Fatty acid composition of some pine seed oils

The fatty acid composition of seeds from seven species of the genusPinus (P. pinaster, P. griffithii, P. pinea, P. koraiensis, P. sylvestris, P. mughus, andP. nigra) was established. Pine seeds are rich in oil (31–68% by weight) and contain several unusual polymethylene-interrupted unsaturated fatty acids with acis-5 ethylenic bond. These are thecis-5,cis-9 18:2,cis-5,cis-9,cis-12 18:3,cis-5,cis-11 20:2, andcis-5,cis-11,cis-14 20:3 acids, with a trace ofcis-5,cis-9,cis-12,cis-15 18:4 acid. Their percentage relative to total fatty acids varies from a low of 3.1% (P. pinea) to a high of 30.3% (P. sylvestris), depending on the species. The majorcis-5 double bond-containing acid is generally thecis-5,cis-9,cis-12 18:3 acid (pinolenic acid). In all species, linoleic acid represents approximately one-half the total fatty acids, whereas the content of oleic acid varies in the range 14–36% inversely to the sum of fatty acids containing acis-5 ethylenic bond. The easily available seeds fromP. koraiensis appear to be a good source of pinolenic acid: their oil content isca. 65%, and pinolenic represents about 15% of total fatty acids. These values appear to be rather constant.Pinus pinaster, which is grown on several thousand acres in the southwest of France, is an interesting source ofcis-5,cis-11,cis-14 20:3 acid (7% in the oil, which isca. 35% of the dehulled seed weight), an acid sharing in common three double bonds with arachidonic acid. Apparently,P. sylvestris seed oil contains the highest level ofcis-5 double bond-containing acids among pine seed oils that have ever been analyzed.     

Characterization of naturally occurring α-hydroxylinolenic acid

The seed oil ofThymus vulgaris L. (Labiatae) contains 13% of a new unsaturated hydroxy fatty acid which has been characterized as α-hydroxylinolenic acid. This oil also contains the previously unknown norlinolenic (all-cis-8,11,14-heptadecatrienoic) acid (2%) and linolenic acid (55%). The co-occurrence of these three acids suggests that the C₁₇ acid is biosynthesized by α-oxidation of linolenic acid. Presented at the AOCS-AACC Joint Meeting, Washington, D. C., April 1968. No. Utiliz. Res. Dev. Div., ARS, USDA.     

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.     

Stereospecific hydration of unsaturated fatty acids by bacteria

Three new 10-hydroxy fatty acids, all optically active, have been prepared by the anaerobic microbiological hydration of acis-9 double bond. Substrates that formed these new hydroxy fatty acids are linoleic, linolenic, and ricinoleic acids. The hydroxyl group has the D configuration and the methyl esters are levorotatory. Infrared, mass spectral, specific rotation and ultraviolet data on these compounds were determined. There was no migration of the unreated double bonds at C₁₂ and C₁₅ in linoleic or linolenic acids. The presence of a double bond in the 10-hydroxy fatty acids significantly increased the optical rotation of the methyl esters. The hydratase enzyme showed unusual specificity among Δ⁹ unsaturated acids. While it hydrates methylene interrupted and hydroxy unsaturated acids, it failed to hydrate either 9-decenoic, 12,13-epoxy- or 12-keto-cis-9-octadecenoic acids or sterculic acid. Presented at the AOCS Meeting, San Francisco, April 1969. No. Marketing and Nutrition Res. Div., ARS, USDA.     

Occurrence ofcis-5,cis-9-Hexacosadienoic andcis-5,cis-9,cis-19-Hexacosatrienoic acids in the marine spongeMicrociona prolifera

Fatty acid analysis of the total lipids from the marine spongeMicrociona prolifera by gas liquid chromatography on an EGSS-X column revealed two major peaks with equivalent chain length values of 27.08 and 27.74. Each of these components was isolated as a separate band by thin layer chromatography on AgNO₃-silicic acid. Characterization of the two unknowns by IR spectroscopy, NMR, hydrogenation, and gas liquid chromatography revealed that the unknown acids weren-26∶2 andn-26∶3 containing only nonmethylene interruptedcis-double bonds. Reductive ozonolysis identified the 26∶2 ascis-5,cis-9-hexacosadienoic acid and the 26∶3 ascis-5,cis-9,cis-19-hexacosatrienoic acid. Analysis of the fatty acid composition ofMicrociona total lipids showed 14% 26∶2 and 31% 36∶3. The neutral lipids, phosphatidylethanomaline, and phosphatidylserine all contained >41% C₂₆ acids; but only 4% C₂₆ was present in the phosphatidylcholine.     

Analysis of seed oils containing cyclopentenyl fatty acids by combined chromatographic procedures

The fatty acids of seed oils of the Flacourtiaceae,Hydnocarpus anthelmintica, Caloncoba echinata andTaraktogenus kurzii, have been examined by a combination of capillary gas chromatography, silver ion high performance liquid chromatography and gas chromatography-mass spectrometry. In addition to the common range of cyclopentenyl fatty acids found in such oils, 13-cyclopent-2-enyltridec-4-enoic acid was a major component ofH. anthelmintica and was identified by mass spectrometry as its picolinyl ester and dimethyldisulphide adduct. It has not previously been found in nature. In the other seed oils, the isolated double bond in the corresponding fatty acid was in position 6, as expected. Similarly,cis-4-hexadecenoic acid and C₁₆ and C₁₈ cyclopentyl fatty acids were identified for the first time inH. anthelmintica. Iso- andanteiso-methylbranched fatty acids were present in trace amounts.     

Fatty acids and sterols ofCronartium fusiforme basidiospores

The hydrocarbons, fatty acids, and sterols ofCronartium fusiforme basidiospores were examined by gas chromatography and mass spectrometry. Trace quantities of aliphatic hydrocarbons were detected, but these were probably not fungal products. Principal nonsubstituted fatty acids were palmitic (11.7%), linoleic (17.2%), and linolenic (16.1%) acids; the predominant acid was 9,10-cis-epoxyoctadecanoic acid (40.7%). Four sterols were detected, three of which were identified as stigmast-7-enol (57.6%), stigmasta-5,7-dienol (22.7%), and ergost-7-enol (16.0%). The fourth sterol (4%) is a C₂₈ diene. Lipids of the aeciospores and basidiospores ofC. fusiforme are compared.     

Structure-activity relationship of unsaturated fatty acids as mosquito ovipositional repellents

Various straight-chain unsaturated fatty acids from C₁₄ to C₂₄ were evaluated for their ovipositional repellency against gravid females of the southern house mosquitoCulex quinquefasciatus Say, and the relationship between the structures of the fatty acids and their ovipositional repellency was determined. A double bond withZ configuration was prerequisite for an unsaturated fatty acid to be highly repellent;E isomers were less active or even inactive. No relationship was found between the repellency and the number of double bonds in the unsaturated fatty acids. In C₁₈ monounsaturated fatty acids, (Z)-9 acid was more active than (Z)-11 and (Z)-6 acids, indicating that a double bond at the 9 position rendered an acid highly repellent. Among (Z)-9-alkenoic acids of different chain lengths, the most repellent was C₁₈ acid which was also more active than (Z)-11-C₂₀, (Z)-13-C₂₂, and (Z)-15-C₂₄ acids. Oleic[(Z)-9-octadecenoic]acid, which met all these criteria, was the most ovipositionally repellent among the unsaturated fatty acids tested.Diptera: Culicidae.     

cis-5-olefinic unusual fatty acids in seed lipids of gymnospermae and their distribution in triacylglycerols

Open-tubular gas chromatographic analysis of fatty acids in the lipids from the seeds of 20 species of Gymnospermae showed that they all contained nonmethylene-interrupted polyenoic (NMIP) acids as minor components and palmitic, oleic, linoleic and α-linolenic acids as major components. The NMIP acids have an additional 5,6-ethylenic bond in ordinary plant unsaturated fatty acids and the following C₂ elongation acids:cis-5,cis-9-octadecadienoic acid (5,9–18∶2) (I); 5,9,12–18∶3 (II); 5,9,12,15–18∶4, 5,11–20∶2, 5,11,14–20∶3 (III); and 5,11,14,17–20∶4 (IV). The main NMIP acids found in neutral lipids are I in two species ofTaxus, II in seven species of Pinaceae, III in two species of Podocarpaceae,Torreya nucifera, Cycas revoluta, andGinkgo biloba, and III and IV in each of three species of Taxodiaceae, and Cupressaceae. The polar lipids constitute the minor fraction of seed lipids in general. The content and composition of NMIP acids in these lipids differe considerably from those in neutral lipids. Analysis of the partial cleavage products of triacylglycerols showed that the NMIP acids distribute mainly in the 1,3-position.     

Tuna fatty acids: I. initial studies on the composition of the light and dark meats of bluefin tuna (Thunnus thynnus)-structural isomers of the monoenoic fatty acids

Bluefin tuna (Thunnus thynnus) is consumed in substantial amounts by humans. However, little has been reported on the fatty acid composition of bluefin body oil and on the isomeric structures of the unsaturated fatty acids. Because of the probable nutritional significance of unsaturated fatty acids, the present work was undertaken as an introductory study of the composition and structure of the fatty acids of tuna. The fatty acid composition of the light and dark meats from three bluefin tuna was determined by gas-liquid chromatography. A wide variety of saturated and polyunsaturated fatty acids were present in the oil from the meat of these speciments. the monoemoic fatty acid fraction, which comprises 34% of the total fatty acids was isolated and the isomers determined. Isomers found werecis-9-hexadecenoic acid,cis-9-octadecenoic acid,cis-11-octadecenoic acid,cis-9-eicosenoic acid,cis-11-eicosenoic acid,cis-11-docosenoic acid, andcis-13-docosenoic acid. Division of Industrial Research, U.S. Fish and Wildlife Service, Department of the Interior.     

Stereospecific analysis of triacylglycerols and major phosphoglycerides fromLipomyces lipoferus

The stereospecific distribution of fatty acids in triacylglycerols, phosphatidylcholines and phosphatidylethanolamines ofLipomyces lipoferus was determined. Position sn-1 of the triacylglycerols had a predominance of unsaturated fatty acids of which C_18∶1 (61%) was the major component. Position sn-2 of the triacylglycerols contained 88% C_18∶1 and was more unsaturated than position sn-1 by 24.6%. Position sn-3 had equal proportions of saturated and unsaturated fatty acids. Phosphatidylcholine had a quantitatively distinctive fatty acid distribution in that position sn-2 was 26.7% more unsaturated than position sn-1. In phosphatidylethanolamine, position sn-2 was 10.8% more unsaturated than position sn-1. Positions sn-1 and sn-2 of these phosphoglycerides had a different fatty acid profile from positions sn-1 and sn-2 of the triacylglycerols. These results suggest a nonrandom distribution of fatty acids in the triacylglycerols and phosphoglycerides. Because triacylglycerols and phosphoglycerides are both derived from 1,2-diacylglycerols, these data suggest two possibilities: some selectivity in utilization of species of diacylglycerols to form triacylglycerols and phosphoglycerides or modification of the triacylglycerols and phosphoglycerides after they are formed or both. This study is the first of its kind in a yeast. Presented in part at the AOCS Fall Meeting, Ottawa, Canada, September 1972.     

New long-chain hydroxy acids fromGrevillea decora

In addition to the ω-5 olefinic acids found in otherGrevillea species, about 10% of the acyl groups ofG. decora seed oil contain a hydroxy group and an ω-5 double bond. The chainlengths of these acids are from C₂₂ to C₃₀, with the largest concentration at the C₂₆ and C₂₈ chainlengths. The hydroxy group is located on odd carbons from carbon-5 through carbon-13. These acids previously were unknown in nature. The most abundant of these are 7-hydroxy-cis-17-docosenoic, 7-hydroxy-cis-19-tetracosenoic, 9-hydroxy-cis-19-tetracosenoic, 9-hydroxy-cis-21-hexacosenoic, 11-hydroxy-cis-21-hexacosenoic, and 13-hydroxy-cis-23-octacosenoic acids. The oil also contains the largest known concentration of the unoxygenated C₂₆ and C₂₈ ω-5 monoenes.     

Lipids of the pawpaw fruit: Asimina triloba

The fatty acid composition and structure of pawpaw fruit (Asimina triloba) triglycerides were examined and found to contain fatty acids ranging from C₆ to C₂₀. Octanoate represented 20% of the fatty acids while other medium-chain fatty acids were present in low amounts. Analysis of the intact triglycerides by high-temperature gas-liquid chromatography gave an unusual three-cycle carbon number distribution. Analysis of triglyceride fractions separated according to degree of unsaturation suggested that one octanoate was paired with diglyceride species containing long-chain fatty acids. Determination of the double-bond positions of monoene fatty acids revealed cis Δ9 and cis Δ11 hexadecenoate and cis Δ9, cis Δ11, and cis Δ13 octadecenoate isomers were present in significant quantities. Octanoate and positional monoene fatty acid isomers were found only in the fruit lipids and not in the seed lipids. Phenacyl esters of fatty acids were found to be useful derivatives for structure determination using multiple types of analyses.     

cis/trans isomerization of unsaturated fatty acids as possible control mechanism of membrane fluidity inPseudomonas putida P8

Exponentially growing cells ofPseudomonas putida had an increased ratio of saturated to unsaturated fatty acids in response to increased growth temperatures. Resting cells in which fatty acid biosynthesis was stopped reacted to a thermal increase by convertingcis-monounsaturated fatty acids totrans isomers.cis/trans isomerization of up to 60% of the unsaturated fatty acids was also activated by alcohols of different chain length. Their effective concentrations apparently depended on the lipophilic character of the alcohols. Also, a salt shock caused by the addition of NaCl resulted in the production oftrans fatty acids. However, cells that were adapted to growth media of high osmolarity synthesized cyclopropane fatty acids instead oftrans fatty acids. Activity ofcis/trans-isomerase was dependent on the growth phase and was significantly higher during logarithmic growth than during the stationary phase. The results of this study agree with the hypothesis that the isomerization ofcis intotrans unsaturated fatty acids is an emergency action of cells ofP. putida to adapt membrane fluidity to drastic changes of environmental conditions.     

Caltha palustris L. Seed Oil. A source of four fatty acids withcis-5-unsaturation

The seed oil ofCaltha palustris L. yields two unusual polyunsaturated components, all-cis-5,11,14-eicosatrienoic acid (23%) and all-cis-5,11,14,17-eicosatetraenoic acid (1%). The C₁₈ monoene fraction (26%) is a mixture ofcis-5- andcis-9-octadecenoic acids (2∶1). The C₂₀ monoene fraction (12%) is a mixture ofcis-11- andcis-5-isomers (3∶1). No. Utiliz. Res. Dev. Div., ARS, USDA.     

Fatty acid composition of danish margarines and shortenings,with special emphasis ontrans fatty acids

Trans fatty acids from hydrogenated vegetable and marine oils could be as hypercholesterolemic and atherogenic as saturated fatty acids. Hence, it is important to know the fatty acid composition in major food contributors, e.g., margarines and shortenings. In 1992 margarines were examined, and in 1995 brands covering the entire Danish market were examined. Significant amounts oftrans-18∶1 were found only in hard margarines (mean: 4.2±2.8%) and shortenings (mean: 6.8 ±3.1%), whereas the semisoft and soft margarines contained substantially lesstrans-18∶1 in 1995 than in 1992. Where marine oils had been used to a larger degree the meantrans-monoenoic content was about 15%, of which close to 50% was made up of long-chain (C₂₀ and C₂₂)trans fatty acids. A note-worthy decrease in the content oftrans-18∶1 had occurred for the semisoft margarines, from 9.8±6.1% in 1992 to 1.2±2.2% in 1995. Calculated from sales figures, the supply oftrans-18∶1 plus saturated fatty acids from margarines had decreased over this three-year period by 1.4 g/day, which has been replaced bycis monounsaturated and polyunsaturated fatty acids.     

GC-FID/MS Analysis of Fatty Acids in Indian Cultivars of Moringa oleifera: Potential Sources of PUFA

In the present investigation, the fatty acid profile was analysed in vegetative and reproductive parts of eight commercially cultivated Indian cultivars of Moringa oleifera and verified by gas chromatography mass spectra. In leaves, α-linolenic acid (C_18:3, cis-9,12,15) was found in the highest quantity (49–59 %) followed by palmitic acid (C_16:0) (16–18 %), and linoleic acid (C_18:2, cis-9,12) (6–13 %). The total content of saturated fatty acids and unsaturated fatty acids showed a ratio of 0.33 (cv. DHANRAJ) to 0.39 (cv. PKM-2) in leaves, 0.53 in flowers and 0.56 in tender pods. Similarly, polyunsaturated fatty acids and total monounsaturated fatty acids were found in a ratio of 5.68 (cv. DHANRAJ) to 9.71 (cv. CO-1) in leaves, 1.11 in flowers and 2.79 in tender pods. The total lipid content was recorded in the range of 1.92 % (flowers) to 4.82 % (leaves, cv. CO-1). When considering health benefits, M. oleifera leaves contain low amounts of saturated fatty acids, a high mono- and polyunsaturated fatty acid content, which can enhance the health benefits of Moringa-based products.     

Free fatty acids in the protective coats ofSpongilla wagneri gemmules

A gas chromatographic and mass spectrometric analysis of the free fatty acids found in the resistant coat ofSpongilla wagneri gemmules was performed. The coats were found to contain 8.79% extractable lipids with 18.53% free fatty acids, ranging in chain length from C₁₀ to C₂₄. The unsaturated acids were in relatively low concentrations with the preponderant saturated being palmitic and behenic. Distinct differences in distribution were observed when compared to the total gemmule fatty acids.     

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.     

Essential fatty acid-deficient rats: II. On the fatty acid composition of partially hydrogenated arachis,soybean and herring oils and of normal,refined arachis oil

The fatty acid composition of partially hydrogenated arachis (HAO), partially hydrogenated soybean (HSO) and partially hydrogenated herring (HHO) oils and of a normal, refined arachis oil (AO) was studied in detail by means of direct gas liquid chromatography, ultraviolet and infrared spectrophotometry and by thin layer chromatography fractionation on silver nitrate-silica gel plates followed by gas liquid chromatography. It was shown that the partially hydrogenated oils all contained fatty acids withtrans double bonds. In the plant oils, thetrans acids were present mainly as elaidic acid. The HHO showed an almost equal distribution betweentrans 18∶1 ω9,trans 20∶1 ω>9 andtrans 22∶1 ω>9. Sometrans configuration was also found in the C₂₀-and C₂₂-dienes and trienes of the HHO. In all the oils, conjugated fatty acids were present in minor amounts only (<0.5%). Special attention was given to the ω-acids known to be of specific nutritional value. The HSO contained about 32% linoleic acid, whereas the content ofcis, trans+trans, cis andtrans, trans octadecadienoic isomers was 1.7% and 0.5%, respectively. The amount of linoleic acid in the HSO was even higher than that of AO (29%). The HAO contained only 0.8% 18∶2 ω6 (linoleic acid). Further, two 18∶2 fatty acids with ω>6, acis, cis and atrans, trans isomer, were present in small amounts. The HHO contained 0.5% 18∶2 ω6 (linoleic acid). Isomers of 18∶2 ω>6 were also found in the HHO. They may be hydrogenation products of higher unsaturated C₁₈-acids orginally present. All the C₂₀- and C₂₂-dienes and trienes were shown to have an ω-chain greater than 6. Fatty acids with ω6-structure were not formed during partial hydrogenation of the oils studied.