Lipid Structure of <Emphasis Type="Italic">Lallemantia</Emphasis> Seed Oil: A Potential Source of Omega-3 and Omega-6 Fatty Acids for Nutritional Supplements

The lipid composition of the seed oil of three varieties (L-74, VIR-11 and BGR-455) of Lallemantia iberica Fisch. &; Mey. (Lamiaceae) harvested in Bulgaria was examined in detail. Triacylglycerols (TAG >90%), phospholipids (<3%), sterol esters (~0.2%), and accompanying compounds—sterols (~0.3%) and tocopherols (336–499 mg/kg)—were determined for the first time. In addition, the specific distribution of fatty acids between the lipid classes was elucidated. Nineteen TAG species were unambiguously identified and quantified and of these the highly unsaturated trilinolenin, dilinolenyl linoleate and dilinolenyl palmitate comprised 59% of the total TAG. Phosphatidylcholine, phosphatidylinositol and phosphatidylethanolamine were the main phospholipids. Beta-sitosterol was the main sterol component, followed by campesterol and stigmasterol. Gamma-tocopherol predominated (>90%) in the tocopherol fraction. Palmitic acid (16:0) was the major fatty acid of the phospholipids and oleic acid (cis 9-18:1) dominated in the sterol ester fraction. The three varieties have similar lipid compositions with BGR-455 being slightly more saturated. Due to its composition, Lallemantia oil might compete successfully with flax and other plant oils as a source of linolenic fatty acid in industrial and dietary applications.     

Variations in Fatty Acids,Phospholipids and Sterols During the Seed Development of a High Oleic Sunflower Variety

The changes in the content and composition of total fatty acids, phospholipids and sterol esters, and their fatty acids, and of free sterols and tocopherols in developing seeds of a selection of high oleic acid sunflower varieties grown in Bulgaria were examined over a period of 15th to 90th day after flowering by means of various chromatographic methods. Under the climatic and geographical conditions typical for the South-East Balkans phospholipid, sterol-, sterol ester- and tocopherol- species are formed practically completely in the first 15 days after flowering. Until the 90th day, only quantitative changes were detected to give a product with 65% oil content, 1% phospholipids, 0.3% total sterols and 0.09% tocopherols. Oleic acid is the main component in all acyl derivatives, reaching 85% of the total fatty acids while palmitic and stearic acid content is about 4% each. The product is a good quality HOSO with beneficial content of FA and good prospects as a salad and cooking oil.     

The specific chemical profile of Mediterranean propolis from Malta

Seventeen Maltese propolis samples were studied by GC–MS after silylation. They exhibited the typical Mediterranean chemical profile, rich in diterpene compounds (18–92% of TIC, GC–MS): 32 individual diterpenes were identified; 22 of them were present in each specimen. The other abundant compound group was that of sugars and sugar derivatives. In some samples, however, another compound group was observed (0–12% of TIC, GC–MS); the corresponding mass spectra were consistent with mono- and sesquiterpenyl esters of substituted benzoic acids. Two new propolis constituents of this group, daucane diterpene esters of hydroxybenzoic acids, were isolated. Their origin is suggested to be Ferula communis, as they are taxonomic markers for this species. All propolis samples were active against Staphylococcus aureus but only those with high concentrations of terpenyl esters showed antifungal activity against Candida albicans. The present results confirm that Mediterranean propolis is a valuable natural product with potential to improve human health.     

Determination of Triacylglycerol Classes and Molecular Species in Seed Oils with High Content of Linoleic and Linolenic Fatty Acids

Soya bean and linseed oils were analysed by successive application of silver-ion and reversed-phase thin-layer chromatography and densitometry. Direct quantitative determination of all the 20 possible triacylglycerol (TAG) classes including critical pairs (SD₂+S₂T; M₂T+D₃; SDT+MDT; ST₂+MT₂) was performed. TAG molecular species down to 0·1% (32 in soya bean oil and 26 in linseed oil) were identified and quantified. The detection limit was 0·2 μg and the standard deviation between 0·1% and 1·0% for silver ion thin-layer chromatography (TLC) and between 0.1% and 3.9% for reversed-phase TLC determinations. The accuracy of the analysis was confirmed by the good agreement between the quantitative results for the fatty acid composition as determined by gas chromatography and as calculated from the densitometric data for the TAG composition.     

Stereospecific analysis of triacyl-sn-glycerolsvia resolution of diastereomeric diacylglycerol derivatives by high-performance liquid chromatography on silica

The compositions of positionssn-1, 2 and 3 of triacylglycerols can be determined by partial hydrolysis with ethyl magnesium bromide, derivatization of the total products with (S)-(+)-1-(1-naphthyl)ethyl isocyanate and isolation of the diacyl-sn-glycerol urethane derivatives by chromatography on solid-phase extraction columns containing an octadecylsilyl phase. The diastereomericsn-1,2-and 2,3-diacylglycerol derivatives are separated by high-performance liquid chromatography on silica for determination of their fatty acids by gas chromatography. Each step in the process has been evaluated rigorously. The compositions of all three positions can be calculated with good accuracy from the analyses of these compounds and that of the total triacylglycerols. Although the 1,3-sn-diacylglycerol derivatives can also be isolated easily, they do not give reliable results for the composition of positionsn-2 because acyl migration occurs during their generation. The stereospecific analysis procedure has been applied to some plant and animal triacyl-sn-glycerols of commercial and scientific interest, containing predominantly C₁₆ and C₁₈ fatty acids,i.e. safflower, sunflower, olive and palm oils, tallow, egg and rat adipose tissue. The method is not at present suited to the analysis of more complex triacylglycerols, such as milk fat or fish oils, and problems associated with these are discussed.     

The structure of the triacylglycerols of meadowfoam oil

The triacylglycerols of meadowfoam oil have been resolved by HPLC in the silver ion and reversed-phase modes, and by the two techniques used in a complementary fashion. The fractions obtained were collected and quantified by gas chromatography of their methyl esters in the presence of an internal standard. Silver ion chromatography gave a distinctive resolution in which fractions differing solely in the position and chain-length of a single monoenoic fatty acyl group were resolved, the order of elution being 11−20∶1, 5−20∶1, 13−22∶1, 5−18∶1 and 9−18∶1. Reversed-phase chromatography also gave fractions containing single positional isomers, (11−20∶1<5−20∶1<13−22∶1<5−22∶1), but the pattern was more difficult to discern since fractions containing 22∶2 tended to overlap with those containing 20∶1. The species (5−20∶1)(5−20∶1)(22∶2), (5−20∶1)(5−20∶1)(5−20∶1) and (5−20∶1)(5−20∶1)(13−20∶1) were found to be the most abundant, and together comprised 67% of the total. A small but significant trilinolein fraction was detected and its presence may have biosynthetic implications.     

Bis‐methylene‐interrupted octadecadienoic fatty acids in Bulgarian bovine butter fats

Preparative silver nitrate thin‐layer chromatography of fatty acid methyl esters and gas chromatography‐mass spectrometry of 4,4‐dimethyloxazoline derivatives were applied in combination to analyze the cis,cis octadecadienoic (18:2) fraction in commercial samples of bovine butter fat in Bulgaria. The main component, 9,12–18:2 was accompanied by a series of bis‐methylene‐interrupted isomers, cis,cis‐5,9‐; 6,10‐; 9,13‐ and 11,15–18:2, which were unambiguously identified by their specific mass spectra. The latter are characterized by the presence of very intensive diagnostic fragments which help to correctly locate the position of the double bond system in the carbon chain. The cis,cis‐5,9–18:2 isomer was found for the first time in butter fat, and the 6,10–18:2 isomer has not been described as yet.