Search Results (619)

Metal nanoclusters assembled using short peptides as templates exhibit significant potential for development and application in the fields of catalysis and biomedicine, owing to their distinctive electronic structure, favorable optical properties, and biocompatibility. Among them, tripeptides exhibit a simpler structure and greater flexibility, enabling them to readily co-assemble with other functional components to create novel materials with significant application value. They can be assembled with copper ions to synthesize highly efficient luminescent nanoclusters, which can serve as an effective fluorescent probe. Here, we report a method for the synthesis of copper nanoclusters (Cu NCs) using tripeptides as templates, which also act as stabilizers and reducing agents. The synthesis conditions and properties were explored and optimized. Under optimal conditions, the Cu NCs exhibit excellent stability and are strongly fluorescent. The Cu NCs can detect 0.1–1.0 μmol/L of ascorbic acid with a low detection limit of 0.075 μmol/L, demonstrating high sensitivity and offering significant application potential for the trace of ascorbic acid in various substances. It also provides new ideas for the assembly of metal nanoclusters and the construction of fluorescent probe sensing platforms. Full article

A stable and efficient porous nickel phosphate (p-NiPO/Ti) electrocatalyst on titanium sheets was developed via electrochemical deposition and low-temperature phosphatization. For obtaining the optimal performance of the p-NiPO/Ti electrocatalyst, the optimized experimental parameters of deposition and phosphatization were determined by parallel experiments. After the preparation, XPS and XRD were used to validate the chemical and amorphous structure, with SEM and TEM simultaneously validating a distinct nanosheet/nanocluster crosslinked microstructure. In particular, with phosphatization conditions maintained at 300 °C for 10 min, the p-NiPO/Ti produced demonstrated excellent charge transfer and catalytic characteristics in 1.0 M KOH. The electrocatalytic results revealed that the optimal p-NiPO/Ti with excellent catalytic performance and excellent stability (~24 h) needs lower HER overpotentials (128 mV at 10 mA cm⁻² and 242 mV at 100 mA cm⁻²) as inputs. This research provides a promising strategy with which to use transition metal materials as catalysts in alkaline electrocatalytic hydrogen production. Full article

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. Full article

The amorphous materials of the Ti₄₅Zr₃₈Ni₁₇ composition synthesized by mechanical alloying are widely recognized for their ability to store hydrogen with gravimetric densities above 2 wt.%. It is also known that those alloys can form a quasicrystalline state after thermal treatment and their structural and hydrogen sorption properties can be altered by doping with various elements. Therefore, in this paper, the results of the studies on the Ti₄₅Zr₃₈Ni₁₇ system with yttrium substituted for titanium and zirconium are presented. We demonstrate that these alloys are able to absorb hydrogen with a concentration of up to 2.7 wt.% while retaining their amorphous structure and they transform into the unique glassy-quasicrystal phase upon annealing. Furthermore, we demonstrate that the in-situ hydrogenation of those new materials is an effortless procedure in which the decomposition of the alloy can be avoided. Moreover, we prove that, in that process, hydrogen does not bind to any specific component of the alloy, which would otherwise cause the formation of simple hydrides or nanoclusters. Full article

Pt-based intermetallic compound (IMC) nanoparticles have been considered the most promising catalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFC). Herein, we propose a strategy for producing ordered Pt₃(CoNi) ternary IMC nanoparticles supported on N-doped carbon materials. Particularly, the Co and Ni are originally embedded into ZIF-derived carbon, which diffuse into Pt nanocrystals to form Pt₃(CoNi) nanoparticles. Moreover, a thin layer of carbon develops outside of Pt₃(CoNi) nanoparticles during the cooling process, which contributes to stabilizing the Pt₃(CoNi) on carbon supports. The optimal Pt₃(CoNi) nanoparticle catalyst has achieved significantly enhanced activity and stability, exhibiting a half-wave potential of 0.885 V vs reversible hydrogen electrode (RHE) and losing only 16 mV after 10,000 potential cycles between 0.6 and 1.0 V. Unlike the direct-use commercial carbon (VXC-72) for depositing Pt, we utilized ZIF-derived carbon containing dispersed Co and Ni nanocluster or nanoparticles to prepare ordered Pt₃(CoNi) intermetallic catalysts. Full article

The proposed paper describes a simple and environmentally friendly method for the synthesis of three-component polymer–inorganic composites, which includes the modification of zinc oxide or montmorillonite (MMT) with chitosan (CS), followed by the immobilization of palladium on the resulting two-component composites. The structures and properties of the obtained composites were characterized by physicochemical methods (IRS, TEM, XPS, SEM, EDX, XRD, BET). Pd–CS species covered the surface of inorganic materials through two different mechanisms. The interaction of chitosan polyelectrolyte with zinc oxide led to the deprotonation of its amino groups and deposition on the surface of ZnO. The immobilization of Pd on CS/ZnO occurred by the hydrolysis of [PdCl₄]²⁻, followed by forming PdO particles by interacting with amino groups of chitosan. In the case of CS/MMT, protonated amino groups of CS interacted with negative sites of MMT, forming a positively charged CS/MMT composite. Furthermore, [PdCl₄]²⁻ interacted with the –NH³⁺ sites of CS/MMT through electrostatic force. According to TEM studies of 1%Pd–CS/ZnO, the presence of Pd nanoclusters composed of smaller Pd nanoparticles of 3–4 nm in size were observed on different sites of CS/ZnO. For 1%Pd–CS/MMT, Pd nanoparticles with sizes of 2 nm were evenly distributed on the support surface. The prepared three-component CS–inorganic composites were tested through the hydrogenation of 2-propen-1-ol and acetylene compounds (phenylacetylene, 2-hexyn-1-ol) under mild conditions (T—40 °C, P_H2—1 atm). It was shown that the efficiency of 1%Pd–CS/MMT is higher than that of 1%Pd–CS/ZnO, which can be explained by the formation of smaller Pd particles that are evenly distributed on the support surface. The mechanism of 2-hexyn-1-ol hydrogenation over an optimal 1%Pd–CS/MMT catalyst was proposed. Full article

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. Full article

The ability to fabricate bimetallic clusters with atomic precision offers promising prospects for elucidating the correlations between their structures and properties. Nevertheless, achieving precise control at the atomic level in the production of clusters, including the quantity of dopant, characteristic of ligands, charge state of precursors, and structural transformation, have remained a challenge. Herein, we report the synthesis, purification, and characterization of a new bimetallic hydride cluster, [AuCu₁₁(H){S₂P(OⁱPr)₂}₆(C≡CPh)₃] (AuCu₁₁H). The hydride position in AuCu₁₁H was determined using DFT calculations. AuCu₁₁H comprises a ligand-stabilized defective fcc Au@Cu₁₁ cuboctahedron. AuCu₁₁H is metastable and undergoes a spontaneous transformation through ligand exchange into the isostructural [AuCu₁₁(Cl){S₂P(OⁱPr)₂}₆(C≡CPh)₃] (AuCu₁₁Cl) and into the complete cuboctahedral [AuCu₁₂{S₂P(OⁱPr)₂}₆(C≡CPh)₄]⁺ (AuCu₁₂) through an increase in nuclearity. These structural transformations were tracked by NMR and mass spectrometry. Full article

This study uses density functional theory to investigate boron nitride nanoclusters functionalized with amino acids for enhanced binding of bisphenols A (BPA) and Z (BPZ) to mimic the estrogen-related receptor gamma. Three categories of nanoclusters were examined: pristine B₁₂N₁₂, and those which were germanium-doped for boron or nitrogen. The study reveals that hydrogen bonding patterns and molecular stability are significantly influenced by the type of functional group and the specific amino acids involved. Ge-doping generally enhances the binding stability and spontaneity of the nanocluster–amino acid–bisphenol complexes, with Glu 275 emerging as the most stable binding site. The analysis of electronic properties such as energy gap, ionization potential, electron affinity, and chemical hardness before and after bisphenol binding indicates a general trend of increased reactivity, particularly in Ge-doped nanoclusters. The findings highlight the potential of these nanocluster composites in applications requiring high reactivity and electron mobility, such as pollutant removal and drug delivery. Full article

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. Full article

We analyzed a process to fabricate a superhydrophilic surface on copper by forming various laser-induced periodic surface structures (LIPSS) using a Ti/sapphire femtosecond laser. For these structured surfaces, the correlation between the surface structure and the wetting characteristics was analyzed by scanning electron microscopy, atomic force microscopy, and contact angle (CA) measurement. X-ray photoelectron spectroscopy (XPS) was also employed to analyze variation of the elemental composition of the surfaces. The laser treatment produced micro/nanostructures composed of ripples whose length and width are in microscale and nanoscale, respectively. At specific conditions, the CA of a water droplet was reduced to less than 1°. The superhydrophilcity is attributed to the effect of nanoholes and nanoclusters, which consist of copper (II) oxide and copper hydroxide, having a hydrophilic effect on LIPSS. However, the pristine superhydrophilic surface spontaneously became hydrophobic after being exposed to air at room temperature for about 10 days. According to XPS analysis, the surface’s transition to hydrophobic is attributed not only to the decomposition of Cu(OH)₂ but also to the adsorption of oxygen molecules and/or airborne organic molecules containing carbon, which further influences the wettability. Full article

Super-resolution single-molecule localization microscopy (SMLM) of presynaptic active zones (AZs) and postsynaptic densities contributed to the observation of protein nanoclusters that are involved in defining functional characteristics and in plasticity of synaptic connections. Among SMLM techniques, direct stochastic optical reconstruction microscopy (dSTORM) depends on organic fluorophores that exert high brightness and reliable photoswitching. While multicolor imaging is highly desirable, the requirements necessary for high-quality dSTORM make it challenging to identify combinations of equally performing, spectrally separated dyes. Red-excited carbocyanine dyes, e.g., Alexa Fluor 647 (AF647) or Cy5, are currently regarded as “gold standard” fluorophores for dSTORM imaging. However, a recent study introduced a set of chemically modified rhodamine dyes, including CF583R, that promise to display similar performance in dSTORM. In this study, we defined CF583R’s performance compared to AF647 and CF568 based on a nanoscopic analysis of Bruchpilot (Brp), a nanotopologically well-characterized scaffold protein at Drosophila melanogaster AZs. We demonstrate equal suitability of AF647, CF568 and CF583R for basal AZ morphometry, while in Brp subcluster analysis CF583R outperforms CF568 and is on par with AF647. Thus, the AF647/CF583R combination will be useful in future dSTORM-based analyses of AZs and other subcellularly located marker molecules and their role in physiological and pathophysiological contexts. Full article

Multifunctional targeted drug delivery systems have been explored as a novel cancer treatment strategy to overcome limitations of traditional chemotherapy. The combination of photodynamic therapy and chemotherapy has been shown to enhance efficacy, but the phototoxicity of traditional photosensitizers is a challenge. In this study, we prepared a multi-sensitive composite hydrogel containing gold nanoclusters (Au NCs) and the temperature-sensitive antitumor drug 5-fluorourac il (5-FU) using carboxymethyl cellulose (Carr) as a dual-functional template. Au NCs were synthesized using sodium borohydride as a reducing agent and potassium as a promoter. The resulting Au NCs were embedded in the Carr hydrogel, which was then conjugated with lactobionic acid (LA) as a targeting ligand. The resulting Au NCs/5-FU@Carr-LA composite hydrogel was used for synergistic photodynamic therapy (PDT), photothermal therapy (PTT), and chemotherapy. Au NCs/5-FU@Carr-LA releases the drug faster at pH 5.0 due to the acid sensitivity of the Carr polymer chain. In addition, at 50 °C, the release rate of Au NCs/5-FU@Carr-LA is 78.2%, indicating that the higher temperature generated by the photothermal effect is conducive to the degradation of Carr polymer chains. The Carr hydrogel stabilized the Au NCs and acted as a matrix for drug loading, and the LA ligand facilitated targeted delivery to tumor cells. The composite hydrogel exhibited excellent biocompatibility and synergistic antitumor efficacy, as demonstrated by in vitro and in vivo experiments. In addition, the hydrogel had thermal imaging capabilities, making it a promising multifunctional platform for targeted cancer therapy. Full article

Graphene oxide-silver poly(vinylidene fluoride) membranes (PVDF@GO-Ag) were successfully synthesized by the electrospinning method, which exhibited a high catalytic activity using the hydrogenation of 4-nitrophenol (4-NP) as a model reaction in a batch reaction study. The hybrid membranes doped with 1 wt% GO and 2 wt% Ag (PVDF-1-2) exhibited the most desired performance for the catalytic reduction of 4-NP. Importantly, PVDF-1-2 exhibited excellent cycling stability in 10 catalytic cycle tests and was highly amenable to separation. This property effectively addresses the significant challenges associated with the practical application of nanocatalysts. Furthermore, density-functional theory (DFT) calculations have demonstrated that the GO-Ag nanocomposites exhibit the strongest adsorption capacity for 4-NP⁻ when a specific ratio of GO and Ag is achieved, accompanied by the loading of Ag nanoclusters onto GO. Additionally, the study demonstrated that an increase in temperature significantly accelerated the reaction rate, in line with the van’t Hoff rule. This study provides an effective and environmentally friendly solution for the treatment of 4-NP in wastewater. Full article

Luminescent Ag nanoclusters (Ag NCs) are a promising probe material for sensing and bioimaging applications. However, the intrinsic obstacle of poor water stability and photostability greatly restrict their practical application in biological systems. Herein, we report the intracellular hypochlorite (ClO⁻) detection with amphiphilic copolymer-modified luminescent Ag NCs with good biocompatibility and photostability. The Ag NCs were synthesized by using chemically inert hydrophobic ligands and then modified with an amphiphilic (1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(poly(ethylene glycol))-2000]) (DSPE-PEG-2000) and sodium dodecyl sulfonate (SDS) for phase transfer. It was found that the approach of the removal of organic solvents during the phase transfer has remarkable influences on the properties of the Ag NCs, including their size, luminescence property, and aqueous stability. Furthermore, the silver core of Ag NCs could be oxidatively damaged by ClO⁻, thereby causing photoluminescence (PL) quenching. The ClO⁻-induced PL quenching was specific over the other common reactive oxygen species (ROS) as well as some common interferences. Finally, they have been successfully applied as a fluorescent nanoprobe for detecting exogenous and endogenous ClO⁻ in living cells. Full article