Heat treatment of vegetable oils. II. GC-MS and GC-FTIR spectra of some isolated cyclic fatty acid monomers

Gas liquid chromatography coupled with mass spectrometry (GC-MS) showed that the cyclic fatty acid monomers (CFAM) isolated from a heated linseed oil have two ethylenic bonds, while the CFAM isolated from heated sunflower oils were saturated and monoethylenic isomers. GC-MS studies also showed the presence of cyclohexenic derivatives in the case of linseed oil.

Geometry of conjugated double bonds of CLA isomers in a commercial mixture and in their hepatic 20∶4 metabolites

Rats were fed a fat-free diet for 2 wk. After this period, while maintaining the animals on the same diet, the rats were given intragastrically 180 mg per day of a mixture of conjugated linoleic acids (CLA) as triacylglycerols. Gas chromatography mass spectrometry (GC-MS) analyses of this mixture, as well as hydrazine reduction and GC-MS and GC-Fourier transform infrared analyses of the resulting monoenes, revealed the presence of two major isomers, the 9c,11t- and the 10t,12c-18:2 accompanied by smaller amounts of the 8t, 10c and the 11c, 13t-18:2 isomers. Minor quantities of cis,cis and trans,trans conjugated isomers also were detected. The total fatty acid methyl esters from the liver li…

A detailed identification study on high-temperature degradation products of oleic and linoleic acid methyl esters by GC–MS and GC–FTIR

GC-MS and GC-FTIR were complementarily applied to identify oxidation compounds formed under frying conditions in methyl oleate and linoleate heated at 180ºC. The study was focused on the compounds that originated through hydroperoxide scission that remain attached to the glyceridic backbone in fats and oils and form part of non-volatile molecules. Twenty one short-chain esterified compounds, consisting of 8 aldehydes, 3 methyl ketones, 4 primary alcohols, 5 alkanes and 1 furan, were identified. In addition, twenty non-esterified volatile compounds, consisting of alcohols, aldehydes and acids, were also identified as major non-esterified components. Furanoid compounds of 18 carbon atoms form…

Incorporation and metabolism of trans 20∶5 in endothelial cells. Effect on prostacyclin synthesis

To study the ability of long-chain trans fatty acids (FA) to be incorporated and metabolized into endothelial cells, bovine aortic endothelial cells were incubated with medium enriched eicosapentaenoic acid (EPA) bound to albumin (M2) or one of its geometrical isomers: 20:5 5c,8c,11t,14c,17c (M3), 20:5 5c,8c,11c,14c,17t (M4), or 20:5 5c,8c,11t,14c,17t (M5). After 48 h of incubation, supernatant and cells were harvested and their lipids were analyzed, including prostacyclin synthesis. EPA and 22:5n-3 of endothelial cells incubated with M2 were, respectively, three and two times higher than in control cells (incubated in M1, without any fatty acid added), whereas 22:6n-3 increased only in the…

Cyclic fatty acid monomers : synthesis and characterization of methyl w-(2-alkylcyclopentyl) alkenoates and alkanoates

Abstract Some 1,2-disubstituted cyclopentanes were synthesized. These were methyl 9-(2-butyl-cyclopentyl)-8-nonenoate, methyl 7-(2-hexyl-cyclopentyl)-6-heptenoate and methyl 5-(2-octyl-cyclopentyl)-4-pentenoate and their corresponding alkanoates. The synthesis involved a Michael addition of alkylmagnesium bromide to an unsaturated cyclic ester. The resulting cis and trans ethyl 2-alkylcyclopentane carboxylate were further converted to the alcohols then to the aldehydes. The aldehydes were condensed with the ylide derived from the (ω-carboxyalkyl)-triphenylphosphonium bromide and methylsulfinylmethide in DMSO to give unsaturated C18 cyclic fatty acid monomers. These cyclic fatty acids were f…

18:2Δ 9c,12t and 18:2 Δ9t,12c are present in our diet, as result of heat treatment of vegetable oils. A nutritional study was carried out in order to obtain more precise information on the conversion of these two isomers into long chain polyunsaturated fatty acids (PUFA) by rat tissues. This in vivo study performed using rat fed with small quantities of mono trans linoleic acid isomers (0.6% of total energy) showed that 18:2 Δ9c,12t was converted into 20:4 Δ5c,8c,11c,14t while 18:2 Δ9t,12c was only slightly converted into 20:4 Δ5c,8c,11t,14c. Furthermore 18:2 Δ9t,12c was preferentially elongated into 20:2 Δ11t,14c. Each C20 metabolite of these mono trans 18:2 isomers was isolated as methyl …

Silver ion chromatography and gas chromatography-mass spectrometry in the structural analysis of cyclic dienoic acids formed in frying oils

The nature of the cyclic monoenoic fatty acids formed from linoleic acid in sunflower oil heated to 275°C has been determined by gas chromatography-mass spectrometry of the picolinyl ester derivatives, before and after hydrogenation and deuteration, and following simplification by silver ion high-performance liquid chromatography. In addition, they were examined by gas chromatography-Fourier transform infrared spectroscopy. Cyclopentene fatty acids (50% of the total monoenes) were formed from C-8 to C-12 and C-10 to C-14 of the original chain in equal amounts with unique stereochemistry. In some isomers the double bond appeared to remain in its original position, and in others it migrated t…

Effect of 18:3 n-3 geometrical isomers of heated linseed oll on the biosynthesis of arachidonic acid in rat

Abstract The influence of dietary heated linseed oil on the fatty acid composition of rat liver, platelet and plasma phospholipids (PL) with particular reference to the metabolism of linoleic acid (18:2 n-6) were studied. Δ6 and Δ5 desaturase activities and fatty acid composition of hepatic microsomal total lipids (TL) also were determined. Two groups of male weanling rats were fed, for 6 weeks, diets containing 10% (in weight) of a fresh linseed oil (LO group) and of a heated linseed oil (HLO group). The contents of geometrical isomers of linolenic acid (18:3 n-3) were high in the oil heated at 240°C for 10 hours. The pattern of arachidonic acid (20:4 n-6) in the different lipid fractions …