Fatty acid composition ofThalictrum L. seed oils

The fatty acid composition of five representatives of theThalictrum L. genus of the plant familyRanunculaceae has been investigated. The fatty acids include mainly acids with double bonds in thetrans-5 position (about 60%). Although the main component of the fatty acids is a triene acid (trans-5,cis-9,cis-12-octadecatrienoic acid), the oils investigated are semidrying.     

An unusual fatty acid pattern inEranthis seed oil

The current discussion on “renewable resources”, and the possibility of gene transfer into rapeseed, has led to many investigations into the biosynthetic pathways leading to industrially useful fatty acids. The various tribes and genera of the plant familyRanunculaceae contain a large variety of unusual fatty acids. Seed fatty acid patterns differ considerably from genus to genus and are chemotaxonomically significant indicators.Eranthis seed oil has now been found to contain a fatty acid pattern that deviates significantly from the eleven different fatty acid patterns that had been described in this plant family. The main fatty acid (up to 57%) is 13-cis, 16-cis-docosadienoic acid. Other, minor fatty acids found are Δ5-cis-monoenoic,-dienoic, and-trienoic fatty acids that had already been reported to be constituents of the genus-specific seed oil fatty acid patterns of various genera from this plant family. Capillary gas-liquid chromatographic retention data indicate that 22:3Δ5cis, 13cis, 16cis is probably also present. Seed fatty acid chemotaxonomic evidence thus points to a different position ofEranthis within the tribes of this plant family. These findings again indicate that the plant familyRanunculaceae would be an ideal object to study fatty acid biosynthesis and phylogenetic evolution, because in other genera of this family other types of desaturation and chain elongation mechanisms predominate.     

A Facile and Efficient Method for the Synthesis of Labeled and Unlabeled Very Long Chain Polyunsaturated Fatty Acids

Several methods are available for elongation of fatty acid acyl chains. The present paper describes adaptation to the fatty acid field of a previously published protocol for manganese-based Wurtz type coupling of alkyl bromides. 22-Bromo-3(Z),6(Z),9(Z),12(Z),15(Z),18(Z)-docosahexaene, easily prepared from 4(Z),7(Z),10(Z),13(Z),16(Z),19(Z)-docosahexaenoic acid, was coupled to homologous ω-bromoesters by stirring for 4 hours at 40°C in the presence of manganese powder, a nickel catalyst and terpyridine. This afforded in yields of 70–75% a series of ω3-hexaenoates of chain lengths of 32–40 carbons. The corresponding fatty acids of >98% purity were obtained following saponification and final purification. By using methyl [2,2,3,3,4,4-²H₆]10-bromodecanoate as coupling partner it was possible to prepare a very long chain fatty acid in isotopically labeled form, i.e., [2,2,3,3,4,4-²H₆]14(Z),17(Z),20(Z),23(Z),26(Z),29(Z)-dotriacontahexaenoic acid. Also prepared were the monounsaturated long chain fatty acids 15(Z)-octadecenoic acid and 15(Z)-tetracosenoic acid. Very long chain fatty acids have been isolated from retina and other tissues and are of biological relevance. The methodology described will assist in further analytical and biological studies in this field.     

Production of hydroxy fatty acids from unsaturated fatty acids byFlavobacterium sp. DS5 hydratase,a C-10 positional- andcis unsaturation-specific enzyme

A new microbial isolate,Flavobacterium sp. DS5, converted oleic and linoleic acids to their corresponding 10-keto-and 10-hydroxy fatty acids. The hydration enzyme seems to be specific to the C-10 position. Conversion products from α- and γ-linolenic acids were identified by gas chromatography/mass spectrometry, Fourier transform infrared, and nuclear magnetic resonance as 10-hydroxy-12(Z),15(Z)-octadecadienoic and 10-hydroxy-6(Z),12(Z)-octadecadienoic acids, respectively. Products from other 9(Z)-unsaturated fatty acids also were identified as their corresponding 10-hydroxy- and 10-keto-fatty acids.Trans unsaturated fatty acid was not converted. From these results, it is concluded that strain DS5 hydratase is indeed a C-10 positional-specific andcis-specific enzyme. DS5 hydratase prefers an 18-carbon monounsaturated fatty acid. Among the C₁₈ unsaturated fatty acids, an additional double bond at either side of the 9,10-position lowers the enzyme hydration activity. Because hydratases from other microbes also convert 9(Z)-unsaturated fatty acids to 10-hydroxy fatty acids, the C-10 positional specificity of microbial hydratases may be universal.     

Positional Distribution of Fatty Acids on Oilseed Phosphatidylcholines and Phosphatidylethanolamines

Positional distribution of fatty acids in the phosphatidylcholines (PCs) and phosphatidylethanolamines (PEs) of coriander (Coriandrum sativum), carrot (Daucus carota), papaya (Carica papaya), palash (Butea monosperma), sunflower (Helianthus annuus), karanja (Pongamia glabra) and jangli badam (Sterculia foetida) seeds was studied. PCs and PEs contained 58 to 83% of unsaturated fatty acids. The fatty acids liberated by phospholipase A₂ hydrolysis from 2-position consisted mainly of unsaturated acids. The PC and PE classes namely US, SU and UU in terms of saturated (S) and unsaturated (U) fatty acids in the 1- and 2-positions were calculated from the proportions of saturated fatty acids in total PC/PE and in the 2-position. The amount of disaturated class was absent in all PCs and PEs as determined by mercuric acetate adduct formation and subsequent TLC separation. SU and UU classes were found to be predominant in all PCs and PEs.     

Mass spectral studies of deuterium-labelled picolinyl fatty esters in the determination of double-bond positions

Deuteration (with Wilkinson’s catalyst) of methyl 12:1(3c), 14:1(5c), 18:1(9c), 18:2(9c,12c), 18:3(9c,12c,15c), 20:4(5c,11c,14c,17c), 20:5(5c,8c,11c,14c,17c) and 22:6(4c,7c,10c,13c,16c,19c) fatty acids gave the corresponding deuterium-labelled saturated fatty esters. The mass spectral analysis of their picolinyl esters gave clear diagnostic ion fragments, which permitted the facile and accurate determination of the positions of the double bonds (up to six) in the alkyl chain of the fatty ester.     

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.     

trans fatty acids. 4. Effects on fatty acid composition of colostrum and milk

trans Isometric fatty acids of partially hydrogenated fish oil (PHFO) consist oftrans 20∶1 andtrans 22∶1 in addition to thetrans isomers of 18∶1, which are abundant in hydrogenated vegetable oils, such as in partially hydrogenated soybean oil (PHSBO). The effects of dietarytrans fatty acids in PHFO and PHSBO on the fatty acid composition of milk were studied at 0 (colostrum) and 21 dayspostpartum in sows. The dietary fats were PHFO (28%trans), or PHSBO (36%trans) and lard. Sunflower seed oil (4%) was added to each diet. The fats were fed from three weeks of age throughout the lactation period of Experiment 1. In Experiment 2 PHFO or “fully” hydrogenated fish oil (HFO) (19%trans), in comparison with coconut oil (CF) (0%trans), was fed with two levels of dietary linoleic acid, 1 and 2.7% from conception throughout the lactation period. Feedingtrans-containing fats led to secretion oftrans fatty acids in the milk lipids. Levels oftrans 18∶1 andtrans 20∶1 in milk lipids, as percentages of totalcis+trans 18∶1 andcis+trans 20∶1, respectively, were about 60% of that of the dietary fats, with no significant differences between PHFO and PHSBO. The levels were similar for colostrum and milk. Feeding HFO gave relatively lesstrans 18∶1 andtrans 20∶1 fatty acids in milk lipids than did PHFO and PHSBO. Only low levels ofcis+trans 22∶1 were found in milk lipids. Feedingtrans-containing fat had no consistent effects on the level of polyenoic fatty acids but reduced the level of saturated fatty acids and increased the level ofcis+trans monoenoic fatty acids. Increasing the dietary level of linoleic acid had no effect on the secretion oftrans fatty acids but increased the level of linoleic acid in milk. The overall conclusion was that the effect of dietary fats containingtrans fatty acids on the fat content and the fatty acid composition of colostrum and milk in sows were moderate to minor.     

Divinyl ethers and hydroxy fatty acids from three species ofLaminaria (brown algae)

Three species of brown algae,Laminaria sinclairii, L. saccharina andL. setchellii, have been investigated for the presence of oxylipins. From one,L. sinclairii, three new divinyl ether fatty acids have been characterized as methyl ester derivatives (methyl 12-[1′ (Z),3′(Z)-hexadienyloxy]-6(Z), 9(Z), 11(E)-dodecatrienoate, methyl 12-[1′ (Z), 3′ (Z)-hexadienyloxy]-9(Z), 11(E)-dodecatrienoate, and methyl 14-[1′ (Z),3′ (Z)-hexadienyloxy]-9(Z),11(E)-dodecadienoate, and methyl 14-[1′ (Z),3′(Z)-hexadienyloxy]-5(Z),8(Z),11(Z),13(E)-tetradecatetraenoate) by a variety of spectroscopic methods. In addition, one new [13(S)-hydroxy-6(Z),9(Z),11(E),15(Z)-octadecatetraenoic acid] and four known monohydroxy polyunsaturated fatty acids have been isolated from all three species as their methyl ester derivatives. The occurrence of these compounds in brown algae strongly suggests that these organisms possess an active lipoxygenase(s) with ω6 specificity. A preliminary summary of this work was presented at the XIVth International Seaweed Symposium, Brest, France, August 1992 (10).     

The phospholipid fatty acids of the marine spongeXestospongia muta

The rare phospholipid fatty acids 3,7,11-trimethyldodecanoic (1), 5,9-hexadecadienoic (2) and 12-methyl-hexadecanoic (3) were identified in the marine spongeXestospongia muta. Branched fatty acids inX. muta accounted for 35% of the total fatty acid mixture. It was observed that the occurrence of the 5,9-hexadecadienoic acid (2) coincides with the complete absence of the very long chain fatty acid 5,9-hexacosadienoic. The acid 5,9,19-octacosatrienoic seems to be found in mostXestospongia species.     

Fatty acid and triacylglycerol compositions of seed oils of five Amaranthus accessions and their comparison to other oils

This paper reports the fatty acid and triacylglycerol (TAG) compositions of five Amaranthus accessions (RRC1011, R149, A.K343, A.K432, and A. K433) representing two species and a cross between one of these and a third species. Seed oils of these were analyzed by gas chromatography and reversed-phase high-performance liquid chromatography, and their compositional properties compared with buck-wheat (Fagopyrum esculentum), corn (Zea mays), rice bran (Oryza sativa), soybean (Glycine max L. Merr.), sesame (Sesamum indicum), quinoa (Chenopodium quinoa), and cottonseed (Gossypium hirsutum) oils. All Amaranthus accessions were relatively high in palmitic (21.4–23.8%) and low in oleic (22.8–31.5%) and linolenic (0.65–0.93%) acids when compared to most of the grain and seed oils. The fatty acid composition of Amaranthus accessions K343, K433, and K432 (group I) were different from R149 and RRC1011 (group II) in mono and polyunsaturated fatty acids, but the saturate/unsaturate (S/U) ratios were very similar. All Amaranthus accessions were similar in TAG type, but showed slight differences in percentage. High similarities in UUU, UUS, and USS composition were observed among Amaranthus K343, K433 and K432, and between R149 and RRC1011. The fatty acid compositions of Amaranthus oil (group I) and cottonseed oil were similar, but their TAG compositions were different. The grain and oilseed oils were different from each other and from the Amaranthus accessions oils in terms of fatty acid composition, S/U, and TAG ratios. The UUU, UUS, and USS percentages were very diverse in grain and seed oils. The percentages of squalene in the TAG sample from the Amaranthus accessions were 8.05% in K343, 11.10% in K433, 11.19% in K432, 9.96% in R149, and 9.16% in RRC1011. Squalene was also tentatively identified in quinoa and ricebran oils at levels of 3.39 and 3.10%, respectively.     

Differential Expression of Lipid Metabolism Related Genes in Porcine Muscle Tissue Leading to Different Intramuscular Fat Deposition

Intramuscular fat (IMF) content affects meat quality and varies in different pig breeds. However, the underlying mechanisms of different IMF depositions in different genetic backgrounds of pigs have not been fully elucidated as yet. Lipid metabolism theoretically contributes to the variation of IMF content. The expression levels of genes and proteins as well as enzyme activities implicated in muscle lipid metabolism were investigated, which included lipogenetic genes (SREBP-1c and FAS), fatty acid transporting genes (H-FABP and A-FABP), fatty acid oxidative gene (CPT-1B) and lipolytic genes (ATGL and HSL) as well as the desaturated fatty acid gene (SCD). Longissimus muscle samples were collected from fatty Wujin pigs and lean Landrace pigs. Results showed that the average daily gain of Wujin pigs was lower than that of Landrace pigs. Wujin pigs had greater adipocyte diameter, IMF content and PUFA percentage than that of Landrace pigs. Compared with Landrace pigs, Wujin pigs exhibited higher expression levels, both in mRNA and protein, of FAS, SREBP-1c, SCD, A-FABP and H-FABP genes and lower expression levels of CPT-1B, HSL and ATGL genes. Overall, Wujin pigs possessed higher mRNA abundance, protein expression or enzyme activities of anabolism, fatty acid transportation and desaturation, and lower catabolism. Therefore, the mechanism of higher IMF content in fatty pigs may be due to the higher capacity of lipogenesis and fatty acid transportation and the lower capacity of lipolysis.     

6-methyl-8-hexadecenoic acid: A novel fatty acid from the marine spongeDesmapsama anchorata

The novel fatty acid 7-methyl-8-hexadecenoic (1) was identified in the marine spongeDesmapsama anchorata. Other interesting fatty acids identified were 14-methyl-8-hexadecenoic (2), better known through its methyl ester as one of the components of the sex attractant of the female dermestid beetle, and the saturated fatty acid 3-methylheptadecanoic (3), known to possess larvicidal activity. The main phospholipid fatty acids encountered inD. anchorata were palmitic (16∶0), behenic (22∶0) and 5,9-hexacosadienoic acid (26∶2), which together accounted for 50% of the total phospholipid fatty acid mixture.     

Effect of the degree of hydrogenation of dietary fish oil on the trans fatty acid content and enzymatic activity of rat hepatic microsomes

The degree of fat hydrogenation and the trans fatty acid content of the diet affect the fatty acid composition of membranes, and the amount and the activity of some membrane enzymes. We describe the effects of four isocaloric diets containing either sunflower oil (SO, 0% trans), fish oil (FO, 0.5% trans), partially hydrogenated fish oil (PHFO, 30% trans), or highly hydrogenated fish oil (HHFO, 3.6% trans) as fat sources on the lipid composition and the trans fatty acid content of rat hepatic microsomes. We also describe the effect of these diets on the cytochrome P-450 content and on the aminopyrine N-demethylase, aniline hydroxylase, and UDP-glucuronyl transferase microsomal activities. Cytochrome P-450 content was dependent on the degree of unsaturation of the diet, being higher for the FO-containing diet and lower for the HHFO diet. Aminopyrine N-demethylase activity also correlated with the degree of unsaturation of the diet as did the cytochrome P-450 content did (FO>SO>PHFO>HHFO). Aniline hydroxylase activity appeared to be independent of the degree of unsaturation of the dietary fat, but correlated with the trans fatty acid content of the diet, which was also reflected in the trans content of the microsomal membranes. UDP-glucuronyl transferase activity was higher for the FO-containing diet than for the SO diet, showing intermediate values after the PHFO and HHFO diets.     

A pathway for biosynthesis of divinyl ether fatty acids in green leaves

[1-¹⁴C]α-Linolenic acid was incubated with a particulate fraction of homogenate of leaves of the meadow buttercup (Ranunculus acris L.). The main product was a divinyl ether fatty acid, which was identified as 12-[1′(Z),3′(Z)-hexadienyloxy]-9(Z), 11(E)-dodecadienoic acid. Addition of glutathione peroxidase and reduced glutathione to incubations of α-linolenic acid almost completely suppressed formation of the divinyl ether acid and resulted in the appearance of 13(S)-hydroxy-9(Z), 11(E), 15(Z)-octadecatrienoic acid as the main product. This result, together with the finding that 13(S)-hydroperoxy-9(Z), 11(E), 15(Z)-octadecatrienoic acid served as an efficient precursor of the divinyl ether fatty acid, indicated that divinyl ether biosynthesis in leaves of R. acris occurred by a two-step pathway involving an ω6-lipoxygenase and a divinyl ether synthase. Incubations of isomeric hydroperoxides derived from α-linolenic and linoleic acids with the enzyme preparation from R. acris showed that 13(S)-hydroperoxy-9(Z), 11(E)-octadecadienoic acid was transformed into the divinyl ether 12-[1′(Z)-hexenyloxy]-9(Z), 11(E)-dodecadienoic acid. In contrast, neither the 9(S)-hydroperoxides of linoleic or α-linolenic acids nor the 13(R)-hydroperoxide of α-linolenic acid served as precursors of divinyl ethers.     

Novel oxylipins from the temperate red alga polyneura latissima: Evidence for an arachidonate 9(S)-lipoxygenase

The oxylipin chemistry of the temperate red alga Polyneura latissima has been investigated. The structures of three novel oxylipins, 8-[1′(Z),3′(Z),6′(Z)-dodecatriene-1′-oxyl-5(Z),7(E)-octadienoic acid, 7(S ^*)-hydroxy-8(S ^*),9(S ^*)-epoxy-5(Z), 11(Z),14(Z)-eicosatrienoic acid, 7(R ^*)-hydroxy-8(S ^*), 9(S ^*)-epoxy-5(Z), 11(Z),14(Z)-eicosatrienoic acid, together with two known eicosanoids, 9(S)-hydroxy-5(Z), 7(E), 11(Z), 14(Z)-eicosatetraenoic acid, and 9, 15-dihydroxy-5(Z),7(E),11(Z),13(E)-eicosatetraenoic acid, were elucidated by spectroscopic methods and chemical degradation. The oxygenation pattern of these oxylipins suggests that P. latissima metabolizes polyunsaturated fatty acids via a 9(S)-lipoxygenase.     

Synthesis of dimer and oligomers from (R)-methyl hydnocarpate

We report synthesis and characterization of dimer and oligomer acids from chaulmoogra oil. (R)-Methyl hydnocarpate (methyl ester of the major fatty acid component of chaulmoogra oil) was brominated to give threo-2,3-dibromocyclopentane-1-methyl undecanoate. Formation of two diastereoisomers, viz., threo-2(R),3(R)-dibromocyclopentane-1(R)-methyl undecanoate and threo-2(S),3(S)-dibromocyclopentane-(R)-1-methyl undecanoate, was observed. Dehydrobromination of bromo derivatives using alcoholic KOH gave a cyclopentadiene derivative as intermediate, which underwent Diels-Alder reaction to give dimer and oligomer fatty acids. The products were characterized by ultraviolet, direct exposure probe-mass spectroscopy, ¹H nuclear magnetic resonance (NMR), and ¹³C NMR spectroscopic techniques.     

Fatty acid composition of selected roes from some marine species

Fifteen roes from different marine fish species available in Spain were analyzed in order to determine their fatty acid (FA) composition, especially the eicosapentaenoic acid (20:5n‐3, EPA) and docosahexaenoic acid (22:6n‐3, DHA) contents. Roes from Atlantic bonito (Sarda sarda), European squid (Loligo vulgaris), cuttlefish (Sepia spp.), lumpfish (Cyclopterus lumpus), European hake (Merluccius merluccius), Atlantic salmon (Salmo salar) and gonads of male Atlantic mackerel (Scomber scombrus) reached EPA + DHA amounts higher than 30% of the total FA, and among them, roes from lumpfish, European hake and salmon provide different FA type ratios that could make them adequate as dietary sources of EPA and DHA.