Search Results (55)

Ni/Siral catalysts with different Si/Al ratios were prepared by incipient wetness impregnation (IWI) to assess the impact of support composition on Ni²⁺ speciation and ethylene oligomerization (EO) performance. The catalysts were characterized by X-ray photoelectron spectroscopy (XPS), H₂ temperature-programmed reduction (TPR), X-ray diffraction (XRD), NH₃ temperature-programmed desorption (TPD), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) with energy-dispersive X-ray (EDX) analysis, and diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS). The EO catalysts were tested in a fixed-bed reactor at 225 °C under 11 bar ethylene and at 120 °C under 26 bar ethylene. Ni/Siral-70 was the most active catalyst investigated, but Ni/Siral-30 also exhibited good performance. The active sites were inferred to be isolated Ni²⁺ ions on amorphous SiO₂-Al₂O₃ containing interstitial Al³⁺ ions that enhance Brønsted acidity; Ni/Siral-70 displayed the highest concentration of these sites based on CO DRIFTS. Formation of NiAl₂O₄ surface species limited the activity of Ni/Siral-30 and especially Ni/Siral-5. The catalysts were also tested using a simulated ethane oxidative dehydrogenation (ODH) product stream containing 44% ethylene, 44% ethane, 4.5% methane, 2% H₂, 4.5% CO₂, 0.9% propylene, and 0.1% CO. The simulated ODH mixture gave lower EO conversion than 50/50 ethylene/N₂ at 225 °C and 11 bar over Ni/Siral-30, consistent with catalyst poisoning. In contrast, EO conversion over the Ni/Siral-70 catalyst was unaffected under these conditions. Catalyst testing at 120 °C and 26 bar revealed catalyst poisoning by feed impurities for both catalysts. Low-temperature/high-pressure EO activity was not recovered by simple thermal regeneration of Ni/Siral-30 at 300 °C. Full article

Silver (Ag) and gold (Au) nanoparticles (NPs) are widely used in biomedicine, electronics, and catalysis, but their potential toxicity raises occupational health concerns. This study assessed the cytotoxicity and cellular interactions of Ag and Au NPs in human bronchial epithelial cells (BEAS-2B) using a standardized OECD three-tiered approach, alongside characterization of lung-deposited surface area (LDSA) concentrations during NP synthesis, which remained within ranges typically reported in occupational environments. Transmission electron microscopy revealed that AgNPs formed irregular clusters (~8.7 nm primary size, >30 nm aggregates), whereas AuNPs remained spherical (~13.4 nm). Real-time cytotoxicity analysis (xCELLigence) showed acute toxicity of AgNPs at 5 μg/cm², while AuNPs exhibited no cytotoxic effects. Dark-field and 3D hyperspectral imaging demonstrated that some AgNPs were internalized by BEAS-2B cells, whereas AuNPs remained mostly on the cell surface, indicating that uptake alone does not determine cytotoxicity. The greater dissolution potential of AgNPs and possible release of Ag⁺ ions may contribute to the enhanced cytotoxic effects observed in comparison to AuNPs, as suggested in previous studies. Although oxidative stress, mitochondrial dysfunction, and related cellular mechanisms were not directly assessed in the present study, the findings demonstrate differential cellular responses following nanoparticle exposure under realistic occupational exposure conditions. These results contribute to understanding nanoparticle–cell interactions and support the need for further mechanistic investigations to inform safer nanomaterial use. Full article

The influence of pre-deformation on the microstructure and mechanical properties of a Mg-rich high-Cu Al-Mg-Si-Cu alloy was systematically investigated by hardness measurement, tensile test, and atomic resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). With the increase in pre-deformation strain (0–10%), the hardness and strength of the alloy after PB hardening increased progressively, accompanied by a continuous reduction in tensile elongation. Notably, increasing pre-deformation strain from 2% to 10% did not bring a significant enhancement in bake hardening response, despite the gradual improvement in the strain hardening capability of the alloy. An optimal pre-deformation strain of 5% is identified, which enabled the alloy to achieve a superior and industrially feasible combination of strength and ductility, balancing practical forming demand (T4 temper) and service performance (PB state). Pre-deformation can significantly affect the morphology and atomic structure of precipitates for the alloy. Dislocations introduced by pre-deformation acted as heterogeneous nucleation sites, inducing the formation of elongated and string-like precipitates along dislocation lines. A distinct Cu segregation behavior was observed in the pre-deformed alloy with the majority of Cu atoms segregated at the precipitate/α-Al interface, which was in sharp contrast to their dominant distribution within the precipitate interior in the non-pre-deformed alloy. These findings provide new insights into deformation-assisted precipitation regulation in Mg-rich high-Cu Al-Mg-Si-Cu alloys and offer practical guidance for optimizing the strength–ductility synergy of such alloys for automotive lightweight manufacturing applications. Full article

Catalytic ozonation often suffers from a low ozone utilization rate and incomplete mineralization of organic pollutants. To address these challenges, we designed and prepared a novel catalyst via a one-step thermal polymerization method, anchoring single-atom manganese on a glucose-derived carbon network-modified C₃N₅ framework (Mn/C-C₃N₅). Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) on an FEI Titan Themis Z microscope confirmed the atomic dispersion of Mn sites, while Raman spectroscopy using a Renishaw inVia Reflex laser micro-Raman spectrometer verified the successful incorporation of a graphitic carbon network within the C₃N₅ matrix. Moreover, electrochemical analyses, including electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) performed on a Bio-Logic SP-150 electrochemical workstation, demonstrated that the integration of the conductive carbon matrix substantially enhanced the interfacial charge transfer capability. The optimized Mn/C-C₃N₅ catalyst demonstrated exceptional performance in phenol mineralization, achieving a 97% total organic carbon (TOC) removal within 60 min, a remarkable improvement compared to pristine C₃N₅ (30%). Furthermore, the catalyst exhibited excellent operational stability, preserving more than 95% of its original activity over five repeated runs. Mechanistic investigations, including electron paramagnetic resonance (EPR) spectroscopy and radical quenching experiments, revealed that the Mn/C-C₃N₅ system accelerated the generation of multiple oxidizing radicals (•O₂⁻, ¹O₂, and •OH), with •OH identified as the predominant reactive species responsible for complete mineralization. This work establishes an integrated catalytic platform and provides fundamental insights into electronic structure modulation for designing advanced oxidation catalysts. Full article

Magnetic nanoparticles (MNPs) provide a platform for target detection because of their magnetic responsiveness to alternating magnetic fields (AMFs). We developed a detection method using MNPs modified with tumor-homing peptides (THPs), PL1 and PL3, which selectively bind to protein components enriched in malignant tissues. THP-MNPs were synthesized using maleimide-PEG-NHS linkers and characterized using transmission electron microscopy. Human glioblastoma cancer U87MG and normal tissue-derived HEK293 cells were incubated with THP-MNPs, and the magnetic signals were measured using a high-temperature superconducting quantum interference device (SQUID) magnetometer under an AMF (1.06 kHz). Dark-field microscopy confirmed the preferential binding of THP-MNPs to U87MG cells. In the absence of cells, THP-MNPs exhibited AMF-dependent signal enhancement, which correlated with particle size reduction due to THP release. This increase was completely suppressed in the presence of U87MG cells, indicating a strong THP-mediated interaction. PL3-MNPs exhibited superior discrimination between malignant and non-malignant cells. These results demonstrate that SQUID-based magnetic measurements using THP-MNPs enable rapid and label-free cancer cell detection. Full article

Single-atom catalysts are highly efficient electrocatalysts for water splitting with exceptional atomic utilization, but atomic aggregation can impair their catalytic performance. To address this challenge, a Fe-Co-Ni single-atom bifunctional catalyst supported on nitrogen-doped graphene oxide was designed and employed for overall water splitting in alkaline electrolyte. The catalyst’s composition, structure, and morphology were systematically characterized using XRD, XPS, SEM, and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). Electrochemical evaluations were performed to assess its activity and stability toward both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The results demonstrate that strong metal-nonmetal interactions between the Fe, Co and Ni single atoms and the nitrogen-doped graphene oxide support facilitate stable and uniform anchoring of the metal centers on the wrinkled carbon framework. The total metal loading reaches approximately 6.78 wt%, ensuring a high density of accessible active sites. Furthermore, synergistic electronic coupling among the Fe, Co, and Ni centers enhances charge transfer kinetics and modulates the D-band electronic states of the metal atoms. This effect weakens the adsorption strength of hydrogen and oxygen-containing intermediates, thus promoting faster reaction kinetics for both HER and OER. Consequently, the FeCoNi/CNG catalyst delivers low overpotentials of 77 mV for HER and 355 mV for OER at a current density of 10 mA cm⁻² in alkaline conditions. When integrated into an alkaline water electrolyzer, the system achieves a cell voltage of only 1.68 V to attain a current density of 10 mA cm⁻², underscoring its outstanding bifunctional catalytic performance. Full article

Microplastic (MP) analysis via microspectroscopy typically examines only 1–10% of filter substrates due to time constraints, requiring reliable extrapolation methods for quantitative environmental monitoring. Current subsampling strategies suffer from heterogeneous particle dispersion, leading to 50–80% error in MP quantification. Additionally, MP researchers require enhanced environmental MP mass datasets, necessitating reliable conversion algorithms from two-dimensional morphological data to mass estimates. This study introduces an area-based extrapolation technique for organic rich samples that compares the MP-to-generic particle area ratio within a rectangular field of view against total particle area on the entire filter membrane, combined with a simplified fragment morphology-to-mass conversion model (SFMM). First, two Sphagnum moss samples were analyzed using Raman microspectroscopy and critical angle darkfield illumination microscopy. The results demonstrated stable MP concentrations (17% RSD [n = 8]) despite heterogeneous generic particle distribution (31% RSD [n = 8]), with mean particle-area coverage of 2.4% per subsample. Then, twenty EasyMP^TM fragment reference materials (10 µm to 1500 µm), of known composite mass, were used to calibrate two different volume (V) expressions, one based on analyzed particle area (A) and minimum Feret diameter (F_Min, i.e., width), yielding V = 0.34 × F_Min × A. A second more approximate expression based on only the maximum Feret diameter (F_Max, i.e., length) yielded V = 0.097 × (F_Max)³. These methods enable MP quantification and mass estimation from limited spectroscopic analysis. Full article

Endocytic uptake and lysosomal localization are suggested to be the key mechanisms underlying the toxicity of metal oxide nanoparticles (MONPs), with dissolution in the acidic milieu driving the response. In this study, we aimed to investigate if MONPs of varying solubility are similarly sequestered intracellularly, including in lysosomes and the role of the acidic lysosomal milieu on toxicity induced by copper oxide (CuO) nanoparticles (NPs), nickel oxide (NiO) NPs, aluminum oxide (Al₂O₃) NPs, and titanium dioxide (TiO₂) NPs of varying solubility in FE1 lung epithelial cells. Mitsui-7 multi-walled carbon nanotubes (MWCNTs) served as contrasts against particles. Enhanced darkfield hyperspectral imaging (EDF-HSI) with fluorescence microscopy was used to determine their potential association with lysosomes. The v-ATPase inhibitor Bafilomycin A1 (BaFA1) was used to assess the role of lysosomal acidification on toxicity. The results showed co-localization of all MONPs with lysosomes, with insoluble TiO₂ NPs showing the greatest co-localization. However, only acute toxicity induced by soluble CuO NPs was affected by the presence of BaFA1, showing a 14% improvement in relative survival. In addition, all MONPs were found to be associated with large actin aggregates; however, treatment with insoluble TiO₂ NPs, but not soluble CuO NPs, impaired the organization of F-actin and α-tubulin. These results indicate that MONPs are sequestered similarly intracellularly; however, the nature or magnitude of their toxicity is not similarly impacted by it. Future studies involving a broader variety of NPs are needed to fully understand the role of differential sequestration of NPs on cellular toxicity. Full article

Background and aim. Gold nanoparticles (AuNPs) offer promising potential as nanocarriers in vaccine development due to their biocompatibility, tunable surface properties and capacity to enhance antigen presentation. This study aimed to evaluate the in vitro cytocompatibility, cellular uptake and antigen processing of carcinoembryonic antigen (CEA)-functionalized AuNPs as a nanovaccine candidate. Materials and Methods. AuNPs were synthesized by citrate reduction and subsequently functionalized with CEA through physical adsorption. Nanoparticle size, morphology, and surface charge were characterized using UV–Vis spectroscopy, dynamic light scattering (DLS), and transmission electron microscopy (TEM). Cytocompatibility was assessed via MTT assay on RAW 264.7 murine macrophages. Cellular uptake and antigen processing were evaluated using hyperspectral dark-field microscopy and fluorescence microscopy with proteasomal pathway markers. Results. The synthesized AuNPs displayed a uniform spherical morphology with a mean hydrodynamic diameter of ~50 nm and a stable zeta potential. CEA conjugation slightly altered the surface charge and spectral profile. MTT assays confirmed good cytocompatibility across tested concentrations. Hyperspectral and confocal microscopy revealed the efficient uptake of CEA-AuNPs by RAW 264.7 cells and colocalization with lysosomal compartments, suggesting successful antigen processing. Conclusions. The in vitro data support the safety and biological interaction of CEA-functionalized AuNPs with macrophages. These findings highlight their potential as a nanovaccine delivery platform and warrant further in vivo evaluation to assess immunogenicity and protective efficacy. Full article

The topical administration of drugs on the skin by nanovesicular systems can represent a tool to treat skin pathologies. The study of nanovesicle biodistribution after skin administration is crucial to understanding their transdermal potential. A formative study enabled us to investigate the influence of some methods in the production of nanovesicles based on phosphatidylcholine, differing in their ethanol amount. Particularly, both liposomes and ethosomes produced by different methods, i.e., microfluidics and solvent injection, were considered. The evaluation of size distribution, shape and internal morphology was performed using photon correlation spectroscopy, cryogenic electron microscopy, hyperspectral dark-field microscopy and small-angle X-ray scattering. Transmission electron microscopy was then used to observe and compare the transdermal passage of selected liposomes and ethosomes applied to human skin explants in a bioreactor. The mean diameters of nanovesicles prepared by the ethanol injection method were smaller with respect to those obtained by microfluidics, measuring roughly 140 and 230 nm, respectively. The uni- or multilamellar ultrastructure of the vesicles was influenced by the solvent injection procedure. Ultrastructural analysis of skin penetration revealed (i) the ability of intact vesicles to cross the different skin layers, with ethosomes produced by the water injection method showing greater transdermal potential and (ii) the role of ethanol as a penetration enhancer. Full article

Owing to global energy demands and climate change resulting from fossil fuel use, technologies capable of converting greenhouse gases into renewable energy resources are needed. One such technology is photocatalytic CO₂ reduction, which utilises solar energy to transform CO₂ into value-added hydrocarbons. However, the application of photocatalytic CO₂ reduction is limited by the inefficiency of existing photocatalysts. In this study, we developed a nitrogen-deficient g-C₃N₄-confined PtCu dual-atom catalyst (PtCu/V_N-C₃N₄) for photocatalytic CO₂ reduction. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectroscopy confirmed the atomic-level anchoring of PtCu pairs onto the nitrogen-vacancy-rich g-C₃N₄ nanosheets. The optimised PtCu/V_N-C₃N₄ exhibited superior photocatalytic performance, with CO and CH₄ evolution rates of 13.3 µmol/g/h and 2.5 µmol/g/h, respectively, under visible-light irradiation. Mechanistic investigations revealed that CO₂ molecules were preferentially adsorbed onto the PtCu dual sites, initiating a stepwise reduction pathway. In situ diffuse reflectance infrared Fourier-transform spectroscopy identified the formation of a key intermediate (HCOO*), whereas interfacial wettability studies demonstrated efficient H₂O adsorption on PtCu sites, providing essential proton sources for CO₂ protonation. Photoelectrochemical characterisation further confirmed the enhanced charge-transfer kinetics in PtCu/V_N-C₃N₄, which were attributed to the synergistic interplay between the nitrogen vacancies and dual-atom sites. Notably, the dual-active-site architecture minimised the competitive adsorption between CO₂ and H₂O molecules, thereby optimising the surface reaction pathways. This study establishes a rational strategy for designing atomically precise dual-atom catalysts through defect engineering, achieving concurrent improvements in activity, selectivity, and charge carrier utilisation for solar-driven CO₂ conversion. Full article

Pulmonary exposure to carbon nanotubes (CNTs) has been linked to a series of adverse respiratory effects in animal models, including inflammation, genotoxicity, fibrosis, and granuloma formation, the degree and characteristics of which are considered dependent upon the detailed physicochemical properties of the material as inhaled. To further explore the effect of variations in physicochemical properties on pulmonary effects, two different multi-walled CNTs (MWCNTs) were tested in vivo: a pristine MWCNT (pMWCNT) (NM-401) and a surface-modified MWCNT (MWCNT-COOH). Female Sprague–Dawley rats were whole-body exposed for 28 days to MWCNT aerosols (pMWCNT (0.5 and 1.5 mg/m³) and MWCNT-COOH (1.5 and 4.5 mg/m³)) and followed up to 1 year post-exposure. The inhalation exposures resulted in relatively low estimated lung deposition. Bronchoalveolar lavage fluid (BALF) analysis indicated inflammation levels broadly consistent with deposited dose levels. Lung histopathology indicated that both MWCNTs produced very limited toxicological effects; however, global mRNA expression levels in lung tissue and BALF cytokines indicated different characteristics for the two MWCNTs. For example, pMWCNT but not MWCNT-COOH exposure induced osteopontin production, suggestive of potential pre-fibrosis/fibrosis effects linked to the higher aspect ratio aerosol particles. This is of concern as brightfield and enhanced darkfield microscopy indicated the persistence of pMWCNT fibres in lung tissue. Full article

Aluminum nanoparticles (Al NPs) are interesting for energetic and plasmonic applications due to their enhanced size-dependent properties. Passivating the surface of these particles is necessary to avoid forming a native oxide layer, which can degrade energetic and optical characteristics. This work utilized a radiofrequency (RF)-driven capacitively coupled argon/hydrogen plasma to form surface-modified Al NPs from aluminum trichloride (AlCl₃) vapor and 5% silane in argon (dilute SiH₄). Varying the power and dilute SiH₄ flow rate in the afterglow of the plasma led to the formation of varying nanoparticle morphologies: Al–SiO₂ core–shell, Si–Al₂O₃ core–shell, and Al–Si Janus particles. Scanning transmission electron microscopy with a high-angle annular dark-field detector (STEM-HAADF) and energy-dispersive X-ray spectroscopy (EDS) were employed for characterization. The surfaces of the nanoparticles and sample composition were characterized and found to be sensitive to changes in RF power input and dilute SiH₄ flow rate. This work demonstrates a tunable range of Al–SiO₂ core–shell nanoparticles where the Al-to-Si ratio could be varied by changing the plasma parameters. Thermal analysis measurements performed on plasma-synthesized Al, crystalline Si, and Al–SiO₂ samples are compared to those from a commercially available 80 nm Al nanopowder. Core–shell particles exhibit an increase in oxidation temperature from 535 °C for Al to 585 °C for Al–SiO₂. This all-gas-phase synthesis approach offers a simple preparation method to produce high-purity heterostructured Al NPs. Full article

In recent years, machine learning algorithms have seen extensive application in chemical science, especially in cell detection technologies. Machine learning, a branch of artificial intelligence, is designed to automatically discover patterns in data. This review provides an overview of cell detection methods such as bright-field microscopy (BL), dark-field microscopy (DL), surface-enhanced Raman scattering (SERS), and fluorescence detection (FL). We highlight key computational models like support vector machines and convolutional neural networks that significantly enhance the precision and efficiency of automated cell detection. Relevant research applications are discussed, along with future prospects for machine learning in cell analysis. Full article

A two-dimensional array of microfluidic ports with remote-controlled valve actuation is of great interest for applications involving localized chemical stimulation. Herein, a macroporous silicon-based platform where each pore contains an independently controllable valve made from poly(N-isopropylacrylamide) (PNIPAM) brushes is proposed. These valves are coated with silica-encapsulated gold nanorods (GNRs) for NIR-actuated switching capability. The layer-by-layer (LBL) electrostatic deposition technique was used to attach the GNRs to the PNIPAM brushes. The deposition of GNRs was confirmed by dark-field optical microscopy, and the localized surface plasmon resonance (LSPR) of the deposited GNRs was analyzed using UV-Vis spectra. To evaluate the chemical release behaviors, fluorescein dye was employed as a model substance. The chemical release properties, like OFF-state diffusion through the valve, the ratio between ON-state and OFF-state chemical release, and the rapidness of chemical modulation of the valve, were investigated, varying the PNIPAM brush thickness. The results indicate that enhancing the thickness of the PNIPAM brush in our platform improves control over the chemical modulation properties. However, excessive increases in brush length may lead to entanglement, which negatively impacts the chemical modulation efficiency. Full article