Synthesis Of Nanoclusters Research Articles

Synthesis of Silver Nanoclusters and Nanoparticles in the Medium of Hyperbranched Polyester Polyamine, and the Morphology and Aggregation Properties of the Metal–Polymer Nanocomposite

Synthesis of Silver Nanoclusters and Nanoparticles in the Medium of Hyperbranched Polyester Polyamine, and the Morphology and Aggregation Properties of the Metal–Polymer Nanocomposite

Towards Green Synthesis of Fluorescent Metal Nanoclusters.

In the modern development of nanoscience and nanotechnology, metal nanoclusters have emerged as a foremost category of nanomaterials exhibiting remarkable biocompatibility and photo-stability having dramatically distinctive optical, electronic, and chemical properties. This review focuses on synthesizing fluorescent metal nanoclusters in a greener way to make them suitable for biological imaging and drug delivery application. The green methodology is the desired route for sustainable chemical production and should be utilized for any form of chemical synthesis including nanomaterials. It aims to eliminate harmful waste, uses non-toxic solvents, and employs energy-efficient processes for the synthesis. This article provides an overview of conventional synthesis methods, including stabilizing nanoclusters by small organic molecules in organic solvents. Then we focus on the improvement of properties, applications of green synthesized metal nanoclusters, challenges involved, and further advancement required in the direction of green synthesis of MNCs. There are plenty of problems for scientists to solve to make nanoclusters suitable for bio-applications, chemical sensing, and catalysis synthesized by green methods. Using bio-compatible and electron-rich ligands, understanding ligand-metal interfacial interactions, employing more energy-efficient processes, and utilizing bio-inspired templates for synthesis are some immediate problems worth solving in this field that requires continued efforts and interdisciplinary knowledge and collaboration.

The synthesis of gold nanoclusters with high stability and their application in fluorometric detection for Hg2+ and cell imaging

Sensing Hg2+ is significant to protecting human health and environmental ecosystems, for its toxicity and genotoxicity. Here, highly stable fluorescent folic acid (FA)-protected Au nanoclusters (FA-AuNCs) were synthesized by optimizing the reactive parameters with high quantum yield of 34.7%. Main components of Au4L were confirmed by MALDI-TOF, and the electron-rich residues of FA shell enabled FA-AuNCs excellent photostability. FA-AuNCs exhibited sensitive response behavior to Hg2+ with a minimum detectability of 1.3 nM, and presented extreme effect to the detection of Hg2+ in real water. Notably, the cellular imaging and in-situ detection of Hg2+ in cells can be achieved visually. The high selectivity was attributed to the chemical bond formed between Au+ (4f145d10) and Hg2+ (4f145d10). And the internal filter effect and static quenching effect were proved triggering the quenching of FA-AuNCs. The ultra-stable FA-AuNCs provide a potential promising opportunity for the in-situ tracing Hg2+ from environmental and biological samples.

A universal approach for synthesis of copper nanoclusters templated by G-rich oligonucleotide sequences and their applications in sensing

Herein, five common G4 sequences have been selected, including three different length of telomere DNA, hemin aptamer, and thrombin aptamer, to synthesize Cu nanoclusters (Cu NCs) in-situ. All G4s are proper templates for Cu NCs with low temperature treatment. The particles (G4-Cu NCs) smaller than 3 nm in diameter were obtained and showed light green fluorescence. This is the first report of metal clusters templated by G4s in-situ. As proof of the concept, hemin and alkaline phosphatase (ALP) were used as the targets to test whether the system can monitor the interaction between G4s and its substrate. The results suggest that G4-Cu NCs can indicate the behavior of G4 and its interaction with hemin, and sensing ALP is achieved with the aid of ATP. The linear ranges of hemin and ALP are 300–4000 nM and 10–500 U/L, respectively, and the corresponding limits of detection as low as 97 nM for hemin and 2.8 U/L for ALP. Moreover, this present system has been successfully applied for the detection of ALP in human serum samples with satisfactory recoveries. This synthesis approach is universal, and it can be easily extended to evaluating the formation of G4, or monitoring the interaction between G4 and its substrate, or selective targeting individual G4, or sensitive detection of other important biomarkers by changing template G4 sequence.

Exploration of the Atomic Pathway of Seed-Mediated Growth from Icosahedral [Au25(SR)18]− to Bi-Icosahedral Au38(SR)24 and Au44(SR)26 Clusters Based on the 2e– Hopping Mechanism

Size growth is ubiquitous in the gold nanocluster synthesis. However, the atomic-level mechanism of seed-mediated growth of gold clusters remains mysterious. In this study, the seed-mediated growth pathway from the icosahedral [Au25(SR)18]- cluster to the bi-icosahedral Au38(SR)24 and Au44(SR)26 clusters is studied based on the two-electron (2e-) hopping mechanism. First, atomic structures of three key intermediate clusters, [Au29(SR)20]-, [Au33(SR)22]-, and Au41(SR)25, are predicted based on the 2e--unit decomposition strategy. The theoretically simulated UV-Vis spectra based on the predicted structure model of [Au29(SR)20]- and [Au33(SR)22]- matched well with the experimental curves reported previously. Based on the predicted intermediate cluster structures, the size growth pathway from the eight-electron (8e-) [Au25(SR)18]- cluster to 14-electron (14e-) Au38(SR)24 and 18-electron (18e-) Au44(SR)26 clusters is determined. In the step of formation of bi-icosahedral Au38(SR)24 from icosahedral [Au25(SR)18]-, two Au4 units are first formed. The third 2e- hopping step results in formation of an icosahedron unit. The present studies offered new insights into the formation and size conversion mechanism of ligand-protected gold nanoclusters containing icosahedral cores.

Carbon-Anchored Molybdenum Oxide Nanoclusters as Efficient Catalysts for the Electrosynthesis of Ammonia and Urea.

The electrochemical NO3 - reduction and its coupling with CO2 can provide novel and clean routes to synthesize NH3 and urea, respectively. However, their practical application is still impeded by the lack of efficient catalysts with desirable Faradaic efficiency (FE) and yield rate. Herein, we report the synthesis of molybdenum oxide nanoclusters anchored on carbon black (MoOx /C) as electrocatalyst. It affords an outstanding FE of 98.14 % and NH3 yield rate of 91.63 mg h-1 mgcat. -1 in NO3 - reduction. Besides, the highest FE of 27.7 % with a maximum urea yield rate of 1431.5 μg h-1 mgcat. -1 toward urea is also achieved. The formation of electron-rich MoOx nanoclusters with highly unsaturated metal sites in the MoOx /C heterostructure is beneficial for enhanced catalytic performance. Studies on the mechanism reveal that the stabilization of *NO and *CO2 NOOH intermediates are critical for the NH3 and urea synthesis, respectively.

Carbon‐Anchored Molybdenum Oxide Nanoclusters as Efficient Catalysts for the Electrosynthesis of Ammonia and Urea

AbstractThe electrochemical NO3− reduction and its coupling with CO2 can provide novel and clean routes to synthesize NH3 and urea, respectively. However, their practical application is still impeded by the lack of efficient catalysts with desirable Faradaic efficiency (FE) and yield rate. Herein, we report the synthesis of molybdenum oxide nanoclusters anchored on carbon black (MoOx/C) as electrocatalyst. It affords an outstanding FE of 98.14 % and NH3 yield rate of 91.63 mg h−1 mgcat.−1 in NO3− reduction. Besides, the highest FE of 27.7 % with a maximum urea yield rate of 1431.5 μg h−1 mgcat.−1 toward urea is also achieved. The formation of electron‐rich MoOx nanoclusters with highly unsaturated metal sites in the MoOx/C heterostructure is beneficial for enhanced catalytic performance. Studies on the mechanism reveal that the stabilization of *NO and *CO2NOOH intermediates are critical for the NH3 and urea synthesis, respectively.

Crown Ether-Capped Gold Nanoclusters as a Multimodal Platform for Bioimaging.

The distinct polarity of biomolecule surfaces plays a pivotal role in their biochemistry and functions as it is involved in numerous processes, such as folding, aggregation, or denaturation. Therefore, there is a need to image both hydrophilic and hydrophobic bio-interfaces with markers of distinct responses to hydrophobic and hydrophilic environments. In this work, we present a synthesis, characterization, and application of ultrasmall gold nanoclusters capped with a 12-crown-4 ligand. The nanoclusters present an amphiphilic character and can be successfully transferred between aqueous and organic solvents and have their physicochemical integrity retained. They can serve as probes for multimodal bioimaging with light (as they emit near-infrared luminescence) and electron microscopy (due to the high electron density of gold). In this work, we used protein superstructures, namely, amyloid spherulites, as a hydrophobic surface model and individual amyloid fibrils with a mixed hydrophobicity profile. Our nanoclusters spontaneously stained densely packed amyloid spherulites as observed under fluorescence microscopy, which is limited for hydrophilic markers. Moreover, our clusters revealed structural features of individual amyloid fibrils at a nanoscale as observed under a transmission electron microscope. We show the potential of crown ether-capped gold nanoclusters in multimodal structural characterization of bio-interfaces where the amphiphilic character of the supramolecular ligand is required.

Guiding Metal Organic Framework Morphology via Monolayer Artificial Defect-Induced Preferential Facet Selection.

Guiding metal organic framework (MOF) morphology, especially without the need for chemical additives, still remains a challenge. For the first time, we report a unique surface guiding approach in controlling the crystal morphology formation of zeolitic imidazole framework-8 (ZIF-8) and HKUST-1 MOFs on disrupted alkanethiol self-assembled monolayer (SAM)-covered Au substrates. Selective molecule removal is applied to generate diverse SAM matrices rich in artificial molecular defects in a monolayer to direct the dynamic crystal growth process. When a 11-mercaptoundecanol alkanethiol monolayer is ruptured, the hydroxyl tail groups of surface residue molecules act as nucleating sites by coordination with precursor metal ions. Meanwhile, the exposed alkane chain backbones stabilize a particular facet of MOF nuclei in the dynamic growth by slowing down their crystal growth rates along a specific direction. The competitive formation between the [110] and [100] planes of ZIF-8 ultimately regulates the crystal shapes from rhombic dodecahedron, truncated rhombic dodecahedron, and truncated cube to cube. Similarly, changeable morphologies of HKUST-1 crystals are also achieved from cube and tetrakaidekahedron to octahedron, originating from the competitive selection between the [100] and [111] planes. In addition to the artificial matrix preferred orientation of initial nucleation, parameters such as temperature also play a crucial role in the resulting crystal morphology. Standing on the additive-free MOF crystal morphology growth control, porous architectures prepared in this approach can act as templates for ligand-free metal (Au, Ag, and Cu) nanocluster synthesis. The nanocluster-embedded MOF structures represent distinct crystal morphology-dependent optical properties, and interestingly, their fluorescence emission can be highly enhanced by facet-induced nanocluster packing alignments. These findings not only provide a unique thought on MOF crystal morphology guidance but also pave a new route for the accompanied property investigation and further application.

Rapid microwave heating and fast quenching for the highly efficient production of long-term stable supported Ag nanoclusters

Given the exciting potential of metallic clusters in a variety of fields, the development of novel preparation methods to accurately controlling the cluster size has become a research priority. Specifically, for catalytic applications, the synthesis and deployment of metallic nanoclusters on a proper substrate is perhaps the main bottleneck. Here, we have adopted an alternative reactor that uses simultaneous ice cooling and microwave heating (unlike water ice is a low microwave absorber) for the synthesis of Ag nanoclusters directly over a support with ordered mesopores (SBA-15). The reactor design exploits the selectivity of microwave heating, assuring a rapid localized nucleation followed by a nearly instantaneous quenching that largely avoids the aggregation of nascent clusters as well as Ostwald ripening mechanisms. We have compared this new synthesis approach with some previously reported methods for the production of supported silver nanoclusters: conventional batch reactor and also a continuous flow microreactor. The resulting Ag clusters were initially analyzed in terms of size distribution, textural properties and catalytic activity in the reduction of 4-nitrophenol. Finally, encouraged by the good results obtained, these nanoclusters were also employed in the production of different cyclic organic compounds, building blocks for pharmaceutical and photochemical applications. The nanoclusters displayed a high catalytic activity, lowering the metal loading required to achieve high yield and selectivity. Furthermore, the stabilization of the clusters over the mesoporous substrate allowed their reuse in several reaction cycles. In fact, the method produced exceptionally stable Ag clusters, whose catalytic properties were preserved even after one year of storage.

Microwave-assisted synthesis of blue fluorescent molybdenum nanoclusters with maltose-cysteine Schiff base for detection of myoglobin and γ-aminobutyric acid in biofluids.

The fabrication of stable fluorescent MoNCs (molybdenum nanoclusters) in aqueous media is quite challenging as it is not much explored yet. Herein, we report a facile and efficient strategy for fabricating MoNCs using 2,3 dialdehyde maltose-cysteine Schiff base (DAM-cysteine) as a ligand for detecting myoglobin and γ-aminobutyric acid (GABA) in biofluids with high selectivity and sensitivity. The DAM-cysteine-MoNCs displayed fluorescence of bright blue color under a UV light at 365 nm with an emission peak at 444 nm after excitation at 370 nm. The synthesized DAM-cysteine-MoNCs were homogeneously distributed with a mean size of 2.01 ± 0.98 nm as confirmed by the high-resolution transmission electron microscopy (HR-TEM). Further, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR) techniques were utilized to confirm the elemental oxidation states and surface functional groups of the DAM-cysteine-MoNCs. After the addition of myoglobin and GABA, the emission peak of DAM-cysteine-MoNCs at 444 nm was significantly quenched. This resulted in the development of a quantitative assay for the detection of myoglobin (0.1-0.5μM) and GABA (0.125-2.5μM) with the lower limit of detection as 56.48 and 112.75 nM for myoglobin and GABA, respectively.

Direct continuous synthesis of macroRAFT-grafted Fe3O4 nanoclusters for the preparation of magnetic nanocomposites

A new method for synthesizing magnetic nanocomposite latex particles with a significant magnetic response and high coating rate is reported herein. Based on a micro-flow platform, Fe3O4 nanoclusters grafted with macroRAFT agents were continuously synthesized within 90 s. The obtained clusters present high mono-dispersity, narrow size distribution, and excellent saturation magnetization. Moreover, the macroRAFT polymer chains grafted on the surface of the nanoclusters can be reactivated for polymerizing hydrophobic monomers without using any surfactant, to achieve the coating of magnetic particles. The resulting polymer shell can protect the magnetic core and maintain a substantial magnetic response. Furthermore, by optimising the reaction conditions, the encapsulation efficiency can be significantly improved for the efficient preparation of magnetic nanocomposites.

Effect of membrane depolarization against Aspergillus niger GM31 resistant by ultra nanoclusters characterized by Ag2+ and Ag3+ oxidation state

To date, the impossibility of treating resistant forms of bacteria and fungi (AMR) with traditional drugs is a cause for global alarm. We have made the green synthesis of Argirium silver ultra nanoclusters (Argirium-SUNCs) very effective against resistant bacteria (< 1 ppm) and mature biofilm (0.6 ppm). In vitro and preclinical tests indicate that SUNCs are approximately 10 times less toxic in human cells than bacteria. Unique chemical-physical characteristics such as particle size < 2 nm, a core composed of Ag0, and a shell of Ag +, Ag2+ , Ag3+ never observed before in stable form in ultra pure water, explain their remarkable redox properties Otto Cars (Lancet Glob. Health 9:6, 2021). Here we show that Argirium-SUNCs have strong antimicrobial properties also against resistant Aspergillus niger GM31 mycelia and spore inactivation (0.6 ppm). The membrane depolarization is a primary target leading to cell death as already observed in bacteria. Being effective against both bacteria and fungi Argirium-SUNCs represent a completely different tool for the treatment of infectious diseases.

N-doped and sulfur vacancy-rich TiO2@SnS2 nanoporous arrays for the plasmonic photocatalytic H2 evolution

An elegant templating method has been developed for the rational design and synthesis of hierarchical SnS2 nanoclusters composed of ultrathin nanosheets and embedded inside TiO2 nanoporous arrays. Herein, benefiting from their unique structural merits and metal-like plasmonic activity, the TiO2@SnS2 heterostructures exhibit enhanced photocatalytic H2 evolution properties in terms of good cycling performance. S vacancies and N-doping are proved to be vitally important to the electronic structures and bandgap of SnS2, thus influence the plasmonic property and separation of photo-carriers. The optimized TiO2@6nmSnS2/N nanoporous arrays give an ultra-high H2 yield rate of 285 μmol h−1cm−2 under a low catalyst loading mass, that comparable to most noble metal catalysts. Remarkable cycling performance with a capability retention of 90% is achieved after 30 h under solar light illumination. As an innovative exploration, this study demonstrates that the photocatalytic activities of nonmetal, earth-abundant SnS2 can be enhanced with plasmonic effect, which may serve as an excellent catalytic agent for solar energy conversion to chemical fuel.

The synthesis of tunable fluorescence iron nanoclusters and the detection of pH value and hydroxyl radical

In this work, we developed a novel route for the synthesis of fluorescent iron nanoclusters (Hb-Fe NCs) in aqueous solution with natural protein and amino acid as the original materials. Moreover, the fluorescence emission of Hb-Fe NCs were adjustable from red to blue fluorescence by regulating the dosage of sodium hydroxide in the synthesis process. We have examined the fluorescence response of Hb-Fe NCs in various temperature, metal ions or biomolecules environment, and exhibited excellent stability in the complex environment. Furthermore, the fluorescence of Hb-Fe NCs gradually enhanced as the pH value of environment increased from 5.0 to 9.0. More importantly, the fluorescence of Hb-Fe NCs can be inhibited significantly by hydroxyl radical (OH·).

Self-assembly and phase transition of gold nanoclusters in natural deep eutectic solvent for visual detection of toxicants in water environment

Ecological damage derived from water pollution has increased greatly accompanying by the development of industries, which promotes the exploration of water environment monitoring platform. Structure-oriented synthesis of gold nanoclusters (NADES-Au NCs) based on novel natural deep eutectic solvent (NADES), has been successfully obtained without the use of any stabilizer or capping agents. With the pH stability and photobleaching resistance in the complex environment, spongy NADES-Au NCs showed superior optical properties than other forms. Moreover, this green sensing platform based on NADES-Au NCs displayed two well-separated emission peaks at 440 and 669 nm, respectively. There was a linear range of 0.5–200 µM with a detection limit of 0.25 µM for Hg2+ and a linear range of 1–150 µM with a detection limit of 0.12 µM for nitroanilines. Such NADES-Au NCs demonstrated the satisfactory recoveries and reliabilities in water samples, which presented great potential of water pollution detection. Simultaneously, the application of NADES as a green solvent for the synthesis of metal nanoclusters may provide new avenues for sensing platform.

Synthesis of Se nanoclusters via Ostwald ripening process: in vitro antibacterial and antioxidant activity

Synthesis of Se nanoclusters via Ostwald ripening process: in vitro antibacterial and antioxidant activity

Facile Biological-Based Synthesis of Size-Controlled Palladium Nanoclusters Anchored on the Surface of Geobacter sulfurreducens and Their Application in Electrocatalysis

Metal nanoclusters can be synthesized following the top-down or bottom-up approaches involving multiple chemical and/or physical steps where strong ligands, toxic chemicals, and high temperature and pressure are normally applied. In contrast, biological methods eliminate the use and generation of hazardous substances and do not require the application of high temperature and pressure during the synthesis process. Biological methods based on the extracellular electron transfer (EET) capability of electroactive bacteria (EAB) are considered a promising sustainable route for the synthesis of metal nanoparticles; however, a fine control of the size of the nanoparticles has not been achieved yet. Herein, we report a facile biological-based synthesis method of size-controlled palladium (Pd) nanoclusters using the EET capability of Geobacter sulfurreducens. By controlling the metal precursor concentrations and dosing and incubation times, we synthesized size-controlled Pd nanoclusters (1.0 ± 0.6 to 4.8 ± 1.4 nm) anchored on the surface of G. sulfurreducens. The as-synthesized Pd nanoclusters anchored on the surface of G. sulfurreducens cells (Pd/GS) were tested for their performance as bifunctional electrocatalysts for the overall alkaline water splitting reaction. Despite a very low mass loading of 0.002 mg Pd cm–2, the hybrid material (i.e., Pd/GS) showed exceptionally higher activity for hydrogen evolution reaction (HER) when compared to benchmark 10 wt % Pt/C and Pd/C. Similarly, Pd/GS showed higher activity for oxygen evolution reaction (OER) when compared to Pd/C and comparable OER activity when compared to benchmark IrO2. The findings in this study provide a promising sustainable route for designing size-controlled metal nanoclusters anchored on the surface of EAB as efficient and low-cost electrocatalysts for various applications.

An amplified logic gate driven by in situ synthesis of silver nanoclusters for identification of biomarkers.

An amplified DNA logic sensor was constructed for the identification of multiple biomarkers, in which the inputs of targets triggered the disassembly of a V-shaped probe (VSP) structure by a strand displacement reaction, leading to the synthesis of silver nanoclusters (AgNCs) for electrocatalytic reduction of H2O2. The sensing platform achieved sensitive detection of methylated DNA and microRNA 122 with detection limits down to 3.4 and 4.1 fM, respectively, and can be used for the assay of clinical serum samples from healthy volunteers and liver injury patients with satisfactory results. The DNA logic sensor exhibited the advantages of convenience, low cost, and versatility without the involvement of electroactive label modification, which is helpful for disease diagnosis as well as the fundamental investigation of interfacial electrochemistry and molecular biology.

Анализ термического профиля при моделировании начального этапа синтеза из газовой фазы наночастиц Cu-Au

The production of particles from the gas phase is one of the main physical methods for the synthesis of nanostructured materials, the obvious advantages of which include good control of the target composition of the resulting nanomaterial. However, the determination of clear dependences between the initial parameters of experimental setups and the size of nanoparticles is not an easy task, requiring a detailed study of the processes of formation, growth, and agglomeration of nanoclusters. Another problem is that metal nanoparticles of identical chemical composition and size can be in different structural states or have different levels of defects. The processes underlying the formation of the structure of such nanoparticles are also not completely clear, especially at the very initial stage of synthesis from the moment of decomposition of precursors to the formation of primary stable nuclei. Therefore, in the presented work, the molecular dynamics method was used to simulate the process of synthesis of Cu-Au nanoclusters of various target compositions from the high-temperature gas phase. Based on the data obtained, conclusions were drawn about the main stages of the evolution of the model system. It is shown that the initial stage of synthesis consists of five different stages, gradually leading to the formation of primary spherical CuAu binary alloy nanoparticles with a clear extrusion of gold atoms to the surface.