Superoxide cleavage reactions

In acid solutions, but also in neutral solutions at high steady-state radical concentrations, the superoxide elimination becomes too slow compared with the bimolecular decay of these peroxyl radicals [reactions (28)-(31)]. This leads to a very different product distribution, as seen in Table 5. There is evidence that in their bimolecular decay peroxyl radicals can give rise to the formation of oxyl radicals which may undergo fragmentation (see, e.g., [37, 38]) [e.g., reaction (30)], leading to products with the pyrimidine cycle destroyed (e.g., l-N-formyl-5-hydroxyhydantoin. Other pyrimidine-ring cleavage reactions are conceivable but at present not supported by product data). 

A variety of chalcones are cleaved by potassium superoxide [13] according to equation 8.10 to yield a mixture of two, and sometimes three, carboxylic acids. Labeling experiments indicate that the superoxide transfers an electron to the enone followed by reaction of the resulting radical with molecular oxygen. An overall mechanism has been postulated for this reaction [13]. The results of a number of chalcone cleavage reactions are presented in Table 8.6. 

Unlike conventional chemical reactions, the altered reactivity of chemical reactions undergoing ultrasonic irradiation is principally due to acoustic cavitation which essentially involves the free radical formation. The ultrasound produces highly reactive free radical species like H and OH radicals from the homolytic cleavage of water. Further they may react with any of other free radicals present or with neutral molecules like 02 and O3 to produce peroxy species, superoxide, hydrogen peroxide or hydrogen. When the aqueous solution is saturated with 02, extra... 

Here we presented two general aspects of the interactions between superoxide and metal centers. One is the catalytic decomposition of superoxide by non-heme metal centers (Scheme 9) and the role of the ligand structure in it, and another is the reversible binding of superoxide to the heme metal center and the nature of the product metal(lll)-peroxo species (Scheme 17). In both cases through the same redox reaction steps a metal(III)-peroxo species is formed as the intermediate (Scheme 9), in the catalytic cycle, or the product of stoichiometric reaction (Scheme 17). The crucial difference is in the protonation step. If the protonation of peroxo species is followed by efficient release of hydrogen peroxide (and not 0-0 bond cleavage,... 

The biological mechanism of action is helieved to involve the production of superoxides near the DNA strand, resulting in DNA backbone cleavage and cell apoptosis. The actual mechanism is not yet known, but is believed to proceed from the reduction of molecular oxygen into superoxide via an unusual auto-redox reaction on a hydroxyquinone moiety of the compound following. There is also some speculation the compound becomes activated into its reactive oxazolidine form. 

Transition metal hydroperoxo species are well established as important intermediates in the oxidation of hydrocarbons (8,70,71). As they relate to the active oxygenating reagent in cytochrome P-450 monooxygenase, (porphyrin)M-OOR complexes have come under recent scmtiny because of their importance in the process of (poiphyrin)M=0 formation via 0-0 cleavage processes (72-74). In copper biochemistry, a hydroperoxo copper species has been hypothesized as an important intermediate in the catalytic reaction of the copper monooxygenase, dopamine P-hydroxylase (75,76). A Cu-OOH moiety has also been proposed to be involved in the disproportionation of superoxide mediated by the copper-zinc superoxide dismutase (77-78). Thus, model Cun-OOR complexes may be of... 

Although hydroxyl radical is commonly assumed to be the most toxic of the oxygen radicals (with little direct evidence), other direct reactions are more likely to be important for understanding the cytotoxicity of peroxynitrite. A second oxidative pathway involves the heterolytic cleavage of peroxynitrite to form a nitronium-like species (N02 ), which is catalyzed hy transition metals (Beckman et al., 1992). Low molecular weight metal complexes as well as metals bound in superoxide dismutase and other proteins catalyze the nitration of a wide range of phenolics, including tyrosine residues in most proteins (Beckman et al., 1992). 

Oxidation of cobalt(ll) to cobalt(lll) by oxygen in the presence of N-hydroxyethylethylenediamine and carbon produces large amounts of ethylenediamine. Other products are formaldehyde, formic acid, and ammonia. The sum of the moles of ethylenediamine and ammonia produced is equal to the total number of moles of cobalt(ll) oxidized. A steady-state concentration of Co(ll)-Co(lll) is established in which the ratio Co(lll)/ Co(ll) = 1.207. Thus cobalt ion behaves as a true catalyst for cleavage of the N-hydroxyethyl-ethylenediamine. The total amount of cobalt(ll) oxidized per unit time, X, was calculated from the derived equation X = 3.8 + 7.0 k2 T — 3.8e-2-2k 1, where k2 = 0.65 hr.—1 The observed rate of formation of ethylenediamine plus ammonia also follows this equation. It is proposed that the cobalt ion serves as a center where a superoxide ion [derived from oxidation of cobalt-(II) by oxygen] and the ligand are brought together for reaction. 

The N.N-diethylamides listed in Table 10 are sufficiently acidic to react with the superoxide/dioxygen reagent. Yields are low and these reactions have limited preparative value. It is noteworthy, however, that N,N-diethyldiphenylacetamide undergoes oxygenation with concomitant cleavage, presumably in a manner analogous to that depicted in Scheme 19. 

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Perkins MJ (1996) A radical reappraisal of Gif reactions. Chem Soc Rev 25 229-236 Phulkar S, Rao BSM, Schuchmann H-P, von Sonntag C (1990) Radiolysis of tertiary butyl hydroperoxide in aqueous solution. Reductive cleavage by the solvated electron, the hydrogen atom, and, in particular, the superoxide radical anion. Z Naturforsch 45b 1425-1432 Pimblott SM, LaVerne JA (1997) Stochastic simulation of the electron radiolysis of water and aqueous solutions. J Phys Chem A 101 5828-5838... 

Influence of chemical and physical factors. Int J Radiat Biol 35 473-476 Redpath JL, Zabilansky E, Morgan T, Ward JF (1981) Cerenkov light and the production of photore-activatable damage in X-irradiated E. coli. Int J Radiat Biol 39 569-575 Reich KA, Marshall LE, Graham DR, Sigman DS (1981) Cleavage of DNA by 1,10-phenanthroline-cop-per ion complex. Superoxide mediates the reaction dependent on NADEI and hydrogen peroxide. J Am Chem Soc 103 3582-3584... 

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