Silver Nanoclusters Research Articles

Chemiluminescent Fe3O4@Nickel-Cobalt Double Hydroxide Magnetic Core-Shell Nanomaterial as an Analytical Interface for Label-Free CYFRA21-1 Immunosensing.

Cytokeratin 19 fragment (CYFRA21-1) is considered to be a potential marker for the diagnosis and of classification of lung cancer. It is highly desired to develop rapid and highly sensitive label-free chemiluminescence (CL) immunosensors for the detection of CYFRA21-1. In this work, magnetic core-shell nanocomposite Fe3O4@nickel-cobalt double hydroxide (Fe3O4@DH) was used for the first time as a carrier to synthesize N-(4-aminobutyl)-N-ethylisoluminol (ABEI) and gold and silver nanocluster (AuAgNC) bifunctionalized magnetic nanomaterials Fe3O4@DH/AuAgNCs-ABEI. The resulting Fe3O4@DH/AuAgNCs-ABEI demonstrated excellent CL performance, attributed to the exceptional catalytic capability of nickel-cobalt double hydroxide (NiCo-DH) and AuAgNCs, as well as the large specific surface area of NiCo-DH for AuAgNCs and ABEI enrichment. Moreover, Fe3O4@DH/AuAgNCs-ABEI exhibited superior stability compared to Fe3O4-based CL-functionalized magnetic nanomaterials, owing to the presence of NiCo-DH shells. On this basis, a label-free CL immunosensor using CYFRA21-1 antibody-modified Fe3O4@DH/AuAgNCs-ABEI as an analytical interface was constructed for the detection of CYFRA21-1 in the range from 1.0 × 10-13 to 1.0 × 10-8 g/mL. The detection limit of this CL immunosensor was 47.7 fg/mL, 4 orders of magnitude lower than existing CL methods. The CL immunosensor was able to accurately detect the concentration of CYFRA21-1 in serum samples, as evidenced by ELISA results. More importantly, it not only distinguished well between healthy persons and lung cancer patients (90.0% sensitivity and 90.0% specificity), but also effectively distinguished between patients with non-small cell lung cancer and small cell lung cancer (80.0% sensitivity and 86.7% specificity).

Physical, optical properties and antibacterial activity of silver nanoparticles: Nanoclusters to nanoparticles formation on glass substrate by in-situ annealing

Silver nanoparticles (AgNPs) formed on in-situ annealed microscopic glass substrates from silver nanoclusters (AgNCs) generated by DC magnetron sputtering with inert gas condensation (IGC) technique. The substrate’s annealing temperature was below and above the glass transition temperature of 500 ºC and 600 ºC. The influence of annealing temperature on the surface morphology was studied using atomic force microscopy (AFM). X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) were employed to investigate the surface composition, chemical states, and electronic states of the AgNPs on the glass substrates. On the in-situ annealed glass substrate at 500 ºC, the produced AgNPs revealed accumulation and aggregation. For in-situ annealed at 600 ºC, a homogeneous distribution of AgNPs on the glass substrate was witnessed. The refractive index test revealed that AgNPs deposition at 600 ºC achieved higher sensitivity with 27nm/RIU (Refractive index unit). The antibacterial activity of AgNPs was also investigated using Escherichia coli and Bacillus cereus. In contrast, better antibacterial activity was obtained with in-situ annealing at 500 ºC, where 4-fold reductions compared with the control sample. Pre-determined properties can be precisely executed to achieve the desired performance as the so-called application-oriented engineered surface in the UHV system is established. This research highlighted the differences between two different annealing temperatures' effect on the base substrate material, which subsequently impacts the structure of AgNPs and their applications. Furthermore, the outcome of this work could contribute to the multifunctional surface for detecting heavy metals, various organic pollutants, and disinfection of water and food-borne pathogenic diseases.

Self-priming dumbbell probe-mediated cascade isothermal amplification for sensitive and label-free MICRORNA detection using fluorescence light-up silver nanocluster

Given the critical significance of microRNAs (miRNAs) in cancer diagnosis and classification (e.g., glioma), there is a need for the advancement of sensitive, specific, quantitative, and cost-effective approach for assessing miRNA expression levels. We present an effective amplification technology for ultrasensitive miRNA analysis by combining a self-priming dumbbell probe-mediated cascade isothermal amplification strategy with fluorescence-enhanced silver nanoclusters (DNA-AgNCs). The approach depends on the disassociation of the stem portion of the dumbbell probe through the binding of target miRNA, followed by self-priming mediated target recycling, DNA polymerase/endonuclease facilitated chain extension, and catalytic hairpin assembly (CHA) to provide an amplified signal. The CHA procedure generates an LP-AgNCs/LP-G duplex, wherein the fluorescence signals of DNA-AgNCs can be significantly amplified when in close proximity to guanine-rich (G-rich) DNA sequences. The proposed label-free assay, characterized by high sensitivity, a wide dynamic range (spanning 6 orders of magnitude), excellent specificity (capable of detecting single-base differences), and simple operation, has been successfully utilized for the detection of miRNA in real samples. This demonstrates its potential as a compelling alternative for miRNA analysis in gene expression profiling and molecular diagnostics, especially for early glioma cancer detection.

Single-atom “surgery” on chiral all-dialkynyl-protected superatomic silver nanoclusters

Single-atom “surgery” on chiral all-dialkynyl-protected superatomic silver nanoclusters

In situ synthesis of well-dispersed silver nanoparticles from silver nanoclusters hydrogel for catalytic reduction of 4-Nitrophenol

In situ synthesis of well-dispersed silver nanoparticles from silver nanoclusters hydrogel for catalytic reduction of 4-Nitrophenol

Electroless Copper Patterning on TiO2-Functionalized Mica for Flexible Electronics

The formation of conductive copper patterns on mica holds promise for developing cost-effective flexible electronics and sensing devices, though it is challenging due to the low adhesion of mica’s atomically flat surface. Herein, we present a wet-chemical method for copper patterning on flexible mica substrates via electroless copper deposition (Cu-ELD). The process involves pre-functionalizing 50 µm thick muscovite mica with a titanium dioxide (TiO2) layer, via a sol–gel dip-coating method with a titanium acetylacetonate-based sol. Photolithography is employed to selectively activate the TiO2-coated mica substrates for Cu-ELD, utilizing in situ photodeposited silver (Ag) nanoclusters as a catalyst. Copper is subsequently plated using a formaldehyde-based Cu-ELD bath, with the duration of deposition primarily determining the thickness and electrical properties of the copper layer. Conductive Cu layers with thicknesses in the 70–130 nm range were formed within 1–2 min of deposition, exhibiting an inverse relationship between plating time and sheet resistance, which ranged from 600 to 300 mΩ/sq. The electrochemical thickening of these layers to 1 μm further reduced the sheet resistance to 27 mΩ/sq. Finally, the potential of Cu-ELD patterning on TiO2-functionalized mica for creating functional sensing devices was demonstrated by fabricating a functional resistance temperature detector (RTD) on the titania surface.

Automatic metabolism modulator for glycolytic intervention‐induced cascade cancer therapy

AbstractEffective intervention in glycolytic metabolism is a promising way to inhibit tumor malignant invasion. However, the inherent hypoxia environment and unitary regulating model subsequently compromise its therapeutic efficacy. Herein, a facile way to design an automatic metabolism modulator (auto‐MMOD) is developed by loading glucose oxidase (GOx) and DNA‐templated silver nanoclusters (DNA‐AgNCs) into a pH‐responsive zeolitic imidazolate frameworks‐8 (ZIF‐8) nanocarrier, which can activate a cascaded metal ion‐killing effect during GOx‐regulated glycolysis metabolism. When the acidic lysosome microenvironment induces ZIF‐8 decomposition, the released GOx can effectively consume glucose and generate H2O2, thus inhibiting Adenosine Triphosphate synthesis and accelerating tumor starvation. Moreover, the released Ag+ in response to H2O2 can disturb bioenergy metabolism to inhibit tumor proliferation, which further enhances the tumor‐killing effect in hypoxic microenvironments. This study achieves effective tumor suppression in vitro and in vivo by integrating ion therapy into glycolysis intervention, which establish a promising strategy for nano‐theranostics.

Dynamically Confined Active Silver Nanoclusters with Ultrawide Operating Temperature Window in CO oxidation.

Supported metal nanoclusters are often highly active in many catalytic reactions but less stable particularly under harsh reaction conditions. Here, we demonstrate that this activity-stability trade-off can be efficiently broken through rational design of surrounding microenvironment of the supported nanocatalyst including gas adsorbate overlayer and underneath support surface chemistry. Our studies reveal that chemisorbed oxygen species on Ag surface and surface hydroxyl groups on oxide support, which are dynamically consumed during reaction but sustained by reaction environment (O2 and H2O vapor), drive spontaneous redispersion of Ag particles and stabilization of highly active Ag nanoclusters. Such a dynamic confinement effect from gas-catalyst-support interaction enables the Ag nanoclusters to exhibit complete catalytic oxidation of CO over a wide temperature window of 25 - 500 °C under dry conditions and 200 - 800 °C under wet conditions as well as remarkable stability at 300 °C over 1000 h.

Dynamically Confined Active Silver Nanoclusters with Ultrawide Operating Temperature Window in CO oxidation

Supported metal nanoclusters are often highly active in many catalytic reactions but less stable particularly under harsh reaction conditions. Here, we demonstrate that this activity‐stability trade‐off can be efficiently broken through rational design of surrounding microenvironment of the supported nanocatalyst including gas adsorbate overlayer and underneath support surface chemistry. Our studies reveal that chemisorbed oxygen species on Ag surface and surface hydroxyl groups on oxide support, which are dynamically consumed during reaction but sustained by reaction environment (O2 and H2O vapor), drive spontaneous redispersion of Ag particles and stabilization of highly active Ag nanoclusters. Such a dynamic confinement effect from gas‐catalyst‐support interaction enables the Ag nanoclusters to exhibit complete catalytic oxidation of CO over a wide temperature window of 25 ‐ 500 °C under dry conditions and 200 ‐ 800 °C under wet conditions as well as remarkable stability at 300 °C over 1000 h.

Silver Nanoclusters-Decorated Porous Microneedles Coupling Duplex-Specific Nuclease-Assisted Signal Amplification for Sampling and Detection of MicroRNA in Interstitial Fluid.

MicroRNAs (miRNAs) in dermal interstitial fluid (ISF) have recently been recognized as clinically promising biomarkers for the diagnosis and prognosis of cancer. However, the detection poses significant challenges, primarily due to the low abundance of miRNAs and the limitations of current sampling techniques. To address this issue, we develop novel porous microneedles (PMNs) array-based sensor composed of poly(vinyl alcohol) porous hydrogel and DNA-templated silver nanoclusters (AgNCs) to facilitate the enrichment and highly sensitive detection of ISF miRNA. Leveraging the capillary action facilitated by its unique porous structure and the swelling properties of the hydrogel, the PMNs array can efficiently extract 2.7 ± 0.3 mg of ISF within 5 min. Additionally, the interconnected pores within the PMNs array contribute to an increased specific surface area, thereby offering a convenient platform for the decoration of DNA-templated AgNCs. The immobilized large amount of AgNCs effectively capture the target miRNA from the extracted ISF, resulting in miRNA-induced fluorescence quenching of AgNCs. Subsequently, the introduction of the duplex-specific nuclease leads to the cleavage of DNA in DNA-RNA heteroduplexes, which release miRNA to interact with other AgNCs. This process of target recycling triggers a further reduction in fluorescence intensity, thereby enabling sensitive detection of the low-abundant miRNA down to 1.6 pM. Both in vitro and in vivo experiments validate the efficacy of the AgNCs immobilized PMNs array for the detection of miRNA biomarkers in ISF within minutes. These results indicate that the proposed PMNs array-based sensor holds great potential for the development of noninvasive personalized diagnostic strategies.

Active Learning of Boltzmann Samplers and Potential Energies with Quantum Mechanical Accuracy.

Extracting consistent statistics between relevant free energy minima of a molecular system is essential for physics, chemistry, and biology. Molecular dynamics (MD) simulations can aid in this task but are computationally expensive, especially for systems that require quantum accuracy. To overcome this challenge, we developed an approach combining enhanced sampling with deep generative models and active learning of a machine learning potential (MLP). We introduce an adaptive Markov chain Monte Carlo framework that enables the training of one normalizing flow (NF) and one MLP per state, achieving rapid convergence toward the Boltzmann distribution. Leveraging the trained NF and MLP models, we compute thermodynamic observables such as free energy differences and optical spectra. We apply this method to study the isomerization of an ultrasmall silver nanocluster belonging to a set of systems with diverse applications in the fields of medicine and catalysis.

Innovative fluorescent aptasensor for sensitive tropomyosin detection in shrimp products using DNA-templated silver nanoclusters and catalytic hairpin assembly

Innovative fluorescent aptasensor for sensitive tropomyosin detection in shrimp products using DNA-templated silver nanoclusters and catalytic hairpin assembly

Stirring-Controlled Synthesis of Ultrastable, Fluorescent Silver Nanoclusters.

This paper describes how macroscopic stirring of a reaction mixture can be used to produce nanostructures exhibiting properties not readily achievable via other protocols. In particular, it is shown that by simply adjusting the stirring rate, a standard glutathione-based method-to date, used to produce only marginally stable fluorescent silver nanoclusters, Ag NCs-can be boosted to yield nanoclusters retaining fluorescence for unprecedented periods of over 2 years. This enhancement derives not simply from increased homogenization of the reaction mixture but mainly from an appropriately timed delivery of oxygen from above the reaction mixture. In effect, oxygen serves as a reagent that dictates size, structure, stability, and functional properties of the growing nanoobjects.

A Fluorescence Enhancement Sensor Based on Silver Nanoclusters Protected by Rich-G-DNA for ATP Detection.

In this study, a turn-on fluorescence sensor for the detection of adenosine 5'-triphosphate (ATP) was developed and tested using ATP-DNA2-Ag NCs. The results showed that the fluorescence of ATP-DNA2-Ag NCs was significantly enhanced with the addition of ATP. The fluorescence enhancement was a result of the specific binding activity of the ATP aptamer and ATP, which caused G-rich sequences to approach the dark DNA-Ag NCs, owing to the alteration in ATP aptamer conformation. The proposed sensor demonstrated a good linear range of 18-42 mM and a limit of detection (LOD) of 2.8 μM. The sensor's features include sensitivity, selectivity, and simple operation. In addition, the proposed sensor successfully measured ATP in 100-fold diluted fetal bovine serum.

Multi-Objective Design of DNA-Stabilized Nanoclusters Using Variational Autoencoders With Automatic Feature Extraction.

DNA-stabilized silver nanoclusters (AgN-DNAs) have sequence-tuned compositions and fluorescence colors. High-throughput experiments together with supervised machine learning models have recently enabled design of DNA templates that select for AgN-DNA properties, including near-infrared (NIR) emission that holds promise for deep tissue bioimaging. However, these existing models do not enable simultaneous selection of multiple AgN-DNA properties, and require significant expert input for feature engineering and class definitions. This work presents a model for multiobjective, continuous-property design of AgN-DNAs with automatic feature extraction, based on variational autoencoders (VAEs). This model is generative, i.e., it learns both the forward mapping from DNA sequence to AgN-DNA properties and the inverse mapping from properties to sequence, and is trained on an experimental data set of DNA sequences paired with AgN-DNA fluorescence properties. Experimental testing shows that the model enables effective design of AgN-DNA emission, including bright NIR AgN-DNAs with 4-fold greater abundance compared to training data. In addition, Shapley analysis is employed to discern learned nucleobase patterns that correspond to fluorescence color and brightness. This generative model can be adapted for a range of biomolecular systems with sequence-dependent properties, enabling precise design of emerging biomolecular nanomaterials.

Simultaneous detection of CaMV35S and NOS using fluorescence sensors with dual-emission silver nanoclusters and catalytic hairpin amplification strategy.

Adual-emission fluorescent biosensing method was developed for simultaneous determinationof CaMV35S and NOS in genetically modified(GM) plants. Two designed hairpin DNA (H1, H2) sequences were used as templates to synthesize H1-AgNCs (λex = 570nm, λem = 625nm) and H2-AgNCs (λex = 470nm, λem = 555nm). By using H1-AgNCs and H2-AgNCs as dual-signal tags, combined with signal amplification strategy of magnetic separation to reduce background signal and an enzyme-free catalytic hairpin assembly (CHA) signal amplification strategy, a novel multi-target fluorescent biosensor was fabricated to detect multiple targets based on FRET between signal tags (donors) and magnetic Fe3O4 modified graphene oxide (Fe3O4@GO, acceptors). In the presence of the target NOS and CaMV35S, the hairpin structures of H1 and H2 can be opened respectively, and the exposed sequences will hybridize with the G-rich hairpin sequences HP1 and HP2 respectively, displacing the target sequences to participate in the next round of CHA cycle. Meanwhile, H1-HP1 and H2-HP2 double-stranded DNA sequences (dsDNA) were formed, resulting in the desorption of dsDNA from the surface of Fe3O4@GO due to weak π-π interaction between dsDNA and Fe3O4@GO and leading to the fluorescence recovery of AgNCs. Under optimal conditions, the linear ranges of this fluorescence sensor were 5 ~ 300nmol L-1 for NOS and 5 ~ 200nmol L-1 CaMV35S, and the LODs were 0.14nmol L-1 and 0.18nmol L-1, respectively. In addition, the fluorescence sensor has good selectivity for the detection of NOS and CaMV35S in GM soybean samples, showing the potential applications in GM screening.

Dual emission BSA-capped bimetallic nanoclusters for detection of acrylamide in certain food matrices based on thiol-ene Michael addition click reaction

Dual-emissive gold and silver nanoclusters stabilized by bovine serum albumin (BSA@Au-Ag NCs) were engineered for the precise and sensitive estimation of acrylamide (ACM). The probe demonstrated emissions at 630 nm and 405 nm upon excitation at 320 nm. Decreasing the fluorescence of the probe at 630 nm was observed upon cysteine (Cys) addition while the emission band at 405 nm experienced a slight increase. The introduction of ACM into the probe led to the recovery of fluorescence at 630 nm, while the fluorescence at 405 nm remained largely unaffected. This selective response provides a ratiometric method for determining ACM. A linear relationship between the response ratio (F630/F405) and ACM concentration was established in the range of 0.12–450 µM, with LOD of 0.03 µM. The fluorescent probe boasts several advantages, including a low LOD, robustness against interference, and reliability. Furthermore, the synthesized probe was deployed for detecting ACM in certain food matrices. The recovery percentages ranged from 96.5 to 102.6 %, with RSD between 2.98 and 4.87 %, thus affirming the potential practical applications of the fluorescent probe.

Bacterial-responsive biodegradable silver nanoclusters composite hydrogel for infected wound therapy

Skin wounds are susceptible to bacterial infections, which hinder healing and extend recovery. Herein, we designed a silver nanoclusters (Ag NCs) composite hydrogel for infected wound treatment via bacterial enzymatic degradation and Ag release. Using biocompatible gelatine and polyethylene glycol as the main components, DNA-templated Ag NCs were covalently linked to a polymer network to obtain the final nanocomposite hydrogel. This hydrogel exhibited good compressive and tensile stiffness, bioadhesion and water absorption. The overexpressed bacterial enzymes protease and DNase in the infected wound were hydrolysed by the gel matrix, subsequently releasing antibacterial Ag ions. In vitro experimental results proved that the hydrogel demonstrated excellent bactericidal effect on Staphylococcus aureus and Escherichia coli, which are commonly implicated in clinical wound infections. Animal experiments revealed that the hydrogel considerably promoted cell proliferation and wound healing with less inflammatory responses. Thus, these results demonstrate strategies for bacterial enzyme–responsive Ag release for infected wound healing, facilitating further development of intelligent bandages.

Conversion of Ultrasmall Glutathione-Coated Silver Nanoparticles during Dispersion in Water into Ultrasmall Silver Sulfide Nanoparticles.

Ultrasmall silver nanoparticles (2 nm) were prepared by reduction with sodium borohydride (NaBH4) and stabilized by the ligand glutathione (a tripeptide: glycine-cysteine-glutamic acid). NMR spectroscopy and optical spectroscopy (UV and fluorescence) revealed that these particles initially consist of silver nanoparticles and fluorescing silver nanoclusters, both stabilized by glutathione. Over time, the silver nanoclusters disappear and only the silver nanoparticles remain. Furthermore, the capping ligand glutathione eliminates hydrogen sulfide (H2S) from the central cysteine and is released from the nanoparticle surface as tripeptide glycine-dehydroalanine-glutamic acid. Hydrogen sulfide reacts with the silver core to form silver sulfide. After four weeks in dispersion at 4 °C, this process is completed. These processes cannot be detected by transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), or differential centrifugal sedimentation (DCS) as these methods cannot resolve the mixture of nanoparticles and nanoclusters or the nature of the nanoparticle core. X-ray photoelectron spectroscopy showed the mostly oxidized state of the silver nanoparticle core, Ag(+I), both in freshly prepared and in aged silver nanoparticles. These results demonstrate that ultrasmall nanoparticles can undergo unnoticed changes that considerably affect their chemical, physical, and biological properties. In particular, freshly prepared ultrasmall silver nanoparticles are much more toxic against cells and bacteria than aged particles because of the presence of the silver clusters.

Synthesis of a Gold–Silver Alloy Nanocluster within a Ring‐Shaped Polyoxometalate and Its Photocatalytic Property

AbstractAlloying is an effective method for modulating metal nanoclusters to enrich their structural diversity and physicochemical properties. Recent investigations have demonstrated that polyoxometalates (POMs) can act as effective multidentate ligands for silver (Ag) nanoclusters to endow them with synergistic properties, reactivity, catalytic properties, and stability. However, the application of POMs as ligands has been confined predominantly to monometallic nanoclusters. Herein, we report a synthetic method for fabricating surface‐exposed gold (Au)−Ag alloy nanoclusters within a ring‐shaped POM ([P8W48O184]40−). Reacting an Ag nanocluster stabilized by the ring‐shaped POM with Au ions (Au+) was found to substitute several Ag atoms at the core of the nanocluster with Au atoms. The resultant {Au8Ag26} alloy nanocluster demonstrated superior photocatalytic activity and stability compared to the pristine Ag nanocluster in the aerobic oxidation of α‐terpinene under visible‐light irradiation. These findings provide fundamental insights into the formation and catalytic properties of POM‐stabilized alloy nanoclusters and advance exploration into the synthesis and applications of diverse metal nanoclusters.