Search Results (436)

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

Ti-6Al-4V thin-walled specimens were fabricated by gas tungsten arc welding-based wire arc additive manufacturing under controlled oxygen concentrations of 1, 500 and 1000 ppm, with ambient air used as a severe oxygen-exposure reference. The effects of oxygen concentration on oxygen uptake, microstructure, oxidation behavior and mechanical properties were investigated. Within the controlled range, the internal oxygen content increased from 0.07 to 0.15 wt.%, remaining below the ASTM B381-2013 limit. These specimens retained sound interlayer bonding and were mainly composed of α-Ti with a small amount of β-Ti, without detectable crystalline TiO₂ by X-ray diffraction. Controlled oxygen uptake refined the α lamellae and increased deformation resistance through interstitial solid-solution strengthening, increasing hardness from approximately 320 HV to 330–350 HV and tensile strength from 880 to 940 MPa, while reducing elongation from 11.5% to 9.5%. In contrast, the ambient-air specimen reached an oxygen content of 0.36 wt.%, developed an approximately 90 μm oxidation-affected layer and showed TiO₂-related oxides, α-colony aggregation and interface weakening. Its tensile strength and elongation decreased sharply to 295 MPa and 1.9%, respectively. These results indicate that atmosphere control in WAAM Ti-6Al-4V should prevent the transition from controlled oxygen strengthening to excessive oxygen-induced embrittlement. Full article

Background/Objectives: Idiopathic pulmonary fibrosis (IPF) and other progressive fibrotic interstitial lung diseases (F-ILD) are characterised by progressive loss of lung function, worsening symptoms, and poor prognosis. Current antifibrotic therapies slow disease progression but do not arrest or reverse fibrosis and are frequently associated with adverse effects. Senicapoc, a selective KCa3.1 channel inhibitor, has shown antifibrotic effects in preclinical models, human lung myofibroblasts, and ex vivo human lung tissue. This study aims to determine whether senicapoc reduces the rate of decline in forced vital capacity (FVC) over 26 weeks, compared with placebo, in patients with IPF or other progressive F-ILD, while also characterising safety and tolerability. Methods: This is an investigator-initiated, prospective, randomised, double-blind, placebo-controlled, multicentre phase II trial. Adults with IPF or other F-ILD with documented progression despite optimised antifibrotic management according to standard care and individual tolerability will be randomised 1:1 to receive senicapoc 30 mg once daily or a matching placebo for 26 weeks in addition to standard care. The primary outcome is the rate of decline in FVC over 26 weeks. Secondary outcomes include changes in diffusion capacity, 6 min walk distance, dyspnoea, health-related quality of life, adverse events, and senicapoc plasma concentrations, with mortality and exacerbations assessed as exploratory outcomes. The planned sample size is 140 participants. The primary analysis will be conducted in the intention-to-treat population using a linear mixed-effects model for repeated measurements. Results: No results are available, as this article describes the study protocol. Conclusions: This study will provide proof of concept for the efficacy, safety, and tolerability of senicapoc in progressive fibrotic interstitial lung disease. If successful, it will support further clinical development of KCa3.1 inhibition as a novel antifibrotic strategy. Full article

High-entropy alloys and the broader class of compositionally complex alloys have recently attracted significant attention as promising materials for solid-state hydrogen storage. Their potential arises not only from high configurational entropy but also from the possibility of tailoring phase composition, crystal structure, local chemical environment, and defect states that govern hydrogen sorption thermodynamics and kinetics. This review summarizes current understanding of hydrogen interaction mechanisms in HEAs and discusses the role of body-centered cubic (BCC), face-centered cubic (FCC), and Laves phases in determining hydrogen capacity, reversibility, and cyclic stability. The limitations of commonly used descriptors, including valence electron concentration (VEC), atomic size mismatch δ, enthalpy of mixing ΔH_mix, and Ω parameter, in predicting hydrogen storage behavior are critically analyzed. Particular attention is given to the effects of processing methods, phase transformations during hydrogenation/dehydrogenation, and the energetic heterogeneity of interstitial sites in multicomponent systems. The review highlights that future progress will depend on the transition from empirical alloy discovery toward physically informed multiparametric design integrating CALPHAD, DFT modeling, machine learning, and in situ/operando characterization techniques for the development of efficient and durable hydrogen storage materials. Full article

Magnesium antimonide (Mg₃Sb₂) has emerged as a promising high-performance thermoelectric material, yet its efficiency is fundamentally determined by intrinsic point defects. In this study, we present a comprehensive investigation of defects in the intermetallic compound Mg₃Sb₂ using first laws of thermodynamics and density functional theory (DFT) within the generalized gradient approximation (GGA). By calculating the energy of defect formation and the charge transition energy between energy levels, it was determined how the change in chemical potential associated with phase synthesis affects the phase stability and carrier concentrations. Calculations show that donor defects dominate in Mg-rich alloys, primarily antimony vacancies and magnesium atoms in interstitial positions. This means that in a phase with a slight magnesium excess, e.g., Mg_3.01Sb_1.99 at 1400 K, n-type conductivity dominates. In the opposite case, i.e., in an Sb-rich alloy, magnesium vacancies spontaneously form in the Wyckoff 1a position. These ionized acceptors induce strong self-compensation, blocking the Fermi level about 0.38 eV above the valence band maximum. As a result of this process, the Mg₃Sb₂ phase, at elevated temperatures, becomes the non-stoichiometric Mg_2.99Sb_2.01 phase, which causes the material to retain p-type conductivity and actively block doping-induced n-type conductivity. The conducted studies demonstrate that the homogeneity range of the Mg-Sb system, although traditionally considered narrow, has a significant impact on the semiconducting properties of the material. Furthermore, they also point to the need for continued research on high temperature in the area of synthetic defect engineering, interface engineering, and optimization of the thermoelectric properties of materials based on Mg-Sb alloys. Full article

Body-centered cubic (BCC) high-entropy alloys (HEAs) are among the most promising HEA-based solid-state hydrogen-storage materials, yet their behavior is still too often discussed through composition, average phase label, or storage capacity alone. This Perspective argues that such descriptions remain incomplete because hydrogen accommodation in BCC HEAs is governed by the interplay among local interstitial accessibility, site hierarchy, and hydrogen-induced structural evolution. We therefore recast the problem around three linked questions: where hydrogen resides first, how the relative accessibility of tetrahedral and octahedral environments evolves with loading, and how that evolving occupancy redirects the host lattice toward specific hydride-transformation pathways. Recent experimental and computational studies show that hydrogen occupation in BCC HEAs is mixed, selective, and concentration-dependent, rather than fixed to a single ideal interstitial type. They also show that direct BCC-to-FCC/BCT-type hydrogenation routes, as well as pathway failure in structurally unstable BCC-related systems, are best understood from this occupancy-centered viewpoint. On this basis, we suggest that future design of BCC HEA hydrides should move beyond composition screening toward an occupancy-informed framework in which local site hierarchy, pathway integrity, and hydrogen-induced phase switching are treated as central design variables. Full article

The critical metal lithium (Li) is increasingly sourced from spodumene and petalite pegmatite deposits due to their relatively high grades, lower mining environmental impacts and widespread global distribution. However, there are numerous gaps in our understanding of their genesis and the formation of unzoned or poorly zoned Li pegmatites is particularly difficult to explain. To investigate this, both spodumene-bearing and non-mineralized pegmatites and aplites are studied in the Moylisha segment of the Leinster pegmatite belt of SE Ireland, which were emplaced within the East Carlow Deformation Zone (ECDZ). Trace element modeling suggests that granite melts can achieve Li concentrations high enough (~5000 ppm) to crystallize spodumene. However, once crystallization begins, Li levels will drop rapidly below this threshold. While Li could be replenished by incoming melts, there is no supporting textural evidence for this, such as internal magmatic contacts, crosscutting relationships, or mingling. We test the hypothesis that low viscosity, Li-rich fluids from underlying reservoirs, most likely almost fully crystallized granite magmas or mush, continuously migrate through the heterogeneously crystallizing pegmatite-forming melts by percolative reactive flow, refertilizing interstitial melt by diffusion under favorable geochemical gradients. The flow of fluids is likely maintained due to their low relative density and periodic shearing within the ECDZ. Fluids with >10,000 ppm Li, derived by >95% crystallization (Rayleigh fractionation) of a granite magma, are shown to be capable of refertilizing a pegmatitic crystal mush after its emplacement. Supporting evidence includes macro- and micro-textures indicative of paragenetically late spodumene crystallization along apparent fluid flow pathways in mineralized pegmatites and aplites. Similar features are common in spodumene pegmatites worldwide and suggest that Li upgrading by fluid flow through crystallizing spodumene pegmatites may be a key process in enhancing Li grades and in some cases in producing economically favored low-Fe spodumene. Full article

We propose a reaction–diffusion phase-field model to simulate the microstructure evolution of voids in systems with low vacancy concentration under irradiation. In this model, void growth and shrinkage are governed by reactions between vacancies/interstitials and the void surface, while an order parameter is introduced to describe void morphology. By avoiding the sharp increase in vacancy concentration near the void interface, the model enables the simulation of void evolution in low vacancy concentration matrices over enlarged time scales. When combined with classical nucleation theory, the approach enables quantitative, accurate three-dimensional simulations of slow void evolution processes, achieving comparability with rate theory models. Numerical results demonstrate that the model accurately captures the evolution of voids under dilution conditions. At the same time, its inherent scalability makes it broadly applicable to other material systems characterized by low solute concentrations. Full article

Mangroves rank among the most productive ecosystems on Earth, yet they are increasingly threatened by climate change and the expansion of agricultural land use. Among agricultural pollutants reaching coastal environments, glyphosate-based herbicide formulations (GBHFs) are of particular concern owing to their widespread application and environmental persistence. This study evaluated the phytotoxic effects of a GBHF (commercial product Velfosato, 48% active ingredient) on Rhizophora mangle L. seedlings under controlled experimental conditions simulating the intertidal regime of the collection site. Propagules were collected from the Los Petenes Biosphere Reserve (Campeche, Mexico), established in experimental tanks containing mangrove soil, and grown until uniform seedling development was achieved. Once seedlings reached uniform development, they were exposed to nominal concentrations of 0.003, 0.03, 0.3, 3.0, and 10 mg L⁻¹ of the formulation dissolved in interstitial water. The experiment followed a completely randomized design (three replicate tanks per treatment plus a triplicate control; n = 1170 seedlings total). All inferential tests used the tank as the experimental unit (n = 3 per treatment). Total chlorophyll concentration was significantly lower in treated seedlings than in the control across all tested concentrations (ANOVA F_5,12 = 4.55, p = 0.015). Height growth rates were significantly reduced at concentrations ≥ 3 mg L⁻¹ (F_5,12 = 6.84, p = 0.003). Lenticel number increased significantly at the two highest concentrations (F_5,24 = 3.63, p = 0.014). Mangrove soil exhibited significant increases in pH and decreases in redox potential across the concentration gradient (p < 0.001 and p = 0.001, respectively). These findings indicate that sublethal exposure to a GBHF is associated with alterations in key ecophysiological processes and soil physicochemical conditions in R. mangle seedlings under controlled conditions, highlighting the sensitivity of early developmental stages to GBHF exposure. Full article

Ovarian cancer (OC) remains one of the leading causes of gynecologic cancer mortality, largely due to late diagnosis, frequent relapse, and the emergence of chemoresistance. An important but often-overlooked contributor to treatment failure is the heterogeneous penetration of anticancer drugs within tumors. Structural and biochemical barriers—including abnormal vasculature, elevated interstitial pressure, dense extracellular matrix, drug efflux transporters, and malignant ascites—generate steep intratumoral concentration gradients that conventional preclinical models fail to capture. As a result, systemic pharmacokinetic measurements frequently provide limited insight into tumor-level drug exposure. Patient-derived organoids (PDOs) have emerged as physiologically relevant 3D models that preserve the genetic, architectural, and functional characteristics of the original tumor. These systems enable controlled investigation of pharmacokinetic and pharmacodynamic processes, including drug penetration, metabolism, retention, and exposure–response relationships. Adding cell-free malignant ascites supernatant enhances PDOs’ ability to mimic the metastatic peritoneal microenvironment of OC. This review discusses recent advances in PDO technologies and examines how PDO-derived data can inform intratumoral pharmacokinetics and dosing strategies using physiologically based pharmacokinetic modeling and in vitro–in vivo extrapolation. Emerging hybrid platforms, including organoid-on-chip systems, vascularized co-cultures, and multi-omics integration, are crucial to improve translational prediction and support precision oncology. Full article

Continuous, in vivo drug and biomarker measurements could transform healthcare, enabling both the high-precision personalization of drug dosing and the real-time monitoring of health status. A practical realization of this vision, however, requires an improved understanding of the relationship between concentrations measured in the easily accessible dermal interstitial fluid (ISF) that correlate with the plasma concentrations that guide clinical decision making. As a preliminary step towards this goal, here we have used electrochemical, aptamer-based (EAB) sensors to perform seconds-resolved vancomycin measurements in the plasma and subcutaneous ISF of live rats. Concentrations of the antibiotic in the ISF vary rather little between different subcutaneous sites and, after the very rapid initial distribution phase is complete, they are well correlated with the plasma concentrations (mean R² = 0.88). Likewise, a simple, two-compartment, two-parameter model describes our six paired plasma and ISF drug time courses quantitatively. Together, these findings provide further evidence of the viability of the drug concentration measurements performed in the subcutaneous or dermal ISF as a less invasive approach to real-time drug monitoring in individual patients. Full article

Cartilage regeneration remains an unmet clinical challenge. Despite the great advances in the production of hydrogels as support matrices for cartilage regeneration, the resulting mechanical properties remain low. Granular composite hydrogels appear as ideal candidates due to their injectability and modularity in design. Here, we report on the fabrication and characterization of heterogeneous composite granular hydrogels based on methacrylated chitosan (CHIMA) and gelatin (GelMA) microparticles supported by an interstitial methacrylated alginate (ALMA) matrix. Microparticles were prepared by an oil-emulsion method and their size and morphology optimized, resulting in CHIMA and GelMA microparticles of 10.8 µm (95% CI 9.2, 13.1) and 115.8 µm (95% CI 107.5, 137.6) in diameter, respectively. The microparticles were mixed with ALMA and crosslinked to form granular hydrogels that demonstrated reduced swelling and weight loss. The storage modulus increased from 33 to 66.4 kPa for CHIMA/ALMA hydrogels and from 11.5 to 19.5 kPa for GelMA/ALMA hydrogels when the particle concentration increased from 10 to 50%, and was higher than traditional ALMA hydrogels. Hydrogels of 50:50 CHIMA:GelMA permitted a 6.6-fold increase in cell number after 28 days of culture, and promoted the chondrogenic differentiation of embedded mouse mesenchymal stem cells with a glycosaminoglycan deposition of over 15 µg and the expression of chondrogenic markers. Full article

Irradiation creep of engineering alloys in nuclear reactor cores differs from the creep that is observed outside of the irradiation environment. It exhibits characteristics like high temperature thermal creep because it occurs in an environment of elevated vacancy point defect concentrations, but one must also consider the effect of interstitial point defects and the effect of both vacancy and interstitial concentrations, which are greater than the thermal equilibrium values, on an evolving microstructure. Irradiation creep is dependent on the point defect flux to different sinks and can be modelled using conventional rate theory. The net interstitial or vacancy point defect flux to different sinks determines the strain rate in a direction that can be considered perpendicular to the plane of the sink, which is the extra half plane of an edge dislocation or the plane of a grain boundary. There has been increasing evidence that, for complex alloys such as Zr-2.5Nb pressure tubing in CANDU reactors, the irradiation creep is largely dependent on the grain structure (size and shape). While the maximum amount of thermal creep by dislocation slip will be proportional to the distance a dislocation travels, i.e., proportional to the grain dimension in the direction of slip, observations indicate that the magnitude of irradiation creep is inversely proportional to the grain dimensions, indicating a creep mechanism dependent on diffusional mass transport. Mechanistic modelling of irradiation creep based on rate theory is described and used to account for high diametral creep rates observed for pressure tubes with unusual microstructures fabricated by non-standard fabrication routes. Full article

Photoluminescence (PL) imaging techniques combined with a minority carrier lifetime measurement system were utilized to investigate the effects of heating temperature on the interstitial iron (Fe_i) concentration, the recombination activity of structural defects, and the minority carrier lifetime in cast multicrystalline silicon (mc-Si). The results indicate that heating mc-Si wafers to 800 °C followed by natural cooling led to a 21.4% increase in Fe_i concentration, a 121% increase in recombination-active dislocations, a 142% increase in recombination-active grain boundaries, a 158% rise in the “dark area percentage,” and a 46.6% decrease in minority carrier lifetime. When the heating temperature was increased to 1000 °C followed by natural cooling, the Fe_i concentration rose by a factor of 11.87, and the “dark area percentage” increased by 8668%, suggesting widespread metal impurity—particularly iron contamination across the entire wafer, which resulted in an extremely low minority carrier lifetime of only 0.224 μs. Full article

Glucose data regarding extreme elite performances in athletes without diabetes remains limited. The purpose is to characterize continuous glucose monitoring (CGM) responses in elite athletes across distinct high-performance contexts. This descriptive case series includes three separate elite athletes who used a CGM during their respective sporting events. The first is an ultra-endurance relay cycling world-record performance (Race Across the West, RAW), the second is a continuous high-intensity Everesting Challenge cycling record attempt, and the third is a maximal constant-weight no-fins breath-hold depth dive performed in international competition. Glycemic outcomes, as measured by CGM, included mean, maximum, and minimum glucose, glucose standard deviation (SD), and the percentage of time in tight glucose range (TITR: 70–140 mg/dL; 3.9–7.8 mmol/L), time below range (TBR: <70 mg/dL; <3.9 mmol/L), and time above range (TAR140: >140 mg/dL; >7.8 mmol/L). Other performance data, including peak power, heart rate, and lactate, are also provided where available. During the RAW challenge lasting 44 h and 20 min, mean glucose was 91 ± 23.2 mg/dL (mean ± SD) with 9.15% TBR and 35.58% TITR during cycling and 115 ± 24.7 mg/dL with 9.11% TBR and 43.16% TITR during resting periods. In contrast, the Everesting Challenge cycling record attempt demonstrated a persistently elevated glucose profile (160 ± 5.7 mg/dL), minimal variability (CV 3.5%), and 100% TAR140. Following the maximal breath-hold depth dive, interstitial glucose was 100% TAR140 during recovery (187 ± 18.5 mg/dL), alongside marked elevations in blood lactate concentrations (peak 13.4 mmol/L). The series of case studies demonstrate that substantial deviations from traditional euglycemic ranges are common during elite performance in athletes without diabetes. Interpretation of CGM data in athletic settings should therefore be performance- and context-specific rather than based on clinical glycemic thresholds. Full article