Prooxidant Activity of Oxidized α-Tocopherol in Vegetable Oils

ABSTRACT:  The effect of oxidized α-tocopherol on the oxidative stabilities of soybean, corn, safflower, and olive oils and the oxidation of oleic, linoleic, and linolenic acids were studied. The 0, 650, 1300, and 2600 ppm oxidized α-tocopherol were added to soybean, corn, safflower, and olive oils and 10000 ppm oxidized α-tocopherol to the mixture of oleic, linoleic, and linolenic acids. Samples in the gas-tight vials were stored in the dark for 6 or 35 d at 55 °C. The oxidative stabilities of oils were determined by headspace oxygen with GC and peroxide value. Fatty acids were determined by GC. As the concentration of oxidized α-tocopherol in soybean, corn, safflower, and olive oils increased, the depletion of headspace oxygen and the peroxide values of oils increased during storage. The prooxidant effects of oxidized α-tocopherol on soybean and corn oils with about 55% linoleic acid were greater than those on safflower and olive oils with about 12% linoleic acid, respectively ( P  < 0.05). The changes of fatty acids during storage showed that the oxidation ratios of oleic, linoleic, and linolenic acids were 1 : 2 : 3, 1 : 12 : 26, and 1 : 8 : 16 after 5, 30, and 35 d of storage, respectively. The oxidation of α-tocopherol in oil should be prevented and the oxidized α-tocopherol should be removed to improve the oxidative stability of oils.     

α-, γ- and δ-Tocopherol Effects on Chlorophyll Photosensitized Oxidation of Soybean Oil

The effects of 0, 1.0, 2.0 and 4.0 (x 10^?3 M) α-, γ- or δ-tocopherol on chlorophyll b photosensitized oxidation of soybean oil in methylene chloride were studied by peroxide values and headspace oxygen. As concentrations of tocopherols increased, peroxide values decreased and headspace oxygen increased (P < 0.05). At 1.0 × 10^?3 M, α-tocopherol showed highest antioxidant effect, γ-tocopherol second and then δ-tocopherol. α- and -γ-Tocopherols had similar effects and δ-tocopherol had lower effect at 2.0 × 10^?3 M (P < 0.05). However, the three tocopherols were not different (P > 0.05) at 4.0 × 10^?3 M. α-Tocopherol quenched singlet oxygen to reduce the photosensitized oxidation of oil. The quenching rate constants of α-tocopherol were 2.7 × 10⁷M^?1sec^?1 by peroxide value and 2.6 × 10⁷ M^?1sec^?1 by headspace oxygen.     

α-Tocopherol Content and Oxidative Stability of Egg Yolk as Related to Dietary α-Tocopherol

Hens fed diets with 0.0, 7.5, 15.0, 30.0, 60.0 and 120.0 mg supplemental α-tocopherol/kg feed produced egg yolks with 25,30,35,45,50 and 75 μg/g yolk, respectively. The correlation coefficient between dietary α-tocopherol (mg/kg diet) and egg yolk α-tocopherol (μg/g egg yolk) after 28 days feeding was 0.99. The supplemented dietary α-tocopherol had an effect on the α-tocopherol in egg yolk (p<0.05). The oxidative stability of yolk was determined by measuring the oxygen and volatile compounds in the headspace of bottled yolk. α-Tocopherol had an effect on the stability of yolk as an antioxidant at 25, 45 and 50 μg/g yolk and a prooxidant at 75 μg/g or above (p<0.05). The addition of 60.0 mg α-tocopherol/kg diet resulted in the best egg yolk stability. The correlation coefficient between headspace oxygen disappearance and volatile compound formation in the headspace of bottled egg yolk was 0.84.     

α-Tocopherol and Ascorbate Delay Oxymyoglobin and Phospholipid Oxidation In Vitro

An oxymyoglobin liposome model was used to study the effects of α-tocopherol and/or ascorbate upon oxymyoglobin and lipid oxidation. Both oxidations were delayed (P<0.05) by increased concentrations of α-tocopherol alone and α-tocopherol/ascorbate relative to controls. The 14 μ Mα-tocopherol/140 μM ascorbate treatment resulted in greatest delay in both oxymyoglobin and lipid oxidation. Ascorbate alone delayed oxymyoglobin oxidation; effectiveness diminished as ascorbate increased. Ascorbate showed a prooxidant effect toward lipid oxidation which was unchanged in the presence of EDTA. Results support the hypothesis that α-tocopherol retards lipid oxidation directly and OxyMb oxidation indirectly.     

Color Stability and Microbial Growth Relationships in Beef as Affected by Endogenous α-Tocopherol

Longissimus muscle from Holstein steers supplemented with vitamin E at 500 or 2000 mg/head/day showed less surface metmyoglobin accumulation than controls during 12 days storage at 4°C. Temperature abuse at 25°C for 24 hr increased metmyoglobin formation; vitamin E supplementation diminished the adverse effect of temperature abuse. No differences (P > 0.05) in bacterial load were observed among the 3 vitamin E treatments during storage. Sensory panelists preferred vitamin E-supplemented beef steaks in visual acceptance. Panelist assessment of discoloration correlated highly with a value and hue angle. In general, elevated α-tocopherol concentrations in beef steaks did not affect panelist assessment of meat spoilage.     

Effects of α-, γ-, and δ-Tocopherols on Oxidative Stability of Soybean Oil

The effectts of 0, 100, 250, 500 and 1000 ppm of α-, γ-, or δ-tocopherol on oxidative stability of purified soybean oil in the dark at 55°C were studied. We measured peroxide value and headspace oxygen consumption in the samples. Purified soybean oil was prepared by liquid column chromatography. Tocopherols acted as antioxidants or prooxidants depending on their concentration. Optimum concentrations of α -, γ -, and δ– tocopherols to increase oxidative stability was 100, 250 and 500 ppm, respectively. The tocopherols had significant prooxidant effect (P < 0.05) at higher concentrations above this.     

番茄红素在油脂氧化时的稳定性初探

对番茄红素在大豆色拉油和猪油光敏氧化过程中的稳定性进行了研究。将8、12、20×10-6浓度的番茄红素分别添加于大豆色拉油和猪油中,32℃时,在光照条件下,在亚甲基蓝试剂的引发下,其自身随着光照时间的延长,其残存率逐渐降低,稳定性下降;番茄红素在豆油中的氧化稳定性好于在猪油中的氧化稳定性;添加25、80×10-6的α-生育酚于大豆色拉油和猪油中,两种浓度均能明显增加番茄红素在猪油光敏氧化中的稳定性,使其残存率明显增加;但不能增加番茄红素在大豆色拉油光敏氧化过程中的稳定性。     

Stability of α-Tocopherol, Thiamin, Riboflavin and Retinol in Pork Muscle and Liver during Heating as Affected by Dietary Supplementation

The α-tocopherol (Vit E) and ascorbic acid (Vit C) supplementation of pig diets increased (P<0.05) liver α-tocopherol concentrations. After heating, the liver samples of both treated groups and the longissimus dorsi muscle samples of the vitamin C group showed increased riboflavin retention (P<0.05). The supplemented and control groups did not show differences regarding retention of α-tocopherol, retinol and thiamin in heated liver and longissimus dorsi. Dietary vitamin C resulted in higher liver vitamin E and was most effective in protecting riboflavin against loss during heating of liver or longissimus dorsi.     

Thiamin, Riboflavin and α-Tocopherol Retention in Processed and Stored Irradiated Pork

Combination treatments for preservation of irradiated pork were investigated with respect to vitamin loss. Ground pork was prepared under nitrogen and packaged in anaerobic foil. The samples were enzyme denatured by heating before and after irradiation, then cooked and stored. Irradiation resulted in thiamin loss, but neither riboflavin nor α-tocopherol was affected. Neither thiamin nor riboflavin was affected by heat denaturation, cooking or storage, but heating and cooking increased the measured α-tocopherol. The lack of loss of the vitamins was attributed to the exclusion of oxygen.     

α-Tocopherol, β-Carotene and Ascorbic Acid as Antioxidants in Stored Poultry Muscle

Broilers were fed α-tocopherol or β-carotene for 3 wk or L-ascorbic acid for 24 hr prior to slaughter. α-Tocopherol maintained the redness of unheated meat stored for 8 wk (—20°C). Values for thiobarbituric acid reactive substances in ground, stored meat showed that L-ascorbic acid produced results similar to the control while a-tocopherol produced results lower than the control. Panelists rated meat with added α-tocopherol as different from the control for smell and flavor. β-Carotene was a pro-oxidant compared to the control and other additives. Meat from broilers fed β-carotene had lower α-tocopherol content than the control. Vitamin A in livers of birds fed β-carotene was 64% higher than that of the control.     

Singlet Oxygen Oxidation Rates of ∝-, γ-, and δ-Tocopherols

ABSTRACT:  The reaction rate constants of 5 × 10⁻⁴ M, 10 × 10⁻⁴ M, and 20 × 10⁻⁴ M α-, γ-, and δ-tocopherols with singlet oxygen in methylene chloride containing 1 × 10⁻⁵ M chlorophyll under light at 25 °C for 60 min were studied. The oxidation of tocopherols determined by a spectrophotometric method showed that the losses of 20 × 10⁻⁴ M α-, γ-, and δ-tocopherols after 60 min under light were 21%, 16%, and 9%, respectively. The degradation of α-, γ-, and δ-tocopherols was undetectable in the absence of chlorophyll under light or in the presence of chlorophyll in dark. The losses of tocopherols under light were mainly due to singlet oxygen oxidation. The degradation rates of 20 × 10⁻⁴ M α-, γ-, and δ-tocopherols were 6.6 ×10⁻⁶ M/min, 5.0 × 10⁻⁶ M/min, and 2.9 × 10⁻⁶ M/min, respectively. The reaction rates between α-, γ-, or δ-tocopherol and singlet oxygen were 4.1 ×10⁶/M s, 3.3 × 10⁶/M s, and 1.4 × 10⁶/M s, respectively. The singlet oxygen oxidation rate of δ-tocopherol was significantly lower than α- or γ-tocopherol at α= 0.05. As the electron density in the chromanol ring of tocopherol increased, the singlet oxygen oxidation was increased.     

Effects of Ascorbic Acid and α-Tocopherol on Antioxidant Activity of Polyphenolic Compounds

The effects of ascorbic acid and α‐tocopherol on the antioxidant activity of 15 phenolic compounds were compared with 2 in vitro assays. Combination of ascorbic acid or α‐tocopherol plus polyphenolic compounds resulted in an additive effect as shown with DPPH–HPLC method. With the liposome oxidation method, combination of quercetin or catechins plus α‐tocopherol showed synergistic effects.     

Dietary Pigmentation and Deposition of α-Tocopherol and Carotenoids in Rainbow Trout Muscle and Liver Tissue

Rainbow trout (Oncorhynchus mykiss) were fed diets supplemented with canthaxanthin, oleoresin paprika and α-tocopherol. Canthaxanthin was more efficiently absorbed (3.8–7.9 mg/kg) in the flesh of rainbow trout than the paprika carotenoids (2.4–3.1 mg/kg). With increased pigmentation, decrease in lightness (L*) and hue angle, and increase in redness (a*) of the muscle were observed. Canthaxanthin produced more desirable reddish-pink color. Deposition of α-tocopherol in liver and muscle tissue increased with increase in dietary α-tocopheryl acetate. Fish receiving lower α-tocopheryl acetate reached maximum deposition levels earlier than those fed higher levels. There was no effect of α-tocopherol and carotenoid levels on muscle fatty acid composition.     

Oxymyoglobin and Lipid Oxidation in Phosphatidylcholine Liposomes Retarded by α-tocopherol and β-carotene

An n-3 fatty acid-constructed oxymyoglobin liposome model was used to study the effects of 10 μM α-tocopherol and/or various concentrations of β-carotene on oxymyoglobin and lipid oxidation. Oxidation was delayed by α-tocopherol or β-carotene treatments alone (p < 0.05). β-Carotene at 1.5 μM and 2μM caused greater delay in oxymyoglobin oxidation than α-tocopherol (p < 0.05). For lipid oxidation inhibition, 2 μM β-carotene was similar in effect to α-tocopherol. With α-tocopherol plus 1.5 or 2 μM β-carotene, greater oxidation delaying effect resulted for both oxymyoglobin and lipid oxidations than with 1.5 or 2 μM β-carotene treatment alone (p < 0.05).     

Effects and prooxidant mechanisms of oxidized alpha-tocopherol on the oxidative stability of soybean oil

ABSTRACT:  α-Tocopherol was oxidized in methanol containing methylene blue for 30 h under light. The effects of 0, 250, 500, 1000, and 1500 ppm of oxidized α-tocopherol on the oxidative stability of purified soybean oil in the dark at 55 °C were studied by measuring the peroxide values and headspace oxygen contents in sample bottles. As the concentrations of oxidized α-tocopherol increased, the peroxide values increased and the headspace oxygen contents decreased during the 6 d of storage. The oxidized α-tocopherol compounds acted as prooxidant on the peroxide values and headspace oxygen contents of purified soybean oil. Tukey's test showed that oxidized α-tocopherol had a significant effect on the peroxide value and headspace oxygen disappearance of oil at P < 0.05. The prooxidant mechanisms of oxidized α-tocopherol may be due to α-tocopherol peroxy radical, α-tocopherol oxy radical, hydroxy radical, and singlet oxygen formed from the α-tocopherol. The oxidized α-tocopherol containing polar and nonpolar groups in the same molecule may reduce the surface tension of oil to increase the transfer of headspace oxygen to oil and accelerate the oil oxidation.     

Oxidative Stability of Soybean and Sesame Oil Mixture during Frying of Flour Dough

ABSTRACT: Effects of roasted sesame seed oil on the oxidative stability of soybean oil during frying of flour dough at 160 °C were studied by determining fatty acid composition and conjugated dienoic acid (CDA), p -anisidine (PA), and free fatty acid (FFA) values. Concentration of sesame oil in frying oil was 0%, 10%, 20%, or 30% (v/v). Tocopherols and lignan compounds in the frying oil were also determined by high-performance liquid chromatography. As the number of fryings performed by the oil increased, linolenic acid content in frying oil decreased, and the decreasing rate was lower in frying oil containing sesame oil than in the oil containing no sesame oil. CDA and FFA values of frying oil increased during frying and their relative values to the initial value were lower in frying oil containing sesame oil than in the oil containing no sesame oil. This indicates that the addition of sesame oil improved thermooxidative stability of frying oil, possibly due to the presence of lignan compounds in sesame oil. Tocopherols and lignan compounds in frying oil decreased during frying. As the amount of sesame oil in frying oil increased, degradation of tocopherols increased and lignan compounds degradation decreased. Tocopherols were suggested to protect lignan compounds in sesame oil from decomposition during frying.     

Dietary α-Linolenic Acid and Mixed Tocopherols, and Packaging Influences on Lipid Stability in Broiler Chicken Breast and Leg Muscle

Addition of α-linolenic acid alone or plus mixed tocopherols, to the diet of broiler chickens had significant effects on composition of muscle fatty acids. Degree of unsaturation in both neutral lipids and phospholipids was increased. Both the tocopherols in the tissues and the storage stability of the meat were affected by the degree of polyunsaturation in fatty acids and dietary tocopherols. The amount of tocopherols in leg meat was higher than that of breast meat, and the antioxidant effect of dietary tocopherols was significant in cooked leg meat with hot- and cold-vacuum packaging. Dietary tocopherols were not effective in the control of lipid oxidation in loosely packaged cooked meat. Lipid oxidation in α-linolenic acid-enriched cooked broiler meat could be controlled by hot-vacuum packaging, but the antioxidant effect of hot packaging plus dietary tocopherol was greater than hot packaging or tocopherol alone.     

Influence of Dietary Supplementation with α-Tocopheryl Acetate and Canthaxanthin on Cholesterol Oxidation in ω3 and ω6 Fatty Acid-enriched Spray-dried Eggs

ABSTRACT: The effect of feeding laying hens linseed oil or sunflower oil, with and without α-tocopheryl acetate and/or canthaxanthin, was evaluated on cholesterol oxidation in spray-dried whole egg at various storage periods. Storage of spray-dried eggs at room temperature in the dark resulted in an increase in cholesterol oxidation products from 18.1 μg/g, after spray drying, to 39.3 μg/g, at 12 mo of storage. No differences were found with either dietary oil or canthaxanthin supplementation. However, α-tocopheryl acetate supplementation resulted in a lower formation of cholesterol oxidation products during storage. No synergistic effect between α-tocopherol and canthaxanthin was detected.     

Effect of γ-Oryzanol on the Flavor and Oxidative Stability of Refrigerated Cooked Beef

ABSTRACT: γ-Oryzanol and α-tocopherol were added to beef patties as natural antioxidants. Beef patties containing 100 ppm γ-oryzanol had higher oxidative stability ( P <0.05) during storage at 4 °C than did beef patties with other antioxidants and without antioxidant. Thiobarbituric acid-reactive substances (TBARS) values, warmed over flavor (WOF) scores, C-7 oxidized cholesterol derivatives (OCDs), and concentrations of both hydroperoxide and hexanal in the cooked beef containing γ-oryzanol were significantly lower than those of other treatments ( P < 0.05). All variables had similar trends during the refrigerated storage. Significant correlations were found between TBARS and C-7 OCDs, TBARS and WOF, hydroperoxide and hexanal, and hexanal and WOF ( P < 0.05).     

Measurements of δD and δ18O Stable Isotope Ratios in Milk

ABSTRACT: This study explores the possibility of distinguishing raw and reconstituted milk by stable isotope ratio mass spectrometry. Considering variations from different areas and seasons, milk and groundwater samples were collected from dairy farms in different seasons to measure δD and δ¹⁸O values. Results showed differences between raw and reconstituted milk prepared with groundwater from a laboratory and a farm. The plot of values in each mixed level of raw and reconstituted milk had a correlation coefficient > 0.9. Data showed raw milk is related to the groundwater from that farm. We concluded that the charcoal treatment method is a suitable method for large-scale monitoring of raw milk samples. The measurement of δD and δ¹⁸O values in raw milk and groundwater provides a reference to detect adulteration.