Search Results (1,680)

Despite increasing evidence that cigarette smoke is a significant source of indoor fine particulate matter (PM_2.5), quantitative emission factors (EFs) for PM_2.5 and its toxic chemical composition in mainstream (MS) and sidestream (SS) smoke are still not well defined. In this study, we employed a custom-designed chamber to separately collect MS (intermittent puff) and SS (continuous sampling) smoke from eleven cigarette models, representing six brands and two product types, under controlled conditions. PM_2.5 was collected on quartz-fiber filters and analyzed for carbon fractions (using the thermal–optical IMPROVE-A protocol), nine water-soluble inorganic ions (by ion chromatography), and twelve trace elements (via ICP-MS). SS smoke exhibited significantly higher mass fractions of total analyzed species (84.7% vs. 65.9%), carbon components (50.6% vs. 44.2%), water-soluble ions (17.1% vs. 13.7%), and elements (17.0% vs. 7.0%) compared to MS smoke. MS smoke is characterized by a high proportion of pyrolytic organic carbon fractions (OC₁–OC₃) and specific elements such as vanadium (V) and arsenic (As), while SS smoke shows elevated levels of elemental carbon (EC1), water-soluble ions (NH₄⁺, NO₃⁻), and certain elements like zinc (Zn) and cadmium (Cd). The toxicity-weighted distribution indicates that MS smoke primarily induces membrane disruption and pulmonary inflammation through semi-volatile organics and elements, whereas SS smoke enhances oxidative stress and cardiopulmonary impairment via EC-mediated reactions and secondary aerosol formation. The mean OC/EC ratio of 132.4 in SS smoke is an order of magnitude higher than values reported for biomass or fossil-fuel combustion, indicative of extensive incomplete combustion unique to cigarettes and suggesting a high potential for oxidative stress generation. Emission factors (µg/g cigarette) revealed marked differences: MS delivered higher absolute EFs for PM_2.5 (422.1), OC (8.8), EC (5.0), Na⁺ (32.6), and V (29.2), while SS emitted greater proportions of NH₄⁺, NO₃⁻, Cl⁻, and carcinogenic metals (As, Cd, Zn). These findings provide quantitative source profiles suitable for receptor-oriented indoor source-apportionment models and offer toxicological evidence to support the prioritization of comprehensive smoke-free regulations. Full article

Reductive amination of cyclohexanone with NH₃ and H₂ over Rh and Rh-Ni catalysts on SiO₂ has been studied. Research has focused on the catalytic efficiency of monometallic and bimetallic catalysts in the production of cyclohexylamine, a key intermediate in the synthesis of numerous fine chemicals. Through the wet impregnation method, Rh and Rh-Ni catalysts with varying nickel loadings (1, 2, 5, and 10 wt.%) were synthesized and characterized using techniques such as N₂ physisorption, TEM, HAADF-STEM, XRD, XPS, H₂-TPR, and NH₃-TPD. The catalytic reactions were conducted under controlled conditions using a glass-coated reactor, using ammonia as nitrogen source. Rh-Ni bimetallic catalysts exhibited the highest conversion rates on reductive amination, attributed to enhanced dispersion and advantageous surface properties. High metal dispersion and small particle sizes were confirmed by TEM, HAADF-STEM, and XRD. XPS analysis confirmed the reduced state of Rh and mainly oxidized state of Ni, while H₂-TPR and NH₃-TPD results indicated improved reducibility and acidity, respectively, which are critical for catalytic activity. Monometallic Rh/SiO₂ catalyst showed 83.4% of conversion after 300 min and selectivity of 99.1% toward the desired product cyclohexylamine. The addition of nickel, a cheap and easily available metal, increases the activity without compromising selectivity. At 300 min of the reaction, the 2 wt.% NiRh/SiO₂ catalyst exhibited the highest conversion, yield, and selectivity for the desired product cyclohexylamine, 99.8%, 96.4%, and 96.6% respectively. Additionally, this catalyst is recyclable after the fourth cycle, showing 99.5% selectivity and 74.0% yield for cyclohexylamine at 75.7% conversion. Recycling tests confirmed the stability of bimetallic catalysts, maintaining performance over multiple cycles without significant deactivation. Full article

In biochemical reaction control loops, the fast response and accuracy of the system are often at odds with stability. Especially when the system faces external changes in different situations, the control system needs to be more robust. To address this problem, a novel ultrasensitive quasi-fuzzy proportional integral (QFPI) molecular controller using a covalent modification cycle is designed. The quasi-fuzzy control performance is achieved through a symmetric dual-rail covalent modification cycle structure. It can effectively suppress the impact of external changes on the controlled process and overcome the limitation of finite-time regulation caused by substrate consumption. At the same time, the time performance of the controller is significantly improved by utilizing the fast response characteristics of the ultrasensitive response. Subsequently, a single-rail optimization of the chemical reaction network (CRN) of the QFPI controller is performed to design a modified ultrasensitive quasi-fuzzy PI (M-QFPI) molecular controller. The M-QFPI controller not only significantly reduces the number of chemical reactions required to implement the controller, but also effectively improves the temporal performance and robustness of the controller. Finally, the effectiveness of the ultrasensitive quasi-fuzzy PI molecular controller for the control of the phosphorylation reaction process is verified. The results show that the ultrasensitive quasi-fuzzy PI control strategy provides an effective solution for the co-optimization of response speed, robustness and stability. Full article

The consistent quality control of ultrapure water (UPW) in semiconductor manufacturing depends on removing trace organonitrogen compounds such as urea. Due to its high solubility, chemical stability, and neutral polarity, urea is inadequately removed by conventional processes. Even at low concentrations, it elevates total organic carbon (TOC) and reduces electrical resistivity. The use of reclaimed water as a sustainable feed stream amplifies this challenge because its nitrogen content is variable and persistent. Conventional methods such as reverse osmosis, ultraviolet oxidation, and ion exchange remain limited in treating urea due to its uncharged, low-molecular-weight nature. This review examines the performance and limitations of these processes and explores electrochemical oxidation (EO) as an alternative. Advances in EO are analyzed with attention to degradation pathways, electrode design, reaction selectivity, and operational parameters. Integrated systems combining EO with membrane filtration, adsorption, or chemical oxidation are also reviewed. Although EO shows promise for selectively degrading urea, its application in UPW production is still in its early stages. Challenges such as low conductivity, byproduct formation, and energy efficiency must be addressed. The paper first discusses urea in reclaimed water and associated removal challenges, then examines both conventional and emerging treatment technologies. Subsequent sections delve into the mechanisms and optimization of EO, including electrode materials and operational parameters. The review concludes with a summary of main findings and a discussion of future research directions, aiming to provide a comprehensive foundation for validating EO as a viable technology for producing UPW from reclaimed water. Full article

This study assessed the physico-chemical and sensory effects of enriching composite cereal porridges, typically consumed in Uganda, with undried house crickets (Acheta domesticus), a rich source of protein and vitamin B₁₂. Composite flours containing 8.3% undried crickets, 66.7% maize, and 25.0% millet were compared to a control formulation with 73.0% maize and 27.0% millet, both extruded at 140 °C. Cricket enrichment slightly reduced lightness L* (59.99 vs. 61.28) and significantly increased aroma intensity (23,450 × 10⁴ AU vs. 18,210 × 10⁴ AU; p < 0.05), attributable to higher extrusion-induced Strecker degradation, Maillard reaction, and lipid oxidation. Rheological analysis revealed that paste made from cricket-enriched flour had lower critical strain (≈0.01%) and softened sooner than the control paste (≈0.03%) without becoming fragile. Both flours displayed stable paste-like behavior at stresses >10 Pa, with elastic moduli under 10⁴ Pa, which is typical for soft pastes. Reduced pasting values relative to native flours are attributable to starch pre-gelatinization during extrusion. Sensory evaluation showed positive hedonic ratings for both porridges, and a choice test indicated no significant consumer preference. Generally, physico-chemical and sensory changes were minimal, supporting the use of house crickets for nutrient enrichment of composite cereal porridges. Full article

In response to the growing issue of iron and manganese pollution in water bodies, this study systematically investigated the adsorption performance of municipal sludge-derived biochar prepared at pyrolysis temperatures ranging from 300 to 700 °C for the removal of Fe²⁺ and Mn²⁺. Among the series of adsorbents (BC300–BC700), BC600—with its well-developed pore structure and high specific surface area—exhibited the best adsorption performance for both metal ions. Kinetic and isothermal adsorption experiments, in combination with XPS characterization, collectively revealed that (1) the adsorption mechanisms of Fe and Mn differ markedly, with Fe adsorption primarily governed by physical interactions, whereas Mn adsorption is largely controlled by chemical processes; (2) Fe²⁺ adsorption occurs mainly via electrostatic interactions and hydrogen bonding; and (3) Mn²⁺ forms carbonate precipitates with C=O groups during redox reactions. Thermodynamic analysis further indicated that the adsorption process was spontaneous and endothermic. Moreover, BC600 demonstrated excellent reusability for Fe adsorption across different water matrices, maintaining efficiencies above 95% after five cycles, although the adsorption performance for Mn declined. This study provides theoretical support for the application of sludge-derived biochar as a cost-effective and efficient adsorbent for metal ion remediation. Full article

The pyrolysis of polydimethylsiloxane (PDMS) for silicon carbide (SiC) fabrication endows precursor materials with exceptional microstructural controllability and complex geometry retention capability, rendering it widely applicable in flexible electronic packaging and microscale complex-structured heat exchangers. Nevertheless, the widespread adoption of pyrolytic SiC has been constrained by the low yield and process complexity inherent to conventional pyrolysis methods. In response, we developed a multiscale simulation framework integrating macroscopic thermal distribution with microscopic chemical reaction kinetics. The secondary pyrolysis protocol, designed based on simulation results, enhanced the SiC yield from <25% (conventional methods) to 79.2% while simultaneously improving crystalline quality. This simulation framework not only provides theoretical guidance for optimizing laser direct writing pyrolysis, but the proposed secondary ablation strategy also significantly expands the application potential of SiC-PDMS systems in device fabrication. 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

Per- and polyfluoroalkyl substances (PFASs) are widespread in the environment, bioaccumulate in humans, and lead to disease and organ injury, such as liver steatosis. However, we lack a clear understanding of how these chemicals cause organ-level toxicity. Here, we aimed to analyze PFAS-induced metabolic perturbations in male and female rat livers by combining a genome-scale metabolic model (GEM) and toxicogenomics. The combined approach overcomes the limitations of the individual methods by taking into account the interaction between multiple genes for metabolic reactions and using gene expression to constrain the predicted mechanistic possibilities. We obtained transcriptomic data from an acute exposure study, where male and female rats received a daily PFAS dose for five consecutive days, followed by liver transcriptome measurement. We integrated the transcriptome expression data with a rat GEM to computationally predict the metabolic activity in each rat’s liver, compare it between the control and PFAS-exposed rats, and predict the benchmark dose (BMD) at which each chemical induced metabolic changes. Overall, our results suggest that PFAS-induced metabolic changes occurred primarily within the lipid and amino acid pathways and were similar between the sexes but varied in the extent of change per dose based on sex and PFAS type. Specifically, we identified that PFASs affect fatty acid-related pathways (biosynthesis, oxidation, and sphingolipid metabolism), energy metabolism, protein metabolism, and inflammatory and inositol metabolite pools, which have been associated with fatty liver and/or insulin resistance. Based on these results, we hypothesize that PFAS exposure induces changes in liver metabolism and makes the organ sensitive to metabolic diseases in both sexes. Furthermore, we conclude that male rats are more sensitive to PFAS-induced metabolic aberrations in the liver than female rats. This combined approach using GEM-based predictions and BMD analysis can help develop mechanistic hypotheses regarding how toxicant exposure leads to metabolic disruptions and how these effects may differ between the sexes, thereby assisting in the metabolic risk assessment of toxicants. Full article

Biomass gasification represents a pivotal technology for sustainable energy and chemical production, yet its efficiency and product quality are critically dependent on catalyst performance. This comprehensive review systematically synthesizes recent advancements in catalyst design, mechanistic insights, and process integration in biomass gasification. Firstly, it details the development and performance of catalysts in diverse categories, including metal-based catalysts, Ca-based catalysts, natural mineral catalysts, composite/supported catalysts, and emerging waste-derived catalysts. Secondly, this review delves into the fundamental catalytic reaction mechanisms governing key processes such as tar cracking/reforming, water–gas shift, and methane reforming. It further explores sophisticated strategies for catalyst structure optimization, focusing on pore structure/surface area control, strong metal–support interactions (SMSIs), alloying effects, nanodispersion, and crystal phase design. The critical challenges of catalyst deactivation mechanisms and the corresponding activation, regeneration strategies, and post-regeneration performance evaluation are thoroughly discussed. Thirdly, this review addresses the crucial integration of zero CO₂ emission concepts, covering in situ CO₂ adsorption/conversion, carbon capture and storage (CCS) integration, catalytic CO₂ reduction/valorization, multi-energy system synergy, and environmental impact/life cycle analysis (LCA). By synthesizing cutting-edge research, this review identifies key knowledge gaps and outlines future research directions towards designing robust, cost-effective, and environmentally benign catalysts for next-generation, carbon-neutral biomass gasification systems. Full article

This field study describes the successful implementation and evaluation of a Polymer-free Delayed Acid System, a next-generation acid retarder system that is chemically superior to traditional emulsified acid systems with an amphoteric-based surfactant. It is a polymer-free system that stimulates ultra-tight carbonate reservoirs in extreme sour and high-temperature conditions. The candidate well, located in an onshore gulf region field, for a major oil and gas company demonstrated chronically unstable production behavior for over two years, with test volumes fluctuating unpredictably between 200 and 400 barrels of oil per day. This indicated severe near-wellbore damage, high skin, and limited matrix permeability (<0.3 mD). The well was chosen for a pilot trial of the Polymer-free Delayed Acid System technology after a thorough formation study, which included mineralogical characterization and capillary diagnostics. The innovative acid retarder formulation, designed for deep matrix penetration and controlled acid–rock reaction, uses intrinsic encapsulation kinetics to significantly increase the acid’s reactivity, allowing it to bypass damaged zones, minimize acid leak-off, and initiate dominant wormhole propagation into the tight formation. The stimulation procedure began with a custom pre-flush designed to change nanoscale wettability and interfacial tension, so increasing acid displacement and assuring effective contact with the formation rock. Real-time injectivity testing and operational data collecting were performed prior to, during, and following the acid job, with pre-stimulation injectivity peaking at 1.2 bpm, indicating poor formation conductivity. Treatment with the Polymer-free Delayed Acid System resulted in a 592% increase in post-stimulation injectivity, indicating significant increases in near-wellbore permeability and successful propagation. However, a substantial operational difficulty arose: the well remained shut down for more than two months following the acid stimulation work due to surface infrastructure delays, notably the scheduling and execution of a flowline cleanup campaign. This lengthy closure slowed immediate flowback analysis and impeded direct assessment of treatment performance because production could not be tracked in real time. Despite this, once the surface system was operational and the well was open to flow, a structured production testing program was carried out over four quarterly intervals. The well regularly produced at an average stable rate of 500 bbl/day, more than doubling pre-treatment performance and demonstrating the long-term effectiveness and mechanical durability of the acid-induced wormhole network. Despite the post-job shut-in, the Polymer-free Delayed Acid System maintained the stimulating impact even under non-ideal settings, demonstrating its robustness. The Polymer-free Delayed Acid System outperforms conventional emulsified acid systems, giving better control over acid placement and reactivity, especially under severe reservoir conditions with bottomhole temperatures reaching 200 °F. This project offers a field-proven methodology that combines advanced chemical engineering, formation-specific design, and live diagnostics, as well as a scalable blueprint for unlocking hydrocarbon potential in similarly complicated, low-permeability reservoirs. Full article

The utilization of ammonia as a fuel for gas turbines involves practical challenges due to its low reactivity, narrow flammability limits, and slow laminar flame propagation. One of the potential solutions to enhance the combustion reactivity of ammonia is co-firing with syngas. This paper presents an experimental and numerical investigation of the laminar burning velocity (LBV) of ammonia/syngas/air mixtures under elevated pressures (up to 10 bar) and temperatures (up to 473 K). Experiments were conducted in a constant-volume combustion chamber with a total volume of 11 L equipped with a dual-electrode capacitive discharge ignition system. A systematic sensitivity analysis was conducted to experimentally evaluate the system performance under various syngas compositions and equivalence ratios from 0.7 to 1.6 and ultimately identify the factors with the most impact on the system. As a complement to the experiments, a detailed numerical simulation was carried out integrating available kinetic mechanisms—chemical reaction sets and their rates—to support advancements in the understanding and optimization of ammonia/syngas co-firing dynamics. The sensitivity analysis results reveal that LBV is significantly enhanced by increasing the hydrogen content (>50%). Furthermore, the LBV of the gas mixture is found to increase with the use of a rich flame, higher mole fractions of syngas, and higher initial temperatures. The results indicate that higher pressure reduces LBV by 40% but at the same time enhances the adiabatic flame temperature (by 100 K) due to an equilibrium shift. The analysis was also extended to quantify the impact of syngas mole fractions and elevated initial temperatures. The kinetics of the reactions are analyzed through the reaction pathways, and the results reveal how the preferred pathways vary under lean and rich flame conditions. These findings provide valid quantitative design data for optimizing the combustion kinetics of ammonia/syngas blends, offering valuable design data for ammonia-based combustion systems in industrial gas turbines and power generation applications, reducing NOₓ emissions by up to 30%, and guiding future research directions toward kinetic models and emission control strategies. Full article

In this study, a series of novel alkoxylated resorcinarenes were synthesized using secondary and tertiary alcohols under mild catalytic conditions involving iminodiacetic acid. Structural characterization, including single-crystal X-ray diffraction, confirmed the successful incorporation of branched alkyl chains and highlighted the influence of substitution patterns on molecular packing. Notably, detailed mass spectrometric analysis revealed that, under specific conditions, the reaction pathway may shift toward the formation of defined oligomeric species with supramolecular characteristics—an observation that adds a new dimension to the synthetic potential of this system. To complement the chemical analysis, selected derivatives were evaluated for biological activity, focusing on bacterial growth and biofilm formation. Using four clinically relevant strains (Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Bacillus subtilis), we assessed both planktonic proliferation (OD₆₀₀) and biofilm biomass (crystal violet assay). Compound 2c (2-pentanol derivative) consistently promoted biofilm formation, particularly in S. aureus and B. subtilis, while having limited cytotoxic effects. In contrast, compound 2e and the DMSO control exhibited minimal impact on biofilm development. The results suggest that specific structural features of the alkoxy chains may modulate microbial responses, potentially via membrane stress or quorum sensing interference. This work highlights the dual relevance of alkoxylated resorcinarenes as both supramolecular building blocks and modulators of microbial behavior. Full article

The interface between high-performance thermoelectric materials and electrodes critically governs the conversion efficiency and long-term reliability of thermoelectric generators under high-temperature operation. Here, we propose Al_xCoCrFeNi high-entropy alloys (HEA) as barrier layers to bond Cu-W electrodes with p-type skutterudite (p-SKD) thermoelectric materials. The HEA/p-SKD interface exhibited excellent chemical bonding with a stable and controllable reaction layer, forming a dense, defect-free (Fe,Ni,Co,Cr)Sb phase (thickness of ~2.5 μm) at the skutterudites side. The interfacial resistivity achieved a low value of 0.26 μΩ·cm² and remained at 7.15 μΩ·cm² after aging at 773 K for 16 days. Moreover, the interface demonstrated remarkable mechanical stability, with an initial shear strength of 88 MPa. After long-term aging for 16 days at 773 K, the shear strength retained 74 MPa (only 16% degradation), ranking among the highest reported for thermoelectric materials/metal joints. Remarkably, the joint maintained a shear strength of 29 MPa even after 100 continuous thermal cycles (623–773 K), highlighting its outstanding thermo-mechanical stability. These results validate the Al_xCoCrFeNi high-entropy alloys as an ideal interfacial material for thermoelectric generators, enabling simultaneous optimization of electrical and mechanical performance in harsh environments. Full article

Novel solid strong base catalysts have attracted considerable attention in fine chemical synthesis owing to their unique advantages. In this work, a magnetic solid strong base catalyst with controlled morphology and porous carbon shell structure was successfully fabricated using low-cost carbon sources combined with Fe₃O₄ nanoparticles. KOH was used to introduce strong basic sites through ultrasonic-assisted impregnation. The carbon shell acted as a protective barrier to suppress detrimental interactions between basic species and the support while maintaining structural integrity after high-temperature activation without morphology degradation. The obtained K/C/Fe₃O₄ catalyst exhibits excellent catalytic performance and near-ideal superparamagnetic behavior. In the transesterification reaction for dimethyl carbonate (DMC) synthesis, the K/C/Fe₃O₄ catalyst provides superior performance than conventional solid base catalysts and maintains stable activity over six consecutive cycles. Notably, efficient solid–liquid separation was achieved successfully via magnetic separation, demonstrating practical applicability for the K/C/Fe₃O₄ catalyst. Full article