Aggregation Inducing Reversible Conformational Isomerization of Surface Staple in Au18SR14 Nanoclusters.

The conformation of molecules and materials is crucial in determining their properties and applications. Here, this work explores the reversible transformation between two distinct conformational isomers in metal nanoclusters. This work demonstrates the successful manipulation of a controllable and reversible isomerization of Au18SR14 within an aqueous solution through two distinct methods: ethanol addition and pH adjustment. The initial driver is the alteration of the solution environment, leading to the aggregation of Au18SR14 protected by ligands with smaller steric hindrance. At the atomic level, the folding mode of the unique Au4SR5 staple underpins the observed structural transformation. The reversal of staple conformation leads to color shifting between green and orange-red, and tailors a second emission peak at 725 nm originating from charge transfer from the thiolate to the Au9 core. This work not only deepens the understanding of the surface structure and dual-emission of metal nanoparticles, but also enhances the comprehension of their isomerization.

Discovering of Atomically Precise Metal Nanoclusters by High-Throughput Syntheses Platform.

Understanding the complete structure of noble metal nanoclusters is both academically and practically significant. However, progress has been hindered by the low synthetic efficiency of many nanocluster syntheses. In this study, we present the first high-throughput syntheses of homo-gold, homo-copper, and gold-copper alloy nanoclusters in dichloromethane at room temperature. Through high-throughput screening, we successfully obtained three nanoclusters in a single reaction: Au18(SC6H11)14, [Au41Cu66(SC6H11)44](SbF6)3, and an unidentified copper cluster (referred to as Au18, Au41Cu66 , and Cu-NC). The optimized synthesis route was achieved with the assistance of machine learning for experimental data analysis, which also guided the synthesis of other metal nanoclusters such as Au40Cu34(4-S-PhF)40 (Au40Cu34), [Au6Cu6(SPh)12]n ([Au6Cu6]n), and Au18Cu32(3,5-C8H9S)36 (Au18Cu32)). This research demonstrates that high-throughput screening can be a valuable tool in accelerating the development of nanocluster syntheses.

Strategic framework for harnessing luminescent metal nanocluster assemblies in biosensing applications.

The distinctive physicochemical attributes of ultra-small metal nanoclusters (MNCs) resembling those of molecules make them versatile constituents for self-assembled frameworks. This critical review scrutinizes the influence of assembly on the photoluminescence (PL) properties of MNCs and investigates their utility in biosensing applications. The investigation is initiated with an assessment of the shift from individual MNCs to assemblies and its repercussions on PL efficacy. Subsequently, two distinct biosensing modalities are explored: assembly-driven detection mechanisms and detection predicated on structural modifications in assembled MNCs. Through meticulous examination, we underscore the potential of self-assembly methodologies in tailoring the PL behavior of MNCs for the detection of diverse biological analytes and diseases.

Photochemical Route for Synthesizing Atomically Precise Metal Nanoclusters from Disulfide.

Practical approaches to the synthesis of atomically precise metal nanoclusters are in high demand as they provide the structural basis for investigating nanomaterials' structure-property correlations with atomic precision. The Brust-Schiffrin method has been widely used, while the essential reductive ligands (e.g., thiols) limit the application of this method for synthesizing metal nanoclusters with specific frameworks and surface ligands. In this work, we developed a photochemical route for synthesizing atomically precise metal nanoclusters by applying disulfide, which is a widely available, stable, and environmentally friendly sulfur source. This method enables the construction of structurally diverse metal nanoclusters and especially features the synthesis of PhS-protected metal nanoclusters that were not easily achieved previously and the gram-scale synthesis. A reduction-oxidation cascade mechanism has been revealed for the photochemical route. This work is expected to open up new opportunities for metal nanocluster synthesis and will contribute to the practical applications of this kind of nanomaterial.

Exceptionally Bifunctional ORR/OER Performance via Synergistic Atom-Cluster Interaction.

The single-atom sites (SAs) have achieved enhanced performance toward oxygen reduction reaction (ORR) with the effective utilization of the active sites. However, the excess adsorption of the intermediates and the limited stability hinders performance improvement. Metal clusters with promising stability and weak adsorption can be used as potential substitutions, but the lack of active sites is considered undesirable for catalytic reactions. Herein, a framework of Fe nanoclusters combined with SAs on One dimensional (1D) carbon nanotubes (Fe3 C-NCNTs 90 min CC-1 ) is synthesized to confirm the synergistic atom-cluster interaction. The composite exhibits strong polarization and electron redistribution between nanocluster and SAs. The electron redistribution will significantly boost the electron transport and the desorption of the intermediates, which is confirmed by off-axis holography and DFT calculation. The electrocatalytic performance is significantly enhanced as the half-wave potential of ORR increased 75 mV and the potential of OER increased 133 mV compared with the sample without nanoclusters. Furthermore, such a bifunctional catalyst endows homemade Zn-air batteries (ZABs) with high power density and long-term stability. This work paves a facile route to design bifunctional ORR/OER electrocatalysts consisting of 0D composite structures.

Nitrogen Donor Protection for Atomically Precise Metal Nanoclusters.

Surface organic ligands are critical in dictating the structures and properties of atomically precise metal nanoclusters. In contrast to the conventionally used thiolate, phosphine and alkynyl ligands, nitrogen donor ligands have not been used in the protection for well-defined metal nanoclusters until recently. This review focuses on recent developments in atomically precise metal nanoclusters stabilized by different types of nitrogen donor ligands, in which the synthesis, total structure determination and various properties are covered. We hope that this review will provide insights into the rational design of N donor-protected metal nanoclusters in terms of structural and functional modulation.

White-emitting Protein-Metal Nanocluster Phosphors for Highly Performing Biohybrid Light-Emitting Diodes.

This work presents a simple in situ synthesis and stabilization of fluorescent gold nanoclusters (AuNCs) with different sizes using engineered protein scaffolds in water. The protein-AuNC hybrids show a dual emission (450 and 700 nm) with a record photoluminescence quantum yield of 20%. These features impelled us to apply them to biohybrid light-emitting diodes as color down-converting filters or biophosphors. Efficient white emission (x/y CIE color coordinates of 0.31/0.29) and stabilities of more than 800 h were achieved. This represents a 2 orders of magnitude enhancement compared to the prior art. Besides the outstanding performance, the protein scaffold also infers a unique anisotropic emission character that is considered as a proof-of-concept of high interest for single-point lighting and display.

Determination of iron(II) and iron(III) via static quenching of the fluorescence of tryptophan-protected copper nanoclusters.

"Tryptophan-coated blue fluorescent copper nanocluster (CuNC@Trp) was prepared by a strategy where Trp acts as both the reducing and capping agent. The fluorescence of the CuNC, with excitation/emission peaks at 340/405 nm, is selectively quenched by iron(II) and iron(III) ions. Studying the mechanism of this interaction revealed that Fe2+ and Fe3+ ions can make a ground state complex with the protecting ligand which can result in quenching of the cluster emission. Structural and optical properties of the modified CuNC were investigated by ESI-MS, DLS, TEM, UV-vis and photoluminescence. The effects of pH value and temperature, time of interaction, and cluster volume were optimized. Under optimized conditions, the probe response is linear in concentration range of 10-1000 µM for Fe(II) and Fe(III) with the relative standard deviations of 0.13 and 0.14% (n = 5) respectively. The respective limits of detection are 3.0 and 2.2 µM. The method was successfully used for determination of trace amount of both ions in spiked water, blood and iron supplement tablets. The results were in good agreement with those obtained by the ICP-AES method." Graphical abstractThe scheme represents the synthesis of CuNC@Trp at basic conditions and at elevated temperature. The emission of the cluster decreases due to static quenching of fluorescence by iron ions.

Conversion of Metal-Organic Cage to Ligand-Free Ultrasmall Noble Metal Nanocluster Catalysts Confined within Mesoporous Silica Nanoparticle Supports.

Supported ultrasmall noble metal nanocluster-based (UNMN-based) catalysts are one of the most important classes of solid materials for heterogeneous catalysis. In this work, we present a novel strategy for the controlled synthesis of ligand-free UNMN nanocatalysts based on in situ reduction of a palladium-based (Pd-based) metal-organic cage (MOC) confined within monosized, thiol-modified mesoporous silica nanoparticle (MSN) supports. By taking advantage of the high mutual solubility of MOCs and MSNs in DMSO and the strong interactions between the thiol-modified MSN pore wall and MOC surface, a good dispersion of MOC molecules was achieved throughout the MSN support. The close correspondence of the MSN pore diameter (ca. 5.0 nm) with the diameter of the MOC (ca. 4.0 nm) confines MOC packing to approximately a monolayer. Based on this spatial constraint and electrostatic binding of the MOC to the thiol-modified MSN pore surface, in situ MOC reduction followed by metal atom diffusion, coalescence, and anchoring on the active sites resulted in ligand-free Pd-based UNMNs of approximately 0.9 ± 0.2 nm in diameter decorating the MSN pore surfaces. Control experiments of the reduction of a conventional palladium source or the reduction of free, unconstrained cages in solution under the same conditions only produced large metal nanocrystals (NP, >2 nm), confirming the importance of confined reduction to achieve a highly catalytically active surface. In light of this strategy, two catalytic experiments including the reaction of 4-nitrophenol to 4-aminophenol and the Suzuki C-C coupling reaction show superior catalytic activity of the engineered MSN-supported UNMN nanocatalysts compared to their free form and state of the art commercial catalysts. We believe that our new strategy will open new avenues for artificially designed UNMN-inspired nanoarchitectures for wide applications.

Interrogation of the Effect of Polymorphism of a Metal-Organic Framework Host on the Structure of Embedded Pd Guest Nanoparticles.

Metal-organic frameworks (MOFs) are very promising host materials for nanoscale guest materials. However, some MOFs such as MIL-53 are known to undergo phase transitions which can complicate the guest particle size control. In this study, Pd nanoparticles embedded in Al-MIL-53 were synthesised via (a) electrodeposition and (b) gas-phase reduction. A thorough structural investigation revealed that each synthesis method most likely favoured a different phase of Al-MIL-53, presenting the possibility of MOF phase selection as a technique for size control of embedded nanoparticles. For the first time, we hereby report the use of pair distribution function analysis to successfully investigate the structure and morphology of guest particles embedded in a MOF host.

A novel signal amplification strategy based on the use of copper nanoclusters for ratiometric fluorimetric determination of o-phenylenediamine.

Copper nanoclusters (CuNCs) were synthesized starting from glutathione and copper(II) nitrate. They show blue fluorescence peaking at 432 nm when excited at 334 nm. In the presence of o-phenylenediamine (OPD), the blue fluorescence is decreased, but a yellow fluorescence appears with a peak at 557 nm. UV-visible absorptiometry, fluorometry and fluorescence lifetime measurements were used to show that OPD is oxidized by the small fraction of copper(II) ions present in the CuNCs to form the oxidized form of o-phenylenediamine (oxOPD) which displays weak yellow fluorescence, while the blue fluorescence decreases. The ratio of fluorescences at 557 and 432 nm increases linearly in the 0.15 to 110 µg·L-1 OPD concentration range, and the detection limit is 93 ng·L-1. Compared to the method based on the use of dissolved Cu(II), the employment of CuNCs reduces the detection limit by a factor of 40. The method was applied to the determination of OPD in spiked environmental water and industrial wastewater samples. Recoveries ranged from 96.8 to 100.3%. Graphical abstract Schematic presentation of a ratiometric fluorometric method for detection of o-phenylenediamine (OPD) based on copper nanoclusters (CuNCs). OPD is oxidized by Cu2+ present in CuNCs to form the oxidized form of o-phenylenediamine (oxOPD). FRET occurred between oxOPD and CuNCs, and the F557/F432 value is amplified.

A highly selective colorimetric sulfide assay based on the inhibition of the peroxidase-like activity of copper nanoclusters.

The authors report that sulfide ions are capable of inhibiting the peroxidase-like activity of copper nanoclusters (CuNCs). The catalytic activity of CuNCs toward the oxidation of the chromogenic substrate 3,3',5,5'-tetramethylbenzidine by H2O2 is remarkably decreased in the presence of sulfide. Based on this finding, a colorimetric assay was developed for the rapid determination of sulfide. Best operated at a wavelength of 652 nm, it has a 0.5 µM detection limit. The method is highly selective and has been successfully applied to the quantification of sulfide in environmental water samples. Graphical abstract The catalytic activity of CuNCs toward the oxidation of 3,3',5,5'-tetramethylbenzidine by H2O2 is remarkably decreased in the presence of sulfide ions. This finding has been applied to design a method for colorimetric quantification of sulfide ions in environmental samples.

Parasitism in Metal Nanoclusters: A Case Study of (AuAg)25·(AuAg)27.

Studying the interactions of atomically precise metal nanoclusters in their assembly systems is of great significance in the nanomaterial research field, which has attracted increasing interest in the last few decades. Herein, we report the cocrystallization of two oppositely charged atomically precise metal nanoclusters in one unit cell: [Au1Ag24(SR)18]- ((AuAg)25 for short) and [AuxAg27-x(Dppf)4(SR)9]2+ (x = 10-12; (AuAg)27 for short) with a 1:1 ratio. (AuAg)27 could maintain its structure in the presence of (AuAg)25, whether in the crystalline and the solution state, while the metastable (AuAg)27 component underwent a spontaneous transformation to (AuAg)16(Dppf)2(SR)8 after dissociating the (AuAg)25 component from this cocrystal, demonstrating the "parasitism" relationship of the (AuAg)27 component over (AuAg)25 in this dual-cluster system. This work enriches the family of cluster-based assemblies and elucidates the delicate relationship between nanoparticles of cocrystals.

Structure Effects of Ligands in Gold-Ligand Complexes for Controlled Formation of Gold Nanoclusters.

Metal nanoclusters (NCs) are a special class of nanoparticles composed of a precise number of metal atoms and ligands. Because the proportion of ligands to metal atoms is high in metal NCs, the ligand type determines the physical properties of metal NCs. Furthermore, ligands presumably govern the entire formation process of the metal NCs. However, their roles in the synthesis, especially as factors in the uniformity of metal NCs, are not understood. It is because the synthetic procedure of metal NCs is highly convoluted. The synthesis is initiated by the formation of various metal-ligand complexes, which have different numbers of atoms and ligands, resulting in different coordinations of metal. Moreover, these complexes, as actual precursors to metal NCs, undergo sequential transformations into a series of intermediate NCs before the formation of the desired NCs. Thus, to resolve the complicated synthesis of metal NCs and achieve their uniformity, it is important to investigate the reactivity of the complexes. Herein, we utilize a combination of mass spectrometry, density functional theory, and electrochemical measurements to understand the ligand effects on the reactivity of AuI-thiolate complexes toward the reductive formation of Au NCs. We discover that the stability of the complexes can be increased by either van der Waals interactions induced by the long carbon chain of ligands or by non-thiol functional groups in the ligands, which additionally coordinate with AuI in the complexes. Such structural effects of thiol ligands determine the reduction reactivity of the complexes and the amount of NaBH4 required for the controlled synthesis of the Au NCs.

White Light Emission from Zn(II) and DMSO-Induced Copper Nanocluster Assembly.

An assembly of metal nanoclusters driven by appropriate surface ligands and solvent environment may engender entirely new photoluminescence (PL). Herein, we first synthesize histidine (His) stabilized copper nanoparticles (CuNPs) and, subsequently, copper nanoclusters (CuNCs) from it using 3-mercaptopropionic acid (MPA) as an etchant. The CuNCs originally emit bluish-green (λem=470 nm) PL with a low quantum yield (QY∼1.8%). However, it transformed into a dual-emissive nanocluster assembly (Zn-CuNCs) in the presence of Zn(II) salt, having a distinct blue emission band (λem = 420 nm) and a red emission band (λem = 615 nm) with eight times QY (∼9.1%) enhancement. Adding dimethyl sulfoxide (DMSO) further modifies the emission intensities; the red band was amplified four times, while the blue band was diminished by 2.5 times. The transmission electron microscopy (TEM) images unveiled that the Zn-CuNCs are a large assembly of tiny nanoclusters, which become more compact in DMSO. The blue emission possesses steady-state fluorescence anisotropy, while the red emission shows no anisotropy. Further, near-perfect white light emission(WLE) was rendered with CIE coordinates of (0.33, 0.32) by combining the dual emission of the Zn-CuNCs with the original green emission of the CuNCs.

Recent advances in the biomolecules mediated synthesis of nanoclusters for food safety analysis.

The development of nanoclusters based on incorporating biomolecules like proteins, lipids, enzymes, DNA, surfactants, and chemical stabilizers creates a stable and high fluorescence bio-sensors promising future due to their high sensitivity, high level of detection and better selectivity. This review addresses a comprehensive and systematic overview of the recent development in synthesizing metal nanocluster by various strategized synthesis techniques. Significantly, the application of nanometal clusters for the detection of various food contaminants such as microorganisms, antibodies, drugs, pesticides, metal contaminants, amino acids, and other food flavors have been discussed briefly concerning the detection techniques, sensitivity, selectivity, and lower limit of detection. The review further gives a brief account on the future prospects in the synthesis of novel metal nanocluster-based biosensors, and their advantages, shortcomings, and potential perspectives toward their application in the field of food safety analysis.

Metal Nanoclusters Synthesized in Alkaline Ethylene Glycol: Mechanism and Application.

The "unprotected" metal and alloy nanoclusters (UMCs) prepared by the alkaline ethylene glycol method, which are stabilized with simple ions and solvent molecules, have the advantages of a small particle size, a narrow size distribution, good stability, highly efficient preparation, easy separation, surface modification and transfer between different phases. They can be composited with diverse materials to prepare catalytic systems with controllable structures, providing an effective means of studying the different factors' effects on the catalytic properties separately. UMCs have been widely used in the development of high-performance catalysts for a variety of functional systems. This paper will review the research progress on the formation mechanism of the unprotected metal nanoclusters, exploring the structure-function relationship of metal nanocluster catalysts and the preparation of excellent metal catalysts using the unprotected metal nanoclusters as building blocks or starting materials. A principle of the influence of carriers, ligands and modifiers in metal nanocluster catalysts on the catalytic properties is proposed.

Development and Functionalization of Visible-Light-Driven Water-Splitting Photocatalysts.

With global warming and the depletion of fossil resources, our fossil fuel-dependent society is expected to shift to one that instead uses hydrogen (H2) as a clean and renewable energy. To realize this, the photocatalytic water-splitting reaction, which produces H2 from water and solar energy through photocatalysis, has attracted much attention. However, for practical use, the functionality of water-splitting photocatalysts must be further improved to efficiently absorb visible (Vis) light, which accounts for the majority of sunlight. Considering the mechanism of water-splitting photocatalysis, researchers in the various fields must be employed in this type of study to achieve this. However, for researchers in fields other than catalytic chemistry, ceramic (semiconductor) materials chemistry, and electrochemistry to participate in this field, new reviews that summarize previous reports on water-splitting photocatalysis seem to be needed. Therefore, in this review, we summarize recent studies on the development and functionalization of Vis-light-driven water-splitting photocatalysts. Through this summary, we aim to share current technology and future challenges with readers in the various fields and help expedite the practical application of Vis-light-driven water-splitting photocatalysts.

Emerging Strategies in Enhancing Singlet Oxygen Generation of Nano-Photosensitizers Toward Advanced Phototherapy.

The great promise of photodynamic therapy (PDT) has thrusted the rapid progress of developing highly effective photosensitizers (PS) in killing cancerous cells and bacteria. To mitigate the intrinsic limitations of the classical molecular photosensitizers, researchers have been looking into designing new generation of nanomaterial-based photosensitizers (nano-photosensitizers) with better photostability and higher singlet oxygen generation (SOG) efficiency, and ways of enhancing the performance of existing photosensitizers. In this paper, we review the recent development of nano-photosensitizers and nanoplasmonic strategies to enhance the SOG efficiency for better PDT performance. Firstly, we explain the mechanism of reactive oxygen species generation by classical photosensitizers, followed by a brief discussion on the commercially available photosensitizers and their limitations in PDT. We then introduce three types of new generation nano-photosensitizers that can effectively produce singlet oxygen molecules under visible light illumination, i.e., aggregation-induced emission nanodots, metal nanoclusters (< 2 nm), and carbon dots. Different design approaches to synthesize these nano-photosensitizers were also discussed. To further enhance the SOG rate of nano-photosensitizers, plasmonic strategies on using different types of metal nanoparticles in both colloidal and planar metal-PS systems are reviewed. The key parameters that determine the metal-enhanced SOG (ME-SOG) efficiency and their underlined enhancement mechanism are discussed. Lastly, we highlight the future prospects of these nanoengineering strategies, and discuss how the future development in nanobiotechnology and theoretical simulation could accelerate the design of new photosensitizers and ME-SOG systems for highly effective image-guided photodynamic therapy.

Silver-enhanced fluorescence of bimetallic Au/Ag nanoclusters as ultrasensitive sensing probe for the detection of folic acid.

Folic acid (FA) is the natural form of water-soluble vitamins widely found in most plants and animal products and its deficiency leads to several human body abnormalities. The advancements of metal nanoclusters are highly increasing due to their molecule-like optical properties and attractive applications. Because of increasingly demand of noble metal nanoclusters as sensing templates, different synthesis methods have been developed for facile synthesis of noble metal nanoclusters. Herein, red-emitting fluorescent bovine serum albumin (BSA)-capped Au-Ag bimetallic NCs are facilely synthesized through green one-pot synthetic approach. The effect of silver on the fluorescence properties of Au NCs was investigated and it was found that introduction of silver can enhance the fluorescence intensity. The fluorescence intensity of the as-prepared Au-Ag nanoclusters gets quenched in the presence of folic acid in an aqueous medium and it was used as ultrasensitive sensing probe for FA detection. The developed Au-Ag NCs-based sensing probe shows linear response in the wide range of 0-100 µM and the detection limit is as low as 0.47 nM. Its applicability has also been confirmed successfully in real human serum, urine and FA tablet samples. Due to the high stability, sensitivity and selectivity, the developed bimetallic cluster sensing system is highly promising to be applied in the pharmaceutical and clinical laboratories.