linoleic-acid and 6-hydroxy-2-5-7-8-tetramethylchroman-2-carboxylic-acid

The antioxidant activity and protective effect in the toxicity model of H

Topics: 2-Propanol; Antioxidants; Arachidonic Acid; Arachidonic Acids; Cell Line, Tumor; Choline; Chromans; Docosahexaenoic Acids; Drug Screening Assays, Antitumor; Fatty Acids; Free Radicals; Humans; Hydrogen Peroxide; Linoleic Acid; Oleic Acid

The study was focused on the activity of propolis from Amaicha del Valle, Argentina (ProAV) as a promoter and scavenger of Riboflavin (Rf)--photogenerated reactive oxygen species (ROS).. Through a kinetic and mechanistic study, employing stationary and time-resolved photochemical and electrochemical techniques, the protecting activity of ProAV was investigated.. In the absence of light and Rf, ProAV exerted a relatively efficient inhibitory effect on 1,1-diphenyl-2-picrylhydrazyl radicals and acts as a protector of artificially promoted linoleic acid oxidation. Under aerobic visible-light-irradiation conditions, in the presence of Rf as the only light-absorber species, a complex picture of competitive processes takes place, starting with the quenching of singlet and triplet electronically excited states of Rf by ProAV. The species O2(1 g), O2(•-), H2O2, and OH(•) are generated and interact with ProAV.. ProAV behaves as an efficient ROS scavenger. It is scarcely photo-oxidized by interaction with the mentioned ROS. Quantitative results indicate that ProAV is even more resistant to photo-oxidation than the recognized antioxidant trolox. Two dihydroxychalcones, mostly present in the ProAV composition, are responsible for the protecting activity of the propolis.

Topics: Antioxidants; Biphenyl Compounds; Chalcones; Chromans; Free Radical Scavengers; Hydrogen Peroxide; Light; Linoleic Acid; Oxygen; Phenol; Photochemistry; Photolysis; Photosensitizing Agents; Picrates; Promoter Regions, Genetic; Propolis; Reactive Oxygen Species; Riboflavin; Spectrometry, Fluorescence; Tryptophan

The antioxidant activity of the aminodi(hetero)arylamines, prepared by C-N coupling of the methyl 3-aminothieno[3,2-b]pyridine-2-carboxylate with bromonitrobenzenes and further reduction of the obtained nitro compounds, was evaluated by chemical, biochemical and electrochemical assays. The aminodi(hetero)arylamine with the amino group ortho to the NH and a methoxy group in para, was the most efficient in radical scavenging activity (RSA, 63 µM) and reducing power (RP, 33 µM), while the aminodiarylamine with the amino group in para to the NH, gave the best results in β-carotene-linoleate system (41 µM) and inhibition of formation of thiobarbituric acid reactive substances in porcine brain cells homogenates (7 µM), with EC50 values even lower than those obtained for the standard trolox. This diarylamine also presented the lowest oxidation potential, lower than the one of trolox, and the highest antioxidant power in the electrochemical assays. The para substitution with an amino group enables higher antioxidant potential.

Topics: Amines; Animals; beta Carotene; Brain; Chromans; Electrochemical Techniques; Free Radical Scavengers; Linoleic Acid; Lipid Peroxidation; Nitrobenzenes; Pyridines; Structure-Activity Relationship; Swine; Thiobarbiturates; Tissue Extracts

Literature data are scarce on the activities of analogous pairs of hydrophilic and lipophilic antioxidants related to the 'polar paradox' distinguishing antioxidants based on their partitioning between lipids and water. The peroxidation of linoleic acid (LA) in the presence of either Cu(II) ions alone or Cu(II) ions combined with Trolox (TR), ascorbic acid (AA), hydroquinone (HQ) and gallic acid (GA), as hydrophilic antioxidants, or with α-tocopherol (TocH), ascorbyl palmitate (AP), tert-butyl hydroquinone (TBHQ) and propyl gallate (PG), as their respective lipophilic analogues, was investigated in aerated and incubated emulsions at 37 °C and pH 7.. LA peroxidation induced by Cu(II) followed pseudo-first-order kinetics with respect to the formation of primary (hydroperoxides) and secondary (aldehyde- and ketone-like) oxidation products, which were determined by ferric thiocyanate (Fe(III)-SCN) and thiobarbituric acid-reactive substances (TBARS) methods respectively. With the exception of TocH at certain concentrations, the tested compounds showed antioxidant behaviour depending on their polarities. The results were evaluated in the light of structure-activity relationships and the polar paradox.. The results of this study partly confirm the hypothesis that the polar paradox experiences limitations in oil-in-water emulsions and that its validity is also dependent on the concentrations of the antioxidants employed.

Topics: alpha-Tocopherol; Antioxidants; Ascorbic Acid; Chromans; Copper; Emulsions; Gallic Acid; Hydrophobic and Hydrophilic Interactions; Hydroquinones; Iron; Kinetics; Linoleic Acid; Lipid Peroxidation; Peroxides; Propyl Gallate; Structure-Activity Relationship; Thiobarbituric Acid Reactive Substances; Thiocyanates

Herbaceous plants containing antioxidants can protect against DNA damage. The purpose of this study was to evaluate the antioxidant substances, antioxidant activity, and protection of DNA from oxidative damage in human lymphocytes induced by hydrogen peroxide (H2O2). Our methods used acidic methanol and water extractions from six herbaceous plants, including Bidens alba (BA), Lycium chinense (LC), Mentha arvensis (MA), Plantago asiatica (PA), Houttuynia cordata (HC), and Centella asiatica (CA).. Antioxidant compounds such as flavonol and polyphenol were analyzed. Antioxidant activity was determined by the inhibition percentage of conjugated diene formation in a linoleic acid emulsion system and by trolox-equivalent antioxidant capacity (TEAC) assay. Their antioxidative capacities for protecting human lymphocyte DNA from H2O2-induced strand breaks was evaluated by comet assay.. The studied plants were found to be rich in flavonols, especially myricetin in BA, morin in MA, quercetin in HC, and kaemperol in CA. In addition, polyphenol abounded in BA and CA. The best conjugated diene formation inhibition percentage was found in the acidic methanolic extract of PA. Regarding TEAC, the best antioxidant activity was generated from the acidic methanolic extract of HC. Water and acidic methanolic extracts of MA and HC both had better inhibition percentages of tail DNA% and tail moment as compared to the rest of the tested extracts, and significantly suppressed oxidative damage to lymphocyte DNA.. Quercetin and morin are important for preventing peroxidation and oxidative damage to DNA, and the leaves of MA and HC extracts may have excellent potential as functional ingredients representing potential sources of natural antioxidants.

Topics: Adult; Antioxidants; Biological Assay; Cells, Cultured; Chromans; Comet Assay; Drugs, Chinese Herbal; Female; Flavonols; Humans; Hydrogen Peroxide; Linoleic Acid; Lipid Peroxidation; Lymphocytes; Male; Methanol; Middle Aged; Nucleic Acid Denaturation; Oxidative Stress; Plants, Medicinal; Polyphenols; Solvents; Water

Lipid peroxidation is a common feature of many chemical and biological processes, and is governed by a complex kinetic scheme. A fundamental stage in kinetic investigations of lipid peroxidation is the accurate determination of the rate of peroxidation, which in many instances is heavily reliant on the method of finite differences. Such numerical approximations of the first derivative are commonly employed in commercially available software, despite suffering from considerable inaccuracy due to rounding and truncation errors. As a simple solution to this, we applied three empirical sigmoid functions (viz. the Prout-Tompkins, Richards & Gompertz functions) to data obtained from the AAPH-mediated peroxidation of aqueous linoleate liposomes in the presence of increasing concentrations of Trolox, evaluating the curve fitting parameters using the widely available Microsoft Excel Solver add-in. We have demonstrated that the five-parameter Richards' function provides an excellent model for this peroxidation, and when applied to the determination of fundamental rate constants, produces results in keeping with those available in the literature. Overall, we present a series of equations, derived from the Richards' function, which enables direct evaluation of the kinetic measures of peroxidation. This procedure has applicability not only to investigations of lipid peroxidation, but to any system exhibiting sigmoid kinetics.

Topics: Amidines; Chromans; Kinetics; Linoleic Acid; Lipid Peroxidation; Liposomes; Water

The in vitro hepatoprotective effect of the methanolic extract from Ficus gnaphalocarpa (Miq.) Steud. ex A. Rich (Moraceae) on the CCl₄-induced liver cell damage as well as the possible antioxidant mechanisms involved in this protective effect, were investigated. The phytochemical investigation of this methanolic extract led to the isolation of six compounds identified as: betulinic acid (1); 3-methoxyquercetin (2); catechin (3); epicatechin (4); quercetin (5); and quercitrin (6). The hepatoprotective activity of these compounds was tested in vitro against CCl₄-induced damage in rat hepatoma cells. In addition, radical-scavenging activity, β-carotene-linoleic acid model system, ferric-reducing antioxidant parameter and microsomal lipid peroxidation assays were used to measure antioxidant activity of crude extract and isolated compounds. Silymarin and trolox were used as standard references and, respectively, exhibited significant hepatoprotective and antioxidant activities. (5), (6) and (2) showed significant antioxidant and hepatoprotective activities as indicated by their ability to prevent liver cell death and lactate dehydrogenase leakage during CCl₄ intoxication. These results suggest that the protective effects of crude extract of F. gnaphalocarpa against the CCl₄-induced hepatotoxicity possibly involve the antioxidant effect of these compounds.

Topics: Animals; Antioxidants; beta Carotene; Cell Death; Cell Line, Tumor; Chemical and Drug Induced Liver Injury; Chromans; Ficus; Free Radical Scavengers; L-Lactate Dehydrogenase; Linoleic Acid; Lipid Peroxidation; Liver; Methanol; Microsomes, Liver; Plant Extracts; Rats; Silymarin

L-adrenaline belongs to a group of the compounds known as catecholamines, which play an important role in the regulation of physiological process in living organisms. The antioxidant activity and antioxidant mechanism of L-adrenaline was clarified using various in vitro antioxidant assays including 1,1-diphenyl-2-picryl-hydrazyl (DPPH), 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS), N,N-dimethyl-p-phenylenediamine (DMPD(+)), and superoxide anion radicals (O(2)(-)) scavenging activity, hydrogen peroxide (H(2)O(2)), total antioxidant activity, ferric ions (Fe(3+)) and cupric ions (Cu(2+)) reducing ability, ferrous ions (Fe(2+)) chelating activity. L-adrenaline inhibited 74.2% lipid peroxidation of a linoleic acid emulsion at 30 microg/mL concentration. On the other hand, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), alpha-tocopherol and trolox displayed 83.3, 82.1, 68.1 and 81.3% inhibition on the peroxidation of linoleic acid emulsion at the same concentration, respectively. BHA, BHT, alpha-tocopherol and trolox were used as reference antioxidants and radical scavenger compounds. Moreover, this study will bring an innovation for further studies related to antioxidant properties of L-adrenaline. According to present study, L-adrenaline had effective in vitro antioxidant and radical scavenging activity.

Topics: alpha-Tocopherol; Antioxidants; Benzothiazoles; Biphenyl Compounds; Butylated Hydroxyanisole; Butylated Hydroxytoluene; Chromans; Copper; Dose-Response Relationship, Drug; Epinephrine; Ferrous Compounds; Free Radical Scavengers; Hydrogen Peroxide; Linoleic Acid; Lipid Peroxidation; Oxidation-Reduction; Picrates; Piperidones; Structure-Activity Relationship; Sulfonic Acids; Superoxides

The antioxidant activities of curcumin, its natural demethoxy derivatives (demethoxycurcumin, Dmc and bisdemethoxycurcumin, Bdmc) and metabolite hydrogenated derivatives (tetrahydrocurcumin, THC; hexahydrocurcumin, HHC; octahydrocurcumin; OHC) were comparatively studied using 2,2-diphenyl-1-picrylhydrazyl (DDPH) radical, 2,2'-azobis(2-amidinopropane)dihydrochloride (AAPH) induced linoleic oxidation and AAPH induced red blood cell hemolysis assays. Hydrogenated derivatives of curcumin exhibited stronger DPPH scavenging activity compared to curcumin and a reference antioxidant, trolox. The scavenging activity significantly decreased in the order THC>HHC=OHC>trolox>curcumin>Dmc>>>Bdmc. Stronger antioxidant activities toward lipid peroxidation and red blood cell hemolysis were also demonstrated in the hydrogenated derivatives. By the model of AAPH induced linoleic oxidation, the stoichiometric number of peroxyl radical that can be trapped per molecule (n) of hydrogenated derivatives were 3.4, 3.8 and 3.1 for THC, HHC and OHC, respectively. The number (n) of curcumin and Dmc were 2.7 and 2.0, respectively, which are comparable to trolox, while it was 1.4 for Bdmc. The inhibition of AAPH induced red blood cell hemolysis significantly decreased in the order OHC>THC=HHC>trolox>curcumin=Dmc. Results in all models demonstrated the lower antioxidant activity of the demethoxy derivatives, suggesting the ortho-methoxyphenolic groups of curcumin are involved in antioxidant activities. On the other hand, hydrogenation at conjugated double bonds of the central seven carbon chain and beta diketone of curcumin to THC, HHC and OHC remarkably enhance antioxidant activity.

Topics: Amidines; Antioxidants; Biphenyl Compounds; Chromans; Curcumin; Diarylheptanoids; Erythrocyte Membrane; Free Radical Scavengers; Free Radicals; Hemolysis; Humans; Hydrogenation; In Vitro Techniques; Linoleic Acid; Lipid Peroxidation; Molecular Structure; Oxidants; Picrates; Structure-Activity Relationship; Time Factors

Caffeic acid (3,4-dihydroxycinnamic acid) is among the major hydroxycinnamic acids present in wine; sinapic acid, which is a potent antioxidant. It has also been identified as one of the active antioxidant. In the present study, the antioxidant properties of the caffeic acid were evaluated by using different in vitro antioxidant assays such as 2-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical scavenging, 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH) scavenging, total antioxidant activity by ferric thiocyanate method, total reductive capability using the potassium ferricyanide reduction method, superoxide anion radical scavenging and metal chelating activities. alpha-Tocopherol, trolox, a water-soluble analogue of tocopherol, butylated hydroxyanisole (BHA), and butylated hydroxytoluene (BHT) were used as the reference antioxidant compounds. At the concentrations of 10 and 30 microg/mL, caffeic acid showed 68.2 and 75.8% inhibition on lipid peroxidation of linoleic acid emulsion, respectively. On the other hand, 20 microg/mL of standard antioxidant such as BHA, BHT, alpha-tocopherol and trolox indicated an inhibition of 74.4, 71.2, 54.7 and 20.1% on peroxidation of linoleic acid emulsion, respectively. In addition, caffeic acid is an effective ABTS(+) scavenging, DPPH scavenging, superoxide anion radical scavenging, total reducing power and metal chelating on ferrous ions activities.

Topics: alpha-Tocopherol; Antioxidants; Benzothiazoles; Biphenyl Compounds; Butylated Hydroxyanisole; Butylated Hydroxytoluene; Caffeic Acids; Chelating Agents; Chromans; Dose-Response Relationship, Drug; Emulsions; Ferricyanides; Ferrous Compounds; Free Radical Scavengers; Hydrazines; Iron; Linoleic Acid; Lipid Peroxidation; Picrates; Reducing Agents; Sulfonic Acids; Superoxides; Thiocyanates

L-carnitine plays an important regulatory role in the mitochondrial transport of long-chain free fatty acids. In this study, the antioxidant activity of L-carnitine was investigated as in vitro. The antioxidant properties of the L-carnitine were evaluated by using different antioxidant assays such as 1, 1-diphenyl-2-picryl-hydrazyl free radical (DPPH.) scavenging, total antioxidant activity, reducing power, superoxide anion radical scavenging, hydrogen peroxide scavenging and metal chelating activities. Total antioxidant activity was measured according to ferric thiocyanate method. alpha-tocopherol and trolox, a water-soluble analogue of tocopherol, were used as the reference antioxidant compounds. At the concentrations of 15, 30 and 45 microg/mL, l-carnitine showed 94.6%, 95.4% and 97.1% inhibition on lipid peroxidation of linoleic acid emulsion, respectively. On the other hand, 45 microg/mL of standard antioxidant such as alpha-tocopherol and trolox indicated an inhibition of 88.8% and 86.2% on peroxidation of linoleic acid emulsion, respectively. In addition, L-carnitine had an effective DPPH. scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging, total reducing power and metal chelating on ferrous ions activities. Also, those various antioxidant activities were compared to alpha-tocopherol and trolox as references antioxidants.

Topics: alpha-Tocopherol; Antioxidants; Biphenyl Compounds; Carnitine; Chromans; Free Radical Scavengers; Free Radicals; Hydrazines; Hydrogen Peroxide; In Vitro Techniques; Linoleic Acid; Lipid Peroxidation; Picrates

The objective in this work is to determine the antioxidant capacity and effectiveness of icariin (2-(4'-methoxylphenyl)-3-rhamnosido-5-hydroxyl-7-glucosido-8-(3'-methyl-2-butylenyl)-4-chromanone), the major component in herba epimedii being used widely in traditional Chinese medicine for the treatment of artherosclerosis and neuropathy, in which 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH)-induced peroxidation of linoleic acid (LH) in sodium dodecyl sulfate (SDS) acts as the experimental system. By containing an intramolecular hydrogen bond, icariin protects LH against AAPH-induced peroxidation of LH only in SDS, an anionic micelle. The number of trapping peroxyl radicals (LOO(*)), n, by icariin is just 0.0167 whereas alpha-tocopherol (TOH) and L-ascorbyl-6-laurate (VC-12) are 2.14 and 1.25, respectively, with reference to the n of 6-hydroxyl-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox), 2.00. This is also related to how the intramolecular hydrogen bond enhances the bond dissociation enthalpy (BDE) of O-H in icariin. However, calculation of the inhibition rate constant, k(inh), a kinetic parameter to describe the reaction between the antioxidant and LOO(*), results in a k(inh) of icariin at about one magnitude larger than those of Trolox, TOH, and VC-12. This fact reveals that, by the view of kinetics, icariin is an antioxidant with much higher effectiveness. In addition, the antioxidant capacities of icariin used together with other antioxidants have been determined and the results indicate that the n of icariin decreases markedly while the n values of Trolox and TOH increase, even if the n of icariin is a negative value in the presence of VC-12. Furthermore, an analysis of k(inh) in this case reveals that the k(inh)(icariin) increases nearly one magnitude with the decrease of k(inh)(Trolox) and no remarkable change occurs for k(inh)(TOH). The negative value of k(inh)(icariin) in the presence of VC-12 can be regarded as the icariin functions as a prooxidant that can be rectified by VC-12 effectively. These findings implicate that the evaluation of antioxidant activity should not only focus on an n value, a thermodynamic possibility, but k(inh) and the charge property of the micelle should be also taken into account. To some extent, the latter factors are more important than the thermodynamic possibility.

Topics: Algorithms; Antioxidants; Ascorbic Acid; Chromans; Flavonoids; Free Radicals; Hydrogen Bonding; Kinetics; Lauric Acids; Linoleic Acid; Lipid Peroxidation; Micelles; Sodium Dodecyl Sulfate

The antioxidant capacity (AOC) of three representative citrus limonoids, limonin, nomilin, and limonin glucoside, was examined by the oxygen radical absorbance capacity (ORAC), Trolox equivalent antioxidant capacity (TEAC), beta-carotene-linoleic acid bleaching, and 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical scavenging assays. Pure compounds and proper negative (cinnamic acid) and positive (2,6-di-tert-butyl-4-methylphenol (BHT) and ascorbic acid) controls were used to remove any ambiguity in interpreting results. In all cases, limonin and nomilin gave results equivalent to those of cinnamic acid, indicating that they do not possess any inherent AOC and should not be considered antioxidants. Similar results were observed for limonin glucoside, with the exception of an anomalous result obtained from the beta-carotene-linoleic acid bleaching assay. Limonin glucoside was deemed not to be an antioxidant on the basis of the three unequivocal assays.

Topics: Antioxidants; Benzoxepins; beta Carotene; Biphenyl Compounds; Chromans; Glucosides; Limonins; Linoleic Acid; Picrates; Reactive Oxygen Species

Several oat brans (crunchy oat bran, oat bran alone, and oat breakfast cereal) and wheat brans (wheat bran alone, wheat bran powder, wheat bran with malt flavor, bran breakfast cereal, tablet of bran, and tablet of bran with cellulose) used as dietary fiber supplements by consumers were evaluated as alternative antioxidant sources (i) in the normal human consumer, preventing disease and promoting health, and (ii) in food processing, preserving oxidative alterations. Products containing wheat bran exhibited higher peroxyl radical scavenging effectiveness than those with oat bran. Wheat bran powder was the best hydroxyl radical (OH*) scavenger. In terms of hydrogen peroxide (H2O2) scavenging, wheat bran alone was the most effective, while crunchy oat bran, oat bran alone, and oat breakfast cereal did not scavenge H2O2. The shelf life of fats (obtained by the Rancimat method for butter) increased most in the presence of crunchy oat bran. When the antioxidant activity during 28 days of storage was measured by the linoleic acid assay, all of the oat and wheat bran samples analyzed showed very good antioxidant activities. The Trolox equivalent antioxidant capacity (TEAC) assay was used to provide a ranking order of antioxidant activity. The wheat bran results for TEAC (6 min), in decreasing order, were wheat bran powder > wheat bran with malt flavor > or = wheat bran alone > or = bran breakfast cereal > tablet of bran > tablet of bran with cellulose. The products made with oat bran showed lower TEAC values. In general, avenanthramide showed a higher antioxidant level than each of the following typical cereal components: ferulic acid, gentisic acid, p-hydroxybenzoic acid, protocatechuic acid, syringic acid, vanillic acid, vanillin, and phytic acid.

Topics: Antioxidants; Avena; Chromans; Deoxyribose; Dietary Fiber; Free Radical Scavengers; Hydrogen Peroxide; Hydroxyl Radical; Linoleic Acid; Lipid Peroxidation; Oxidation-Reduction; Peroxides; Phospholipids

A quantitative study of the phenolic constituents of wild and cultivated leaves of Sclerocarya birrea(Anacardiaceae) was carried out by HPLC-UV/PDA and LC-MS. Phytochemical analysis of the methanol extract of wild plants led to the isolation of one new flavonol glycoside, quercetin 3-O-alpha-l-(5' '-galloyl)-arabinofuranoside (1), and eight known phenolic compounds; two epicatechin derivatives were also isolated from the same extract of the cultivated species. The antioxidant activity of all isolated compounds was determined by measuring free radical scavenging effects using the Trolox equivalent antioxidant capacity assay and the coupled oxidation of beta-carotene and linoleic acid (autoxidation assay).

Topics: Anacardiaceae; Antioxidants; beta Carotene; Chromans; Chromatography, High Pressure Liquid; Chromatography, Liquid; Flavonols; Free Radical Scavengers; Glycosides; Linoleic Acid; Mass Spectrometry; Methanol; Oxidation-Reduction; Phenols; Plant Extracts; Plant Leaves

Scavenging effects of L-ascorbic acid 2-[3,4-dihydro-2,5,7,8- tetramethyl-2-(4,8,12-trimethytridecyl)-2H-1-benzopyran- 6-yl-hydrogen phosphate] potassium salt (EPC-K1) on hydroxyl radicals, alkyl radicals and lipid radicals were studied with ESR spin trapping techniques. The inhibition effects of EPC-K1 on lipid peroxidation were assessed by TBA assay. The kinetics of EPC-K1 reacting with hydroxyl radicals and linoleic acid radicals were studied by pulse radiolysis. The active site of EPC-K1 and the structure-antioxidative activity relationships were discussed. The superoxide radicals scavenging capacity of the brain homogenate of EPC-K1-treated rats was measured. The results revealed that in comparison with Trolox and vitamin C, EPC-K1 showed better overall antioxidative capacity in vitro and in vivo. EPC-K1 was a moderate scavenger on hydroxyl radicals and alkyl radicals, a potent scavenger on lipid radicals, and an effective inhibitor on lipid peroxidation. EPC-K1 could react with hydroxyl radicals with a rate constant of 7.1 x 10(8) dm3 mol-1 s-1 and react with linoleic acid radicals with a rate constant of 2.8 x 10(6) dm3 mol-1 s-1. The active site of EPC-K1 was the enolic hydroxyl group. After administration of EPC-K1, the ability of rat brain to scavenge superoxide radicals was significantly increased. The potent scavenging effects of EPC-K1 on both hydrophilic and hydrophobic radicals were relevant with its molecular structure, which consisted of both hydrophilic and hydrophobic groups.

Topics: Animals; Antioxidants; Ascorbic Acid; Brain; Chromans; Electron Spin Resonance Spectroscopy; Free Radical Scavengers; Hydroxyl Radical; Linoleic Acid; Lipid Peroxidation; Male; Molecular Structure; Peroxides; Pulse Radiolysis; Rats; Rats, Wistar; Spectrophotometry; Structure-Activity Relationship; Vitamin E

We investigated the ability of plasma membrane CoQ reductase (PMQR) purified from pig liver to reduce phenoxyl radicals of a vitamin E homologue, Trolox. We report that NADH-driven one-electron reduction of CoQ0 catalyzed by PMQR produced CoQ0 semiquinone radical and CoQoH2. These in turn, recycle vitamin E homologue, Trolox, via reducing its phenoxyl radical. A significant part of NADH/PMQR-catalyzed reduction of CoQ0 (and Trolox recycling) was superoxide-dependent. Overall, our results demonstrate that PMQR in the model system used can act as an antioxidant enzyme that recycles water-soluble homologues of coenzyme Q and vitamin E.

Topics: Animals; Benzoquinones; Catalysis; Cell Membrane; Chromans; Electron Transport Complex I; Linoleic Acid; Lipoxygenase; NADH, NADPH Oxidoreductases; Oxidation-Reduction; Phenols; Superoxides; Swine; Vitamin E

We have reported that the peroxyl radicals derived from methyl eicosapentaenoate (20:5n-3) are more polar than those from methyl linoleate (18:2n-6) since the former peroxyl radicals have at least two molecules of oxygen in a molecule while the latter peroxyl radical has one. This lowers the oxidizability for 20:5n-3 in aqueous Triton X-100 micelles by enhancing the termination reaction rate for peroxyl radicals and by reducing the rate of propagation since there may be more polar peroxyl radicals derived from 20:5n-3 at the surface than within the micelle core. In this study, we measured the effect of three antioxidants, di-tert-butyl-4-methylphenol (BHT), 2,2,5,7,8-pentamethyl-6-chromanol (PMC) and 2-carboxy-2,5,7,8-tetramethyl-6-chromanol (Trolox), on the oxidation of lipids in aqueous micelle. Antioxidants give a clear induction period during oxidation of 18:2n-6 initiated with a water-soluble radical initiator, and its induction length decreases in the order of BHT > PMC > Trolox. This is consistent with the proposed location of three antioxidants: being in the core of micelle, at the surface, or in aqueous phase, respectively. However, BHT does not inhibit the oxidation of 20:5n-3 efficiently, and its rate of oxidation is slower than that observed in the oxidation of 18:2n-6, supporting the idea that polar peroxyl radicals derived from 20:5n-3 are preferentially located at the surface of the micelle. Similar results were obtained when oxidation was initiated with a lipid-soluble radical initiator except antioxidants had lesser effect on the oxidation rate of 20:5n-3.

Topics: Aerobiosis; Antioxidants; Azo Compounds; Butylated Hydroxytoluene; Chromans; Eicosapentaenoic Acid; Free Radicals; In Vitro Techniques; Linoleic Acid; Micelles; Nitriles; Oxidation-Reduction; Water

The monoazaaromatics, pyridine (1), hexyl nicotinate (2), and quinoline (3) and diazaaromatics, pyrimidine (4) and purine (5), readily act as photo-initiators for the peroxidation of methyl linoleate in 0.50 M SDS at 37 degrees C giving free radical chain oxidations of linoleate. Quantitative kinetic runs on the order in substate, RH, and in the rate of chain initiation, Ri, showed that the classical rate law for autoxidation, -d[O2]/dt = (kp/(2 kt 1/2))[RH] x Ri 1/2, is applicable to these photo-initiated oxidations. The oxidizability of methyl linoleate under these conditions is 2.92 x 10(-2) M-1/2 s-1/2. These peroxidations were inhibited by chromanol phenolic antioxidants of the vitamin E class, such as lipid-soluble 2,2,5,7,8-pentamethyl-6-hydroxychroman (PMHC) and water-soluble 2-carboxy- 2,5,7,8-tetramethyl-6-hydroxychroman (Trolox) and derived rate constants for inhibition of peroxidation were kinh (PMHC) = 4.35 x 10(4) M-1 s-1 and k(inh) (Trolox) = 2.81 x 10(4) M-1 s-1 during inhibited oxidation of methyl linoleate photo-initiated by 4. The products from photo-initiated peroxidation of methyl linoleate by 1 through 5 were determined by reduction and high-performance liquid chromatography analyses to be the 9- and 13-positional hydroperoxides of the four geometrical isomers: cis-9, trans-11 (6), trans-10, cis-12 (7), trans-9, trans-11 (8), and trans-10, trans-12 (9)-octadecadienoates typical of the free radical chain mechanism of lipid peroxidation. Products from dye-sensitized oxidation by Methylene Blue or Rose Bengal of methyl linoleate gave a product distribution of six hydroperoxides typical of oxidation by singlet oxygen. Thermal or photo-initiated peroxidation of methyl linoleate in SDS gave some selectivity of oxidation at the 13-position of the linoleate chain. The ratio of 13- to 9-oxidation varied in the range 1.23 to 1.14 as the cis/trans to trans/trans ratio of geometrical isomers varied from 0.44 to 1.25 during photooxidation of increased amounts of linoleate in SDS. This selectivity is attributed to loss of the pseudo symmetry around the pentadienyl system in the lipid chain in the SDS system during the peroxidation.

Topics: Antioxidants; Chromans; Free Radicals; Kinetics; Linoleic Acid; Linoleic Acids; Lipid Peroxidation; Micelles; Models, Chemical; Nicotinic Acids; Photochemistry; Purines; Pyridines; Pyrimidines; Quinolines