Search Results (42)

Background/Objectives: Dietary guidelines recommend limiting trans fatty acid (TFA) intake to avoid adverse health effects. However, the impact of TFA intake in type 1 diabetes mellitus (T1DM) remains unclear. The aim of the present study was to investigate the levels of TFAs in plasma and erythrocyte membrane lipids of young diabetic patients and healthy controls. Methods: Data were re-analyzed from three case-control studies including diabetic children (n = 40, mean age: 12.0 years), diabetic young adults (n = 34, mean age: 21.8 years), and children with diabetic ketoacidosis (DKA, n = 9, mean age: 16.0 years). In these studies, TFA data were quantified by gas chromatography, but data have not yet been published. Results: Diabetic young adults and diabetic children had significantly lower TFAs in plasma lipids compared to healthy controls (sum of TFA in plasma sterol esters: 0.54 [0.34] versus 0.64 [0.37] and 0.51 [0.13] versus 0.65 [0.29], %, median [interquartile range], p < 0.05). However, children with DKA had significantly higher TFA levels in almost all plasma lipid fractions than the other two diabetic groups. Several negative correlations were observed between TFA and n-3 and n-6 long-chain polyunsaturated fatty acid levels in all groups, especially in the erythrocyte membrane lipid fractions. However, in the plasma fractions the correlation was less clear; both positive and negative correlations were found in each of the groups studied. Conclusions: Lower TFA values in young adults and children with diabetes may be associated with dietary patterns lower in TFAs, while elevated TFA values in DKA may be linked to challenges in adherence to dietary guidelines. Full article

The development of alternative energies has become a concern for all countries to ensure domestic energy supply and provide environmental friendliness. One of the providential alternative energies is biodiesel. Biodiesel, commonly stated as fatty acid alkyl ester (FAAE), is a liquid fuel intended to substitute petroleum diesel. Nevertheless, implementation of pure biodiesel is not recommended for conventional diesel engines. It holds poor values of cold flow properties, as the effect of high saturated FAAE content contributes to this constraint. Several processes have been proposed to enhance cold flow properties of biodiesel, but this work focuses on the skeletal isomerization process. This process rearranges the skeletal carbon chain of straight-chain FAAE into branched isomeric products to lower the melting point, related to the good cold flow behavior. This method specifically requires an acid catalyst to elevate the isomerization reaction rate. And then, sulfated tin(IV) oxide emerged as a solid superacid catalyst due to its superiority in acidity. The results of biodiesel isomerization over this catalyst and its modification with iron had not satisfied the expectation of high isomerization yield and significant CFP improvement. However, they emphasized that the skeletal isomers demonstrated minimum impact on biodiesel oxidation stability. They also affirmed the role of an acid catalyst in the reaction mechanism in terms of protonation, isomerization, and deprotonation. Furthermore, the metal promotion was theoretically necessary to boost the catalytic activity of this material. It initiated the dehydrogenation of linear hydrocarbon before protonation and terminated the isomerization by hydrogenating the branched carbon chain after deprotonation. Finally, the overall findings indicated promising prospects for further enhancement of catalyst performance and reusability. Full article

Charge-free gaseous molecules labeled with deuterium ²H (D) atoms elute earlier than their protium-analogs ¹H (H) from most stationary GC phases. This effect is known as the chromatographic H/D isotope effect (hdIE_C) and can be calculated by dividing the retention times (t_R) of the protiated (t_R(H) ) to those of the deuterated (t_R(D)) analytes: hdIE_C = t_R(H)/t_R(D). Analytes labeled with ¹³C, ¹⁵N or ¹⁸O have almost identical retention times and lack a chromatographic isotope effect. Derivatives of cis- and trans-analytes such as cis- and trans-fatty acids also differ in their retention times. Analytes that contain trans-C=C-double bonds elute earlier in gas chromatography-mass spectrometry (GC-MS) than their cis-C=C-double bonds containing congeners. The chromatographic cis/trans-effect (ctE_C) can be calculated by dividing the retention times of the cis- by those of the trans-analytes: ctE_C = t_R(c)/t_R(t). In the present work, the hdIE_C and ctE_C values of endogenous and exogenous substances were calculated from previously reported GC-MS analyses and found to range each between 1.0009 and 1.0400. The examination suggests that the H/D-isotope effects and the cis/trans-effects observed in GC-MS are based on differences in the inter-molecular interaction strengths of the analyte derivatives with the stationary phase of GC columns. The deuterium atoms, being larger than the H atoms of the analytes, attenuate the interaction of the skeleton of the molecules with the GC stationary phase. The angulation of trans-analytes decreases the interaction of the skeleton of the molecules with the GC stationary phase, as only parts of the molecules are close enough to the GC stationary phase to interact. Other chromatographic effects caused by hydrogen (H) and fluorine (F) atoms and by stereo-isomerism are considered to be based on a similar mechanism due to the different orientation of the side chains. Full article

This review provides an overview of the main vegetable oils of different botanical origin and composition that can be used for frying worldwide (olive and extra-virgin olive oil, high-oleic sunflower oil, rapeseed oil, peanut oil, rice bran oil, sunflower oil, corn oil, soybean oil, cottonseed oil, palm oil, palm kernel oil and coconut oil) and their degradation during this process. It is well known that during this culinary technique, oil’s major and minor components degrade throughout different reactions, mainly thermoxidation, polymerization and, to a lesser extent, hydrolysis. If severe high temperatures are employed, isomerization to trans fatty acyl chains and cyclization are also possible. The factors conditioning frying medium degradation are addressed, including oil composition (unsaturation degree, fatty acyl chain length and “free” fatty acid content, and presence of beneficial and detrimental minor components), together with frying conditions and food characteristics. Likewise, this review also tackles how the frying oil and other processing conditions may impact on fried food quality (oil absorption, texture, flavor and color). Finally, potential health implications of fried food consumption are briefly reviewed. Full article

The most commonly used homogeneous catalyst for fatty acid esterification is a corrosive sulphuric acid. However, this requires costly investment in non-corrosive equipment, presents a safety risk, is time consuming, and increases effluent generation. In this study, inorganic 3D heteroborane cluster strong acids are employed for the first time as homogeneous catalysts. Three novel isomeric tetrachlorido and tetrabromido derivatives of 3,3′-commo-bis[undecahydrido-closo-1,2-dicarba-3-cobaltadodecaborate](1−) [1⁻] were synthesised and fully characterised using a range of analytical techniques, including NMR, TLC, HPLC, MS, UV-Vis, melting point (MP), CHN analyses, and XRD. Ultimately, H₃O[8,8′-Cl₂-1⁻] was identified as the most efficient, reusable, and non-corrosive homogeneous catalyst for the esterification of four fatty acids. The reactions are conducted in an excess of alcohol at reflux. The effective absorption of water vapour provided by the molecular sieves maximises acid conversion. The hydrophobic dye Sudan black B was employed as an acid-base indicator to facilitate a comparison of the H₀ acidity function of sulphuric acid and halogenated heteroboranoic acids when dissolved together in methanol. The ²³Na NMR analysis demonstrated that the application of dry methanol resulted in the displacement of Na⁺ ions from zeolite, which subsequently exchanged the H₃O⁺ ions of the acid. This process led to a gradual reduction in the efficiency of the catalysts, particularly with repeated use. The solution to this issue is to regenerate the catalyst on the ion exchanger following each reaction. In contrast to the published methods, our new approach meets 10 of 12 green chemistry principles. Full article

To achieve a krill meal of high quality, a two-stage drying involving hot-air drying and vacuum drying was investigated. Five experimental groups were established according to the different drying conditions in the second stage, including 95 °C and 101 kPa, 95 °C and 60 kPa, 75 °C and 101 kPa, 75 °C and 60 kPa, and 75 °C and 20 kPa. The results showed that reducing the drying temperature and vacuum pressure in the second stage had a significant impact on the drying characteristics, sensory quality, and bioactive compounds of krill meal. Among all five groups, the drying condition of 75 °C and 60 kPa maintained a high drying rate while preserving a phospholipid content of 30.01 mg/kg and an astaxanthin content of 37.41 mg/kg. It also effectively reduced the isomerization of astaxanthin and the oxidation of unsaturated fatty acids. These results suggested that the two-stage drying method may contribute to the production of high-quality krill meal. Full article

This study determined whether the isomeric or isoenergetic/isoproteic substitution of corn in the diet of Jersey heifers in the rearing phase with cracker residue would impair growth and health, as well as reducing production costs. Fourteen Jersey females in the growth phase were used, separated into two treatments with seven animals in each lot in collective pens. The experiment used 7-month-old animals (169.8 ± 2.89 kg) and lasted for four months. In Experiment I, the animals were divided into two groups: treatment, with the partial replacement of 40% corn with cracker residue, and control, in which the animals consumed the same diet with 100% corn (isometric diet kg for kg). In Experiment II, the animals with a body weight of 200.2 ± 3.85 kg were divided into two groups: Treatment, replacing 100% of the corn with cracker residue, and control, in which the animals consumed an isoprotein and isoenergetic diet but with 100% of the corn in the formulation. The diet consisted of concentrate, Tifton 85 hay, and corn silage, supplied twice a day individually, with animals contained in their feeders by kennels. There was water ad libitum in the bay. Biweekly weighing and monthly blood analysis were performed, totaling four collections per part for hematologic evaluation, carbohydrate, lipid, and protein metabolism variables. At the end of each experiment, ruminal fluid was collected to measure the volatile fatty acid profile, and feces were collected to determine the apparent digestibility coefficient (ADC). Experiments I and II showed no effect of treatment on body weight, weight gain, average daily weight gain, feed intake, and feed efficiency. There was no effect of treatment on leukocyte, erythrocyte, lymphocyte, neutrophil, monocyte, and eosinophil counts, hematocrit, and hemoglobin concentration (p > 0.05). Experiment I showed a difference between groups for the variables albumin, globulin, total proteins, cholesterol, glucose, and urea, which did not happen in Experiment II. In both experiments, a higher ADC of nutrients was found in the treatment group which had cracker residue (p > 0.05). The concentration of volatile fatty acids in Experiment I was higher in the control group, unlike in Experiment II, where the highest concentration was in the treatment group (p > 0.05). Because experiment I had an isometric substitution, the diets had different bromatological composition, which is the probable cause of the difference between groups; this did not happen in experiment II, in which the diets consumed by the animals was isoproteic and isoenergetic. Based on these data we conclude that the substitution of cracker residue in an isomeric or isoenergetic/isoproteic form does not negatively affect weight gain and animal health, as well as reduces the cost of the concentrate, consequently reducing the cost of production of these animals. Full article

Elaeagnus moorcroftii Wall.ex Schlecht. (EWS) has extensive nutrients and functional active ingredients, which makes it an excellent potential substrate for fermentation. The improvement in the antioxidant activity of Elaeagnus moorcroftii Wall.ex Schlecht. juice (EWSJ) fermented by Bifidobacterium animalis subsp. lactis HN-3 (B.an3) could be attributed to the metabolism and biotransformation of plant-based products by the bacterial strain. To reveal the underlying mechanism, non-targeted metabolomics was applied in this study. After fermentation, the structure of downregulated carbohydrates, amino acids, fatty acids, and flavonoids was changed by Bifidobacterium biotransformation (included four reductions, three hydrolyses, four isomerizations, three deglycosidations, and five other reactions). The structure of these converted upregulated products has a higher antioxidant ability to reduce free radicals than their precursors, such as the flavonoids in the form of hydrolyzed conjugates, amino acids with multiple sulfhydryls or hydroxys, carbohydrates with reactive oxygen on benzene rings and fatty acids with unsaturated bonds, short chains, and glycosides. These findings shed light on the mechanism of the metabolism and biotransformation of EWSJ by B.an3, facilitate the study of the interaction between probiotics and fermented plant-based products, and provide a theoretical basis for the development of Bifidobacterium-fermented plant products with stronger functional activities. Full article

In George Wald’s Nobel Prize acceptance speech for “discoveries concerning the primary physiological and chemical visual processes in the eye”, he noted that events after the activation of rhodopsin are too slow to explain visual reception. Photoreceptor membrane phosphoglycerides contain near-saturation amounts of the omega-3 fatty acid docosahexaenoic acid (DHA). The visual response to a photon is a retinal cis–trans isomerization. The trans-state is lower in energy; hence, a quantum of energy is released equivalent to the sum of the photon and cis–trans difference. We hypothesize that DHA traps this energy, and the resulting hyperpolarization extracts the energized electron, which depolarizes the membrane and carries a function of the photon’s energy (wavelength) to the brain. There, it contributes to the creation of the vivid images of our world that we see in our consciousness. This proposed revision to the visual process provides an explanation for these previously unresolved issues around the speed of information transfer and the purity of conservation of a photon’s wavelength and supports observations of the unique and indispensable role of DHA in the visual process. Full article

Plasmalogens are membrane phospholipids with two fatty acid hydrocarbon chains linked to L-glycerol, one containing a characteristic cis-vinyl ether function and the other one being a polyunsaturated fatty acid (PUFA) residue linked through an acyl function. All double bonds in these structures display the cis geometrical configuration due to desaturase enzymatic activity and they are known to be involved in the peroxidation process, whereas the reactivity through cis-trans double bond isomerization has not yet been identified. Using 1-(1Z-octadecenyl)-2-arachidonoyl-sn-glycero-3-phosphocholine (C18 plasm-20:4 PC) as a representative molecule, we showed that the cis-trans isomerization can occur at both plasmalogen unsaturated moieties, and the product has characteristic analytical signatures useful for omics applications. Using plasmalogen-containing liposomes and red blood cell (RBC) ghosts under biomimetic Fenton-like conditions, in the presence or absence of thiols, peroxidation, and isomerization processes were found to occur with different reaction outcomes due to the particular liposome compositions. These results allow gaining a full scenario of plasmalogen reactivity under free radical conditions. Moreover, clarification of the plasmalogen reactivity under acidic and alkaline conditions was carried out, identifying the best protocol for RBC membrane fatty acid analysis due to their plasmalogen content of 15–20%. These results are important for lipidomic applications and for achieving a full scenario of radical stress in living organisms. Full article

The enoyl reductase from Mycobacterium tuberculosis (MtInhA) was shown to be a major target for isoniazid, the most prescribed first-line anti-tuberculosis agent. The MtInhA (EC 1.3.1.9) protein catalyzes the hydride transfer from the 4S hydrogen of β-NADH to carbon-3 of long-chain 2-trans-enoyl thioester substrates (enoyl-ACP or enoyl-CoA) to yield NAD⁺ and acyl-ACP or acyl-CoA products. The latter are the long carbon chains of the meromycolate branch of mycolic acids, which are high-molecular-weight α-alkyl, β-hydroxy fatty acids of the mycobacterial cell wall. Here, stopped-flow measurements under single-turnover experimental conditions are presented for the study of the transient of reactants. Single-turnover experiments at various enzyme active sites were carried out. These studies suggested isomerization of the MtInhA:NADH binary complex in pre-incubation and positive cooperativity that depends on the number of enzyme active sites occupied by the 2-trans-dodecenoyl-CoA (DD-CoA) substrate. Stopped-flow results for burst analysis indicate that product release does not contribute to the rate-limiting step of the MtInhA-catalyzed chemical reaction. The bearings that the results presented herein have on function-based anti-tuberculosis drug design are discussed. Full article

Background: Fish oil is one of the most common lipidic substances that is consumed as a dietary supplement. The high omega-3 fatty acid content in fish oil is responsible for its numerous health benefits. Fish species such as mackerel, herring, tuna, and salmon are particularly rich in these lipids, which contain two essential omega-3 fatty acids, known as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). Objectives: Due to the scarcity of information in the literature, this study aimed to conduct a qualitative and quantitative characterization of triglycerides (TAGs) in crude tuna fish oil using HPLC/HRMS. Fatty acid (FA) determination was also performed using GC/MS. The tuna fish oils analyzed were produced using a green, low-temperature process from the remnants of fish production, avoiding the use of any extraction solvents. Results: The analyses led to the tentative identification and semi-quantitation of 81 TAGs. In silico saponification and comparison with fatty acid methyl ester results helped to confirm the identified TAGs and their quantities. The study found that the produced oil is rich in EPA, DHA, and erucic acid, while the negligible isomerization of fatty acids to trans-derivatives was observed. Full article

The use of oleogels as an alternative to solid fats to reduce the content of saturated and trans-isomeric fatty acids is a developing area of research. Studies devoted to the search for methods of obtaining oleogels with given properties are of current interest. Ultrasonic treatment as a method for modifying oleogel properties has been used to solve this problem. The number of publications on the study of the effect of ultrasonic treatment on oleogel properties is increasing. This review aimed to systematize and summarize existing data. It allowed us to identify the incompleteness of this data, assess the effect of ultrasonic treatment on oleogel properties, which depends on various factors, and identify the vector of this direction in the food industry. A more detailed description of the parameters of ultrasonic treatment is needed to compare the results between various publications. Ultrasonic treatment generally leads to a decrease in crystal size and an increase in oil-binding capacity, rheological properties, and hardness. The chemical composition of oleogels and the concentration of gelators, the amplitude and duration of sonication, the cooling rate, and the crystallization process stage at which the treatment occurs are shown to be the factors influencing the efficiency of the ultrasonic treatment. Full article

Dumped waste is not only a problem from an aesthetic point of view, but also has an environmental polluting effect, or can even pose a direct danger if the waste is dumped in illegal landfills in an uncontrolled manner with unknown composition. In the case of soil pollution, the assessment of the changing microbial state can be used as an indicator of initial changes, since waste as a pollutant impacts the diversity of the landfill’s microbial community. The degree of change depends on the qualitative and quantitative composition of the pollutants, which can be measured through the microbial phospholipid fatty acid (PLFA) pattern. The aim was a comprehensive assessment of the soil microbiological and toxicological hazards of various illegal landfill. Cluster-analysis of the average principal component revealed significant differences between the experimental sites. In comparison with the control site, the percentage of fatty acid biomarkers of Gram-positive bacteria was significantly higher in the contaminated areas, as well as the ratio of trans/cis isomerization in the case of 16:1ω7 and 18:1ω7 fatty acids. The inverse tendency was observed in the relative quantities of fatty acid biomarkers of Gram-negative bacteria compared to Actinomycetes, and in the fungal-bacterial ratio. Full article

The development and inclusion of novel oils derived from genetically modified (GM) oilseeds into aquafeeds, to supplement and supplant current terrestrial oilseeds, as well as fish oils, warrants a more thorough investigation into lipid biochemical alterations within finfish species, such as Atlantic salmon. Five tissues were examined across two harvesting timepoints to establish whether lipid isomeric alterations could be detected between a standard commercial diet versus a diet that incorporated the long-chain polyunsaturated fatty acids (LC-PUFA), EPA (eicosapentaenoic acid), and DHA (docosahexaenoic acid), derived from the GM oilseed Camelina sativa. Tissue-dependent trends were detected, indicating that certain organs, such as the brain, have a basal limit to LC-PUFA incorporation, though enrichment of these fatty acids is possible. Lipid acyl alterations, as well as putative stereospecific numbering (sn) isomer alterations, were also detected, providing evidence that GM oils may modify lipid structure, with lipids of interest providing a set of targeted markers by which lipid alterations can be monitored across various novel diets. Full article