Superoxide radical, reactions

Deeble DJ, von Sonntag C (1992) Decarboxylation of 3,4-dihydroxymandelic acid induced by the superoxide radical anion a chain reaction. Int J Radiat Biol 62 105 Deeble DJ, Parsons BJ, Phillips GO (1987) Evidence for the addition of the superoxide anion to the anti- oxidant -propyl gallate in aqueous solution. Free Rad Res Commun 2 351-358 Deeble DJ, Parsons BJ, Phillips GO, Schuchmann H-P, von Sonntag C (1988) Superoxide radical reactions in aqueous solutions of pyrogallol and n-propyl gallate the involvement of phenoxyl radicals. A pulse radiolysis study. Int J Radiat Biol 54 179-193 Denisov ET, Denisova TG (1993) The polar effect in the reaction of alkoxy and peroxy radicals with alcohols. Kinet Catal 34 738-744... 

The electron transfer from oxygen to the sarcophaginate cation (Reaction (134)) is the rate-determining stage. The next fast step may be either the oxidation of [Co(sep)] + cation with the superoxide radical (Reactions 136 and 137) or disproportionation (Reaction 138). 

The overall reaction is initiated by an electron transfer from ascorbate to 4-NQO with the production of A and 4-NQO" (Reaction 46, l). The 4-NQO" radical reacts rapidly [reported values for similar compounds range from 10 to 10 M V (62,63)] with molecular oxygen to yield superoxide radical (Reaction 46, 2), which dismutates to peroxide and oxygen (Reaction 46, 3) or reacts with ascorbate (Reaction 46, 4). Specific tests with superoxide dismutase and catalase suggest that OH radicals are formed in this system by a Haber-Weiss (64) and/or Fenton (65) type reaction ... 

Superoxide Radical. Reactions of the superoxide and hydroperoxyl radicals are studied primarily because of the role of the radicals in normal and abnormal biological systems. Bielski and co-workers (20) compiled a list of reaction rate constants for HO2 and O2 " and other properties of the radicals. Unhke the majority of the radicals discussed here, the self-reactions of HO2 and O2 " are slow (Figure 4). In particular, it is probable that no self-reaction occurs with the superoxide radical itself, and that observed decays result from reaction with H02 or solution wmponents or contaminants. 

Fig. 8.9 Possible mechanisms of the bioluminescence reaction of dinoflagellate luciferin, based on the results of the model study (Stojanovic and Kishi, 1994b Stojanovic, 1995). The luciferin might react with molecular oxygen to form the luciferin radical cation and superoxide radical anion (A), and the latter deproto-nates the radical cation at C.132 to form (B). The collapse of the radical pair might yield the excited state of the peroxide (C). Alternatively, luciferin might be directly oxygenated to give C, and C rearranges to give the excited state of the hydrate (D) by the CIEEL mechanism. Both C and D can be the light emitter.

A parallel set of determinations was done with Cu2+ added, since this metal ion has been reported to oxidize the superoxide radical ion very rapidly. Thus, with added Cu2+ the first reaction proceeded as shown, but the second was replaced by... 

Not all oxidants formed biolc cally have the potential to promote lipid peroxidation. The free radicals superoxide and nitric oxide [or endothelium-derived relaxing aor (EDRF)] are known to be formed in ww but are not able to initiate the peroxidation of lipids (Moncada et tU., 1991). The protonated form of the superoxide radical, the hydroperoxy radical, is capable of initiating lipid peroxidation but its low pili of 4.5 effectively precludes a major contribution under most physiological conditions, although this has been suggested (Aikens and Dix, 1991). Interestingly, the reaction product between nitric oxide and superoxide forms the powerful oxidant peroxynitrite (Equation 2.6) at a rate that is essentially difiiision controlled (Beckman eta/., 1990 Huie and Padmaja, 1993). 

NADH, which enters the Krebs cycle. However, during cerebral ischaemia, metabolism becomes anaerobic, which results in a precipitous decrease in tissue pH to below 6.2 (Smith etal., 1986 Vonhanweh etal., 1986). Tissue acidosis can now promote iron-catalysed free-radical reactions via the decompartmentalization of protein-bound iron (Rehncrona etal., 1989). Superoxide anion radical also has the ability to increase the low molecular weight iron pool by releasing iron from ferritin reductively (Thomas etal., 1985). Low molecular weight iron species have been detected in the brain in response to cardiac arrest. The increase in iron coincided with an increase in malondialdehyde (MDA) and conjugated dienes during the recirculation period (Krause et al., 1985 Nayini et al., 1985). 

Shimizu, N., Kobayashi, K. and Hayashi, K. (1984). The reaction of superoxide radical with catalase. J. Biol. Chem. 259, 4414-4418. 

Generation of superoxide radical under physiological conditions ultimately leads to the production of hydroxyl radical through a cascade of redox reactions. Initially, sn-peroxide disproportionates to generate hydrogen peroxide (Eq. 3, Scheme 8.36) Superoxide radical exists in equilibrium with its protonated form (H02, = 5). 

Under physiological conditions, the disproportionation of superoxide radical is very fast and involves reaction of the radical anion 02 with a molecule of the neutral radical, H02 (Eq. 2, Scheme 8.36). Disproportionation yields one molecule of molecular oxygen and one molecule of hydrogen peroxide. 

J.M. McCord and I. Fridovich, Utility of superoxide dismutase in studying free radical reactions. II. Mechanism of the mediation of cytochrome c reduction by a variety of electron carriers. J. Biol. Chem. 245,1374-1377 (1970). 

Selenoureas are prepared by reaction of isoselenocyanates with amines, or by reaction of carbodiimides with a mixture of LiAlH4/Se and by reaction of cyanamides with LiAlH4/Se.267 272 The tyrosinase inhibitory activity and superoxide radical scavenger effect of selenoamides and selenoureas have been investigated (Scheme 84).273 275... 

Several authors observed CL emission based on reduction reactions. Lu et al. [59] developed a method by applying a Jones reductor for producing unstable reductants. A column (100 X 3 mm i.d.) filled with Zn-Hg particles was inserted into the flow stream of a flow injection system. CL was measured using a homemade CL analyzer. Although the Jones reductor was more effective for the species studied in 0.5-5 mol/L H2S04 solution, the authors found that a lower acid concentration improved the CL emission. Hie optimal pH was 6.5 for V(II), 2.5 for Mo(III), 3.5 for U(III), 3.0 for W(III), 3.0 for Cr(II), 2.5 for Ti(III), and 2.5 for Fe(II). The methods allowed determination of the above-mentioned species at pg/mL to ng/mL levels. It was assumed that the CL reactions were related to the production of superoxide radicals by dissolved oxygen in the solutions. The proposed methods could be successfully applied to the determination of V [60], Mo [61], and U [62] in water or steel samples. 

There are two possible initial steps of photosensitized reactions, leading to the formation of superoxide radical ... 

Figure 1 shows the graphs of the PCL that were recorded with riboflavin as the photosensitizer and luminol as the detector for free radicals [21], The course of the PCL reaction has two maxima at approximately 30 s and 3 min after the start of irradiation. It has been demonstrated by analysis of kinetics after addition of the reactants at varying times that the first maximum is riboflavin-dependent. Luminol is needed only for visualization of the superoxide radicals. 

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