Phytoprostanes and phytofurans: Bioactive compounds in aerial parts of Acacia cyanophylla Lindl.

The relevance of oxylipins as biomarkers of oxidative stress has been established in recent years. Phytoprostanes and phytofurans are plant metabolites derived from peroxidation of α-linolenic acid (ALA) induced by ROS. Previous findings have suggested new valuable biological properties for these new active compounds in the frame of diverse pathophysiological situations and health constraints. Lipidomic profiling of different aerial parts of the same Acacia cyanophylla Lindl. specimen, was evaluated for the first time here, using LC-MS/MS technology. Analysis revealed the existence of six PhytoPs and three PhytoFs. Stems have the highest amount of these metabolites with 179.35 ng/g and 320.79 ng/g respectively. This first complete profile paves the way to explore Acacia cyanophylla Lindl. as a source of plant oxylipins for therapeutic or pharmaceutical uses.

Bioactive Oxylipins Profile in Marine Microalgae.

Microalgae are photosynthetic microscopic organisms that serve as the primary food source in aquatic environments. Microalgae can synthesize a wide variety of molecules, such as polyunsaturated fatty acids (PUFAs) of the omega-3 and omega-6 series. Oxidative degradation of PUFA due to radical and/or enzymatic conversion leads to the formation of oxylipins, which are compounds known for their bioactive properties. In the present study, we aim to profile oxylipins from five microalgae species grown in 10-L photo-bioreactors under optimal conditions. During their exponential phase, microalgae were harvested, extracted and analyzed by LC-MS/MS to determine the qualitative and quantitative profile of oxylipins for each species. The five different selected microalgae revealed a high diversity of metabolites, up to 33 non-enzymatic and 24 enzymatic oxylipins present in different concentrations. Taken together, these findings highlight an interesting role of marine microalgae as a source of bioactive lipids mediators, which we hypothesize have an important function in preventive health measures such as amelioration of inflammation. The rich mixture of oxylipins may display advantages to biological organisms, especially by providing for human health benefits including antioxidant, anti-inflammatory, neuroprotective or immunomodulator activities. Some oxylipins are also well known for their cardiovascular properties.

Phytoprostanes from Date Palm Fruit and Byproducts: Five Different Varieties Grown in Two Different Locations As Potential sources.

Date palm fruit has been considered for centuries as an ancient nutritional constituent in the human diet. Recently, global trade in dates increased at an average that, simultaneously, will be accompanied by an increase in date palm byproducts. Supported by date phytochemicals and their health benefits, the aim of this work is to evaluate for the first time the presence of special metabolites of plant called phytoprostanes (PhytoPs) in five different varieties of the Phoenix dactylifera L. pulps and pits using a microLC-ESI-QTrap-MS/MS methodology. Results obtained showed the interest of using these matrices as potential sources of several PhytoPs (ent-16-B1-PhytoP; ent-9-L1-PhytoP; and epimers of ent-16-F1t-PhytoP and of 9-F1t-PhytoP). The variation in concentration between different varieties and different DPF parts was also evaluated. Results obtained will help to unravel the biological activities associated with DPF consumption that could be related to these bioactive metabolites.

Chemical Compositional Changes in Over-Oxidized Fish Oils.

A recent study has reported that the administration during gestation of a highly rancid hoki liver oil, obtained by oxidation through sustained exposure to oxygen gas and incident light for 30 days, causes newborn mortality in rats. This effect was attributed to lipid hydroperoxides formed in the omega-3 long-chain polyunsaturated fatty acid-rich oil, while other chemical changes in the damaged oil were overlooked. In the present study, the oxidation condition employed to damage the hoki liver oil was replicated, and the extreme rancidity was confirmed. A detailed analysis of temporal chemical changes resulting from the sustained oxidative challenge involved measures of eicosapentaenoic acid/docosahexaenoic acid (EPA/DHA) omega-3 oil oxidative quality (peroxide value, para-anisidine value, total oxidation number, acid value, oligomers, antioxidant content, and induction time) as well as changes in fatty acid content, volatiles, isoprostanoids, and oxysterols. The chemical description was extended to refined anchovy oil, which is a more representative ingredient oil used in omega-3 finished products. The present study also analyzed the effects of a different oxidation method involving thermal exposure in the dark in contact with air, which is an oxidation condition that is more relevant to retail products. The two oils had different susceptibility to the oxidation conditions, resulting in distinct chemical oxidation signatures that were determined primarily by antioxidant protection as well as specific methodological aspects of the applied oxidative conditions. Unique isoprostanoids and oxysterols were formed in the over-oxidized fish oils, which are discussed in light of their potential biological activities.

Characterization and modulation of brain lipids content of rainbow trout fed with 100% plant based diet rich in omega-3 long chain polyunsaturated fatty acids DHA and EPA.

Brain functions are known to be mainly modulated by adequate dietary intake. Inadequate intake as can be an excess or significant deficiency affect cognitive processes, behavior, neuroendocrine functions and synaptic plasticity with protective or harmful effects on neuronal physiology. Lipids, in particular, ω-6 and ω-3 long chain polyunsaturated fatty acids (LC-PUFAs) play structural roles and govern the different functions of the brain. Hence, the goal of this study was to characterize the whole brain fatty acid composition (precursors, enzymatic and non-enzymatic oxidation metabolites) of fish model of rainbow trout fed with three experimental plant-based diet containing distinct levels of eicosapentaenoic acid (EPA, 20:5 ω-3) and docosahexaenoic acid (DHA, 22:6 ω-3) (0% for low, 15.7% for medium and 33.4% for high, total fatty acid content) during nine weeks. Trout fed with the diet devoid of DHA and EPA showed reduced brain content of total ω-3 LC-PUFAs, with diminution of EPA and DHA. Selected enzymatic (cyclooxygenases and lipoxygenases) oxidation metabolites of arachidonic acid (AA, 20:4 ω-6) decrease in medium and high ω-3 LC-PUFAs diets. On the contrary, total selected enzymatic oxidation metabolites of DHA and EPA increased in high ω-3 LC-PUFAs diet. Total selected non-enzymatic oxidation metabolites of DHA (not detected for EPA) increased in medium and high ω-3 LC-PUFAs diets. In conclusion, this work revealed for the first time in fish model the presence of some selected enzymatic and non-enzymatic oxidation metabolites in brain and the modulation of brain lipid content by dietary DHA and EPA levels.

First Total Syntheses of Novel Non-Enzymatic Polyunsaturated Fatty Acid Metabolites and Their Identification in Edible Oils.

Oxidative stress (OS) is an in vivo process leading to free radical overproduction, which triggers polyunsaturated fatty acid (PUFA) peroxidation resulting in the formation of racemic non-enzymatic oxygenated metabolites. As potential biomarkers of OS, their in vivo quantification is of great interest. However, since a large number of isomeric metabolites is formed in parallel, their quantification remains difficult without primary standards. Three new PUFA-metabolites, namely 18-F3t -isoprostane (IsoP) from eicosapentaenoic acid (EPA), 20-F4t -neuroprostane (NeuroP) from docosahexaenoic acid (DHA) and 20-F3t -NeuroP from docosapentaenoic acid (DPAn-3 ) were synthesized by two complementary synthetic strategies. The first one relied on a racemic approach to 18(RS)-18-F3t -IsoP using an oxidative radical anion cyclization as a key step, whereas the second used an enzymatic deracemization of a bicyclo[3.3.0]octene intermediate obtained from cyclooctadiene to pursue an asymmetric synthesis. The synthesized metabolites were applied in targeted lipidomics to prove lipid peroxidation in edible oils of commercial nutraceuticals.

Identification and quantification of phytoprostanes and phytofurans of coffee and cocoa by- and co-products.

Phytoprostanes (PhytoPs) and phytofurans (PhytoFs) are isoprostanoids that result from the peroxidation of α-linolenic acid and are biomarkers of oxidative stress in plants and humans. These compounds exhibit several interesting biological activities (e.g. neuroprotection and anti-inflammatory activities). The aim of this research was to add value to coffee pulp (CP), cocoa husk (CH) and cocoa pod husk (CPH) by identifying and quantifying PhytoPs and PhytoFs by liquid chromatography-tandem mass spectrometry. The contents of PhytoPs and PhytoFs in CP, CH, and CPH were, respectively, 654.6, 474.3 and 179.9, and 543.2, 278.0 and 393.8 ng per g dry weight (dw). The main PhytoP found in CP (171.37 ng per g dw) and CPH (37.12 ng per g dw) was 9-epi-9-F1t-PhytoP, while ent-9-L1t-PhytoP was the most abundant in CH (109.78 ng per g dw). The main PhytoF found in all sources was ent-16(RS)-13-epi-ST-Δ14-9-PhytoF, at 196.56, 126.22, and 207.57 ng per g dw in CP, CH, and CPH, respectively. We provide the first complete profile of PhytoPs and PhytoFs for these agro-residues, which could be used in the functional food industry for enriching food or as nutritional supplements.

Effects of Cyclic Fatty Acid Monomers from Heated Vegetable Oil on Markers of Inflammation and Oxidative Stress in Male Wistar Rats.

This study assesses the effects of cyclic fatty acid monomers (CFAM) from heated vegetable oils on oxidative stress and inflammation. Wistar rats were fed either of these four diets for 28 days: canola oil (CO), canola oil and 0.5% CFAM (CC), soybean oil (SO), and soybean oil and 0.5% CFAM (SC). Markers of oxidative stress and inflammation were determined by micro liquid chromatography tandem mass spectrometry (micro-LC-MS/MS) and enzyme-linked immunosorbent assay (ELISA) kits, respectively. Analysis of variance (ANOVA) for a 2 × 2 factorial design was performed to determine the CFAM and oil effects and interactions between these two factors at P ≤ 0.05. For significant interactions, a post hoc multiple comparison test was performed, i.e., Tukey HSD (honest significant difference) test. CFAM induced higher plasma levels of 15-F2t-IsoP (CC, 396 ± 43 ng/mL, SC, 465 ± 75 ng/mL vs CO, 261 ± 23 ng/mL and SO, 288 ± 35 ng/mL, P < 0.05). Rats fed the SC diet had higher plasma 2,3-dinor-15-F2t-IsoP (SC, 145 ± 9 ng/mL vs CC, 84 ± 8 ng/mL, CO, 12 ± 1 ng/mL, and SO, 12 ± 1 ng/mL, P < 0.05), urinary 2,3-dinor-15-F2t-IsoP (SC, 117 ± 12 ng/mL vs CC, 67 ± 13 ng/mL, CO, 15 ± 2 ng/mL, and SO, 18 ± 4 ng/mL, P < 0.05), and plasma IL-6 (SC, 57 ± 10 pg/mL vs CC, 48 ± 11 pg/mL, CO, 46 ± 9 pg/mL, and SO, 44 ± 4 pg/mL, P < 0.05) than the other three diet groups. These results indicate that CFAM increased the levels of markers of oxidative stress, and those effects are exacerbated by a CFAM-high-linoleic acid diet.

Thermal Stress in Melon Plants: Phytoprostanes and Phytofurans as Oxidative Stress Biomarkers and the Effect of Antioxidant Supplementation.

The extreme temperatures generated in the melon crop, early harvest, induce an increase in reactive oxygen species (ROS) plant levels leading to oxidative stress. Phytoprostanes (PhytoPs) and phytofurans (PhytoFs) are plant metabolites derived from α-linolenic acid oxidation induced by ROS. The aims of this work were to evaluate PhytoPs and PhytoFs as oxidative stress biomarkers in leaves of melon plants thermally stressed. In addition, to fortify melon plant antioxidant defenses, foliar spraying was assayed using salicylic and gallic acid solutions and Ilex paraguariensis extract. PhytoP and PhytoF concentration ranges were 109-1146 and 130-4400 ng/g, respectively. Their levels in stressed plants were significantly higher than in nonstressed samples. In stressed samples treated with I. paraguariensis, PhytoP and PhytoF levels were significantly lower than in stressed samples without antioxidants. PhytoPs and PhytoFs represent relevant oxidative stress biomarkers in melon leaves. The use of natural antioxidants could reduce plant oxidative stress.