ascorbic-acid and methyl-linoleate

The mechanisms and dynamics of antioxidant action of ubiquinol have been studied. Ubiquinol scavenges peroxyl radical faster than alpha-tocopherol. However, it is autooxidized rapidly to give hydroperoxyl radical and/or superoxide and hence its antioxidant potency is smaller than that of alpha-tocopherol. The side chain of ubiquinol reduces the mobility between the membranes. It was concluded that ubiquinol acts as a potent antioxidant in combination with alpha-tocopherol.

Topics: Animals; Antioxidants; Ascorbic Acid; Drug Synergism; Humans; Linoleic Acids; Lipid Peroxidation; Oxidation-Reduction; Peroxides; Phenylenediamines; Reactive Oxygen Species; Ubiquinone; Vitamin E

Topics: 1-Propanol; Animals; Ascorbic Acid; Carbon Tetrachloride; Cell Membrane; Chemical Phenomena; Chemistry; Cytochrome P-450 Enzyme System; Electron Spin Resonance Spectroscopy; Fatty Acids; Free Radicals; Glutathione; Kinetics; Linoleic Acids; Lipid Peroxides; Liposomes; Oxidation-Reduction; Oxygen Consumption; Peroxides; Structure-Activity Relationship; Styrene; Styrenes; Vitamin E

A novel L-ascorbyl fatty acid ester, L-ascorbyl linoleate was successfully prepared by enzymatic esterification and transesterification in a non-aqueous medium using immobilized lipase as biocatalyst. Changes in enzymatic activity and product yield were studied for the following variable: the nature of the fatty acid, the fatty acid concentration and water content. The yield of synthesis for the C18 unsaturated fatty acids were higher than for the C18 saturated fatty acid. Initial enzyme concentration does not affect the equilibrium of the reaction. And the product yield (33.5%) in the transesterification was higher than that of the esterification (21.8%) at a high-substrate concentration 0.3 M. The medium water content was found to have a distinct influence on the L-ascorbyl linoleate synthesis.

Topics: Ascorbic Acid; Enzymes, Immobilized; Fungal Proteins; Linoleic Acid; Linoleic Acids; Lipase; Organic Chemicals; Solvents

The oxidation of methyl linoleate (ML) was studied in the presence of Fe(II) alone and its combination with either ascorbic acid (AsAH(2)) or hydrogen peroxide (H(2)O(2)) at different molar ratios. Reactions were carried out in micellar solutions of TTAB (tetradecyltrimethylammonium bromide) and SDS (sodium dodecyl sulfate), respectively, and were monitored by UV spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Fe(II) alone was able to catalyze the oxidation of ML in micellar solutions of TTAB, but not in those of SDS. The combination of H(2)O(2) with Fe(II) showed catalytic effect only in the TTAB medium, leading to different ML and Fe(II) oxidation kinetics compared to the Fe(II)-only catalyzed reactions. The AsAH(2)/Fe(II) combination demonstrated to be a good catalyst for the oxidation of ML in SDS micellar solutions, but not in TTAB micellar solutions; the activity of the catalyst was dependent on the AsAH(2)/Fe(II) molar ratio. The obtained results confirm that, for the ML oxidation to be initiated, the presence of a Fe(II)/Fe(III) couple is essential, which is related to the pH of micellar solutions. The catalytic properties of the AsAH(2)/Fe(II) combination were explained by taking into account the anti-oxidant and pro-oxidant properties of AsAH(2), as well as the possible formation of an iron/ascorbate complex as the initiator of the ML oxidation.

Topics: Ascorbic Acid; Catalysis; Colloids; Hydrogen Peroxide; Iron; Linoleic Acids; Micelles; Oxidation-Reduction

Nitroxyl radicals are known to act as radical scavenging antioxidants. In the present study, a lipophilic nitroxyl radical, cyclohexane-1-spiro-2'-(4'-oxyimidazolidine-1'-oxyl)-5'-spiro-1"-cyclohexane (nitroxyl radical I) was synthesized and its antioxidant capacity was assessed in comparison with a hydrophilic nitroxyl radical, 4-hydroxy-2,2,6,6-tetra-methylpiperidine-N-oxyl (Tempol). Both nitroxyl radical I and Tempol inhibited methyl linoleate oxidation induced by free radicals, and the efficacy increased with decreasing partial pressure of oxygen, the effect being more pronounced for nitroxyl radical I than Tempol. Their hydroxylamines inhibited lipid peroxidation more effectively than their corresponding parent nitroxyl radicals. In liposomal membranes, a synergistic effect was observed in the combination of nitroxyl radical I with ascorbic acid, whereas only an additive effect was observed between Tempol and ascorbic acid. The present study suggests that nitroxyl radical I and its hydroxylamine may act as potent antioxidants, especially in combination with ascorbic acid under hypoxic conditions.

Topics: Air; Antioxidants; Ascorbic Acid; Benzhydryl Compounds; Biochemistry; Cell Hypoxia; Cyclohexanes; Drug Synergism; Free Radicals; Hydroxylamine; Imidazolidines; Linoleic Acids; Lipid Peroxidation; Nitrogen; Nitrogen Oxides; Oxidation-Reduction; Oxygen; Pressure; Spiro Compounds

With increasing evidence suggesting the involvement of oxidative stress in various disorders and diseases, the role of antioxidants in vivo has received much attention. 2,3-Dihydro-5-hydroxy-2,2-dipentyl-4,6-di-tert-butylbenzofuran (BO-653) was designed, synthesized and has been evaluated as a novel antiatherogenic drug. In order to further understand the action of BO-653 and also radical-scavenging antioxidants in general, the dynamics of inhibition of oxidation by BO-653 were compared with those of the related compounds, 2,3-dihydro-5-hydroxy-2,2-dimethyl-4,6-di-tert-butylbenzofuran (BOB), 2,3-dihydro-5-hydroxy-2,2,4,6-tetramethylbenzofuran (BOM), alpha-tocopherol and 2,2,5,7,8-pentamethyl-6-chromanol (PMC), aiming specifically at elucidating the effects of substituents and side chain length of the phenolic antioxidants. These five antioxidants exerted substantially the same reactivities toward radicals and antioxidant capacities against lipid peroxidation in organic solution. When compared with di-methyl side chains, the di-pentyl side chains of BO-653 reduced its inter-membrane mobility but exerted less significant effect than the phytyl side chain of alpha-tocopherol on the efficacy of radical scavenging within the membranes. Di-tert-butyl groups at both ortho-positions made BO-653 and BOB more lipophilic than di-methyl substituents and reduced markedly the reactivity toward Cu(II) and also the synergistic interaction with ascorbate. The results of the present study together with those of the previous work on the effect of substituents on the stabilities of aryloxyl radicals suggest that tert-butyl group is more favorable than methyl group as the substituent at the ortho-positions and that di-pentyl side chains may be superior to a phytyl side chain.

Topics: alpha-Tocopherol; Antioxidants; Ascorbic Acid; Benzhydryl Compounds; Benzofurans; Copper; Electron Spin Resonance Spectroscopy; Free Radical Scavengers; Iron; Linoleic Acids; Lipid Peroxidation; Lipid Peroxides; Liposomes; Oxidation-Reduction; Phenols; Phosphatidylcholines; Vitamin E

Carboxyethyl-6-hydroxychromans (CEHC), the major metabolites of both tocopherols (Toc) and tocotrienols (Toc-3), have been found in human plasma. In the present study, the antioxidant properties of alpha- and gamma-CEHC were measured and compared with alpha- and gamma- tocopherols. Following results were obtained: (1)alpha- and gamma-CEHC have the same reactivities toward radicals and exert the same antioxidant activities against lipid peroxidation in organic solution as the corresponding parent tocopherols respectively; (2) the partition coefficient decreased in the order alpha-Toc (3.36) > gamma-Toc (3.14) > alpha-CEHC (2.26) > pentamethyl-6-chromanol (1.92) > gamma-CEHC (1.83) > 0 > Trolox (-0.97); (3) alpha- and gamma-CEHC scavenge aqueous radicals more efficiently but they inhibit the lipid peroxidation within the membranes less efficiently than the corresponding alpha- and gamma-Toc, respectively; (4) alpha-CEHC inhibits the oxidation synergistically with ascorbate; and (5) alpha- and gamma-CEHC reduce Cu(II) to give Cu(I) and corresponding quinones as major product, but the prooxidant effect of CEHC in the presence of cupric ion was small. These results imply that CEHC may act as an antioxidant in vivo especially for those who take tocopherol supplement.

Topics: Antioxidants; Ascorbic Acid; Chromans; Copper; Free Radicals; Linoleic Acids; Lipid Peroxidation; Liposomes; Micelles; Oxidation-Reduction; Peroxides; Propionates; Solutions; Spectrophotometry; Tocopherols

To develop a novel potent radical-scavenging antioxidant, the ideal structure of a phenolic compound was designed considering the factors that determine antioxidant potency. 2,3-Dihydro-5-hydroxy-2,2-dipentyl-4, 6-di-tert-butylbenzofuran (BO-653) was thus synthesized and its antioxidant activity was evaluated against lipid peroxidations in vitro. The electron spin resonance study showed that the phenoxyl radical derived from BO-653 was more stable than alpha-tocopheroxyl radical. BO-653 reduced alpha-tocopheroxyl radical rapidly, but alpha-tocopherol did not reduce the phenoxyl radical derived from BO-653. However, the chemical reactivity of BO-653 toward peroxyl radical was smaller than that of alpha-tocopherol. This was interpreted as the steric effect of bulky tert-butyl groups at both ortho positions which hindered the access of peroxyl radical to the phenolic hydrogen. However, the tertbutyl substituents increased the stability of BO-653 radical and also lipophilicity, and its antioxidant potency against lipid peroxidation in phosphatidylcholine liposomal membranes was superior to that of alpha-tocopherol. Ascorbic acid reduced the phenoxyl radical derived from BO-653 and spared BO-653 during the oxidation of lipid in the homogeneous solution. On the other hand, ascorbic acid did not spare BO-653 in the oxidation of liposomal membranes. It was concluded that BO-653 is a potent novel radical-scavenging antioxidant.

Topics: Antioxidants; Ascorbic Acid; Azo Compounds; Benzhydryl Compounds; Benzofurans; Chromatography, High Pressure Liquid; Drug Design; Electron Spin Resonance Spectroscopy; Free Radical Scavengers; Kinetics; Linoleic Acids; Lipid Peroxidation; Liposomes; Molecular Structure; Nitriles; Oxidation-Reduction; Peroxides; Phenols; Phosphatidylcholines; Spin Labels; Vitamin E

The antioxidant activities of various natural and synthetic carbazoles were studied in the oxidations of methyl linoleate in homogeneous solution and soybean phosphatidylcholine (PC) liposomes in aqueous dispersion induced by free radicals. Carazostatin, 1-heptyl-3-hydroxy-2-methyl carbazole, which was isolated from a culture of Streptomyces chromofuscus, was found to be a strong antioxidant in both oxidation systems. Carbazomycin B, 4-hydroxy-3-methoxy-1,2-dimethylcarbazole, showed a moderate antioxidant activity. Other derivatives from these carbazoles without a free hydroxy group did not suppress the oxidation appreciably. The antioxidant activity of carazostatin in the oxidation of soybean PC liposome was stronger than that of alpha-tocopherol, although the latter exhibited stronger antioxidant activity than carazostatin in the oxidation in homogeneous solution. Vitamin C acted as a synergist in combination with carazostatin in the oxidation of soybean PC liposomes.

Topics: Antioxidants; Ascorbic Acid; Benzhydryl Compounds; Carbazoles; Drug Synergism; Electron Spin Resonance Spectroscopy; Free Radicals; Linoleic Acids; Liposomes; Oxidation-Reduction; Phosphatidylcholines; Solutions; Streptomyces

The rates of reaction with ozone of some biological antioxidants and simple polyunsaturated fatty acids (PUFA) have been measured in water or in aqueous micellar solutions. At pH 7.0 the rate constants are ca. 10(6) M-1 sec-1 for urate, alpha-tocopherol, and PUFA, and 6 X 10(7) M-1 sec-1 for ascorbate. When ozone-containing air is breathed, ascorbate in the lung may undergo direct ozonation. However, alpha-tocopherol is probably spared direct reaction with ozone because it doesn't effectively compete with PUFA in pulmonary membranes; rather, tocopherol is used to scavenge radicals produced from the ozone-PUFA reaction.

Topics: Antioxidants; Ascorbic Acid; Chemical Phenomena; Chemistry; Fatty Acids, Unsaturated; Linoleic Acid; Linoleic Acids; Oleic Acid; Oleic Acids; Ozone; Uric Acid; Vitamin E

The oxidation of methyl linoleate in solution initiated with azo compounds has been studied in the absence and presence of vitamin E and vitamin C. Both vitamin E and vitamin C acted as a chain-breaking antioxidant and they suppressed the oxidation and produced an induction period. The inhibition rate constant for the scavenging of peroxy radical was calculated at 37 degrees C as kinh = 5.1 X 10(5) M-1 s-1 and 7.5 X 10(4) M-1 s-1 for vitamin E and vitamin C, respectively. It was suggested that each vitamin E could trap two peroxy radicals, whereas vitamin C could trap only one peroxy radical under the reaction conditions employed in this study. When both vitamin E and vitamin C were present, the oxidation was suppressed quite efficiently and the apparent inhibition rate constant was obtained as kinh = 4.0 X 10(5) M-1 s-1. Furthermore, vitamin E remained almost unchanged and only vitamin C was consumed at the initial stage and vitamin E was consumed after vitamin C was exhausted. It was concluded that vitamin E trapped the peroxy radical and the resulting alpha-chromanoxy radical reacted with vitamin C to regenerate vitamin E.

Topics: Ascorbic Acid; Chemical Phenomena; Chemistry; Free Radicals; Kinetics; Linoleic Acids; Oxidation-Reduction; Solutions; Vitamin E

The neutral alpha-tocopheroxyl radicals, generated in monolayers on silica gel containing alpha-tocopherol and partly autoxidised methyl linoleate at 90 degrees C, were detected and identified by ESR spectroscopy. Addition of ascorbic acid to the monolayer resulted in the complete quenching of the alpha-tocopheroxyl radical spectrum. This lends support to the view that ascorbate transfers hydrogen to alpha-tocopheroxyl radicals thus regenerating alpha-tocopherol.

Topics: Ascorbic Acid; Free Radicals; Linoleic Acids; Membranes, Artificial; Models, Biological; Oxidation-Reduction; Vitamin E

Topics: Acetates; Androgens; Androsterone; Ascorbic Acid; Barbiturates; Butyrates; Estradiol; Estriol; Estrone; Gonadal Steroid Hormones; Hexestrol; Linoleic Acid; Linoleic Acids; Lipid Metabolism; Liver; Mitochondria; Niacin; Niacinamide; Nicotinic Acids; Pharmacology; Propionates; Pyridines; Rats; Research; Sulfonic Acids; Testosterone