Radicals lipid peroxyl radical

Fig. 7.3 Reactions showing the generation of ROS during lipid peroxidation and oxidative stress. Hydroxyl radical ( OH) lipid radical ( lipid), peroxyl radical (lipid-OO ) lipid peroxide (lipid-OOH) nitric oxide ( NO) nitrogen dioxide (N02) peroxynitrite anion (ONOO-) hypochlorous acid (HOC1), and hydrogen peroxide (H202)...

Peroxyl radicals are formed in the oxidation of many organic and biological molecules and they can propagate chain reactions. They are usually formed via the reaction of oxygen with carbon-centered radicals. Lipid peroxyl radicals are produced during hpid peroxidation, which is a complex process but can be divided into stages [3] ... 

Fig. 16.5 Synergistic regeneration of a-tocopherol by quercetin at a lipid-water interphase. a-tocopherol is reacting with a lipid peroxyl radical in a chain-breaking reaction. According to the standard reduction potential, the phenoxyl radical of quercetin can further be regenerated by ascorbate.

MbFe(IV)=0 and with lipid peroxyl radicals (Castellucio et al, 1995). It may accordingly be concluded that the most relevant single parameter for predicting the antioxidative activity of a new plant phenol would be the standard reduction potential, E . 

Mooradian (1993) has studied the antioxidant properties of 14 steroids in a non-membranous system in which the fluorescence of the protein phycoerythrin was measured in the presence of a lipid peroxyl radical generator (ABAP). Oxidation of the protein produces a fluorescent species. Quenching of fluorescence by a test compound indicates antioxidant activity. Oestrone, testosterone, progesterone, androstenedione, dehydroepian-drosterone, cortisol, tetrahydrocortisone, deoxycorti-... 

As the superoxide radical is a precursor of the other reactive oxygen species and interacts with blood plasma components under physiological and pathological conditions as well, systems related to its generation are biologically relevant. It should be noted, however, that with respect to the initiation of lipid peroxidation as one of the main causes of oxidative cell damage, its own reactivity is very weak and that only in protonized form is its toxicity comparable to that of lipid peroxyl radicals [18]. 

As mentioned earlier, when NO concentration exceeds that of superoxide, nitric oxide mostly exhibits an inhibitory effect on lipid peroxidation, reacting with lipid peroxyl radicals. These reactions are now well studied [42-44]. The simplest suggestion could be the participation of NO in termination reaction with peroxyl radicals. However, it was found that NO reacts with at least two radicals during inhibition of lipid peroxidation [50]. On these grounds it was proposed that LOONO, a product of the NO recombination with peroxyl radical LOO is rapidly decomposed to LO and N02 and the second NO reacts with LO to form nitroso ester of fatty acid (Reaction (7), Figure 25.1). Alkoxyl radical LO may be transformed into a nitro epoxy compound after rearrangement (Reaction (8)). In addition, LOONO may be hydrolyzed to form fatty acid hydroperoxide (Reaction (6)). Various nitrated lipids can also be formed in the reactions of peroxynitrite and other NO metabolites. 

FIGURE 32-6 Lipid peroxidation leads to fragmentation or oxidation of polyunsaturated fatty acids (PUFA). HO, hydroxyl radical LO, lipid alkoxylradical LOO, lipid peroxyl radical 0 2, superoxide radical O, atomic oxygen radical. (From Hall in [3].)... 

O DormeU, V. B., Chumley, P. H., Hogg, N., Bloodsworth, A., Darley-Usmar, V. M., and Freeman, B. A., 1997, Nitric oxide inhibition of Upid peroxidation kinetics of reaction with lipid peroxyl radicals and comparison with alpha-tocopherol, Biochemistry 36 15216-15223. 

Oxidation to CO of biodiesel results in the formation of hydroperoxides. The formation of a hydroperoxide follows a well-known peroxidation chain mechanism. Oxidative lipid modifications occur through lipid peroxidation mechanisms in which free radicals and reactive oxygen species abstract a methylene hydrogen atom from polyunsaturated fatty acids, producing a carbon-centered lipid radical. Spontaneous rearrangement of the 1,4-pentadiene yields a conjugated diene, which reacts with molecular oxygen to form a lipid peroxyl radical. 

Lipoxygenases (LOX), cycloxygenases (COXs), and xanthine oxidase (XO) are metalloen-zymes whose catalytic cycle involves ROS such as lipid peroxyl radicals, superoxide, and hydrogen peroxide. LOXs and COXs catalyze important steps in the biosynthesis of leuco-trienes and prostaglandins from arachidonic acid, which is an important cascade in the development of inflammatory responses. XO catalyzes the ultimate step in purine biosynthesis, the conversion of xanthine into uric acid. XO inhibition is an important issue in the... 

The inhibition of lipid (LH) oxidation may be considered as one of the most important chemical reaction mechanisms that could explain the antioxidant function of flavonoids. In general terms, chain-breaking antioxidants (AH) inhibit or retard lipid oxidation (reactions 1-7) by interfering with initiation [generically represented by reaction 1] or with chain propagating reactions (reactions 2 and 3) by readily donating hydrogen atoms to lipid peroxyl radicals (LOO ) or lipid radicals (L ) (reactions 4 and 5) [Frankel, 1998] ... 

FIGURE 29.1 Pathways of the chain-breaking action of vitamin E in lipid peroxidation and its subsequent regeneration. LOOH lipid hydroperoxide, LOO lipid peroxyl radical, vitamin C ascorbate radical (semi-dehydroascorbate), vitamin E a-tocopheroxyl radical. The lipid peroxyl radical is reduced to lipid hydroperoxide by tocopherol. The resulting tocopheroxyl radical can be re-reduced by ascorbate. The thus formed ascorbate radical can be reduced to ascorbate by the NADH-dependent semidehydroascorbate reductase. 

Rubbo, H., Radi, R., Ansehni, D., Kirk, M., Barnes, S., Butler, J., Eiserich, J. P., and Freeman, B. A., 2000, Nitric oxide reaction with lipid peroxyl radicals spares alpha-tocopherol during lipid peroxidation. Greater oxidant protection from the pair nitric oxide/alpha-tocopherol than alpha-tocopherol/ascorbate, J. Biol. Chem. 275 10812-10818. 

The lung also possesses nonenzymatic antioxidants such as vitamin E, beta-carotene, vitamin C, and uric acid. Vitamin E is lipid-soluble and partitions into lipid membranes, where it is positioned optimally for maximal antioxidant effectiveness. Vitamin E converts superoxide anion, hydroxyl radical, and lipid peroxyl radicals to less reactive oxygen metabolites. Beta-carotene also accumulates in cell membranes and is a metabolic precursor to vitamin A. Furthermore, it can scavenge superoxide anion and react directly with peroxyl-free radicals, thereby serving as an additional lipid-soluble antioxidant. Vitamin C is widely available in both extracellular and intracellular spaces where it can participate in redox reactions. Vitamin C can directly scavenge superoxide and hydroxyl radical. Uric acid formed by the catabolism of purines also has antioxidant properties and primarily scavenges hydroxyl radical and peroxyl radicals from lipid peroxidation. 

LH = polyunsaturated L = lipid radical LO = lipid peroxyl radical... 

Lipid hydroperoxides arise in membranes and in oxidised LDL as a direct consequence of the intervention by a-T in terminating chain reactions, as well as from the chain reactions themselves. The possibility exists that catalysis by divalent transition metal cation complexes may cause the re-formation of lipid-peroxyl radicals or of other radical species such as the alkoxyl radical. The rate of reaction of Fe3+ with lipid hydroperoxides is much slower than the rate of... 

Reactions 11,13) as well as recycling the haem proteins for further oxidative events. The lipid peroxyl radicals formed during the modification of the polyunsaturated fatty acid sidechains of lipids, can amplify lipid peroxidation, oxidise cholesterol and can react with proteins, impairing the functions of critical enzyme and receptor systems ... 

In the second experiment, mice were irradiated with the highest dose from the dose-response experiment. Concentrations of lipid hydroperoxides and lipophilic antioxidants were measured simultaneously on single skin samples from irradiated and non-irradiated sides of each mouse. The lipid hydroperoxide assay directly measured lipid peroxidation and thus was superior to the TBARS assay, which is indirect. Lipid-peroxyl radicals have been linked to chemically induced cutaneous carcinogenesis [31] as well as to UV-light-induced cutaneous carcinogenesis [32],... 

Cyanidin inhibits epidermal growth factor receptor tyrosine kinase (EGF-RTK), a-glycosidase and COX-1 and COX-2. Delphinidin (3,5,7,3, 4, 5 -hexahydroxyflavylium) also inhibits EGF-RTK. Anthocyanidins and anthocyanins can be anti-inflammatory antioxidants by acting as free radical scavengers. Thus, nasunin (delphinidin-3-(j6-coumaroylrutinoside)-5-glucoside) scavenges OH (hydroxyl), 02 (superoxide) and lipid peroxyl radicals and inhibits lipid peroxidation. 

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