Two novel phospholipid fatty acids from the caribbean spongeGeodia gibberosa

The novel fatty acids (Z)-6-nonadecenoic acid (1) and (Z)-17-pentacosenoic acid (2) were characterized in the spongeGeodia gibberosa. These fatty acids were mainly found in phosphatidylethanolamine and phosphatidylcholine.     

Isoprenoid fatty acids from marine sponges. Are sponges selective?

The burrowing spongesAnthosigmella varians andSpheciospongia vesparium were found to be rich in the isoprenoid phospholipid fatty acid 4,8,12-trimethyltridecanoic (5.2% and 23%, respectively, of the total fatty acid composition), while the burrowing spongeChondrilla nucula and the demospongeAgelas dispar contained the acid 3,7,11,15-tetramethylhexadecanoic (13.8% and 8.6%, respectively, of the total phospholipid fatty acid composition). No other isoprenoid fatty acid was found, and the two acids described in this work did not occur concomitantly in the same sponge.     

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.     

New phospholipid fatty acids from the marine spongeCinachyrella alloclada uliczka

The fatty acid composition of phospholipids from the Senegalese spongeCinachyrella alloclada was examined. Two new fatty acids not hitherto found in nature, namely 10,13-octadecadienoic acid and 16-tricosenoic acid, were identified. 8-Hexadecenoic, 13-nonadecenoic and 5,9,13-trimethyltretradecanoic fatty acids were also found for the first time in sponges. The latter compound (1.4% of the total fatty acid mixture), an isoprenoid fatty acid, accompanies the major fatty acid 4,8,12-trimethyltridecanoic acid (19.7%). The monomethyl branched fatty acids (22%) identified include 23-methylpentacosanoic acid (anteiso-26∶0), not previously observed in sponged. The major long-chain fatty acids encountered were the known 17-tetracosenoic 19-heptacosadienoic and 5,9,23-tricontatrienoic acid. Some sixty fatty acids were identified as methyl esters andN-acyl pyrrolidides by gas chromatography and gas chromatography/mass spectrometry.     

Two novel naturally occurring α-methoxy acids from the phospholipids of two caribbean sponges

The novel (5Z)-2-methoxy-5-hexadecenoic acid (1) was identified in the phospholipids of the spongeTethya crypta while the also novel acid (6Z)-2-methoxy-6-hexadecenoic acid (2) was found in the phospholipids of the Caribbean spongeSpheciospongia cuspidifera. The methoxy-fatty acids were mainly associated with phosphatidylethanolamine. The double bond positions were determined by gas chromatography/mass spectrometry on the corresponding dimethyl-disulfide adducts and the double bond stereochemistry was ascertained by gas chromatography/Fourier transform infrared spectroscopy. The fatty acid composition of the two sponges is reported.     

Novel brominated phospholipid fatty acids from the Caribbean spongeAgelas sp.

The very long-chain fatty acids, (5E,9Z)-6-bromo-5,9-tetracosadienoic, (5E,9Z)-6-bromo-23-methyl-5,9-tetracosadienoic, (5E,9Z)-6-bromo-5,9-pentacosadienoic and (5E,9Z)-6-bromo-24-methyl-5,9-pentacosadienoic acids, were identified in the phospholipids (mainly phosphatidylethanolamine) of the spongeAgelas sp. Structure elucidation was accomplished by means of mass spectrometry and chemical transformations, including deuteration with Wilkinson's catalyst. All of the sterols from the sponge had the Δ5,7 nucleus, with 24-methylcholesta-5,7,22-trien-3β-ol (ergosterol) and 24-ethylcholesta-5,7,22-trien-3β-ol being the most abundant.     

Phospholipid studies of marine organisms: III. New phospholipid fatty acids fromPetrosia ficiformis

The fatty acyl components of the phospholipids from the spongePetrosia ficiformis consisted predominantly of branched, especially iso and anteiso acids. The two major components of the complex mixture are the hitherto unknown Z,Z-25-methyl-5,9-hexacosadienoic and Z,Z-24-methyl-5,9-hexacosadienoic acids. Other unknown acids are: 7,13,16-docosatrienoic acid, 15-methyldocosanoic acid, 15-methyltricosanoic acid and 24-methyl-5,9-pentacosadienoic acid. Short branched-chain fatty acids, presumably of bacterial origin, are considered to be the possible bioprecursors of these novel phospholipid constituents. The major phospholipids were PE, PC, PG, PS and PI. The distribution of fatty acids among the phospholipid classes was also studied.     

The rare caribbean spongeLeucosolenia canariensis: Phospholipid fatty acids and sterols

The phospholipid fatty acid composition of the Calcarean spongeLeucosolenia canariensis was studied, and no Δ^5,9 fatty acids were detected. These results are in contrast to the phospholipids from sponges belonging to the class Demospongiae where Δ5,9 fatty acids are predominant. Odd branched-chain fatty acids between 17 and 19 carbons accounted for 26% of the total fatty acids ofL. canariensis, while straight-chain fatty acids between 16 and 22 carbons accounted for 61% of the total fatty acid composition. The sterol composition ofL. canariensis is also reported, and only Δ^5,7,22 sterols were observed.     

New phospholipid fatty acids from the Caribbean spongeEctyoplasia ferox

The phospholipid fatty acids from the Caribbean spongeEctyoplasia ferox were studied. The novel fatty acids 25-methyl-5,9-heptacosadienoic (1) and 26-methyl-5,9-heptacosadienoic (2) were identified in 3.4 and 2.0% abundance, respectively, representing the longest set of Δ5,9iso andanteiso acids yet isolated from a marine sponge. The new acid 10,13-dimethyltetradecanoic (3), the unusual acid 15-methyl-11-hexadecenoic (4) and the also novel acid 9-methyl-11-hexadecenoic (5) were also identified inE. ferox. The principal sterols isolated fromE. ferox were 24-ethylcholest-5-en-3β-ol (46%) and 24(R)-methylcholesta-5,22-dien-3β-ol (14%).     

The origin of the marine polyunsaturated fatty acids. Composition of some marine plankton

Summary and Conclusions Shrimp, crabs, the marine diatomNitzschia closterium, Platymonas sp., and the fresh water algaChlorella pyrenoidosa were maintained or cultured in the laboratory. The crustacea were fed low-fat, cottonseed oil, and menhaden oil rations. The fatty acid composition of all groups, as well as that of native phytoplankton and zooplankton catches, were determined as the extinction coeffcients, (E _1% ^1cm. ), at wavelengths of maximum absorption. It was found that both shrimp and crabs lost much of their polyunsaturated acids on the fat-free diet and regained it again by ingestion, as do fish. The shrimp however appeared to synthesize more highly unsaturated acids from cottonseed oil than did other aquatic animals. Phytoplankton do produce a high level of polyunsaturated fatty acids. The importance of the determination of the structure of aquatic plant and animal fatty acids in the problem of the origin of the acids and their mechan ism of synthesis was discussed. Contribution from the Departments of Oceanography and Meteorology and of Biochemistry and Nutrition of the Agricultural and Mechanical College System of Texas, Oceanography and Meteorology Series No. 137; supported in part by Grant No. A-777 from the National Institutes of Health and Grant No. A-020 from the Robert A. Welch Foundation.     

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.     

The effects of partially hydrogenated marine oils on the mitochondrial function and membrane phospholipid fatty acids in rat heart

The influence of dietary partially hydrogenated marine oils containing docosenoic acid on rat heart mitochondrial membrane phospholipid fatty acid composition was studied with particular reference to cardiolipin and oxidative phosphorylation. Five groups of male weanling rats were fed diets containing 20% (w/w) peanut oil (PO), partially hydrogenated peanut oil (HPO), partially hydrogenated Norwegian capelin oil (HCO), partially hydrogenated herring oil (HHO), and rapeseed oil (RSO) for 10 weeks. All the cardiac phospholipids investigated were influenced by the experimental diets. An increased amount of arachidonic acid observed in phosphatidylethanolamine (PE) after feeding partially hydrogenated oils suggests a changed regulation of the arachidonic acid metabolism in comparison with PO treatment. 22∶1 originating from the dietary oils was incorporated only to a small extent into phosphatidylcholine (PC) and PE. A selective incorporation of 18∶1 isomers into the 1- and 2-positions of PC and PE with respect to geometry and position of the double bond was observed. Large amounts of 18∶1trans were incorporated into the 1-position of PC and PE, irrespective of the amount of 18∶2 supplemented to the diets, replacing a considerable proportion of stearic acid in this position. After feeding HHO and RSO, the content of 22∶1 in mitochondrial cardiolipin of rat heart was found to be 3% (mainly cetoleic acid) and 10% (mainly erucic acid), respectively, indicating a high affinity forcis isomers of 22∶1, but also a considerable resistance against incorporation oftrans isomers was observed. The ability of rat cardiac mitochondria to oxidize palmitoylcarnitine and to synthesize ATP was depressed after feeding HHO and RSO. Dietarycis isomers of 22∶1 seem to have a specific ability to interfere with cardiac ATP synthesis and also to alter the fatty acid composition of cardiolipin of rat heart.     

Linking chemical and microbial diversity in marine sponges: possible role for poribacteria as producers of methyl-branched fatty acids

Many marine sponges contain massive numbers of largely uncultivated, phylogenetically diverse bacteria that seem to be important contributors to the chemistry of these animals. Insights into the diversity, origin, distribution, and function of their metabolic gene communities are crucial to dissect the chemical ecology and biotechnological potential of sponge symbionts. This study reveals a sharp dichotomy between high and low microbial abundance sponges with respect to polyketide synthase (PKS) gene content, the presence of methyl-branched fatty acids, and the presence of members of the symbiotic candidate phylum "Poribacteria". For the symbiont-rich sponge Cacospongia mycofijiensis, a source of the tubulin-inhibiting fijianolides (=laulimalides), near-exhaustive large-scale sequencing of PKS gene-derived PCR amplicons was conducted. Although these amplicons exhibit high diversity at the sequence level, almost all of them belong to a single, architecturally unique group of PKSs present in "Poribacteria" and are proposed to synthesize methyl-branched fatty acids. Three components of this PKS were studied in vitro, providing initial insight into its biochemistry.     

Localization of a source of marine odd chain-length fatty acids. II. Seasonal propagation of odd chain-length monoethylenic fatty acids in a marine food chain

The unusual occurrence of elevated levels of odd chain length fatty acids (OCFA) in smelt taken during winter months in Jeddore Harbour, Nova Scotia, is due to the dietary intake of large numbers of the amphipodPontoporeia femorata (Kröyer). Sampling over two winters confirms that the seasonal peak period for this amphipod, in stomachs is mid-December to the end of February. The distributions of monoethylenic isomers are compared to distinguish exogenous and endogenous smelt dietary features in terms of the geographically limited phenomenon of high OCFA levels and the essential absence of biological activity for these acids.     

The separation of solid fatty acids from liquid fatty acids by the formation of acid soaps. I. Tallow soaps

The formation of acid soaps has been used successfully for the separation of a mixture of fatty acids into high and low iodine value fractions. The acid soaps of saturated acid can be made to crystallize from water leaving their unsaturated counter parts in solution. Acid soaps of saturated fatty acids are well characterized compounds with the formula R-COOM.R-COOH, where R is a straight alkyl chain, and M is sodium, potassium or ammonium. Optimum crystallization conditions involve a soap concentration of 2–5%, pH adjustment to between 7.0 and 8.0, an initial crystallization temperature not below 25C, and a crystallization period of at least 4 hr during which time cooling to a final temperature of 5–10C must be gradual, and agitation gentle.     

Temperature acclimation in the crayfish: Effects on phospholipid fatty acids

Acclimation to different temperatures by a poikilothermous animal must include modification of its membrane lipids to maintain the proper physical properties. The simplest way to achieve this acclimation would seem to be by modification of the phospholipid fatty acids. In a freshwater cray-fish,Procambarus clarkii, rapid changes in the degree of unsaturation of newly synthesized phospholipid fatty acids were correlated with changes in environmental temperature, both in whole animals and in slices of hepatopancreas tissue. At 5 C, the rate of fatty acid synthesis was about half that occurring at 23 C. Hepatopancreas tissue from animals acclimated to either 5 C or 23 C, when incubated for 2 hr at 5 C, incorporated a higher percentage of exogenous [1-¹⁴C] acetate into polyunsaturated acids (27–38% of the radioactivity in total fatty acids) than when incubated at 23 C (12–14%); conversely, more saturated fatty acids were synthesized at 23 C (73–80% vs 51–73%). The higher average unsaturation of the fatty acids biosynthesized at 5 C constitutes an effective response to the animal's need for modification of lipids to maintain adequate membrane function at the lower environmental temperature. Presented at the AOCS meeting in Mexico City, Mexico, April 27–May 2, 1974. Work done at the Laboratory of Nuclear Medicine and Radiation Biology, University of California, Los Angeles, CA 90024.     

GC-MS structural characterization of fatty acids from marine aerobic anoxygenic phototrophic bacteria

The FA composition of 12 strains of marine aerobic anoxygenic phototrophic bacteria belonging to the genera Erythrobacter, Roseobacter, and Citromicrobium was investigated. GC-MS analyses of different types of derivatives were performed to determine the structures of the main FA present in these organisms. All the analyzed strains contained the relatively rare 11-methyloctadec-12-enoic acid, and three contained 12-methyl-octadec-11-enoic acid, which has apparently never been reported before. High amounts of the very unusual octadeca-5,11-dienoic acid were present in 9 of the 12 strains analyzed. A FA containing a furan ring was detected in three strains. Analytical data indicated that this FA was 10,13-epoxy-11-methyloctadeca-10,12-dienoic acid. A very interesting enzymatic peroxidation of the allylic carbon 10 of cis-vaccenic acid was observed in three strains. Deuterium labeling and GC-MS analyses enabled us to demonstrate that this enzymatic process involves the initial dioxygenase-mediated formation of 10-hydroperoxyoctadec-11(cis)-enoic acid, which is then isomerized to 10-hydroperoxyoctadec-11(trans)-enoic acid and converted to the corresponding hydroxy-acids and oxoacids. Different biosynthetic pathways were proposed for these different compounds.     

Component fatty acids of marine fish liver oils

Summary 1. Two liver oils (Elasmobranch) fromCarcharias melanopterus andPristis cuspidatus, caught off the Madras coast are studied, and their component fatty acids are reported. 2. The mixed acids were separated into three groups (varying unsaturation) of acids, and their methylesters were fractionated. 3. The liver oils are found to belong to the fourth group of Tsujimoto’s classification of Elasmobranch fish liver oils.Carcharias melanopterus liver oil contains 31.1% unsaturated acids (myristic 3.1, palmitic 18.4, stearic 9.5, and 0.1% arachidic) and 68.9% unsaturated acids (C₁₆ 10.8, C₁₈ 19.7, C₂₀ 15.2, C₂₂ 17.1, C₂₄ 5.3%, and traces of C₁₄ monoethenoid).Pristis cuspidatus liver oil contains 36.9% saturated acids (myristic 1.2, palmitic 22.9, stearic 12.7, and arachidic 0.1%) and 67.1% unsaturated acids (C₁₆ 8.2, C₁₈ 28.5, C₂₀ 16.4, C₂₂ 5.2, C₂₄ 4.6%, and traces of C₁₄ monoethenoid). The unsaturations of the different groups of acids are almost of the same order. 4. The abnormal content of saturated acids can be explained by the process of bio-hydrogenation. The relatively less amount of saturated acids inCarcharias melanopterus liver oil along with its higher content of polyethylenic acids (C₂₀ and above) points strongly to the possible presence of intermediate types of fats among the four groups of Elasmobranch oils.     

Isolation of brominated long-chain fatty acids from the phospholipids of the tropical marine spongeAmphimedon terpenensis

Preliminary investigation of the phospholipid fatty acid composition of the tropical marine spongeAmphimedon terpenensis by gas chromatography/mass spectrometry revealed the presence of some novel brominated fatty acids. Two new brominated fatty acids, (5E, 9Z)-6-bromo-5,9-tetracosadienoic acid (2a) and (5E, 9Z)-6-bromo-5,9-pentacosadienoic acid (3a) were subsequently isolated from a chloroform/methanol (3∶1, vol/vol) extract of the sponge and characterized as their methyl esters 2b and 3b. The known brominated fatty acid (5E, 9Z)-6-bromo-5,9-hexacosadienoic acid (4a) was also isolated. The new fatty acid methyl esters were confirmed as brominated δ5,9 acid derivatives by chemical ionization mass spectrometry. The position of the bromine substituent was determined to be C-6 by nuclear magnetic resonance techniques while the stereochemistry of the two double bonds was deduced by nuclear Overhauser enhancement difference spectroscopy. The biosynthetic implications of the co-occurrence of the three brominated acids are discussed.     

15,18,21,24-triacontatetraenoic and 15,18,21,24,27-triacontapentaenoic acids: New C30 fatty acids from the marine spongeCliona celata

The marine sponseCliona celata contains 3.5% 30∶4ω6 and 7.0% 30∶5w3 in its total fatty acids. These C₃₀ polyunsaturated structures are unknown in other living organisms. Both acids occur mainly as phosphatidylserine esters.