Search Results (59)

Hydroperoxyalkylperoxy radicals (•OOQOOH) are important intermediates in the low-temperature oxidation chemistry of conventional fuels. In these species, a hydrogen atom may migrate from a non-adjacent carbon to the peroxy group, forming a dihydroperoxyalkyl radical (•P(OOH)₂). This research delves into the theoretical kinetics of a set of 110 H-migration reactions in normal-alkyl cyclohexanes, calculating high-pressure limit rate constants for these reactions. The reactions are further classified into 15 subclasses based on distinctions in the reaction center and its environment, with rate rules derived by averaging the rate constants within each subclass. A comparison of our calculated rate constants for specific H-migration reactions of •OOQOOH with existing mechanisms and similar reactions in non-cyclic alkanes reveals significant disparities, emphasizing the necessity for precise rate constants tailored to normal-alkyl cyclohexanes. Ethyl cyclohexane mechanisms and n-propyl cyclohexane mechanisms sourced from studies have been improved with high-pressure limit rate constants from this study. Simulations of the low-temperature combustion of ethyl cyclohexane and n-propyl cyclohexane show that the predictions from the updated mechanisms align more closely with the experimental data under specific conditions compared to the original mechanism. Full article

Alkyl sulfobetaine shows a strong advantage in the compounding of surfactants due to the defects in the size matching of hydrophilic and hydrophobic groups. The interfacial tensions (IFTs) of alkyl sulfobetaine (ASB) and xylene-substituted alkyl sulfobetaine (XSB) with oil-soluble (Span80) and water-soluble (Tween80) nonionic surfactants on a series of n-alkanes were studied using a spinning drop tensiometer to investigate the mechanism of IFT between nonionic and betaine surfactants. The two betaine surfactants’ IFTs are considerably impacted differently by Span80 and Tween80. The results demonstrate that Span80, through mixed adsorption with ASB and XSB, can create a relatively compacted interfacial film at the n-alkanes–water interface. The equilibrium IFT can be reduced to ultra-low values of 5.7 × 10⁻³ mN/m at ideal concentrations by tuning the fit between the size of the nonionic surfactant and the size of the oil-side vacancies of the betaine surfactant. Nevertheless, Tween80 has minimal effect on the IFT of betaine surfactants, and the betaine surfactant has no vacancies on the aqueous side. The present study provides significant research implications for screening betaine surfactants and their potential application in enhanced oil recovery (EOR) processes. Full article

The aim of this study was to determine the effect of progressive pig slurry (PS) rates, applied over a 12-year period, on the molecular composition of soil organic matter in a calcareous soil. Annual organic matter rates of PS ranged from 1.0 to 4.8 Mg ha⁻¹. Humic acids (HAs) were extracted from field plots treated with PS, including a control (no PS applied). These HAs were analysed using pyrolysis–gas chromatography–mass spectrometry. The proportions of the 122 major compounds released from the soil HAs indicated that PS stimulated humification processes, with the degree of enhancement depending on the application rate. The applied PS contained a high proportion of aliphatic compounds, but only steroids and triterpenes accumulated in the HA soil fraction, and this was only observed at low PS rates. These results suggest that the application of PS leads to a dose-dependent increase in alkyl compounds, mainly alkanes and olefins. Aromatic compounds also showed a dose-dependent increase, but not in terms of the demethoxylated compounds typical of mature humic substances found in the original soil. Instead, the increase in aromatics was observed in the form of methoxyphenols, suggesting a recent incorporation of lignin derivatives from crop residues into the HA. Full article

Five representatives of a novel type of di(hydroperoxy)alkane adducts of phosphine oxides have been synthesized and fully characterized, including their solubility in organic solvents. The phosphine oxide Cy₃PO (1) has been used in combination with the corresponding aldehydes to create the adducts Cy₃PO·(HOO)₂CHCH₃ (2), Cy₃PO·(HOO)₂CHCH₂CH₃ (3), Cy₃PO·(HOO)₂CH(CH₂)₂CH₃ (4), Cy₃PO·(HOO)₂CH(CH₂)₃CH₃ (5), and Cy₃PO·(HOO)₂CH(CH₂)₇CH₃ (6). All adducts crystallize easily and contain the peroxide and phosphine oxide hydrogen-bonded in 1:1 ratios. The single crystal X-ray structures of 2–6 and their unique features are discussed. The ³¹P NMR spectra of the adducts 2–6 show downfield-shifted signals as compared to Cy₃PO. In the IR spectra, the ν(P=O) wavenumbers of the adducts have smaller values than the neat phosphine oxide. All spectroscopic results of 2–6 show that the P=O bond is weakened by hydrogen-bonding to the di(hydroperoxy)alkane moieties. Adduct 6 selectively oxidizes PPh₃ to OPPh₃ within minutes, and nonanal is reformed in the process. The easy synthesis, handling, and administration of these stable, solid, and soluble peroxides with well-defined composition will have a positive impact on synthetic chemistry. Full article

Nanotechnological methods for creating multifunctional fabrics are attracting global interest. The incorporation of nanoparticles in the field of textiles enables the creation of multifunctional textiles exhibiting UV irradiation protection, antimicrobial properties, self-cleaning properties and photocatalytic. Nanomaterials-loaded textiles have many innovative applications in pharmaceuticals, sports, military the textile industry etc. This study details the biosynthesis and characterization of silver nanoparticles (AgNPs) using the aqueous mycelial-free filtrate of Aspergillus flavus. The formation of AgNPs was indicated by a brown color in the extracellular filtrate and confirmed by UV-Vis spectroscopy with a peak at 426 nm. The Box-Behnken design (BBD) is used to optimize the physicochemical parameters affecting AgNPs biosynthesis. The desirability function was employed to theoretically predict the optimal conditions for the biosynthesis of AgNPs, which were subsequently experimentally validated. Through the desirability function, the optimal conditions for the maximum predicted value for the biosynthesized AgNPs (235.72 µg/mL) have been identified as follows: incubation time (58.12 h), initial pH (7.99), AgNO₃ concentration (4.84 mM/mL), and temperature (34.84 °C). Under these conditions, the highest experimental value of AgNPs biosynthesis was 247.53 µg/mL. Model validation confirmed the great accuracy of the model predictions. Scanning electron microscopy (SEM) revealed spherical AgNPs measuring 8.93–19.11 nm, which was confirmed by transmission electron microscopy (TEM). Zeta potential analysis indicated a positive surface charge (+1.69 mV), implying good stability. X-ray diffraction (XRD) confirmed the crystalline nature, while energy-dispersive X-ray spectroscopy (EDX) verified elemental silver (49.61%). FTIR findings indicate the presence of phenols, proteins, alkanes, alkenes, aliphatic and aromatic amines, and alkyl groups which play significant roles in the reduction, capping, and stabilization of AgNPs. Cotton fabrics embedded with AgNPs biosynthesized using the aqueous mycelial-free filtrate of Aspergillus flavus showed strong antimicrobial activity. The disc diffusion method revealed inhibition zones of 15, 12, and 17 mm against E. coli (Gram-negative), S. aureus (Gram-positive), and C. albicans (yeast), respectively. These fabrics have potential applications in protective clothing, packaging, and medical care. In silico modeling suggested that the predicted compound derived from AgNPs on cotton fabric could inhibit Penicillin-binding proteins (PBPs) and Lanosterol 14-alpha-demethylase (L-14α-DM), with binding energies of −4.7 and −5.2 Kcal/mol, respectively. Pharmacokinetic analysis and sensitizer prediction indicated that this compound merits further investigation. Full article

In this work, we present new methods of synthesis of different molecules including a 2-pyridone nucleus. First, we prepared a series of 1H-free 2-pyridones and N-alkyl 2-pyridones from ethyl cyanoacetate, aromatic aldehydes, various acetophenone derivatives and ammonium acetate or diamino-alkane. These molecules have served as building blocks that, in conjunction with acyl chloride derivatives, glycoside derivatives, etc. have resulted in various heterocyclic hybrid structures carrying a 2-pyridone ring. Moreover, based on the cyano group reactivity of the 2-pyridone ring, we synthesized 5-pyridone 1H-tetrazole in a single step by a cycloaddition reaction [3 + 2] between 3-cyano-2-pyridone nitriles and sodium azide in the presence of metal-free L-proline. Full article

A theory for the micelle formation of nonionic head-tail amphiphiles (detergents) in aqueous solutions is derived based on the traditional molecular thermodynamic modeling approach and a variant of the Flory–Huggins theory that goes beyond lattice models. The theory is used to analyze experimental values for the critical micelle concentration of n-alkyl-ß-D-maltosides within a mass action model. To correlate those parts of the micellization free energy, which depend on the transfer of hydrophobic molecule parts into the aqueous phase, with molecular surfaces, known data for the solubility of alkanes in water are reanalyzed. The correct surface tension to be used in connection with the solvent-excluded surface of the alky tail is ~30 mN/m. This value is smaller than the measured surface tension of a macroscopic alkane–water interface, because the transfer free energy contains a contribution from the incorporation of the alkane or alkyl chain into water, representing the change in free volume in the aqueous phase. The Flory–Huggins theory works well, if one takes into account the difference in liberation free energy between micelles and monomers, which can be described in terms of the aggregation number as well as the thermal de Broglie wavelength and the free volume of the detergent monomer. Full article

Current global challenges associated with energy security and climate emergency, caused by the combustion of fossil fuels (e.g., jet fuel and diesel), necessitate the accelerated development and deployment of sustainable fuels derived from renewable biomass-based chemical feedstocks. This study focuses on the production of long-chain (straight and branched) ketones by direct α-alkylation of short chain ketones using both homogenous and solid base catalysts in water. Thus, produced long-chain ketones are fuel precursors and can subsequently be hydrogenated to long-chain alkanes suitable for blending in aviation and liquid transportation fuels. Herein, we report a thorough investigation of the catalytic activity of Pd in combination with, (i) homogenous and solid base additives; (ii) screening of different supports using NaOH as a base additive, and (iii) a comparative study of the Ni and Pd metals supported on layered double oxides (LDOs) in α-alkylation of 2-butanone with 1-propanol as an exemplar process. Among these systems, 5%Pd/BaSO₄ with NaOH as a base showed the best results, giving 94% 2-butanone conversion and 84% selectivity to alkylated ketones. These results demonstrated that both metal and base sites are necessary for the selective conversion of 2-butanone to alkylated ketones. Additionally, amongst the solid base additives, Pd/C with 5% Ba/hydrotalcite showed the best result with 51% 2-butanone conversion and 36% selectivity to the alkylated ketones. Further, the screening of heterogenous acid-base catalysts 2.5%Ni/Ba_1.2Mg₃Al₁ exhibited an adequate catalytic activity (21%) and ketone selectivity (47%). Full article

As the world aims to address the UN Sustainable Development Goals (SDGs), it is becoming more urgent for heavy transportation sectors, such as shipping and aviation, to decarbonise in an economically feasible way. This review paper investigates the potential fuels of the future and their capability to mitigate the carbon footprint when other technologies fail to do so. This review looks at the technologies available today, including, primarily, transesterification, hydrocracking, and selective deoxygenation. It also investigates the potential of fish waste from the salmon industry as a fuel blend stock. From this, various kinetic models are investigated to find a suitable base for simulating the production and economics of biodiesel (i.e., fatty acid alkyl esters) and renewable diesel production from fish waste. Whilst most waste-oil-derived biofuels are traditionally produced using transesterification, hydrotreating looks to be a promising method to produce drop-in biofuels, which can be blended with conventional petroleum fuels without any volume percentage limitation. Using hydrotreatment, it is possible to produce renewable diesel in a few steps, and the final liquid product mixture includes paraffins, i.e., linear, branched, and cyclo-alkanes, with fuel properties in compliance with international fuel standards. There is a wide range of theoretical models based on the hydrodeoxygenation of fatty acids as well as a clear economic analysis that a model could be based on. Full article

This study conducted in situ combustion oxidation experiments on crude oil from Block D within the Liaohe Oilfield, utilizing a kettle furnace low-pressure oxidation reaction method at various temperatures. The molecular composition of oxidation products was analyzed using gas chromatography–mass spectrometry (GC–MS) and high-resolution mass spectrometry. The results reveal that the molecular composition of the products remains relatively stable up to 300 °C, exhibiting a slight increase in C₁₃-C₃₀ alkanes. The ratio of the peak area for C₂₁ to bisnorhopane is 0.082. From 300 °C to 450 °C, compounds with long alkyl chains gradually undergo thermal cracking, resulting in a significant increase in the production of alkanes within the C₁₀–C₃₀ range. The concentration of saturated hydrocarbons produced through thermal cracking reaches its maximum at a temperature of 400 °C. The most abundant peak of n-alkane is observed at C₂₁, with a quantified ratio of peak area for C₂₁ to bisnorhopane at 6.5, indicating a two-order magnitude increase compared to crude oil. From 500 °C to 600 °C, compounds undergo more profound thermal cracking and condensation processes. The predominant hydrocarbons consist of aromatic molecules containing two to six rings substituted with short side chains. The double bond equivalent (DBE) values of carbazoles and carboxylic acids are determined as 30 and 25, respectively. At 600 °C, the peak area ratio of naphthalene to biodecane is 300, indicating a remarkable increase of five orders of magnitude compared to the crude oil. The present study elucidates the correlation between the characteristics of combustion components in crude oil and the corresponding combustion temperature. Primary cracking reactions within crude oil are promoted effectively when keeping the combustion zone at 350 °C and 450 °C. This process significantly reduces the viscosity of heavy oil and enhances its fluidity. Full article

The aims of this work are to study the rheological behaviors of a microemulsion of Glucopone–water–hydrocarbon systems and to use a fractional model to describe several experimental results of these systems. Four different types of hydrocarbons were considered. The frequency dependent storage, G′, and loss modulus, G″, were investigated below the critical strain. The critical strain was found to decrease as the alkane chain lengths increased, while the opposite behavior was observed for zero shear viscosity, η₀. Most of the microemulsions exhibited stable elastic fluid behavior (G′ > G″) below 10 rad s⁻¹ angular frequency. For all systems, elastic modulus values were found to be greater than loss modulus in the frequency range studied, indicating more elastic behaviors. Shear-thinning behaviors were observed, and the complex viscosity decreased with an increase in hydrocarbon chain lengths. The effects of hydrocarbon types on the rheological behaviors were more profound in the dodecane systems which showed maximum values of G′ and η₀. The Friedrich–Braun model was introduced and was used to describe several experimental results on Alkyl polyglocoside solutions. Fractional rheology successfully described the viscoelastic phenomena in Glucopone surfactant solutions and the comparisons between the experimental results and the theoretical predictions were found to be satisfactory. Full article

The vegetation of the Canary Islands is characterized by a large number of endemic species confined to different altitudinal levels. It can be assumed that these circumstances determine the characteristic features of the chemical composition of local beekeeping products, including propolis. We report, for the first time, the chemical composition of propolis from Tenerife (Canary Islands). The volatile emissions of three propolis samples collected from different apiaries are represented by 162 C₁–C₂₀ compounds, of which 144 were identified using the HS-SPME/GC-MS technique. The main group of volatiles, consisting of 72 compounds, is formed by terpenoids, which account for 42–68% of the total ion current (TIC) of the chromatograms. The next most numerous groups are formed by C₆–C₁₇ alkanes and alkenes (6–32% TIC) and aliphatic C₃–C₁₁ carbonyl compounds (7–20% TIC). The volatile emissions also contain C₁–C₆ aliphatic acids and C₂–C₈ alcohols, as well as their esters. Peaks of 138 organic C₃–C₃₄ compounds were recorded in the chromatograms of the ether extracts of the studied propolis. Terpene compounds form the most numerous group, but their number and content in different samples is within very wide limits (9–63% TIC), which is probably due to the origin of the samples from apiaries located at different altitudes. A peculiarity of the chemical composition of the extractive substances is the almost complete absence of phenylcarboxylic acids and flavonoids, characteristic of Apis mellifera propolis from different regions of Eurasia and North America. Aromatic compounds of propolis from Tenerife are represented by a group of nine isomeric furofuranoid lignans, as well as alkyl- and alkenyl-substituted derivatives of salicylic acid and resorcinol. Full article

Under certain conditions, ultrasonic treatment of certain foods and ingredients can contribute to the appearance of an extraneous odor, which is not usual for them, especially in fat-containing products. Since the food sector uses high-intensity ultrasound to control the crystallization of fats, the development of foreign smells and secondary fat oxidation products may impact the quality and safety of such items. In this work, we studied the volatile compounds’ profiles of oleogels structured with individual fractions of beeswax using ultrasonic treatment. For this work, six samples of oleogels were obtained. Sunflower oil was used as a fatty base, and three fractions of beeswax were used as gelators: hydrocarbon fraction (>99%), monoester fraction (>95%), and a mixture fraction of wax di- and triesters (10.1%), free fatty acids (40.1%), and free fatty alcohols (49.8%). The influence of ultrasonic treatment on the properties of oleogels was assessed using light microscopy in polarized light, texture analysis, gas chromatography with flame ionization, and mass spectrometric detection. Ultrasonic treatment affected the crystallization of oleogels and led to the formation of smaller crystals. At the same time, sonication led to both an increase and a decrease in the firmness of oleogels, depending on the composition of the gelator. As regards volatile compounds, a total of 121 fragrant substances were identified in all samples, including such groups as alkanes, alkenes, alkadienes, alkynes, alkadiynes, alcohols, ketones, aldehydes, terpenes, alkyl alkane, and alkyl benzene derivatives. Ultrasonic treatment caused formation of new volatile unsaturated compounds. Some of them are known to have an unpleasant odor and thus might be responsible for the extraneous odor formation in studied fatty systems. Those were mainly (E)-2-octene, 1-heptene, 1,3-butadiene, and 1,3-octadiene in all oleogel samples. Sonicated samples B and C additionally had but-1-en-3-yne, pentenyne, and 1,3-butadiyne, whose odor can also be characterized as extraneous and distasteful. Several volatile compounds, supposed to be products of lipid oxidation, were also identified. Here we assume a reasonable approach is needed when selecting sonication conditions to prevent undesirable taste and flavor in oleogels and oleogel-based food products. Full article

A series of cationic p-tert-butylcalix[4]arenes, with side-arms that are functionalized with imidazolium groups, have been synthesized in good yields. The parent tetrahydroxy para-t-butyl-calix[4]arene was dialkylated at the phenolic hydrogen atoms using α,ω-dibromo-alkanes to yield bis(mono-brominated) alkoxy-chains of variable length. The brominated side-arms in these compounds were then further alkylated with substituted imidazoles (N-methylimidazole, N-(2,4,6-trimethyl-phenyl)imidazole, or N-(2,6-di-isopropylphenyl)imidazole) to yield a series of dicationic calixarenes with two imidazolium groups tethered, via different numbers of methylene spacers (n = 2–4), to the calixarene moiety. Related tetracationic compounds, which contain four imidazolium units linked to the calix[4]arene backbone, were also prepared. In all of these compounds, the NMR data show that the calixarenes adopted a cone configuration. All molecules were characterized by NMR spectroscopy and by MS studies. Single crystal X-ray diffraction studies were attempted on many mono-crystals of these cations, but significant disorder problems, partly caused by occluded solvent in the lattice, and lack of crystallinity resulting from partial solvent loss, precluded the good resolution of most X-ray structures. Eventually, good structural data were obtained from an unusually disordered single crystal of 5a, (1,3)-Cone-5,11,17,23-tetra-t-butyl-25,27-di-hydroxy-26,28-di-[2-(N-2,6-diisopropylphenyl-imidazolium)ethoxy]calix[4]arene dibromide and its presumed structure was confirmed. The structure revealed the presence of H-bonded interactions and some evidence of π-stacking. Some of these imidazolium salts were reacted with nickelocene to form the nickel N-heterocyclic carbene (NHC) complexes 7a–7d. A bis-carbene nickel complex 8 was also isolated and its structure was established by single crystal X-ray diffraction studies. The structure was disordered and not of high quality, but the structural data corroborated the spectroscopic data. Full article

Group contribution (GC) methods to predict thermochemical properties are eminently important to process design. Following earlier work which presented a GC model in which, for the first time, chemical accuracy (1 kcal/mol or 4 kJ/mol) was accomplished, we here discuss classes of molecules for which the traditional GC approach does not hold, i.e., many results are beyond chemical accuracy. We report new ring-strain-related parameters which enable us to evaluate the heat of formation of alkyl-substituted cycloalkanes. In addition, the definition of the appropriate group size is important to obtain reliable and accurate data for systems in which the electron density varies continuously but slowly between related species. For this and in the case of ring strain, G4 quantum calculations are shown to be able to provide reliable heats of formation which provide the quantitative data which we can use, in the case of absence of experimental data, to establish group and nearest-neighbour interaction parameters to extend the range of applicability of the GC method whilst retaining chemical accuracy. We also found that the strong van der Waals that overlap in highly congested branched alkanes can be qualitatively investigated by applying DFT quantum calculations, which can provide an indication of the GC approach being inappropriate. Full article