Performance evaluation of hexane-extracted oils from genetically modified soybeans

Soybeans produced by induced mutation breeding and hybridization were cracked, flaked and hexane-extracted, and the recovered crude oils were processed to finished edible oils by laboratory simulations of commercial oil-processing procedures. Three lines yielded oils containing 1.7, 1.9 and 2.5% linolenic acid. These low-linolenic acid oils were evaluated along with oil extracted from the cultivar Hardin, grown at the same time and location, and they were processed at the same time. The oil from Hardin contained 6.5% linolenic acid. Low-linolenic acid oils showed improved flavor stability in accelerated storage tests after 8 d in the dark at 60°C and after 8h at 7500 lux at 30°C, conditions generally considered in stress testing. Room odor testing indicated that the low-linolenic oils showed significantly lower fishy odor after 1 h at 190°C and lower acrid/pungent odor after 5 h. Potatoes were fried in the oils at 190°C after 5, 10 and 15 h of use. Overall flavor quality of the potatoes fried in the low-linolenic oils was good and significantly better after all time periods than that of potatoes fried in the standard oil. No fishy flavors were perceived with potatoes fried in the low-linolenic oils. Total volatile and polar compound content of all heated oils increased with frying hours, with no significant differences observed. After 15 h of frying, the free fatty acid content in all oils remained below 0.3%. Lowering the linolenic acid content of soybean oil by breeding was particularly beneficial for improved oil quality during cooking and frying. Flavor quality of fried foods was enhanced with these low-linolenic acid oils.     

Phytosterol accumulation in canola, sunflower, and soybean oils: Effects of genetics, planting location, and temperature

To assess the potential of traditional selection breeding to develop varieties with increased phytosterol content, we determined concentrations of those sterols in canola, sunflower, and soybean seed oils produced from breeding lines of diverse genetic backgrounds. Seed oils were extracted and saponified, and the nonsaponifiable fractions were subjected to silylation. The major phytosterols brassicasterol, campesterol, stigmasterol and β-sitosterol, were quantified by capillary gas chromatography with flame-ionization detection. Canola contained approximately twice the amount of total phytosterols (4590–8070 μg g⁻¹) as sunflower (2100–4540 μg g⁻¹) or soybean (2340–4660 μg g⁻¹) oils. Phytosterol composition varied among crops as expected, as well as within a crop. Both genetic background and planting location significantly affected total phytosterol concentrations. Soybean plants were maintained from flower initiation to seed maturity under three temperature regimes in growth chambers to determine the effect of temperature during this period on seed oil phytosterol levels. A 2.5-fold variability in total phytosterol content was measured in these oils (3210–7920 μg g⁻¹). Total phytosterol levels increased with higher temperatures. Composition also changed, with greater percent campesterol and lower percent stigmasterol and β-sitosterol at higher temperatures. In these soybean oils, total phytosterol accumulation was correlated inversely with total tocopherol levels. Owing to the relatively limited variability in phytosterol levels in seed oils produced under field conditions, it is unlikely that a traditional breeding approach would lead to a dramatic increase in phytosterol content or modified phytosterol composition.     

Oxidative and flavor stabilities of soybean oils with low-and ultra-low-linolenic acid composition

The effects of linolenic acid (18∶3) concentration, combined with TBHQ addition, temperature, and storage time, on the oxidative and flavor stabilities of soybean oils (SBO) were evaluated. During storage under fluorescent light at both 21 and 32°C, the SBO with ultra-low-18∶3 concentration (1.0%, ULSBO) generally had greater oxidative stability than did SBO with low-18∶3 concentration (2.2%, LLSBO). The ULSBO had about half the p-anisidine value of LLSBO throughout storage. Although the ULSBO initially had significantly greater PV and poorer (lower) sensory scores for overall flavor quality than did LLSBO, significant differences disappeared with storage. The ULSBO had a lower content of polar compounds and greater oil stability indices than did LLSBO when TBHQ was present. All oils were more oxidatively stable with TBHQ addition, but the TBHQ addition did not result in improved flavor stability early in storage. In all tests, oils stored at 32°C were less stable than oils stored at 21°C. The TBHQ had a better antioxidant capacity when the 18∶3 concentration was lower. The retardation effect of TBHQ on lipid oxidation and the improved stability of ULSBO over LLSBO were more easily detected when the storage temperature was higher.     

Wax composition of sunflower seed oils

Waxes are natural components of sunflower oils, consisting mainly of esters of FA with fatty alcohols, that are partially removed in the winterization process during oil refining. The wax composition of sunflower seed as well as the influence of processing on the oil wax concentration was studied using capillary GLC. Sunflower oils obtained by solvent extraction from whole seed, dehulled seed, and seed hulls were analyzed and compared with commercial crude and refined oils. The main components of crude sunflower oil waxes were esters having carbon atom numbers between 36 and 48, with a high concentration in the C₄₀−C₄₂ fraction. Extracted oils showed higher concentrations of waxes than those obtained by pressing, especially in the higher M.W. fraction, but the wax content was not affected significantly by water degumming. The hull contribution to the sunflower oil wax content was higher than 40 wt%, resulting in 75 wt % in the crystallized fraction. The oil wax content could be reduced appreciably by hexane washing or partial dehulling of the seed. Waxes in dewaxed and refined sunflower oils were mainly constituted by esters containing fewer than 42 carbon atoms, indicating that these were mostly soluble and remained in the oil after processing.     

trans-Polyunsaturated fatty acids in French edible rapeseed and soybean oils

The fatty acid compositions of rapeseed and soybean oils marketed in France have been determined by gas liquid chromatography on a fused-silica capillary column coated with a 100% cyanopropyl polysiloxane stationary phase. Under the operating conditions employed, methyl esters of linolenic acid geometrical isomers could be separated and quantitated easily without any other complementary technique. With only one exception, all samples under study (eight salad oils and five food samples) contain geometrical isomers of linolenic acid in measurable, although variable, amounts. Totaltrans-18:3 acids may account for up to 3% of total fatty acids. This value corresponds to a degree of isomerization (percentage oftrans isomers relative to total octadecatrienoic acids) of 30%. Examination of our data indicates that the distribution pattern of linolenic acid geometrical isomers does not depend on the degree of isomerization. The two main isomers always have thec,c,t and thet,c,c configurations. These isomers occur in the almost invariable relative proportions of 47.8±1.7% and 41.1±1.0%, respectively. The third mono-trans isomer is present in lower amounts−6.5±0.7%. The only di-trans isomer that can be quantitated with sufficient accuracy is thet,c,t isomer (4.9±1.5%). Mono-trans isomers of linoleic acid are also present in these oils. However, their maximum percentages are lower than those determined for linolenic acid geometrical isomers. In the oils showing the highest degrees of isomerization,trans isomers of linoleic acid account for 0.5% (rapeseed oils) and 1% (soybean oils) of total fatty acids. Taking into account all data, it would appear that the probability of isomerization of linolenic acid is about 13–14 times that of linoleic acid.     

A comparative study on the susceptibilities of soybean,sunflower and peanut oils to singlet molecular oxygen photooxidation

The susceptibilities of crude soybean, sunflower and peanut oils to singlet oxygen photooxidation were determined in a kinetic study. The accumulation of photosensitized hydroperoxides, determined spectroscopically, and the quenching of singlet molecular oxygen phosphorescence by the crude oils and their fatty acid methyl esters were compared. The relative tendency to photooxidation for the oils and the methyl esters was soybean ≫ sunflower > peanut. This trend was independent of the method employed in the determination of initial photodamaging. Soybean oil was demonstrated to be the most unstable product, not only due to the presence of highly unsaturated fatty acids, but also due to the absence of natural constituents, capable of providing a protective antioxidant effect. This protection was more effective in sunflower and peanut oils.     

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.     

High-temperature stability of soybean oils with altered fatty acid compositions

One canola oil and six soybean oils with different fatty acid compositions were heated intermittently, and bread cubes were fried in them to determine the stability of the oils. Two of the soybean oils were commercial varieties Hardin and BSR 101. The other soybean oils were from experimental lines developed at Iowa State University, and included A17 with 1.5% linolenate (18:3) and 15.1% palmitate (16:0), A16 with 1.9% 18:3 and 10.6% 16:0, A87-191039 with 1.8% 18:3 and 29.1% oleate (18:1) and A6 with 27.7% stearate (18:0). The soybean seeds were cold-pressed and crude canola oil was obtained without additives. Oils were refined, bleached and deodorized under laboratory conditions with additions. Each oil (300 mL) was heated to 180 ± 5°C in a minifryer. Bread cubes were fried at the beginning of heating, and half of the cubes were used for analyses. The second half was analyzed after storage at 60°C for seven days. Heating of the oils was continued for 20 h, cooled for 10 h, and then reheated for another 20 h, after which additional bread cubes were fried and analyzed. Results of sensory evaluation of the fried cubes, the peroxide values (PV) of oils extracted from the cubes and the conjugated dienoic acid values of the oils showed that the A17, A16, A87-191039 and A6 oils had better stabilities than did Hardin, BSR 101 and canola oils. The initial 18:3 contents of oils predicted their oxidative and flavor stabilities under heating and frying conditions (for PVvs. 18:3, r=0.89,P=0.008; for flavor qualityvs. 18:3, r=−0.93,P=0.002; for flavor intensityvs. 18:3, r=−0.91,P=0.004).     

Effect of triacylglycerol composition and structures on oxidative stability of oils from selected soybean germplasm

The oxidative stability of soybean oil triacylglycerols was studied with respect to composition and structure. Crude soybean oils of various fatty acid and triacylglycerol composition, hexane-extracted from ground beans, were chromatographed to remove non-triacylglycerol components. Purified triacylglycerols were oxidized at 60°C, in air, in the dark. The oxidative stability or resistance of the substrate to reaction with oxygen was measured by determination of peroxide value and headspace analysis of volatiles of the oxidized triacylglycerols (at less than 1% oxidation). The correlation coefficients (r) for rates of peroxide formation (r=0.85) and total headspace volatiles (r=0.87) were related positively to oxidizability. Rate of peroxide formation showed a positive correlation with average number of double bonds (r=0.81), linoleic acid (r=0.63), linolenic acid (r=0.85). Rate of peroxide formation also showed a positive correlation with linoleic acid (r=0.72) at the 2-position of the glycerol moiety. A negative correlation was observed between rate of peroxide formation and oleic acid (r=−0.82). Resistance of soybean triacylglycerols to reaction with oxygen was decreased by linolenic (r=0.87) and increased by oleic acid (r=−0.76)-containing triacylglycerols. Volatile formation was increased by increased concentration of linolenic acid at exterior glycerol carbons 1,3 and by linoleic acid at the interior carbon 2. Headspace analysis of voltiles and high-performance liquid chromatography of hydroperoxides indicated that as oxidation proceeded there was a slight decrease in the linolenic acid-derived hydroperoxides and an increase in the linoleic acid-derived hydroperoxides. The oxidative stability of soybean oil triacylclycerols with respect to composition and structure is of interest to the development of soybean varieties with oils of improved odor and flavor stability. Presented at the 81st Annual American Oil Chemists' Society Meeting, Baltimore, MD, April 18–21, 1990.     

Cyclic fatty acids in sunflower oils during frying of frozen foods with oil replenishment

Frying of frozen foods has become popular because it considerably reduces cooking time. Polymers and cyclic fatty acid monomers (CFAM) formed during frying are potentially toxic and therefore their production should be minimized. Twenty discontinuous fryings of different frozen foods were carried out over ten consecutive days, in sunflower oil (SO) and in high‐oleic acid sunflower oil (HOSO), by adding fresh oil after each frying to bring the volume of the fryer oil back to 3 L. CFAM methyl ester derivates were hydrogenated, isolated, concentrated and quantified by HPLC using a reverse‐phase column, followed by gas chromatography. After 20 fryings, significantly higher contents of polar material, polymers and CFAM (all p <0.001) were found in SO than in HOSO. Bicyclic compound formation was four times higher in SO (p <0.001). The fat from the fried potatoes presented a polymer content very similar to that of their corresponding oils. The 100‐g rations of the SO‐fried potatoes from the 20^th frying supply 49 or 15%, respectively, more polymers and CFAM and 1 mg more bicyclic fatty acids than the 100‐g rations of HOSO‐fried potatoes. Because digestion and absorption of polar material, polymers and CFAM occur, the data clearly show the advantageousness and advisability of frying with HOSO rather than SO.     

Photooxidation of soybean oils as affected by triacylglycerol composition and structure

The photooxidation of soybean oil was determined and correlated with triacylglycerol composition and structure. Purified triacylglycerols were photooxidized at room temperature under fluorescent light. Rates of peroxide formation and total headspace volatiles were related positively (P<0.5 significance) to oxidizability (r=0.75, r=0.76); content of linolenic acid (r=0.80, r=0.85) and linoleic acid (r=0.61, r=0.57); linoleic acid on carbon 2 (r=0.64, r=0.64); and average number of double bonds (r=0.76, r=0.76). Negative correlations were observed with respect to oleic acid (r=−0.70, r=−0.70). Soybean oil stability was decreased by linolenic acid-containing triacylglycerols and increased by oleic acid-containing triacylglycerols. Trilinoleoylglycerol and dilinoleoyl-oleoylglycerol were the most important oxidation product precursors. However, for high-linolenic acid soybean oil, dilinoleoyl-linolenoylglycerol and trilinoleoylglycerol were the most important oxidation product precursors. The most abundant volatile produced from thermal decomposition at 140°C of photooxidized triacylglycerols was 2-heptenal, except for high-linolenic acid oils, where the most abundant volatile was propanal. The photooxidative stability of soybean oil triacylglycerols with respect to composition and structure is of interest for the development of soybean varieties with oils of improved odor and flavor stability. Presented at the 20th ISF World Congress 83rd Annual American Oil Chemists’ Society Meeting, May 10–14, 1992, Toronto, Canada.     

Frying stability of soybean and canola oils with modified fatty acid compositions

Pilot plant-processed samples of soybean and canola (lowerucic acid rapeseed) oil with fatty acid compositions modified by mutation breeding and/or hydrogenation were evaluated for frying stability. Linolenic acid contents were 6.2% for standard soybean oil, 3.7% for low-linolenic soybean oil and 0.4% for the hydrogenated low-linolenic soybean oil. The linolenic acid contents were 10.1% for standard canola oil, 1.7% for canola modified by breeding and 0.8% and 0.6% for oils modified by breeding and hydrogenation. All modified oils had significantly (P<0.05) less room odor intensity after initial heating tests at 190°C than the standard oils, as judged by a sensory panel. Panelists also judged standard oils to have significantly higher intensities for fishy, burnt, rubbery, smoky and acrid odors than the modified oils. Free fatty acids, polar compounds and foam heights during frying were significantly (P<0.05) less in the low-linolenic soy and canola oils than the corresponding unmodified oils after 5 h of frying. The flavor quality of french-fried potatoes was significantly (P<0.05) better for potatoes fried in modified oils than those fried in standard oils. The potatoes fried in standard canola oil were described by the sensory panel as fishy.     

Rheological and thermal properties of soybean oils with modified FA compositions

Rheological and thermal properties of five soybean oils with modified FA compositions were studied. Viscosity decreased with increasing temperature at different rates for the different oils. Oil with a high-oleic acid content had higher viscosity and a greater rate of change than did oils with typical FA compositions, oil with low-saturated FA or low-linolenic acid content, or oil from lipoxygenase-free soybeans. The melting and crystallization behaviors of the oils were examined using DSC. The high-oleic acid oil and the oil with low-saturated FA content had different DSC profiles compared with the other oils. Specific heat capacities of oils were estimated using a mathematical model; the high-oleic acid oil had a higher specific heat value, and the low-saturated FA oil had a lower value than did the other oils.     

Pan-heating of low-linolenic acid and partially hydrogenated soybean oils

Genetically modified low-linolenic acid soybean oil (LL-SBO) was compared to partially hydrogenated soybean oil (PH-SBO). Samples were heated on a Teflon pan at ∼180°C until a selected end point of ≥20% polymer content was reached. High-performance size-exclusion chromatography analysis indicated the PH-SBO contained >20% polymer after 20 min of heating, whereas the LL-SBO sample contained >20% polymer after 10 min. Supercritical fluid chromatography analysis indicated degradation rates of 0.161±0.011 min⁻¹ for LL-SBO and 0.086±0.004 min⁻¹ for PH-SBO. The volatile compounds were identified and quantitated with static head-space-GC-MS. 1-Heptene (239.9 ppm) and hexanal (1486.1 ppm) were present at the greates concentration among the volatile compounds in LL-SBO. The volatile compounds present in the greatest concentrations in heated PH-SBO were hexanal (376.9 ppm) and pentane (82.1 ppm). After 10 min of heating, the LL-SBO oil FFA value (2.66%), p-anisidine value (386.5 abs/g oil), Food Oil Sensor reading (18.75), and color intensity (Y=4.0, R=1.0) were significantly greater than those of PH-SBO after 14 min of heating (4.28%, 298.5 abs/g oil, 16.08, Y=1.0, R=0.1, respectively). There was a significant difference in the degradation rates between LL-SBO and PH-SBO (P<0.05). The PH-SBO was more stable than the LL-SBO.     

Tocopherols in breeding lines and effects of planting location, fatty acid composition, and temperature during development

As the use of tocopherols as natural antioxidants increases, it is economically and agronomically important to determine the range, composition, and factors that affect their levels in oilseed crops, a major commercial source. In this study, tocopherols were quantified from seeds of wheat, sunflower, canola, and soybean. The breeding lines analyzed possessed a broad range of economically important phenotypic traits such as disease or herbicide resistance, improved yield and agronomic characteristics, and altered storage oil fatty acid composition. Complete separation of all four native tocopherols was achieved using normal-phase high-performance liquid chromatography with ultraviolet detection. Total tocopherol concentration among wheat germ oil samples ranged from 1947 to 4082 μg g⁻¹. Total tocopherol concentration ranges varied from 534 to 1858 μg g⁻¹ in sunflower, 504 to 687 μg g⁻¹ in canola, and 1205 to 2195 μg g⁻¹ among the soybean oils surveyed. Although the composition of tocopherols varied substantially among crops, composition was stable within each crop. Total tocopherol concentration and the percentage linolenic acid were correlated positively in soybean oils with modified and unmodified fatty acid compositions. Tocopherol concentration and degree of unsaturation were not correlated in sunflower or canola seeds with genetically altered fatty acid composition. These findings suggest that breeding for altered storage oil fatty acid composition did not negatively impact tocopherol concentrations in sunflower and canola as they apparently did in soybeans. When 12 soybean breeding lines were grown at each of five locations, significant correlations were observed among planting location, breeding line, tocopherol concentration, and fatty acid composition. Analysis of seeds that matured under three different controlled temperature regimes suggests that the relationship between tocopherol concentration level and unsaturated fatty acids in commodity (not genetically modified for fatty acid composition) oil types is due to temperature effects on the biosynthesis of both compounds.     

Refining normal and genetically enhanced soybean oils obtained by various extraction methods

Four different extraction methods, extrusion-expelling, conventional flaking-solvent extraction, expander-solvent extraction, and screw pressing, were used to separate oil and meal of a commodity soybean. The quality and refining characteristics of oils obtained by these methods were evaluated, and the effects of extraction method on oil quality were determined. The screw-pressed oil was more oxidized and hydrolyzed than the oils from the other extraction methods. The extruded-expelled oil had oxidative status similar to the solvent-extracted oils, although it contained the lowest amount of tocopherols. Five genetically enhanced soybeans were also processed by extrusion-expelling and solvent extraction methods, and differences in refining of these oils were examined. Overall, extruded-expelled oils were significantly different from the solvent-extracted oils in that they contained less tocopherols and were more oxidized than the solvent-extracted oils during refining. The differences between oils from the two extraction methods were magnified owing to the inclusion in the experiment of oils with modified compositions. The more unsaturated oils underwent significantly more oxidative degradation during refining than did the more saturated ones.     

Frying quality and stability of low-and ultra-low-linolenic acid soybean oils

To determine effects of very low levels of linolenic acid on frying stabilities of soybean oils, tests were conducted with 2% (low) linolenic acid soybean oil (LLSBO) and 0.8% (ultra-low) linolenic acid soybean oil (ULLSBO) in comparison with cottonseed oil (CSO). Potato chips were fried in the oils for a total of 25 h of oil use. No significant differences were found for either total polar compounds or FFA between samples of LLSBO and ULLSBO; however, CSO had significantly higher percentage of polar compounds and FFA than the soybean oils at all sampling times. Flavor evaluations of fresh and aged (1, 3, 5, and 7 wk at 25°C) potato chips showed some differences between potato chips fried in different oil types. Sensory panel judges reported that potato chips fried in ULLSBO and aged for 3 or 7 wk at 25°C had significantly lower intensities of fishy flavor than did potato chips fried in LLSBO with the same conditions. Potato chips fried in ULLSBO that had been used for 5 h and then aged 7 wk at 25°C had significantly better quality than did potato chips fried 5 h in LLSBO and aged under the same conditions. Hexanal was significantly higher in the 5-h LLSBO sample than in potato chips fried 5 h in ULLSBO. The decrease in linolenic acid from 2 to 0.8% in the oils improved flavor quality and oxidative stability of some of the potato chip samples.     

Electrochemical hydrogenation of edible oils in a solid polymer electrolyte reactor. Sensory and compositional characteristics of low Trans soybean oils

Soybean oils were hydrogenated either electrochemically with Pd at 50 or 60°C to iodine values (IV) of 104 and 90 or commercially with Ni to iodine values of 94 and 68. To determine the composition and sensory characteristics, oils were evaluated for triacylglycerol (TAG) structure, stereospecific analysis, fatty acids, solid fat index, and odor attributes in room odor tests. Trans fatty acid contents were 17 and 43.5% for the commercially hydrogenated oils and 9.8% for both electrochemically hydrogenated products. Compositional analysis of the oils showed higher levels of stearic and linoleic acids in the electrochemically hydrogenated oils and higher oleic acid levels in the chemically hydrogenated products. TAG analysis confirmed these findings. Monoenes were the predominant species in the commercial oils, whereas dienes and saturates were predominant components of the electrochemically processed samples. Free fatty acid values and peroxide values were low in electrochemically hydrogenated oils, indicating no problems from hydrolysis or oxidation during hydrogenation. The solid fat index profile of a 15∶85 blend of electrochemically hydrogenated soybean oil (IV=90) with a liquid soybean oil was equivalent to that of a commercial stick margarine. In room odor evaluations of oils heated at frying temperature (190°C), chemically hydrogenated soybean oils showed strong intensities of an undesirable characteristic hydrogenation aroma (waxy, sweet, flowery, fruity, and/or crayon-like odors). However, the electrochemically hydrogenated samples showed only weak intensities of this odor, indicating that the hydrogenation aroma/flavor would be much less detectable in foods fried in the electrochemically hydrogenated soybean oils than in chemically hydrogenated soybean oils. Electrochemical hydrogenation produced deodorized oils with lower levels of trans fatty acids, compositions suitable for margarines, and lower intensity levels of off-odors, including hydrogenation aroma, when heated to 190°C than did commercially hydrogenated oil.