Autoxidation rates of 5-olefinic monoenoic and denoic fatty acids from sea urchin lipids and meadoefoam oils

Autoxidation rates of the 5-olefinic monoenoic and dienoic fatty acids from sea urchin lipids and meadow-foam oils were compared with those of normal monoenoic and dienoic fatty acids by gas-liquid Chromatographic determination of the unoxidized fatty acid methyl esters remaining through the autoxidation period. The fatty acids are classified into five groups shown below according to the oxidation rate of their methyl esters: I 5-olefinic monoenoic acids (c5-18:l, c5-20:l and c5-22:1), II normal monoenoic acids (c9-18:l, cll-18:l, c9-20:1, cl3-20:l and cl3-22:l), III 5-olefinic dienoic acids (c5,cll-20:2, c5,cl3-20:2 and c5,cl3-22:2), IV 7-olefinic dienoic acids (c7,cl3-22:2 and c7,cl5-22:2) and V normal dienoic acids (c6,c9-18:2, c9,cl2-18:2 and cll,cl4-20:2). The oxidation rates of these groups increased during autoxidation in order from I to V. These results show that the 5-olefinic monoenoic and dienoic acids are more stable to autoxidation than the normal monoenoic and dienoic acids, respectively. The higher stabilities of the 5-olefinic monoenoic and dienoic acids in organisms are shown from these results.     

OxygenatedTrans-3-olefinic acids in aStenachaenium seed oil

Interesting differences were found in oils from two samples ofStenachaenium macrocephalum (Compositae) seed with dissimilar storage histories. One contained significant amounts of epoxy acids (6.5%) and hydroxy conjugated dienoic acids (5.6%), but the other contained no more than 1% of these oxygenated acids. Characterization of components in the former oil established that the principal epoxy acid (4.0%) is the previously unknowncis-9, 10-epoxy-trans-3,cis-12-octadecadienoic acid. The conjugated dienols include two additional new acids with Δ3 unsaturation (2.5%): 9-hydroxy-trans-3,-trans-10,cis-12-octadecatrienoic and 13-hydroxy-trans-3,cis-9,trans-11-octadecatrienoic acoids. The nonoxygenated acids, except for the large amount (40%) oftrans-3,cis-9,cis-12-octadecatrienoic, are those that commonly occur in seed oils. Presented at the AOCS Meeting, San Francisco, April 1969. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Distribution of Δ5-olefinic acids in the triacylglycerols fromPinus koraiensis andPinus pinaster seed oils

Purified triacylglycerols (TAG) fromPinus koraiensis andP. pinaster seed oils, which are interesting and commercially available sources of Δ5-olefinic acids (i.e.,cis-5,cis-9,cis-12 18:3 andcis-5,cis-11,cis-14 20:3 acids) were fractionated by reversed-phase high-performance liquid chromatography, and each fraction was examined by capillary gas-liquid chromatography for its fatty acid composition. A structure could be assigned to more than 92% of TAG from both oils. In both instances, ca. 48% of the TAG were shown to contain at least one δ5-olefinic acid. In the great majority of TAG, our data showed that there is only one molecule of δ5-olefinic acid per molecule of TAG. This is compatible with theoretical calculations based on the proportion of total δ5-olefinic in the oils. Thecis-5,cis-9,cis-12 18:3 acid (14.2 and 8.6% of total fatty acids in the seed oils ofP. koraiensis andP. pinaster, respectively) and thecis-5,cis-11,cis-14 20:3 acid (1.1 and 8.1% of total fatty acids in the seed oils ofP. koraiensis andP. pinaster, respectively) are preferentially associated with two molecules of linoleic acid, and to a lesser extent, to one molecule of linoleic acid and one molecule of oleic acid, or two oleic acid molecules. However, several other combinations occur, each in low amounts. The distribution of δ5-olefinic acids in TAG is evidently not random. Combining these results with the known preferential esterification of δ5-olefinic acids to the 1,3-positions of TAG would suggest that most of these acids are present at only one of these positions at a time.     

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.     

Fatty glycols and isostearyl alcohol as lipstick components

It is now possible to formulate lipsticks with a minimum number of ingredients. By using isostearyl alcohol as the oil phase and the appropriate vicinal glycols as the wax phase, both of which are good bromo solvents, a wide range of plastic properties may be obtained. The necessity of using oxidation inhibitors and couplers for incompatible bromo solvents is avoided. These raw materials are colorless, nearly odorless and tasteless, nontoxic, nonirritating, oxidation-stable, miscible with waxes, and are good emollients. Presented at the AOCS Meeting Chicago, October 1967.     

Positional distribution of Δ5-olefinic acids in triacylglycerols from conifer seed oils: General and specific enrichment in the sn-3 position

Triacylglycerols (TAG) were purified from the storage lipids extracted from the seeds of several conifer species (Taxus baccata, Larix decidua, Sciadopytis verticillata, and Juniperus communis), each species belonging to one of the four families Taxaceae, Pinaceae, Taxodiaceae, and Cupressaceae, respectively. Each species was characterized by a high content of 5,9-18:2, 5,9,12-18:3, 5,11,14-20:3, or 5,11,14,17-20:4 acids, respectively. TAG were partially deacylated with ethylmagnesium bromide, and the resulting 1,2-, 2,3-diacylglycerols (DAG), and 2-monoacylglycerols (MAG) were purified by thin-layer chromatography. 1,2- and 2,3-DAG were further fractionated by chiral column high-performance liquid chromatography of the 3,5-dinitrophenylurethane derivatives. Alternately, TAG were subjected to porcine pancreatic lipase, and the resulting 2-MAG were purified for further analysis. Gas-liquid chromatography of fatty acid methyl esters prepared from the separated DAG and MAG, coupled with appropriate calculations, indicated that the Δ5-olefinic acids, irrespective of the species, chainlengths and number of ethylenic bonds, were considerably enriched in the sn-3 position of TAG where they accounted for ca. 35 to 74 mole% of fatty acids esterified to this position (depending on the initial level of total Δ5-olefinic acids in TAG), which corresponded to 79–94% of Δ5-olefinic acids esterified to the three positions. On the other hand, Δ5-olefinic acids were less than 10% in the sn-2 position and less than 6% in the sn-1 position of TAG. This specific enrichment of Δ5-olefinic acids in the sn-3 position thus appears to be a general characteristic of conifer seed TAG. These results were extended to TAG from the seeds of two pine species (Pinus koraiensis and P. pinaster) that are rich in Δ5-olefinic acids and available commercially on a ton-scale.     

Fatty acids of lipid fractions in extracellular polymeric substances of activated sludge flocs

Phospholipid (PL), glycolipid (GL), and neutral lipid (NL) FA, and the lipopolysaccharide 2- and 3-hydroxy (LPS 2-OH and 3-OH) FA of activated sludges and extracted extracellular polymeric substances (EPS) were determined on samples collected from two wastewater treatment plants. EPS extracted from sludges by means of sonication and cation exchange contained proteins (43.4%), humic-like substances (11.5%), nucleic acids (10.9%), carbohydrates (9.9%), and lipid-bound FA (1.8%). The lipids associated with EPS were composed of GL, PL, NL, and LPS acids in proportions of 61, 21, 16, and 2%, respectively. The profiles of lipid-bound FA in activated sludges and EPS were similar (around 85 separate FA were identified). The FA signatures observed can be attributed to the likely presence of yeasts, fungi, sulfate-reducing bacteria, gram-positive and gram-negative bacteria, and, in lesser quantities, mycobacteria. Comparison of data from the dates of sampling (January and September) showed that there were more unsaturated PLFA in the EPS extracted from the activated sludges sampled in January. This observation could be partly related to microorganism adaptation to temperature variations. The comparison between two wastewater treatment plants showed that the FA profiles were similar, although differences in microbial community structure were also seen. Most of the FA in sludges had an even number of carbons.     

Δ5-olefinic acids in the edible seeds of nut pines (Pinus cembroides edulis) from the United States

The fatty acid composition of the edible seeds from Pinus cembroides edulis (a nut pine), that might have been a commercial source of Δ5-olefinic acids in the United States, has been established. The dehulled seeds are rich in oil (64% by weight) and are characterized by high levels of both oleic and linoleic acids (ca. 47 and 41%, respectively), with only 10% of saturated acids. Δ5-Olefinic acids, which were not reported previously in this species, are exceptionally low as compared to most other conifer species: 5,9-18:2 acid, 0.1%; 5,9,12-18:3 acid, 0.4%; 5, 11, 14-20:3 acid, 0.3%. In this respect, P. cembroides edulis seed oil closely resembles that of P. pinea (a circum-Mediterranean species), which emphasizes the morphological and taxonomic relationship between the sections to which the two species belong (Parryana and Pinea, respectively).     

Fatty acids as biological markers for bacterial symbionts in sponges

Analyses of fatty acids with carbon numbers between C12 and C22 are reported for five Great Barrier Reef sponges. These analyses indicate that phototrophic cyanobacterial symbionts (blue-green algae) present in three of the sponges are chemically distinct, whereas the other two sponges do not contain cyanobacterial symbionts. All the sponges contain other, nonphototrophic bacteria. The fatty acid analyses indicate that the non-phototrophic bacterial populations present in the different sponges are distinct in both their chemical compositions and their abundances. Nonphototrophic bacteria are estimated to account for between 60 and 350 micrograms/g (extractable fatty acids:tissue wet weight), whereas cyanobacteria account for between 10 and 910 micrograms/g. One sponge (Pseudaxinyssa sp.) contains a relatively large amount of the isoprenoid acid, 4, 8, 12-trimethyltridecanoic acid; this acid is presumed to be derived from phytol, a degradation product of chlorophyll. This sponge also contains relatively large amounts of the nonmethylene interrupted fatty acid, octadeca-5,9-dienoic acid. Analyses of interior and cyanobacteria-rich surface tissues of this sponge indicate that these two acids are probably not associated with the symbiotic cyanobacteria.     

Effect of age on plasma bile acids and lipid components in the rat

With increasing age, total plasma bile acid contents increased in rats over a period of 11 months, and also total plasma cholesterol and carcass fat contents increased in the same manner. Plasma showing high bile acid levels at 11 months was found by means of high performance liquid chromatography to contain cholic acid as one of the major components, chenodeoxycholic acid and trace deoxycholic acid. These results suggest that there are close relationships between the plasma bile acids and age-dependent changes of lipid components in the rat.     

ω3 Fatty acids increase spontaneous release of cytosolic components from tumor cells

Mice fed menhaden (fish) oil or coconut oil-rich diets were inoculated intraperitoneally with a rapidly growing leukemia, T27A. After one week, the tumor cells were harvested, and⁵¹Cr was used to label intracellular molecules. Spontaneous release of⁵¹Cr was used as a measure of plasma membrane permeability. Compared to cells from mice fed coconut oil (rich in saturated fatty acids), tumor cells from mice fed menhaden oil (rich in long chain polyunsaturated ω3 fatty acids) showed an increased level of spontaneous⁵¹Cr release, which was exacerbated by increased temperature and reduced by extracellular protein. At physiological salt concentrations, the releated⁵¹Cr was detected in particles of ∼2700 daltons. Enhanced permeability correlated with the incorporation of dietary (fish oil) ω3 polyunsaturated fatty acids docosahexaenoic and eicosapentaenoic acid into the tumor cells. The results demonstrate that ω3 fatty acids are incorporated into cellular constituents of tumor cells and change properties associated with the plasma membrane. This result suggests that dietary manipulation may be used to enhance tumor cell permeability and contribute to tumor eradication.     

trans Fatty acids in milkfat

Milkfat is extremely complex, with ca. 500 different fatty acids reported in the triglycerides. Seasonal feed variation results in higher unsaturated fatty acid levels in summer than in winter. Rumen microbes hydrogenate unsaturated feed lipids to yield a mixture of geometrical and positional isomers which are transmitted to the milk. Total isolatedtrans fatty acids in milkfat reported in the literature range from 2 to 11% with maximal values in summer and minimal values in winter. A study was undertaken about the use of AOCS Method Cd 14-61 for the determination of isolatedtrans levels in milkfat. The triglycerides of milkfat were analyzed using trielaidin as a standard and milkfat methyl esters were analyzed using methyl elaidate as a standard. Corrections were made, for the loss of the methyl esters of the short-chain fatty acids. The apparent levels oftrans found by using the triglycerides were considerably higher than by using the methyl esters. Infrared spectra of pure triglycerides of saturated fatty acids showed measurable absorption at 10.36 μm, whereas methyl esters of saturated andcis unsaturated fatty acids did not.     

Fatty acids and polar lipid content of cheese and mould‐contaminated cheese

Unintended infestation of food with viable mould irreversibly leads to spoilage of food. However, little data existed on the fatty acid composition and polar lipid content of mould grown on cheese and the potential influence of these parameters in mould‐infested cheese. In this study, we thus focused on the fatty acids composition and polar lipid content of cheese, mould isolated from mould‐infested cheese, as well as inoculation of cheese with cultures of isolated moulds. For this purpose, we stored three cheese samples (gouda, brown cheese, and parmesan) over extended periods in order to force mould infestation from air. The moulds grown on gouda and brown cheese were identified as Penicillium brevicompactum and Penicillium roqueforti, respectively, while a mixed culture was obtained from parmesan. From these contaminated samples, mould spores were isolated and cultivated. Finally, the (pure) cheeses were inoculated with mould spores. Three subsamples, (1) cheeses, (2) moulds isolated from cheese, and (3) cheeses infested with the isolated moulds were studied with regards to their fatty acid distribution in the neutral and the polar lipids. The different amounts of polar lipids of cheese (0.39–2%), moulds (11–30.7%), and mould‐infested cheese (1.5–5%) allowed calculating the mould content of the mould‐infested cheeses.     

Trace components of tall oil fatty acids:Trans-3, 5-dimethoxystilbene

2,2″-Methylenebis (trans-3,5-dimethoxystilbene) has been isolated from tall oil fatty acid after reaction with paraformaldehyde in the presence of an acid catalyst.     

Acrylic-functional aminocarboxylic acids and derivatives as components of pressure-sensitive adhesives

High-performance thermoplastic pressure-sensitive adhesives have been prepared by copolymerization of N-acryloylamino acid and acid derivatives with long-chain alkyl acrylate esters. A comparative study with equivalent copolymers made from conventional polar comonomers and long-chain alkyl acrylate esters has shown that the N-acryloylamino acids and derivatives impart generally higher levels of tack, adhesion, and cohesion than their conventional counterparts.     

Fatty acids and fatty alcohols of wax esters in the orange roughy: Specific textures of minor polyunsaturated and branched-chain components

Open-tubular gas chromatography was carried out on fatty acids and alcohols obtained from wax esters of the orange roughy,Hoplostethus atlanticus, caught at sea off New Zealand. The major (above 5%) components were 16∶1(n−7), 18∶1(n−9) and (n−7), 20∶1(n−9) and (n−7), and 22∶1(n−11, n−13) as fatty acids, and 16∶0, 18∶0, 18∶1(n−9), 20∶1(n−9) and (n−7), and 22∶1(n−11, n−13) as fatty alcohols. The total percentages of the minor components were 10% in the acids and 26% in the alcohols. The 22∶1/20∶1 ratio of the fatty alcohols obtained in this study was less than 1.0, although the ratio for the Atlantic orange roughy has been reported as being greater than 1.0. The contents of polyenes were as low as 2.48% in the acids and 0.95% in the alcohols, but their compositions showed some specific features. The percentages of the C₁₆−C₂₂ dienes in the total polyenes were remarkably high, 57.7% of these acids and 53.1% of these alcohols. The most important dienes were 18∶2(n−6) in the acids and 20∶2(n−6) in the alcohols.     

Fatty acids in lipids of maturing wheat

Two varieties of hard red winter wheat were sampled at various stages of maturity. The lipids in those samples were fractionated into free polar, free nonpolar and bound lipids. Fatty acids of those fractions were determined. Major acids present were palmitic, oleic, linoleic and linolenic. Both wheat samples showed similar qualitative, but not quantitative patterns in distribution of fatty acids during maturation. In the free polar lipid fraction, the palmitic acid content decreased with maturation while the linoleic acid content increased. The free nonpolar fractions showed a slight increase in linoleic acid; the concentration of other acids decreased slightly as the wheat matured. The bound lipid fraction showed a marked increase in linoleic acid, accompanied by decreases in the other major fatty acids, especially linolenic. Cooperative investigations of Kansas Agricultural Experiment Station and Crops Research Div., ARS, USDA.     

Fatty acids and oil content in white lupin seed as affected by production practices

Characteristics of the seed oil of white lupin (Lupinus albus L.), a potential alternative winter crop in the mid-Atlantic region of the United States, are not well established. Replicated experiments were conducted during the 1998–1999 and 1999–2000 growing seasons with a determinate and an indeterminate cultivar to characterize oil and FA in lupin seed in relation to production practices. The experiments were planted in early October, late October, and mid-November using row spacings of 0.3, 0.6, and 0.9 m at each planting time. Seeds from the planting date of early October had significantly (P<0.05) higher oil content than the later plantings (late October and mid-November). A closer row spacing (0.3 m) also had significantly (P<0.05) higher oil content than the wider row spacing (0.9 m). Planting data effects on FA content were significant for some FA, but row spacing did not affect FA contents. Oil content in the seed varied from 7.2 to 8.2% (w/w). The oil from white lupin seed contained FA in the order of 18∶1>18∶2> 18∶3>16∶0>20∶1>22∶1>22∶0>18∶0>24∶0>20∶0. The saturated FA/unsaturated FA ratio in lupin oil was 0.14. White lupin seed contained higher contents of oil and FA than literature values for seed of navy, kidney, and pinto beans.