Search Results (4,020)

The integration of microstructured current collectors offers a potential pathway to enhance interface properties in solid-state battery architectures. In this work, we investigate the influence of surface morphology on the electrochemical performance of Zn/Na_2.99Ba_0.005OCl/Cu electrodeless pouch cells by fabricating copper thin films on microstructured parylene-C substrates using a combination of colloidal lithography and reactive ion etching. O₂ plasma etching times ranging from 0 to 15 min were used to tune the surface topography, resulting in a systematic increase in root-mean-square roughness and a surface area enhancement of up to ~30% for the longest etching duration, measured via AFM. Kelvin probe force microscopy-analyzed surface potential showed maximum differences of 270 mV between non-etched and 12-minute-etched Cu collectors. The results revealed that the chemical potential is the property that relates the surface of the Cu current collector/electrode with the cell’s ionic transport performance, including the bulk ionic conductivity, while four-point sheet resistance measurements confirmed that the copper layers’ resistivity maintained values close to those of bulk copper (1.96–4.5 µΩ.cm), which are in agreement with electronic mobilities (−6 and −18 cm²V⁻¹s⁻¹). Conversely, the charge carrier concentrations (−1.6 to −2.6 × 10²³ cm⁻³) are indirectly correlated with the performance of the cell, with the samples with lower CCC_bulk (fewer free electrons) performing better and showing higher maximum discharge currents, interfacial capacitance, and first-cycle discharge plateau voltage and capacity. The data were further consolidated with Scanning Electron Microscopy and X-Ray Photoelectron Spectroscopy analyses. These results highlight that the correlation between the surface morphology and the cell is not straightforward, with the microstructured current collectors’ surface chemical potential and the charge carriers’ concentration being determinant in the performance of all-solid-state electrodeless sodium battery systems. Full article

This research presents a novel methodology to classify copper tailings according to their potential as alkali-activated materials (AAMs) for construction applications. The methodology includes geochemical and mineralogical characterization via QEMSCAN and X-ray fluorescence, with mechanical performance evaluation through compressive strength test (UCS). A three-phase diagram based on Al₂O₃, Fe₂O₃, and CaO-MgO-K₂O is proposed for a fast screening of copper tailing potential to be used as a construction material. In this paper, three copper tailings were chosen to test the methodology, and a set of five samples for each tailing have been geopolymerized for testing. Copper tailing samples were mixed with 0, 2.5, 5, 7.5 and 10% by mass of Ordinary Portland Cement (OPC) to evaluate the effect on performance when a chemical co-activator is used to improve material reactivity. Compressive strength testing was applied on 2 cm³ cubes after 28 days of curing at 60 °C, yielding values from 6 to 26.1 MPa. The best performing sample featured a Si/Al ≅ 3 ratio and a mineralogy with significant presence of reactive species such as plagioclase and K-feldspar (≅42%). In contrast, high levels of Fe₂O₃ (≥12%), clay (≥7%), and pyrite (≥4%) were associated with reduced mechanical performance. Full article

Ultrahigh dose rate (UHDR) radiotherapy, also known as FLASH radiotherapy (FLASH-RT), has shown potential for increasing tumor control while sparing normal tissue. In parallel, gold nanoparticles (GNPs) have been extensively explored as radiosensitizers due to their high atomic number and ability to enhance the generation of reactive oxygen species (ROS) through water radiolysis. In this study, we investigate the synergistic effects of UHDR electron beams and GNP-mediated radiosensitization using Monte Carlo (MC) simulations based on the Geant4-DNA code. A spherical water phantom with embedded GNPs of varying sizes (5–100 nm) was irradiated using pulsed electron beams (100 keV and 1 MeV) at dose rates of 60, 100, and 150 Gy/s. The chemical yield of ROS near the GNPs was quantified and compared to an equivalent water nanoparticle model, and the yield enhancement factor (YEF) was used to evaluate radiosensitization. Results demonstrated that YEF increased with smaller GNP sizes and at lower UHDR, particularly for 1 MeV electrons. A maximum YEF of 1.25 was observed at 30 nm from the GNP surface for 5 nm particles at 60 Gy/s. The elevated ROS concentration near GNPs under FLASH conditions is expected to intensify DNA damage, especially double-strand breaks, due to increased hydroxyl radical interactions within nanometric distances of critical biomolecular targets. These findings highlight the significance of nanoparticle size and beam parameters in optimizing ROS production for FLASH-RT. The results provide a computational basis for future experimental investigations into the combined use of GNPs and UHDR beams in nanoparticle-enhanced radiotherapy. Full article

Resistive switching (RS) phenomena are nowadays one of the most studied topics in the area of microelectronics. It can be observed in Metal–Insulator–Metal (MIM) structures that are the basis of resistive switching random-access memories (RRAMs). In the case of commercial use of RRAMs, it is beneficial that the applied materials would have to be compatible with Complementary Metal-Oxide-Semiconductor (CMOS) technology. Fabricating methods of these materials can determine their stoichiometry and structural composition, which can have a detrimental impact on the electrical performance of manufactured devices. In this study, we present the influence of the Ar/N₂ ratio during reactive magnetron sputtering of titanium nitride (TiN) electrodes on the resistive switching behavior of MIM devices. We used silicon oxide (SiOx) as a dielectric layer, which was characterized by the same properties in all fabricated MIM structures. The composition of TiN thin layers was controlled by tuning the Ar/N₂ ratio during the deposition process. The fabricated conductive materials were characterized in terms of chemical and structural properties employing X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis. Structural characterization revealed that increasing the Ar content during the reactive sputtering process affects the crystallite size of the deposited TiN layer. The resulting crystallite sizes ranged from 8 Å to 757.4 Å. The I-V measurements of fabricated devices revealed that tuning the Ar/N₂ ratio during the deposition of TiN electrodes affects the RS behavior. Our work shows the importance of controlling the stoichiometry and structural parameters of electrodes on resistive switching phenomena. Full article

The present study explores the sustainable potential of volcanic ash sourced from the active Sakurajima volcano (Japan) as an eco-friendly alternative to Portland cement—a binder known for its high carbon emissions—in concrete and mortar production. The abundant pyroclastic material, currently a waste burden for the residents of Sakurajima and the Kagoshima Bay region, presents a unique opportunity for valorization in line with circular economy principles. Rather than treating this ash as a disposal problem, the research investigates its transformation into a valuable supplementary cementitious material (SCM), contributing to more sustainable construction practices. The investigation focused on the material characterization of the ash (including chemical composition, morphology, and PSD) and its pozzolanic activity index, which is a key indicator of its suitability as a cement replacement. Mortars were prepared with 25% of the commercial binder replaced by volcanic ash—both in its raw form and after mechanical activation—and tested for compressive strength after 28 and 90 days of water curing. Additional assessments included workability of the fresh mix (flow table test), apparent density, and flexural strength of the hardened composites. Tests results showed that the applied volcanic ash did not influence the workability of the mix and showed negligible effect on the apparent density (changes of up to 3.3%), although the mechanical strength was deteriorated (decrease by 15–33% after 7 days, and by 25–26% after 28 days). However, further investigation revealed that the simple mechanical grinding significantly enhances the pozzolanic reactivity of Sakurajima ash. The ground ash achieved a 28-day activity index of 81%, surpassing the 75% threshold set by EN 197-1 and EN 450-1 standards for type II mineral additives. These findings underscore the potential for producing low-carbon mortars and concretes using locally sourced volcanic ash, supporting both emissions reduction and sustainable resource management in construction. Full article

Photocatalysis is an emerging technology that harnesses light energy to facilitate chemical reactions. It has garnered considerable attention in the field of catalysis due to its promising applications in environmental remediation and sustainable energy generation. Recently, researchers have been exploring innovative techniques to improve the surface reactivity of ferroelectric materials for catalytic purposes, leveraging their distinct properties to enhance photocatalytic efficiency. With their switchable polarization and improved charge transport capabilities, ferroelectric materials show promise as effective photocatalysts for various reactions, including carbon dioxide (CO₂) reduction. Through a blend of experimental studies and theoretical modeling, researchers have shown that these materials can effectively convert CO₂ into valuable products, contributing to efforts to reduce greenhouse gas emissions and promote a cleaner environment. An artificial neural network (ANN) was employed to analyze parameter relationships and their impacts in this study, demonstrating its ability to manage training data errors and its applications in fields like speech and image recognition. This research also examined changes in charge separation, light absorption, and surface area related to variations in band gap and polarization, confirming prediction accuracy through linear regression analysis. Full article

Theoretical studies have indicated that borophene is a promising two-dimensional material characterized by remarkable chemical, mechanical, and electrical properties. Nonetheless, its practical applications in areas such as catalysis and gas sensing are hindered by the limited density of reactive sites in its pristine form. To address this limitation, the present study explores the controlled fluorination of borophene nanoflakes as a strategy to modify their surface chemistry and enhance the availability of active sites. Furthermore, it is anticipated that surface fluorination will improve hydrophobicity, which is crucial for reducing humidity-related interference in sensing applications. In this study, we report the successful functionalization of borophene nanoflakes with fluorine using a plasma arc discharge technique for the first time. Borophene nanolayers were synthesized via a sonochemical-assisted exfoliation method, yielding nanosheets with an average lateral dimension of approximately 100 nm. The fluorinated samples were characterized using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HRTEM). A systematic investigation of plasma exposure durations demonstrated that fluorine was effectively introduced as a dopant while maintaining the crystallinity of the borophene lattice. Full article

A new Schiff base, (E)-2-(((1,10-phenanthrolin-5-yl)imino)methyl)-4,6-di-tert-butylphenol (Fen-IHB), was designed to incorporate an intramolecular hydrogen bond (IHB) between the phenolic OH and the azomethine nitrogen with the goal of modulating its physicochemical and biological properties. Fen-IHB was synthesized by condensation of 5-amino-1,10-phenanthroline with 3,5-di-tert-butyl-2-hydroxybenzaldehyde and exhaustively characterized by HR-ESI-MS, FTIR, 1D/2D NMR (¹H, ¹³C, DEPT-45, HH-COSY, CH-COSY, D₂O exchange), and UV–Vis spectroscopy. Cyclic voltammetry in anhydrous CH₃CN revealed a single irreversible cathodic peak at −1.43 V (vs. Ag/Ag⁺), which is consistent with the intramolecular reductive coupling of the azomethine moiety. Density functional theory (DFT) calculations, including MEP mapping, Fukui functions, dual descriptor analysis, and Fukui potentials with dual descriptor potential, identified the exocyclic azomethine carbon as the principal nucleophilic site and the phenolic ring (hydroxyl oxygen and adjacent carbons) as the main electrophilic region. Noncovalent interaction (NCI) analysis further confirmed the strength and geometry of the intramolecular hydrogen bond (IHB). In vitro antimicrobial assays indicated that Fen-IHB was inactive against Gram-negative facultative anaerobes (Salmonella enterica serovar Typhimurium and Typhi, Escherichia coli) and strictly anaerobic Gram-positive species (Clostridioides difficile, Roseburia inulinivorans, Blautia coccoides), as any growth inhibition was indistinguishable from the DMSO control. Conversely, Fen-IHB displayed measurable activity against Gram-positive aerobes and aerotolerant anaerobes, including Bacillus subtilis, Streptococcus pyogenes, Enterococcus faecalis, Staphylococcus aureus, and Staphylococcus haemolyticus. Overall, these comprehensive characterization results confirm the distinctive chemical and electronic properties of Fen-IHB, underlining the crucial role of the intramolecular hydrogen bond and electronic descriptors in defining its reactivity profile and selective biological activity. Full article

The photochemistry of 1,3,4-oxadiazoles remains poorly understood, despite their recognized importance in medicinal chemistry and materials science. In this work, we report a detailed matrix-isolation study of 2-amino-5-(4-methoxyphenyl)-1,3,4-oxadiazole, combining low-temperature infrared spectroscopy with broadband UV photolysis and quantum chemical calculations. Theoretical analysis predicts the gas-phase molecule to exist exclusively as the amino tautomer, populating two nearly isoenergetic conformers (anti and syn) defined by the relative orientation of the amino and methoxy groups. Experimental IR spectra of the compound isolated in Ar and Xe matrices at 15 K confirm sole trapping of the amino tautomer. Annealing of the Xe matrix to the highest achievable temperature induced no detectable spectral changes, consistent with the predicted isoenergetic character of the conformers. Upon broadband UV irradiation (λ > 200 nm), the compound undergoes ring opening through N−N and C−O bond cleavages, paralleling the behavior of unsubstituted 1,3,4-oxadiazole system. Isocyanates emerge as the predominant photoproducts from these photochemical pathways. Additionally, spectroscopic evidence supports an alternative reaction pathway involving early-stage amino−imino tautomerization, followed by ring-opening of the imino tautomer through isocyanic acid extrusion, leading to the formation of a nitrilimine intermediate. This reactive species subsequently photorearranges into a carbodiimide via a diazirine-mediated pathway. All photoproducts were unambiguously identified through their distinct IR signatures, supported by quantum chemical calculations and reference data from structurally related systems. These findings provide unprecedented insight into the photochemical behavior of substituted 1,3,4-oxadiazoles and unveil new reaction pathways modulated by substituent effects, expanding the understanding of their photoreactivity. Full article

The HYPEX^® process is a novel method for conditioning spent ion exchange resins from nuclear power plants, aiming to reduce final waste volume and carbon emissions by stabilizing the resins in metakaolin-based geopolymers. This study addresses the challenge posed by the natural variability of commercial metakaolin and defines a testing strategy to ensure consistent performance of the final matrix. The reactivity of two batches of metakaolin, characterized by comparable chemical composition and BET surface area, was evaluated by monitoring temperature evolution during geopolymerization at varying water-to-solid ratios. The resulting geopolymers were tested for compressive strength, water permeability, and strontium leachability to assess correlations between precursor properties and final matrix performance. Despite similar compositions, the two batches showed marked differences in compressive strength that could be linked to early thermal behavior. These findings demonstrate that conventional precursor characterization is insufficient to guarantee reproducibility and that thermal profiling is useful to predict mechanical performance. The results suggest the implementation of thermal response monitoring as a quality control tool to ensure the reliability of geopolymer wasteforms in nuclear applications. A simplified analytical model for the thermal evolution during geopolymerization was also developed, matching qualitatively the measured evolution, to suggest scale-up rules from laboratory specimens to full-scale drums, which should be achieved while preserving the thermal evolution. Full article

Candida albicans, listed by WHO as a priority fungal (yeast) pathogen, can cause invasive infections resistant to drugs, thus demanding novel strategies of disinfection. This study examines the inactivation, reactivation in darkness, and susceptibility to fluconazole of an antifungal-resistant C. albicans strain through UVC photolysis, chemical oxidation, and photooxidation using hydrogen peroxide (H₂O₂), peroxydisulfate (PDS), or peroxymonosulfate (PMS). Tests were performed in deionized water over very short treatment times (0–80 s). Also, standardized CLSI methods for antifungal sensitivity studies and morphological microscopic views were carried out. The fungus disinfection order was UVC/H₂O₂ > UVC/PDS > UVC/PMS > UVC. The photooxidation processes followed pseudo-first-order kinetics, with the highest rate constant for the UVC/H₂O₂ process. Direct oxidation, photoinactivation, and attacks of radical species were responsible for the inactivation of the antifungal-resistant microorganism. The fluconazole susceptibility of yeasts was significantly decreased (from 64 to 8 µg mL⁻¹) by the action of UVC/H₂O₂. A low reactivation in the dark and strong changes in the yeast morphology were found, indicating that the use of UVC light and radical-based processes is an effective alternative for fluconazole-resistant yeasts and could be promising to deal with hospital wastewater loaded with resistant fungi. Full article

Plants are frequently exposed to a range of abiotic stresses, including drought, salinity, extreme temperatures, and heavy metals, that severely impair their growth and productivity. Among the adaptive mechanisms that plants have evolved, the accumulation of glycine betaine (GB), a naturally occurring, zwitterionic, and chemically stable osmoprotectant, has been widely recognized as a key strategy for stress tolerance. In higher plants, GB is primarily synthesized via the two-step oxidation of choline, catalyzed by choline monooxygenase (CMO) and betaine aldehyde dehydrogenase (BADH). GB contributes to cellular homeostasis by modulating osmotic balance, regulating ion flux, scavenging reactive oxygen species (ROS), enhancing antioxidant defense systems, and stabilizing proteins and membrane structures. Both exogenous application of GB and genetic engineering approaches aimed at enhancing endogenous GB biosynthesis have been shown to significantly improve plant tolerance to a variety of abiotic stresses. In this review, we provide a comprehensive overview of recent advances in the understanding of GB biosynthesis, its regulatory mechanisms, and its multifaceted roles in plant stress responses. We also highlight emerging prospects for leveraging GB-centered strategies to enhance crop resilience in challenging environmental conditions. Full article

Terminal alkynes, characterized by sp-hybridized carbon atoms at the molecular termini, possess high electron density and exceptional chemical reactivity. These properties make them ideal candidates for the synthesis of one-dimensional molecular wires and two-dimensional networks. Advances in nanoscale characterization techniques, such as scanning tunneling microscopy and atomic force microscopy, have enabled the real-space visualization of molecular assembly and chemical reactions of terminal alkynes and in situ atomic-level manipulations under surface-confined conditions. In addition, through the combination of spectroscopic measurements, physicochemical properties of and information about resulting nanostructures have been achieved. Moreover, density functional theory calculations provide deeper insights into the underlying reaction pathways and mechanisms. From this perspective, this review summarizes recent progress in the assembly and chemical transformations of terminal alkynes on noble metal surfaces. It discusses strategies for structural modulation and reaction selectivity control, including direct incorporation of heteroatoms or functional groups into precursors, the selection of metal surfaces, the introduction of extrinsic components into molecular systems, and atomic-scale manipulations using scanning probes. Full article

Plants are constantly exposed to various environmental challenges, such as drought, flooding, heavy metal toxicity, and pathogen attacks. To cope with these stresses, they employ several adaptive strategies. This review highlights the potential of plant-derived smoke (PDS) solution as a natural biostimulant for improving plant health and resilience, contributing to both crop productivity and ecological restoration under abiotic and biotic stress conditions. Mitigating effects of PDS solution against various stresses were observed at morphological, physiological, and molecular levels in plants. PDS solution application involves strengthening the cell membrane by minimizing electrolyte leakage, which enhances cell membrane stability and stomatal conductance. The increased reactive-oxygen species were managed by the activation of the antioxidant system including ascorbate peroxidase, superoxide dismutase, and catalase to meet oxidative damage caused by challenging conditions imposed by flooding, drought, and heavy metal stress. PDS solution along with other by-products of fire, such as charred organic matter and ash, can enrich the soil by slightly increasing its pH and improving nutrient availability. Additionally, some studies indicated that PDS solution may influence phytohormonal pathways, particularly auxins and gibberellic acids, which can contribute to root development and enhance symbiotic interactions with soil microbes, including mycorrhizal fungi. These combined effects may support overall plant growth, though the extent of PDS contribution may vary depending on species and environmental conditions. This boost in plant growth contributes to protecting the plants against pathogens, which shows the role of PDS in enduring biotic stress. Collectively, PDS solution mitigates stress tolerance in plants via multifaceted changes, including the regulation of physico-chemical responses, enhancement of the antioxidant system, modulation of heavy metal speciation, and key adjustments of photosynthesis, respiration, cell membrane transport, and the antioxidant system at genomic/proteomic levels. This review focuses on the role of PDS solution in fortifying plants against environmental stresses. It is suggested that PDS solution, which already has been determined to be a biostimulant, has potential for the revival of plant growth and soil ecosystem under abiotic and biotic stresses. Full article

An activated biochar was produced from post-coagulation sludge (also called water treatment residuals or water treatment sludge) in the pyrolysis process at 800 °C in a nitrogen atmosphere and chemical activation using NaOH. The produced adsorption material was characterised by an S_BET surface area of 439 m²/g, a total volume of pores of 0.301 cm³/g, and an average pore size of 1.4 nm. FTIR analysis reveals the presence of primarily C-H, C-O, N-H, C-N, and O-H groups on the activated biochar surface. The batch adsorption process was conducted for three dyes: Acid Red 18, Acid Green 16, and Reactive Blue 81. In the study, the effect of pH, contact time, adsorption kinetics, and adsorption isotherm was determined. The studies showed that, for all dyes, the highest efficiency of the process was achieved at a pH of 2. The results indicate the occurrence of a chemical adsorption process, as evidenced by the best fit to the experimental results obtained with the pseudo-second-order kinetics model and the Elovich model. In the case of the adsorption isotherm, the SIPS model best describes the adsorption for Acid Red 18 and Reactive Blue 81, and the Jovanovic model describes the adsorption of Acid Green 16. Full article