Search Results (6,813)

Pyrrolidinyl-substituted silacyclopentane (CH₂)₄Si(Pyr)₂ and α-amino isobutyric acid (H₂Aib) react with the release of one equivalent pyrrolidine (HPyr) and the formation of the pentacoordinate silicon bis-chelate (Aib)Si(CH₂)₄(HPyr), which features the di-anion of the amino acid as an (O,N)-chelator and one equivalent of pyrrolidine as an additional lone-pair donor. Crystallographic analyses of the chloroform solvate (Aib)Si(CH₂)₄(HPyr)·(CHCl₃), which undergoes a phase transition at 200 K, and a solvent-free modification (Aib)Si(CH₂)₄(HPyr), which features two crystallographically independent molecules of the complex, revealed that the N atom of the HPyr ligand, as well as the carboxylate of Aib, occupy the axial positions in the trigonal bipyramidal Si coordination sphere; the Si–C bonds of the silacyclopentane rest on equatorial sites. For the isolated molecule in a solvent environment, computational analyses revealed that the energy difference between this configuration and the related isomer with an equatorial HPyr and equatorial–axial positioning of the silacyclopentane motif is marginal. In DMSO solution, the adduct (Aib)Si(CH₂)₄(HPyr) decomposed, forming the hexacoordinate Si complex (HAib)₂Si(CH₂)₄ as one of the decomposition products. In a deliberate manner, this compound was accessible from the diethylamino-substituted silacyclopentane (CH₂)₄Si(NEt₂)₂ and H₂Aib with the liberation of diethylamine. (HAib)₂Si(CH₂)₄ features two mono-anions of the α-amino acid as (O,N)-chelators, their carboxylate O atoms are trans-disposed to silacyclopentane, and their NH₂ groups are mutually trans. Full article

Background: Egg allergy is one of the most common food allergies in early childhood and is traditionally managed through strict avoidance diets, which may negatively affect nutrition and quality of life. Early oral immunotherapy (OIT) may represent an alternative therapeutic strategy; however, controlled studies in children younger than two years remain limited. Methods: We conducted a prospective observational study using historical controls. Thirty-one children younger than two years with IgE-mediated egg allergy underwent OIT using pasteurized liquid egg white (maximum dose: 30 mL; 3300 mg protein). Twelve children managed with an avoidance diet served as the historical control group. Outcomes included desensitization rates, adverse reactions, and longitudinal changes in skin prick test (SPT) wheal diameters, serum-specific IgE (sIgE), specific IgG4 (sIgG4), and sIgE/total IgE ratios. Results: At six months, 29/31 children (93.5%) in the OIT group did not experience allergic reactions after ingestion of any egg preparation, compared with none in the historical control group (p < 0.001). In the control group, 7/12 children (58.3%) continued to react to less-cooked egg preparations, whereas 5/12 (41.7%) remained reactive to all forms of eggs. During the induction phase, 24/31 OIT-treated children (77.4%) experienced mild adverse reactions, predominantly isolated cutaneous or gastrointestinal symptoms, and no patient required intramuscular adrenaline administration. In contrast, allergic reactions occurred in 11/12 controls, including anaphylaxis in 6/12 (50.0%) patients (p = 0.0301). The OIT group demonstrated significant reductions in SPT wheal diameters, sIgE levels, and sIgE/total IgE ratios (all p < 0.001), accompanied by increased sIgG4 levels. Conclusions: Early OIT with pasteurized egg white in children younger than two years with IgE-mediated egg allergy was associated with high desensitization rates, favorable short-term safety outcomes, and significant immunological changes. These findings support the potential role of early active intervention as an alternative to exclusive avoidance strategies in infants with egg allergy. Full article

This article reviews the linear solvers available in OpenFOAM and assesses their impact on the convergence behaviour of the SIMPLE algorithm. The discretisation of transport equations in CFD results in large and sparse linear systems, for which the choice of linear solver strongly influences the computational time. Although the solver does not change the final discrete solution, the difference in speed and robustness between the solvers can be more than one order of magnitude. A brief overview is given concerning how the velocity and pressure fields are decoupled in OpenFOAM, followed by a detailed review of the main linear solver families, including direct methods, basic iterative methods, multigrid methods and Krylov subspace methods, with attention to their practical strengths and weaknesses. The performance of the most advanced solvers is evaluated on a full-scale non-reacting kiln case consisting of 2.3 million cells. The pressure-corrector equation is identified as the main bottleneck in the SIMPLE algorithm. The conjugate gradient (CG) solver with a multigrid (MG) preconditioner is found to be the fastest and most stable method, achieving speed-ups of up to a factor of 7 compared to the slower advanced methods. Using MG as a preconditioner also improves the robustness of the Bi-CGStab method. Full article

Control charts are used in statistical process control (SPC) to keep track of processes and identify changes in the way that they work. The control limits around the center line are uniform, which means they react the same way to changes going in either direction. In contrast, linear charts use imbalance to make it easier to identify individual data points. Therefore, using imbalance in the creation of control charts helps keep track of and maintain consistency with data that has a big impact on results when it goes beyond predetermined limits. In this study, we look at both one-sided and two-sided control charts by getting an explicit closed-form formula for the double-modified EWMA control chart’s average run length (ARL). The study is mostly about developing better ways to spot things using autoregressive fractionally integrated models and external variables (ARX and ARFIX) in the presence of exponential white noise. The ARL is used to test how well the proposed chart works in both modeling systems. The NIE method is used to prove that the explicit closed-form ARL formula works. The closed-form ARL expression is shown to be valid under the given ARX and ARFIX model assumptions, exponential white noise errors, stationarity conditions, and fixed one-sided or two-sided control limits. The results show that %RPC has a value below 10⁻⁶, and the computation times for the ARX and ARFIX models remain below 1.6 s and 3 s, respectively, after that point. To show how much better it is, the suggestion is compared to Type-EWMA control charts, such as classical and modified EWMA charts, in terms of run-length efficiency using ARL and SDRL, as well as overall efficiency by the relative index and with mean and standard deviation. The simulation study checks how well the proposed chart works in both symmetric two-sided and asymmetric one-sided frameworks. For the crude oil application, the one-sided upper control chart is used to detect abrupt upward price shifts, which may indicate precautionary demand shocks, market uncertainty, and risk spillovers to financial markets. According to the findings, the suggested chart is able to identify shifts at a faster rate than both traditional EWMA charts and modified EWMA charts, which demonstrates that it is beneficial in a real setting. Full article

Endoscopic resection (ER) has become the preferred curative-intent treatment for early upper gastrointestinal cancer, given its superior safety profile compared to surgery. Over the past decade, technological and procedural innovation has substantially expanded the scope, safety, and precision of endoscopic submucosal dissection (ESD) and related techniques. This review synthesises current evidence on key advances relevant to upper gastrointestinal ESD practice. Enhanced imaging modalities have improved lesion detection and characterisation, as well as recognition of intraoperative anatomical structures during third-space endoscopy. A new generation of therapeutic endoscopes combines high-definition optics with substantially improved tip-down angulation and channel size, addressing a longstanding gap between diagnostic-class image quality and procedural capability. Resection strategies—including mechanical traction systems, saline immersion therapeutic endoscopy (SITE), and luminal drainage techniques—have reduced procedural complexity and improved dissection conditions. Dedicated closure technologies have improved management of large resection defects, potentially reducing resection-related morbidity. Deep resection techniques, including submucosal tunnelling endoscopic resection (STER), device-assisted endoscopic full-thickness resection (FTRD), knife-assisted full-thickness resection (kFTR), and endoscopic intermuscular dissection (EID), are extending organ-preserving resection to deeply invasive cancers and subepithelial lesions. Management of non-curative ESD resections is being refined through multicentre risk stratification studies. Advances in simulation, competency-based training, and artificial intelligence hold promise for standardising technique acquisition and real-time procedural support. Together, these innovations are reshaping upper gastrointestinal oncology by positioning minimally invasive, organ-preserving digestive endoscopy as a central therapeutic strategy. Full article

Corrosion of pipelines by flue gas desulfurization (FGD) wastewater compromises the normal operation of the desulfurization tower, and corrosion under high-chloride conditions in particular severely damages the tower’s internal structure. To further elucidate the corrosion mechanism at elevated Cl⁻ concentrations, the corrosion behavior of 20 steel exposed to high-chloride FGD wastewater at different Cl⁻ concentrations was investigated through weight-loss measurements, electrochemical tests, immersion corrosion experiments, composition analysis, and microscopic morphology characterization. The results revealed that higher Cl⁻ concentrations corresponded to lower corrosion rates: the corrosion rate reached 0.1964 mm/y in the absence of Cl⁻, but decreased to 0.1537 mm/y at a Cl⁻ concentration of 100,000 mg/L. XPS analysis showed that as the Cl⁻ concentration increased, the corrosion film gradually transformed from porous FeOOH into dense Fe₃O₄. Localized pitting analysis indicated a positive correlation between Cl⁻ concentration and pitting susceptibility. At Cl⁻ concentrations of 0 and 100,000 mg/L, the corrosion current density decreased from 32.44 μA/cm² to 6.43 μA/cm² after 72 h, decreasing by a factor of approximately 5.05. This behavior is attributed to the fact that Cl⁻ increases solution conductivity in high-chloride environments, thereby promoting the formation rate of the corrosion film. Additionally, high Cl⁻ levels reduce dissolved oxygen in the solution, causing the corrosion film to progressively react and form denser Fe₃O₄. Nevertheless, the high penetrability of Cl⁻ continues to aggravate pitting corrosion of 20 steel. Full article

This paper presents a comprehensive augmented reality (AR)-based rehabilitation system for upper-limb recovery that integrates AR-assisted art therapy, automated markerless goniometry, and the interval mathematical modeling of rehabilitation dynamics. The proposed platform combines four interconnected subsystems: a Python-based markerless video analysis module utilizing three stationary IP cameras, MediaPipe Pose Landmarker, and Kalman filtering; an AR art-therapy application developed for the Magic Leap 2 headset using Unity/OpenXR; a server-side subsystem implemented in NestJS/TypeScript; and (iv) a physiotherapist-oriented web application developed in React. The primary objective of the study is the real-time automated assessment of shoulder joint kinematics during AR-assisted rehabilitation sessions, including flexion (160–180°), extension (50–60°), and abduction (up to 180°). To describe and forecast rehabilitation dynamics, interval mathematical models based on recurrent difference equations were developed, enabling the prediction of subsequent joint angle values using the previous 3–4 observations. Structural and parametric identification of the interval models was performed using the artificial bee colony optimization algorithm. Experimental validation was conducted on rehabilitation data collected from five patients with different clinical diagnoses, including bursitis, epicondylitis, capsulitis, osteoarthritis, and fracture-related impairments. Under the considered experimental conditions, the proposed approach demonstrated promising predictive performance, with an angular prediction error below 5° and a correlation exceeding 95% between predicted and measured rehabilitation trajectories. The developed system implements a unified rehabilitation cycle of “execution–measurement–prediction–adaptation”, enabling the continuous monitoring of recovery dynamics, adaptive adjustment of rehabilitation scenarios, and estimation of the rehabilitation duration required to achieve target motor outcomes. The proposed approach contributes to the development of intelligent AR-based rehabilitation systems by combining markerless motion analysis, predictive interval modeling, and adaptive art-therapy mechanisms within a single clinical framework. Full article

The rapid growth of user-generated reviews on e-commerce platforms has created a significant decision-making challenge for both consumers and sellers, particularly in morphologically rich low-resource languages such as Turkish. This study proposes a unified artificial intelligence framework for Turkish e-commerce review intelligence by integrating transformer-based sentiment classification, instruction-tuned large language model summarization, and explainable fuzzy logic-based product evaluation within a single end-to-end architecture. A balanced dataset containing 183,333 Turkish reviews was constructed from Trendyol, Amazon Turkey, and Hepsiburada using LLM-assisted annotation and stratified downsampling. Experimental evaluations demonstrated that the fine-tuned BERTurk 128k model achieved a macro F1-score of 0.9243 on the held-out test set. To overcome the limitations of multilingual news-oriented summarization models on informal review text, the framework employed the Turkish instruction-tuned Kumru-2B model together with structured prompt engineering to generate sentiment-aware abstractive summaries. In addition, a Mamdani-type fuzzy inference system was designed to combine sentiment distribution, seller reliability, star ratings, and review volume into an interpretable product-level score. The complete pipeline was integrated into a FastAPI and React-based web platform capable of processing approximately 850 reviews in under 60 s. The findings demonstrate that domain-specific Turkish language models combined with explainable reasoning mechanisms can provide accurate, scalable, and human-interpretable decision support for large-scale e-commerce environments. Full article

A new method has been established for determining trace amounts of platinum in water using ion liquid (IL)-dispersive liquid–liquid microextraction (DLLME) combined with graphite furnace atomic absorption spectroscopy (GFAAS). The method is based on the use of a self-prepared reagent, 5-(5-cyano-2-pyridineazo)-2,4-diaminotoluene (5-CN-PADAT), as a chelating agent, which reacts with Pt(IV) to form a hydrophobic chelate. The extraction solvent is 1-octyl-3-methylimidazolium hexafluorophosphate ([C₈mim][PF₆]), and ethyl acetate is used as the dispersive solvent. After the extraction is completed, the extraction phase formed by [C₈mim][PF₆] and ethyl acetate has a relatively low viscosity and can be directly used for the determination of GFAAS. A single-factor rotational method was employed to optimize conditions affecting DLLME extraction efficiency. The interactions among the factors affecting DLLME were analyzed using response surface optimization (RSM). Under optimal conditions, platinum concentrations exhibited good linearity within the range of 40–280 ng/mL, with a detection limit of 0.3 ng/mL. AGREEprep was used to discuss the ecological friendliness of the method, demonstrating its low cost, ease of operation, simple equipment requirements, and environmental friendliness. When applied to determining trace amounts of platinum in water samples, the results were satisfactory. Full article

The application of urea in agricultural practices leads to carbon dioxide (CO₂) emissions through hydrolysis. Urea, when applied to soil, reacts with water and undergoes hydrolysis, releasing ammonia (NH₃) and CO₂. This reaction is facilitated by soil enzymes such as urease. The released NH₃ can further undergo nitrification, producing nitrate (NO₃⁻) and nitrous oxide (N₂O). While CO₂ from urea hydrolysis is relatively small compared to other sources, cumulative emissions from agricultural activities contribute significantly to climate change and agriculture’s carbon footprint. A straightforward calculation model (CO₂ = A × 0.73) was employed to approximate CO₂ emissions in various countries based on annual urea usage. In this model, China led emissions with 40,483 Gg yr⁻¹, followed by India (26,031 Gg yr⁻¹) and the USA (12,032 Gg yr⁻¹). Out of total annual emissions (94,763 Gg), China contributed 43%, India 27%, the USA 13%, the EU 8%, Pakistan 5%, and Indonesia 4%. China’s CO₂ emissions from urea were 16% higher than India, 30% higher than the USA, 35% higher than the EU, 38% higher than Pakistan, and 39% higher than Indonesia. As expected from the deterministic IPCC formula (CO₂ = Urea × 0.73), the relationship between urea consumption and CO₂ emissions is linear with a slope of 0.73. Linear regression shows that for every 1000-ton increase in urea consumption, CO₂ emissions increase by 730 tons (0.73 Gg) (R² = 0.99, p < 0.001). Pakistan’s urea consumption grew at an average annual rate of 2.2% from 2015 to 2023, with corresponding CO₂ emissions increasing from 4015 to 4788 Gg yr⁻¹ (total increase of 20% over eight years). Optimizing fertilizer application rates, timing, and methods to enhance nutrient uptake efficiency, along with sustainable agricultural practices (organic matter management, conservation tillage, and precision agriculture), can help mitigate environmental impacts. This study emphasizes implementing sustainable agricultural practices and integrated nutrient management to minimize CO₂ emissions from urea application, enabling agricultural systems to contribute to climate change mitigation and reduced carbon footprints. Full article

Background/Objectives: African Swine Fever (ASF) represents one of the most serious threats to animal health and global food security. The causative agent of ASF is the African swine fever virus (ASFV), a DNA virus belonging to the Asfarviridae family. Here, we describe ex vivo results for an original anti-ASFV vaccine approach based on the cellular immune response induced by extracellular vesicles (EVs) engineered to express four ASFV proteins. EV engineering was achieved by expressing a DNA vector encoding a biologically inactive HIV-1 Nef protein (Nef^mut), which exhibits unusually high efficiency of incorporation into EVs, even when fused to foreign proteins. Previous studies have demonstrated that intramuscular injection of Nef^mut-based vectors leads to the engineering of Evs, spontaneously released by muscle cells, and induction of antigen-specific CD8⁺ T cell immunity. Methods: We designed DNA vectors expressing the fusion products between Nef^mut and each of the four ASFV structural proteins p30, p54, pp62, and p72. Engineered EVs were molecularly characterized by Western blot and nanotrack analysis, and their potential immunogenicity was assessed by priming and cross-presentation assays. Results: We assessed that the four fusion proteins were successfully expressed in transfected mammalian cells, with the release of valuable amounts of engineered EVs. When immature swine dendritic cells were challenged with the engineered EVs and then co-cultivated with autologous peripheral blood lymphocytes in priming assays, lymphocyte subpopulations specifically reacting against each ASFV antigen were elicited, as detected by an IFN-γ ELISpot assay. In addition, we provide evidence that the Nef^mut-based fusion products incorporated into the engineered EVs can be cross-presented by professional antigen-presenting cells, leading to cross-priming of autologous lymphocytes. Conclusions: These results represent the best premise to go forward with experiments examining immunogenicity and antiviral efficiency in pigs. Full article

Clay mineral authigenesis and transformation are key diagenetic processes that influence the evolution of sandstone reservoir quality. Although smectite formation and its transformation to illite have been widely studied in clay-rich and feldspathic systems, their development in highly quartz-rich sands remains less well constrained. This study investigates the experimental formation of authigenic smectite and its subsequent illitization in a quartz-dominated sand under controlled hydrothermal experiments. Quartz-rich glass sand from the Middle Jurassic Mariedal Formation (Skåne, Sweden) was reacted with natural Red Sea water in sealed reactors at 80, 150, 200, and 250 °C for 14 days to simulate progressive burial diagenesis. Mineralogical, textural, and geochemical changes were evaluated using thin-section petrography, SEM-EDS, WD-XRF, XRD, and ICP-OES. The starting material is composed predominantly of quartz (91.3%), with minor K-feldspar (6.2%) and muscovite (1.4%), providing limited but sufficient reactive components for clay mineral formation. Dissolution of K-feldspar and muscovite began at 80 °C and continued throughout the experiments. Authigenic smectite was first detected at 150 °C as discontinuous grain-coating phases, indicating nucleation through dissolution–precipitation reactions linked to feldspar alteration and uptake of Mg from the reacting fluid. At 200 °C, the smectite coating became thicker and more extensive, with the onset of transformation to illite through mixed layer stages. By 250 °C, illite becomes the dominant clay mineral, recording progressive smectite illitization with increasing temperature. Fluid chemistry shows systematic variations with temperature, including decreasing Mg and evolving K concentrations, reflecting progressive mass transfer between solid and fluid phases. These results demonstrate that even highly quartz-rich sands can generate authigenic clay minerals when minor reactive phases and suitable fluid chemistry are present. The experiments provide a process-based analogue for clay mineral evolution in quartz-rich sandstone reservoirs and highlight the importance of coupled mineral–fluid reactions during burial diagenesis. Full article

Magnesium-based hydrides remain among the most intensively studied solid-state hydrogen storage materials because they combine high theoretical hydrogen capacity, elemental abundance, and relatively low cost. Yet their practical behavior often varies far more strongly than nominal composition alone would suggest. Materials described under similar chemical labels may show markedly different activation profiles, sorption kinetics, reversible capacities, and cycling responses, even when they appear compositionally comparable. This Perspective argues that such discrepancies are best understood by recognizing that Mg-based hydrogen storage materials are not fully defined by composition, catalyst identity, and equilibrium thermodynamics alone. Instead, they react from historically written states produced by synthesis, activation, and cycling. These histories generate hidden state variables, including defects, residual strain, metastable structural motifs, interfacial topology, and catalyst transformation states, that reshape the operative hydrogen sorption pathway. The discussion therefore moves from a conventional composition-centered view toward a pathway-centered interpretation of reactivity. First, it examines how hidden state variables are written into Mg-based materials through processing, activation, and repeated use. It then shows how metastability serves as the structural bridge that allows these variables to persist into the reaction window. On that basis, the article argues that hydrogen sorption in Mg-based hydrides is fundamentally pathway-dependent, with history influencing hydrogen entry, transport-network selection, interfacial route construction, and pathway evolution during cycling. This perspective also provides a more coherent explanation for the long-standing reproducibility problem in the field, which is reinterpreted here as a pathway-mismatch problem arising from comparisons among historically different reactive states. Finally, a metadata-aware, pathway-aware, and boundary-aware design framework is proposed as a more realistic basis for cumulative materials development. From this viewpoint, the future of Mg-based solid-state hydrogen storage depends not only on better compositions, but on better-defined, better-constructed, and better-preserved reactive pathways under clearly specified internal and external constraints. Full article

Glauconite-rich sands can generate authigenic clays during burial, as glauconite breaks down and supplies material for smectite that may subsequently transform into illite. The smectite-to-illite transformation is a key burial diagenetic reaction that strongly influences sandstone reservoir quality; however, the reaction pathways and resulting textures in glauconite-rich sands remain insufficiently documented. To better constrain illitization in glauconitic systems, we conducted four hydrothermal batch experiments using glauconitic greensand from the Arnager Greensand Formation (Bornholm Island, Denmark), reacted with Red Sea water at 80 °C, 150 °C, 200 °C, and 250 °C for 21 days. Reaction products were characterized using bulk and clay-fraction XRD, XRF, and SEM–EDS, together with pre- and post-reaction fluid chemistry. At 80 °C, early dissolution of glauconite and other detrital components (K-feldspar, muscovite and calcite) was observed, resulting in increased concentrations of dissolved ions in the fluid but no authigenic clay formation. Authigenic smectite first developed at 150 °C, occurring primarily as grain-coating clay. With further heating to 200 °C, smectite began to transform into mixed-layer illite–smectite, accompanied by the first clear development of illite textures. At 250 °C, illitization advanced significantly, and the reacted products were dominated by wavy to fibrous illite. The resulting clay minerals and their grain-coating morphologies are comparable to coatings reported from buried sandstone reservoirs. These findings suggest that glauconite alteration can generate grain-coating clays that may help limit quartz cement growth and preserve porosity. However, the development of wavy/fibrous illite may also obstruct pore spaces and reduce permeability. Overall, glauconite-derived clay evolution may preserve porosity while still degrading permeability, and the net reservoir effect depends on the morphology and distribution (thickness and coverage) of the newly developed clay minerals. Full article

High-zinc blast furnace dust is a zinc-bearing solid waste generated during ironmaking. Efficient de-zincing and iron enrichment are required for its resource utilization. This study investigated the high-temperature reduction behavior and kinetic transition mechanism of cold-bonded briquettes made from high-zinc blast furnace dust with a small addition of iron ore powder, with particular emphasis on the effects of reduction temperature (1000–1200 °C) and holding time (10–60 min). The results show that reduction at 1200 °C for 60 min can effectively remove zinc and enrich iron. The de-zincing rate reached 92%, and the TFe grade increased to 50 wt.%, achieving the goal of efficiently removing zinc while improving the TFe grade of the reacted briquettes. During the middle and later stages of reduction (1100–1200 °C, 30–60 min), the content of newly formed metallic iron increased, which restored the briquette strength to 524 N after reduction. In addition, the reduction kinetics of the system evolved from interfacial chemical reaction control in the initial stage to three-dimensional internal diffusion control in the middle and later stages. These results provide a theoretical basis and technical reference for the resource utilization of high-zinc blast furnace dust. Full article