Fatty acid composition of oil from soybean leaves grown at extreme temperatures

Leaves from soybean (Glycine max (L.) Merr.) plants were assayed to determine if the relationship between temperature and relative fatty acid composition observed in the seed oil also existed for the triglycerides in the leaf oil. Leaf samples were harvested from eight soybean lines (A5, A6, C1640, Century, Maple Arrow, N78-2245, PI 123440 and PI 361088B) grown at 40/30,28/22 and 15/ 12°C day/night. At 40/30 and 28/22°C, seven fatty acids were observed at a level greater than 1.0%. These included the five major fatty acids found in the seed oil: palmitic (16:0), stearic (18:0), oleic (18:1), linoleic (18:2) and linolenic (18:3) acid; plus two fatty acids that had retention times the same as palmitoleic (16:1) and γ-linolenic (18:3 g) acid. In addition, an eighth fatty acid that had a retention time the same as behenic (22:0) acid was found in the leaves of all lines at 15/12°C. Palmitic, palmitoleic and stearic acid content did not differ significantly over temperatures. The oleic and linoleic acid content were each highest at 15/12°C, while the γ-linolenic and the linolenic acid content were each highest at 40/30°C. The fatty acid composition of the triglyceride portion of the leaf oil did not display the same pattern over temperatures as that observed for seed oil.     

A review of soybean oil reversion flavor

Crude soybean oil has a characteristic “greenbeany” flavor, which during refining, bleaching and deodorization is eliminated to produce a bland tasting, light colored oil. However, flavor returns during storage and has been characteristically called the “reversion flavor” of soybean oil. This deleterious characteristics flavor has influenced the utilization of soybean oil and its fatty acids. Several theories for the cause of reversion flavor include: (a) oxidation of linolenic acid; (b) oxidation of isolinoleic acid of the 9,15-diene structure; (c) phosphatide reactions; (d) unsaponifiables; and (e) oxidative polymers. References are presented that support or contradict these theories. Recent publications concerning the isolation and characterization of the components of reversion flavor indicate slight oxidation of the fatty acids is the major cause. Techniques that are effective in increasing the flavor stability of soybean oil are presented.     

The Interaction of the Soybean Seed High Oleic Acid Oil Trait With Other Fatty Acid Modifications

Oil value is determined by the functional qualities imparted from the fatty acid profile. Soybean oil historically had excellent use in foods and industry; the need to increase the stability of the oil without negative health consequences has led to a decline in soybean oil use. One solution to make the oil stable is to have high oleic acid (>70%) and lower linolenic acid content in the oil. Other fatty acid profile changes are intended to target market needs: low‐saturated fatty acid and high stearic acid content in the oil. The objective of this study is to determine the interaction of the high oleic acid oil trait with other alleles controlling fatty acid profiles. Soybean lines containing high oleic acid allele combinations plus other fatty acid modifying alleles were produced, and the seed was produced in multiple field environments over 2 years. Stable high oleic acid with low linolenic acid (<3.0%) was achieved with a 4‐allele combination. The target of >20% stearic acid in the seed oil was not achieved. Reducing total saturated fatty acids below 7% in a high oleic acid background was possible with mutant alleles of both an acyl‐ACP thioesterase B and a β‐ketoacyl‐[acyl‐carrier‐protein] synthase III gene. The results identified allele combinations that met the target fatty acid profile thresholds and were most stable across environments.     

Analysis of soybean oil from Ohio

Five soybean cultivars-Pella 86, Ripley, Sherman, Williams 82, and Zane—were analyzed to determine the total fatty acid composition and triglyceride fatty acid composition. Palmitic, stearic, oleic, linoleic, and linolenic were the major fatty acids in these cultivars. Zane was significantly higher in saturated fatty acid content and lower in linolenic acid content than the other cultivars. Resolution by argentation thin-layer chromatography decreased with increased triglyceride unsaturation.     

Relation of days after flowering to chemical composition and physiological maturity of sunflower seed

Hybrid sunflower seed (achene) were collected from plants at 7-day intervals after the initiation of flowering which occurred 58 days after planting. The seed were analyzed for moisture, total oil, free fatty acids, lipid classes, and fatty acid composition. Seed dry weight, oil and triglyceride contents were maximum 35 days after the initiation of flowering (DAF) when the seed moisture content was about 36%. This point was defined as “physiological maturity” for sunflowers. The fatty acid composition of the oil extracted from the seed was determined at each stage of maturity. Total saturated fatty acids were 27% at 7 DAF and then decreased to a constant 9% by 35 DAF. At 7 DAF, linolenic acid content was 10.7% then decreased to less than 0.1% by 28 DAF. Oleic acid was about 12% at 7 DAF, increased to 59.6% at 14 DAF, and then gradually decreased to 31.4% by 56 DAF. On the other hand, linoleic acid was about 48% at 7 DAF, decreased to 23% by 14 DAF, but then gradually increased to 59.2% by 56 DAF. An analysis of variance of linoleic and oleic acid contents from 21 DAF to 70 DAF showed a highly significant change in composition with maturation time. The changes in the composition of these fatty acids from 21 DAF to 70 DAF appeared to be related to the environmental temperature which gradually decreased until 56 DAF. Increase in free fatty acids after physiological maturity indicated that deterioration of seed oil was beginning to occur.     

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.     

Fatty acid composition of oil from soybean seeds grown at extreme temperatures

Temperature during seed development is known to influence the level of the various fatty acids in soybean [Glycine max (L.) Merr.] oil. In order to determine the range of values that can be obtained for each fatty acid, five lines (A5, C1640, N78-2245, PI 123440 and PI 361088B) known to possess low linolenic acid (18:3) levels, one line (A6) known to possess a high stearic acid (18:0) level, and two cultivars (Century and Maple Arrow) were grown at 40/30, 28/22, and 15/12°C day/night. At 40/30°C, high oleic acid (18:1), low linoleic acid (18:2), and low linolenic acid levels were obtained that were beyond the range of levels reported for the soybean germplasm. The linolenic acid levels for A5, C1640 and N78-2245 grown at 40/30°C were below 2.0%, and are the lowest values reported for soybean oil. A6 displayed a high level of stearic acid at 28/22 and 40/30°C but displayed a relatively low level at 15/12°C. This indicates that temperature may affect the expression of thefas ^a allele, which is responsible for high stearic acid levels in A6. The linolenic acid levels of PI 361088B and C1640, both possessing thefan allele, were the lowest for all lines grown at 15/12°C. Therefore, thefan allele is an appropriate source for the development of low linolenic acid lines adapted to cool areas.     

Oxidative stability of natural and randomized high-palmitic-and high-stearic-acid oils from genetically modified soybean varieties

The oxidative stability of soybean oil triacylglycerols (TAG) obtained from genetically modified soybeans was determined before and after chemical randomization. Soybean oil oxidative studies were carried out under static oxygen headspace at 60°C in the dark and oxidative deterioration was monitored by peroxide value, monometric and oligomeric oxidation products, and volatile compounds. Randomization of the soybean oil TAG improved the oxidative stability compared to the natural soybean oil TAG. Oxidative stability was improved by three factors. Factor one was the genetic modification of the fatty acid composition in which polyunsaturated acids (such as linolenic and linoleic acids) were decreased and in which monounsaturated fatty acids (such as oleic) and saturated acids (palmitic and stearic) were increased. Factor two was the TAG compositional modification with a decrease in linolenic and linoleic-containing TAG and an increase in TAG with stearic and palmitic acids in combination with oleic acid. Factor three was the TAG structure modification accomplished by an increase in saturated fatty acids and a decrease in linoleic and linolenic acids at the glycerol moiety carbon 2. Presented at the AOCS Annual Meeting & Expo, Chicago, IL, May 10–13, 1998.     

Improvement of Oil Quality in Soybean [<Emphasis Type="Italic">Glycine max </Emphasis>(L.) Merrill] by Mutation Breeding

Low oxidative stability, off-flavor and rancidity are the major drawbacks of soybean oil. Modification of the fatty acid composition of soybean [Glycine max (L.) Merrill] oil can improve its quality and value for processors and acceptability among consumers. Mutation breeding of soybean was therefore initiated with the objective of identifying stable soybean mutants with altered fatty acid composition for improved oxidative stability and nutritional quality. Seeds of soybean cultivar ‘MACS 450’ were treated with γ-radiation and/or ethyl methane sulfonate (EMS). The harvest of M₁ plants was evaluated for fatty acid composition by gas chromatography. Highly significant variation in all the fatty acids except palmitic acid was observed. Treatment of EMS in higher concentrations as well as combined treatment of both the mutagens, i.e., γ-radiation and EMS were effective in increasing the variability for the fatty acid content in soybean oil. The variability was skewed towards high levels of oleic (35–42%) and low levels of linolenic acid (3.77–5.00%). M₃ and M₄ generations of desirable variants were analyzed for the stability of the mutated trait_. Only high oleic variants were stable in M₃ and M₄ generations. Based on fatty acid values, oxidative stability index (OSI), nutritional quality index (NQI) and ratio of essential fatty acids (ω₆/ω₃) were calculated for the control and M₂, M₃ and M₄ generations. The ω₆/ω₃ ratio in all the high oleic mutants was within the World Health Organization (WHO) recommended value (5–10%). A significant positive correlation between OSI and oleic acid content (P < 0.001) indicated improved oxidative stability of the oil while retaining nutritional quality. These high oleic lines could be utilized further in breeding programs for improvement of soybean oil quality.     

Fat-based dibasic acids

Aside from “dimer acids” (E.C. Leonard’s paper), the best known fat-based dibasic acids consist of eight product types of which only four are commercially important. These are described in detail in this paper: (a.) Azelaic acid produced from oleic acid by either chrome oxidation or ozonolysis of oleic acid also, “brassylic” acid from mixed 55% erucic-containing crambe oil fatty acids. (b). Sebacic acid from castor oil or possibly dodecanedioic acid from lesquerolic acid by caustic fusion. (c) C-21 Dibasic acid by Diels Alder reaction between isomerized TOFA and acrylic acid. (d.) C-19 Dibasic acids (carboxystearic acids) from oleic acid by carboxylation. (e.) Mixed C-11/C-12 Dibasic acids by several routes. Both the alkali cleavage and gentle nitric acid oxidations of certain hydroxy fatty acids (e.g., 12-hydroxystearic acid from hydrogenation of ricinoleic acid, etc.) can be used to afford mixed C-11/C-12 dibasic acids. (f.) Dibasic acid mixtures by nitric acid oxidations. Depending upon conditions, both saturated and unsaturated fatty acids are oxidized to a heterogeneous mixture of mono- and dibasic acids by oxidation with nitric acid.     

Fatty acid spectrum of mediterranean wild cruciferae

Seed samples of 54 species of wild Cruciferae were newly collected from natural populations of the west Mediterranean and adjacent areas in a search for “new” oil crops. Oil contents and fatty acid compositions were determined simultaneously by gas liquid chromatography using methyl heptadecanoate as the internal standard. The study revealed large variations in oil content (6–48.8%), oleic acid (5–31.3%), linoleic acid (2–24.8%), linolenic acid (1.7–64.1%), and erucic acid (0–55.1%). Correlation coefficients between component fatty acids inter se and oil content were determined separately for all species, the tribe Brassiceae, and the genusBrassica. The promising species identified are being studied further.     

Fatty acid composition and its relationship with physicochemical properties of pecan (Carya illinoensis) oil

The composition and physicochemical properties of pecan (Carya illinoensis) kernels and oils from different native trees of the central region of Mexico were investigated. The main compositional characteristic of the kernel was the high lipid content (70–79% w/w on dry basis) with elevated concentration of oleic acid (55–75% w/w). The results confirmed the relationship in the biosynthesis of linoleic and linolenic acids from oleic acid existing in oilseeds. Our results indicate that in pecans such relationship is a function of pecan tree age. The proportion of oleic, linoleic, and linolenic fatty acids determined the oxidative stability, viscosity, and melting/crystallization behavior of pecan oil. In general, these properties in pecan oils were similar or superior to extra-virgin olive oil and unrefined sesame oil. Although all native pecan oils studied showed a significant concentration of oleic acid, a particular group of native Mexican pecan trees produces an oil with a fatty acid composition with the nutritional appeal that consumers demand nowadays (i.e., very high oleic acid, 60–75%), with excellent natural oxidative stability (i.e., induction time for oxidation between 8.5 and 10.8 h), and substantially higher concentrations of α-, γ-, and δ-tocopherol than in pecan varieties previously reported in the literature.     

Oxidative stability of blends and interesterified blends of soybean oil and palm olein

Improvement of oxidative stability of soybean oil by blending with a more stable oil was investigated. Autoxidation of blends and interesterified blends (9∶1, 8∶2, 7∶3 and 1∶1, w/w) of soybean oil and palm olein was studied with respect to fatty acid composition, fatty acid location and triacylglycerol composition. Rates of formation of triacylglycerol hydroproxides, peroxide value and volatiles were evaluated. The fatty acid composition of soybean oil was changed by blending. Linolenic and linoleic acids decreased and oleic acid increased. The triacylglycerol composition of blends and interesterified blends was different from that of soybean oil. Relative to soybean oil, LnLL, LLL, LLO, LLP, LOO and LLS triacylglycerols were lowered and POO, POP and PLP were higher in blends and interesterified blends (where Ln, L, O, P and S represent linolenic, linoleic, oleic, palmitic and stearic acids, respectively). Interesterification of the blends leads to a decrease in POO and POP and an increase in LOP. Linoleic acid concentration at triacylglycerol carbon-2 was decreased by blending and interesterification. Rates of change for peroxide value and oxidation product formation confirmed the improvement of soybean oil stability by blending and interesterification. But, blends were more stable than interesterified blends. Also, the formation of hexanal, the major volatile of linoleate hydroperoxides of soybean oil, was decreased by blending and interesterification.     

Association of seed size with genotypic variation in the chemical constituents of soybeans

Ten soybean genotypes grown in 1992 with seed size ranging from 7.6 to 30.3 g/100 seeds and maturity group V or VI were selected and tested for oil and protein content and for fatty acid composition. In these germplasm, protein varied from 39.5 to 50.2%, oil, 16.3 to 21.6%, and protein plus oil, 59.7 to 67.5%. Percentages of individual fatty acids relative to total fatty acids varied as follows: palmitic, 11.0 to 12.8; stearic, 3.2 to 4.7; oleic, 17.6 to 24.2; linoleic, 51.1 to 56.3 and linolenic, 6.9 to 10.0. Seed size showed no significant correlations with individual saturated fatty acids, protein or oil content. However, significant correlations were found between seed size and individual unsaturated fatty acids: positive with oleic, and negative with linoleic and linolenic. Oil and protein content were negatively correlated with each other. Among the major fatty acids, only the unsaturated were significantly correlated with each other: negative between oleic and linoleic or linolenic, and positive between linoleic and linolenic. A subsequent study with soybeans grown in 1993 generally confirmed these findings. Variation in relative percentages of unsaturated fatty acids andr values for most pairs of relationships were even higher than those obtained from the 1992 crop. Presented at the 85th AOCS Annual Meeting and Expo, Atlanta, Georgia, May 8–12, 1994.     

Some relationships between fat acid composition and the iodine number of linseed oil

Summary RESULTS of analysis of 148 linseed oil samples are summarized. When the constituent fat acid glycerides are plotted against the iodine number the points fall close to a straight line in the cases of saturated acids, oleic acid and linolenic acid. In the case of linoleic acid, however, the points were so dispersed that no significant relationship to the iodine number was apparent. Correlation coefficients between iodine number and the fat acids were: Linolenic, +.97: oleic, −.94; saturated, −.80; and linoleic. −.27. It is possible to estimate within limits the amount of linolenic, oleic and saturated acids in linseed oil by applying equations where the iodine number is the only variable. In the case of linoleic acid, however, the standard deviation along the regression line is almost equal to the standard deviation from the mean. Real differences in composition which are independent of the iodine number exist, however, because the dispersion of the points along the regression lines is greater than would result from errors of precision in the analyses. Presented before the meeting of the American Chemical Society at Cleveland, Ohio, April, 1944. Published by permission of the Director, N. Dak. Agr. Expt. Station. This work was carried out under Purnell project 95, “The Chemistry of Flaxseed”.     

Soybean seed composition under high day and night growth temperatures

High diurnal temperatures often affect development of soybean [Glycine max (L.) Merr.], but little is known about the relative influence of high day and night temperatures on the chemical composition of the seed. This study was conducted to determine the effects of combinations of high day and night temperatures during flowering and pod set (R1–R5), seed fill and maturation (R5–R8), and continuously during the reproductive period (R1–R8) on soybean seed oil, protein, and fatty acid composition. Day/night temperatures of 30/20, 30/30, 35/20, and 35/30°C were imposed on the soybean cultivar Gnome 85 in growth chambers. The day/night temperature combinations during R1–R5 had little effect on the oil and protein concentration and the fatty acid composition of seed produced. As mean daily temperature increased from 25 (30/20) to 33 (35/30)°C during R5–R8 and 25 (30/20) to 33 (35/30)°C during R1–R8, and oil concentration decreased and protein concentration increased. Increased day temperature during R5–R8 and R1–R8, averaged across the two night temperatures, increased oleic acid and decreased linoleic and linolenic acids. When night temperature was increased at 30°C day temperature during R5–R8 and R1–R8, oleic acid decreased and linoleic acid increased. When night temperature was increased at 35°C day temperature during R1–R8, oleic acid increased, and linoleic and linolenic acids decreased. These results indicate the importance of high day and night temperatures during seed fill and maturation in the oil, protein, and fatty acid composition of soybean seed.     

Fatty acid composition of seed oil triglycerides inCoincya (Brassicaceae)

Oil and triglyceride contents and fatty acid composition were determined for seeds in nine taxa belonging to the genusCoincya (Brassicaceae) on the Iberian Peninsula (Spain and Portugal). The oil content ranges from 11.1 to 24.6%, triglycerides from 68.7 to 88.5%. The major fatty acids were erucic (24.6–30.5%), linolenic (17.7–27.7%), linoleic (13.9–24.6%) and oleic acid (12.3–21.8%).     

Fractionation of tallow fatty acids. Preparation of purified oleic acid and an inedible olive oil substitute

Summary Tallow fatty acids have been fractionally crystallized from acetone at temperatures ranging from 0° to −60° C. By crystallizing at 0° to −20° C., a saturated acid fraction which amounts to 40 to 50% by weight of the starting material has been obtained. This fraction corresponds to “double- or triple-pressed stearic acid.” The filtrate acids from the crystallization at −20° C. contain over 90% of the oleic acid present in the starting material, and in fatty acid composition this mixture is similar to olive oil. From this fraction. which amounts to about 50% by weight of the starting material, a synthetic triglyceride with, properties approximating those of olive oil has been prepared. By low-temperature crystallization of this oleic-acid-rich fraction at −50° to −60° C., followed by fractional distillation, a good yield of purified oleic acid (oleic acid content, over 95%) has been obtained. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, United States Department of Agriculture.     

Characterization of polar and nonpolar seed lipid classes from highly saturated fatty acid sunflower mutants

The seed lipids from five sunflower mutants, two with high palmitic acid contents, one of them in high oleic background, and three with high stearic acid contents, have been characterized. All lipid classes of these mutant seeds have increased saturated fatty acid content although triacylglycerols had the highest levels. The increase in saturated fatty acids was mainly at the expense of oleic acid while linoleic acid levels remained unchanged. No difference between mutants and standard sunflower lines used as controls was found in minor fatty acids: linolenic, arachidic, and behenic. In the high-palmitic mutants palmitoleic acid (16∶1n−7) and some palmitolinoleic acid (16∶2n−7, 16∶2n−4) also appeared. Phosphatidylinositol, the lipid with the highest palmitic acid content in controls, also had the highest content of palmitic or stearic acids, depending on the mutant type, suggesting that saturated fatty acids are needed for its physiological function. Positional analysis showed that mutant oils have very low content of saturated fatty acids in the sn-2 position of triacylglycerols, between the content of olive oil and cocoa butter.     

Measurement of Whole Soybean Fatty Acids by Near Infrared Spectroscopy

Whole soybean fatty acid contents were measured by near infrared spectroscopy. Three calibration algorithms—partial least squares (PLS), artificial neural networks (ANN), and least squares support vector machines (LS-SVM)—were implemented. Three different validation strategies using independent sets and part of calibration samples as validation sets were created. There was a significant improvement of the prediction precision of all fatty acids measured on relative concentration of oil compared with previous literature using PLS (standard error of prediction of 0.85, 0.42, 1.64, 1.67, and 0.90% for palmitic, stearic, oleic, linoleic and linolenic acids respectively). ANN and LS-SVM methods performed significantly better than PLS for palmitic, oleic and linolenic acids. Calibration models developed on relative concentrations (% of oil) were compared to prediction models created on absolute fatty acid concentration (% of weight) and corrected to relative concentration by multiplying by the predicted oil content. While models were easier to develop in absolute concentration (higher coefficients of determination), the multiplication of errors with the total oil content model resulted in no net precision improvement.