Chemical Composition and Nutritional Characteristics of the Seed Oil of Wild <Emphasis Type="Italic">Lathyrus</Emphasis>, <Emphasis Type="Italic">Lens</Emphasis> and <Emphasis Type="Italic">Pisum</Emphasis> Species from Southern Spain

The fatty acid composition of the seed oil of 19 wild legume species from southern Spain was analyzed by gas chromatography. The main seed oil fatty acids ranged from C_14:0 to C_20:0. Among unsaturated fatty acids, the most abundant were linoleic, oleic and linolenic acids, except for Lathyrus angulatus, L. aphaca, L. clymenum, L. sphaericus and L. nigricans where C_18:3 contents were higher than C_18:1 contents. Palmitic acid was the most abundant saturated acid in studied species, ranging from 11.6% in Lathyrus sativus to 19.3% in Lens nigricans. All studied species showed higher amounts of total unsaturated fatty acids than saturated ones. Among studied species, the ω6/ω3 ratio was variable, ranging from 2.0% in L. nigricans to 13.8% in L. sativus, there being eight species in which the ω6/ω3 ratio was below 5. The fatty acids observed in these plants supports the use of these plants as a source of important dietary lipids.     

Glyceride structure ofCardamine impatiens L. Seed oil

A group of unusual triglycerides, in which one of the acyl groups is a vicinal dihydroxy acid with one of the hydroxyl groups acetylated, has been isolated fromCardamine impatiens L. (Cruciferae) seed oil. Hydrolysis of these triglycerides with castor bean lipase facilitated isolation and identification of a mixture of C₁₈, C₂₀, C₂₂, and C₂₄ hydroxy acetoxy fatty acids. Pancreatic lipase hydrolysis data revealed that these monoacetylated dihydroxy acid residues are esterified exclusively with one of the α-positions of the glycerol moiety. The remaining acyl groups are comprised of ordinary C₁₈ unsaturated acids (which occupy 98% of the β-position), palmitic acid, and C₂₀, C₂₂, and C₂₄ monoenoic fatty acids. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Reaction of mono-epoxidized conjugated linoleic acid ester with boron trifluoride etherate complex

The reaction of methyl 11, 12-E-epoxy-9Z-octadecenoate (1) with boron trifluoride etherate furnished a mixture of methyl 12-oxo-10E-octadecenoate (3a) and methyl 11-oxo-9E-octadecenoate (3b) in 66% yield. Methyl 9, 10-Z-epoxy-11 E-octadecenoate (2) with boron trifluoride etherate furnished a mixture of methyl 9-oxo-10 E-octadecenoate (4a, 45%) and methyl 10-oxo-11 E-octadecenoate (4b, 19%). A plausible mechanism is proposed for these reactions, which involves the attack on the epoxy ring system by BF₃, followed by deprotonation, oxo formation, and double bond migration to give a mixture of two positional α,β-unsaturated C₁₈ enone ester derivatives (3a/3b, 4a/4b). The structures of these C₁₈ enone ester derivatives (3a/3b, 4a/4b) were identified by a combination of NMR spectroscopic and mass spectrometric analyses.     

Distribution of individual fatty acids in the crystallization fractions of lard

Distribution of the individual fatty acids in the triglycerides of lard was determined by fractional crystallization, partial enzymatic hydrolysis with steapsin, and fatty acid analyses by GLC. It was found that none of the individual fatty acids corresponded to a random distribution in the crystallization fractions, but that the distribution of the total saturated and total unsaturated acids was very nearly random. The short chain fatty acids, C₁₄ and C₁₆, both saturated and unsaturated, were found to be more predominant in the 2-position than in the 1- and 3-positions of the lard triglycerides. All of the C₁₈ fatty acids were found to be more predominant in the 1- and 3-positions.     

Synthesis and Surface Active Properties of Sulfonated Acrylate Esters Based on Al‐Cedre Oil

Sulfonated acrylate esters have been synthesized by using renewable raw materials such as fatty alcohols of Al‐Ceder oil. Mixed fatty acids were isolated from Al‐Ceder oil by hydrolysis; both saturated and unsaturated fatty acids were isolated from the mixed fatty acids. The methyl esters of mixed fatty acid, saturated and unsaturated acids of Al‐Cedre oil were subjected to reduction with (LiAlH4) to give the corresponding fatty alcohols. The products of the reduction process were saponified and the hydroxyl values were estimated to further confirm the reduction occurrence. The acrylate esters were synthesized by esterification of acrylic acid with fatty alcohols of C_16:0, C_18:0, C_18:1, and C_18:2 mixed saturated, mixed unsaturated and mixed fatty acids of Al‐Cedre oil, respectively. This esterification was followed by addition of NaHSO₃ to form bisulfite adducts. The structures of the prepared surfactants were characterized by IR and ¹HNMR spectroscopy. A series of useful surface parameters, stability towards acids and base hydrolysis and calcium stability have been determined.     

Fatty Acid Composition in Ergosteryl Esters and Triglycerides from the Fungus Ganoderma lucidum

Free and esterified ergosterols are detected almost solely in fungi and are often employed as a biomarker of living fungi. In this work, the fatty acid composition and δ¹³C values of major fatty acids in triglycerides and ergosteryl esters from the fungus Ganoderma lucidum were analyzed by gas chromatography–mass spectrometer and gas chromatography–isotopic ratio mass spectrometer, respectively. The results showed that the fatty acid profiles varied in triglycerides and ergosteryl esters. The percentage of saturated fatty acids in ergosteryl esters was remarkably higher than that in triglycerides, where C_18:1^Δ9c was the predominant fatty acid and constituted 61.26 % of the total fatty acids. In contrast, C_16:0 was the predominant fatty acid and constituted 71.88 % of the total fatty acids in ergosteryl esters. The study suggests that, after fungal death, free ergosterols in the cell membrane of the dead fungus were esterified with preferentially saturated fatty acids, mainly C_16:0, from triglycerides and then stored in lipid particles for a longer period while free ergosterol markedly decreased. The δ¹³C values of C_16:0, C_18:0, C_18:1 and C_18:2 in ergosteryl esters exhibit a pronounced depletion in ¹³C compared with that in triglycerides within the range of ?1.3 to ?0.9 ‰, supporting the above inference. It is again suggested that free ergosterol in the cell membrane should be used as an indicator of living fungi, and ergosteryl esters in the lipid particles should not be included in the measurement of living fungal biomass.     

Electrochemical polymerization of phenanthrene in mixed electrolytes of boron trifluoride diethyl etherate and concentrated sulfuric acid

A novel high‐quality polyphenanthrene (PPH) film with electrical conductivity of 10^?1 S cm^?1 was synthesized electrochemically by direct anodic oxidation of phenanthrene in boron trifluoride diethyl etherate containing 10% concentrated sulfuric acid (v/v). The oxidation onset potential of phenanthrene in this medium was measured to be only 0.91 V versus saturated calomel electrode (SCE), which was lower than that determined in acetonitrile + 0.1 mol L^?1 Bu₄NBF₄ (1.56 V versus SCE). As‐formed PPH films from this medium showed good electrochemical behavior and stability. De‐doped PPH films were thoroughly soluble in dimethylsulfoxide or CHCl₃. The structure and morphology of the polymer were investigated using UV‐visible and Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy. FTIR and ¹H NMR spectra showed that the PPH was grown via the coupling of the monomer mainly at the C₄, C₅, C₉ and C₁₀ positions. Fluorescence spectral studies indicated that PPH was a blue‐green light emitter. Copyright © 2007 Society of Chemical Industry     

Characterization of skin-surface lipids from the monkey (Macaca fascicularis)

Skin-surface lipids from the monkeyMacaca fascicularis are composed of sterol esters (38%), cholesterol (4%) and two types of wax diesters, identified as Type II (IIa and IIb, 17% and 40%, respectively). Type IIa contained diesters of 1,2-alkanediols esterified with two molecules of long-chain (C₁₄−C₃₄) fatty acids having straight and branched chains. In the diesters IIa, fatty acids shorter than C₁₉ predominated in position 1, and fatty acids longer than C₂₀ predominated in position 2. Type IIb contained diesters of 1,2-alkanediols esterified with C₄ and C₅ branched-chain fatty acids (predominantly isovaleric acid) at position 1 and long-chain (C₁₄−C₂₇) acids, having straight and branched chains, at position 2. The shortchain acids were converted to 2-nitrophenylhydrazides and analyzed by high-performance liquid chromatography (HPLC). Ammonia chemical ionization (CI)-gas chromatography (GC)-mass spectrometry (MS) resolved the intact diesters IIb into 12 peaks corresponding to molecular weights ranging from 597 to 748, and showed that the molecular species, such as C₂₁−C₁₆−C₅ (diol, fatty acid in position 2, fatty acid in position 1), C₂₂−C₁₆−C₅ and C₂₃−C₁₆−C₅, were prevalent. The fatty acids from both diesters were mostly (>98%) saturated. The 1,2-alkanediols from both diesters consisted of C₁₆−C₂₆ saturated straight- and branched-chain components. The acyl groups of sterol esters contained 86% C₁₄−C₃₄ branched-chain acids. The unsaturated fatty acids (5.4%) belonged to a straight-chain monoenoic series having extremely long chains (C₁₈−C₃₄). The branched-chain structures in the fatty acids and diols were iso and anteiso. These results show the species-specific profile for the skin-surface lipid synthesis.     

Studies on the substrate specificity of purified human milk lipoprotein lipase

The fatty acid specificity of purified human milk lipoprotein lipase was studied using the C₁₈ to C₅₄ (total acyl carbon number) saturated and the C₅₄ mono-, di- and triunsaturated monoacid triacylglycerols. Kinetic determinations indicated that the medium-chain triacylglycerols were better substrates than long- or very short-chain saturated triacylglycerols. The unsaturated triacylglycerols were hydrolyzed at rates comparable to that of tricaprylin with triolein having the highest rate of hydrolysis of the unsaturated species tested. The enzyme attacked the primary ester bond much more readily than the secondary ester bond. The purified human milk lipoprotein lipase showed a preferential stereospecific lipolysis of thesn-1-position of the triacylglycerol molecule.     

Polyunsaturated fatty glyceride syntheses by microbial lipases

The degree of glyceride syntheses by lipase TOYO (Chromobacterium viscosum) and lipase OF (Candida cylindracea) using individual free fatty acids C_18∶1, C_18∶2, C_18∶3, C_18∶4, C_20∶4, C_20∶5 and C_22∶6 were compared. Lipase TOYO incorporated each of the fatty acids into glycerol at levels of greater than 89%. Lipase OF incorporated most of the fatty acids at levels above 70% (docosahexaenoic acid incorporation was 63%). It was concluded that these two lipases are feasible for producing glycerides from unsaturated fatty acids.     

The rearrangement of fatty cyclopropenoids in the presence of boron trifluoride

The destruction of the cyclopropenoid ring system of methyl 9,10 methyleneoctadec-9-enoate (methyl sterculate) with boron trifluoride etherate has been shown to give a complex mixture of products, including methyl esters of C₁₉ allenes (12%), a C₁₈ alkyne (11%) and a variety of C₁₉ and C₂₀ conjugated dienes containing either a methyl or methylene branch. The methylene group lost from the methyl sterculate reactant in the formation of methyl octadec-9-ynoate is incorporated into a second molecule of reactant to yield a mixture of methyl 9-methylene-trans-nonadec-10-enoate and the 11-methylene-trans-9-isomer.     

The co-dominance theory: Genetic interpretations of analyses of mesocarp oils fromelaeis guineensis,elaeis oleifera and their hybrids

Determination of the fatty acid and triglyceride compositions of the F,(Elaeis guineensis X E. oleifera), F₂ and the backcross hybrid mesocarp oils demonstrated that most fatty acid and triglyceride compositions of oils from hybrid palms are intermediate between those of their respective parentals. These data, as well as the acyl group (saturated/palmitate and unsaturated/oleate) distribution of triglycerides of the F₂ mesocarp oils provide genetic proof for codominance in the F₂ generation which shows a characteristic segregation into the co-dominance ratio of 1:2:1 (i.e., 1 E.guineensis: 2 F₁ hybrid: 1E. oleifera). Similar analyses into the backcross hybrid mesocarp oils on the whole confirmed co-dominance when the backcross ratio of 1:1 was obtained. These results are used to develop the Co-Dominance Theory ofElaeis palm hybridization which makes successful predictions for mesocarp oils from the different hybrid palms.     

Unusual Totally Selective Cyclodimerization of Epoxides: Synthesis of a Pair of Diastereoisomers of Enantiopure 2,5‐Disubstituted‐1,4‐Dioxanes with C2 Symmetry

The synthesis of the C₂‐symmetrical (2R,5R)‐ and (2S,5S)‐2,5‐bis‐[(S)‐1‐(dibenzylaminoalkyl)]‐1,4‐dioxanes 1 or 2 in enantiopure form is reported. Compounds 1 and 2 were obtained by a completely selective and unusual cyclodimerization of chiral (2R,1′S)‐ or (2S,1′S)‐2‐(1‐aminoalkyl)epoxides 3 or 4 promoted by a mixture of diisopropylamine and boron trifluoride⋅diethyl etherate complex. The structure of the obtained dioxane was established by single‐crystal X‐ray diffraction analysis. A mechanism has been proposed to explain this transformation.     

Macrocyclic lactones and isopentenyl esters in the Dufour's gland secretion of halictine bees (Hymenoptera: Halictidae)

The volatile components of the Dufour's gland secretion of female halictid bees have been examined in 18 Nearctic species belonging toAgapostemon, Augochlora, Augochlorella, Augochloropsis, Dialictus, Evylaeus, Halictus, andLasioglossum. Nine saturated and unsaturated macrocyclic lactones ranging from C₁₈ to C₂₆ have been identified. Four of these compounds, the saturated C₂₆ and the unsaturated C₂₀, C₂₂, and C₂₄ lactones, are new natural products reported for halictine bees. A series of eight esters containing branched C₅-alkenols and fatty acids has been identified in several species. The cell linings and pollen ball inAugochlora pura pura contain the same major lactones as the Dufour's gland. A discussion of the significance of the Dufour's gland secretion for apoid systematics and its function in the Halictidae is presented.     

Alkyl-and alkenylresorcinols inRapanea laetevirens seed lipids

The seed lipids ofRapanea laetevirens (Myrsinacea) were found to contain a series of 5-alkylresorcinols. Some of these alkylresorcinols have been reported previously in other plant families, but never before in the Myrsinaceae. The various homologs were shown by mass spectrometry to have alkyl side chains that included C₁₁ and C₁₃ saturated as well as C₁₁, C₁₃, and C₁₅ monoenoic substituents. This is the first report of the natural occurrence of tridecenylresorcinol, the homolog with the C₁₃ monoenoic side chain. The positions of the double bonds in the side chains were determined by mass spectrometry of their methoxy trimethylsilyloxy derivatives. Also found were embelin and rapanone, benzoquinone pigments which occur commonly in the Myrsinaceae. The fatty acid composition ofRapanea seed triglycerides was not unusual, consisting mainly of 16∶0 (27%), 18∶1 (22%), and 18∶2 (44%).     

Studies on characterization and variation in triglyceride fatty acids from punt/us sarana body lipids

Body lipids of P. sarana of four different sizes were fractionated into phospholipids, neutral lipids, nonsaponifiables, total fatty acids, polyunsaturated, monounsaturated and saturated fatty acid fractions. Percentage composition of each fraction was determined. The triglyceride fatty acids were identified by thin layer and gas liquid chromatography. C₈ to C₂₃ fatty acids including both odd numbered and branched chain acids were detected. The major constituents were C₁₄, C₁₅, C₁₆, C_16:1, C₁₈ C_18:1, C_18:2, C_18:3; forty-three other acids were detected in lower proportions. Composition of each fatty acids and their variation with size have been discussed.tP. sarana body lipids in general showed a behavior typical of fresh water fish by having a higher percentage of saturated C₁₆ and unsaturated C₁₈ acids and a lower percentage of unsaturated C₂₀ acid.     

Composition of wax esters,triglycerides and diacyl glyceryl ethers in the jaw and blubber fats of the Amazon River dolphin (Inia geoffrensis)

The lower jaw fat of the Amazon River dolphinInia geoffrensis contains 52.8% wax ester, 44.7% triglyceride and 2.5% diacyl glyceryl ether, while its dorsal blubber fat is >98% triglyceride. Examination of the intact lipids, the derived fatty acids and the derived fatty alcohols by gas chromatography reveals that the blubber triglycerides show characteristics of freshwater fish fats, but the jaw fat lipids have several distinctive features. Jaw fat wax esters, triglycerides and diacyl glyceryl ethers are all rich in C₁₀, C₁₂ and C₁₄ fatty acids and contain no polyunsaturated acids. The fatty alcohols in the wax esters are over 90% saturated. The major carbon numbers in the jaw fat triglycerides (C₃₈–C₄₆) are considerably lower than those of the blubber triglycerides (C₄₈–C₅₄). The possible adaptation of the jaw lipids for use in the underwater echolocation process of this dolphin is discussed.     

Direct determination of saturated fatty acids in fats,oils, and methyl esters

Summary A direct gravimetric method has been developed for the determination of saturated fatty acids in fats, oils, and methyl esters. The procedure involves methanolysis of the triglycerides to produce methyl esters, followed by oxidation of the unsaturated methyl esters by potassium permanganate. The undesired, acidic oxidation products are removed by alkaline washing and the saturated methyl esters thus isolated are weighed directly. The method is intended for the determination of saturated fatty acids having C₁₆ or longer carbon chains. Small quantities of C₁₄ saturated acids will be included in the determination if present with other higher saturated acids. The method is applicable to both natural and hydrogenated vegetable oils. It is not applicable to oils containing large amounts of C₁₄ and lower saturated acids. Concentrations of saturated acids ranging from 3 to 90% in known glyceride mixtures and from 0.3 to 95% in mixtures of methyl esters were determined with an average difference from the calculated value of 0.8%. Replicate determinations on samples in the 10 to 30% saturates range gave a standard deviation of 0.3 to 0.4%. Presented at the spring meeting, American Oil Chemists’ Society, New Orleans, La., April 28 to May 1, 1957     

Fullerene lipids: Synthesis of C60 fullerence derivatives bearing a long-chain saturated or unsaturated triester system

Tris(hydroxymethyl)aminomethane was successfully esterified with saturated and unsaturated long-chain fatty acids. The resulting amino-triester intermediates were successively reacted with chloroacetyl chloride, sodium azide, and C₆₀ fullerene. Spectral evidence showed that the aziridine ring is joined to the junction of [6,6]-fused rings of the fullerene. The structures of the various C₆₀ fullerene derivatives bearing a long-chain saturated or unsaturated triester system were characterized by spectroscopic and spectrometric methods.     

Contribution of triglycerides from cocoa butter to the physical properties of milkfat fractions

Milkfat was separated into major chainlength fractions by solid-phase extraction. The effect on thermal behavior and texture of replacing both saturated and monounsaturated long-chain triglycerides from milkfat by long-chain monounsaturated triglycerides with an unsaturated fatty acid in thesn-2 position is reported. Increasing proportions of cocoa butter were added to fractions of short-to medium-chain triglycerides (C₂₂−C₄₄) and medium- to long-chain triglycerides (C₃₆−C₄₈) isolated from milkfat. Thermal behavior and texture of the mixtures were measured. Results indicated that long-chain monounsaturated triglycerides from cocoa butter enhanced co-crystallization and co-operative melting and did not induce polymorphic transitions upon crystallization and melting of the fractions. At 4°C, they acted as texture builder if present in proportions of more than 30%, whereas below this level, they acted as texture softeners. The effect of the long-chain monounsaturated triglycerides on the texture of fractions that melt at low temperature could not be predicted from the proportion of solid fat at that temperature. Presented at the 1995 AOCS Annual Meeting & Expo, San Antonio, Texas, May 1995.