The freeze fracture ultrastructure of peanut oil and other natural and synthetic triacylglycerol droplets

The freeze fracture morphology of some emulsified natural and synthetic triacylglycerol oils was examined. Emulsions were frozen by two methods, immersion in liquid melted Freon 22 (rate ～ 100 K/ sec) or by a jet of liquefied propane (rate ～ 10,000 K/sec). Emulsion droplets appeared spherical regardless of freezing method. Droplets frozen with propane appeared featureless in cross-fracture and demonstrated smooth cores regardless of oil type. Those frozen by immersion possessed cores exhibiting lamellae embedded in an amorphous matrix. Pure unsaturated oils such as triolein appeared structureless regardless of freezing rate, whereas natural oils exhibited characteristic morphologies which were partially related to their saturated fatty acid content. Immersion frozen peanut oil possessed, in addition to interior laminations, distinct surface laminations regardless of droplet size, emulsion preparation technique or buffer pH. The laminations were 100 Å thick and extended 3–15 layers deep into the droplet and were caused by long chain C₂₀, C₂₂ and C₂₄ fatty acids. Six kinds of peanut oil were examined and their droplet surface laminations could be grouped into three structural classes. There was no correlation between structural features of the peanut oils and their atherogenicity. The type of surface lamination that a peanut oil exhibited appeared to be related to its ratio of oleic to linoleic acid. The cryoprotectant glycerol was soluble in olive oil to < 0.1% and produced no morphological alterations of the droplet.     

Acylglycerol structure of genetic varieties of peanut oils of varying atherogenic potential

Detailed investigation was made of the triacylglycerol structure of three varieties of peanut oils of varying atherogenic activity. By means of chromatographic and stereospecific analyses, it was shown that all the oils had markedly nonrandom enantiomeric structures with the long chain saturated fatty acids (C₂₀−C₂₄) confined exclusively to thesn-3-position, whereas the palmitic and oleic acids were distributed about equally between thesn-1-andsn-3-positions, with the linoleic acid being found preferentially in thesn-2-position. On the basis of detailed studies of the molecular species of the separatesn-1,2-,sn-2,3- andsn-1,3-diacylglycerol moieties, it was concluded that the fatty acids in the three positions of the glycerol molecule are combined with each other solely on the basis of their relative molar concentrations. As a result, it was possible to calculate the composition of the molecular species of the peanut oil triacylglycerols (including the content of the enantiomers and the reverse isomers) by means of the 1-random 2-random 3-random distribution. In general, the three peanut oils possessed triacylglycerol structures which where closely similar to that derived earlier for a commercial peanut oil of North American origin. Since their oil has exhibited a high degree of atherogenic potential, it was anticipated that the present oils would likewise be atherogenic, which has been confirmed by biological testing. However, there are certain differences in the triacylglycerol structures among these oils, which can be correlated with the variations in their atherogenic activity. The major differences reside in the linoleic/oleic acid ratios in the triacylglycerols, especially in thesn-2-position, and in the proportions in which these acids are combined with the long chain fatty acids. On the basis of the characteristic structures identified in the earlier analyzed atherogenic peanut oil, the peanut oil of South American origin would be judged to possess the greatest atherogenic potential and this has been borne out by biological testing.     

Oil Content,Oil Yield and Fatty Acid Profile of Groundnut Germplasm in Mediterranean Climates

A high amount of good-quality vegetable oil in seeds has an overwhelming contribution to the groundnut (Arachis hypogaea L.) cultivation throughout the world. In order to take into account great variation in oil characteristics in Arachis subspecies and botanical varieties, 256 groundnut genotypes including ICRISAT’s mini core collection were investigated. Significant variability in oil content (31.7–57.0%) was detected among groundnut genotypes. Oil yield varied from 9.5 to 179.3 kg da^?1 with the average being 67.7 kg da^?1. Significant genotypic differences were also observed for all the fatty acids studied. Oleic and linoleic acids accounted for the major fraction with mean values of 45.3 and 32.1% in the ranges of 35.3–60.9% and 16.1–43.6%, respectively. Significant negative correlation was observed between oleic and linoleic acid. In the present investigation, desirable values were obtained for oil traits which would be useful to develop nutritional and health-beneficial cultivars.     

Nachweis und Bestimmung von cyclischen C18-Fettsäuren in isomerisiertem Leinöl

Detection and Determination of Cyclic C₁₈-Fatty Acids in Isomerised Linseed Oil When linseed oil is isomerised with ethylene glycol and KOH under conditions which are employed for the UV-spectrophotometric determination of linoleic and linolenic acids, isomeric C₁₈-cyclic fatty acids to an extent of 10% of the linseed oil (20% of linolenic acid) are formed besides straight chain conjugated fatty acids. Lesser amount of cyclic acids are formed if the isomerisation is carried out with NaOH-ethylene glycol or K-tert-butylate. Ilinol, a linseed oil obtained by catalytic isomerisation with Ni/S, was found to contain ca. 5% cyclic C₁₈ fatty acids. The cyclic fatty acids are mixtures of many isomers, their composition being dependent on the conditions employed for isomerisation.     

Studies in interesterification. II. Acidolysis of some vegetable oils with lauric acid

Acidolysis reactions of cottonseed oil, peanut oil, mahua oil (Madhuca latifolia), and palm oil with lauric acid were investigated with special reference to the influence of catalysts and the relative proportions of oil and lauric acid on the extent and type of fatty acids displaced from an oil. Catalysts such as sulfuric acid, zinc oxide, calcium oxide, magnesium oxide, aluminum oxide, and mercuric sulfate were used. The reaction generally was carried out by heating oil and lauric acid at 150C±2 for 3 hr. The reaction products were separated and then analyzed by UV spectrophotometry and GLC. Sulfuric acid was found to be the best catalyst with 1 part of oil and 1.2 parts of the displacing acid (lauric acid) for displacement of high-molecular-weight fatty acids from an oil by low-molecular-weight fatty acids. The nature of the displacement of fatty acids varied from oil to oil, depending on their compositions. It was further indicated that linoleic acid was displaced preferentially over oleic acid in an amount dependent on its initial content in an oil with a corresponding increase in saturated acids content. A broad similarity in displacement patterns, in general, was noted; the fatty acids above C₁₈ were not displaced as in the case of peanut oil. The results demonstrate the feasibility of introducing lauric acid in the vegetable oils for the production of interesting oils with vastly different physical and chemical properties.     

Effect of maternal dietary arachidonic or linoleic acid on rat pup fatty acid profiles

Rapidly growing neonatal mammals accrete relatively large quantities of long chain (≥C₂₀) polyunsaturated fatty acids (LCP) in membrane phospholipids. We have examined accumulation of ω6 LCP in suckling neonatal rat pups during the first 14 d of life when their dams received essential fatty acids in the form of triglycerides containing linoleic acid or arachidonic acid. Dietary levels of these fatty acids were either 1 or 5% of total dietary fatty acids. The fatty acid profile of pup stomach contents (composed solely of the dams' milk) and plasma lipids, as well as liver and brain phospholipids, were determined. Stomach linoleic and arachidonic acid levels reflected the diet of the dams. Pup plasma and liver arachidonic acid levels increased progressively from the group receiving 1% linoleic acid to 5% linoleic acid and from 1% arachidonic acid to 5% arachidonic acid. Interestingly, brain phosphatidylethanolamine and phosphatidylcholine arachidonic acid levels were more stable than plasma or liver levels. These results suggest that the brain may be capable of either selective transport of ω6 LCP or chain elongation/desaturation of linoleic acid. These data indicate that care must be exercised when adding LCP to infant formula since widely divergent accretion rates of arachidonic acid may occur in various tissues.     

Lipoxygenase inhibition by naturally occurring monoenoic fatty acids

Lipoxygenase activity was not detected in preparations from several varieties of rapessed. Erucic acid, one of the main components of rapessed oil, competitively inhibited both soybean and peanut lipoxygenases. Various other long-chain monoenoic fatty acids were assayed for their effects on lipoxygenase activity with linoleic acid as substrate. Fatty acid chain length, from C₁₆, to C₂₄, was not a significant factor, but position of the point of unsaturation did affect enzyme activity. The position of the double bond from the carboxyl group seemed to be more significant than the distance between the point of unsaturation and the methyl terminal group in terms of inhibition.     

Fatty acid variation among U.S. Runner-type peanut cultivars

Fatty acid composition was determined among seven U.S. runner-type peanut (Arachis hypogaea L.) cultivars: Florunner, Sunrunner, GK-7, Southern Runner, Sunbelt Runner, Okrun, and Langley. Significant year and cultivar differences were found within these fatty acid profiles. Southern Runner had the best oleic to linoleic ratio and iodine values; whereas Florunner, Sunrunner, and Langley were the highest in unsaturated and lowest in saturated and long-chain fatty acids. For the future, breeding programs need to continue developing peanut cultivars with improved oil quality.     

Effect of resin components on the degradation of guayule rubber

All natural rubbers are likely to contain some long chain fatty acids or their esters. The individual effect of the four C₁₈ fatty acids (stearic, oleic, linoleic, and linolenic acid) present in the guayule resin on the degradation of guayule rubber has been investigated concurrently by stress–relaxation of radiation cured rubber networks and by gel permeation chromatography studies on the raw rubber in the temperature zone 70–125°C. C₁₈ unsaturated fatty acids enhance the degradation of rubber several fold. The rate of degradation follows the order: rubber ≤ rubber + stearic acid < rubber + oleic acid < rubber + linoleic acid < rubber + linolenic acid. The thermal degradation is slower than the thermooxidative. The rate of degradation monotonically increased with the number of conjugated double bonds and is first order with respect to acid concentration. The activation energy for the chain scission for both thermal and thermooxidative degradation has been found to be 95 ± 10 kJ/mol. The mechanism of degradation of guayule rubber in the presence of fatty acids is discussed.     

Quantification and Compositional Diversity of Fatty Acid Methyl Esters Profile in Nigella sativa L. Germplasm

Nigella sativa L. is an annual underutilized crop of enormous significance, it contains more than 100 bioactive constituents having both pharmaceutical and industrial applications. Nigella sativa L. germplasm consisting of 32 genotypes was quantified for palmitic acid, stearic acid, oleic acid, linoleic and linolenic acid and results obtained varied in percentage. Lipid extracted by chloroform methanol 2:1 (24–37 %) was higher compared to n-hexane (18–35 %) and chloroform methanol 1:3 (18–34 %). Extraction with solvent chloroform methanol 2:1 yielded a higher quantity of oil contents, hence recommended. The polyunsaturated fatty acids were higher than monounsaturated fatty acids. Stearic and palmitic acids were positively correlated as were stearic and linoleic acids. It is inferred that breeding for increased stearic acid, linolenic acid and reduced palmitic acid can be achieved through modern breeding methods. The genotypes rich in oil and oleic-linoleic acid, viz., Pk-020545, Pk-020576, Pk-020609, Pk-020620, Pk-020654, Pk-020699, Pk-020720, Pk-020780, Pk-020874 and Pk-020878, have been suggested for crop improvement programs and could augment the supply of edible oil as well as a biofuel substitute with large scale cultivation.     

Supercritical Carbon Dioxide Fractionation of Anhydrous Milk Fat

Supercritical carbon dioxide was used to fractionate anhydrous milk fat. Six fractions were produced at 40, 50 and 60 °C using pressure values of 10, 20, 25, 30, 33 and 36 MPa. The fractions were analyzed for fatty acids, thermal behavior, iodine and color values. Composition and yield of fatty acid methyl esters were evaluated at different fractionation conditions in relation to the original milk fat values. Short chain fatty acids (C₄–C₈), medium chain fatty acids (C₁₀–C₁₄) and total saturated fatty acids were decreased from fraction obtained in the order of 10–36 MPa, while long chain fatty acids (C₁₆–C_18:2) and total unsaturated fatty acids were increased. Fractions obtained in the raffinate stage of the fractionation exhibited higher melting behavior that obtained at the low CO₂ pressures. The higher iodine value of raffinate fraction indicated that fraction was richer in oleic acid. Fractions produced at low pressures had lower melting behavior than those obtained at high pressures. Yellowness Index and b* values increased in raffinate fraction due to concentration of carotenoids.     

Full Characterisation of Crambe abyssinica Hochst. Seed Oil

This work was dedicated to reporting the full chemical and physical characterisation of Crambe abyssinica Hochst. seed oil. The oil from the seeds was extracted using n-hexane. The seeds contain about 30?% oil. Density, refractive index, colour, smoke point, viscosity, acidity, saponification value, iodine value, fatty acid methyl esters, the relative position of fatty acids in C₁ and C₃ carbon glycerol, sterols, tocopherols, peroxide value, $ \mathop E\nolimits_{{1{\text{cm}}}}^{1\,\% } $ at 232?nm, and the susceptibility to oxidation measured by the Rancimat method were determined. The oil was found to contain high levels of unsaturated fatty acids, especially C22:1 (63.77?%). The dominant saturated acid was C22:0 (2.14?%). The oil was also found to contain high levels of β-sitosterol (51.93?%), campestanol (21.98?%), and brassicasterol (12.35?%). α-, γ-, and δ-Tocopherols were detected up to levels of 7.67, 125.04, and 3.99?mg/kg, respectively. The induction period (at 110?°C and 20?l/h) of the oil was 8.83?h. The relative position of fatty acids in C₁ and C₃ position was as follows: linoleic 0.45?%, oleic 8.84?%, and erucic 90.72?%. The thermal profile of the oil presented a single peak at ?20.94?°C.     

Marine-derived fatty acids of fish oils as raw materials for fatty acids manufacture

Fish oils, often an abundant source of C₂₀ and C₂₂ fatty acids, could supplement rapessed oil in the manufacture of long chain saturated fatty acids. Herring oil, traditionally the fish oil of choice, is in very short supply due to depletion of fishery stocks. Menhaden oil, when made from fish caught in the Atlantic, could furnish a steady supply with long chain acids at about the 30% level. Oil made from other species such as anchovy or pilchard need further data on fatty acid content and variability. Manufacture of polyunsaturated fatty acids from fish oils is hampered by lack of suitable procedures. Potential markets for fish oil polyunsaturates especially in the pharmaceutical field seem promising.     

Chemical Examination of Iberis odorata Seed Oil

Iberis odorata seeds of cruciferae plant family yield 26.0 percent of fatty oil which has an iodine value 107.5. The oil is investigated for its fatty acid composition by reversed phase partition chromatography. The fatty acids in the seed oil constitute 39.6% erucic, 3.5% eicosenoic and 3.2% docosadienoic acids, in addition to the usual oleic (13.6%), linoleic (25.7%) and linolenic acids (3.1%). Saturated acids (C₁₂) to (C₂₂) amount to 11.3% of the component acids.     

GC-FID/MS Analysis of Fatty Acids in Indian Cultivars of Moringa oleifera: Potential Sources of PUFA

In the present investigation, the fatty acid profile was analysed in vegetative and reproductive parts of eight commercially cultivated Indian cultivars of Moringa oleifera and verified by gas chromatography mass spectra. In leaves, α-linolenic acid (C_18:3, cis-9,12,15) was found in the highest quantity (49–59 %) followed by palmitic acid (C_16:0) (16–18 %), and linoleic acid (C_18:2, cis-9,12) (6–13 %). The total content of saturated fatty acids and unsaturated fatty acids showed a ratio of 0.33 (cv. DHANRAJ) to 0.39 (cv. PKM-2) in leaves, 0.53 in flowers and 0.56 in tender pods. Similarly, polyunsaturated fatty acids and total monounsaturated fatty acids were found in a ratio of 5.68 (cv. DHANRAJ) to 9.71 (cv. CO-1) in leaves, 1.11 in flowers and 2.79 in tender pods. The total lipid content was recorded in the range of 1.92 % (flowers) to 4.82 % (leaves, cv. CO-1). When considering health benefits, M. oleifera leaves contain low amounts of saturated fatty acids, a high mono- and polyunsaturated fatty acid content, which can enhance the health benefits of Moringa-based products.     

Autoxidation of fatty acid monolayers adsorbed on silica gel: III. Effects of saturated fatty acids and cholesterol

Autoxidation of fatty acid monolayers on silica consisting of multiple components to simulate biomembranes has been studied by the rate of fatty acid disappearance and the products formed. When palmitic acid was incorporated into linoleic acid monolayers, the decrease in rate was proportional to the amounts of plamitic acid present. The protective effect of the saturated fatty acid diminished rapidly as the chain length of the saturated fatty acid decreased below C₁₂. With acids of medium chain length, C₁₂ was more effective than C₁₆. In pure linoleic acid monolayers, when the surface coverage was reduced to only 5% of the available adsorption sites, and in the case of palmitic acid-linoleic acid monolayers, the rate dropped drastically and the major identified product formed was hydroxyepoxyoctadecenoic acid. On the contrary, the major product formed in the case of saturated monolayers of pure linoleic acid was a mixture of unsubstituted epoxy acids. The inclusion of cholesterol in linoleic acid monolayers increased the rate of disappearance of linoleic acid slightly, whereas cholesteryl acetate decreased the rate. The protective effect exerted by cholesteryl acetate appeared to be similar to that of palmitic acid.     

Antimicrobial agents derived from fatty acids

The author reviews his research, since 1966, for the ideal germicide. The relationship between structure of fatty acids, their corresponding esters, and antimicrobial activity is presented. Saturated fatty acids have their highest activity when the chain length is twelve carbons (C₁₂) long; monounsaturated fatty acids reach their peak with palmitoleic acid (C_16∶1); the most active polyunsaturated fatty acid is linoleic.Trans isomers are not active against microorganisms. The esterification of fatty acids to monohydric alcohols leads to inactive derivatives, whereas esterification to polyhydric alcohols increases biological activity. Examples of glycerol and sucrose esters are reviewed. In general, the lauroyl derivatives are the most active. A few examples of esters as active pharmacological agents against organisms causing bovine mastitis are presented as well as the use of monolaurin (Lauricidin^®) as cosmetic and food preservatives. The safety and efficacy of fatty acid esters as potential germicides offer new and expanded roles for oleochemicals.     

Fractional vacuum distillation of herring oil methyl esters

Methyl esters of a Canadian Atlantic herring oil containing 62% monoethylenic fatty acids were subjected to batch fractional distillation under vacuum on a pilot plant scale, to study the feasibility of fractionating fatty acid esters of marine oils of low iodine value into monounsaturated fractions with increased commercial value for industrial chemical uses. A total of 64 methyl ester fractions were collected and analyzed by gas liquid chromatography. Recoveries of the major saturated and monounsaturated acids were close to 100%, and some fractions contained over 90% of the desired 22:1 long chain monounsaturated acids. The short chain polyunsaturated acids were recovered in good yields, but the long chain highly unsaturated acids were recovered in yields of 60% or less due to oxidative and thermal decomposition in the particular apparatus employed. If small amounts of unsaturated acids are acceptable, fractional distillation of low iodine value marine oils could inexpensively supply fractions with high concentrations of methyl esters of longer chain (C₂₀ and C₂₂) monounsaturated and shorter chain (C₁₄) saturated acid or (C₁₆) saturated-monounsaturated acid mixture.     

Oil Content and Fatty Acid Composition in Seeds of Three Safflower Species

Seeds of six safflower (C. tinctorius L.) genotypes and 19 accessions of two wild species were analyzed for oil and fatty acid composition. Oil content ranged from 29.20 to 34.00, 20.04 to 30.80 and 15.30 to 20.80% in C. tinctorius, C. oxyacantha Bieb. and C. lanatus L., respectively. The main fatty acids of oleic, linoleic, palmitic and stearic acids composed 96–99% of the total fatty acids in all species. The sum of myristic, palmitoleic, arachidic, and behenic fatty acids in oil of the species ranged from 0.43 to 0.57%. The oleic acid in seed oil of C. tinctorius, C. oxyacantha and C. lanatus ranged from 12.24 to 15.43, 14.11 to 19.28 and 16.70 to 19.77%, respectively. The corresponding ranges for linoleic acid were 71.05 to 76.12, 63.90 to 75.43 and 62.47 to 71.08%. Palmitic acid in seed oil varied from 5.48 to 7.59% in C. tinctorius, 6.09 to 8.33% in C. oxyacantha and 7.44 to 8.78% in C. lanatus. The stearic acid of the seed oil showed a variation of 1.72 to 2.86, 2.50 to 4.87 and 3.14 to 4.79% in genotypes of these species, respectively. The fatty acids composition of oil among the cultivated and wild species were not considerably different, indicating that seed oil of the wild safflower is possibly suitable for human consumption and industrial purposes.     

Opportunities and problems in modification of levels of rapeseed C18 unsaturated fatty acids

Selections for different levels of C₁₈ fatty acids in rapeseed to date have had only limited success, due in part to the low frequency of occurrence of desired genotypes with increased linoleic and decreased linolenic acid. In the progeny of mutation experiments with seeds of the variety Oro (linolenic acid content 8–10%) two stable mutants were selected, one with 5% and the other with 20% linolenic acid in the seed oil. The level of linoleic acid in the two mutants is the same as Oro (16–20%), but the levels of oleic and linolenic acids are inversely altered. In this paper several problems associated with selecting for linoleic and linolenic acids, which became apparent during the mutation studies, are discussed. Many selections made from the mutated material were unstable, reverting to the original Oro fatty acid composition after two or three self-pollinated generations. This fact plus environmental and maternal effects made selection difficult. However, with the use of rapid and simple analytical methods and space-saving growing techniques, these difficulties were overcome. One of six papers presented in the symposium “Rapeseed Marketing and Breeding,” AOCS Meeting, Ottawa, September 1972.