Antioxidant Activity Of Tocopherols Research Articles

Tocopherols as antioxidants in lipid-based systems: The combination of chemical and physicochemical interactions determines their efficiency.

Lipid oxidation is a major concern in the food, cosmetic, and pharmaceutical sectors. The degradation of unsaturated lipids affects the nutritional, physicochemical, and organoleptic properties of products and can lead to off-flavors and to the formation of potentially harmful oxidation compounds. To prevent or slow down lipid oxidation, different antioxidant additives are used alone or in combination to achieve the best possible efficiency with the minimum possible quantities. In manufactured products, that is, heterogeneous systems containing lipids as emulsions or bulk phase, the efficiency of an antioxidant is determined not only by its chemical reactivity, but also by its physical properties and its interaction with other compounds present in the products. The antioxidants most widely used on the industrial scale are probably tocopherols, either as natural extracts or pure synthetic molecules. Considerable research has been conducted on their antioxidant activity, but results regarding their efficiency are contradictory. Here, we review the known mechanisms behind the antioxidant activity of tocopherols and discuss the chemical and physical features that determine their efficacy. We first describe their chemical reactivity linked with the main factors that modulate it between efficient antioxidant capacity and potential prooxidant effects. We then describe their chemical interactions with other molecules (phenolic compounds, metals, vitamin C, carotenes, proteins, and phospholipids) that have potential additive, synergistic, or antagonist effects. Finally, we discuss other physical parameters that influence their activity in complex systems including their specific interactions with surfactants in emulsions and their behavior in the presence of association colloids in bulk oils.

Contribution of the Ratio of Tocopherol Homologs to the Oxidative Stability of Commercial Vegetable Oils.

The antioxidant activity of tocopherols in vegetable oils was shown to chiefly depend on the amount and the tocopherol homolog present. However, the most effective ratio of tocopherol homologs with regard to the antioxidant capacity has not been elucidated so far. The present study analyzed the effect of different tocopherol concentrations, homologs and ratios of homologs on markers of lipid oxidation in the most commonly consumed vegetable oils (canola, sunflower, soybean oil) stored in a 12 h light/dark cycle at 22 ± 2 °C for 56 days under retail/household conditions. After 56 days of storage, the α-tocopherol-rich canola and sunflower oil showed the strongest rise in lipid peroxides, yielding 25.1 ± 0.03 meq O2/kg (+25.3-fold) and 24.7 ± 0.05 meq O2/kg (+25.0-fold), respectively. ESR experiments, excluding effects of the oils’ matrices and other minor constituents, confirmed that a food representative tocopherol ratio of (γ + δ)/α = 4.77, as represented in soybean oil, led to a more pronounced delay of lipid oxidation than a lower ratio in canola (1.39) and sunflower oil (0.06). An optimum (γ + δ)/α -tocopherol ratio contributing to the oxidative quality of vegetable oils extending their shelf life has to be investigated.

Impact of phosphatidylethanolamine on the antioxidant activity of α-tocopherol and trolox in bulk oil.

The amphiphilic phospholipids dioleoylphosphatidylcholine (DOPC) and dioleoylphosphatidylethanolamine (DOPE), can form reverse micelles in bulk oils, which affects lipid oxidation chemistry. Previous studies showed that reverse micelles formed by DOPC and DOPE shorten the oxidation lag phase of stripped soybean oil. This study examined how these reverse micelles influence the activity of primary antioxidants such as the nonpolar α-tocopherol and the polar trolox in stripped and commercial soybean oils. The results showed that DOPC reverse micelles decreased the activity of 100 μM α-tocopherol or trolox. On the other hand, DOPE increased the antioxidant activity of both α-tocopherol and trolox. The polar trolox exhibited better antioxidant activity than the nonpolar α-tocopherol in the presence of both DOPC and DOPE reverse micelles because trolox partitioned more at the interfaces, which was confirmed by a fluorescence steady state study. Different ratios of DOPE to DOPC were added to oil containing 100 μM α-tocopherol, and antioxidant activity increased with increasing DOPE/DOPC ratio. Addition of DOPE to commercial oil inhibited lipid oxidation, whetrsd DOPC was ineffective. HPLC showed that DOPE regenerated α-tocopherol. This study indicates that the antioxidant activity of tocopherols could be improved by utilizing phosphatidylethanolamine (PE) to engineer the properties of reverse micelles in bulk oil.

In vitro antioxidant activity of tocopherols and tocotrienols and comparison of vitamin E concentration and lipophilic antioxidant capacity in human plasma

A comparative study investigated four tocopherols, four tocotrienols, and alpha-tocopheryl acetate on their antioxidative activities in five different popular assays, which were adapted to non-polar antioxidants. alpha-Tocopherol, used as calibration standard, showed the highest ferric reducing antioxidant power. Greater ring methyl substitution not only led to an increase of scavenging activity against the stable 2,2-diphenyl-1-picrylhydrazyl radical, but also to a decrease in oxygen radical absorbance capacity. Regarding alpha-tocopherol equivalent antioxidant capacity no significant differences in the antioxidant activity of all vitamin E isoforms were found. In contrast, a significantly lower peroxyl radical-scavenging activity of alpha-tocochromanols was determined in a chemiluminescence assay. Except oxygen radical absorbance capacity, no significant differences of the antioxidant activity related to the side chain could be detected. The data show that the reducing ability and radical chain-breaking activity of the several vitamin E forms depends on the circumstances under which the assays are performed. In our opinion, the used lipophilic methods can be useful for estimating the antioxidant activity of strong non-polar antioxidants, e.g. carotenoids, too. Furthermore, we could show a significant correlation between the total tocopherol content in human plasma and the lipophilic antioxidant capacity measured by alpha-tocopherol equivalent antioxidant capacity and 2,2-diphenyl-1-picrylhydrazyl.

Differential modulation of biomarkers of Metabolic Syndrome (MetS) in C57BL/6J mice by isomers of tocopherol

Antioxidant activities of tocopherols are well documented. However, it has become evident they also exhibit other biologic activities. We investigated the effects of alpha (α) and gamma (γ) tocopherol on biomarkers of MetS in mice including, adipocyte peroxisome proliferator activated receptor (PPAR‐γ), uncoupling protein (UCP), fatty acid binding protein 4 (fabp4), CD36, hepatic PPAR α, and acyl CoA oxidase (ACO) expressions. C57BL/6J mice (n=75) were divided into 5 groups and placed on five different dietary regimens as follows. Groups 1 and 5 (control): low‐fat (LF) and high‐fat (HF) diets for 25 weeks, respectively; groups 2–4: HF diet for 15 weeks followed by 10 weeks on HF supplemented with αT, γT, αT + γT, respectively. Animals were sacrificed at the end of 25 weeks. α‐T and αT + γT significantly reduced weight gain and improved insulin sensitivity indices. Protein and mRNA expressions of adipocyte PPAR‐γ, UCP, fabp 4, CD36, hepatic PPAR α, and ACO were significantly increased with α‐T and αT + γT but not γT alone. ACO and fatty acid synthetase expressions in treatment groups were not different from HF controls. αT alone and in combination with γT led to modulation of biomarkers of MetS in mice. The study for the first time demonstrates the ability of αT to function as dual PPAR agonist in modulating biomarkers of MetS in vivo.Supported by grants from Texas Department of Agriculture, Human Nutrition Fund

Does dietary tocopherol level affect fatty acid metabolism in fish?

Fish are a rich source of the n-3 polyunsaturated fatty acids (PUFA), particularly the highly unsaturated fatty acids (HUFA) eicosapentaenoic (EPA; 20:5n-3) and docosahexaenoic (DHA; 22:6n-3) acids, which are vital constituents for cell membrane structure and function, but which are also highly susceptible to attack by oxygen and other organic radicals. Resultant damage to PUFA in membrane phospholipids can have serious consequences for cell membrane structure and function, with potential pathological effects on cells and tissues. Physiological antioxidant protection involves both endogenous components, such as free-radical-scavenging enzymes, and exogenous dietary micronutrients including tocopherols and tocotrienols, the vitamin E-type compounds widely regarded as the primary lipid-soluble antioxidants. The antioxidant activities of tocopherols are imparted by their ability to donate their phenolic hydrogen atoms to lipid (fatty acid) free radicals, resulting in the stabilization of the latter and the termination of the lipid peroxidation chain reaction. However, tocopherols can also prevent PUFA peroxidation by acting as quenchers of singlet oxygen. Recent studies on marine fish have shown correlations between dietary and tissue PUFA/tocopherol ratios and incidence of lipid peroxidation, as indicated by the levels of thiobarbituric-acid reactive substances (TBARS) and isoprostanes. These studies also showed that feeding diets containing oxidized oil significantly affected the activities of liver antioxidant defence enzymes and that dietary tocopherol partially attenuated these effects. However, there is evidence that dietary tocopherols can affect fatty acid metabolism in other ways. An increase in membrane PUFA was observed in rats deficient in vitamin E. This was suggested to be due to overproduction of PUFA arising from increased activity of the desaturation/elongation mechanisms responsible for the synthesis of PUFA. Consistent with this, increased desaturation of 18:3n-3 and 20:5n-3 in hepatocytes from salmon fed diets deficient in tocopherol and/or astaxanthin has been observed. Although the mechanism is unclear, tocopherols may influence the biosynthesis of n-3PUFA through alteration of cellular oxidation potential or peroxide tone.

Antioxidant Activity of Tocopherols by the Simultaneous Use of Toc Derivatives.

Antioxidant Activity of Tocopherols by the Simultaneous Use of Toc Derivatives.

The effect of temperature on the antioxidant activity of tocopherols

The effect of temperature on the antioxidant activity of α- and δ-tocopherol (at 100 mg/kg level) was studied in pork lard, using the Oxipres apparatus, in the temperature range from 80 to 150 °C. The antioxidant activity of δ-tocopherol decreased with increasing working temperature in the whole temperature range studied. The activity of α-tocopherol was practically constant in the temperature range from 80 to 110 °C and decreased with increasing temperature at temperatures higher than 110 °C. Both tocopherols were ineffective at 150 °C (p <0.05). Due to different temperature effects on the antioxidant activities of α- and δ-tocopherol, the δ-tocopherol activity was approximately two times higher than the α-tocopherol activity at 80 °C, but their activities were the same (p <0.05) at 130 °C.

Antioxidant activities of tocopherols

Tocopherols are known to show high antioxidant activities. Their action mechanism, however, has not yet been discussed sufficiently. In this study tocopherols were investigated kinetically, together with p-methoxyphenol. The rate equation shows that a tocopherol can trap more mol of radicals than two, namely 2.3–2.9 mol, per mol of tocopherol, and can trap alkyl radicals as well as peroxy radicals. The rate equation for p-methoxyphenol, on the other hand, suggested that it behaves similarly to a tocopherol in antioxidant action. The action mechanism of a tocopherol, thus, is estimated from detailed study on the antioxidant action of the smaller and simpler p-methoxyphenol, namely study on the kinetic evaluation and qualitative and quantitative analyses of products obtained after the antioxidant action of p-methoxyphenol.

Antioxidant activity of tocopherols, tocotrienols, and gamma-oryzanol components from rice bran against cholesterol oxidation accelerated by 2,2'-azobis(2-methylpropionamidine) dihydrochloride.

The antioxidant activities of vitamin E (alpha-tocopherol, alpha-tocotrienol, gamma-tocopherol, and gamma-tocotrienol) and gamma-oryzanol components (cycloartenyl ferulate, 24-methylenecycloartanyl ferulate, and campesteryl ferulate) purified from rice bran were investigated in a cholesterol oxidation system accelerated by 2,2'-azobis(2-methylpropionamidine) dihydrochloride. All components exhibited significant antioxidant activity in the inhibition of cholesterol oxidation. The highest antioxidant activity was found for 24-methylenecycloartanyl ferulate, and all three gamma-oryzanol components had activities higher than that of any of the four vitamin E components. Because the quantity of gamma-oryzanol is up to 10 times higher than that of vitamin E in rice bran, gamma-oryzanol may be a more important antioxidant of rice bran in the reduction of cholesterol oxidation than vitamin E, which has been considered to be the major antioxidant in rice bran. The antioxidant function of these components against cholesterol oxidation may contribute to the potential hypocholesterolemic property of rice bran.

Evaluation of Antioxidant Activity of Natural Products

The methods for evaluating antioxidant property of natural products in in vitro and in vivo lipid peroxidation systems are reviewed. Antioxidant activity of tocopherols, carotenoids, flavonoids and curcuminoids have been demonstrated against lipid peroxidation induced in microsomes, erythrocytes, plasma lipoproteins and in animal trials. Recently, in vivo antioxidant function of natural products was extensively investigated in humans together with explanation of their absorbability and metabolic fate.

Antioxidant activity of tocopherols and phenolic compounds of virgin olive oil

AbstractThe antioxidant effects of hydrophilic phenols and tocopherols on the oxidative stability in virgin olive oils and in purified olive oil have been evaluated. Total hydrophilic phenols and the oleosidic forms of 3,4‐dihydroxyphenolethanol (3,4‐DHPEA) were correlated (r=0.97) with the oxidative stability of virgin olive oil. On the contrary, tocopherols showed low correlation (r=0.05). Purified olive oil with the dialdehydic form of elenolic acid linked to 3,4‐DHPEA, an isomer of oleuropeine aglycon, and 3,4‐DHPEA had good oxidative stability. A synergistic effect was observed in the mixture of 3,4‐DHPEA and its oleosidic forms with α‐tocopherol in purified olive oil by the Rancimat method at 120°C.

Antioxidant activities of tocopherols on Fe2+-ascorbate-induced lipid peroxidation in lecithin liposomes.

The antioxidant activities of 4 tocopherols, tocol, and a water-soluble model analog of alpha-tocopherol were compared. Egg lecithin liposomes were used and oxidation was catalyzed by Fe2+-ascorbate. The activities decreased in the order alpha greater than beta greater than gamma greater than delta-tocopherol greater than tocol, in agreement with their potencies in vivo. The water-soluble analog was the least effective. Activity depended on the molar ratio of antioxidant to unsaturated lipid, with one molecule each of the alpha-, beta-, gamma-, delta-tocopherol and tocol capable of protecting, respectively, 220, 120, 100, 30 and 20 molecules of polyunsaturated fatty acid. The mechanism of possible antioxidant effect of the compounds used is discussed.

Antioxidant activity of tocopherols, ascorbyl palmitate, and ascorbic acid and their mode of action.

AbstractIn the quest to use antioxidant compounds occurring in nature or related compounds, extensive studies have been made on vegetable oils, animal fats, apocarotenal, and vitamin A as substrates with ascorbyl palmitate, tocopherols, and ascorbic acid as antioxidants. Antioxidant efficiency varies with the substrate. Ascorbyl palmitate at a level of 0.01% provides a useful increase in the shelf‐life of vegetable oils. Alone it is better than butylated hydroxytoluene and butylated hydroxyanisole and in combinations with other known antioxidants improves the shelf‐life of all vegetable oils, as well as potato chips. Solubility problems with ascorbyl palmitate and other esters of ascorbic acid are discussed. The tocopherols have their greatest effect in protection of animal fats, carotenoids, and vitamin A. Experiments utilizing tocopherols and tocopherol combinations are presented. The activity of ascorbic acid, an excellent scavenger of oxygen, is reviewed. Quenchers of singlet oxygen do not inhibit the direct oxidation of fats and oils under the conditions used.