New branched-chain fatty acids from the senegalese gorgonianLeptogorgia piccola (white and yellow morphs)

Fatty acids from total lipids of the gorgonianLeptogorgia piccola (white and yellow morphs), collected from the same area at two different periods with regard to the average water temperature, were studied. More than fifty fatty acids were identified as methyl esters andN-acyl pyrrolidides by gas chromatography and gas chromatography/mass spectrometry. Three new, branched-chain unsaturated fatty acids were identified in addition to the unusual 7-methyl-6-hexadecenoic acid, namely 10-methyl-6-hexadecenoic, 7,9-dimethyl-6-hexadecenoic, and 10-methyl-6,9-heptadecadienoic acids. Also 6,9-heptadecadienoic acid was identified. The fatty acid patterns of specimens harvested in colder waters were quite different from those harvested in warmer waters in that the former contained high amounts of methylene-interrupted polyunsaturated acids, including tetracosapolyenoic acids, especially 6,9,12,15,18–24∶5 (up to 15.8% of the total acid mixture) and 6,9,12,15,18,21–24∶6 (up to 5.3%). Arachidonic acid was, nevertheless, a major component in all the fatty acid mixtures studied (13.6–20.5%). Based on gas chromatography/Fourier transform infrared experiments, the double bonds were assigned the (Z) configuration. Several fatty aldehydes and their dimethyl acetals were also detected, of which the most abundant was octadecanal.     

Phospholipid and fatty acid composition of Bulgarian nut oils

The phospholipid and fatty acid composition of three Bulgarian nut oils were investigated. Phospholipids were separated by Folch′s method and two-directional thin-layer chromatography. Their content was determined spectrophotometrically. Phospholipids were present at levels of 0.8% in almond oil, 2.8% in hazelnut oil, and 0.9% in walnut oil. Phosphatidylcholine (18—50%), phosphatidylinositol (18—45%), and phosphatidylethanolamine (8—16%) were found to be the major components. Small amounts of phosphatidylserine, phosphatidic acids, phosphatidylglycerols, lysophosphatidylcholine, and lysophosphatidylethanolamine were also detected. The fatty acid composition of glyceride oils and of the four main phospholipids, namely phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol and phosphatidic acids was identified by capillary gas chromatography of their methyl esters. The predominant fatty acid present in almond and hazelnut oils was linoleic (83.2% and 80.8%, respectively). Oleic acid (18.7%), linoleic acid (48.5%), and linolenic acid (15.8%) were the major components in walnut oil. Higher quantities of saturated fatty acids (27.8—81.2%) were found to be in the phospholipids than in the corresponding oils (9.5—16.7%).     

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.     

Carduus nigrescens seed oil—A rich source of pentacyclic triterpenoids

Pentacyclic triterpene alcohols (3%), their acetates (18%), and their long chain fatty acid esters (11%), together with triterpene acids (18%), represent ca. 50% of the oil from the seed and pericarp of the thistleCarduus nigrescens Vill. (Compositae). Along with the usual fatty acids, alkaline hydrolysis of this oil gave triterpene alcohols, some of which were identified by gas chromatography-mass spectrometry. Composition of the triterpenoid fraction, as indicated by gas chromatography of the corresponding acetates, was: α-amyrin (6%), β-amyrin (15%), lupeol plus ϕ-taraxasterol (3%), erythrodiol (6%), and oleanolic acid (3%). Several components, representing 16% of the oil, were not identified. The content of pentacyclic triterpenoids is the largest found in plant seed oils.     

Sponge fatty acids. 3. Occurrence of series of n−7 monoenoic andiso-5,9 dienoic long-chain fatty acids in the phospholipids of the marine spongeCinachyrella aff.schulzei keller

The fatty acid composition of phospholipids from the New Caledonian spongeCinachyrella aff.schulzei Keller was studied. More than 60 fatty acids were identified as methyl esters andN-acyl pyrrolidides by gas chromatography and gas chromatography/mass spectrometry. Two isoprenoid fatty acids also were shown to be present, namely 4,8,12-trimethyltridecanoic and 5,9,13-trimethyltetradecanoic acids. The unusual 6-tetradecenoic, 6-pentadecenoic, 12-nonadecenoic and 26-methylheptacosanoic (iso-28∶0) acids were found for the first time in sponge phospholipids. A series of six n−7 monoenoic long-chain fatty acids (C₂₃ to C₂₈) were identified, including the rare 16-tricosenoic, 18-pentacosenoic and 21-octacosenoic acids. Fifteen fatty acids possessing the typical 5,9 dienoic moiety accounted for 30% of the total fatty acid mixture. Two new fatty acids were identified, namely 5(Z)-octacosenoic and 27-methyl-5(Z),9(Z)-octacosadienoic (iso-5,9-29∶2). Based on gas chromatography/Fourier transform infrared experiments, the double bonds were assigned the (Z) configuration. For part 2 of this series, see Reference 1.     

Lipid,sterol and fatty acid composition of antarctic krill (Euphausia superba Dana)

The lipid classes, fatty acids of total and individual lipids and sterols of Antarctic krill (Euphausia superba Dana) from two areas of the Antarctic Ocean were analyzed by thin layer chromatography (TLC), gas liquid chromatography (GLC) and gas liquid chromatography/mass spectrometry (GLC/MS). Basic differences in the lipid composition of krill from the Scotia Sea (caught in Dec. 1977) and krill from the Gerlache Strait (caught in Mar. 1981) were not observed. The main lipid classes found were: phosphatidylcholine (PC) (33–36%), phosphatidylethanolamine (PE) (5–6%), triacylglycerol (TG) (33–40%), free fatty acids (FFA) (8–16%) and sterols (1.4–1.7%). Wax esters and sterol esters were present only in traces. More than 50 fatty acids could be identified using GLC/MS, the major ones being 14∶0, 16∶0, 16∶1(n−7), 18∶1(n−9), 18∶1(n−7), 20∶5(n−3) and 22∶6(n−3). Phytanic acid was found in a concentration of 3% of total fatty acids. Short, medium-chain and hydroxy fatty acids (C≤10) were not detectable. The sterol fraction consisted of cholesterol, desmosterol and 22-dehydrocholesterol.     

The fatty acids of the spongeDysidea fragilis from the black sea

The fatty acid composition of the sponge,Dysidea fragilis, from the Black Sea has been determined by analytical gas chromatography, silver ion high-performance liquid chromatography and gas chromatography/mass spectrometry. More than a hundred different fatty acids were identified, of which many were similar to those in sponges from tropical seas. On the other hand, some of the fatty acids identified have not been found previously in sponges or other marine sources and perhaps are new to science. These include 13-methyl-tetradec-4-enoic and 14-methyl-hexadec-6-enoic acids, together with demospongic acids,i.e. 5,9,17-tetracosatrienoic, 5,9,17-pentacosatrienoic and 5,9,19-pentacosatrienoic acids. From the elution behavior on silver nitrate chromatography, all the double bonds were of thecis-configuration.     

Novel branched-chain fatty acids in certain fish oils

Methyl-branched fatty acids, which are usually minor components (≤0.1%) in fish oils, were concentrated in the non-urea-complexing fraction along with polyunsaturated fatty acids during the enrichment of omega-3 fatty acids from certain fish oils via the urea complexation process. The methyl-branched fatty acids in the omega-3 polyunsaturated fatty acid concentrates, which were prepared from three fish body oils, were characterized by gas chromatography and gas chromatography/mass spectrometry. Among the major branched-chain fatty acids expected and identified were the known isoprenoid acids—mainly 4,8,12-trimethyltridecanoic, pristanic, and phytanic—and the well-known iso and anteiso structures. Two novel phytol-derived multimethyl-branched fatty acids, 2,2,6,10,14-pentamethylpentadecanoic and 2,3,7,11,15-pentamethylhexadecanoic, were identified in redfish (Sebastes sp.) oil. These two fatty acids were absent in oils from menhaden (Brevoortia tyrannus) and Pacific salmon (mixed, but mostly from sockeye,Oncorhynchus nerka). The major branched-chain fatty acid in the salmon oil, 7-methyl-7-hexadecenoic acid, was also present to a moderate extent in menhaden oil. A novel vicinal dimethyl-branched fatty acid, 7,8-dimethyl-7-hexadecenoic was detected in all of the fish oils examined, but was most important in the salmon oil. Three monomethyl-branched fatty acids, 11-methyltetradecanoic acid, and 11- and 13-methylhexadecanoic, hitherto undescribed in fish lipids, were also detected in salmon, redfish and menhaden oils. Presented in part at the First Annual Meeting of the Amer. Oil. Chem. Soc. Canadian Section, Guelph, Ontario, Oct. 8–9, 1986.     

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.     

Fatty acid and 3‐hydroxy fatty acid composition of two Hypericum species from Turkey

The fatty acid compositions of flowering tops of Hypericum perforatum L. and Hypericum retusum Aucher (Guttiferae) were analyzed by gas chromatography and gas chromatography‐mass spectrometry. The major components were C16:0 (24.87%), C18:3 n‐3 (21.94%), 3‐OH‐C18:0 (18.46%) and 3‐OH‐C14:0 (14.22%) for H. perforatumL. and 3‐OH‐C14:0 (28.29%), C18:0 (16.47%) and C16:0 (14.17%) for H. retusum Aucher. Besides widespread plant fatty acids, 3‐hydroxy fatty acids, namely 3‐hydroxytetradecanoic acid (3‐OH‐C14:0) and 3‐hydroxyoctadecanoic acid (3‐OH‐C18:0) were also obtained.     

Phospholipid composition of some fruit-stone oils of Rosaceae species

The phospholipid composition of five types of vegetable oil extracted from the nuts of plum (Prunus domestica L.), peach (Prunus persica L.), apricot (Prunus armeniaca L.), cherry (Prunus aviumL.), and morello-cherry (Prunus cerasus L.) was determined spectrophotometrically after fractionation and separation to individual components by means of two-directional thin-layer chromatography. The content of phospholipids in the oils varied from 0.4% to 1.1%, while in the corresponding nuts it varied from 0.2 to 0.5%. The major components in the phospholipid fraction were phosphatidylcholine (37.1–59.0%), phosphatidylinositol (13.8–31.6%) and phosphatidylethanolamine (12.9–19.5%). The fatty acid composition of the triacylglycerols and of the major phospholipids was determined by capillary gas chromatography. Larger quantities of saturated fatty acids, mainly palmitic and stearic acid, were identified in the phospholipids.     

The steryl ester and phospholipid fatty acids of the spongeAgelas conifera from the Colombian Caribbean

The steryl ester and phospholipid fractions of the marine spongeAgelas conifera were isolated and analyzed. The fatty acyl components of the steryl ester and phospholipid fractions as determined by gas chromatography and gas chromatography/mass spectrometry were very similar and consisted of 56.8 and 62.7% of C₁₄−C₂₀ acids (normal; branched, especiallyiso andanteiso; and monounsaturated, particularly Δ⁹ and Δ¹¹ acids) and of 43.1 and 35.5% of C₂₄−C₂₆ acids (Δ^5,9 diunsaturated acids), respectively. The major constituent fatty acids detected were 13-methyltetradecanoic,n-hexadecanoic, 10-methylhexadecanoic, 11-octadecenoic, 12-methyloctadecanoic, 5,9-pentacosadienoic and 5,9-hexacosadienoic acids. The phospholipids isolated were identified as phosphatidylcholine (37%), phosphatidylserine (34%), phosphatidylethanolamine (16%) and phosphatidylinositol (11%). The distribution of fatty acids within the phospholipid classes was also determined.     

Betula platyphylla var.japonica Seed Oil: A rich source of linoleic acid

Component fatty acids of the oil extracted fromBetula platypbylla Sukatchev var.japonica Hara (Betulaceae) seeds were analyzed by gas liquid chromatography. The predominant fatty acid was linoleic acid (87%), and together with oleic and linolenic acids the 18-carbon unsaturated acids amounted to 97% of the total acids.     

Unsaturated C18 α-hydroxy acids inSalvia nilotica

The oil ofSalvia nilotica Jacq. (Labiatae) seed contains 0.6% α-hydroxyoleic, 4.2% α-hydroxylinoleic, and 5.4% α-hydroxylinolenic acids. The first two have not been found previously in seed oils. In addition to the common fatty acids, also identified were small amounts of three unsaturated C₁₇ acids and one branched chain C₁₇ acid. Methyl esters of the component fatty acids were fractionated by both column and thin-layer chromatography. These esters were identified by combination of gas chromatography, GC-mass spectrometry, ozonolysis-GC, infrared, and nuclear magnetic resonance.     

Determination of fatty acids and some undesirable fatty acid isomers in selected Turkish margarines

The fatty acid composition and total trans fatty acid content in 10 margarines produced in Turkey were determined by capillary gas chromatography and Fourier transform‐infrared spectroscopy (FT‐IR) spectroscopy. The fatty acid composition ranged as follows: saturated fatty acids, C16:0 (palmitic) 11.3 to 31.8% and C18:0 (stearic) 5.7 to 8.7%, monounsaturated fatty acids, C18:1 (oleic) 21.8 to 35.7% and C18:1 trans isomers 0.4 to 27.4%, polyunsaturated fatty acid, C18:2 linoleic acid 5.2 to 40.2%. Some positional isomers of C18:1 as cis‐11‐octadecenoic acid varied from 0.7 to 4.6% and cis‐13 trace to 2.4%. The total trans fatty acid contents were between 0.9 and 32.0% when measured with capillary gas chromatography and between 0 and 30.2% with FT‐IR spectroscopy. Some of the margarines analyzed contained trace amount of trans fatty acids which could not be detected by FT‐IR spectroscopy.     

Trans fatty acids in adipose tissue of French women in relation to their dietary sources

This study reports the fatty acid composition of subcutaneous adipose tissue in French women with special emphasis on the content of trans fatty acids originating from two main dietary sources, ruminant fats and partially hydrogenated vegetable oils (PHVO). Adipose tissue trans fatty acid levels from 71 women, recruited between 1997 and 1998, were determined using a combination of capillary gas chromatography and silver nitrate thin-layer chromatography. Results indicate that on average cis monounsaturates accounted for 47.9% of total fatty acids, saturates for 32.2%, and linoleic acid for 14.4%. Cis n−3 polyunsaturates represented only 0.7%. Total content of trans fatty acids was 2.32±0.50%, consisting of trans 18∶1 (1.97±0.49%), trans 18∶2 (0.28±0.08%), and trans 16∶1 (0.06±0.03%). Trans 18∶3 isomers were not detectable. The level of trans fatty acids found in adipose tissue of French women was lower than those reported for Canada, the United States, and Northern European countries but higher than that determined in Spain. Therefore, trans fatty acid consumption in France appears to be intermediate between that of the United States or North Europe and that of Spain. Based on the equation of Enig et al., we estimated the mean daily trans 18∶1 acid intake of French women at 1.9 g per person. The major trans 18∶1 isomer in adipose tissue was Δ11trans, as in ruminant fats. Estimates of relative contribution of trans fatty acid intake were 55% from ruminant fats and 45% from PHVO. This pattern contrasts sharply with those established for Canada and the United States where PHVO is reported to be the major dietary source of trans fatty acids.     

The fatty acid composition of the seeds ofGinkgo biloba

The fatty acid composition of seeds ofGinkgo biloba has been examined by a combination of capillary gas chromatography, silver ion high-performance liquid chromatography and gas chromatography/mass spectrometry. Some of the fatty acids identified are unusual in plants and were rather different from those reported earlier. These include ananteiso-methyl branched fatty acid, 14-methylhexadecanoic acid, 5,9-octadecadienoic acid, and 5,9,12-octadecatrienoic acid. Fourier-transform infrared spectroscopy confirmed that all of the double bonds were of thecis-configuration.     

Identification of nine acetylenic fatty acids, 9-hydroxystearic acid and 9,10-epoxystearic acid in the seed oil ofJodina rhombifolia hook et arn. (Santalaceae)

In addition to some usual fatty acids, the seed oil ofJodina rhombifolia (Santalaceae) contains nine acetylenic fatty acids [9-octadecynoic acid (stearolic acid) (1.1%),trans-10-heptadecen-8-ynoic acid (pyrulic acid) (20.1%), 7-hydroxy-trans-10-heptadecen-8-ynoic acid (2.3%),trans-10,16-heptadecadien-8-ynoic acid (0.7%), 7-hydroxy-trans-10,16-heptadecadien-8-ynoic acid (0.1%),trans-11-octadecen-9-ynoic acid (ximenynic acid) (20.3%), 8-hydroxy-trans-11-octadecen-9-ynoic acid (12.2%),trans-11,17-octadecadien-9-ynoic acid (1.5%), 8-hydroxy-trans-11,17-octadecadien-9-ynoic acid (1.3%), 9-hydroxystearic acid (<0.1%) and 9,10-epoxystearic acid (0.7%)]. The fatty acids have been analyzed by gas chromatography/mass spectrometry of their methyl ester and 4,4-dimethyloxazoline derivatives. The hydroxy fatty acid methyl esters have been examined also as trimethyl-silyl ethers. Furthermore, the fatty acid methyl esters (FAME) have been fractionated according to their polarity (FAME-A: nonhydroxy; FAME-B: hydroxy fatty acids) and to their degree of unsaturation (FAME-A1/A2; FAME-B1/B2) by preparative thin-layer chromatography and argentation chromatography, respectively. All of these fractions have been analyzed by ultraviolet and infrared spectroscopy, and the fractions FAME-A and FAME-B have been analyzed further by nuclear magnetic resonance (¹H,¹³C, 2D H/C, attached proton test) spectroscopy and gas chromatography/mass spectrometry. This work is dedicated to the 65th birthday of Prof. Dr. K. Pfeilsticker, Institut of Food Science, University Bonn (Germany).     

A Method for Identifying Germplasm that Exhibit Multiple Mutations in the Fatty Acid Synthetic Pathway of Perilla frutescens

A method using gas chromatography–mass spectroscopy (GC–MS) was developed to assess phenotypic differences in the fatty acid composition of 143 accessions of Perilla frutescens varieties that originated from different Chinese provinces, Japan, and Britain. Thirty-six compounds identified in the analysis included a number of saturated fatty acids and positional isomers of unsaturated fatty acids. A wide range in phenotypic variation was noted within each of five major fatty acids [16:0, 6.8–11.5%; 18:0, 1.7–11.9%; 18:1 (n-9), 12.3–28.0%; 18:2 (n-9,12), 9.6–21.6%; 18:3 (n-9,12,15), 41.4–56.6%]. Many accessions exhibited potential gene mutations or differences in gene copy number for multiple steps of fatty acid synthesis. For example, PCA models were developed to distinguish groups of accessions that exhibited low-16:0, low-18:1, high-18:3 traits, and others that exhibited high-16:0, high-18:1, low-18:3 traits. We believe this approach should improve the process for the identification of genetic resources that help reveal the complex nature of biological regulation not only of fatty acid metabolism but other metabolic processes as well.     

Lipid composition of the sponge Verongia aerophoba from the Canary Islands

The fatty acid composition of the lipids from the sponge Verongia aerophoba was investigated and 60 acids were identified. Two of them were new and their structures were elucidated by gas chromatography‐mass spectrometry. These acids were identified as 20‐methylhexacosanoic and Δ5, 9, 22‐nonacosatrienoic. Only 13 sterols were present, and aplysterol predominated. In the volatile fraction 13 compounds were identified, mainly fatty acids, their esters and hydrocarbons, while in the n‐butanol fraction we found mainly free fatty acids and free amino acids.