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.     

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.     

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.     

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.     

New fatty acids from outer space

A recent space exploration has revealed that in the far reaches of outer space matter attains a state of complete weightlessness. Herman Brown, reporting on his latest spaced-out venture, indicates that weightless fatty acids obtained from the Superba Galaxy are ideally suited for the manufacture of improved food additives. What a magnificent way to provide the diet-control foodstuffs of the 21st Century!     

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.     

2-Hydroxy fatty acids from marine sponges 2. The phospholipid fatty acids of the caribbean spongesVerongula gigantea andAplysina archeri

The α-hydroxy fatty acids 2-hydroxy-eicosanoic (1) acid, 2-hydroxyheneicosanoic (2) acid, 2-hydroxydocosanoic (3) acid, 2-hydroxytetracosanoic (4) acid, 2-hydroxy-23-methyl-tetracosanoic acid and 2-hydroxypentacosanoic (5) acid were isolated from the Caribbean spongesVerongula gigantea andAplysina archeri. The very long chain fatty acids 5,9-nonacosadienoic acid (29∶2) and 5,9,23-tricontatrienoic acid (30∶3) were also identified together with theiso-prenoid fatty acid 3,7,11,15-tetramethylhexadecanoic (phytanic) acid that seems to be common in the Aplysinidae.A. archeri contained an extremely long chain fatty acid tentatively characterized as dotricontaenoic (32∶1) acid. These acids were found to occur in phosphatidylserine, phosphatidylinositol, phosphatidylethanolamine, phosphatidylcholine and traces of phosphatidylglycerol.     

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.     

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.     

New cyclopentenone fatty acids formed from linoleic and linolenic acids in potato

[1-¹⁴C]Linoleic acid was incubated with a whole homogenate preparation from potato stolons. The reaction product contained four major labeled compounds, i.e., the α-ketol 9-hydroxy-10-oxo-12(Z)-octadecenoic acid (59%), the epoxy alcohol 10(S),11(S)-epoxy-9(S)-hydroxy-12(Z)-octadecenoic acid (19%), the divinyl ether colneleic acid (3%), and a new cyclopentenone (13%). The structure of the last-mentioned compound was determined by chemical and spectral methods to be 2-oxo-5-pentyl-3-cyclopentene-1-octanoic acid (trivial name, 10-oxo-11-phytoenoic acid). Steric analysis demonstrated that the relative configuration of the two side chains attached to the five-membered ring was cis, and that the compound was a racemate comprising equal parts of the 9(R), 13(R) and 9(S), 13(S) enantiomers. Experiments in which specific trapping products of the two intermediates 9(S)-hydroperoxy-10(E), 12(Z)-octadecadienoic acid and 9(S), 10-epoxy-10, 12(Z)-octadecadienoic acid were isolated and characterized demonstrated the presence of 9-lipoxygenase and allene oxide synthase activities in the tissue preparation used. The allene oxide generated from linoleic acid by action of these enzymes was further converted into the cyclopentenone and α-ketol products by cyclization and hydrolysis, respectively. Incubation of [1-¹⁴C]linolenic acid with the preparation of potato stolons afforded 2-oxo-5-[2′(Z)-pentenyl]-3-cyclopentene-1-octanoic acid (trivial name, 10-oxo-11, 15(Z)-phytodienoic acid), i.e., an isomer of the jasmonate precursor 12-oxo-10, 15(Z)-phytodienoic acid. Quantitative determination of 10-oxo-11-phytoenoic acid in linoleic acid-supplied homogenates of different parts of the potato plant showed high levels in roots and stolons, lower levels in developing tubers, and no detectable levels in leaves.     

Remodeling of phospholipid fatty acids in mitochondrial membranes of estivating snails

The effects of estivation on the phospholipid-specific fatty acid composition of mitochondrial membranes in the hepatopancreas of the terrestrial snail Cepaea nemoralis were investigated. The fatty acid composition of all phospholipids was significantly altered in snails estivating for 6 wk, indicating that substantial remodeling occurs. The most profound changes occurred in cardiolipin (CL). CL of estivating snails was 13-fold more saturated, contained 9-fold more monoenes, and had 45% fewer polyenes than in active snails. These differences were due, in part, to a reduction in linoleic acid (18:2n-6) content of CL from estivators. As in mammals, CL of active snails appears to preferentially incorporate 18:2n-6, which accounts for 60% of the acyl chains in this phospholipid. This proportion was reduced by 50% in estivators. Changes in the fatty acyl content of other phospholipids of estivating snails included increased monoenes in phosphatidylethanolamine (PE) and phosphatidylinositol, reduced ratios of n-3/n-6 polyenes in PE and phosphatidylcholine (PC), and an increased n-3/n-6 ratio in phosphatidylserine (PS). Arachidonic acid (20:4n-6) levels were reduced in PS but increased in CL and PC. Taken together, these alterations to fatty acid composition are consistent with decreased biological activity of membrane-related processes which occur in conjunction with the reduction of mitochondrial aerobic metabolism observed during estivation.     

New additives derived from fatty acids for water-based cutting fluids

A variety of derivatives from long chain fatty acids were prepared, and corrosion and lubricity tests for these products as water-based cutting fluid additives were carried out. We have found that triethanolamine salts of 11-(carboxymethylthio)-undecanoic acid (II), 10,11-dichloromethylene undecanoic acid (IV) and 12-isovaleroyloxy stearic acid (VI) showed effective rust-inhibiting and anti-wear properties for water-based cutting fluids.     

Production of fatty alcohols from fatty acids

Detergent-range alcohols from natural feedstock can be produced by high pressure hydrogenation of either methyl esters or fatty acids. The increasing quantities of fats and oils on the world market secure a reliable and economically priced material. Although fatty acid is an abundant worldwide commodity, most alcohol producers hydrogenate methyl esters, because direct hydrogenation of fatty acids is difficult as the catalyst is sensitive to acid attack. The process described here makes it possible to hydrogenate fatty acids directly to alcohols of high quality without prior esterification. The reaction takes place in the liquid phase over a fine-grained copper chromite slurry in a single reactor vessel. A special reactor design with an optimum arragement of the feeding nozzles causing an appropriate circulation of the reacting components inside the reactor facilitates the rapid “in situ” esterification reaction. This minimizes the free fatty acid concentration in the reactor to nearly zero. This results in a low consumption of catalyst. The most important advantages of the process are: direct feed of fatty acids of various origins, use of reasonably priced raw materials such as soapstock fatty acids and lower grade tallow acids, no process steps with methanol, and excellent economics. The process is industrially proven.     

New developments in synthetic fatty acids

New developments in synthetic fatty acids have occurred in the last few years in Russia, Japan, the United States and Canada. In 1959 Russia decided to replace 40% of natural fatty acids in soaps with synthetic fatty acids. In 1966, 548 million pounds of C₅–C₃₀ synthetic fatty acids were produced including 288 million pounds of C₁₀–C₂₀ fatty acids. Forty million pounds of fatty acids are converted directly to the fatty alcohols for detergent use. A conservative estimate predicts that one billion pounds of synthetic fatty acids will be produced in Russia by the end of the current five-year program. Reports say that the Japanese have been interested in the oxidation of not only paraffin hydrocarbons but naphthenic petroleum hydrocarbons as well. Production of lower homology fatty acids up to butyric acid is being seriously considered in Japan. In America the most likely syntheses aside from “oxo” syntheses being considered for the manufacture of products like lauric acid is the carboxylation of the Ziegler intermediates prepared from ethylene polymerization. Some data on the current and future coconut oil consumption by major end-use for Canada and the United States are presented. Synthetic lauric acid is predicted for 1970 in the United States. Prepared from an address given at a meeting of the Northeast Section, New York, June 1968.     

Synthesis of phospholipids and phospholipid fatty acids by isolated perfused rat lung

Synthesis of phospholipids and phospholipid fatty acids in isolated perfused rat lung was studied. The perfusion fluid was a Krebs-Ringer bicarbonate buffer containing a¹⁴C labeled substrate. It was found that 1-¹⁴C-acetate, 1-¹⁴C-laurate, 1-¹⁴C-palmitate, 1-¹⁴C-stearate, 1-¹⁴C-oleate, or U-¹⁴C-D-glucose was incorporated into tissue lipids in the isolated perfused lung at a rate geeater than that in incubated minced tissue. However, the patterns of the newly synthesized lipids from these two systems were similar. In 1 hr of perfusion, 6.8, 3, 14.5, 7.5, 7, and 2% of the initial¹⁴C-radioactivity of 1-¹⁴C-acetate, 1-¹⁴C-laurate, 1-¹⁴C-palmitate, 1-¹⁴C-stearate, 1-¹⁴C-oleate, and U-¹⁴C-D-glucose, respectively, were incorporated into phospholipids. Phospholipid fatty acids accounted for 95–96% total phospholipids-¹⁴C when¹⁴C-substrates, other than glucose, were used. For glucose, only 20% phospholipids-¹⁴C was in phospholipid fatty acids. More than 80% phospholipid fatty acids-¹⁴C was in palmitic acid when 1-¹⁴C-acetate and U-¹⁴C-D-glucose were used, while 37, 61, 80, and 94% phospholipid fatty acid-¹⁴C from 1-¹⁴C-laurate, 1-¹⁴C-sterate, 1-¹⁴C-oleate, and 1-¹⁴C-palmitate, respectively were recovered in the original form of the fatty acid used. The newly synthesized phospholipid fatty acid (13–24%) from 1-¹⁴C-laurate, 1-¹⁴C-stearate, and 1-¹⁴C-oleate was palmitic, and 10% of phospholipid fatty acid from 1-¹⁴C-stearate was in oleic acid. Hydrolysis by phospholipase A showed that¹⁴C from perfused substrates was esterified to both α and β positions of phospholipids. It was found that positional selectivity of phospholipid fatty acids was determined by chain length, degree of unsaturation, and source of fatty acid.     

Estolides from meadowfoam oil fatty acids and other monounsaturated fatty acids

The formation of estolides was detected during the studies on dimerization of meadowfoam oil fatty acids. By adjusting the reaction conditions, it was possible to produce monoestolides with little dimer or trimer formations. Estolides have potential use in lubricant, cosmetic and ink formulations and in plasticizers. This paper reports the conditions for production of estolides from mixed meadow-foam fatty acids, commercial oleic acid, high-oleic sun-flower oil fatty acids,cis-5,cis-13-docosadienoic acid, petroselinic acid and linoleic acid.     

Dietary fish oil dose-response effects on ileal phospholipid fatty acids and contractility

We have reported that dietary fish oil (FO) leads to the incorporation of long-chain n−3 PUFA into the gut tissue of small animal models, affecting contractility, particularly of rat ileum. This study examined the FO dose response for the incorporation of n−3 PUFA into ileal tissue and how this correlated with in vitro contractility. Groups of ten to twelve 13-wk-old Wistar-Kyoto rats were fed 0, 1, 2.5, and 5% FO-supplemented diets balanced with sunflower seed oil for 4 wk, after which ileal total phospholipid FA were determined and in vitro contractility assessed. For the total phospholipid fraction, increasing the dietary FO levels led to a significant increase first evident at 1% FO, with a stepwise, nonsaturating six-fold increase in n−3 PUFA as EPA (20∶5n−3), DPA (docosapentaenoic acid, 22∶5n−3), and DHA, but mainly as DHA (22∶6n−3), replacing the n−6 PUFA linoleic acid (18∶2n−6) and arachidonic acid (20∶4n−6) over the dosage range. There was no difference in KCl-induced depolarization-driven contractility. However, a significant increase in receptor-dependent maximal contractility occurred at 1% FO for carbachol and at 2.5% FO for prostaglandin E₂, with a concomitant increase in sensitivity for prostaglandin E₂ at 2.5 and 5% FO. These results demonstrate that significant increases in ileal membrane n−3 PUFA occurred at relatively low doses of dietary FO, with differential receptor-dependent increases in contractility observed for muscarinic and prostanoid agonists.     

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.     

Cyclic fatty acids: Separation from straight-chain fatty acids by urea adducting

A mixture containing 37% cyclic and 63% straight-chain fatty acids, made by high-temperature treatment of linseed oil fatty acids with alkali, was separated by the urea adduct method to give unsaturated cyclic fatty acids (nonadduct) in 95% purity and 90–95% yeild. Previous reports from this Laboratory describe a process for separating cyclic fatty acids from stearic acid by hydrogenation followed by crystallization at −40C. The urea adduct method avoids hydrogenation and low-temperature crystallization, and furthermore, unsaturated cyclic and unsaturated straight-chain products can be recovered as individual fractions. Then, by readducting the unsaturated straight-chain fatty acid fraction, the small amounts of palmitic and stearic acids are removed leaving an unsaturated fraction containing oleic, nonconjugated and conjugated linoleic and some unsaturated cyclic fatty acids. Presented at AOCS Meeting, Los Angeles, April 1966. No. Utiliz. Res. Dev. Div., ARS, USDA.