Antioxidant Activity Evaluation of Tocored through Chemical Assays,Evaluation in Stripped Corn Oil,and CAA Assay

γ‐Tocopherol‐5,6‐quinone (tocored) is a crucial oxidized product of γ‐tocopherol (γ‐T) found in edible oil. Previously published studies on antioxidant activity (AOA) of tocored are not consistent. This study aims to monitor its AOA comprehensively through chemical assays (1,1‐diphenyl‐2‐picrylhydrazyl [DPPH] and ferric reducing antioxidant power [FRAP]), antioxidant evaluation in a food model system (stripped corn oil), and cellular antioxidant activity (CAA) assay, which would reasonably widen the knowledge of the AOA of γ‐T and tocored. In both DPPH and FRAP assays, tocored shows less AOA than γ‐T. Results of chemical properties in the Schaal oven test show that tocored possesses better AOA than γ‐T. Correlation coefficients of γ‐T and tocored between peroxide and K₂₃₄ or p‐AnV are 0.8784–0.9875 and 0.8716–0.9879, respectively. The CAA assay also shows that tocored possesses better cellar AOA than γ‐T, with an EC₅₀ at 21.55 µg mL^?1. Drawing conclusions from the results from chemical assays, evaluation in stripped corn oil, and CAA assay, tocored is verified as a potent antioxidant in edible vegetable oils compared to γ‐T. Practical Applications: The present work widens the knowledge of antioxidant activity of tocored and gamma‐tocopherol, and contributes to the understanding of existing antioxidant activity when gamma tocopherol is depleted when edible oils are in storage and processing processes.     

Iron‐Catalyzed Reaction of γ‐Tocopherol with Methyl Linoleate Hydroperoxides in Solutions

γ‐Tocopherol is one of the main constituents in vegetable oils and acts as an antioxidant by trapping lipid‐peroxyl radicals. This study reports reaction products of γ‐tocopherol with lipid‐peroxyl radicals formed by iron‐catalyzed decomposition of methyl linoleate hydroperoxides (MeLOOH) in toluene and methanol solutions. The products in toluene solution were tocored, methyl (8a‐dioxy‐γ‐tocopherone)‐epoxyoctadecenoates (γT‐OO‐epoxyMeL), methyl (8a‐dioxy‐γ‐tocopherone)‐octadecadienoates (γT‐OO‐MeL), γ‐tocopherol biphenyl dimer (γTBD), γ‐tocopherol diphenylether dimer (γTED), and adducts of γ‐tocopherol dimers with the MeLOOH‐derived peroxyl radicals (γTED‐OO‐epoxyMeL, γTBD‐OO‐MeL, and γTED‐OO‐MeL). The iron‐catalyzed reaction in toluene proceeded slowly, whereas the reaction in methanol was relatively fast. The reaction products in methanol were γT‐OO‐epoxyMeL and γTED‐OO‐epoxyMeL together with tocored, γTBD, and γTED. The results indicate that the iron‐catalyzed decomposition of MeLOOH in toluene produces both epoxyperoxyl and peroxyl radicals and that the decomposition in methanol yields only the epoxyperoxyl radicals. These peroxyl radicals could react with the 8a‐carbon‐centered radical of γ‐tocopherol or its dimers.     

Effect of Moisture and Heat Treatment of Corn Germ on Oil Quality

The changes in the quality of crude corn oil caused by moisture and two different thermal pretreatments (oven heating and steam heating) of wet‐milled corn germ were evaluated and compared with those of untreated oil. Increasing the moisture content of the corn germ from 8 to 25% before oil extraction increased the acid value (AV) (3.02–4.01 mg KOH g^?1), peroxide value (PV) (0.52–1.05 meq kg^?1), and the red value (7.3–8.7) and decreased the content of total tocopherols by 37% and that of γ‐tocopherols by 31%. Oven heating tended to decrease the AV and PV while steam heating significantly increased the total and individual tocopherol contents (P < 0.05). The different moisture contents and thermal pretreatments of corn germ caused no significant differences in the fatty acid composition and the contents of total and individual phytosterols of the crude oils. The γ‐tocopherol contents were found to be highly correlated with the red values (the corresponding R² reached 0.9977 and 0.9089 for moisture and heat pretreatments, respectively).     

Comparison of four accelerated stability methods for lard and tallow with and without antioxidants

The oxidative stability of lard and tallow with and without antioxidants was evaluated by four accelerated stability methods, the active oxygen method (AOM), the oxygen bomb test, the Rancimat method, and the Schaal oven test. The results indicated that the oxidative stability of animal fats and the relative effectiveness of an antioxidant in the fats could have different mechanisms. When the protective index was used to demonstrate the relative effectiveness of the antioxidants, the results suggested that the Rancimat Method may be the least reliable method compared with AOM, oxygen bomb test, and Schaal oven test. More than one accelerated stability method is recommended for evaluating the effectiveness of an antioxidant or the oxidative stability of fats.     

Thermostability of genetically modified sunflower oils differing in fatty acid and tocopherol compositions

The objective of the study was to investigate the performance at frying temperature of a new sunflower oil with high content of oleic and palmitic acid (HOHPSO) and containing γ‐tocopherol as the most abundant natural antioxidant. HOHPSO either containing α‐ or γ‐tocopherol (HOHPSO‐α and HOHPSO‐γ, respectively) were obtained from genetically modified sunflower seeds and refined under identical conditions. The oil stability against oxidation, as measured by Rancimat at 120 °C, was much higher for the oil containing γ‐tocopherol, suggesting the higher effectiveness of γ‐tocopherol as compared to α‐tocopherol to delay oxidation. Experiments at high temperature (180 °C) simulating the conditions applied in the frying process clearly demonstrated that, for the same periods of heating, the oil degradation and the loss of natural tocopherol were significantly lower for the oil containing γ‐tocopherol. Comparison of different genetically modified sunflower oils with different fatty acid compositions confirmed that oil degradation depended on the fatty acid composition, being higher at a higher degree of unsaturation. However, the loss of tocopherol for a similar level of oil degradation was higher as the degree of unsaturation decreased. Overall, the results showed that HOHPSO‐γ had a very high stability at frying temperatures and that mixtures of HOHPSO‐α and HOHPSO‐γ would be an excellent alternative to fulfill the frying performance required by the processors and the vitamin E content claimed by the consumers.     

Effects of tocopherols and their mixtures on the oxidative stability of olive oil and linseed oil under heating

The tested tocopherols (γ,δ,α) showed antioxidative activity at all levels of addition to the monounsaturated olive oil, the effects increased as a function of concentrations (maximum: +287% with 800 mg γ‐tocopherol/100 g oil compared to the control oil). In the highly unsaturated linseed oil, which contains 58 mg/100 g initial concentration of γ‐tocopherol, γ‐tocopherol showed antioxidative behavior up to the addition of 100 mg/ 100 g oil. Additions of more than the 100 mg/100 g affected the oil, resulting in a faster oxidation. Mixtures of γ/δ‐tocopherols in olive oil were found to protect more efficiently than both vitamins when added separately α‐tocopherol reduced effects of other tocopherols in both plant oils. The stabilizing effect of added tocopherols and their mixtures (100 mg/100 g oil each) in olive oil are γ/δ‐T>γ‐T>δ‐T>γ/α‐T>δ/α‐T>α‐T and in linseed oil γ‐T>γ/δ‐T>δ‐T>γ/α‐T>α‐T>α/δ‐T.     

Interaction of tocored with unsaturated fatty esters

Tocored, an oxidation product of tocopherol and its model, 2,2,7,8-tetramethyl-5,6-chromanquinone reacted with methyl linoleate at an elevated temperature to form an adduct with isomerized linoleate. Oxidation of tocored in fatty esters produced a variety of products, depending on the degree of unsaturation of the esters. With methyl palmitate no addition product was detected but tocopurple and tocoreddimer were identified as minor products irrespective of the degree of saturation. A mechanism involving the interaction of tocored with lipid radicals to yield an adduct as the consequence of antioxidative action of tocored is postulated.     

Quality of corn germ oil obtained by aqueous enzymatic extraction

Aqueous enzymatic extraction of corn germ oil was investigated. By applying hydrothermal pretreatment of corn germ, it was possible to inactivate native enzymes present in the germ and to loosen its structure. The corn was then ground and treated with enzymes. After the oil had been released by the enzyme reaction, it was separated by centrifugation. The quality of oil obtained by enzymatic extraction (Pectinex Ultra SP-L at 37°C, pH 5.2, for 6 h) was good. The oil had 1.5% free fatty acids; a total content of oxidation product value of 8.1; light yellow color (AOCS photometric color, 12.7; dominant wavelength λ_D=575 nm); 0.022% phosphatides; 1350 mg/kg total tocopherol; and an oxidative stability value (Rancimat test, 100°C) of 14.6 h.     

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.     

Antioxidant activity of amino acids bound to trolox-C

Various amino acids, selected for their potential antioxidant activity, were, covalently attached to 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox-C), a lower homolog of vitamin E that has great antioxidant effectiveness. The resulting Troloxylamino acids (T-AA) had greater antioxidant effectiveness than Trolox-C in a linoleate emulsion system oxidized by hemoglobin. Troloxyl-tryptophan-methyl ester and Troloxyl-methionine-methyl ester were the most effective T-AA evaluated in the linoleate emulsion. However, butylated hydroxyanisole (BHA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and α-tocopherol were more antioxidant than any T-AA in the emulsion system. In a Schaal oven test at 45 C. Trolox-C was by by far the most effective antioxidant evaluated in corn oil. BHT and Troloxylcysteine had significant antioxidant activity in corn oil, but no other T-AA was antioxidant in corn oil. In butter oil, Trolox-C again had the highest antioxidant activity, and BHA and BHT were also highly antioxidant. All t-AA had antioxidant activity in butter oil, with Troloxyl-methioninc and Troloxyl-cysteine having the grcatest antioxidant effectiveness. The T-AA of highest antioxidant activity were hydrolyzed by chymotrypsin and/or trypsin, in vitro.     

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.     

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 %).     

Antioxidant activity in soybean oil of extracts from thompson grape bagasse

The phenolic compounds of Thompson grape bagasse were extracted using a 95:5 (vol/vol) ethanol/water mixture. Measurement of the antioxidant activity in refined soybean oil of bagasse grape extract was performed by using two different methods, the Rancimat method and the Schaal oven method in conjunction with peroxide value determination. The antioxidant activity of the extract was compared to the tertiary butyl hydroquinone (TBHQ) and butylated hydroxyanisole (BHA) activity. The bagasse grape extract showed similar antioxidant activities in both methods employed. At all concentrations tested [0.1, 0.3 and 0.5% of total phenols (TP)] the extract exhibited appreciable activity, which exceeded the activity of BHA. At some concentrations (0.3 and 0.5% TP) the extract exhibited activity comparable to that of TBHQ. Bagasse is a byproduct with a high content of phenolic compounds and is a good source of natural antioxidants.     

Determination of polyphenols,tocopherols, and antioxidant capacity in virgin argan oil (Argania spinosa,Skeels)

This study establishes data on polyphenols, tocopherols, and antioxidant capacity (AC) of virgin argan oil. A total of 22 samples from Morocco were analyzed. Total polyphenol content ranged between 6.07 and 152.04 mg GAE/kg. Total tocopherols varied between 427.0 and 654.0 mg/kg, being γ‐tocopherol the major fraction (84.68%); α‐, β‐, and δ‐tocopherols represent 7.75, 0.33, and 7.29%, respectively. No influence of oil extraction method on total tocopherols was observed. The AC of argan virgin oils determined by the ABTS method in n‐hexane oils dilution ranged between 14.16 and 28.02 mmol Trolox/kg, and by the ABTS, DPPH, and FRAP methods in methanolic oil extracts between 2.31–14.15, 0.19–0.87, and 0.62–2.32 mmol Trolox/kg, respectively. A high correlation was found between ABTS and DPPH methods applied to a methanolic oil extract. Virgin argan oil presents a higher polyphenol and tocopherol content, and total AC than other edible vegetable oils.     

Antioxidative activity of sage (Salvia officinalis L.), savory (Satureja hortensis L.) and borage (Borago officinalis L.) extracts in rapeseed oil

The antioxidant activity (AA) of acetone oleoresins (AcO) and deodorised acetone extracts (DAE) of sage (Salvia officinalis L.), savory (Satureja hortensis L.) and borage (Borago officinalis L.) were tested in refined, bleached and deodorised rapeseed oil applying the Schaal Oven Test and weight gain methods at 80 °C and the Rancimat method at 120 °C. The additives (0.1 wt‐%) of plant extracts stabilised rapeseed oil efficiently against its autoxidation; their effect was higher than that of the synthetic antioxidant butylated hydroxytoluene (0.02%). AcO and DAE obtained from the same herbal material extracted a different AA. The activity of sage and borage DAE was lower than that of AcO obtained from the same herb, whereas the AA of savory DAE was higher than that of savory AcO. The effect of the extracts on the oil oxidation rate measured by the Rancimat method was less significant. In that case higher concentrations (0.5 wt‐%) of sage and savory AcO were needed to achieve a more distinct oil stabilisation.     

The influence of moisture content and cooking on the screw pressing and prepressing of corn oil from corn germ

Samples of corn germ were obtained from a commercial corn wet mill (factory dried to about 3% moisture) and a commerical corn dry mill (undried, produced in the mill with about 13% moisture). The germ samples (200 g each) were cooked for various times in either a conventional oven at 180°C or a microwave oven at 1500 W. Bench-scale single screw pressing was then performed. With the dry milled corn germ, no oil was obtained from the uncooked germ. A maximal yield of about 5% oil [26% of total oil recovery (TOR), relative to hexane extraction] was obtained by cooking the dry-milled germ for 6.5 min in a conventional oven at 180°C before pressing. A maximal yield of about 7% oil (37% TOR) was obtained by cooking the dry-milled germ for 4.5 min in a microwave oven at 1500 W before pressing. With the wet-milled germ, yields of about 7% oil (18% TOR) were obtained with the uncooked germ and yields increased to a maximum of about 22% oil (56% TOR) by cooking in a conventional oven at 180°C for 5 min or a maximum of about 17% oil (44% TOR) by cooking for 4 min in a microwave oven at 1500 W. These results indicate that microwave and conventional oven cooking are both effective pretreatments before pressing. Microwave preheating resulted in higher oil yields with dry-milled germ, and conventional oven pretreatment resulted in higher oil yields with factory-dried wet-milled corn germ.     

Tocopherols and tocotrienols in grape seeds from 14 cultivars grown in Korea

In this study, the tocopherol (T) and tocotrienol (T3) contents of grape seeds from 14 different varieties grown in Korea were analyzed using saponification extraction followed by normal‐phase liquid chromatography. α‐T, γ‐T, α‐T3, and γ‐T3 were detected in all samples. The total concentration of tocopherol and tocotrienol was in the range of 4.8–9.9 mg/100 g seed (35.3–68.8 mg/100 g oil basis). The Muscat Bailey A cultivar had the highest total tocopherol and tocotrienol contents, followed by Canner and Naples. γ‐T3 ranged from 1.6 to 4.9 mg/100 g seed (11.2 to 53.81 mg/100 g oil basis) and was the main isomer, followed by α‐T3 in most of the samples. Analytical method validation parameters including accuracy and precision were determined. Overall recovery from grape seeds was close to 100%.     

On‐line LC‐NMR‐MS characterization of sesame oil extracts and assessment of their antioxidant activity

Sesame lignans were isolated by solvent extraction and subsequently purified by solvent crystallization from crude, unroasted sesame oil, and a sesame oil deodorizer distillate. In addition, an aliquot of the purified sesame oil extract was treated with camphorsulfonic acid to obtain a sesaminol‐enriched extract. The sesame lignan composition of the extracts was characterized by on‐line liquid chromatography nuclear magnetic resonance spectroscopy mass spectrometry coupling (LC‐NMR‐MS). The effect of the sesame oil extracts as well as pure sesame lignans and γ‐tocopherol on the oxidative stability of sunflower oil (lignan‐free) was studied by the Rancimat assay. The Rancimat assay revealed the following oxidative stability order: sesame oil extract < sesame oil deodorizer distillate < sunflower oil (no added sesame oil extracts) < sesamol < sesaminol‐enriched sesame oil extract. In addition, the radical‐scavenging capacity of these extracts was assessed by the Trolox® equivalent antioxidant capacity (TEAC) assay. The TEAC assay revealed a slightly different AOX activity order: sesamin < sesame oil extract < sesaminol‐enriched sesame oil extract < sesamol. In conclusion, the sesaminol‐enriched extract revealed strong antioxidant activity and is therefore suitable to increase the oxidative stability of edible oils high in polyunsaturated fatty acids.     

Antioxidant effects of flavonoids ofAnthriscus sylvestris in lard

Ethanol/water (7∶3) extracts of the plant speciesAnthriscus sylvestris possess antioxidant activity. Separation and identification of antioxidant components by thin-layer and column chromatography and spectral analysis demonstrated that quercetin and apigenin appeared to be the main flavonoid species inAnthriscus sylvestris. Rutin was one of the major quercetin glycosides. Structures of the isolated compounds were determined by infrared and¹H nuclear magnetic resonance spectroscopies. Ethanolic extract (70%) ofA. sylvestris showed concentration-dependent, strong antioxidant activity as determined by the Schaal Oven test of lard at 60°C. Rancimat analysis at 100°C showed that the antioxidant activity of 70% ethanolic extract ofA. sylvestris was superior to quercetin, apigenin, or a tocopherol mixture.