Search Results (18)

We report the development of highly luminescent, bovine serum albumin (BSA)-stabilized gold–silver bimetallic nanoclusters (Au-AgNCs@BSA) as a novel platform for high-sensitivity, ratiometric intracellular temperature sensing. Precise and non-invasive temperature sensing at the nanoscale is crucial for applications ranging from intracellular thermogenesis monitoring to localized hyperthermia therapies. Traditional luminescent thermometric platforms often suffer from limitations such as high cytotoxicity and low photostability. Here, we synthesized Au-AgNCs@BSA via a one-pot aqueous reaction, achieving significantly enhanced photoluminescence quantum yields (PL QYs, up to 18%) and superior thermal responsiveness compared to monometallic counterparts. The dual-emissive Au-AgNCs@BSA exhibit a linear ratiometric fluorescence response to temperature fluctuations within the physiological range (20–50 °C), enabling accurate and concentration-independent thermometry in live cells. Time-resolved PL and Arrhenius analyses reveal two distinct emissive states and a high thermal activation energy (E_a = 199 meV), indicating strong temperature dependence. Silver doping increases radiative decay rates while maintaining low non-radiative losses, thus amplifying fluorescence intensity and thermal sensitivity. Owing to their small size, excellent photostability, and low cytotoxicity, these nanoclusters were applied to non-invasive intracellular temperature mapping, presenting a promising luminescent nanothermometer for real-time cellular thermogenesis monitoring and advanced bioimaging applications. Full article

Palladium-doped silver nanoclusters (NCs) have been highlighted for their unique physicochemical properties and potential applications in catalysis, optics, and electronics. Anion-directed synthesis offers a powerful route to control the morphology and properties of these NCs. Herein, we report a novel Pd-doped Ag NC, [Pd(H)Ag₁₃(S){S₂P(OⁱPr)₂}₁₀] (PdHAg₁₃S), synthesized through the inclusion of sulfide and hydride anions. This NC features a unique linear S-Pd-H axis enclosed in a 4-5-4 stacked arrangement of silver atoms. The distinctive hydride environment was characterized by NMR spectroscopy, and the total structure was determined by single-crystal X-ray diffraction (SCXRD) and supported by computational studies. Mass spectrometry and X-ray photoelectron spectroscopy (XPS) further confirmed the assigned composition. This unique construct exhibits promising hydrogen evolution reaction (HER) activity. Our findings highlight the potential of anion-directed synthesis for creating novel bimetallic NCs with tailored structures and catalytic properties. Full article

The aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) plays a pivotal role in the synthesis of renewable, biodegradable plastics and sustainable chemicals. Although supported gold nanoclusters (NCs) exhibit significant potential in this process, they often suffer from low selectivity. To address this challenge, a series of gold-M (M means Ni, Fe, Cu, and Pd) bimetallic NCs catalysts were designed and synthesized to facilitate the selective oxidation of HMF to FDCA. Our findings indicate that the introduction of doped metals, particularly Ni and Pd, not only improves the reaction rates for HMF tandem oxidation but also promotes high yields of FDCA. Various characterizations techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), in situ diffuse reflectance infrared Fourier transform spectroscopy of CO adsorption (CO-DRIFTS), and temperature-programmed desorption of oxygen (O₂-TPD), were employed to scrutinize the structural and electronic properties of the prepared catalysts. Notably, an electronic effect was observed across the Au-based bimetallic catalysts, facilitating the activation of reactant molecules and enhancing the catalytic performance. This study provides valuable insights into the alloy effects, aiding in the development of highly efficient Au-based bimetallic catalysts for biomass conversions. Full article

Bimetallic nanoclusters have attracted great interest due to their ability to enhance the catalytic properties of nanoclusters through synergetic effects that emerge from the combination of the metal nanocluster with different transition metal (TM) species. However, their indefinite composition and broad distribution hinder the insightful understanding of the interaction between these invasive metals in bimetallic doped nanoalloys. In this study, we report a density functional theory calculation with the PBEsol exchange-correlation functional for 16-atom Ti_N−1TM (TM = Ni, Ir, Pd) nanoalloys, which provides new insights into the synergetic effect of these invasive metals. The probe into the effect of these metal impurities revealed that the replacement of a Ti atom with Ni, Ir and Pd enhances the relative stability of the nanoalloys, and the maximum stability for a lower bimetallic composition is reached for Ti₄Ir, Ti₅Pd and Ti₇Ni. The most stable nanoalloy is reached for the Ti₁₂Ir cluster in comparison with the Ti₁₂Pd and Ti₁₂Ni clusters and pure Ti₁₃ monoatomic nanocluster. This stability trend is as revealed well by both the binding energy and the dissociation energy. The average HOMO-LUMO gap for the bigger clusters revealed that the valence electrons in the HOMO can absorb lower energy, which is indicatory of a higher reactivity and lower stability. The quantum confinement is higher for the smaller clusters, which illustrates a higher stability and lower reactivity for those systems. Full article

In this paper, we explore the catalytic CO₂ reduction process on 13-atom bimetallic nanoclusters with icosahedron geometry. As copper and nickel atoms may be positioned in different locations and either separated into groups or uniformly distributed, the possible permutations lead to many unnecessary simulations. Thus, we have developed a machine learning model aimed at predicting the energy of a specific group of bimetallic (CuNi) clusters and their interactions with CO₂ reduction intermediates. The training data for the algorithm have been provided from DFT simulations and consist only of the coordinates and types of atoms, together with the related potential energy of the system. While the algorithm is not able to predict the exact energy of the given complex, it is able to select the candidates for further optimization with reasonably good certainty. We have also found that the stability of the complex depends on the type of central atom in the nanoparticle, despite it not directly interacting with the intermediates. Full article

The content of magnesium ions (Mg²⁺) in drinking water is relatively high and the excessive Mg²⁺ ingestion may lead to pathological lesions in the human body system. At present, the detection of Mg²⁺ still relies on costly devices or/and complex organic fluorescence probes. To solve this problem, this work proposed a NaBH₄-mediated co-reduction strategy for the synthesis of glutathione-stabilized bimetallic AuAg nanoclusters (GSH@AuAg NCs) with performance recognition to Mg²⁺. The preparation of GSH@AuAg NCs was simple and rapid and could be performed at mild conditions. The reaction parameters and sampling orders were optimized to understand the formation mechanism of GSH@AuAg NCs. The GSH@AuAg NCs exhibited a sensitive “light on” fluorescence response to Mg²⁺ due to the re-molding of the interfacial physicochemical environment following the Mg²⁺ coordination, which affected the surface charge transfer process, and thus led to a novel method for fluorescence detection of Mg²⁺ with admirable selectivity for Mg²⁺. The proposed method showed a detection limit of 0.2 μM, and its practical utility for the detection of Mg²⁺ in a real sample of purified drinking water was also demonstrated, confirming its practicability in monitoring the Mg²⁺ concentration in drinking water. Full article

Noble Metal nanoclusters (NCs) are promising electrochemiluminescence (ECL) emitters due to their amazing optical properties and excellent biocompatibility. They have been widely used in the detection of ions, pollutant molecules, biomolecules, etc. Herein, we found that glutathione-capped AuPt bimetallic NCs (GSH-AuPt NCs) emitted strong anodic ECL signals with triethylamine as co-reactants which had no fluorescence (FL) response. Due to the synergistic effect of bimetallic structures, the ECL signals of AuPt NCs were 6.8 and 94 times higher than those of monometallic Au and Pt NCs, respectively. The electric and optical properties of GSH-AuPt NCs differed from those of Au and Pt NCs completely. An electron-transfer mediated ECL mechanism was proposed. The excited electrons may be neutralized by Pt(II) in GSH-Pt and GSH-AuPt NCs, resulting in the vanished FL. Furthermore, abundant TEA radicals formed on the anode contributed electrons to the highest unoccupied molecular orbital of GSH-Au_2.5Pt NCs and Pt(II), booming intense ECL signals. Because of the ligand effect and ensemble effect, bimetallic AuPt NCs exhibited much stronger ECL than GSH-Au NCs. A sandwich-type immunoassay for alpha fetoprotein (AFP) cancer biomarkers was fabricated with GSH-AuPt NCs as signal tags, which displayed a wide linear range from 0.01 to 1000 ng·mL⁻¹ and a limit of detection (LOD) down to 1.0 pg·mL⁻¹ at 3S/N. Compared to previous ECL AFP immunoassays, this method not only had a wider linear range but also a lower LOD. The recoveries of AFP in human serum were around 108%, providing a wonderful strategy for fast, sensitive, and accurate cancer diagnosis. Full article

Nanocomposites serving as dual (bimodal) probes have great potential in the field of bio-imaging. Here, we developed a simple one-pot synthesis for the reproducible generation of new luminescent and magnetically active bimetallic nanocomposites. The developed one-pot synthesis was performed in a sequential manner and obeys the principles of green chemistry. Briefly, bovine serum albumin (BSA) was exploited to uptake Au (III) and Fe (II)/Fe (III) ions simultaneously. Then, Au (III) ions were transformed to luminescent Au nanoclusters embedded in BSA (AuNCs-BSA) and majority of Fe ions were bio-embedded into superparamagnetic iron oxide nanoparticles (SPIONs) by the alkalization of the reaction medium. The resulting nanocomposites, AuNCs-BSA-SPIONs, represent a bimodal nanoprobe. Scanning transmission electron microscopy (STEM) imaging visualized nanostructures with sizes in units of nanometres that were arranged into aggregates. Mössbauer spectroscopy gave direct evidence regarding SPION presence. The potential applicability of these bimodal nanoprobes was verified by the measurement of their luminescent features as well as magnetic resonance (MR) imaging and relaxometry. It appears that these magneto-luminescent nanocomposites were able to compete with commercial MRI contrast agents as MR displays the beneficial property of bright luminescence of around 656 nm (fluorescence quantum yield of 6.2 ± 0.2%). The biocompatibility of the AuNCs-BSA-SPIONs nanocomposite has been tested and its long-term stability validated. Full article

A significant emission enhancement (>100-fold) of glutathione-capped bimetallic gold and copper nanoclusters (AuCuNC@GSH) was achieved by assembling with Al³⁺ ions and by assembly-induced emission enhancement (AIEE). Further chelation of myricetin to Al³⁺ resulted in emission quenching of AuCuNC-Al³⁺, which was applied to specifically detect myricetin. Two linear responses were shown in the range of 0–1.5 μM and 1.5–50 μM, separately, leading to a low limit of detection at 8.7 nM. The method was successfully and accurately applied to myricetin determination in grape juice, which showed good application for real samples. Finally, the in-depth mechanism revealed that both the chelation of myricetin and Al³⁺ and the inner filter effect (IFE) between myricetin-Al³⁺ and AuCuNC-Al³⁺ greatly contributed to the quenching response of myricetin. Therefore, the present study provides an easy way to improve the fluorescence property of metal nanoclusters. Additionally, it supplies a cost-effective and easily performed approach to detect myricetin with high selectivity and sensitivity. Full article

Hydrogen gas production can be produced from dimethylamine borane by the catalytic effect of metal nanoparticles. Past research efforts were heavily focused on dehydrogenation in organic solvents. In this study, hydrolysis of the borane in aqueous solutions was investigated, which bears two significant advantages: that two-thirds of the hydrogen generated originate from water and that the hydrogen storage materials are non-flammable. Polymer hydrogels serve as good carriers for metal particles as catalysts in aqueous solutions. Kinetic analysis of hydrogen production was performed for Ni/Pd bimetallic nanoclusters dispersed in a polymer hydrogel with a 3-D network structure. The reaction catalyzed by the bimetallic nanoclusters has an activation energy of only 34.95 kJ/mol, considerably lower than that by Ni or other metal catalysts reported. A significant synergistic effect was observed in the Ni/Pd bimetallic catalysts (Ni–Pd = 20/1) with a higher activity than Pd or Ni alone. This proves the alloy nature of the nanoparticles in the borane hydrolysis and the activation of water and borane by both metals to break the O–H and B–H bonds. The hydrogel with the Ni/Pd metal can be recycled with a much longer lifetime than all the previously prepared catalysts. The aqueous borane solutions with a polymer hydrogel can become a more sustainable hydrogen supplier for long-term use. Full article

The search for a simple and effective method to remove organic dyes and color intermediates that threaten human safety from the water environment is urgent. Herein, we report a simple method for constructing iron/nickel phosphide nanocrystals anchored on N-B-doped carbon-based composites, using steam-exploded poplar (SEP) and graphene oxide (GO) as a carrier. The stability and catalytic activity of N-B-Ni_xFe_yP/SEP and GO were achieved by thermal conversion in a N₂ atmosphere and modifying the Fe/Ni ratio in gel precursors. N-B-Ni₇Fe₃P/SEP was employed for the catalytic hydrogenation of 4-nitrophenol (4-NP) and methylene blue (MB), using sodium borohydride in aqueous media at room temperature. This showed much better catalytic performances in terms of reaction rate constant (0.016 S⁻¹ and 0.041 S⁻¹, respectively) and the activity factor, K (1.6 S⁻¹·g⁻¹ and 8.2 S⁻¹·g⁻¹, respectively) compared to the GO carrier (0.0053 S⁻¹ and 0.035 S⁻¹ for 4-NP and MB, respectively). The strong interaction between the carrier’s morphology and structure, and the vertically grown bimetallic phosphide nanoclusters on its surface, enhances charge transfer, electron transfer kinetics at the interface and Ni-Fe phosphide dispersion on the nanoclusters, and prevents dissolution of the nanoparticles during catalysis, thereby improving stability and achieving catalysis durability. These findings provide a green and simple route to efficient catalyst preparation and provide guidance for the rational selection of catalyst carriers. Full article

Catalytic properties of noble-metal nanoparticles (NPs) are largely determined by their surface morphology. The latter is probed by surface-sensitive spectroscopic techniques in different spectra regions. A fast and precise computational approach enabling the prediction of surface–adsorbate interaction would help the reliable description and interpretation of experimental data. In this work, we applied Machine Learning (ML) algorithms for the task of adsorption-energy approximation for CO on Pd nanoclusters. Due to a high dependency of binding energy from the nature of the adsorbing site and its local coordination, we tested several structural descriptors for the ML algorithm, including mean Pd–C distances, coordination numbers (CN) and generalized coordination numbers (GCN), radial distribution functions (RDF), and angular distribution functions (ADF). To avoid overtraining and to probe the most relevant positions above the metal surface, we utilized the adaptive sampling methodology for guiding the ab initio Density Functional Theory (DFT) calculations. The support vector machines (SVM) and Extra Trees algorithms provided the best approximation quality and mean absolute error in energy prediction up to 0.12 eV. Based on the developed potential, we constructed an energy-surface 3D map for the whole Pd₅₅ nanocluster and extended it to new geometries, Pd₇₉, and Pd₈₅, not implemented in the training sample. The methodology can be easily extended to adsorption energies onto mono- and bimetallic NPs at an affordable computational cost and accuracy. Full article

Exploring the economical, powerful, and durable electrocatalysts for hydrogen evolution reaction (HER) is highly required for practical application. Herein, nanoclusters-decorated ruthenium, cobalt nanoparticles, and nitrogen codoped porous carbon (Ru-pCo@NC) are prepared with bimetallic zeolite imidazole frameworks (ZnCo-ZIF) as the precursor. Thus, the prepared Ru-pCo@NC catalyst with a low Ru loading of 3.13 wt% exhibits impressive HER catalytic behavior in 1 M KOH, with an overpotential of only 30 mV at the current density of 10 mA cm⁻², Tafel slope as low as 32.1 mV dec⁻¹, and superior stability for long-time running with a commercial 20 wt% Pt/C. The excellent electrocatalytic properties are primarily by virtue of the highly specific surface area and porosity of carbon support, uniformly dispersed Ru active species, and rapid reaction kinetics of the interaction between Ru and O. Full article

A highly active hydrotalcite-supported Ag/Pd bimetallic nanocluster catalyst has been developed by a simple, easy and safe chemical reduction method. The catalyst was characterized by high-resolution transmission electron microscopy (HR-TEM), which revealed very small (3.2 ± 0.7 nm) nanoclusters with a narrow size distribution. The bimetallic Ag/Pd catalyst showed strong cooperation between Ag and Pd for the alcohol oxidation reaction. The developed catalyst provided an efficient and environmentally friendly method for alcohol oxidation and one-pot cross-aldol condensation in water. A broad scope of α,β-unsaturated ketones with good to excellent yields were obtained under very mild conditions. This catalytic system offers an easy preparation method with a simple recovery process, good activity and reusability of up to five cycles without significant loss in the catalytic activity. Full article

Until recently, planar carbonaceous structures such as graphene did not show any birefringence under normal incidence. In contrast, a recently reported novel orthorhombic carbonaceous structure with metal nanoparticle inclusions does show intrinsic birefringence, outperforming other natural orthorhombic crystalline materials. These flake-like structures self-assemble during a laser-induced growth process. In this article, we explore the potential of this novel material and the design freedom during production. We study in particular the dependence of the optical and geometrical properties of these hybrid carbon-metal flakes on the fabrication parameters. The influence of the laser irradiation time, concentration of the supramolecular complex in the solution, and an external electric field applied during the growth process are investigated. In all cases, the self-assembled metamaterial exhibits a strong linear birefringence in the visible spectral range, while the wavelength-dependent attenuation was found to hinge on the concentration of the supramolecular complex in the solution. By varying the fabrication parameters one can steer the shape and size of the flakes. This study provides a route towards fabrication of novel hybrid carbon-metal flakes with tailored optical and geometrical properties. Full article