Search Results (215)

Herein, we propose a simple and cost-effective method for fabricating moderate-sensitivity surface-enhanced Raman scattering (SERS) substrates using Cu-plasma polymer fluorocarbon (Cu-PPFC) nanocomposite films fabricated through RF sputtering. The use of a composite target composed of carbon nanotube (CNT), Cu, and polytetrafluoroethylene (PTFE) powders (5:60–80:35–15 wt%) offers the advantage of the simple fabrication of moderate-sensitivity SERS substrates with a single cathode compared to co-sputtering. X-ray photoelectron spectroscopy (XPS) revealed that the film surface was partially composed of metallic Cu with Cu-F bonds and Cu–O bonds, confirming the coexistence of the conducting and plasmon-active domains. UV-VIS spectroscopy revealed a distinct absorption peak at approximately 680 nm, indicating the excitation of localized surface plasmon resonances in the Cu nanoclusters embedded in the plasma polymer fluorocarbon (PPFC) matrix. Atomic force microscopy and grazing incidence small-angle X-ray scattering analyses confirmed that the Cu nanoparticles were uniformly distributed with interparticle distances of 20–35 nm. The Cu-PPFC nanocomposite film with the highest Cu content (80 wt%) exhibited a Raman enhancement factor of 2.18 × 10⁴ for rhodamine 6G, demonstrating its potential as a moderate-sensitivity SERS substrate. Finite-difference time-domain (FDTD) simulations confirmed the strong electromagnetic field localization at the Cu-Cu nanogaps separated by the PPFC matrix, corroborating the experimentally observed SERS enhancement. These results suggest that a Cu-PPFC nanocomposite film, easily fabricated using a composite target, provides an efficient and scalable route for fabricating reproducible, inexpensive, and moderate-sensitivity SERS substrates suitable for practical sensing applications. Full article

Ruthenium-based catalysts supported on TiO₂, SnO₂, and WO₃ were synthesized via a microwave-assisted rapid reduction method and evaluated for the hydrogen evolution reaction (HER) in acidic media. The Ru species existed as highly dispersed nanoclusters, as confirmed by XRD and TEM, and the catalytic activity was strongly dependent on the oxide support. Ru/TiO₂ exhibited the best HER performance, achieving an overpotential of 187 mV at 10 mA·cm⁻² and a Tafel slope of 97.56 mV·dec⁻¹. While particle size differences (1.8–3.7 nm) did not account for the activity trend, XPS revealed distinct metal–support interactions that modulated the electronic state of Ru. Ru/TiO₂ showed an intermediate electron depletion that optimizes the Ru-H binding strength, explaining its superior kinetics. Regulation of Ru loading further identified Ru/15TiO₂ as the optimal catalyst, exhibiting low charge transfer resistance and excellent stability over 17 h. This study highlights the critical role of support-induced electronic modulation and loading engineering in designing efficient Ru-based electrocatalysts for acidic HER. Full article

Since Pt cocatalysts play an important role in photocatalytic H₂ evolution, it is necessary to track Pt over Pt/g-C₃N₄ catalysts during the evolution process to understand the associated photocatalytic deactivation behavior. In this study, bulk g-C₃N₄ (CN) and oxidized g-C₃N₄ (OCN) catalysts containing a Pt cocatalyst were prepared to investigate photocatalytic deactivation behavior through tracking changes in the catalytic properties of the Pt cocatalyst and g-C₃N₄ surface during photocatalytic H₂ evolution. While CN catalysts show a lower photocatalytic activity than OCN catalysts, the former exhibit high resistance to catalytic deactivation with a lower deactivation rate than the latter. The high photocatalytic activity of OCN catalysts is caused by the highly dispersed Pt species on chemically oxidized g-C₃N₄ with abundant O-containing functional groups, relating to the excellent separation efficiency of photogenerated electron/hole pairs. During the evolution process, highly dispersed Pt species over fresh OCN are easily and rapidly agglomerated into large Pt nanoclusters due to its exfoliated thin-layered g-C₃N₄ structure, whereas the three-dimensional multi-layered g-C₃N₄ structure of CN catalysts hinders the agglomeration of Pt over the CN catalyst. In addition, during the photocatalytic H₂ evolution, the O-containing functional groups on the OCN catalyst significantly disappear, which causes a weak metal/support interaction and, eventually, fast photocatalytic deactivation due to the agglomeration of Pt. Full article

Nanomaterials are widely used in biomedical research as drug and antibody carriers, and some nanomaterials have been shown to exhibit antimicrobial activity. Previously, silver nanoclusters (AgNCs) were predicted to interact with the bacterial TolC protein, which is involved in the development of multidrug resistance in pathogens. In this study, glutathione-coated AgNCs were synthesized and characterized. Their toxicological properties were studied in a microplate assay against five bacterial strains, both as single components and in mixtures with heavy metal salts and antibiotics. The resulting AgNCs had a diameter of 2.2 ± 0.5 nm, with excitation and emission maxima of λ = 490 nm and λ = 638 nm, respectively. No significant growth inhibition was observed at the concentrations used in resistance modulation assays (≤2.5 µg/mL Ag), except for transient effects at very high concentrations. A decrease in bacterial resistance to copper (II) and cadmium (II) cations and the antibiotics erythromycin and levofloxacin was observed upon the addition of AgNCs containing 2.5 μg/mL silver to the nutrient medium. A dose-dependent effect of AgNCs on bacterial resistance to toxicants was established. Thus, nanoclusters can be considered as inhibitors of bacterial resistance to heavy metals and antibiotics, which may be useful in studying bacterial adaptation mechanisms and developing technologies for overcoming multidrug resistance in bacteria. Full article

Photo-induced bond linkage isomerization (BLI) in metal–nitrosyl compounds provides a molecular mechanism for controlling light-induced changes in refractive index and phase modulation. In this study, the ground and metastable states of a series of Ru–NO complexes and their Au₂₀, Ag₂₀, and mixed Au₁₀Ag₁₀ nanocluster hybrids were investigated by DFT and TDDFT calculations. The photochemical rearrangement between the linear, side-on, and O-bound forms of Ru–NO was examined together with their electronic transitions, oscillator strengths, and characteristic vibrational shifts. From these data, parameters describing radiative efficiency, non-radiative coupling, and metastable-state stability were derived to identify compounds with favorable properties for holography and photonic applications. Particular attention was given to the [(Salen)Ru(NO)(HS)@Au₂₀] complex, which shows a strong red-to-NIR response and balanced stability among its linkage isomers. Frequency-dependent polarizabilities α(ω) were calculated for its ground and metastable states and compared with those of the classical holographic material [Fe(CN)₅NO]²⁻ (nitroprusside). The refractive-index changes derived from α(ω) reveal that the Au₂₀–salen hybrid produces a much larger and more strongly wavelength-dependent Δn(λ) than nitroprusside. At 635 nm, the modulation reaches approximately 0.06 for the hybrid, compared with 0.02 for nitroprusside. This enhancement reflects the cooperative effect of the Ru–NO chromophore and the Au₂₀ nanocluster, which amplifies both polarizability and optical dispersion. The results demonstrate that coupling molecular photo-linkage isomerism with nanoplasmonic environments can significantly improve the performance of molecular systems for holography and optical-phase applications. Full article

The surface modification of medical implant materials stands as a favorable strategy to enhance their biological properties including their antibacterial effect and biocompatibility. Recently, both in vitro and in vivo studies have shown that film heterostructures based on a combination of noble metal sublayers and an active component, such as silver and gold nanoparticles, offer unique advantages. The present work develops this promising direction and focuses on a series of combinations of noble metal coatings functionalized with bimetallic nanoclusters obtained by vapor-phase deposition methods onto the surfaces of Ti-based implants. This investigation investigates the influence of sequential deposition (AgAu or AuAg) and noble metal component (Ir or Au) on the coating morphology and the active component chemical form and release. Thus, scanning electron microscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma atomic emission spectroscopy have been applied to characterize the samples before and after in vivo biological studies (rat models, 1 and 3 months). Histological and blood analyses confirmed the high biocompatibility of all the heterostructures. The samples also showed a pronounced in vitro biocidal effect against Gram-positive (S. epidermalis) and Gram-negative (P. aeruginosa) bacteria that correlates with a dynamic of silver release. The AuAg/M heterostructures demonstrated superior biological characteristics compared to their AgAu/M counterparts, suggesting enhanced both long-term integration and antibacterial action. Full article

Liquid organic hydrogen carriers (LOHCs) are promising materials for safe, reversible, and high-density hydrogen storage. Atomically dispersed bimetallic Pt–Sn nanocluster catalysts supported on TiO₂ (Pt–Sn/TiO₂) were developed to enhance the hydrogenation step in the toluene-methylcyclohexane cycle, a model LOHC system. Compared with monometallic Pt/TiO₂ and Sn/TiO₂, Pt–Sn/TiO₂ exhibited superior hydrogenation performance. Mechanistic studies, including X-ray photoelectron spectroscopy, kinetic analysis, and H₂-D₂ exchange experiments, revealed that Sn incorporation modulates the electronic structure of Pt, enhancing H₂ activation and spillover. These findings provide insights into the rational design of atomically dispersed bimetallic nanocluster catalysts for efficient and durable hydrogen storage in LOHC-based systems. Full article

Photoactivatable nitric oxide donors (photoNORMs) are promising agents for controlled NO release and real-time optical tracking in biomedical theranostics. Here, we report a comprehensive density functional theory (DFT) and time-dependent DFT (TDDFT) study on a series of hybrid ruthenium–gold nanocluster systems of the general formula [(L)Ru(NO)(SH)@Au₂₀], where L = salen, bpb, porphyrin, or phthalocyanine. Structural and bonding analyses reveal that the Ru–NO bond maintains a formal {RuNO}⁶ configuration with pronounced Ru → π*(NO) backbonding, leading to partial reduction of the NO ligand and an elongated N–O bond. Natural Bond Orbital (NBO), Natural Energy Decomposition Analysis (NEDA), and Extended Transition State–Natural Orbitals for Chemical Valence (ETS–NOCV) analyses confirm that Ru–NO bonding is dominated by charge-transfer and polarization components, while Ru–S and Au–S linkages exhibit a delocalized, donor–acceptor character coupling the molecular chromophore with the metallic cluster. TDDFT results reproduce visible–near-infrared (NIR) absorption features arising from mixed metal-to-ligand and cluster-mediated charge-transfer transitions. The calculated zero–zero transition and reorganization energies predict NIR-II emission (1.8–3.8 μm), a region of high biomedical transparency, making these systems ideal candidates for luminescence-based NO sensing and therapy. This study establishes fundamental design principles for next-generation Ru-based photoNORMs integrated with plasmonic gold nanoclusters, highlighting their potential as multifunctional, optically trackable theranostic platforms. Full article

In this research article, a silicon carbide (SiC) nanocluster has been designed and characterized as an anode electrode for lithium (Li), sodium (Na), potassium (K), beryllium (Be), magnesium (Mg), boron (B), aluminum (Al) and gallium (Ga)-ion batteries through the formation of SiLiC, SiNaC, SiKC, SiBeC, SiMgC, SiBC, SiAlC and SiGaC nanoclusters. A vast study on energy-saving by SiLiC, SiNaC, SiKC, SiBeC, SiMgC, SiBC, SiAlC and SiGaC complexes was probed using computational approaches accompanying density state analysis of charge density differences (CDDs), total density of states (TDOS) and molecular electrostatic potential (ESP) for hybrid clusters of SiLiC, SiNaC, SiKC, SiBeC, SiMgC, SiBC, SiAlC and SiGaC. The functionalization of Li, Na, K, Be, Mg, B, Al and Ga metal/metalloid elements can raise the negative charge distribution of carbon elements as electron acceptors in SiLiC, SiNaC, SiKC, SiBeC, SiMgC, SiBC, SiAlC and SiGaC nanoclusters. Higher Si/C content can increase battery capacity through SiLiC, SiNaC, SiKC, SiBeC, SiMgC, SiBC, SiAlC and SiGaC nanoclusters for energy storage processes and to improve the rate performance by enhancing electrical conductivity. Full article

Gold (Au) and silver (Ag) nanoparticles (NPs) are used for drug transport and plant protection due to their insoluble nature and unique properties. To produce health-friendly NPs, toxic solvents should be replaced with plant-based synthesis. Plants, such as alfalfa (Medicago sativa L.), release biomolecules that reduce metal ions and form nanoclusters without free radicals, showing anti-inflammatory and antioxidant properties. In this study, callus cultures of two M. sativa genotypes, ‘Kometa’ and ‘La Bella Campagnola’, were exposed to two precursors (AgNO₃ and HAuCl₄) for 24 and 48 h to assess the feasibility of biological NP synthesis. Spectrophotometry showed significant (p ≤ 0.05) changes in light absorbance compared with the control. Dynamic light scattering and zeta potential measurements indicated a change in the composition of the liquid compared with the control. To improve image quality and obtain more accurate data, transmission electron microscopy (TEM) analysis was repeated, confirming the presence of quasi-spherical nanoparticles with diameters in the range of 5–25 nm for both AuNPs and AgNPs in the callus culture extracts of both genotypes. Nanoparticle Tracking Analysis demonstrated that the AgNPs and AuNPs from both genotypes displayed polydisperse size distributions, with a mean particle size ranging from 220 to 243 nm. Elemental analysis provided clear evidence that Ag and Au were present only in treated samples, confirming effective NP biosynthesis and excluding contamination. X-ray diffraction (XRD) analysis was performed to characterise the crystalline structure; however, due to the very small particle size (5–25 nm), no clear diffraction patterns could be obtained, as nanocrystals below ~20–30 nm typically produce signals below the detection limit of standard XRD instrumentation. The novelty of this research is the cost-effective, rapid biosynthesis of quasi-spherical AuNPs and AgNPs with diverse sizes and enhanced properties, making them more eco-friendly, less toxic, and suitable for antibacterial and anticancer studies. Full article

Gold (Au) is one of the noble metals most used as a catalyst in the growth of one-dimensional nanostructures. Usually, an ultra-thin Au film is coated followed by thermal annealing to obtain Au nanoclusters. Although annealing temperature, duration and film thickness parameters have been heavily studied, there are no studies on the sputter working gas pressure, which also greatly affects the film microstructure. In this study, low (5 mTorr) and high (15 mTorr) working gas pressures were examined in addition to Au film thicknesses of 2 nm, 5 nm and 8 nm. Additionally, copper indium gallium selenide (CIGS) films were deposited on Au films with different thicknesses and argon (Ar) gas pressures. It was confirmed from SEM and AFM images that the Au films undergo drastic morphology change from smooth to extremely porous film surfaces with increasing thickness regardless of gas pressure. However, the porosity of films is increased at higher growth pressure for each thickness. Specifically, the most porous film was obtained at a 5 nm thickness with 15 mTorr, and it was filled with nanomounds. Not surprisingly, the only apparent columnar-type formation was observed for CIGS deposition, which was carried out on the most porous film. It can be interpreted that Au nanomounds behave like catalysts on which the CIGS nanocolumns grow. Full article

This study presents a novel ratiometric fluorescent sensor based on Förster resonance energy transfer (FRET) between glutathione (GSH)-coated CdTe quantum dots (CdTe/GSH QDs) and bovine serum albumin (BSA)-coated Au nanoclusters (AuNCs/BSA) for dopamine (DA) detection. The nanoparticles were characterized using transmission electron microscopy (TEM), zeta potential measurements, Fourier transform infrared (FTIR) spectroscopy, UV-Vis absorption and fluorescence spectroscopy. Key FRET parameters, including energy transfer efficiency (E), donor–acceptor distance (r), Förster distance (R₀), and the overlap integral (J), were determined. The interactions between the CdTe/GSH-AuNCs/BSA conjugate and DA were investigated, revealing a dual mechanism of QDs fluorescence quenching that involves both energy and electron transfer. The average lifetime values and spectral profiles of CdTe/GSH QDs, both in the absence and presence of DA, suggest a dynamic fluorescence quenching process. The variation in the ratiometric signal with increasing DA concentration demonstrated a linear response within the range of 0–250 µM, with a correlation coefficient of 0.9963 and a detection limit of 6.9 nM. This proposed nanosensor exhibited selectivity against potential interfering substances, including urea, glucose, BSA, GSH, citric acid, and metal ions such as Na⁺ and Ca²⁺. The conjugate also demonstrates excellent cytocompatibility and enhances cell proliferation in HeLa epithelial cells, making it suitable for biological applications. It was successfully employed for DA detection in urine samples, achieving recoveries ranging from 99.1% to 104.2%. The sensor is highly sensitive, selective, rapid, and cost-effective, representing a promising alternative for DA detection across various sample types. Full article

Electrochemical CO₂ reduction reaction (CO₂RR) is a key technology for achieving carbon neutrality and efficient utilization of renewable energy, capable of converting CO₂ into high-value-added carbon-based fuels and chemicals. Copper (Cu)-based catalysts have attracted significant attention due to their unique performance in generating multi-carbon (C₂₊) products such as ethylene and ethanol; however, there are still many controversies regarding their complex reaction mechanisms, active sites, and the dynamic evolution of intermediates. In situ Raman spectroscopy, with its high surface sensitivity, applicability in aqueous environments, and precise detection of molecular vibration modes, has become a powerful tool for studying the structural evolution of Cu catalysts and key reaction intermediates during CO₂RR. This article reviews the principles of electrochemical in situ Raman spectroscopy and its latest developments in the study of CO₂RR on Cu-based catalysts, focusing on its applications in monitoring the dynamic structural changes of the catalyst surface (such as Cu⁺, Cu⁰, and Cu²⁺ oxide species) and identifying key reaction intermediates (such as *CO, *OCCO(*O=C-C=O), *COOH, etc.). Numerous studies have shown that Cu-based oxide precursors undergo rapid reduction and surface reconstruction under CO₂RR conditions, resulting in metallic Cu nanoclusters with unique crystal facets and particle size distributions. These oxide-derived active sites are considered crucial for achieving high selectivity toward C₂₊ products. Time-resolved Raman spectroscopy and surface-enhanced Raman scattering (SERS) techniques have further revealed the dynamic characteristics of local pH changes at the electrode/electrolyte interface and the adsorption behavior of intermediates, providing molecular-level insights into the mechanisms of selectivity control in CO₂RR. However, technical challenges such as weak signal intensity, laser-induced damage, and background fluorescence interference, and opportunities such as coupling high-precision confocal Raman technology with in situ X-ray absorption spectroscopy or synchrotron radiation Fourier transform infrared spectroscopy in researching the mechanisms of CO₂RR are also put forward. Full article

Metallic nanoclusters (NCs), composed of a few to a hundred atoms, occupy a unique space between molecules and nanoparticles, exhibiting discrete electronic states, strong photoluminescence, and size-dependent catalytic activity. Their ultrasmall cores (<3 nm) and ligand-controlled surfaces confer tunable optical, electronic, and catalytic properties, making them attractive for diverse applications. In recent years, significant progress has been made toward developing faster, more reproducible, and scalable synthesis routes beyond classical wet-chemical reduction. Emerging strategies such as microwave-, photochemical-, sonochemical-, and catalytically assisted syntheses, together with smart, automation-driven platforms, have improved efficiency, structural control, and environmental compatibility. These advances have accelerated the deployment of NCs in imaging, sensing, and catalysis. Near-infrared emitting NCs enable deep-tissue, high-contrast fluorescence imaging, while theranostic platforms combine diagnostic precision with photothermal or photodynamic therapy, gene delivery, and anti-inflammatory treatment. NC-based sensors allow ultrasensitive detection of ions, small molecules, and pathogens, and atomically precise NCs have enabled efficient CO₂ reduction, water splitting, and nitrogen fixation. Therefore, in this review, we highlight studies reported in the past five years on the synthesis and applications of metallic NCs, linking emerging methodologies to their functional potential in nanotechnology. Full article

Phase molybdenum disulfide (1T-MoS₂) holds significant promise as an anode material for sodium-ion batteries (SIBs) due to its metallic conductivity and expanded interlayer distance. However, the practical application of 1T-MoS₂ is hindered by its inherent thermodynamic metastability, which poses substantial challenges for the synthesis of high-purity, long-term stable 1T phase MoS₂. Herein, a synergetic ethanol molecule intercalation and electron injection engineering is adopted to induce the formation and stabilization of 1T-MoS₂ (E-1T MoS₂). The obtained E-1T MoS₂ consists of regularly arranged sphere-like ultrasmall few-layered 1T-MoS₂ nanosheets with expanded interlayer spacing. The high intrinsic conductivity and enlarged interlayer spacing are greatly favorable for rapid Na⁺ or e⁻ transport. The elaborated nanosheets structure can effectively relieve volume variation during Na⁺ intercalating/deintercalating processes, shorten transport path of Na⁺, and enhance diffusion kinetics. Furthermore, a novel sodium reaction mechanism involving the formation of MoS₂ nanoclusters during cycling is revealed to produce the higher surface pseudocapacitive contribution to Na⁺ storage capacity, accelerating Na⁺ reaction kinetics, as confirmed by the kinetics analysis and ex-situ structural characterizations. Consequently, the E-1T MoS₂ electrode exhibits an excellent sodium storage performance. This work provides an important reference for synthesis and reaction mechanism analysis of metastable metal sulfides for advanced SIBs. Full article