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.     

Process efficiency and long‐term performance of α‐tocopherol in film‐blown linear low‐density polyethylene

α‐Tocopherol was compared with a commercial phenolic antioxidant (Irganox 1076) as a long‐term and process antioxidant in film‐blown and compression‐molded linear low‐density polyethylene. The antioxidant function of α‐tocopherol was high in the film‐blown material, especially in the processing, according to oxygen induction time measurements with differential scanning calorimetry. The residual content of α‐tocopherol after processing, determined with chromatographic techniques, was less than that of the commercial phenolic antioxidant in both the film‐blown and compression‐molded materials. The process stabilizing efficiency was nevertheless higher for the material containing α‐tocopherol. During the long‐term stabilization, the efficiency of α‐tocopherol was less than that of the commercial phenolic stabilizer Irganox 1076 in the thin films, according to chemiluminescence and infrared measurements. The long‐term efficiency in the compression‐molded samples stabilized with α‐tocopherol or Irganox 1076 was equally good because of the low loss of both α‐tocopherol and Irganox 1076 from the thicker films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2427–2439, 2005     

Addition of α‐tocopherol on poly(lactic acid): Thermal,mechanical, and sorption properties

This work investigates the effect of the addition of a well‐known antioxidant, α‐tocopherol in poly (lactic acid) flexural and barrier properties. For that purpose, films of poly(lactic acid) enriched with 0, 2.2, and 4.4% of α‐tocopherol were prepared. Differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis were used to characterize the changes in the mechanical and thermal properties. The sorption of oxygen and carbon dioxide in the prepared enriched films of poly(lactic acid) was measured at different temperatures between 283 and 313 K and pressures up to atmospheric pressure using a Quartz Crystal Microbalance. Although no significant changes were found in the mechanical and thermal properties, the addition of α‐tocopherol promotes an increasing in the oxygen sorption and the convex shape of the isotherms indicate a strong interaction gas‐polymer. Regarding the sorption of carbon dioxide, no pronounced effect was found. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

γ‐ and δ‐tocopherols are more effective than α‐tocopherol on the autoxidation of a 10% rapeseed oil triacylglycerol‐in‐water emulsion with and without a radical initiator

The antioxidative effects of γ‐ and mainly δ‐tocopherol in a multiphase system were hardly considered up to now. The aim of this study was i) to assess the effects and ii) to follow the degradation of α‐, γ‐ and δ‐tocopherol in concentrations of 0.01%, 0.05%, 0.1% and 0.25% during the oxidation of a 10% purified rapeseed oil triacylglycerol‐in‐water emulsion at 40 °C in the dark for 15 wk in a system containing a low oxygen concentration. Oxidation experiments were performed weekly by assessing the formation of hydroperoxides and hexanal, and the stability of the tocopherols was determined using high‐performance liquid chromatography. Storage tests were conducted with and without the addition of 0.01% α, α′‐azoisobutyronitrile (AIBN), which is a known radical initiator. α‐Tocopherol increased the formation of hydroperoxides in both tests as well as the generation of hexanal when the radical initiator was added; furthermore it was the least stable. γ‐Tocopherol delayed the formation of hexanal and prolonged the stability of the emulsion in a dose‐dependant manner. δ‐Tocopherol was the most stable and also the most effective in delaying lipid oxidation in the emulsions. Each concentration that was tested reduced the rate of hydroperoxide and especially hexanal formation. Hexanal was only formed to a slight extent after 15 wk of oxidation in the test with AIBN and the lowest dose of 0.01% δ‐tocopherol. For all tocopherols, strong correlations were found between tocopherol stability and the extent of oxidation. Results suggest that i) mainly δ‐tocopherol, but also γ‐tocopherol even less pronounced, are very good antioxidants in order to stabilize and prolong the shelf life of oil‐in‐water emulsions, ii) the antioxidative effects were intensified with increasing amounts.     

α‐, γ‐ and δ‐ Tocopherols as inhibitors of isomerization and decomposition of cis,trans methyl linoleate hydroperoxides

The effects of α‐, γ‐ and δ‐tocopherols on the stability and decomposition reactions of lipid hydroperoxides were studied. Isomerization and decomposition of cis,trans methyl linoleate hydroperoxides (cis,trans ML‐OOH) in hexadecane at 40 °C were followed by high‐performance liquid chromatography. Due to its higher hydrogen donating ability, α‐tocopherol was more efficient than γ‐ and δ‐tocopherols in inhibiting the isomerization of cis,trans ML‐OOH to trans,trans ML‐OOH. α‐Tocopherol stabilized hydroperoxides into the cis,trans configuration, whereas γ‐ and δ‐tocopherols allowed hydroperoxides to convert into trans,trans isomers. Thus, the biological importance of α‐tocopherol as compared to other tocopherols may be partly due to its better efficacy in protecting the cis,trans configuration of hydroperoxides formed, for example, in the enzymatic oxidation of polyunsaturated fatty acids. The isomeric configuration of hydroperoxides has an impact on biological activities of further oxidation products of polyunsaturated fatty acids. Paradoxically, the order of activity of tocopherols with regard to hydroperoxide decomposition was different from that obtained for hydroperoxide isomerization. γ‐ and δ‐tocopherols were more efficient inhibitors of ML‐OOH decomposition when compared to α‐tocopherol. A loss of antioxidant efficiency, observed as the tocopherol concentration increased from 2 to 20 mM, was highest for α‐tocopherol but was also evident for γ‐ and δ‐tocopherols. Thus, the differences in the relative effects of tocopherols at differing concentrations seem to result from a compromise between their radical scavenging efficiency and participation in side reactions of peroxidizing nature.     

Two approaches in preparation for cogeneration α‐tocopherol and biodiesel from cottonseed

A two‐step process and a direct alkaline transesterification process in preparation for cogeneration α‐tocopherol and biodiesel (fatty acid methyl esters, FAME) from cottonseeds were studied in this article. The effects of some factors on recovery of α‐tocopherol and conversion of cottonseed oil (triacylglycerols, TAGs) to biodiesel in the two processes were systematically studied by single factor experiments and orthogonal design method. In the two‐step process, α‐tocopherol and biodiesel were produced from extraction with two‐phase solvent followed by base‐catalysed transesterification. Approximately 95.5% TAGs was converted into biodiesel, and 1.008 mg/g (wet basis) α‐tocopherol was detected on the condition: 1:3 petroleum ether/methanol volume rate, 40°C extraction temperature; 7:1 methanol/cottonseed oil molar ratio, 1.1% KOH (w/v) concentration in methanol and 60°C esterification temperature. And in the direct alkaline transesterification reaction, 98.3% conversion of TAGs and 0.986 mg/g content of α‐tocopherol could be achieved at 60°C in 2 h. Both of the two processes were feasible from the economic point of view for further utilisation of cottonseed. © 2011 Canadian Society for Chemical Engineering     

2,2′‐Bis(monoacylglycero) PO4 (BMP), but Not 3,1′‐BMP,Increases Membrane Curvature Stress to Enhance α‐Tocopherol Transfer Protein Binding to Membranes

Previous work revealed that α‐tocopherol transfer protein (α‐TTP) co‐localizes with bis(monoacylglycero)phosphate (BMP) in late endosomes. BMP is a lipid unique to late endosomes and is believed to induce membrane curvature and support the multivesicular nature of this organelle. We examined the effect of BMP on α‐TTP binding to membranes using dual polarization interferometry and vesicle‐binding assay. α‐TTP binding to membranes is increased by the curvature‐inducing lipid BMP. α‐TTP binds to membranes with greater affinity when they contain the 2,2′‐BMP versus 3,1′‐BMP isomers.     

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.     

pH‐responsive hydrogel microparticles as intelligent delivery carriers for α‐MSH antagonists

For a first step in the development of an intelligent delivery system for a nonapeptide as an α‐MSH antagonist, pH‐responsive P(MAA‐co‐EGMA) hydrogel microparticles were prepared and their feasibility as intelligent delivery carriers was evaluated. There was a drastic change in the swelling ratio of P(MAA‐co‐EGMA) microparticles at a pH of around 5 and as the MAA amount in the hydrogel increased, the swelling ratio increased at a pH above 5. The loading efficiency of the nonapeptide at pH 7 increased with the amount of Methacrylic acid (MAA) in the hydrogel and at pH 2, where the electrostatic attraction was greatest, a high loading efficiency was not obtained because of the low swelling ratio of the hydrogel. The P(MAA‐co‐EGMA) microparticles demonstrated a pH‐sensitive release behavior for the nonapeptide. In addition, the P(MAA‐co‐EGMA) microparticles showed a protective ability for the nonapeptide and preserved the stability of the nonapeptide. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Effect of α‐, γ‐, and δ‐tocopherol on the distribution of volatile secondary oxidation products in fish oil

The relative ability of α‐, γ‐ and δ‐tocopherol (TOH) to influence the distribution of volatile secondary oxidation products in fish oil was studied, with particular emphasis on oxidation products expected to be important for adverse flavour formation. Purified fish oil samples with 100 ppm or 1000 ppm of the different tocopherols were analysed by dynamic headspace analysis of the volatiles formed after 2, 5 and 8 d of storage at 30 �C. The tocopherol type and concentration affected not only the overall formation of volatile secondary oxidation products, but also the composition of this group of oxidation products. Principal component analysis of the data obtained suggested that high tocopherol hydrogen‐donating power, i.e. a high tocopherol concentration or the use of αTOH as opposed to γTOH or δTOH, directs the formation of hydrocarbons, unsaturated carbonyl compounds of relatively high molecular weight, as well as the formation of cis, trans isomers of unsaturated aldehydes. Although an active inhibitor of overall volatile formation, αTOH at a high concentration thus appears to direct the formation of the more flavour‐potent aldehydes, such as those linking the carbonyl group with ethylenic conjugated unsaturation.     

Influence of milling conditions on the α‐tocopherol content of Picual olive oil

The aim of this study was to estimate the α‐tocopherol content in Picual extra‐virgin olive oils obtained from the 2004/2005 harvesting season and to evaluate the influence that different extraction processes and sample handling had on the final vitamin E content in the oils. A new experimental oil extraction carried out at 9 °C enabled us to obtain encouragingly high quantities of α‐tocopherol with an average quantity reaching 341.34 ± 50.17 mg/L (n = 13), with significant differences among the same oil types produced from the traditional two‐phase system at low (9 °C, p <0.01) and moderate (21.5 °C, p <0.001; 33 °C, p <0.0001) temperatures. The temperature at which extraction was carried out should be considered as a major factor to be taken into account. Additionally, we also developed a precise method for the extraction of α‐tocopherol from olive oil samples, which enables high recovery (96 ± 2%) for use in subsequent HPLC/DAD/fluorescence quantification.     

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.     

Vitamin E – essential knowledge for supplementation

Misinterpretation of scientific data led vitamin E research in a wrong direction. Scientists focused on α‐tocopherol, ignoring other forms of vitamin E. However, natural α‐tocopherol supplementation significantly increased all‐cause mortality. This paradoxical observation demonstrates flaws in current understanding on vitamin E. Updated knowledge on vitamin E supplementation provides explanation of this paradoxical observation. The less well‐known tocotrienols, but not α‐tocopherol, fulfil the fundamentals for disease prevention which differ from antioxidant activity.     

Chemical Stability of α‐Tocopherol in Colloidal Lipid Particles with Various Morphologies

Colloidal lipid particles (CLPs) are promising encapsulation systems for lipophilic bioactives, such as oil‐soluble antioxidants that are applied in food and pharmaceutical formulations. Currently, there is no clear consensus regarding the relation between particle structure and the chemical stability of such bioactives. Using α‐tocopherol as a model antioxidant, it is shown that emulsifier type (Tween 20 or 40, or sodium caseinate) and lipid composition (tripalmitin, tricaprylin, or combinations thereof) modulated particle morphology and antioxidant stability. The emulsifier affects particle shape, with the polysorbates facilitating tripalmitin crystallization into highly ordered lath‐like particles, and sodium caseinate resulting in less ordered spherical particles. The fastest degradation of α‐tocopherol is observed in tripalmitin‐based CLPs, which may be attributed to its expulsion to the particle surface induced by lipid crystallization. This effect is stronger in CLPs stabilized by Tween 40, which may act as a template for crystallization. This work not only shows how the architecture of CLPs can be controlled through the type of lipid and emulsifier used, but also gives evidence that lipid crystallization does not necessarily protect entrapped lipophilic bioactives, which is an important clue for encapsulation system design. Practical Applications: Interest in enriching food and pharmaceutical products with lipophilic bioactives such as antioxidants through encapsulation in lipid particles is growing rapidly. This research suggests that for efficient encapsulation, the particle architecture plays an important role; to tailor this, the contribution of both the lipid carrier and the emulsifier needs to be considered.     

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 %).     

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.     

Novel Self‐Reinforced Films Based on Poly (3‐Hydroxybutyrate‐Co‐3‐Hydroxyvalerate) (PHBV) and PHBV Microparticles

Biodegradable self‐reinforced films of poly (3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) and PHBV microparticles were prepared through the solvent casting method (srPHBV). Differential scanning calorimetry (DSC), wide angle X‐ray scattering (WAXS) and polarized optical microscopy results confirmed the nucleating effect of PHBV microparticles. WAXS proved that diffractograms of PHBV and srPHBV‐6 films at room temperature contain the main characteristic diffraction peaks of an orthorhombic α‐type crystalline structure. Small angle X‐ray scattering (SAXS) showed a similar decrement rate of long spacing in PHBV and srPHBV films. SAXS/WAXS data revealed that when the amount of filler was increased, lamellae thickness grew. Transmission electron microscopy images illustrated well filler dispersion in the srPHBV films. Scanning electron microscopy results exhibited a significant reduction in porosity for srPHBV films once the PHBV microparticles were added. Atomic force microscopy analysis showed higher surface roughness after filler incorporation. Samples of srPHBV films showed higher barrier properties against water vapor, oxygen, and carbon dioxide. Combined properties of srPHBV films revealed the possibility of being suitable candidates for food packaging applications. POLYM. ENG. SCI., 59:E120–E128, 2019. © 2018 Society of Plastics Engineers     

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 the kinetics of the autoxidation of fats: influence of pro‐oxidants,antioxidants and synergists

The influence of minor amounts of pro‐ and anti‐oxidants on the kinetics of the autoxidation of fat has been evaluated. The reaction rates of oxygen with the substrates were found to follow the same basic equation, hitherto established for pure substrates. There is evidence that the surface of the reaction vessel also acts as a reaction catalyst and its effect is proportional to the area of glass in contact with lipids. Oxidation is enhanced by trace metal ions as well as by surface‐active compounds (e.g. hydroperoxides and sterols). Antioxidants such as α‐tocopherol and butylated hydroxyanisole inhibit the oxidation by delaying the start of oxygen consumption (the induction period) while retarders like amino acids only decrease the rate of oxidation. Thus pro‐ and anti‐ oxidants affect either the start or the rate of oxygen consumption. The empirical formula dx/dt = k [O₂] (1‐x/n) f′(t) was found applicable to the different stages of oxidation.