Precise regulation of metal cluster structures and luminescent properties is critical for the advancement of their practical applications. Copper clusters have garnered extensive attention due to their abundant, inexpensive, and excellent luminescent properties. However, their strong metallophilic interactions often restrict emissions to the red region, making it challenging to controllably tune their emission range-especially toward high-energy bands. In this work, we propose a counterion-induced strategy to modulate the structure and luminescence properties of copper clusters. By adjusting the size of counter cations, we induced varying degrees of distortion in Cu5 anionic cluster structures and directed their crystallization into distinct assembly patterns, successfully obtaining four cluster-based luminescent materials. Theoretical calculations reveal that under the steric effects of counter cations, the four Cu5 clusters exhibit different molecular configurations and intercluster interaction strengths, enabling broad-range emission wavelength modulation (546 -> 687 nm). Notably, Cu 5 -Pr-a and Cu 5 -Et demonstrate unconventional high-energy emissions. This study provides a novel approach and experimental reference for the precise control of metal cluster structures and luminescent properties.

Heterogeneous crystalline materials have recently attracted much attention, but their development is limited by the difficulty of efficient preparation, particularly solid-phase preparation. Here, a photosensitive silver(I) cluster crystal, Ag9(StBu)6(Hdpa)6u00B7(PF6)3 (Ag9-Y), was obtained, which could change from colourless to red, accompanied by a change in photoluminescence (yellow to red) under ultraviolet irradiation. Further studies reveal that the intriguing transformation occurs due to the partial intercluster conversion (from Ag9 to Ag62) on the surface of the Ag9 crystal, resulting in the formation of heterogeneous coreu2013shell crystals (Ag9-YR). Surprisingly, although this transformation causes a significant change in the photophysical properties, the host lattice does not change, and a multilayer heterogeneous crystal is successfully constructed (Ag9-YRY) by combination with the epitaxial growth method. This strategy of utilizing partial photosensitive cluster conversion to achieve differences in crystal zoning properties provides a new approach for constructing multifunctional heterogeneous crystalline materials with broad application prospects.

Abstract Emulating the well-controlled conformational switching of biomacromolecules within artificial supramolecular assemblies remains a long-recognized challenge, especially exploring the synergy effects of metal clusters within metalloproteins. Herein, three types of copper cluster-based metallacages (helical Cu8-X, trigonal Cu12-Cl, and tetrahedral Cu16-SO4) were synthesized through a ligand isolation and anion-templated strategy, in which anion-dependent ligand arrangements and cluster distortions dictated configuration differences, while precise modulation of environmental anions could trigger structural transformations accompanied by significant luminescence modulation. Notably, Cu16SO4 exhibits a dual inner–outer binding mode: when using the highly negatively charged anion (SO42–) as a template, the four counterions are bound in the grooves near the four faces of the tetrahedron, significantly enhancing structural stability. Furthermore, anchoring chiral cations can effectively transfer chirality to the cage framework, endowing it with circularly polarized luminescence property. This work provides a novel strategy for the construction of cluster-based metallacages, and this integrated system of controllable synthesis, stimulus-responsive transformation, and tunable functionality provides inspiration for exploring the dynamic regulation mechanisms of biomolecules.

Constructing metal cluster materials that combine well-defined recognition sites with highly sensitive fluorescent sensing capabilities has remained a significant challenge. Here, we employed ligand engineering to modify reported Cu4 structures, successfully synthesizing a cluster-based bowl-shaped molecule. The ingenious introduction of urea groups endows the inner walls of bowl-shaped molecules with abundant binding sites. Additionally, the flexibility of both the ligands and the cluster allows the pocket to adaptively adjust, enabling interactions with a variety of anions, including BF4-, PF6-, HCOO-, ClO4- and NO3-. Integrating experimental observations with theoretical calculations reveals that nitrate ions demonstrate the strongest binding affinity towards the bowl-shaped cluster molecules, and their binding significantly modulates the electronic transition gap, leading to luminescence quenching of the cluster. Based on this, we investigated the fluorescence sensing properties of the Cu4 cluster targeting NO3-, and further developed a "shut-off"-type sensor for detecting NO3- anions, with a detection limit as low as 0.76 µM.

The research on circularly polarized luminescence (CPL) has received significant attention due to its promising applications in advanced optical technologies. This review summarizes the latest advancements in the development of CPL-active materials across organic, hybrid, and inorganic systems. Particular emphasis is placed on material design strategies that simultaneously achieve high luminescence efficiency and large dissymmetry factors (glum) through chiral induction, molecular engineering, and supramolecular organization. The review further explores the cutting-edge applications of these CPL materials in optoelectronic devices, as well as emerging uses in information encryption, anti-counterfeiting, and chiral sensing. Finally, the review highlights current challenges and future prospects in the field, addressing fundamental limitations in material performance, device integration, and scalability. This review aims to provide valuable insights and inspire future research that will advance CPL technologies toward practical implementation in photonics and optoelectronics.

During long-term use in the firing zone of cement kilns, MgO-MgAl2O4 composites face problems including poor sinterability (difficulty in forming ceramic bonding phases), weak interfacial bonding, high thermal conductivity, and insufficient resistance to slag corrosion, which inevitably restrict the extension of service life and improvement of thermal energy efficiency. To address these problems, this study adopted ZnO and NiO solid solutions to modify sintered magnesia for preparing modified MgO-MgAl2O4 composites and systematically investigated the microstructure and property evolutions of these materials. Results revealed that solid-solution-modified sintered magnesia introduction significantly enhanced the densities and mechanical properties of MgO-MgAl2O4 composites and effectively reduced the thermal conductivities of these materials. At 1000 °C, thermal conductivities of MNA-2 (NiO-based solid-solution-modified sintered magnesia for both matrix and aggregate) and MZA-2 (ZnO-based solid-solution-modified sintered magnesia for both matrix and aggregate) were 45.6% and 37.6% lower than that of the unmodified sample (periclase-spinel), respectively. Additionally, the modified MgO-MgAl2O4 composites exhibited excellent corrosion resistance against to cement clinker, reducing the corroded areas of MNA-2 and MZA-2 by 49.2% and 43.9%, respectively, compared with the unmodified MA sample.

Nanohybrids combining phenylboronic acid-modified carbon dots (PCDs) and proteinase K have been engineered for addressing the formidable challenges of antimicrobial photodynamic therapy (aPDT) against bacterial biofilm infections, overcoming biofilm barrier obstruction, the limited diffusion of reactive oxygen species (ROS), and the inadequate ROS generation of traditional photosensitizers. PCDs are formulated for superior water solubility and robust singlet oxygen (1O2) production, mitigating issues related to dispersion and aggregation-induced quenching typical of conventional photosensitizers. The conjugation of phenylboronic acid to CDs not only enhanced 1O2 generation through increased electron-hole separation but also imparted strong bacterial binding capabilities to the PCDs, enabling broad-spectrum sterilization by maximizing the ROS-mediated bacterial destruction. Proteinase K, serving as a structural "glue", actively breaks down biofilms and facilitates the deep penetration of functional PCDs, aiding effective treatment of biofilm infections. In vivo studies confirm that PCDs-proteinase K nanohybrids dramatically accelerate healing in biofilm-infected wounds by synergizing enhanced photosensitization, potent bacterial adherence, and efficient biofilm elimination and penetration. This approach highlights a straightforward strategy to significantly advance aPDT, promoting the clinical adoption of non-antibiotic methods for combating bacterial biofilm infections. STATEMENT OF SIGNIFICANCE: 1) Phenylboronic acid-modified carbon dots (PCDs) were designed for enhanced water solubility and efficient singlet oxygen generation through surface modulation, also suggesting that surface modification can improve the inherent photosensitizing activity of CDs by promoting electron-hole separation; 2) The conjugation of phenylboronic acid endowed PCDs with strong bacterial binding capabilities, enabling highly efficient and broad-spectrum sterilization by maximizing reactive oxygen species-mediated bacterial destruction; 3) Incorporation of proteinase K (PK) leveraged its specific extracellular polymeric substance degrading capability, along with the stimuli-responsive release of PCDs from the PCDs-PK nanohybrids, facilitating biofilm breakdown and enabling deeper penetration of PCDs, thereby improving the treatment of biofilm infections.

Surface ligands play a crucial role in modifying catalytic environments and enhancing performance through various mechanisms. However, the multivariate synergistic mechanisms, dynamic evolution patterns, and universal design principles of ligand effects remain to be thoroughly investigated. Metal clusters, with their atomically precise structures, serve as ideal models for studying ligand regulation mechanisms. Herein, we synthesized two copper clusters of N,S-bidentate ligand-protected Cu4(PTI)4 and Cu4(BTT)4 featuring identical metallic core structures but distinct ligand architectures and evaluated their catalytic performance for the nitrate reduction reaction (NO3RR). Notably, the Cu4(PTI)4 cluster with stronger electron-withdrawing ligands achieved near-100% Faradaic efficiency at optimal potentials, significantly surpassing the Cu4(BTT)4. Through in situ characterization and theoretical calculations, we unveiled that enhancing the electron-withdrawing capability of ligands induces alterations in the local microenvironment and electronic structure of metal active sites, thereby exerting positive impacts on electrocatalytic NO3RR performance.

The green combustion synthesis method offers significant advantages for the preparation of nano-oxides due to its environmental friendliness, high efficiency, and operational simplicity. However, its practical application is limited by issues such as incomplete combustion, poor control over particle morphology, and the formation of undesirable by-products. In contrast, microwave-assisted heating enables rapid and uniform temperature elevation, thereby improving combustion uniformity and product quality. In this study, a microwave-assisted green combustion approach was employed to synthesise modified MgO nanoparticles. The effects of K+ doping and microwave-assisted synthesis on the microstructure and antibacterial performance of MgO nano-particles was systematically investigated. X-ray diffraction (XRD) analyses confirmed the formation of cubic-phase Mg0.95K0.05O nanoparticles with an average crystallite size of approximately 13 nm. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images further revealed that the synthesised nanoparticles exhibited a spherical morphology. The plate colony counting method demonstrated that Mg0.95K0.05O nanoparticles exhibited excellent antimicrobial activity, achieving inhibition rates of 99.84 % against Escherichia coli and 96.29 % against Staphylococcus aureus (106 CFU/mL) at a concentration of 100 mu g/ mL. Mechanistic investigations demonstrated that the nanoparticles possessed a high density of surface oxygen vacancies, which promoted the generation of reactive oxygen species (ROS) and thereby enhanced antibacterial activity. These findings provide valuable insights into the design of oxygen-vacancy-rich MgO-based nano-materials and offer a promising strategy for the development of high-performance antimicrobial nano-oxides.

Atomically precise metal nanoclusters facilitate the exploration of chiral origin in metal nanomaterials, meanwhile, their structural isomers with subtle variations serve as ideal models for investigating the structure‐property relationship at the atomic level. Here, we obtained two pairs of chiral superatomic cis ‐ trans isomers with the formula [ R/S ‐Ag 28 (SOC 10 H 15 ) 14 (CF 3 COO) 10 ] (denoted as R/S ‐Ag 28 ‐ cis/trans ), where the cis and trans configurations coexist within the R and S chiral forms, respectively. Single crystal X‐ray diffraction (SCXRD) analysis revealed that Ag 28 clusters adopt a chiral core‐shell configuration of Ag 12 @Ag 14 S 12 , consisting of an Ag 12 kernel encapsulated within a chiral Ag 14 S 12 cage. The additional two AgS units are located in a different fashion on the flanks of the framework, leading to the cis ‐ trans isomerism of the silver clusters. DFT calculation reveals the distinctions in electronic structures and optical absorptions of the cis ‐ trans isomers. The enantiomeric R/S ‐Ag 28 exhibit intense red phosphorescence at 740 nm in the crystalline state, and hold a ∼28 nm blueshift in solution. Furthermore, R/S ‐Ag 28 display circularly polarized luminescence (CPL) activity, achieving a maximum (| g lum |) value of 1 × 10 −3 in the crystalline state. This study enriches the diversity of chiral superatomic clusters and introduces cis ‐ trans isomerism in metal clusters, establishing a novel platform to explore structure‐activity relationships.

MgO nanoparticles have garnered significant interest owing to their stability, environmental safety, and biocompatibility. However, the low antimicrobial activity of these nanoparticles limits their widespread utilization. Moreover, conventional methods to synthesize MgO nanoparticles are inefficient, costly, and harmful to the environment. To address these limitations, this study introduces a green synthesis approach using plant extracts as fuels. We systematically investigated the effect of three plant extracts, namely, Moringa oleifera Lam. leaves, Platanus x acerifolia (Aiton) Willd. leaves (London plane tree) and Camellia sinensis (L.) Kuntze leaves, on the microstructure and antimicrobial properties of MgO nanoparticles. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) revealed spherical particles with small sizes (similar to 25nm). X-ray diffraction analysis outcomes confirmed that the synthesized MgO nanoparticles had high purity. Fourier-transform infrared spectroscopy confirmed the presence of Mg-O bonds (400-770cm(-1)). The plate-coating count test confirmed that MgO nanoparticles derived from Moringa oleifera, Platanus x acerifolia and Camellia sinensis displayed excellent antibacterial performance, achieving bactericidal rates of 99.99%, 99.92% and 99.99% against Escherichia coli, respectively, and 99.87%, 99.31% and 99.91% against Staphylococcus aureus, respectively. X-ray photoelectron spectroscopy (XPS) revealed higher oxygen vacancy concentrations in the sample synthesized using C. sinensis extract (61.75%) compared with those synthesized using M. oleifera (52.53%) and P. x acerifolia (46.28%). Electron paramagnetic resonance (EPR) further confirmed the generation of reactive oxygen species (ROS) associated with these vacancies. The zeta potentials of the samples synthesized with C. sinensis, M. oleifera and P. x acerifolia were 6.7mV, 9.8mV and 9.9mV, respectively, which facilitated strong electrostatic interaction with bacterial membranes. Together, these results demonstrate the dual antimicrobial mechanism of ROS-induced cytotoxicity and mechanical damage.

The thermal decomposition (TD) of magnesite is crucial for its high-value applications, and understanding its reaction mechanisms requires establishing accurate kinetic models. This research investigates the TD kinetics of microcrystalline magnesite under varying heating rates (HRs) using thermogravimetry and differential scanning calorimetry (TG-DSC) analysis. Kinetic parameters were derived using the Coats-Redfern (CR), Kissinger-Akahira-Sunose (KAS), and Flynn-Wall-Ozawa (FWO) methods. The influence of HRs on the decomposition process and the resulting MgO morphology was analyzed. The results demonstrated that as HRs increased, the decomposition and reaction rate curves shifted to higher temperatures, necessitating elevated temperatures for similar levels of decomposition. The mean activation energy (Ea${{E}_a}$) was calculated to be 162.45 kJ/mol, with a strong linear correlation between the Ea${{E}_a}$ and pre-exponential factor, suggesting robust kinetic compensation. The TD followed a two-dimensional phase boundary mechanism with cylindrical symmetry. "Original shape pseudomorphs" were found to significantly affect the microstructure, particle size variation, and kinetic behavior of the decomposition products. These findings provide important insights for the industrial processing of microcrystalline magnesite.

Circularly polarized luminescence (CPL) materials have been extensively studied in recent years owing to their widespread applications in 3D display, optical storage, optical anti-counterfeiting, and biological imaging, etc. Copper(I) clusters have emerged as a promising candidate for CPL materials, driven by their cost-effectiveness, superior luminescent properties, precise structure, and low toxicity. Nevertheless, the poor environmental stability of copper(I) clusters renders their synthesis and preservation challenging, thereby significantly impeding their advancement. Herein, we have designed and synthesised a chiral double-coordinated ligand in order to construct copper(I) cluster nodes that can be further assembled. As anticipated, by utilizing stepwise assembly strategy, a Cu4 cluster node co-modified by chiral alkynyl ligands and triphenylphosphine was further assembled with Cd2+ ions to obtain 2D layers structure, L/D-Cu4-Cd. The L/D-Cu4-Cd exhibits excellent stability and optical properties, including bright yellow emission, solvent-responsive luminescence, and CPL activity with a maximum glum up to 2.0 × 10−3, which shows potential applications in the WLED and WCP-light. More interestingly, the material also exhibits deflection ability towards different wavelengths of linearly polarized light, showing certain potential in the preparation of circular polarizer.

This study introduces a novel approach to enhance the properties of sintered magnesium oxide (MgO) aggregates by incorporating nickel oxide (NiO) powder as a solid-solution modification additive. The addition of NiO improves the densification of the specimens and promotes grain growth through the activation of sintering via the solid-solution reaction of MgO-NiO at high temperatures. The formation of the (Mg, Ni)O solid-solution structure enhances the strength of the specimens, while gradually reducing thermal conductivity. However, excessive addition of NiO (>6 mol%) adversely affects the sintering properties of the specimens due to limited diffusive mass transfer rate during sintering and the Zener effect, resulting in diminished grain size and strength. Although thermal conductivity is not significantly affected, at 1000 degree celsius, one specimen (MN-6) demonstrates a 61.03 % decrease in thermal conductivity compared to a specimen without NiO addition. These findings suggest that the incorporation of a moderate amount of NiO enhances the corrosion resistance of the cement clinker of the specimens primarily by increasing densification, grain size, and high-temperature contact angle.

Four fundamental reactions are essential to harnessing energy from water sustainably: oxidation reduction reaction (ORR), oxygen reduction reaction (OER), hydrogen oxidation reaction (HOR), and hydrogen evolution reaction (HER). This review summarizes the research advancements in the electrocatalytic reaction of metal nanoclusters for water splitting. It covers various types of nanoclusters, particularly those at the size level, that enhance these catalytic reactions. The synthesis of cluster-based catalysts and the elucidation of the structure-activity relationships and reaction mechanisms are discussed. Emphasis is placed on utilizing atomically precise cluster materials and the interplay between the carrier and cluster in water catalysis, especially for applying catalytic engineering principles (such as synergy, coordination, heterointerface, and lattice strain engineering) to understand structure-activity relationships and catalytic mechanisms for cluster-based catalysts. Finally, the field of cluster water catalysis is summarized and prospected. We believe that developing cluster-based catalysts with high activity, excellent stability, and high selectivity will significantly promote the development of renewable energy conversion reactions.

Smart stimuli-responsive persistent luminescence materials, combining the various advantages and frontier applications prospects, have gained booming progress in recent years. The trap-controlled property and energy storage capability to respond to external multi-stimulations through diverse luminescence pathways make them attractive in emerging multi-responsive smart platforms. This review aims at the recent advances in trap-controlled luminescence materials for advanced multi-stimuli-responsive smart platforms. The design principles, luminescence mechanisms, and representative stimulations, i.e., thermo-, photo-, mechano-, and X-rays responsiveness, are comprehensively summarized. Various emerging multi-responsive hybrid systems containing trap-controlled luminescence materials are highlighted. Specifically, temperature dependent trapping and de-trapping performance is discussed, from extreme-low temperature to ultra-high temperature conditions. Emerging applications and future perspectives are briefly presented. It is hoped that this review would provide new insights and guidelines for the rational design and performance manipulation of multi-responsive materials for advanced smart platforms.

The efficient treatment of many infectious diseases is hindered by uncontrolled bacterial infections and inflammation induced by reactive oxygen species (ROS). Thus, there is an urgent need for the development of multifunctional therapeutic agents that possessing both antibacterial and antioxidant features. In this study, a novel antibacterial and antioxidant agent, Ga2Se3 nanosheets (NSs), were firstly prepared by the liquid-phase exfoliation method. The Ga2Se3 NSs exhibited broad-spectrum sterilization capabilities, even including multidrug-resistant strains. Noteworthily, Ga2Se3 NSs showed a remarkable 800-fold enhancement in antibacterial efficacy compared to the bulk materials, while also demonstrating low drug resistance compared to the traditional antibiotics. Their superior antibacterial performance is primarily attributed to the disruption of basic bacterial metabolism induced by gallium and selenium components, as well as the dimensional engineering of Ga2Se3 NSs. Cellular studies further confirmed the protective effects of pluronic F127 modified Ga2Se3 NSs against oxidative stress damage, preserving cellular functions through ROS scavenging. This study highlights the superior antibacterial and antioxidant properties of Ga2Se3 NSs, which offers an alternative opportunity for addressing the drug resistance issue in treatment of certain special diseases.

A nanoscale hexagonal flake magnesium hydroxide (MH) flame retardant was prepared by a hydrothermal method using Tibetan microcrystalline magnesite as the raw material. The synthesized samples were characterized by x-ray diffraction (XRD), field-emission scanning electron microscopy (FSEM), thermogravimetric analysis-differential scanning calorimetry (TG-DSC), and laser particle size analysis. When subjected to hydrothermal treatment at 180 degrees C for a duration of 8 h in a solution containing 6 mol l-1 NaOH, and with the incorporation of 4 wt% of the surfactant polyethylene glycol 2000 (PEG2000), hexagonal flake MH, possessing an average particle size of 378.3 nm, was successfully synthesized. The study conducted an examination of the thermal, mechanical, and flame-retardant properties of both EP and EP/MH composites. The results revealed that the incorporation of 9 wt% MH led to a notable reduction in the peak heat release rate, total smoke production, and mass loss rate of the EP/MH composites by 36%, 14.5%, and 33.3% respectively, as compared to the pure EP. Remarkably, the tensile and flexural strength of the composite exhibited minimal impact.

Materials exhibiting X-ray-induced photochromism have consistently piqued the interest of researchers. Exploring the photochromic properties of such materials is valuable for understanding the structural changes and electron transfer processes that occur under high energy radiation, such as X-ray irradiation. Here, a crystalline silver(I) nanocluster synthesized from tert-butylacetylene silver was found to have the ability to exhibit color and photoluminescence changes upon exposure to X-ray radiation. The responsive behavior was observed across a wide temperature range of 100-300 K, with the ability to respond particularly well to soft X-rays (λ > 1 Å) and exhibit light responsiveness to hard X-rays (λ < 1 Å). By combining experimental findings including X-ray diffraction, X-ray photoelectron spectroscopy, electron spin resonance, etc. with theoretical calculations, we have proposed that X-ray irradiation induces electron transfer from chloride (Cl-) located in the center of the silver(I) nanocluster to the surrounding Ag14 in the skeleton. This represents the first documented example in which electron transfer induced by X-ray excitation has been observed, accompanied by a photochromism process, in silver nanoclusters. This study contributes to our understanding of X-ray-induced photochromism and the electron transfer process in silver cluster compounds. It also provides valuable insights and potential design strategies for applications such as photochromism, photoluminescence color change, and photoenergy conversion.