm-to-cold white-light range (with the correlated color temperature varied from 3426 to 24 973 K) by elaborately manipulating the ratio of Au(0) to Au(I) species and thus the electron transfer rate from staple motif to metal kernel. This study not only exemplifies the successful integration of multiple luminescent centers into metal NCs to accomplish efficient white-light emission but also inspires a feasible pathway toward customizing the optical properties of metal NCs by regulating electron transfer kinetics.

Enzyme-Inspired Ligand Engineering of Gold Nanoclusters for Electrocatalytic Microenvironment Manipulation.

Natural enzymes intricately regulate substrate accessibility through specific amino acid sequences and folded structures at their active sites. Achieving such precise control over the microenvironment has proven to be challenging in nanocatalysis, especially in the realm of ligand-stabilized metal nanoparticles. Here, we use atomically precise metal nanoclusters (NCs) as model catalysts to demonstrate an effective ligand engineering strategy to control the local concentration of CO2 on the surface of gold (Au) NCs during electrocatalytic CO2 reduction reactions (CO2RR). The precise incorporation of two 2-thiouracil-5-carboxylic acid (TCA) ligands within the pocket-like cavity of [Au25(pMBA)18]- NCs (pMBA = para-mercaptobenzoic acid) leads to a substantial acceleration in the reaction kinetics of CO2RR. This enhancement is attributed to a more favorable microenvironment in proximity to the active site for CO2, facilitated by supramolecular interactions between the nucleophilic Nδ- of the pyrimidine ring of the TCA ligand and the electrophilic Cδ+ of CO2. A comprehensive investigation employing absorption spectroscopy, mass spectrometry, isotopic labeling measurements, electrochemical analyses, and quantum chemical computation highlights the pivotal role of local CO2 enrichment in enhancing the activity and selectivity of TCA-modified Au25 NCs for CO2RR. Notably, a high Faradaic efficiency of 98.6% toward CO has been achieved. The surface engineering approach and catalytic fundamentals elucidated in this study provide a systematic foundation for the molecular-level design of metal-based electrocatalysts.

Unraveling a Concerted Proton-Coupled Electron Transfer Pathway in Atomically Precise Gold Nanoclusters.

Metal nanoclusters (MNCs) represent a promising class of materials for catalytic carbon dioxide and proton reduction as well as dihydrogen oxidation. In such reactions, multiple proton-coupled electron transfer (PCET) processes are typically involved, and the current understanding of PCET mechanisms in MNCs has primarily focused on the sequential transfer mode. However, a concerted transfer pathway, i.e., concerted electron-proton transfer (CEPT), despite its potential for a higher catalytic rate and lower reaction barrier, still lacks comprehensive elucidation. Herein, we introduce an experimental paradigm to test the feasibility of the CEPT process in MNCs, by employing Au18(SR)14 (SR denotes thiolate ligand), Au22(SR)18, and Au25(SR)18- as model clusters. Detailed investigations indicate that the photoinduced PCET reactions in the designed system proceed via an CEPT pathway. Furthermore, the rate constants of gold nanoclusters (AuNCs) have been found to be correlated with both the size of the cluster and the flexibility of the Au-S framework. This newly identified PCET behavior in AuNCs is prominently different from that observed in semiconductor quantum dots and plasmonic metal nanoparticles. Our findings are of crucial importance for unveiling the catalytic mechanisms of quantum-confined metal nanomaterials and for the future rational design of more efficient catalysts.

Emerging ultrasmall luminescent nanoprobes for in vivo bioimaging.

Photoluminescence (PL) imaging has become a fundamental tool in disease diagnosis, therapeutic evaluation, and surgical navigation applications. However, it remains a big challenge to engineer nanoprobes for high-efficiency in vivo imaging and clinical translation. Recent years have witnessed increasing research efforts devoted into engineering sub-10 nm ultrasmall nanoprobes for in vivo PL imaging, which offer the advantages of efficient body clearance, desired clinical translation potential, and high imaging signal-to-noise ratio. In this review, we present a comprehensive summary and contrastive discussion of emerging ultrasmall luminescent nanoprobes towards in vivo PL bioimaging of diseases. We first summarize size-dependent nano-bio interactions and imaging features, illustrating the unique attributes and advantages/disadvantages of ultrasmall nanoprobes differentiating them from molecular and large-sized probes. We also discuss general design methodologies and PL properties of emerging ultrasmall luminescent nanoprobes, which are established based on quantum dots, metal nanoclusters, lanthanide-doped nanoparticles, and silicon nanoparticles. Then, recent advances of ultrasmall luminescent nanoprobes are highlighted by surveying their latest in vivo PL imaging applications. Finally, we discuss existing challenges in this exciting field and propose some strategies to improve in vivo PL bioimaging and further propel their clinical applications.

Diversification of Metallic Molecules through Derivatization Chemistry of Au25 Nanoclusters.

Derivatization is the fine chemistry that can produce chemical compounds from similar precursors and has been widely used in the field of organic synthesis to achieve diversification of molecular properties and functionalities. Ligand-protected metal nanoclusters (NCs) are metallic molecules with a definite molecular formula, well-defined molecular structure, and molecular-like physical and chemical properties. Unlike organic compounds, which have almost infinite species, until now only hundreds of metal NC species have been discovered, and only a few of them have been structurally resolved. Therefore, the diversification of NC species and functions is highly desirable in nanoscience and nanochemistry. As an efficient approach for generating a library of compounds from a given precursor, derivatization chemistry is not only applicable in producing new organic compounds but also a promising strategy for generating new metal NC species with intriguing properties and functions. The key to the derivatization of metal NCs is to design an efficient derivatization reaction suitable for metal NCs and spontaneously realize the customization of this special macromolecule (metallic molecule) at the atomic and molecular level.In this Account, we use the flagship thiolate-protected NC Au25SR18 (SR denotes a thiolate ligand) as a model to illustrate the derivatization chemistry of metal NCs. In the past 3 years we have developed various derivatization reactions of Au25SR18, including isomerization, redox, ligand addition, alloying, and self-assembly reactions. We discuss the mechanisms that govern these reactions to realize precise customization of the NC structure, size, surface, composition, and interactions. It is particularly noteworthy that advanced techniques such as real-time electrospray ionization mass spectrometry and NMR spectroscopy enable us to have an atomic- and molecular-level understanding of the reaction mechanisms, which will further promote our efforts to design derivatization reactions for metal NCs. Through these delicate derivatization reactions, we can produce Au25SR18 derivatives with new physical, chemical, and biological properties, including electronic structures, photoluminescence, surface reactivity, and antimicrobial properties. Finally, we provide our perspectives on the opportunities and challenges of metal NC derivatization.The derivatization chemistry of metal NCs can not only diversify the properties and functions of metal NCs but also help us understand the structure-property relationship and design principles of metal nanomaterials, which will help advance the research frontier of nanoscience toward atomic precision.

Surface Engineering Assisted Size and Structure Modulation of Gold Nanoclusters by Ionic Liquid Cations.

Surface modification induced core size/structure change is a recent discovery in inorganic nanoparticles research, and has rarely been revealed at the molecular level. Here, we exemplify with atomically precise Au nanoclusters (NCs) that proper surface modification can selectively stabilize the desired Au0 core, conducive to the formation of size/structure-controlled Au NCs. Leveraging π-π enhanced ion-pairing interactions, ionic liquid (IL) cations are bonded to AuI -thiolate complexes. The hydrophobic-hydrophobic interactions between IL cations subsequently provide a good mechanism to prolong the size of the AuI -thiolate complexes, selectively producing small-sized Au NCs upon reduction. Through combined control over the structure and concentration of IL cations, pH and solvent polarity, we are able to produce atomically precise Au NCs with customizable size, atomic packing structure, and surface chemistry. This work also provides a facile means to integrate/synergize the materials functionalities of Au NCs and ILs, increasing their acceptance in diverse fields.

Supported Atomically-Precise Gold Nanoclusters for Enhanced Flow-through Electro-Fenton.

Gold (Au) has been considered catalytically inert for decades, but recent reports have described the ability of Au nanoparticles to catalyze H2O2 decomposition in the Haber-Weiss cycle. Herein, the design and demonstration of a flow-through electro-Fenton system based on an electrochemical carbon nanotube (CNT) filter functionalized with atomically precise Au nanoclusters (AuNCs) is described. The functionality of the device was then tested for its ability to catalyze antibiotic tetracycline degradation. In the functional filters, the Au core of AuNCs served as a high-performance Fenton catalyst; while the AuNCs ligand shells enabled CNT dispersion in aqueous solution for easy processing. The hybrid filter enabled in situ H2O2 production and catalyzed the subsequent H2O2 decomposition to HO·. The catalytic function of AuNCs lies in their ability to undergo redox cycling of Au+/Au0 under an electric field. The atomically precise AuNCs catalysts demonstrated superior catalytic activity to larger nanoparticles; while the flow-through design provided convection-enhanced mass transport, which yielded a superior performance compared to a conventional batch reactor. The adsorption behavior and decomposition pathway of H2O2 on the filter surfaces were simulated by density functional theory calculations. The research outcomes provided atomic-level mechanistic insights into the Au-mediated Fenton reaction.

Unraveling the Impact of Gold(I)-Thiolate Motifs on the Aggregation-Induced Emission of Gold Nanoclusters.

Aggregation-induced emission (AIE) provides an efficient strategy to synthesize highly luminescent metal nanoclusters (NCs), however, rational control of emission energy and intensity of metal NCs is still challenging. This communication reveals the impact of surface AuI -thiolate motifs on the AIE properties of Au NCs, by employing a series of water-soluble glutathione (GSH)-coordinated Au complexes and NCs as a model ([Au10 SR10 ], [Au15 SR13 ], [Au18 SR14 ], and [Au25 SR18 ]- , SR=thiolate ligand). Spectroscopic investigations show that the emission wavelength of Au NCs is adjustable from visible to the near-infrared II (NIR-II) region by controlling the length of the AuI -SR motifs on the NC surface. Decreasing the length of AuI -SR motifs also changes the origin of cluster luminescence from AIE-type phosphorescence to Au0 -core-dictated fluorescence. This effect becomes more prominent when the degree of aggregation of Au NCs increases in solution.

Toward Total Synthesis of Thiolate-Protected Metal Nanoclusters.

Total synthesis, where desired organic- and/or biomolecules could be produced from simple precursors at atomic precision and with known step-by-step reactions, has prompted centuries-lasting bloom of organic chemistry since its conceptualization in 1828 (Wöhler synthesis of urea). Such expressive science is also highly desirable in nanoscience, since it represents a decisive step toward atom-by-atom customization of nanomaterials for basic and applied research. Although total synthesis chemistry is less established in nanoscience, recent years have witnessed seminal advances and increasing research efforts devoted into this field. In this Account, we discuss recent progress on introducing and developing total synthesis routes and mechanisms for atomically precise metal nanoclusters (NCs). Due to their molecular-like formula and properties (e.g., HOMO-LUMO transition, strong luminescence and stereochemical activity), atomically precise metal NCs could be regarded as "molecular metals", holding potential applications in various practical sectors such as biomedicine, energy, catalysis, and many others. More importantly, the molecular-like properties of metal NCs are sensitively dictated by their size and composition, suggesting total synthesis of them as an indispensable basis for reliably realizing their practical applications. Atomically precise thiolate-protected Au, Ag and their alloy NCs are employed as model NCs to exemplify design strategies and governing principles in total synthesis of inorganic nanoparticles. This Account starts with a brief summary of total synthesis methodologies of atomically precise metal NCs. Following the methodological summary is a detailed discussion on the mechanisms governing these synthetic strategies, which is the main focus of this Account. Based on unprecedented precision (at atomic resolution) and ease (ensured by size-dependent properties) of tracking clusters' size/structure changes, mechanisms driving growth (e.g., reduction growth and seeded growth) and functionalization (e.g., alloying reaction and ligand exchange) of metal NCs have been explored at molecular level. With definitive step-by-step reaction routes, two-electron (2 e-) reduction (driving the growth reactions) and surface motif exchange (SME, prompting alloying and ligand exchange reactions) are discussed in depth and details. In addition to those sub- and/or individual-cluster level understandings, the self-assembly chemistry delivering high orderliness and enhanced materials performance in NC assemblies/supercrystals is also deciphered. This Account is then concluded with our perspectives toward potential development of cluster chemistry. Advances in total synthesis chemistry of metal NCs could not only serve as guidelines for future synthetic practice of NCs, but also provide molecular-level clues for many pending fundamental puzzles in nanochemistry, including nucleation growth, alloying chemistry, surface engineering and evolution of metamaterials.

Electrospray Ionization Mass Spectrometry: A Powerful Platform for Noble-Metal Nanocluster Analysis.

Electrospray ionization mass spectrometry (ESI-MS) is an analytical technique that measures the mass of a sample through "soft" ionization. Recent years have witnessed a rapid growth of its application in noble-metal nanocluster (NC) analysis. ESI-MS is able to provide the mass of a noble-metal NC analyte for the analysis of their composition (n, m, q values in a general formula [Mn Lm ]q ), which is crucial in understanding their properties. This review attempts to present various developed techniques for the determination of the composition of noble metal NCs by ESI-MS. Additionally, advanced applications that use ESI-MS to further understand the reaction mechanism, complexation behavior, and structure of noble metal NCs are introduced. From the comprehensive applications of ESI-MS on noble-metal NCs, more possibilities in nanochemistry can be opened up by this powerful technique.

Aurophilic Interactions in the Self-Assembly of Gold Nanoclusters into Nanoribbons with Enhanced Luminescence.

Aurophilic interactions (AuI ⋅⋅⋅AuI ) are crucial in directing the supramolecular self-assembly of many gold(I) compounds; however, this intriguing chemistry has been rarely explored for the self-assembly of nanoscale building blocks. Herein, we report on studies on aurophilic interactions in the structure-directed self-assembly of ultrasmall gold nanoparticles or nanoclusters (NCs, <2 nm) using [Au25 (SR)18 ]- (SR=thiolate ligand) as a model cluster. The self-assembly of NCs is initiated by surface-motif reconstruction of [Au25 (SR)18 ]- from short SR-[AuI -SR]2 units to long SR-[AuI -SR]x (x>2) staples accompanied by structure modification of the intrinsic Au13 kernel. Such motif reconstruction increases the content of AuI species in the protecting shell of Au NCs, providing the structural basis for directed aurophilic interactions, which promote the self-assembly of Au NCs into well-defined nanoribbons in solution. More interestingly, the compact structure and effective aurophilic interactions in the nanoribbons significantly enhance the luminescence intensity of Au NCs with an absolute quantum yield of 6.2 % at room temperature.

Synthesis of Water-Soluble [Au25(SR)18]- Using a Stoichiometric Amount of NaBH4.

Determination of the stoichiometry of reactions is a pivotal step for any chemical reactions toward a desirable product, which has been successfully achieved in organic synthesis. Here, we present the first precise determination of the stoichiometry for the reactions toward gold nanoparticle formation in the sodium borohydride reduction method. Leveraging on the real-time mass spectrometry technique, we have determined a precise balanced reaction, 32/ x [Au(SR)] x + 8 e- = [Au25(SR)18]- + 7 [Au(SR)2]- (here SR denotes a thiolate ligand), toward a stoichiometric synthesis of water-soluble [Au25(SR)18]-, where 8 electrons (from reducing agents) are sufficient to react with every 32 Au atoms, leading to the formation of high-purity [Au25(SR)18]-. More interestingly, by real-time monitoring of the growth process of thiolate-protected Au nanoclusters, we have successfully identified an important yet missing byproduct, [Au(SR)2]-. This study not only provides a new method for Au nanocluster synthesis using only a stoichiometric amount of reducing agent in aqueous solutions (although the synthesis of organic-soluble Au nanoclusters might require a more delicate design of synthetic chemistry) but also promotes the mechanistic understandings of the Au nanocluster growth process.

Molecular-Scale Ligand Effects in Small Gold-Thiolate Nanoclusters.

Because of the small size and large surface area of thiolate-protected Au nanoclusters (NCs), the protecting ligands are expected to play a substantial role in modulating the structure and properties, particularly in the solution phase. However, little is known on how thiolate ligands explicitly modulate the structural properties of the NCs at atomic level, even though this information is critical for predicting the performance of Au NCs in application settings including as a catalyst interacting with small molecules and as a sensor interacting with biomolecular systems. Here, we report a combined experimental and theoretical study, using synchrotron X-ray spectroscopy and quantum mechanics/molecular mechanics simulations, that investigates how the protecting ligands impact the structure and properties of small Au18(SR)14 NCs. Two representative ligand types, smaller aliphatic cyclohexanethiolate and larger hydrophilic glutathione, are selected, and their structures are followed experimentally in both solid and solution phases. It was found that cyclohexanethiolate ligands are significantly perturbed by toluene solvent molecules, resulting in structural changes that cause disorder on the surface of Au18(SR)14 NCs. In particular, large surface cavities in the ligand shell are created by interactions between toluene and cyclohexanethiolate. The appearance of these small molecule-accessible sites on the  NC surface demonstrates the ability of Au NCs to act as a catalyst for organic phase reactions. In contrast, glutathione ligands encapsulate the Au NC core via intermolecular interactions, minimizing structural changes caused by interactions with water molecules. The much better protection from glutathione ligands imparts a rigidified surface and ligand structure, making the NCs desirable for biomedical applications due to the high stability and also offering a structural-based explanation for the enhanced photoluminescence often reported for glutathione-protected Au NCs.

Probing the Microporous Structure of Silica Shell Via Aggregation-Induced Emission in Au(I)-Thiolate@SiO2 Nanoparticle.

An efficient method to investigate the window size of the silica shell generated via the classical Stöber method is reported by making use of the unique aggregation-induced emission property of Au(I)-thiolate complexes, which can precisely probe the porosity of the silica shell in Au(I)-thiolate@SiO2 nanoparticles.

Introducing amphiphilicity to noble metal nanoclusters via phase-transfer driven ion-pairing reaction.

Amphiphilicity is a surface property that has yet to be explored for the noble metal nanoclusters (NCs). This article shows how amphiphilicity may be added to sub-2-nm metal NCs by patching hydrophilic NCs (e.g., Au25(MHA)18 NCs where MHA is 6-mercaptohexanoic acid) with hydrophobic cations (e.g., cetyltrimethylammonium ion, CTA(+)) to about half of a monolayer coverage. Specifically we demonstrate the preparation of amphiphilic Au25(MHA)18@xCTA NCs (x = 6-9 where x is the number of CTA(+) per NC) by the phase-transfer (PT) driven ion-paring reaction between CTA(+) and -COO(-) (derived from the deprotonation of the terminal carboxyl group of MHA). Due to the coexistence of flexible hydrophilic MHA and hydrophobic MHA···CTA ligands in comparable amounts on the NC surface, the Au25(MHA)18@xCTA NCs (x = 6-9) exhibit good amphiphilicity, which enabled them to dissolve in solvents with distinctly different polarities and to self-assemble like a molecular amphiphile. Consequently, the amphiphilic Au25(MHA)18@xCTA NCs (x = 6-9) could self-organize into stacked bilayers at the air-liquid interface, similar to the formation of lyotropic liquid crystalline phases by common surfactants. The good solubility and molecular-amphiphile-like self-assembly properties can significantly increase the utility of noble metal NCs in basic and applied research.

Architectural design of heterogeneous metallic nanocrystals--principles and processes.

CONSPECTUS: Heterogeneous metal nanocrystals (HMNCs) are a natural extension of simple metal nanocrystals (NCs), but as a research topic, they have been much less explored until recently. HMNCs are formed by integrating metal NCs of different compositions into a common entity, similar to the way atoms are bonded to form molecules. HMNCs can be built to exhibit an unprecedented architectural diversity and complexity by programming the arrangement of the NC building blocks ("unit NCs"). The architectural engineering of HMNCs involves the design and fabrication of the architecture-determining elements (ADEs), i.e., unit NCs with precise control of shape and size, and their relative positions in the design. Similar to molecular engineering, where structural diversity is used to create more property variations for application explorations, the architectural engineering of HMNCs can similarly increase the utility of metal NCs by offering a suite of properties to support multifunctionality in applications. The architectural engineering of HMNCs calls for processes and operations that can execute the design. Some enabling technologies already exist in the form of classical micro- and macroscale fabrication techniques, such as masking and etching. These processes, when used singly or in combination, are fully capable of fabricating nanoscopic objects. What is needed is a detailed understanding of the engineering control of ADEs and the translation of these principles into actual processes. For simplicity of execution, these processes should be integrated into a common reaction system and yet retain independence of control. The key to architectural diversity is therefore the independent controllability of each ADE in the design blueprint. The right chemical tools must be applied under the right circumstances in order to achieve the desired outcome. In this Account, after a short illustration of the infinite possibility of combining different ADEs to create HMNC design variations, we introduce the fabrication processes for each ADE, which enable shape, size, and location control of the unit NCs in a particular HMNC design. The principles of these processes are discussed and illustrated with examples. We then discuss how these processes may be integrated into a common reaction system while retaining the independence of individual processes. The principles for the independent control of each ADE are discussed in detail to lay the foundation for the selection of the chemical reaction system and its operating space.

Counterion-assisted shaping of nanocluster supracrystals.

Ag44 (p-MBA)30 (4-) (p-MBA=para-mercaptobenzoic acid) nanocluster (NC) supracrystals (SCs) with customizable shapes can be obtained by simply altering the type and concentration of the counterions of the p-MBA ligands in the dimethylsulfoxide (DMSO)/water crystallization system. Changing the counterion of the p-MBA ligand from H(+) to Cs(+) eliminates the directional hydrogen bonds in the SCs, resulting in the packing of deprotonated Ag44 (p-MBA)30 (4-) NCs into octahedral SCs, which is in stark contrast to the rhombohedral SCs that were formed by the packing of protonated Ag44 (p-MBA)30 (4-) NCs in previous studies. Furthermore, the double layer of deprotonated Ag44 (p-MBA)30 (4-) NCs is sensitive to charge screening induced by increasing the Cs(+) concentration, thereby providing a means to regulate the precipitation kinetics of the Ag44 (p-MBA)30 (4-) NCs for SC shape engineering. Slow precipitation kinetics was found to favor over-growth at the corners and edges of the octahedral SC nuclei, shaping the SCs into concave octahedra.

Balancing the rate of cluster growth and etching for gram-scale synthesis of thiolate-protected Au(25) nanoclusters with atomic precision.

We report a NaOH-mediated NaBH4 reduction method for the synthesis of mono-, bi-, and tri-thiolate-protected Au25 nanoclusters (NCs) with precise control of both the Au core and thiolate ligand surface. The key strategy is to use NaOH to tune the formation kinetics of Au NCs, i.e., reduce the reduction ability of NaBH4 and accelerate the etching ability of free thiolate ligands, leading to a well-balanced reversible reaction for rapid formation of thermodynamically favorable Au25 NCs. This protocol is facile, rapid (≤3 h), versatile (applicable for various thiolate ligands), and highly scalable (>1 g Au NCs). In addition, bi- and tri-thiolate-protected Au25 NCs with adjustable ratios of hetero-thiolate ligands were easily obtained. Such ligand precision in molecular ratios, spatial distribution and uniformity resulted in richly diverse surface landscapes on the Au NCs consisting of multiple functional groups such as carboxyl, amine, and hydroxy. Analysis based on NMR spectroscopy revealed that the hetero-ligands on the NCs are well distributed with no ligand segregation. The unprecedented synthesis of multi-thiolate-protected Au25 NCs may further promote the practical applications of functional metal NCs.

Enzyme-mimic catalytic activities and biomedical applications of noble metal nanoclusters.

Noble metal (e.g., Au and Ag) nanoclusters (NCs), which exhibit structural complexity and hierarchy comparable to those of natural proteins, have been increasingly pursued in artificial enzyme research. The protein-like structure of metal NCs not only ensures enzyme-mimic catalytic activity, including peroxidase-, catalase-, and superoxide dismutase-mimic activities, but also affords an unprecedented opportunity to correlate the catalytic performance with the cluster structure at the molecular or atomic levels. In this review, we aim to summarize the recent progress in programming and demystify the enzyme-mimic catalytic activity of metal NCs, presenting the state-of-the-art understandings of the structure-property relationship of metal NC-based artificial enzymes. By leveraging on a concise anatomy of the hierarchical structure of noble metal NCs, we manage to unravel the structural origin of the catalytic performance of metal NCs. Noteworthily, it has been proven that the surface ligands and metal-ligand interface of metal NCs are instrumental in influencing enzyme-mimic catalytic activities. In addition to the structure-property correlation, we also discuss the synthetic methodologies feasible to tailoring the cluster structure at the atomic level. Prior to the closure of this review with our perspectives in noble metal NC-based artificial enzymes, we also exemplify the biomedical applications based on the enzyme-mimic catalysis of metal NCs with the theranostics of kidney injury, brain inflammation, and tumors. The fundamental and methodological advancements delineated in this review would be conducive to further development of metal NCs as an alternative family of artificial enzymes.

Fluorescent Enhancement of [AgS4] Microplates by Mechanical Force Induced Crystallinity Breaking.

Mechanofluorochromic materials are a type of "smart" material because of their adjustable fluorescent properties under external mechanical force, making them significant members of the materials family. However, as the fluorescent characteristics of these materials highly depend on their microstructures, the still insufficiently in-depth research linking molecular structures to light emission motivates researchers to explore the fluorescent properties of these materials under external stimuli. In this work, based on synthetic [AgS4] microplates, we explore a fascinating mechanical-induced photoluminescent enhancement phenomenon. By applying mechanical force to solid-state [AgS4] to damage the surface morphology, a significant enhancement in photoluminescence is observed. Moreover, the emitted intensity increases with the extent of damage, which can be attributed to alterations in crystallinity. This work provides valuable insights into the relationship among photoluminescence, crystallinity, and mechanical force, offering new strategies for designing luminescent devices.