Search Results (84)

This paper presents the expected and unexpected, but typically substituent-dependent, ferrocene-catalyzed DDQ-mediated oxidative transformations of a series of 5,8-bis(methylthio)-1-aryl-1,2-dihydropyridazino[4,5-d]pyridazines and 8-(3,5-dimethyl-1H-pyrazol-1-yl)-5-(methylthio)-1-aryl-1,2-dihydropyridazino[4,5-d]pyridazines. Under noncatalytic conditions the reactions were sluggish, mainly producing a substantial amount of undefined tarry materials; nevertheless, the ferrocene-catalyzed reactions of the 5,8-bis(methylthio)-substituted precursors gave the aromatic products the expected aromatic products in low yields. Their formation was accompanied by ring transformations proceeding via aryne-generating fragmentation/Diels–Alder (DA)/N₂-releasing retro Diels–Alder (rDA) sequence to construct arene-fused phthalazines. On the other hand, neither the noncatalytic nor the catalytic reactions of the 8-pyrazolyl-5-methylthio-substituted dihydroaromatics yielded the expected aromatic products. Instead, depending on their substitution pattern, the catalytic reactions of these pyrazolyl-substituted precursors also led to the formation of dearylated arene-fused phthalazines competing with an unprecedented multistep fragmentation sequence terminated by the hydrolysis of cationic intermediates to give 4-(methylthio)pyridazino[4,5-d]pyridazin-1(2H)-one and the corresponding 3,5-dimethyl-1-aryl-1H-pyrazole. When 0.6 equivalents of DDQ were applied in freshly absolutized THF, a representative pyrazolyl-substituted model underwent an oxidative coupling to give a dimer formed by the interaction of the cationic intermediate, and a part of the N-nucleophilic precursor remained intact. A systematic computational study was conducted on these intriguing reactions to support their complex mechanisms proposed on the basis of the structures of the isolated products. Full article

Non-catalytic partial oxidation (POX) of natural gas is gaining importance in low-carbon energy systems for methane conversion to acetylene, syngas, and olefins. However, uncontrolled polycyclic aromatic hydrocarbons (PAHs) and soot formation remain challenges. This work developed a Hierarchical-Integrated Mechanism (HI-Mechanism) by constructing detailed C₀-C₆, C₅-C₁₅ and C₁₆ mechanisms, and then hierarchically simplifying C₅-C₁₅ subsystems, ultimately integrating them into a final mechanism with 397 species and 5135 reactions. The HI-Mechanism accurately predicted shock tube ignition delays and major species concentrations. Microkinetic analyses, including production rates and reaction sensitivity, revealed key pathways and enabled reliable product distribution prediction. The HI-Mechanism provides theoretical guidance for optimizing POX of natural gas processes and can be extended to complex systems like heavy oil cracking, supporting clean energy technology development. Full article

Among biomass gasification syngas cleaning methods, non-catalytic reforming emerges as a sustainable and high-efficiency alternative. This study employed integrated experimental analysis and kinetic modeling to examine non-catalytic reforming processes of biomass-derived producer gas utilizing a synthetic tar mixture containing representative model compounds: naphthalene (C₁₀H₈), toluene (C₇H₈), benzene (C₆H₆), and phenol (C₆H₅OH). The experiments were conducted using a high-temperature fixed-bed reactor under varying temperatures (1100–1500 °C) and equivalence ratios (ERs, 0.10–0.30). The results obtained from the experiment, namely the measured mole concentration of H₂, CO, CH₄, CO₂, H₂O, soot, and tar suggested that both reactor temperature and O₂ content had an important effect. Increasing the temperature significantly promotes the formation of H₂ and CO. At 1500 °C and a residence time of 0.01 s, the product gas achieved CO and H₂ concentrations of 28.02% and 34.35%, respectively, while CH₄, tar, and soot were almost entirely converted. Conversely, the addition of O₂ reduces the concentrations of H₂ and CO. Increasing ER from 0.10 to 0.20 could reduce CO from 22.25% to 16.11%, and H₂ from 13.81% to 10.54%, respectively. Experimental results were used to derive a kinetic model to accurately describe the non-catalytic reforming of producer gas. Furthermore, the maximum of the Root Mean Square Error (RMSE) and the Relative Root Mean Square Error (RRMSE) between the model predictions and experimental data are 2.42% and 11.01%, respectively. In particular, according to the kinetic model, the temperature increases predominantly accelerated endothermic reactions, including the Boudouard reaction, water gas reaction, and CH₄ steam reforming, thereby significantly enhancing CO and H₂ production. Simultaneously, O₂ content primarily influenced carbon monoxide oxidation, hydrogen oxidation, and partial carbon oxidation. Full article

In this study, the authors employed first-principles calculations to investigate the adsorption and decomposition processes involved in non-catalytic growth of vapor-growth carbon fiber (VGCF) using a non-catalytic growth method. The adsorption and decomposition mechanisms of methane and its decomposition products on the substrate were investigated with the adsorption energy, transition state analysis, and projected density of states (PDOS). The results indicated that the surface adsorption difficulty for CH₄ and its decomposition products followed the following order: H > CH₄ ≈ CH₃ > CH₂ > CH > C. The adsorption energy analysis indicates that the adsorption of CH₄, CH₃, and H is classified as physical adsorption, whereas the adsorption of CH₂, CH, and C is classified as chemical adsorption. Adsorption of all particles is exothermic and adsorption can occur. The transition state calculations indicate that the decomposition of CH₄ is the rate-determining step in the decomposition reaction. PDOS analysis not only verified the results of adsorption energy analysis but also investigated the effect of adsorption particles. This work is helpful for advancing the application of non-catalytic growth processes to the synthesis of VGCF and enhancing the understanding of the mechanisms governing non-catalytic VGCF formation. Full article

Ammonia, as a hydrogen carrier and an ideal zero-carbon fuel, can be liquefied and stored under ambient temperature and pressure. Its application in internal combustion engines holds significant potential for promoting low-carbon emissions. However, due to its unique physicochemical properties, ammonia faces challenges in achieving ignition and combustion when used as a single fuel. Additionally, the presence of nitrogen atoms in ammonia results in increased NOx emissions in the exhaust. High-temperature selective non-catalytic reduction (SNCR) is an effective method for controlling flue gas emissions in engineering applications. By injecting ammonia as a NOx-reducing agent into exhaust gases at specific temperatures, NOx can be reduced to N₂, thereby directly lowering NOx concentrations within the cylinder. Based on this principle, a numerical simulation study was conducted to investigate two high-pressure injection strategies for sequential diesel/ammonia dual-fuel injection. By varying fuel spray orientations and injection durations, and adjusting the energy ratio between diesel and ammonia under different operating conditions, the combustion and emission characteristics of the engine were numerically analyzed. The results indicate that using in-cylinder high-pressure direct injection can maintain a constant total energy output while significantly reducing NOx emissions under high ammonia substitution ratios. This reduction is primarily attributed to the role of ammonia in forming NH₂, NH, and N radicals, which effectively reduce the dominant NO species in NOx. As the ammonia substitution ratio increases, CO₂ emissions are further reduced due to the absence of carbon atoms in ammonia. By adjusting the timing and duration of diesel and ammonia injection, tailpipe emissions can be effectively controlled, providing valuable insights into the development of diesel substitution fuels and exhaust emission control strategies. Full article

A novel meso-scale 3-channel 5-turn Swiss-roll type combustor was designed and tested. The non-catalytic combustion of lean ethanol–air mixtures was experimentally investigated in relation to the oxygen excess ratio (α), which varied from 1.5 to 7. Depending on the control parameters used, two distinct regimes of combustion were experimentally observed: one with a combustion zone within the central chamber and another with a combustion zone in the inflow channel. The combustion temperature was virtually independent of stoichiometry. For richer mixtures and lower flow rates, the combustion zone is established in the inflow channel, thus limiting the combustion temperature. A qualitative model was proposed for the process and solved analytically; it described how the combustion regime self-adjusted, with the reaction zone moving into the inflow channel from the central chamber. This study confirmed the possibility of the sustainable combustion of ultra-lean fuel mixtures in a Swiss-roll combustor. Full article

In this paper, the aerodynamic performances including shock wave standoff distance (SSD) and heat flux of ELECTRE vehicle at 53.3 km and 4230 m/s for several types of numerical models are investigated. The numerical models include thermal equilibrium/nonequilibrium (1T/2T) assumption, three surface boundary conditions (no-slip/non-catalytic, slip/non-catalytic, slip/fully-catalytic), four chemical kinetic models (DK, Park, Gupta, and No Reaction (NR)) and two controlling temperatures (T_tr^0.7T_ve^0.3, T_tr^0.5T_ve^0.5). The results show that the chemical kinetic model significantly affects the SSD, and its value gradually decreases with the increase in chemical reaction rate. The SSD predicted by the NR model is 20.7% larger than that of the Park model. The SSD is also affected by the proportion of vibro-electronic temperature (T_ve) in the controlling temperature, and the higher the proportion, the larger the SSD. Regarding the heat flux, the catalytic surface setting is crucial, where the value predicted by the fully-catalytic model is 62.2% higher than that by the non-catalytic model. As the chemical reaction rate of Gupta, DK, and Park models increases sequentially, the calculated heat flux decreases in turn. The heat flux predicted by the 2T model is lower than that by the 1T model, and the higher T_ve proportion in the controlling temperature, the smaller the heat flux. The fundamental reason is that the trans-rotational convective heat flux of the 2T model is much lower than that of the 1T model, and the trans-rotational convective heat flux decreases with an increase in the T_ve proportion. Full article

Background: The goal of the current study was to investigate the inhibitory activity of six phenolic compounds, i.e., rosmarinic acid, gallic acid, oleuropein, epigallocatechin gallate (EGCG), 3-hydroxytyrosol, and quercetin, against β-site amyloid precursor protein cleaving enzyme-1 (BACE1), also known as β-secretase or memapsin 2, which is implicated in the pathogenesis of Alzheimer’s disease (AD). Methods and Results: The inhibitory potential against BACE1, molecular docking simulations, as well as neurotoxicity and the effect on the AD-related gene expression of the selected phenolics were tested. BACE1 inhibitory activity was carried out using the ELISA microplate assay via fluorescence resonance energy transfer (FRET) technology. Molecular docking experiments were performed in the human BACE1 active site (PDB code: 2WJO). Neurotoxicity of the compounds was carried out in SH-SY5Y, a human neuroblastoma cell line, by the Alamar Blue method. A gene expression analysis of the compounds on fourteen genes linked to AD was conducted using the real-time polymerase chain reaction (RT-PCR) method. Rosmarinic acid, EGCG, oleuropein, and quercetin (also used as the reference) were able to inhibit BACE1 with their respective IC₅₀ values 4.06 ± 0.68, 1.62 ± 0.12, 9.87 ± 1.01, and 3.16 ± 0.30 mM. The inhibitory compounds were observed to occupy the non-catalytic site of the BACE1. However, hydrogen bonds were found to be present between rosmarinic acid and EGCG and aspartic amino acid D228 in the catalytic site. Oleuropein and quercetin effectively suppressed the expression of PSEN, APOE, and CLU, which are recognized to be linked to the pathogenesis of AD. Conclusions: The outcomes of the work bring quercetin, EGCG, and rosmarinic acid to the forefront as promising BACE1 inhibitors. Full article

The exhaustion of conventional light oils necessitates the shift towards unconventional sources such as biomass, heavy oil, oil shale, and coal. Non-catalytic thermal cracking by a free radical mechanism is at the heart of the upgrading, prior to refining into valuable products. However, thermal pyrolysis is hindered by the formation of asphaltenes, precursors to coke, limiting cracking, causing equipment fouling, and reducing product stability. Free radicals are inherently present in heavy fractions and are generated during thermal processes. This makes these reactive intermediates central to understanding these mechanisms and limiting coking. Electron spin resonance (ESR) spectroscopy facilitates such mechanistic studies. Over the past decade, there has been no review of using in-situ ESR for studying thermal processes. This work begins with a brief description of free radicals’ chain reactions during thermal reactions and the wealth of information ESR provides. We then critically review the literature that uses ESR for mechanistic studies in thermal pyrolysis of biomass, heavy oil, shales, and coal. We conclude that limited literature exist, and more investigations are necessary. The key findings from existing literature are summarized to know the current state of knowledge. We also explicitly highlight the research gaps. Full article

Oxy-steam combustion is a new oxy-fuel combustion technology. This paper focuses on the NO emission characteristics during the combustion of SF (Shen Fu) coal in O₂/N₂ and O₂/H₂O mixtures. Experiments were performed in a drop-tube furnace. Combustion tests were carried out in O₂/N₂ and O₂/H₂O atmospheres for various O₂ concentrations (21%, 30%, 40%, and 60%) at different temperatures (1173 K, 1273 K, and 1373 K). In addition, combustion experiments at different excess oxygen ratios (λ) were conducted in O₂/N₂ and O₂/H₂O atmospheres. The influences of the atmosphere, oxygen concentration, temperature, and excess oxygen ratio on NO emissions were analyzed. The results show that the NO concentrations of SF coal combustion in the 21% O₂/79% H₂O atmosphere were much lower than those in the 21% O₂/79% N₂ atmosphere at the three temperatures considered. This was because a large amount of NO was decomposed during the SF coal combustion in the O₂/H₂O atmospheres. The reasons for the decomposition of NO include the selective non-catalytic reaction (SNCR) mechanism and char’s important role as a catalyst for the destruction of NO, either directly or by reacting with CO or H₂. In oxy-steam combustion, the NO concentrations significantly increased with the increase in the oxygen concentration from 21 vol.% to 60 vol.% and the temperature from 1173 K to 1373 K. The excess oxygen ratio (λ) slightly impacted the NO emissions in the O₂/H₂O atmosphere. Full article

The acrylation degree of vegetable oils plays a relevant role in determining the mechanical properties of the resulting polymers. Both epoxide and acrylate functionalities participate in polymerization reactions, producing various types of chemical bonds in the polymer network, which contribute to specific properties such as molecular size distribution, crosslinking degree, and glass transition temperature (Tg). The accurate identification of epoxide and acrylated groups in triglyceride molecules helps to predict their behavior during the polymerization process. A methodology based on analytical spectrometric techniques, such as direct infusion, mass spectrometry with electrospray ionization, and ultra-high-performance liquid chromatography, is used in combination with FTIR and ¹H NMR to characterize the epoxy and acrylic functionalities in the fatty chains with different numbers of carbon atoms of partially acrylated triglycerides obtained by a non-catalytic reaction. Full article

One of the most important reactions in organic synthesis is esterification, and the compounds generated using this process are esters with a wide range of applications in various industries. Numerous approaches have been employed to enhance the ester yield and reaction rate and establish equilibrium in esterification reactions. This study uses a non-catalytic thermal esterification method to obtain unbranched aliphatic esters C4–C8. The effect of an audio frequency electric field instead of a catalyst on the esterification reaction between acetic acid and linear C4–C8 aliphatic alcohols was studied. The main goal of this study was to design and implement a lab-scale device for the synthesis of aliphatic esters in an environmentally sustainable manner using only specific raw materials and an audio frequency electric field at 3 and 6 kHz at 20 °C and 50 °C. A mechanism for the esterification reaction using an audio frequency electric field is also suggested. The proposed experimental device is designed to produce esters in a green and cost-effective manner and could be used on a large scale in the food, cosmetics, and pharmaceutical industries. Full article

In order to determine the curing reaction model and corresponding parameters of hydroxyl-terminated block copolyether (HTPE) and provide a theoretical reference for its practical application, the non-isothermal differential scanning calorimetry (DSC) method was used to analyze the curing processes of three curing systems with HTPE and N-100 (an aliphatic polyisocyanate curing agent), isophorone diisocyanate (IPDI), and a mixture of N-100 and IPDI as curing agents. The results show that the curing activation energy of N-100 and HTPE was about 69.37 kJ/mol, slightly lower than the curing activation energy of IPDI and HTPE (75.60 kJ/mol), and the curing activation energy of the mixed curing agent and HTPE was 69.79 kJ/mol. The curing process of HTPE conformed to the autocatalytic reaction model. The non-catalytic reaction order (n) of N-100 and HTPE was about 1.2, and the autocatalytic order (m) was about 0.3, both lower than those of IPDI and HTPE. The reaction kinetics parameters of the N-100 and IPDI mixed curing agent with HTPE were close to those of N-100 and HTPE. The verification results indicate a high degree of overlap between the experimental data and the calculated data. Full article

Lignocellulosic biomass such as canola straw is produced as low-value residue from the canola processing industry. Its high cellulose and hemicellulose content makes it a suitable candidate for the production of hydrogen via supercritical water gasification. However, supercritical water gasification of lignocellulosic biomass such as canola straw suffers from low hydrogen yield, hydrogen selectivity, and conversion efficiencies. Cost-effective and sustainable catalysts with high catalytic activity for supercritical water gasification are increasingly becoming a focal point of interest. In this research study, novel wet-impregnated nickel-based catalysts supported on carbon-negative hydrochar obtained from hydrothermal liquefaction (HTL-HC) and hydrothermal carbonization (HTC-HC) of canola straw, along with other nickel-supported catalysts such as Ni/Al₂O₃, Ni/ZrO₂, Ni/CNT, and Ni/AC, were synthesized for gasification of canola straw on previously optimized reaction conditions of 500 °C, 60 min, 10 wt%, and 23–25 MPa. The order of hydrogen yield for the six supports was (10.5 mmol/g) Ni/ZrO₂ > (9.9 mmol/g) Ni/Al₂O₃ > (9.1 mmol/g) Ni/HTL-HC > (8.8 mmol/g) Ni/HTC-HC > (7.7 mmol/g) Ni/AC > (6.8 mmol/g) Ni/CNT, compared to 8.1 mmol/g for the non-catalytic run. The most suitable Ni/ZrO₂ catalyst was further modified using promotors such as K, Zn, and Ce, and the performance of the promoted Ni/ZrO₂ catalysts was evaluated. Ni-Ce/ZrO₂ showed the highest hydrogen yield of 12.9 mmol/g, followed by 12.0 mmol/g for Ni-Zn/ZrO₂ and 11.6 mmol/g for Ni-K/ZrO₂. The most suitable Ni-Ce/ZrO₂ catalysts also demonstrated high stability over their repeated use. The superior performance of the Ni-Ce/ZrO₂ was due to its high nickel dispersion, resilience to sintering, high thermal stability, and oxygen storage capabilities to minimize coke deposition. Full article

Interest in enzymes capable of neutralizing various mycotoxins is quite high. The methods used for the screening and selection of enzymes that catalyze the detoxification of mycotoxins should be sensitive and fast. However toxic compounds can be generated under the action of such enzymes. Thus, the assessment of the overall reduction in the toxic properties of reaction media towards bioluminescent bacteria seems to be the most reasonable control method allowing a quick search for the effective enzymatic biocatalysts. The influence of a wide range of mycotoxins and glucanases, which hydrolyze toxins with different chemical structures, on the analytical characteristics of luminescent photobacteria as a biosensing element has been studied. Different glucanases (β-glucosidase and endoglucanase) were initially selected for reactions with 10 mycotoxins based on the results of molecular docking which was performed in silico with 20 mycotoxins. Finally, the biorecognizing luminescent cells were used to estimate the residual toxicity of reaction media with mycotoxins after their interaction with enzymes. The notable non-catalytic decrease in toxicity of media containing deoxynivalenol was revealed with luminous cells for both types of tested glucanases, whereas β-glucosidase provided a significant catalytic detoxification of media with aflatoxin B₂ and zearalenone at pH 6.0. Full article