Effect of randomization on the oxidative stability of corn oil

Randomized corn oil TAG oxidized much faster than natural oil, but after purification with alumina, they oxidized at the same rate. We showed that this effect could not be attributed to a difference, in total tocopherols in the randomized and natural oils. Polar material recovered from the alumina treatment was fractionated by TLC, and a pro-oxidant effect was found in the fractions containing MAG and DAG. However, MAG and DAG, although mild pro-oxidant could not account for the pro-oxidant effect generated by randomization. No other compounds could be detected in the MAG fraction by MS. The pro-oxidant effect of randomized oil disappeared when EDTA or citric acid was added in sufficient amounts. The pro-oxidant effect of randomized corn oil was increased by the incorporation of additional copper or iron at a concentration that did not catalyze oxidation of the purified oil. Treatment of corn oil with ascorbic acid, ascorbyl-6-palmitate, ethyl acetoacetate, ethyl diacetoacetate, and acetylacetone did not reproduce the effect of the unknown pro-oxidant. Although the identity of the pro-oxidant is still unknown, we have confirmed that it is produced during randomization; it does not have pro-oxidant activity alone, but it facilitates the catalytic activity of the transition metal ions.     

Determination of the oxidative stability of vegetable oils by rancimat and conductivity and chemiluminescence measurements

The oxidative stability of five different oils was determined by Rancimat analysis with conductivity and chemiluminescence measurements for evaluation of the induction periods. Samples of oil, taken at intervals from the Rancimat apparatus, were used for chemiluminescence measurements. The chemiluminescence results were plotted vs. time, and the resulting curves were evaluated with a graphical tangential procedure in the same way as the curves of the Rancimat method (conductivity measurement). Induction periods of the oils assessed by Rancimat and chemiluminescence methods showed a significant linear correlation (r=0.9865). The temperature dependence of the induction periods evaluated by chemiluminescence and by conductivity was investigated with walnut oil. A marked temperature dependence was observed for both.     

Improving the oxidative stability of polyunsaturated vegetable oils by blending with high-oleic sunflower oil

Mixing different proportions of high-oleic sunflower oil (HOSO) with polyunsaturated vegetable oils provides a simple method to prepare more stable edible oils with a wide range of desired fatty acid composition. Oxidative stability of soybean, canola and corn oils, blended with different proportions of HOSO to lower the respective levels of linolenate and linoleate, was evaluated at 60°C. Oxidation was determined by two methods: peroxide value and volatiles (hexanal and propanal) by static headspace capillary gas chromatography. Determination of hexanal and propanal in mixtures of vegetable oils provided a sensitive index of linoleate and linolenate oxidation, respectively. Our evaluations demonstrated that all-cis oil compositions of improved oxidative stability can be formulated by blening soybean, canola and corn oils with different proportions of HOSO. On the basis of peroxide values, a partially hydrogenated soybean oil containing 4.5% linolenate was more stable than the mixture of soybean oil and HOSO containing 4.5% linolenate. However, on the basis of volatile analysis, mixtures of soybean and HOSO containing 2.0 and 4.5% linolenate were equivalent or better in oxidative stability than the hydrogenated soybean oil. Mixtures of canola oil and HOSO containing 1 and 2% linolenate had the same or better oxidative stability than did the hydrogenated canola oil containing 1% linolenate. These studies suggest that we can obviate catalytic hydrogenation of linolenate-containing vegetable oils by blending with HOSO. Presented at the AOCS/JOCS joint meeting, Anaheim, CA, April 25–29, 1993.     

AOCS collaborative study on sensory and volatile compound analyses of vegetable oils

An AOCS collaborative study was conducted to determine the effectiveness of sensory analysis and gas chromatographic analyses of volatile compounds in measuring vegetable oils for levels of oxidation that ranged from none to high. Sixteen laboratories from industry, government, and academia in Canada and the United States participated in the study to evaluate the flavor quality and oxidative stability of aged soybean, corn, sunflower, and canola (low-erucic acid rapeseed) oils. Analytical methods included sensory analyses with both flavor intensity and flavor quality scales and gas-chromatographic volatiles by direct injection, static headspace, and dynamic headspace (purge and trap) techniques. Sensory and volatile compound data were used to rank each of the oils at four levels of oxidation—none, low, moderate, and high. For soybean, canola, and sunflower oils, 85–90% of laboratories correctly ranked the oils by either analysis. For corn oil, only 60% of the laboratories ranked the samples according to the correct levels of oxidation by either analysis. Variance component estimates for flavor scores showed that the variation between sensory panelists within laboratories was lowest for the unaged oils. As storage time increased, the variance also increased, indicating that differences among panelists were greater for more highly oxidized oils. Between-laboratory variance of sensory panel scores was significantly lower than within-laboratory variance.     

Effect of fatty acids and tocopherols on the oxidative stability of vegetable oils

The oxidative stability of vegetable oils is determined by their fatty acid composition and antioxidants, mainly tocopherols but also other non‐saponifiable constituents. The effect of fatty acids on stability depends mainly on their degree of unsaturation and, to a lesser degree, on the position of the unsaturated functions within the triacylglycerol molecule. Vegetable oils contain tocopherols and tocotrienols, especially α‐ and γ‐tocopherols, as their main antioxidants. The antioxidant behavior of tocopherols represents a complex phenomenon as they are efficient antioxidants at low concentrations but they gradually lose efficacy as their concentrations in the vegetable oils increase. The “loss of efficacy” of tocopherols, sometimes referred to as a “pro‐oxidant effect”, is witnessed by an increase in the rate of oxidation during the induction period, despite elongation of this phase. The phenomenon is much obvious for α‐tocopherol, but is also evident for other tocopherols. In agreement with nature's wisdom, the tocopherol levels in vegetable oils seem to be close to the optimal levels needed for the stabilization of these oils. The presence of other antioxidants in the oils, e.g. carotenoids, phenolic compounds, and Maillard reaction products, may synergize with tocopherols and minimize this loss of efficacy.     

Effect of vacuum frying on the oxidative stability of oils

The purpose of this study was to evaluate frying oil quality with different assessment methods during vacuum frying of carrot slices. In six consecutive days, palm oil, lard, and soybean oil were fried under vacuum at 105°C for 20 min each hour in an 8-h shift. Peroxide value, acid value, carbonyl value, total polar components, dielectric constant (Food Oil Sensor reading), viscosity, and fatty acid composition were used to evaluate the quality of these oils. Results showed that palm oil and lard possess greater thermal stability than soybean oil. The decrease in C_18:2/C_16:0 ratio was greater for soybean oil than the other two oils. Of the assessment methods used, peroxide value, carbonyl value, total polar components, and dielectric constant all showed good correlation with frying time and between each other. Viscosity was suitable to assess vacuum-fried lard and soybean oil, but not palm oil. The measurement of dielectric constant, on the other hand, appeared to be unsuitable to assess vacuum-fried soybean oil.     

Oxidative stability of fat substitutes and vegetable oils by the oxidative stability index method

Oxidative Stability Index (OSI) of carbohydrate fatty acid polyesters, fat substitutes and vegetable oils were measured with the Omnion Oxidative Stability Instrument according to the new AOCS Standard Method Cd 12 B-92 (The Official Methods and Recommended Practices of the American Oil Chemists' Society, edited by D. Firestone, AOCS, Champaign, 1991). The stability of crude and refined, bleached and deodorized (RBD) vegetable oils (soybean, hydrogenated soybean and peanut) were determined at 110°C. In addition, OSI times for sucrose polyesters of soybean oil, butterfat, oleate:stearate and methyl glucoside polyester of soybean oil were determined in the absence and in the presence of 0.02 wt% antioxidants, [Tenox TBHQ (tertiary butylhydroquinone, Tenox GT-2 (from Eastman Chemical Products (Kingsport, TN); and vitamin E (from BASF, Wyandotte, MI)], and the results were compared with those of vegetable oils. Crude oils were most stable (20.4–25.9 h), followed by RBD oils (9.3–10.4 h) for soybean and peanut oils, respectively, and fat substitutes (3.8–6.8 h). Overall, Tenox TBHQ was the best antioxidant for improving the oxidative stability of both vegetable oils and fat substitutes. The sucrose polyester made with oleic and stearic acid was more stable than fat substitutes containing more polyunsaturated fatty acids, such as those from soybean oil, or from short-chain fatty acids, such as from butterfat. Antioxidants enhanced the stability of RBD oils (222% increase) and synthetic fat substitutes (421–424% increase) more than that of crude oils (33% increase). The shapes of the induction curves, not the actual OSI times for fat substitutes and vegetable oils, were similar and sharply defined.     

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.     

Analysis of vegetable oil volatiles by multiple headspace extraction

Quantitative determination of the volatiles produced from oxidized vegetable oils is an important indicator of oil quality. Five vegetable oils, low-erucic acid rapeseed, corn, soybean, sunflower and high oleic sunflower, were stored at 60°C for four and eight days to yield oils with several levels of oxidation. Peroxide values of the fresh oils ranged from 0.6 to 1.8 while those of the oxidized oils were from 1.6 to 42. Volatile analysis by the multiple headspace extraction (MHE) technique, which includes a pressure and time controlled injection onto the gas chromatography (GC) column (a chemically bonded capillary column), was compared with that obtained by static headspace gas chromatography (SHS-GC). Several volatile compounds indicative of the oxidation of polyunsaturated fatty acids from the vegetable oils were identified and measured by MHE; pure compounds of twelve major volatiles also were measured by MHE, and peak area was determined. Multiple extractions of the oil headspace provided a more reproducible measure of volatile compounds than was obtained by SHS-GC. Concentration of all volatiles increased with increased oxidation as measured by peroxide value of the oil. Presented at the Annual American Oil Chemists' Society Meeting, May 8–12, 1988, Phoenix, AZ.     

Kinetics of catalytic transfer hydrogenation of some vegetable oils

Catalytic transfer hydrogenation of corn, peanut, olive, soybean, and sunflower oils has been studied with aqueous sodium formate solution as hydrogen donor and palladium on carbon as catalyst. Kinetic constants and selectivity have been determined under intensive stirring in the presence of stabilizing agents. Hydrogenation reactions followed first-order kinetics with respect to fatty acids. Besides good selectivity and short reaction time, this method offers safe and easy handling. The presence of linolenic acid retards the migration of double bonds, which explains why soybean oil is the most appropriate for this hydrogenation process.     

The effect of randomization on the stability of blends of trioleoylglycerol and linseed oil

The effect of fatty acid arrangement on triacylglycerols was determined by assessing the stability of mixtures of trioleoylglycerol (consisting of a comparatively stable fatty acid) and linseed oil (containing a high amount of unstable fatty acids in the form of linoleic and linolenic acids) in the ratios of 90:10, 85:15, 80:20, 70:30 and 60:40 (w/w), respectively, before and after enzymatic randomization. Randomization resulted in increased stability; however, increasing the content of the unstable triacylglycerol resulted in a decrease in this effect. Based on these results, it was concluded that randomization of triacylglycerols can have a positive effect on the oxidative stability of an oil if the content of autoxidatively unstable triacylglycerols is low in the original blend. This results in substantial dilution of unstable fatty acids among the more stable triacylglycerols upon randomization.     

Seed roasting improves the oxidative stability of canola (B. napus) and mustard (B. juncea) seed oils

Animal fats and partially hydrogenated vegetable oils (PHVO) have preferentially been used for deep‐frying of food because of their relatively high oxidative stability compared to natural vegetable oils. However, animal fats and PHVO are abundant sources of saturated fatty acids and trans fatty acids, respectively, both of which are detrimental to human health. Canola (Brassica napus) is the primary oilseed crop currently grown in Australia. Canola quality Indian mustard (Brassica juncea) is also being developed for cultivation in hot and low‐rainfall areas of the country where canola does not perform well. A major impediment to using these oils for deep‐frying is their relatively high susceptibility to oxidation, and so any processing interventions that would improve the oxidative stability would increase their prospects of use in commercial deep‐frying. The oxidative stability of both B. napus and B. juncea crude oils can be improved dramatically by roasting the seeds (165 °C, 5 min) prior to oil extraction. Roasting did not alter the fatty acid composition or the tocopherol content of the oils. The enhanced oxidative stability of the oil, solvent‐extracted from roasted seeds, is probably due to 2,6‐dimethoxy‐4‐vinylphenol produced by thermal decarboxylation of the sinapic acid naturally occurring in the canola seed.     

Preparation and characterization of a biodegradable mulch: Paper coated with polymerized vegetable oils

Kraft paper was coated with resins based on vegetable oils and then tested for mechanical properties, rate of biodegradation in soil, and ability to inhibit weed growth. Resins included oxidatively polymerized linseed oil (LO) and a polyester formed by the reaction of epoxidized soybean oil and citric acid (ESO–CA). Tensile strength of LO-coated paper (82 MPa) was slightly higher than uncoated paper (68 MPa), while the tensile strength of ESO–CA coated paper was somewhat lower (45 MPa). Elongations to break (3–8%) were similar for all samples. The rates of weight loss and tensile strength during soil burial decreased as follows: uncoated paper > LO coated paper > ESO–CA coated paper. The polymerized oils acted as barriers to penetration of microorganisms to the cellulosic fibers. Resin-coated papers inhibited weed growth for > 10 weeks, while uncoated paper was highly degraded and ineffective by 6–9 weeks. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2159–2167, 1999     

Studies on phytosterol oxides. I: Effect of storage on the content in potato chips prepared in different vegetable oils

Potato chips fried in palm oil, sunflower oil, and high-oleic sunflower oil were studied for the content of different phytosterol oxides during 0 to 25 weeks of storage in the dark. Oxidation products of sitosterol (24α-ethyl-5-cholesten-3β-ol) and campesterol (24α-methyl-t-cholesten-3β-ol) were synthesized to help identify the phytosterol oxides. The oxides of phytosterols were analyzed by preparative thin-layer chromatography, solid-phase extraction, capillary column gas chromatography (GC), and GC-mass spectrometry. Epimers of 7-hydroxysitosterol and 7-hydroxycampesterol; 7-ketositosterol and 7-ketocampesterol; epimers of 5,6-epoxy-sitosterol and 5,6-epoxy-campesterol; 24α-ethylcholestane-3β,5,6β-triol (dihydroxysitosterol) and 24α-methylcholestane-3β,5,6β-triol (dihydroxycampesterol) were detected and quantitated in the samples of chips fried in different vegetable oils. Potato chips fried in palm oil had the lowest level of total sterol oxides, ranging from 5 to ca. 9 ppm in the lipids from time 0 to 25 wk of storage. The level of total sterol oxides in chip samples fried in sunflower oil ranged from 46 to 47 ppm, and the lipids in samples fried in high-oleic sunflower oil ranged from 35 to 58 ppm from 0 time to 25 wk of storage. During 25 wk of storage no considerable increase in sterol oxides was observed in the samples of chips fried in palm oil and sunflower oil. The chip samples fried in high-oleic sunflower oil had slightly higher levels of sterol oxides after 10 and 25 weeks of storage. In addition to the levels of individual sterol oxides, a new method for enrichment of phytosterol oxides from the unsaponifiables and full-scan mass spectra of various oxidation products of sitosterol and campesterol are reported in this paper. Part of the results were presented at the 86th Annual Meeting of the AOCS, May 7–11, 1995, San Antonio, TX.     

Antioxidant activity of amino acid sodium and potassium salts in vegetable oils at frying temperatures

Previous studies reported that several amino acids had strong antioxidant activity in vegetable oils under frying conditions. In this study, amino acids were converted to their sodium or potassium salts, and a heating study was conducted with 5.5 mM amino acid salts in soybean oil (SBO) at 180°C. Sodium salts of amino acids including alanine, phenylalanine, and proline and disodium glutamate had significantly stronger antioxidant activity than the corresponding amino acids, and potassium salts had stronger antioxidant activity than sodium salts. Potassium salts of alanine and phenylalanine more effectively retained tocopherols in SBO than the corresponding amino acids during heating. Phenylalanine potassium salt had stronger antioxidant activity than phenylalanine in other vegetable oils including olive, high oleic soybean, canola, avocado, and corn oils. Phenylalanine potassium salt at 5.5 mM more effectively prevented oil oxidation than tert-butyl hydroquinone, a synthetic antioxidant, at its legal concentration limit (0.02%) indicating its feasibility as a new antioxidant for frying.     

Frying quality and oxidative stability of high-oleic corn oils

To determine the frying stability of corn oils that are genetically modified to contain 65% oleic acid, high-oleic corn oil was evaluated in room odor tests and by total polar compound analysis. Flavor characteristics of french-fried potatoes, prepared in the oil, were also evaluated by trained analytical sensory panelists. In comparison to normal corn oil, hydrogenated corn oil and high-oleic (80 and 90%) sunflower oils, high-oleic corn oil had significantly (P<0.05) lower total polar compound levels after 20 h of oil heating and frying at 190°C than the other oils. Fried-food flavor intensity was significantly higher in the normal corn oil during the early portion of the frying schedule than in any of the high-oleic or hydrogenated oils; however, after 17.5 h of frying, the potatoes fried in normal corn oil had the lowest intensity of fried-food flavor. Corn oil also had the highest intensities of off-odors, including acrid and burnt, in room odor tests. High-oleic corn oil also was evaluated as a salad oil for flavor characteristics and oxidative stability. Results showed that dry-milled high-oleic corn oil had good initial flavor quality and was significantly (P<0.05) more stable than dry-milled normal corn oil after oven storage tests at 60°C, as evaluated by flavor scores and peroxide values. Although the high-oleic corn oil had significantly (P<0.05) better flavor and oxidative stability than corn oil after aging at 60°C, even more pronounced effects were found in high-temperature frying tests, suggesting the advantages of high-oleic corn oil compared to normal or hydrogenated corn oils.     

Frying quality and oxidative stability of two unconventional oils

The behavior of crude Sclerocarya birrea kernel oil (SCO) and Sorghum bug (Agonoscelis pubescens) oil (SBO) during deep-frying of par-fried potatoes was studied with regard to chemical, physical, and sensory parameters, such as content of FFA, tocopherols, polar compounds, oligomer TG, volatile compounds, oxidative stability, and total oxidation (TOTOX) value. Palm olein was used for comparison. Whereas potatoes fried in SCO that had been used for 24 h of deep-frying at 175°C were still suitable for human consumption, potatoes prepared in SBO that had been used for 6 to 12 h were not, considering the sensory evaluation. In looking at the chemical and physical parameters, SBO exceeded the limits, after no later than 18 h of use, for the amount of polar compounds, oligomer TG, and FFA recommended by the German Society of Fat Sciences (DGF) as criteria for the rejection of used frying oils. In contrast to SBO, SCO oil did not exceed the limits for the content of polar compounds and oligomer TG during the frying experiment. Only the amount of FFA was exceeded; this was because the amount of FFA at the beginning of the experiment was higher than for refined oils. The results showed that both oils were suitable for deep-frying of potatoes, but remarkable differences in the time during which both oils produced palatable products were found.     

Comparison of rancimat evaluation modes to assess oxidative stability of fish oils

Two Rancimat evaluation modes, the induction period (IP), and the time needed to achieve a selected difference in conductivity (tΔK) were compared for assessing relative stability of anchovy, sardine, and hake liver oils. Mean coefficients of variation were 2.5 and 2.4% for IP and tΔK values, respectively, for oils oxidized in the range 55–90°C. Natural logarithms of IP and tΔK values varied linearly with temperature (P<0.001). A linear relationship (r=0.999) was established between the IP and tΔK values (P<0.001). Relative oxidative stability of fish oils was determined with the same degree of confidence by either IP or tΔK values.     

Predicting oxidative stability of vegetable oils using neural network system and endogenous oil components

The usefulness of Artificial Neural Network Systems (ANNW) to predict the stability of vegetable oil based on chemical composition was evaluated. The training set, comprised of a composition of major and minor components of vegetable oil as inputs and as outputs, induction period and values of slopes for initiation and propagation, was measured by oxygen consumption. The best predictability was achieved for oils stored at 35°C with light exposure, when the major fatty acids, chlorophylls, tocopherols, tocotrienols, and metals were used as predictors. For oils stored at 65°C without light, a good predictability was obtained when composition of the major fatty acids and the amounts of tocopherols and tocotrienols were used. These results suggest that vegetable oil stability can be successfully predicted by ANNW when partial oil composition is known.     

Characteristics of bread and buns made with lard and vegetable oils of different iodine values

A good-quality white loaf of bread or rolls can be baked by substituting liquid vegetable oil (canola, soya and palm) for the standard shortening,i.e. lard, tallow or partially hydrogenated vegetable shortening. Canola oil and soya oil produced lower specific volumes of 5.56 and 5.55 cm³/g and higher softness indices when used with mono- and diglycerides only. Palm oil and lard produced specific volumes of 6.33 and 6.15 cm³/g and lower softness indices with mono- and diglycerides. When a blend of surfactants consisting of mono- and diglycerides and sodium stearyl lactylate (SSL) was used at 0.5% of flour weight, palm, canola, lard and soya gave comparable results in specific volume and compressibility. Rolls baked with the same fats and oils, and addition of ethoxylated stearic acid (MYRJ 45H) or a blend of MYRJ 45H and SSL, all gave good specific volumes ranging from 6.92 to 7.27 cm³/g and a softness index range of 0.71–0.86 and 0.68–0.86 after 48 and 96 h of storage. When a proper surfactant is used, good-quality bread and rolls can be baked with liquid vegetable oil. Furthermore, the usage level of liquid oil can be cut by approximately 30% in comparison to lard or shortening while still maintaining quality.