Degree Of Unsaturation Research Articles

Experimental and numerical study of laminar burning velocity for Diisobutylene+ PRF/TRF mixtures

DIB (Diisobutylene, JC8H16) strongly correlates with real gasoline and significantly impacts the combustion behavior of alternative fuels designed as gasoline substitutes. However, accuracy concerns persist in laminar burning velocity data reported in literature. In this paper, the laminar burning velocities of DIB + air, DIB + PRF + air, and DIB + TRF + air mixtures were measured by the heat flux method at 1 atm. (PRF, Primary Reference Fuel; TRF, Toluene Reference Fuel) The equivalence ratio was controlled within 0.6–1.3, and the initial temperatures were set at 298K, 318K, and 338K. Additionally, by employing the mechanism proposed by Ren et al., the simulated values align with the experimental data, thus prompting the conduction of a reaction kinetic analysis. The analysis of chemical reaction kinetics reveals the reaction pathways of DIB, with a notable observation that an increase in temperature or a decrease in equivalence ratio can both lead to an elevation in the degree of unsaturation in the bonds of intermediate species. During laminar flame combustion, PRF and TRF compete with DIB for oxygen, with PRF appearing to have a stronger ability to capture oxygen. In addition, the laminar burning velocity temperature dependence coefficient α decreases first and then increases with the increase of the equivalence ratio, where the minimum α is obtained at equivalence ratio = 1.1. Additionally, the laminar burning velocity at higher initial temperatures is estimated by the extrapolation method and compared with the experimental data reported in literature.

Unveiling the oxidative stability, phytochemical richness, and nutritional integrity of cold-pressed Linum usitatissimum oil under UV exposure

This study examines the effect of UV irradiation on the oxidation stability of Linum usitatissimum oil, presenting possible changes in the phytochemical profile due to photo-oxidation. GC–MS analysis of the oils identified 11 fatty acid compounds with a high percentage of unsaturated fatty acids, the most important of which is α-linolenic acid (ALA), known as omega-3 (48.88 %), also significant profiles of phytosterol and tcocopherol isomers rich in β-Sitosterol and γ-tocopherols respectively. As well as physicochemical properties such as free fatty acids (FFA %), peroxide value (PV) and iodine value (IV), and nutritional indexes that determine the significant changes observed during the oxidation process, the most important of which is the progressive increase in acidity, peroxide, conjugated dienes and trienes and degrees of unsaturation over 8 h of UV exposure. High levels of carotenoids and phenolic compounds (TPC) protect and enhance oil quality in the face of irradiation, so a significantly small difference is observed between irradiated and non-irradiated oil during photo-oxidation.

Evaluation of antioxidant potential of anthocyanin-rich hydro ethanol extract of Syzygium cumini fruit pulp in various in vitro models and in food supplement enriched with omega-3 fatty acids

Omega-3 fatty acids have immense health benefits but are highly susceptible to oxidation due to high degree of unsaturation in their molecular structure. Therefore, development of omega-3 fatty acids fortified stable functional food is a challenging task. The aim of the study was to evaluate antioxidant potential of anthocyanin-rich hydro ethanol extract of Syzygium cumini fruit pulp extract in various in vitro models and in omega-3 fatty acids enriched food supplement in bulk oil and oil-in-water emulsions model systems along with chemical analysis of the fruit pulp extract and evaluation of its cytotoxic potential, if any. The in vitro antioxidant potential was evaluated by DPPH radical scavenging, ABTS°+ decolorization and Fe2+ ion chelating methods. Antioxidant activity against oxidation of omega-3 fatty acids enriched food supplement in bulk oil and oil-in-water emulsions model systems was evaluated by monitoring primary oxidation, secondary oxidation and total oxidation of the omega-3 enriched oil using AOCS guidelines and iodometric method. Chemical analysis was performed by HR-LCMS analysis technique. Cytotoxic potential was evaluated by Allium cepa test. The test extract exhibited varying degrees of antioxidant activity in various in vitro models as well as against oxidation of omega-3 fatty acids enriched food supplement both in bulk oil and oil-in-water emulsions model systems. Chemical analysis revealed the presence of three major tentatively identified compounds malvidin-3,5-diglucoside, delphinidin-3,5-diglucoside and peonidin-3,5-diglucoside as major components of the extract. Test extract did not show any cytotoxic potential at recommended dosage level with LC50> 1000 µg/ml. The results provide evidence that anthocyanin-rich hydro ethanol extract of Syzygium cumini fruit pulp may serve as a potential source of safe and effective, novel natural antioxidant for retarding oxidation of omega-3 fatty acids enriched food supplement which subsequently may help to develop omega-3 fortified stable functional foods in food industry.

The Lubricity of Gases

A sealed reciprocating tribometer has been used to study the influence of different gaseous environments on the friction and wear properties of AISI52100 bearing steel at atmospheric pressure and 25 °C. Helium, argon, hydrogen, carbon dioxide and nitrogen all give high friction and wear, suggestive of very little, if any tribofilm formation under the conditions studied. Dry air and oxygen also give high friction, slightly lower than the inert gases, but produce extremely high wear, much higher than the inert gases. This is characteristic of the phenomenon of “oxidational wear”. The two gases ammonia and carbon monoxide give relatively low friction and wear, and XPS analysis indicates that this is due to the formation of adsorbed ammonia/nitride and carbonate films respectively. For the hydrocarbon gases studied, two factors appear to control friction and wear, degree of unsaturation and molecular weight. For the saturated hydrocarbons, methane and ethane give high friction and wear but propane and butane give low friction after a period of rubbing that decreases with molecular weight. The unsaturated hydrocarbons all give an immediate reduction in friction with correspondingly low wear. Raman analysis shows that all the hydrocarbons that reduce friction and wear form a carbonaceous tribofilm on the rubbed surfaces.Graphical

Influence of phospholipid head and tail molecular structures on cell membrane mechanical response under tension.

Biological cell membranes are primarily comprised of a diverse lipid bilayer with multiple phospholipid (lipid) types, each of which is comprised of a hydrophilic headgroup and two hydrophobic hydrocarbon tails. The lipid type determines the molecular structure of head and tail groups, which can affect membrane mechanics at nanoscale and subsequently cell viability under mechanical loading. Hence, using molecular dynamics simulations, the current study investigated seven membrane phospholipids and the effect of their structural differences on physical deformation, mechanoporation damage, and mechanical failure of the membranes under tension. The inspected phospholipids showed similar yield stresses and strains, as well as pore evolution and damage, but significantly different failure strains. In general, failure occurred at a lower strain for lipids with a larger equilibrium area per lipid. The obtained results suggest that larger headgroup structure, greater degree of unsaturation, and tail-length asymmetry influenced the phospholipids' ability to pack against each other, increased the fluidity and equilibrium area per lipid of the membrane, and resulted in lower failure strain. Overall, this study provides insights on how different phospholipid structures affect membrane physical responses at the molecular level and serves as a reference for future studies of more complex membrane systems with intricate biophysical properties.

Molecular characterization on the fractionation of organic phosphorus induced by iron oxide adsorption using ESI-FT-ICR MS

The interaction between organic phosphorus (OP) and iron oxide significantly influences the phosphorus cycle in the natural environment. In shallow lakes, intense oxidation-reduction fluctuations constantly alter the existing form of iron oxides, but little is known about their impact on the adsorption and fractionation of OP molecules. In this study, electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS) was used to investigate the fractionation of OP from alkali-extracted sediment induced by crystalline goethite and amorphous ferrihydrite adsorption at a molecular scale. The results showed that ferrihydrite and goethite both exhibited high OP adsorption, and the adsorption amount decreased as the pH increased. The adsorption kinetics matched the pseudo-second-order equation. The ESI-FT-ICR MS analysis showed that 91 P-containing formulas were detected in the alkaline-extracted sediment solution. Ferrihydrite and goethite adsorbed 51 and 24 P-containing formulas, respectively, with adsorption rates of 56.0 % and 26.4 %. Ferrihydrite could adsorb more OP compounds than goethite, but no obvious molecular species selectivity was observed during the adsorption. The P-containing compounds, including unsaturated hydrocarbons-, lignin/carboxyl-rich alicyclic molecule (CRAM)-, tannin-, and carbohydrate-like molecular compounds, were more suitable for iron oxide adsorption. The double bond equivalence (DBE) is a valuable parameter that indicates OP fractionation during adsorption, and P-containing compounds with lower DBE values such as lipid- and protein-like molecular were prone to remain in the solution after adsorption. These research results provide insights into the biogeochemical cycling process of P in the natural environment.

Impact of Nonthermal Plasma Treatment on the Oxidation of Lipids with Different Unsaturation Degrees.

Nonthermal plasma (NTP) treatment of food presents a new technology for the industry but raises concerns about lipid oxidation due to the presence of reactive species. Considering the critical role of the degree of unsaturation in lipid oxidation, this study investigates NTP-induced oxidation across various unsaturated lipids. These lipids are six oil samples primarily containing one of the following methylesters: oleate, linoleate, linolenate, arachidonate, eicosapentaenoate, and docosahexaenoate. Samples were treated with a nonthermal surface dielectric barrier discharge. Plasma-induced effects were first examined by classical lipid oxidation indicators, such as the peroxide value and p-anisidine value. The specific volatile oxidation products, including hexanal, nonanal, trans-2-hexenal, and methyl 9-oxononanoate, were determined to further elucidate the impact of ozone-related oxidation. Monitoring the production of selected nonvolatile oxidation products, such as epoxy-, oxo-, and hydroxy fatty acid methylesters, confirmed that plasma treatment facilitated the decomposition of lipid hydroperoxide. Generally, the level of plasma-induced oxidation increased in parallel with the unsaturation degree of the studied samples, except for the quantity of individual volatile carbonyls. The long-term effect of NTP treatment was investigated by a stability test, revealing that the oxidative stability depended on the input gas of plasma treatment, the sensitivity of the treated sample, and the presence of antioxidants. Except for the focus on the NTP impact, this study offered a case study of a comprehensive investigation into lipid oxidation.

Plasma proteomics and lipidomics facilitate elucidation of the link between Alzheimer's disease development and vessel wall fragility

Proximity Extension Assay (PEA) and mass spectrometry (MS) methodologies were utilized for the proteomic and lipidomic characterization of plasma specimens from patients who developed Alzheimer's disease. Proteomics was performed by both PEA and Liquid Chromatography (LC)/MS in this study, but all the more because LC/MS generally tends to be biased towards proteins with high expression and high variability, generating hypotheses proved challenging. Consequently, attempt was made to interpret the results from the PEA data. There were 150 significantly variable proteins and 68 lipids among 1000 proteins and 400 lipids. Pathway analysis was performed for both total and variable proteins measured to reduce bias, and it appeared that vascular fragility was related to AD. Furthermore, a multitude of lipid-associated proteins exhibited statistical changes. In certain instances, the function of individual proteins affected the factors associated with them, whereas others demonstrated trends contrary to anticipated outcomes. These trends seem indicative of diverse feedback mechanisms that provide homeostatic equilibrium. The degree of unsaturation of fatty acids, correlated with cardiovascular risk, warrants specific attention. Certain bile acids exhibited the potential to cause vascular endothelial damage. Contemplating these discoveries in tandem with previously documented phenomena, subtle shifts in homeostatic functions seem to be linked to the fragility of vascular endothelial cells. This is evidenced by the slow and chronic evolution of Alzheimer's disease from preclinical stages to its manifestation.

Improvement of methane reforming Ni-based catalyst stability by controlling the unsaturated coordination aluminum in metakaolinite

Dry reformation of methane (DRM) is an attractive route to utilize greenhouse gases, which has significant environmental and economic benefits. Ni-based catalysts are one of the most important catalysts in DRM. However, their deactivation induced by sintering and coking remains a major challenge. In this work, a series of metakaolinite-supported Ni catalysts (Ni/MK) with varying content of unsaturated coordinated aluminum were prepared. It was found that the catalytic stability could be improved by controlling the unsaturated coordinated aluminum content. Ni/MK-800, with the highest unsaturated coordinated aluminum content, demonstrated at least 18 times enhanced stability duration compared with Ni/MK-600 with the lowest content. The increasing content of unsaturated coordinated aluminum enhanced the metal-support interaction, which subsequently improved the anti-sintering and anti-coking performance and thus improved the catalytic stability. This work provided an optional strategy for designing highly stable DRM catalysts by controlling the coordinative unsaturation degree of central ions in support.

Lipid metabolites are associated with the risk of osteoporotic fractures

We conducted this cross-sectional study to investigate the independent associations between lipid metabolites and osteoporotic fractures among participants aged 40–69 years from the UK Biobank. Serum lipid, lipoprotein levels and nuclear magnetic resonance (NMR) based metabolic biomarkers were measured at the baseline. We conducted multivariable logistic analyses to investigate potential independent associations between concentrations of lipid metabolites and osteoporotic fractures in both men and women. The odds ratios (ORs) for lipid metabolites were calculated based on their lowest tertile. Over a median follow-up period of 15 years, a total of 978 men and 4515 women were diagnosed with osteoporosis, whereas 138 men and 327 women encountered incident fractures. Statistically significant disparities were identified in NMR-based metabolic biomarkers among men and women with incident fractures compared to those without. Out of the 144 distinct lipid metabolites known, 35 exhibited significant associations with incident fractures in patients diagnosed with osteoporosis. Following the adjustment for confounding factors, degree of unsaturation (p = 0.0066) and docosahexaenoic acids (p = 0.0011) in male patients increased the risk of incident fractures. And high level of different metabolites of HDL (p = 0.0153), 3-Hydroxybutyrate (p = 0.0012) and Sphingomyelins (p = 0.0036) decreased the risk of incident fractures in female patients. This outcome indicates that these identified lipid metabolites may potentially have unique roles in independently contributing to the occurrence of osteoporotic fractures.

Enantiomeric Separation of Triacylglycerols Consisting of Three Different Fatty Acyls and Their Chiral Chromatographic Elution Behavior.

Chromatographic separation of triacylglycerol (TG) enantiomers is a highly challenging task of analytical chemistry because of the similar physicochemical properties. The analysis of chiral TGs is crucial for improving the knowledge of lipid biochemistry and for understanding the nutritional properties of fats and oils. Thus, this study aimed to systematically investigate the chiral resolution of TGs consisting of three different fatty acyls (FAs). Thirty-three asymmetric TG enantiopairs, including 49 synthesized enantiopure TGs and racemic TGs, were analyzed with a recycling chiral HPLC system. Twenty-six enantiopairs were successfully separated. Overall, having both unsaturated and saturated FAs in the outer positions or a difference in carbon chain length between two saturated FAs at the outer positions favored the separation of enantiomers. The retention time at separation correlated negatively with the sn-3 carbon number of the early eluting enantiomer and positively with the carbon number difference between sn-1 and sn-3. When the samples were studied in separate groups based on unsaturation and regioisomers, both the acyl carbon number and the degree of unsaturation of FAs in all three positions influenced the separation and elution behavior of chiral TGs, indicating an active role of both intermolecular interactions and steric hindrances. This is the first systematic study of the chiral separation of TGs consisting of three different FAs using a large number of enantiopairs. The novel findings on the behavior of TG enantiomers in a chiral environment provide important guidance and reference for a stereospecific study of the chemistry and biochemistry of natural lipids.

Studies on Nigerian cashew nut shell liquid: Greening-up extraction process, chemical composition and cost effectiveness

Extractions of cashew nut shell liquid (CNSL) have always widely been carried out with non-environmentally friendly solvents. Hence, greener solvents are desired as alternative to currently used solvents. Herein, batch extractions of Nigerian CNSL with greener solvents: ethyl acetate and cyclohexane mixture in different ratios were investigated in hot and cold system and results compared with conventional solvent (petroleum ether). Compositional studies of the extracted CNSL and its isolated components were done with Fourier-Transformed Infrared (FTIR), Nuclear Magnetic Resonance (NMR) spectroscopy and Ultra High-Performance Liquid Chromatography-Mass Spectrometry (UHPLC-MS). Cost effectiveness analysis for the extraction solvents and methods was also investigated. It was revealed that ethyl acetate and ethyl acetate-cyclohexane mixture at cold and hot conditions recorded higher CNSL yields than previous reports even at a lower liquid-to-solid ratio. Chemical composition and component quantity extracted did not significantly change under hot or cold system. The present composition of the Nigerian CNSL contains unusually higher amount of anarcardic acid (79 %) and cardanol (14 %) than ever reported. Additionally, degree of unsaturation in the alkyl chain of the CNSL is in the order triene>monoene>diene in the anarcardic acid and cardanol components of the liquid. Cost effectiveness analysis at a kilogramme scale revealed that the order of greenness of extraction route based on solvent type, energy requirement and condition of extraction is ethyl acetate-solvent cold system> ethyl acetate-hot system> ethyl acetate-cyclohexane-system> cyclohexane system > pet. ether system.

Causal relationship between serum metabolites and idiopathic pulmonary fibrosis: Insights from a two-sample Mendelian randomization study

BackgroundIdiopathic pulmonary fibrosis (IPF) is an irreversible lung disease with unclear pathological mechanisms. In this study, we utilized bidirectional Mendelian randomization (MR) to analyze the relationship between serum metabolites and IPF, and conducted metabolic pathway analysis. AimTo determine the causal relationship between serum metabolites and IPF using MR analysis. MethodsA two-sample MR analysis was conducted to evaluate the causal relationship between 824 serum metabolites and IPF. The inverse variance weighted (IVW) method was used to estimate the causal relationship between exposure and results. Sensitivity analysis was conducted using MR Egger, weighted median, and maximum likelihood to eliminate pleiotropy. Additionally, metabolic pathway analysis was conducted to identify potential metabolic pathways. ResultsWe identified 12 serum metabolites (6 risks and 6 protective) associated with IPF from 824 metabolites. Among them, 11 were known and 1 was unknown. 1-Eicosatrienoylglycophorophospholine and 1-myristoylglycophorophospholine were bidirectional MR positive factors, with 1-myristoylglycophorophospholine being a risk factor (1.0013, 1.0097) and 1-eicosatrienoylglycophorine being a protective factor (0.9914, 0.9990). The four lipids (1-linoleoylglycerophoethanolamine*, total cholesterol in large high-density lipoprotein [HDL], cholesterol esters in very large HDL, and phospholipids in very large HDL) and one NA metabolite (degree of unsaturation) were included in the known hazardous metabolites. The known protective metabolites included three types of lipids (carnitine, 1-linoleoylglycerophoethanolamine*, and 1-eicosatrienoylglycerophophophorine), one amino acid (hypoxanthine), and two unknown metabolites (the ratio of omega-6 fatty acids to omega-3 fatty acids, and the ratio of photoshopids to total lipids ratio in chylomicrons and extremely large very low-density lipoprotein [VLDL]). Moreover, sn-Glycerol 3-phosphate and 1-Acyl-sn-glycero-3-phosphocline were found to be involved in the pathogenesis of IPF through metabolic pathways such as Glycerolide metabolism and Glycerophospholipid metabolism. ConclusionOur study identified 6 causal risks and 6 protective serum metabolites associated with IPF. Additionally, 2 metabolites were found to be involved in the pathogenesis of IPF through metabolic pathways, providing a new perspective for further understanding the metabolic pathway and the pathogenesis of IPF.

Substrate specificity of commercial lipases activated by a hydration–aggregation pretreatment in anhydrous esterification reactions

Substrate specificity in non-aqueous esterification catalyzed by commercial lipases activated by hydration–aggregation pretreatment was investigated. Four microbial lipases from Rhizopus japonicus, Burkholderia cepacia, Rhizomucor miehei, and Candida antarctica (fraction B) were used to study the effect of the carbon chain length of saturated fatty acid substrates on the esterification activity with methanol in n-hexane. Hydration–aggregation pretreatment had an activation effect on all lipases used, and different chain length dependencies of esterification activity for lipases from different origins were demonstrated. The effects of various acidic substrates with different degrees of unsaturation, aromatic rings, and alcohol substrates with different carbon chain lengths on esterification activity were examined using R. japonicus lipase, which demonstrated the most remarkable activity enhancement after hydration–aggregation pretreatment. Furthermore, in the esterification of myristic acid with methanol catalyzed by the hydrated–aggregated R. japonicus lipase, maximum reaction rate (5.43 × 10−5 mmol/(mg-biocat min)) and Michaelis constants for each substrate (48.5 mM for myristic acid, 24.7 mM for methanol) were determined by kinetic analysis based on the two-substrate Michaelis-Menten model.

Nickel-induced oxidative stress and phospholipid remodeling in cucumber leaves

Nickel phytotoxicity has been attributed, among others, to oxidative stress. However, little is known about Ni-induced phospholipid modifications, including the oxidative ones. Accumulation of reactive oxygen species (ROS), antioxidative enzyme activities, malondialdehyde and the early lipid oxidation products contents, membrane permeability, phospholipid profile as well as phospholipid unsaturation degree were studied in the 1st and the 2nd leaves of hydroponically grown cucumber seedlings subjected to Ni stress. Compared to the 2nd leaf the 1st one showed stronger visual Ni toxicity symptoms, higher Ni, O2.- and H2O2 accumulation as well as greater enhancement in membrane permeability. Enzyme activities were differently influenced by Ni stress, however most pronounced changes were generally found in the 1st leaf. Ni treatment resulted in oxidation of leaf lipids, which was evidenced by appearance of increased contents of MDA and the early produced oxylipins. Among the latter 9-hydroxyoctadecatrienoic acid (9-HOTrE) and 13-hydroxyoctadecatrienoic acid (13-HOTrE) contents showed the most pronounced increase in response to Ni treatment. Exposure to the metal led to the changes in the leaf phospholipid profile and increased degree of phospholipid unsaturation. The obtained results have been discussed in relation to the difference in Ni stress severity between the 1st and the 2nd leaves.

Performance of catalytic wet oxidation on thermochemical aqueous effluents assessed by FT-ICR MS

Aqueous phase (AP) is frequently observed in bio-oil from biomass thermochemical conversion or as an upgrading coproduct. However, AP contains high organic content that can be toxic and that must be reduced or removed to be then treated in existing wastewater plants. A promising method to upgrade these APs is the catalytic wet peroxide oxidation (CWPO) that was applied here on APs of both hydrothermal liquefaction and pyrolysis bio-oils from softwood and hardwood. Efficiency of the CWPO was assessed by investigating the molecular composition of raw and treated APs by ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI) in negative- and positive-ion modes. Combination of FT-ICR MS and multivariate statistical analyses evidenced efficiency of the process with new compounds resulting from the oxidative depolymerization, characterized by lower unsaturation degree and molecular weight, and higher oxygen atom count. Refractory compounds were also observed, which are notably characterized by high unsaturation degrees. Interestingly, both detection modes were shown to be complementary for the understanding of the CWPO process. ESI (-) allowed to assess the completion of the oxidation process in detecting carboxylic acid conversion products and to specifically evidence refractory products. ESI (+) was informative on the CWPO process, especially on the conversion of the basic compounds, with the decrease of the detected species. Eventually, softwood AP was shown to be more reluctant to CWPO than the hardwood one.

Transformation of sedimentary dissolved organic matter in electrokinetic remediation catalogued by FT-ICR mass spectrometry

In electrokinetic remediation (EKR), the sedimentary dissolved organic matter (DOM) could impede remediation by scavenging reactive species and generating unintended byproducts. Yet its transformation and mechanisms remained largely unknown. This study conducted molecular-level characterization of the water-extractable DOM (WEOM) in EKR using negative-ion electrospray ionization coupled to 21 tesla Fourier transform ion cyclotron resonance mass spectrometry (21 T FT-ICR MS). The results suggested that ∼55 % of the ∼7,000 WEOM compounds identified were reactive, and EKR lowered their diversity, molecular weight distribution, and double-bond equivalent (DBE) through a combination of electrochemical and microbial redox reactions. Heteroatom-containing WEOM (CHON and CHOS) were abundant (∼ 35% of the total WEOM), with CHOS generally being more reactive than CHON. Low electric potential (1 V/cm) promoted the growth of dealkylation and desulfurization bacteria, and led to anodic CO2 mineralization, anodic cleavage of -SO and -SO3, and cathodic cleavage of -SH2; high electric potential (2 V/cm) only enriched desulfurization bacteria, and differently, led to anodic oxygenation and cathodic hydrogenation of unsaturated and phenolic compounds, in addition to cathodic cleavage of -SH2. The long-term impact of these changes on soil quality and nitrogen-sulfur-carbon flux may be need to studied to identify unknown risks and new applications of EKR.

Development of oleogel by structuring the blend of corn oil and sunflower oil with beeswax to replace margarine in cookies

Oleogel significantly affects the product's sensory properties, texture, and shelf life. The goal of this study was to create oleogel by combining corn oil and sunflower oil and utilizing beeswax as a structural agent. A variety of physicochemical analyses were done to evaluate the quality of oleogel, including peroxide value, iodine value, saponification value, fatty acid, rheological parameters and firmness. Different percentages of oleogel, ranging from 0% to 75%, were used to substitute margarine in cookies. The cookies' quality was evaluated using proximate analysis, color analysis, texture analysis, calorific value, and sensory analysis. The study yielded substantial results by finding the ideal margarine-to-oleogel mix ratio, allowing for the manufacturing of high-quality cookies with a greater degree of unsaturation. Cookies with oleogel showed higher levels of unsaturation and better properties, making them the preferred option among consumers.

Selective Profiling of Carboxylic Acid in Crude Oil by Halogen Labeling Combined with Liquid Chromatography and High-Resolution Mass Spectrometry.

Carboxylic acids are a small but essential compound class within petroleum chemistry, influencing crude oil behaviors in production and processing and causing environmental impacts. Detailed structural information is fundamental to understanding their influence on petroleum characteristics. However, characterizing acids in crude oil remains challenging due to matrix effects, structural diversity, and low abundance. In this work, we present a new methodology for profiling carboxylic acids by liquid-liquid extraction and selective derivatization using 4-bromo-N-methylbenzylamine (4-BNMA) followed by liquid chromatography and electrospray ionization Orbitrap mass spectrometry (LC-ESI-Orbitrap MS). The fragmentation of 4-BNMA derivatives produces a unique product ion pair, m/z 169/171, enabling the identification of chromatographic fractions containing carboxylic acids. The mass spectra of the corresponding fractions are extracted, and the acids are further computationally isolated based on the isotopic pattern. The method was optimized and validated using acid standards and systematic experimental designs, assuring robustness and sensitivity for nontarget screening purposes. This method detected up to 380 carboxylic acids in six Danish North Sea crude oils, with up to two carboxyl and other heteroatom functionalities (NSO). The results indicated that the most populated species are fatty acids (double bond equivalent (DBE) = 1) and small aromatic acids (DBE = 2-6). The predominance and diversities of compound classes in different samples are consistent with their corresponding bulk properties. Polyfunctional acids (Ox, NxOx, and SxOx) were observed due to exposure to oxidation and biodegradation. Also, the approach's applicability benefits high-resolution MS analysis by simplifying data processing for crude oil and potentially other high-organic and aqueous samples.

Association between blood metabolites and basal cell carcinoma risk: a two-sample Mendelian randomization study.

Circulating metabolites, which play a crucial role in our health, have been reported to be disordered in basal cell carcinoma (BCC). Despite these findings, evidence is still lacking to determine whether these metabolites directly promote or prevent BCC's progression. Therefore, our study aims to examine the potential effects of circulating metabolites on BCC progression. We conducted a two-sample Mendelian randomization (MR) analysis using data from two separate genome-wide association studies (GWAS). The primary study included data for 123 blood metabolites from a GWAS with 25,000 Finnish individuals, while the secondary study had data for 249 blood metabolites from a GWAS with 114,000 UK Biobank participants.GWAS data for BCC were obtained from the UK Biobank for the primary analysis and the FinnGen consortium for the secondary analysis. Sensitivity analyses were performed to assess heterogeneity and pleiotropy. In the primary analysis, significant causal relationships were found between six metabolic traits and BCC with the inverse variance weighted (IVW) method after multiple testing [P < 4 × 10-4 (0.05/123)]. Four metabolic traits were discovered to be significantly linked with BCC in the secondary analysis, with a significance level of P < 2 × 10-4 (0.05/249). We found that all the significant traits are linked to Polyunsaturated Fatty Acids (PUFAs) and their degree of unsaturation. Our research has revealed a direct link between the susceptibility of BCC and Polyunsaturated Fatty Acids and their degree of unsaturation. This discovery implies screening and prevention of BCC.