Oxidation at elevated temperatures: competition between α‐tocopherol and unsaturated triacylglycerols

The competitive oxidation between α‐tocopherol and unsaturated fatty acyls at thermoxidation conditions (180 and 240 °C) was evaluated using purified triacylglycerols from nine fats and oils (refined coconut, palm, tallow, olive, high oleic sunflower, sunflower, corn, soybean, and flaxseed oil). α‐Tocopherol degraded faster in less unsaturated lipids and a linear correlation between the iodine value (x) and the residual tocopherol content (y) was obtained after 2 h of heating at 240 °C (y = 3.72x + 137.5, R² = 0.9463). The formation of polar oxidation products was established and the results were explained by a non‐selective oxidation of unsaturated fatty acyls and α‐tocopherol by highly reactive alkoxyl and hydroxyl radicals generated by decomposition of hydroperoxides.     

Kinetics of antioxidant action of α‐ and γ‐toco‐pherols in sunflower and soybean triacylglycerols

A kinetic analysis was performed to evaluate the antioxidant behavior of α‐ and γ‐to‐copherols (5—2000 ppm) in purified triacylglycerols obtained from sunflower oil (TGSO) and soybean oil (TGSBO) at 100 °C. Different kinetic parameters were determined, viz. the stabilization factor as a measure of effectiveness, the oxidation rate ratio as a measure of strength, and the antioxidant activity which combines the other two parameters. In the low concentration range (up to 400 ppm in TGSBO and up to 700 ppm in TGSO) α‐tocopherol was a more active antioxidant than γ‐tocopherol whereas the latter was more active at higher concentrations. It has been found that the different activity of the tocopherols is not due to their participation in chain initiation reactions, but that the loss of antioxidant activity at high tocopherol concentrations is due to their consumption in side reactions. The rates of these reactions are higher in TGSBO than in TGSO. Both α‐tocopherol itself and its radicals participated more readily in side reactions than γ‐tocopherol and its radicals. Both α‐ and γ‐tocopherol reduce lipid hydroperoxides, thus generating alkoxyl radicals which are able to amplify the rate of lipid oxidation by participating in chain propagation reactions.     

Performance of sunflower oil with high levels of oleic and palmitic acids during industrial frying of almonds,peanuts, and sunflower seeds

High-oleic, high-palmitic sunflower oil (HOHPSO) is a seed oil from a new mutant sunflower line characterized by increased levels of both oleic acid (>50%) and palmitic acid (>25%) and a high oxidative stability. In this study, its performance at frying temperature was compared with that of palm olein in thermoxidative assays (4 h, 180°C). Also, industrial discontinuous frying of almonds, peanuts, and sunflower seeds (200 kg of each product) was carried out to define both the performance of HOHPSO and the main changes undergone by the foods. The evaluation of polar compounds and their distribution in the main groups, i.e., polymers, oxidized monomers, and DAG, as well as changes in tocopherols and oxidative stability, demonstrated the excellent behavior of HOHPSO during thermoxidation and frying. The increase in polar compounds and the loss of tocopherols and stability were much lower for HOHPSO than for palm olein under identical heating conditions. Only 1.3% polar compounds were formed during industrial discontiuous frying for 4 h and the oil stability increased, probably due to the formation of antioxidant compounds. As for the foods, the FA composition of the surface oil was clearly different from that corresponding to the internal oil, the former denoting the presence of HOHPSO in high concentration, particularly in fried sunflower seeds. Changes in oil stability of the foods attributable to the frying process clearly demonstrate the interest in using a highly stable oil such as HOHPSO to protect the surface against oxidation during food storage.     

Mulberry Seed Oil: a Rich Source of δ‐Tocopherol

In the present study, mulberry seed oil (MSO) samples obtained from seeds of different mulberry varieties as well as concentrated mulberry juice production waste (mulberry pomace) were investigated. Radical scavenging capacity, tocopherol and total phenolic content of MSO were determined. It was observed that MSO contain unique amounts of δ‐tocopherol varying between 1645–2587 mg kg^?1 oil depending on the variety. The secondary tocopherol homologue was γ‐tocopherol within a concentration range of 299–854 mg kg^?1 oil. MSO exhibited a very high antioxidant capacity varying in the range of 1013–1743 and 2574–4522 mg α‐tocopherol equivalents (α‐TE) per kg of oil for 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) and freeze‐dried 2,2′‐azino‐bis (3‐ethylbenzothiazoline‐6‐sulfonic acid) (FD‐ABTS) radical cation assays, respectively. Both antioxidant capacity and total phenolic content were higher for mulberry pomace oil compared with the seed oils. Fatty acid composition of MSO was also determined, and linoleic acid was found to be the primary fatty acid (66–80 %).     

Effects of Phosphatidylcholine on Interaction of α-Tocopherol and β-Carotene in Photosensitized Oxidation of Emulsions

The interaction between α‐tocopherol (500 mg/kg) and β‐carotene (10 mg/kg) during chlorophyll‐photosensitized oxidation of a sunflower oil emulsion was studied in the presence or absence of phosphatidylcholine (PC, 250 mg/kg) by determining peroxide (POV) and conjugated dienoic acid (CDA) values. Chlorophyll, α‐tocopherol, β‐carotene, and PC contents in the emulsion were also monitored. α‐Tocopherol and β‐carotene individually and interactively decreased the POV and CDA values of oil in the emulsion by singlet oxygen quenching. PC decreased the POV and CDA values of oil, however, the values of the emulsion with added α‐tocopherol, β‐carotene, and PC were not significantly different from those of the emulsion with added α‐tocopherol and β‐carotene without PC. Contents of α‐tocopherol did not change during 24‐h oxidation, whereas co‐present PC significantly caused α‐tocopherol and chlorophyll degradation. β‐Carotene and PC contents significantly decreased to 45.5 and 51.3 %, respectively, after 24 h, and α‐tocopherol protected β‐carotene from degradation. The results suggest that PC had no net effects on the interactive antioxidant activity of α‐tocopherol and β‐carotene during chlorophyll‐photosensitized oxidation of the emulsion through free radical generation, chlorophyll degradation, and lessening the potency of α‐tocopherol as a singlet oxygen quencher.     

Virgin hemp seed oil: An interesting niche product

Virgin hemp seed oil is not widespread on the market, although it is characterised by an interesting fatty acid composition with a high content of polyunsaturated fatty acids. Linoleic acid is the predominant fatty acid, which comes, together with α‐linolenic acid (18:3n‐3), to approximately 80% of the total fatty acids. From a nutritional point of view, up to 7% γ‐linolenic acid (18:3n‐6) and 2.5% stearidonic acid (18:4n‐3) are very interesting. The total amount of tocopherols is high between 80 and 110 mg/100 g, with γ‐tocopherol as the main tocopherol (85%). Due to the high amount of unsaturated fatty acids, hemp seed oil is very susceptible to oxidative deterioration, which results in a fast impairment of the oil during storage. In addition, the high amounts of chlorophyll in the oil due to harvesting of high amounts of immature seeds require light protection, which is often neglected because of merchandising purposes. The virgin oil is characterised by a nutty taste with a slightly bitter aftertaste. The use of virgin hemp seed oil is recommended during mild processing of food without heat.     

Formation of 4‐Hydroxy‐2‐Trans‐Nonenal,a Toxic Aldehyde,in Thermally Treated Olive and Sunflower Oils

4‐Hydroxy‐2‐trans‐nonenal (HNE) is a toxic aldehyde produced mostly in oils containing polyunsaturated fatty acid due to heat‐induced lipid peroxidation. The present study examined the effects of the heating time, the degree of unsaturation, and the antioxidant potential on the formation of HNE in two light olive oils (LOO) and two sunflower oils (one high oleic and one regular) at frying temperature. HNE concentrations in these oil samples heated for 0, 1, 3, and 5 hours at 185 °C were measured using high‐performance liquid chromatography. The fatty‐acid distribution and the antioxidant capacity of these four oils were also analyzed. The results showed that all oils had very low HNE concentrations (<0.5 μg g^?1 oil) before heating. After 5 hours of heating at 185 °C, HNE concentrations were increased to 17.98, 25.00, 12.51, and 40.00 μg g^?1 in the two LOO, high‐oleic sunflower oil (HOSO), and regular sunflower oil (RSO), respectively. Extending the heating time increased HNE formation in all oils tested. It is related to their fatty‐acid distributions and antioxidant capacities. RSO, which contained high levels of linoleic acid (59.60%), a precursor for HNE, was more susceptible to degradation and HNE formation than HOSO and LOO, which contained only 6–8% linoleic acid.     

A non‐extractable condensed‐tannins fiber reduces thermal oxidation in oils at frying temperature

Several compounds presenting antioxidant properties have been tested in frying oils to delay thermal oxidation of the triglycerides containing unsaturated fatty acids. The present study was designed to evaluate, for the first time, the antioxidant and antipolymerizing effects of addition of Exxenterol®, a denatured carob fiber very rich in non‐extractable tannins, on olive oil (OO), sunflower oil (SO) and a homogeneous blend of both oils. Exxenterol was added to the three oils in amounts of 50, 250, 500 and 1000 mg/kg oil before heating. After 36 h of heating at 180 °C, there was a large and relevant increase of the polar material and the polymer contents, but tocopherol decreased to non‐detectable levels in all three oils. Polar content, polymer and thermal oxidation formation (p ≤0.004) and tocopherol degradation (p ≤0.022) were significantly and dose‐dependently inhibited by Exxenterol. Both polar material and polymer formation were inhibited (at least by 44%) in OO and SO and at least by 27% in the oil blend when 1000 mg/kg oil of this product was added. Small but detectable amounts of tocopherol were found in the oil blend containing 50 mg Exxenterol/kg. The results clearly show that this non‐extractable tannin‐rich fiber can be successfully employed as an additive to prolong oil shelf life at frying temperature.     

Oxidative stability of sunflower oils differing in unsaturation degree during long-term storage at room temperature

The objective of this work was to study the evolution of oxidation in sunflower oils differing in unsaturation degree during long-term storage at room temperature. For this purpose, a combination of adsorption and size-exclusion chromatographies was used for quantification of oxidized triacylglycerol (TG) monomers, dimers, and polymers. Conventional sunflower oil, genetically modified high-oleic sunflower oil, and a 1∶1 mixture of the two were used. Results showed that oxidized TG monomers were the only group of oxidation compounds increasing during the early oxidation stage, and an excellent correlation was found between amounts of oxidized TG monomers and PV during the induction period, independently of the degree of oil unsaturation. Both the rate of formation and the amount of oxidized TG monomers accumulated at the end of the induction period increased as the unsaturation degree of the oils tested was higher. The end of the induction period was marked by the initiation of polymerization and exhaustion of tocopherol. Therefore, the concomitant determination of oxidized TG monomers and polymerization compounds provided a complete picture of the oxidation process.     

Effect of Different Frying Methods on the Total <Emphasis Type="Italic">trans</Emphasis> Fatty Acid Content and Oxidative Stability of Oils

The main objective of this study was to determine the effect of different frying oils and frying methods on the formation of trans fatty acids and the oxidative stability of oils. Sunflower, canola and commercial frying oils, the most commonly used oils for frying potatoes in the fast food industry, were used as the frying medium. The value for total polar compounds was highest when commercial frying oil was used in the microwave oven (22.5 ± 1.1). The peroxide value, as an indicator of oil oxidation, was lowest for microwave oven frying (2.53 ± 0.03). The K₂₃₂ and K₂₇₀ values were 0.41 ± 0.04 and 0.18 ± 0.02, respectively, for commercial frying oil in the microwave oven. The lowest free fatty acid content was recorded for the commercial frying oil used in the deep‐fat fryer at 190 °C. The highest iodine value was measured for sunflower oil used in the deep‐fat fryer (148.14 ± 0.07), indicating a greater degree of unsaturation. The lowest trans fatty acid value was recorded for sunflower oil in the microwave oven (0.17 ± 0.05), with a higher overall amount of total trans fatty acids observed for oils after frying in the electrical deep‐fat fryer compared to the microwave. Sunflower oil was favourable for both frying methods in terms of the trans fatty acid content.     

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.     

Effects of tocopherols and tocotrienols on the inhibition of autoxidation of conjugated linoleic acid

The effect of eight vitamin E homologues, i.e. α‐, β‐, γ‐, and δ‐tocopherol and α‐, β‐, γ, and δ‐tocotrienol, on the inhibition of autoxidation of conjugated linoleic acid (CLA) were investigated. The oxidation was carried out in the dark for 21 days at 50 °C and monitored by peroxide values (PV) and TBA values. The levels of the individual vitamin E homologues in CLA during storage were determined by HPLC. γ‐Tocopherol exhibited the highest antioxidant activity among the homologues tested in this study when the antioxidant activities of the individual homologues in CLA were compared by PV. The order of antioxidant activity of eight homologues was γ‐tocopherol > δ‐tocopherol = δ‐tocotrienol ≥ γ‐tocotrienol > β‐tocopherol = β‐tocotrienol > α‐tocopherol = α‐tocotrienol. The degradation rates of α‐tocopherol and α‐tocotrienol were faster than those of the other homologues, whereas δ‐tocopherol had the highest stability in CLA during storage. All homologues exhibited an antioxidant activity by inhibiting the formation of secondary oxidation products. It appears that α‐tocotrienol and β‐tocotrienol have significantly higher antioxidant activities for secondary oxidation in CLA than α‐tocopherol and β‐tocopherol. Meanwhile, the other homologues, namely γ‐tocopherol, γ‐tocotrienol, δ‐tocopherol, and δ‐tocotrienol, exhibited similar antioxidant activity for secondary oxidation in CLA.     

Antioxidant and prooxidant effects of α‐tocopherol in a linoleic acid‐copper(II)‐ascorbate system

The peroxidation of linoleic acid (LA) in the absence and presence of either Cu(II) ions alone or Cu(II)‐ascorbate combination was investigated in aerated and incubated emulsions at 37°C and pH 7. LA peroxidation induced by either copper(II) or copper(II)‐ascorbic acid system followed pseudo‐first order kinetics with respect to primary (hydroperoxides) and secondary (aldehydes‐ and ketones‐like) oxidation products, detected by ferric‐thiocyanate and TBARS tests, respectively. α‐Tocopherol showed both antioxidant and prooxidant effects depending on concentration and also on the simultaneous presence of Cu(II) and ascorbate. Copper(II)‐ascorbate combinations generally led to distinct antioxidant behavior at low concentrations of α‐tocopherol and slight prooxidant behavior at high concentrations of α‐tocopherol, probably associated with the recycling of tocopherol by ascorbate through reaction with tocopheroxyl radical, while the scavenging effect of α‐tocopherol on lipid peroxidation was maintained as long as ascorbate was present. On the other hand, in Cu(II) solutions without ascorbate, the antioxidant behavior of tocopherol required higher concentrations of this compound because there was no ascorbate to regenerate it. Practical applications: Linoleic acid (LA) peroxidation induced by either copper(II) or copper(II)‐ascorbic acid system followed pseudo‐first order kinetics with respect to primary (hydroperoxides) and secondary (e.g., aldehydes and ketones) oxidation products. α‐Tocopherol showed both antioxidant and prooxidant effects depending on concentration and also on the simultaneous presence of Cu(II) and ascorbate. The findings of this study are believed to be useful to better understand the actual role of α‐tocopherol in the preservation of heterogenous food samples such as lipid emulsions. Since α‐tocopherol (vitamin E) is considered to be physiologically the most important lipid‐soluble chain‐breaking antioxidant of human cell membranes, the results can be extended to in vivo protection of lipid oxidation.     

A Rapid Method for Simultaneous Analysis of Lignan and γ‐Tocopherol in Sesame Oil by Using Normal‐Phase Liquid Chromatography

A novel method for rapid and simultaneous analysis of three lignans and γ‐tocopherol in sesame oil has been established based on a one‐step solvent extraction followed by normal‐phase liquid chromatography. The briefness of the experimental procedure, use of 5 mL of n‐hexane/isopropanol (98:2, v/v) for extraction without any further cleanup process, short analysis time (10 min), and excellent sensitivity and selectivity demonstrated the advantages of this practical and efficient method. All the analytes exhibited satisfactory recoveries ranging from 95.4 to 103.4% at three spiked levels, with the relative SD ranging from 1.1 to 4.4%. The limits of quantitation of this method for four analytes were in the range of 0.3–1.0 μg g^?1. The validated method was successfully applied to the coinstantaneous determination of lignan and γ‐tocopherol in five real sesame oil samples. Furthermore, the results of this study were compared with previously reported method and standard method.     

Efficacy of myricetin as an antioxidant in methyl esters of soybean oil

The antioxidant activity of myricetin, a natural flavonol found in fruits and vegetables, was determined in soybean oil methyl esters (SME) and compared with α‐tocopherol and tert‐butylhydroquinone (TBHQ) over a 90‐day period employing EN 14112, acid value, and kinematic viscosity methods. Myricetin had greater antioxidant activity than α‐tocopherol, but was inferior to TBHQ. Synergism was observed between myricetin and TBHQ, but antagonism between α‐tocopherol and either myricetin or TBHQ was discovered. A binary mixture of myricetin and TBHQ at 1000 ppm (1:1) was the most effective treatment investigated at inhibiting oxidation of SME. Myricetin was not completely soluble in SME at 1000 ppm, suggesting that 500 ppm is a more appropriate treatment level. Pro‐oxidant activity of α‐tocopherol was observed when added to SME obtained from crude soybean oil, but antioxidant behavior was observed in distilled SME. Addition of α‐tocopherol to methyl esters initially free of antioxidants revealed that 600–700 ppm was the optimum concentration for antioxidant activity. Acid value and kinematic viscosity remained within prescribed specifications after 90 days, despite failure of a number of samples with regard to EN 14112, suggesting that these parameters are insufficient as sole indicators of oxidation stability.     

Triacylglycerols from viper bugloss (Echium vulgare L.) seed bio‐oil

Triacylglycerols (TAG) in viper bugloss oil were isolated from raw pressed oil by silicic acid column chromatography. The obtained blend of TAG was separated by silver ion thin‐layer chromatography (TLC Ag⁺) into nine fractions, varying in terms of unsaturation level and molecular polarity. The composition of TAG in viper bugloss oil was determined by HPLC coupled with a diode‐array detector and an evaporative light‐scattering detector. The results showed that the first three fractions were combinations of TAG containing palmitic, oleic and linoleic acids. Fractions 4 and 6 contained TAG of a similar acid composition as above, but with the addition of γ‐linolenic acid. The remaining fractions (7–9) were the most varied in acid composition. They were found to contain 26–39% palmitic acid, 12–15% oleic acid, 13–41% linoleic acid 8–24% γ‐linolenic acid, 1.5–5.5% α‐linolenic acid and 1–5% stearidonic acid. The analysis of fatty acid allocation in TAG of viper bugloss lipids revealed that linoleic acid (ranging from 2 to 100%) was the only acid found in all isolated fractions. In the investigated oil, the predominant TAG included: LnLnG (11.38%), LnLnSt (11.17%), LnGSt (7.71%), LnStSt (6.19%) and LnLnLn (5.44%). Almost 86% of the TAG contained α‐linolenic acid, while γ‐linolenic and stearidonic acids amounted to 49 and 38%, respectively.     

Great globe thistle fruit (Echinops sphaerocephalus L.), a potential new oil crop

New plant oil crops are desirable as renewable resources for energy, for food purposes, and as building blocks in chemical synthesis. Fruit oil of Echinops sphaerocephalus was characterized by a high content of linoleic acid (over 70% of total fatty acids) and by a high tocopherol content (530–970 mg/kg oil). The majority was α‐tocopherol. Echinops sphaerocephalus plants may be cultivated in agricultural dimensions, and fruits may be obtained by a combine harvester. Echinops quinoline alkaloids present a useful by‐product of the oil production.     

Formation of oxidation compounds in sunflower and olive oils under oxidative stability index conditions

The objective of this work was to study the evolution of oxidation under oxidative stability index (OSI) conditions using the Rancimat apparatus. Sunflower oils with different degrees of unsaturation (conventional high‐linoleic sunflower oil, genetically modified high‐oleic sunflower oil, and a 1 : 1 mixture of both of them) and virgin olive oil were used. The sunflower oils were tested at 100 °C, while the olive oil was assayed at 100, 110 and 120 °C. Samples were analyzed at different time points and conductivity values, until the induction period (IP) was overpassed. A combination of adsorption and size‐exclusion chromatography was used for the quantification of oxidized triacylglycerol (TG) monomers, dimers and polymers. Additionally, peroxide values (PV) and ultraviolet absorption at 270 nm (K₂₇₀), as well as losses of tocopherols, were measured. The results showed that oxidized TG monomers were the only group of oxidation compounds that increased during the early oxidation stage. The end of the IP was marked by the initiation of polymerization after the exhaustion of tocopherols. In comparison with reported results obtained at room temperature, the main difference found was that the amounts of oxidation compounds at the end of the IP were much lower at OSI test temperatures. With the exception of the K₂₇₀ values, the results also showed that the IP endpoints provided by the OSI test were slightly higher than those obtained by quantification of oxidized TG monomers or by PV determination.     

Influence of cholesterol on the kinetics of lipid autoxidation and on the antioxidative properties of α‐tocopherol and quercetin

The autoxidation kinetics of triacylglycerols of sunflower oil (TGSO) in the presence of 10% cholesterol (Chol) at 80, 90 and 100 °C has been studied. The process was followed by monitoring the peroxide value and the formation of conjugated dienes. Cholesterol has been found to exhibit a prooxidative effect. During the oxidation of the mixture (TGSO/Chol), cholesterol peroxides were not registered. It is supposed that the initial amount of cholesterol peroxides formed decomposes to free radicals and that these radicals accelerate TGSO oxidation. A kinetic analysis of the antioxidative behavior of α‐tocopherol and quercetin (2.9 x 10^?4‐17.8 × 10^?4 M) in both TGSO and TGSO/Chol at 100 °C was performed. It was found that the effectiveness, strength, and activity of α‐tocopherol are greater in TGSO/Chol than in TGSO, while these parameters for quercetin are practically the same in both lipid systems. The differences in the mechanism of action of α‐tocopherol and quercetin are discussed.