Search Results (194)

The development of ceria (CeO_2−x)-based nanoantioxidants requires fine-tuning of structural and surface properties for enhancing antioxidant behavior in biological environments. In this contest, here ultrasmall water-dispersible CeO_2−x nanoparticles (NPs), characterized by a high Ce³⁺/Ce⁴⁺ ratio, were synthesized in a non-polar solvent and phase-transfer to an aqueous environment through ligand-exchange reactions using citric acid (CeO_2−x@Cit) and post-treatment with dopamine hydrochloride (CeO_2−x@Dopa). The concept behind this work is to enhance via surface engineering the intrinsic antioxidant properties of CeO_2−x NPs. For this purpose, thanks to electron transfer reactions between dopamine and CeO_2−x, the CeO_2−x@Dopa was obtained, characterized by increased surface Ce³⁺ sites and surface functionalized with polydopamine bearing o-quinone structures as demonstrated by complementary spectroscopic (UV–vis, FT-IR, and XPS) characterizations. To test the antioxidant properties of CeO_2−x NPs, the scavenging activity before and after dopamine treatment against artificial radical 1,1-diphenyl-2-picrylhydrazyl (DPPH^·) and the ability to reduce the reactive oxygen species in Diencephalic Immortalized Type Neural Cell line 1 were evaluated. CeO_2−x@Dopa demonstrated less efficiency in DPPH^· scavenging (%radical scavenging activity 13% versus 42% for CeO_2−x@Cit before dopamine treatment at 33 μM DPPH^· and 0.13 mg/mL loading of NPs), while it markedly reduced intracellular ROS levels (ROS production 35% compared to 66% of CeO_2−x@Cit before dopamine treatment with respect to control—p < 0.001 and p < 0.01, respectively). While steric hindrance from the dopamine-derived polymer layer limited direct electron transfer from CeO_2−x NP surface to DPPH^·, within cells the presence of o-quinone groups contributed with CeO_2−x NPs to break the autoxidation chain of organic substrates, enhancing the antioxidant activity. The functionalization of NPs with o-quinone structures represents a valuable approach to increase the inherent antioxidant properties of CeO_2−x NPs, enhancing their effectiveness in biological systems by promoting additional redox pathways. Full article

In the development of deep coalbed methane (CBM) resources, the adsorption behavior of supercritical methane is a key factor restricting reserve evaluation and development efficiency. This study integrates scanning electron microscopy (SEM), low-temperature CO₂ adsorption (LTCO₂A), mercury intrusion porosimetry (MIP), high-temperature and high-pressure CH₄ adsorption experiments (HTHP-CH₄A), and theoretical models to reveal the pore–fracture structure of deep coal seams and the adsorption characteristics of supercritical methane. Based on a predictive model for supercritical methane adsorption capacity, the adsorption capacity of deep methane was predicted. Results show that micro-pores are well-developed in deep coal rocks, but pore connectivity is generally poor, predominantly consisting of fine bottleneck pores and semi-closed pores, with a certain proportion of open pores. The fractal dimension (D_m) of micro-pore structures in deep coal samples ranges from 2.0447 to 2.2439, indicating high micro-pore surface roughness and a large specific surface area, which provide favorable sites for methane adsorption. Pores larger than 100 nm exhibit fractal values between 2.6459 and 2.8833, suggesting that the pore surfaces in deep coal seams approach a three-dimensional pore space with rough surfaces and complex pore structures. As temperature and pressure enter the supercritical region, the adsorption capacity shows an abnormal trend of “first increasing and then decreasing” with increasing pressure. The deep coal rock–supercritical methane adsorption system exhibits two scenarios in low-pressure and high-pressure regions, corresponding to self-adsorption driven by strong methane adsorption potential and external force adsorption or overpressure micro-pore adsorption, respectively. The supercritical adsorption prediction model considering temperature and methane adsorption phase density has extremely low deviation (1.11–1.25%) and high accuracy. The average dispersion between predicted and actual values ranges from 0.44 cm³/g to 0.48 cm³/g, with small error fluctuations and no significant deviation. This study provides theoretical support for the recoverability evaluation and efficient development of deep CBM resources. Full article

Ultrafine fibers from poly(3-hydroxybutyrate) (PHB) and polyvinylpyrrolidone (PVP) and their blends with different component ratios in the range of 0/100 to 100/0 wt.% were obtained, and their structure and dynamic properties were studied. The polymers were obtained via electrospinning in solution mode. The structure, morphology, and segmental dynamic behavior of the fibers were determined using optical microscopy, SEM, EPR, DSC, and IR spectroscopy. The low-temperature maximum on the DSC endotherms provided information on the state of the PVP hydrogen bond network, which made it possible to determine the enthalpies of thermal destruction of these bonds. The PHB/PVP fiber blend ratio significantly affected the structural and dynamic parameters of the system. Thus, at low concentrations of PVP (up to 9%) in the structure of ultra-fine fibers, the distribution of this polymer occurs in the form of tiny particles, which are crystallization centers, which causes a significant increase in the degree of crystallinity (χ) activation energy (E_act) and slowing down of molecular dynamics (τ). At higher concentrations of PVP, loose interphase layers were formed in the system, which caused a decrease in these parameters. The strongest changes in the concentration of hydrogen bonds occurred when PVP was added to the composition from 17 to 50%, which was due to the formation of intermolecular hydrogen bonds both in PVP and during the interaction of PVP and PHB. The diffusion coefficient of water vapor in the studied systems (D) decreased as the concentration of glassy PVP in the composition increased. The concentration of the radical decreased with an increase in the proportion of PVP, which can be explained by the glassy state of this polymer at room temperature. A characteristic point of the 50/50% mixture component ratio was found in the region where an inversion transition of PHB from a dispersion material to a dispersed medium was assumed. The conducted studies made it possible for the first time to conduct a comprehensive analysis of the effect of the component ratio on the structural and dynamic characteristics of the PHB/PVP fibrous material at the molecular scale. Full article

Smectite clay minerals are known to readily form thixotropic physical gels in aqueous media, even at low volume fractions. Although the rheological properties of these gels are closely related to the microstructure of the network, the influence of the clay’s physicochemical characteristics remains insufficiently understood. In this study, we systematically investigated the relationships between particle size, cation exchange capacity, and zeta potential, and the rheological behavior of aqueous dispersions of four synthetic smectites. After thorough deionization, dispersions were prepared at controlled NaCl concentrations. We found that the zeta potential strongly correlates with the fineness of the network structure and governs macroscopic rheological responses such as viscosity, yield stress, and gelation behavior. Even under identical conditions, gel transparency and structural coarseness varied significantly among clay types. Furthermore, the storage modulus was influenced not only by network density but also by the intrinsic stiffness of the clay branches. These findings demonstrate that zeta potential serves as a unified indicator of structure and function in smectite dispersions and offer useful insights for gel design in colloidal and soft matter systems. Full article

This study presented a comprehensive physical–statistical analysis of atmospheric particulate matter (PM₁₀ and PM_2.5) and trace gases (SO₂ and O₃) over Faial Island in the Azores archipelago during 2024. We collected real-time data at the Espalhafatos rural background station, covering 35,137 observations per pollutant, with 15 min intervals. Descriptive statistics, probability distribution fitting (Normal, Lognormal, Weibull, Gamma), and correlation analyses were employed to characterize pollutant dynamics and identify extreme pollution episodes. The results revealed that PM_2.5 (fine particles) concentrations are best modeled by a Lognormal distribution, while PM₁₀ concentrations fit a Gamma distribution, highlighting the presence of heavy-tailed, positively skewed behavior in both cases. Seasonal and episodic variability was significant, with multiple Saharan dust transport events contributing to PM exceedances, particularly during winter and spring months. These events, confirmed by CAMS and SKIRON dust dispersion models, affected not only southern Europe but also the Northeast Atlantic, including the Azores region. Weak to moderate correlations were observed between PM concentrations and meteorological variables, indicating complex interactions influenced by atmospheric stability and long-range transport processes. Linear regression analyses between SO₂ and O₃, and between SO₂ and PM_2.5, showed statistically significant but low-explanatory relationships, suggesting that other meteorological and chemical factors play a dominant role. This result highlights the importance of developing air quality policies that address both local emissions and long-range transport phenomena. They support the implementation of early warning systems and health risk assessments based on probabilistic modeling of particulate matter concentrations, even in remote Atlantic locations such as the Azores. Full article

Ammonium nitrate (NH₄NO₃) is a major constituent of fine particulate matter (PM_2.5), playing a critical role in air quality and atmospheric chemistry. However, the dual regulatory role of ammonia (NH₃) in both the formation and volatilization of NH₄NO₃ under ambient atmospheric conditions remains inadequately understood. To address this gap, we conducted high-resolution field measurements at a clean tropical coastal site in China using an integrated system of Aerosol Ion Monitor-Ion Chromatography, a Scanning Mobility Particle Sizer, and online OC/EC analyzers. These observations were complemented by thermodynamic modeling (E-AIM) and source apportionment via a Positive Matrix Factorization (PMF) model. The E-AIM simulations revealed persistent thermodynamic disequilibrium, with particulate NO₃⁻ tending to volatilize even under NH_3gas-rich conditions during the northeast monsoon. This suggests that NH₄NO₃ in PM_2.5 forms rapidly within fresh combustion plumes and/or those modified by non-precipitation clouds and then undergoes substantial evaporation as it disperses through the atmosphere. Under the southeast monsoon conditions, reactions constrained by sea salt aerosols became dominant, promoting the formation of particulate NO₃⁻ while suppressing NH₄NO₃ formation despite ongoing plume influence. In scenarios of regional accumulation, elevated NH₃ concentrations suppressed NH₄NO₃ volatilization, thereby enhancing the stability of particulate NO₃⁻ in PM_2.5. PMF analysis identified five source factors, with NO₃⁻ in PM_2.5 primarily associated with emissions from local power plants and the large-scale regional background, showing marked seasonal variability. These findings highlight the complex and dynamic interplay between the formation and evaporation of NH₄NO₃ in NH_3gas-rich coastal atmospheres. Full article

This review article focuses on providing an accumulated knowledge on state-of-the-art composite polymer coating technologies that are studied for corrosion protection. A specific focus has been given to epoxy resin-based composite systems, considering their wide use due to remarkable chemical resistance, excellent adhesion to substrate, thermal stability, and mechanical strength. The addition of various functional polymers to the epoxy matrix has spurred significant advancements in the prevention of corrosion. Light has been shed on the epoxy resin composite systems that are produced by blending with functional polymers like conductive polymers, hydrophobic polymers, etc., and nanofillers. In many cases, the formation of a passive layer at the metal/polymer interface was aided by the addition of such a functional polymer and nanofiller to the epoxy matrix. As a result, corrosive ions are prevented from penetrating by the physical barrier that composite coatings provide. Comparable blends of epoxy and polyamide, epoxy and polyester, and epoxy/poly(vinyl alcohol) and epoxy/polyurethane have superior adhesion, wear, barrier, and anticorrosion properties due to the fine dispersion of nanocarbon and inorganic nanoparticles. The several strategies used to prevent metals from corroding are covered in this review article. Full article

This study investigates the interfacial reactions of FeCoNiCr and FeCoNiMn medium-entropy alloys (MEAs) with Sn and Sn-3Ag-0.5Cu (SAC305) solders at 250 °C. The evolution of interfacial microstructures is analyzed over various aging periods. For comparison, the FeCoNiCrMn high-entropy alloy (HEA) is also examined. In the Sn/FeCoNiCr system, a faceted (Fe,Cr,Co)Sn₂ layer initially forms at the interface. Upon aging, the significant spalling of large (Fe,Cr,Co)Sn₂ particulates into the solder matrix occurs. Additionally, an extremely large, plate-like (Co,Ni)Sn₄ phase forms at a later stage. In contrast, the Sn/FeCoNiMn reaction produces a finer-grained (Fe,Co,Mn)Sn₂ phase dispersed in the solder, accompanied by the formation of the large (Co,Ni)Sn₄ phase. This observation suggests that Mn promotes the formation of finer intermetallic compounds (IMCs), while Cr facilitates the spalling of larger IMC particulates. The Sn/FeCoNiCrMn system exhibits stable interfacial behavior, with the (Fe,Cr,Co)Sn₂ layer showing no significant changes over time. The interfacial behavior and microstructure are primarily governed by the dissolution of the constituent elements and composition ratio of the HEAs, as well as their interactions with Sn. Similar trends are observed in the SAC305 solder reactions, where a larger amount of fine (Fe,Co,Cu)Sn₂ particles spall from the interface. This behavior is likely attributed to Cu doping, which enhances nucleation and stabilizes the IMC phases, promoting the formation of finer particles. The wettability of SAC305 solder on MEA/HEA substrates was further evaluated by contact angle measurements. These findings suggest that the presence of Mn in the substrate enhances the wettability of the solder. Full article

Background/Objectives: This study aimed to develop a dry powder inhalation (DPI) formulation of rivaroxaban (RVX) using a combination of bead milling (BM) and jet milling (JM) to enhance lung-targeted delivery for the effective treatment of pulmonary embolism while minimizing systemic exposure. Methods: A carrier-free DPI formulation of RVX was developed using sequential BM and JM, with L-leucine incorporated at various concentrations (1%, 5%, and 10%) as a force control agent. The formulations were characterized for particle morphology, size distribution, crystallinity, and thermal properties. The in-vitro aerodynamic performance was evaluated using a next-generation impactor, while ex-vivo studies assessed anticoagulant activity. Pharmacokinetic and tissue distribution studies were carried out in Sprague Dawley rats following intratracheal administration, and the effects of inhaled RVX were compared with those of oral administration. Results: The optimized BM-JM-5L formulation achieved a Dv50 of 2.58 ± 0.01 µm and a fine particle fraction of 72.10 ± 2.46%, indicating suitability for pulmonary delivery. The two-step milling effectively reduced particle size and enhanced dispersibility without altering RVX’s physicochemical properties. Ex-vivo anticoagulation tests confirmed maintained or improved activity. In-vivo studies showed that pulmonary administration (5 mg/kg) led to a 493-fold increase in lung drug concentration and 2.56-fold higher relative bioavailability vs. oral dosing, with minimal heart tissue accumulation, confirming targeted lung delivery. Conclusions: The two-step milled RVX DPI formulations, particularly BM-JM-5L with 5% leucine, demonstrated significant potential for pulmonary administration by achieving high local drug concentrations, rapid onset, and improved bioavailability at lower doses. These findings highlight the feasibility of RVX as a DPI formulation for pulmonary delivery in treating pulmonary embolism. Full article

Modern industrial systems and biomass-fired furnaces require surface treatments that can withstand aggressive chemical, thermal, and corrosive environments. This study investigates the corrosion and thermal resistance of plasma-sprayed Al₂O₃-TiO₂ coatings produced using a DC air–hydrogen plasma spray process. Coatings of compositions of Al₂O₃, Al₂O₃-3 wt.% TiO₂, Al₂O₃-13 wt.% TiO₂, and Al₂O₃-40 wt.% TiO₂ were deposited on steel substrates with a Ni/Cr bond layer by plasma spraying. The coatings were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD) to evaluate their morphology, elemental composition, and crystalline phases. Electrochemical tests were performed in a naturally aerated 0.5 mol/L NaCl solution and cyclic thermal–chemical exposure tests (500 °C using 35% KCl) to assess their corrosion kinetics and thermal stability. The results indicate that pure Al₂O₃ and low TiO₂ (3 wt.%) coatings exhibit fine barrier properties, while coatings with a higher TiO₂ content develop additional phases (e.g., Ti₃O₅, Al₂TiO₅) that improve thermal resistance but reduce chemical durability. Full article

In recent years, the field of bionic engineering has advanced at a remarkable pace. Numerous engineering challenges have been addressed through inspiration drawn from biological organisms in nature. In this paper, laser cladding was employed to fabricate a bionic unit inspired by the radial ribs of the bivalve shell surface morphology on 20CrMnTi steel, with the aim of enhancing its wear performance. The metallic powder used in the experiments was prepared by blending Ni60 alloy powder with tungsten carbide (WC) in a predetermined ratio. The WC content was maintained within a mass percentage range of 15% to 60% in the composite powder system. The microstructure and properties of the bionic unit were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and a hardness tester, while its dry sliding wear resistance was evaluated using a block-on-ring tribometer. The influence of the WC content on the microstructure, hardness, surface roughness, and wear performance of the bionic unit was investigated. The experimental results revealed that the bionic unit exhibited a dual microstructure comprising equiaxed crystals and fine dendritic structures. The incorporation of WC induced pronounced grain refinement, while the dispersed WC particles formed effective metallurgical bonding with the Ni-substrate. A positive correlation was observed between the WC content and hardness, with peak hardness reaching 1008 HV_0.2 at 60% WC. Tribological analysis demonstrated a wear mechanism transition from dominant abrasive wear to a hybrid abrasive–adhesive wear. The wear volume of the bionic unit decreased with increasing WC content, and the extent of damage was reduced. Full article

Increased emissions of carbon dioxide (CO₂) from industrial activities are the main cause of the growing problem of global warming and climate change, highlighting the needs for efficient CO₂ capture and storage (CCS) techniques. The present work aims to investigate the possibility of CO₂ sequestration using sodium hydroxide (NaOH) in a semi-batch column with an integrated gas lift tower and an ultra-micro bubbles generator, a novel setup designed to enhance mass transfer rates and capture efficiency. Unlike the previously reported setups, our system achieves a 50% faster capture rate with improved mass transfer, enhanced gas-liquid interaction and higher removal efficiency due to finer bubble dispersion, as confirmed by experimental findings. Preliminary tests to ascertain the effectiveness of CO₂ removal were carried out across various CO₂ gas flow rates (3, 5, 7 L/min), NaOH volumes (2, 3, 4 L) and concentrations (0.1, 0.2, 0.3 M). The results indicated that both gas flow rate and NaOH concentration have profound impacts on the CO₂ capture rate. Increasing either of these parameters, or using low concentrations of NaOH, leads to a rapid drop in pH due to a faster rate of neutralization and the formation of carbonic acid (H₂CO₃), a weak acidic solution. For instance, with 0.1 M NaOH and 2 L volume, the pH decreased from 13.07 to 7.02 within 1.5 min at gas flow rate of 7 L/min, while with 0.3 M NaOH, pH reduced to 7.3 after 6 min. Higher volumes and concentrations of NaOH caused a decrease in the capture rate of CO₂ due to reversed reaction with formed sodium carbonate. For instance, with 0.3 M NaOH and 4 L volume, the pH reduced from 13.58 to 8 after 5 min at 7 L/min gas flow rate. Scaling up to a 100 L semi-batch column with an ultra-fine micro bubble generator, as a new approach, reduced the time taken by half in the capture of CO₂. Additionally, the study also investigated the comparison of tap versus deionized water in CO₂ capture reaction. The results demonstrated that dissolved minerals in tap water, particularly Ca²⁺ and Mg²⁺ ions, affected precipitate formation and capture efficiency differently than deionized water, offering practical insights for CCS in varied water sources. Full article

This work presents a new approach for the fabrication of 316L/Al₂O₃ composites, based on a combination of spray granulation, radio frequency (RF) plasma spheroidization and spark plasma sintering (SPS). Initially, a suspension containing 316L and alumina powders is formulated by precisely adjusting the pH and selecting an appropriate dispersant, thereby ensuring homogeneous dispersion of the constituents. The spray granulation process then produces granules with controlled size and morphology. RF plasma spheroidization, carried out using a TekSphero-40 system, is investigated by varying parameters such as the power, gas flow rates, injection position and feed rate, in order to optimize the formation of spherical and dense particles. The analysis reveals a marked sensitivity to heat transfer from the plasma to the particles, with a tendency for fine particles to segregate, which underscores the necessity for precise control of the processing conditions. Finally, SPS densification, performed under a constant pressure and a rigorously controlled thermal cycle, yields composites with excellent density and hardness characteristics. This study thus demonstrates that the proposed hybrid process offers an optimal synergy between a uniform distribution of alumina and a controlled microstructure, opening up promising avenues for the design of high-performance composite materials for demanding applications. Full article

Tamarix chinensis Lour. is a halophytic shrub native to coastal China, commonly used in afforestation and ecological restoration due to its high tolerance to salinity and drought. To understand how this species maintains genetic variation and adapts to extreme environments, we examined the genetic diversity, mating system, and spatial genetic structure of a natural T. chinensis population on the geographically isolated and environmentally harsh Wudi Seashell Island. Using both SSR and ISSR markers, we observed high levels of genetic diversity despite the small population size and spatial fragmentation. SSR markers revealed an average of 11.75 alleles per locus, with an expected heterozygosity (He) of 0.754 and an observed heterozygosity (Ho) of 0.702. ISSR markers showed a polymorphic locus rate of 97.87%, with a mean He of 0.402. Parentage analysis revealed relatively long seed and pollen dispersal distances, with most dispersal occurring within 150 m and seeds and pollens occasionally reaching 948 m and 447 m, respectively. The species exhibited a mixed mating system, with a multilocus outcrossing rate of 0.554, contributing to gene flow and reducing inbreeding. A fine-scale spatial genetic structure was detected within 75 m, consistent across both SSR and ISSR markers, suggesting limited local gene dispersal. These findings provide new insights into the adaptive strategies of T. chinensis in marginal habitats and offer valuable guidance for conservation and restoration efforts in vulnerable coastal ecosystems. Full article

Background: Carbamazepine (CBZ) is a Biopharmaceutical Classification System (BCS) class II drug, that is practically insoluble in water, influencing the oral bioavailability. Polyols are highly hydrophilic crystalline carriers studied for their success in developing solid dispersions (SDs) for improved solubility and dissolution rate. Polyols are generally regarded as safe (GRAS) and maltitol (MAL), xylitol (XYL) and sorbitol (SOR) are among the approved polyols for market use. While xylitol (XYL) and sorbitol, have shown promise in improving the solubility and dissolution rates of poorly soluble drugs, their full potential in the context of improving the solubility of carbamazepine have not been thoroughly investigated. To the best of our knowledge, maltitol (MAL) was not studied previously as a carrier for preparing SDs. Hence, the purpose of this study was to investigate their use in the preparation of CBZ SDs by the fusion method. Methods: CBZ-polyol SDs were prepared in varying molar ratios (2:1, 1:1 and 1:2) and characterised for solid-state nature, solubility and in-vitro dissolution rate. Results: Solid-state characterisation of the CBZ-polyol SDs revealed the existence of the SDs as continuous glass suspensions with fine CBZ crystallites suspended in the amorphous polyol carriers. Among the polyols studied, XYL exhibited good miscibility with CBZ and showed significant improvement in the solubility and dissolution rate. The prepared SDs showed a 2 to 6-folds increase in CBZ solubility and 1.4 to 1.9-folds increase in dissolution rate in comparison with pure CBZ. Conclusions: The study explains the possible use of polyols (XYL and SOR) based SDs of BCS Class II drugs with good glass forming ability for enhanced solubility and dissolution. Full article