Epoxidizable Fatty Amide–Phenol Conjugates

This paper reports the synthesis of a series of novel compounds where carboxylic acids have been linked to a phenol through amidomethyl units. For instance, one, two, or three fatty acids have been selectively appended to the phenol in yields above 75%. The fatty acid used was oleic acid, which was subsequently epoxidized. Other functional groups, such as amino acids, can be incorporated in these compounds. Examples of monomers that are suitable for polymerization were also prepared: one acrylamide, one styrene derivative, and two types of AB₂ diamino acids, all of which contain oleic units that are sites for epoxidation and crosslinking. Fatty acid aryl ethers were prepared using hydroxy fatty acids. These molecules are intended to serve as augmented analogues of epoxidized vegetable oil. Their amide groups should lead to intermolecular aggregation through hydrogen bonding, and the option to covalently include other functional groups may permit tuning of the macroscopic materials properties of films, coatings, or solids constructed from them.     

Lipid and fatty acid biosynthesis by Rhodotorula minuta

Demand for fatty acids is increasing at an annual rate of 17%, due to their increased use in the oleochemical and transport industries. Presently, vegetable oils are the major source of fatty acids, whereas lipids with fatty acids similar to those of some vegetable oils have been reported to be synthesized by oleaginous microorganisms. In the present study, the culturing conditions for the oleaginous yeast Rhodotorula minuta IIP-33 have been optimized. In contrast to the lipid accumulation characteristics of most oleaginous yeasts, a carbon-to-nitrogen ratio of 30 was favorable for maximal accumulation of lipids (48%) with 22.5% conversion of glucose as carbon substrate. The lipids contained fatty acids in the C₇–C₁₈ range, the relative composition of which varied with culture temperature.     

Synthesis and Surface Active Properties of Sulfonated Acrylate Esters Based on Al‐Cedre Oil

Sulfonated acrylate esters have been synthesized by using renewable raw materials such as fatty alcohols of Al‐Ceder oil. Mixed fatty acids were isolated from Al‐Ceder oil by hydrolysis; both saturated and unsaturated fatty acids were isolated from the mixed fatty acids. The methyl esters of mixed fatty acid, saturated and unsaturated acids of Al‐Cedre oil were subjected to reduction with (LiAlH4) to give the corresponding fatty alcohols. The products of the reduction process were saponified and the hydroxyl values were estimated to further confirm the reduction occurrence. The acrylate esters were synthesized by esterification of acrylic acid with fatty alcohols of C_16:0, C_18:0, C_18:1, and C_18:2 mixed saturated, mixed unsaturated and mixed fatty acids of Al‐Cedre oil, respectively. This esterification was followed by addition of NaHSO₃ to form bisulfite adducts. The structures of the prepared surfactants were characterized by IR and ¹HNMR spectroscopy. A series of useful surface parameters, stability towards acids and base hydrolysis and calcium stability have been determined.     

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.     

Fatty acid desaturase systems of hen liver and their inhibition by cyclopropene fatty acids

Hen liver preparations which desaturate stearic acid at the 9,10 position to form oleic acid have been found to desaturate other saturated fatty acids of carbon chain length from 12 to 20 and 22. The 9,10-monoenoic fatty acid of the same chain length as the substrate fatty acid is the major product formed. Minor amounts of the 10,11- and 11, 12-monoenoic acids are also formed. Maximum desaturation occurred with the C₁₄ fatty acid substrate and with the fatty acids C₁₇ and C₁₈, suggesting the presence of at least two desaturating systems. The cyclopropene fatty acids, sterculic and malvalic acids, inhibited the desaturation of all thefatty acids at the 9,10 position but desaturation at the 10,11 and 11, 12 positions was affected only slightly. The effect is not due to inhibition of the primary activating enzyme, the long chain acyl CoA synthetase. Sterculic acid is a more effective inhibitor than either malvalic acid or sterculyl alcohol, probably because these cyclopropene compounds do not block the desaturating site of the enzyme as completely as sterculic acid.     

The occurrence of methyl methoxystearate isomers in the methyl esters prepared from sheep perinephric fat

A fraction has been isolated from sheep perinephric fat and identified by techniques which included mass and infrared spectrometry, as a mixture of the 8 to 14-methoxyoctadecanoic acid isomers. It is postulated that these isomers are artifacts produced by rigorous esterification with methanol and concentrated H₂SO₄ of a large sample of sheep perinephric fatty acids which are presumed to have contained trace amounts of constituent hydroxy fatty acids. It is estimated that these methoxystearic acid isomers represented approximately 0.08% of the total weight of fatty acids.     

UV-curable hyperbranched urethane acrylate oligomers modified with different fatty acids

The UV-curable hyperbranched urethane acrylate oligomers modified with different fatty acids including undecylenic acid (UCA), myristic acid (MA), and oleic oil (OA) are successfully synthesized in this paper. The prepared oligomers are characterized using FTIR, ¹HNMR, GPC, DSC, and TGA. The properties of the UV-curable films formed by these oligomers are also determined. The effects of the oligomer structures including double bond content, chain length of the modified fatty acids, and content of fatty acid and polyurethane acrylate segment, on the properties of the cured films, which are tack-free time, pencil hardness, impact resistance, adhesion, and boiling water resistance, are discussed in detail. It is observed that the curing film formed by HBPE₂-60%UCA-20%PUA shows the best comprehensive performance among the films prepared in this study.     

The Di- and triesters of the lipids of steer and human meibomian glands

Three groups of diesters have been isolated and identified in the lipids of steer meibomian glands. The first group, designated as α Type I, with the abbreviated formula FA-αOHFA-FA1c, consisted of α-hydroxy fatty acids esterified to fatty acids and fatty alcohols in the approximate molar ratio 1∶1∶1. The second group, designated as ω Type I-St, with the abbreviated formula FA-ωOHF A-St, consisted of ω-hydroxy fatty acids esterified to fatty acids and sterols in the approximate molar ratio 1∶1∶1. The third group, designated as α,ω Type II, with the abbreviated formula FA-α,ωdiol-FA, consisted of α,ω-diols esterified to 2 moles of fatty acids. The sum of the different diesters comprised about 9% of total steer meibomian lipids. Capillary GLC of the fatty acids of αType I diesters showed the fatty acids to be a family with a two-cluster profile, one at C₁₂ to C₂₀ and the other at C₂₁ to C₃₁, with anteiso chains predominating. Fatty acids from ωType I-St and α,ωType II diesters gave mainly a one-cluster profile in the short long chain, C₂₃ to C₃₀, with anteiso chains predominating, while the α-hydroxy fatty acids were short chain C₁₃ to C₁₈ acids with C₁₆ predominating. The sterols in diesters ωType I-St were cholesterol (∼60%), Δ7 cholestenol (∼35%) and an unidentified compound (∼5%) with a GLC retention time slightly longer than Δ7 cholestenol on SE-30 phase. The ω-hydroxy fatty acids and α,ω-diols both were of exceedingly long chain lengths, C₂₉−C₃₈, and showed similar GLC profiles. Two types of triesters comprising approximately 1% of total steer meibomian lipids have been isolated but incompletely characterized. In terms of molar ratios, one group of triesters gave fatty acids:ω-hydroxy fatty acids:α-hydroxy fatty acids:sterols + fatty alcohols as approximately 1∶1∶1∶1. The other contained fatty acids, α-hydroxy fatty acids and α,ω-diols in what appears to be a complex mixture of several triesters. Diesters ωType I and α,ωType II also were found in human meibum. Hitherto these two diesters have not been found in any animal tissue.     

Medium-chain fatty acid-rich glycerides by chemical and lipase-catalyzed polyester-monoester interchange reaction

Medium-chain triglycerides (MCT) that contain caprylic acid (C_8:0) and capric acid (C_10:0) have immense medicinal and nutritional importance. Coconut oil can be used as a starting raw material for the production of MCT. The process, based on the interchange reaction between triglycerides and methyl esters of medium-chain fatty acids by chemical catalyst (sodium methoxide) or lipase (Mucor miehei) catalyst, appears to be technically feasible. Coconut oils with 25–28.3% (w/w) and 22.1–25% (w/w) medium-chain fatty acids have been obtained by chemical and lipase-catalyzed interchange reactions. Coconut olein has also been modified with C_8:0 and C_10:0 fatty acids, individually as well as with their mixtures, by chemical and lipase-catalyzed interchange reactions. Coconut olein is a better raw material than coconut oil for production of mediumchain fatty acid-rich triglyceride products by both chemical and lipase-catalyzed processes.     

Alkyd resins modified with cyclic fatty acids a preliminary evaluation

Alkyd resins were modified to 50% oil length with crude, flash-distilled, and 78% pure cyclic fatty acids. These resins were compared with ones modified with naturally occurring fatty acids and with vegetable oils. Those modified with the cyclic acids process more rapidly than those prepared with linseed, safflower, or soybean fatty acids, and they also have good nonyellowing properties. Resins modified with 78% pure cyclic acids show definite improvement in drying time, hardness, and chemical resistance in air-dried films, and an almost equal improvement in baked films, over resins obtained with the other modifiers. Distilled cyclic acids also improve alkyd resins although not to the extent that pure acids do. Both give resins superior to commercial oil-modified resins under the test conditions. Resins with crude cyclic acids are as good in air-dried films as are the others, but are poorer in baked films. Presented at the American Chemical Society Meeting, St. Louis, Missouri, March 21–30, 1961. A laboratory of the Northern Utilization Research and Development Division. Agricultural Research Service, USDA.     

Segregation of fatty acids by preferential neutralization

Summary It has been shown that soybean fatty acids neutralized with a mixture of 40% of sodium hydroxide and 60% of barium hydroxide (on equivalent basis) form about 35% soluble soaps, which after separating from the insoluble soaps and splitting with sulfuric acid, form fatty acids of about 165 iodine number. From these acids a synthetic drying oil was prepared by esterification with glycerol which formed films almost as good as those of linseed oil. It was also shown that the same process applied to fish oil fatty acids, but using in this case 60% of sodium hydroxide and 40% of barium hydroxide, resulted in a yield of about 50% of fatty acids of about 283 iodine number, which when esterified with glycerol gave a very fast drying synthetic drying oil forming tack-free films. Presented at 22nd fall meeting, American oil Chemists' Society, New York City, Nov. 15–17, 1948.     

Polyunsaturated n−3 fatty acids and the development of atopic disease

The relationship between polyunsaturated long-chain fatty acids and atopy has been discussed for decades. Higher levels of the essential fatty acids linoleic acid and α-linolenic acid and lower levels of their longer metabolites in plasma phospholipids of atopic as compared to nonatopic individuals have been reported by several, but not all, studies. Largely similar findings have been reported in studies of cell membranes from immunological cells from atopics and nonatopics despite differences in methodology, study groups, and definitions of atopy. An imbalance in the metabolism of the n−6 fatty acids, particularly arachidonic acid and dihomo-γ-linolenic acid, leading to an inappropriate synthesis of prostaglandin (PG) E₂ and PGE₁ was hypothesized early on but has not been corroborated. The fatty acid composition of human milk is dependent on the time of lactation not only during a breast meal but also the time of the day and the period of lactation. This explains the discrepancies in reported findings regarding the relationship between milk fatty acids and atopic disease in the mother. Prospective studies show disturbances in both the n−6 and n−3 fatty acid composition between milk from atopic and nonatopic mothers. Only the composition of long-chain polyunsaturated n−3 fatty acids was related to atopic development in the children, however. A relationship between lower levels of n−3 fatty acids, particularly eicosapentaenoic acid (20∶5 n−3), and early development of atopic disease is hypothesized.     

Application of silylation to soaps,alcohols and amines in aqueous solutions

Gas chromatographic analysis of many surfactants has been limited due to tailing and adsorption of the analyte on the stationary phase of the column by polar groups such as hydroxyl and amine functionalities. Silylation of these surfactants reduces these unfavorable interactions by replacement of the active hydrogen with a silyl group Si−(CH₃)₃. Although silylation generally is avoided in aqueious solutions some surfactants have been silylated successfully in aqueous solutions. These include fatty acids and their hydroxamine soaps, fatty and other alcohols, fatty amines, and some inorganic acids. Quantitative results have been confirmed by stoichiometric, gas chromatographic and infrared data.     

Homogeneously catalyzed hydrogenation and gas-liquid chromatographic analysis of the methyl esters of cyclopropene fatty acids

Various concentrations of cyclopropene fatty acids have been determined down to 0.2% by the use of gas liquid chromatographic (GLC) analysis of the methyl esters of fatty acids that have been quantitatively hydrogenated using a homogeneous transition metal complex catalyst. The effectiveness of the use of bromotris(triphenylphosphine)-rhodium(I), Br(P(C₆H₅)₃)₃Rh, as a homogeneous hydrogenation catalyst to convert the cyclopropene ring to a cyclopropane ring has been evaluated and compared with the analogous chloro- and iodo-complexes. The hydrogenation/GLC method of analysis has been compared with the method of titration with hydrogen bromide in benzene and with the method involving the use of high resolution nuclear magnetic resonance (NMR).     

Measurement of the metabolic interconversion of deuterium-labeled fatty acids by gas chromatography/mass spectrometry

An analytical method that was developed to analyze deuterium-labeled fatty acids in human blood has been extended to identify labeled fatty acids from C₁₄ to C₂₄ chain length which are formed by metabolic processes such as desaturation, elongation, or shortening of the labeled fatty acids fed. A new computer and a hard-wave adder have been utilized to assure reliable data acquisition. Relative standard derivations for the analysis of labeled fatty acids were measured at 0.02, 0.03, and 0.04 at the 5%, 1%, and 0.2% levels of the labeled fatty acid methyl esters, respectively. The method makes extensive use of standards and computer processing for accuracy and high productivity. Data from a chylomicron triacylglycerol fraction are included to demonstrate the sensitivity of detection of metabolites formed by desaturation and elongation. The mention of firm names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned.     

Some monomethyl-branched fatty acids from ruminant fats: Open-tubular GLC separations and indications of substitution on even-numbered carbon

Isomeric methyl esters of fatty acids in three groups (C₁₅, C₁₇, C₁₉) have been isolated from ruminant fats. Basic structural analysis by physiochemical techniques indicated that these odd-numbered fatty acids were even chain with a single methyl branch on the chain. High resolution open-tubular gas liquid chromatographic studies indicate that, with the exception of iso acid impurities in these fractions, only even-numbered carbons of the fatty acid chains bear the methyl branch.     

A new concept of cellular uptake and intracellular trafficking of long-chain fatty acids

Fatty acids are the main structural and energy sources of the human body. Within the organism, they are presented to cells as fatty acid: albumin complexes. Dissociation from albumin represents the first step of the cellular uptake process, involving membrane proteins with high affinity for fatty acids, e.g., fatty acid translocase (FAT/CD 36) or the membrane fatty acid-binding protein (FABP_pm). According to the thus created transmembrane concentration gradient, uncharged fatty acids can flip-flop from the outer leaflet across the phospholipid bilayer. At the cytosolic surface of the plasma membrane, fatty acids can associate with the cytosolic FABP (FABP _c ) or with caveolin-1. Caveolins are constituents of caveolae, which are proposed to serve as lipid delivery vehicles for subcellular organelles. It is not known whether protein (FABP _c )- and lipid (caveolae)-mediated intracellular trafficking of fatty acids operates in conjunction, or in parallel. Channeling fatty acids to the different metabolic pathways requires activation to acyl-CoA. For this process, the family of fatty acid transport proteins (FATP 1-5/6) might be relevant because they have been shown to possess acyl-CoA synthetase activity. Their variable N-terminal signaling sequences suggest that they might be targeted to specific organelles by anchoring in the phospholipid bilayer of the different subcellular membranes. At the highly conserved cytosolic AMP-binding site of FATP, fatty acids are activated to acyl-CoA for subsequent metabolic disposition by specific organelles. Overall, fatty acid uptake represents a continuous flow involving the following: dissociation from albumin by membrane proteins with high affinity for fatty acids; passive flip-flop across the phospholipid bilayer; binding to FABP _c and caveolin-1 at the cytosolic plasma membrane; and intracellular trafficking via FABP _c and/or caveolae to sites of metabolic disposition. The uptake process is terminated after activation to acyl-CoA by the members of the FATP family targeted intracellularly to different organelles.     

Fatty acids from the scent glands of the Louisiana muskrat

1. The mixture of fatty acids from muskrat scent glands has been analyzed by the ester fractionation method.
2. The esters of myristic, palmitic, hexadecenoic, oleic, and linoleic acids were found present as major components in these glands. Unsaturated acids of the C₂₄ and C₂₆ series are also present to the extent of 8.5% of the total fatty acids. Acids present to less than 1% each include decanoic, dodecanoic, stearic, tetracosanoic, dodecenoic, and tetradecenoic acids.
3. Application of determinants for the solution of simultaneous equations has been presented as a method which greatly simplifies and facilitates the calculations necessary to this type of work.
4. The possible relationship existing between fatty acids and macrocyclic carbinols has been considered and possible mechanisms for such transformations have been presented.

     

Polarized infrared spectra of some crystalline fatty acids

Summary Polarized infrared spectra of thin films of representative samples of form C′, B′, and A′ n-alkyl monocarboxylic acids have been observed. The data obtained on C′ heptadecanoic acid confirm that the type C and type C′ structures are very similar and that the major difference is in the packing of the CH₃ end-groups. The results on type B′ and A′ acids indicate that meaningful polarization data can be obtained on triclinic crystals of n-alkyl carboxylic acids, provided that careful consideration is given to the sample orientation and to the symmetry characteristics of certain portions of the molecules. The P₁ space structure of these crystals and the orthorhombic substructure of the B′ configuration as well as the triclinic substructure of the A′ configuration were confirmed. Some strong infrared bands of the highly irregular triclinic A′ structure did not seem to be appreciably polarized. The data on group-frequency bands which did show clear-cut polarization were in agreement with prediction. The spectra of form A′, B′, and C′ crystals did not coineide with data obtained on KBr pellets. It is concluded that in these pellets fatty acids exist in a form which is not easy to duplicate under more conventional conditions. Eastern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

The electrochemical hydrogenation of edible oils in a solid polymer electrolyte reactor. I. Reactor design and operation

A new electrochemical method has been devised and tested for the moderate temperature/atmospheric pressure hydrogenation of edible oils, fatty acids, and fatty acid methyl esters. The method employed a solid polymer electrolyte (SPE) reactor, similar to that used in H₂/O₂ fuel cells, with water as the source of hydrogen. The key component of the reactor was a membrane-electrode-assembly, composed of a RuO₂ powder anode and either a Pt-black or Pd-black powder cathode that were hot-pressed as thin films onto the opposing surfaces of a Nafion cation-exchange membrane. During reactor operation at a constant applied current, water was back-fed to the RuO₂ anode, where it was oxidized electrochemically to O₂ and H⁺. Protons migrated through the Nafion membrane under the influence of the applied electric field and contacted the Pt or Pd cathode, where they were reduced to atomic and molecular hydrogen. Oil was circulated past the back side of the cathode and unsaturated triglycerides reacted with the electrogenerated hydrogen species. The SPE reactor was operated successfully at a constant applied current density of 0.10 A/cm² and a temperature between 50 and 80°C with soybean, canola, and cottonseed oils and with mixtures of fatty acids and fatty acid methyl esters. Reaction products with iodine values in the range of 60–105 were characterized by a higher stearic acid content and a lower percentage of trans isomers than those produced in a traditional hydrogenation process.