Oxygen Radicals in Biology and Medicine

ion. 31, 32 It is important to remember, however, that subsequent to each of these primary modes, secondary oxidative processes can, and generally do, take over. Let us now examine each of these modes in detail. Electron transfer. Electron transfer is one of the most common modes of 0 7 ' in biological systems and is the essence of the dismutation process (l!auation 2). This is, of course, not surprising considering that the redox potential of the O2/02' couple (vs. NHE) is -O.33V in water and -O.6V in organic solvents. This quarter volt gap between aqueous and aprotic media cannot be attributed to differences in the dielectric constants of the media since the electrochemical potential of oxygen is relatively insensitive to the differing dielectric constants of a variety of aprotic solvents. 33-36 To understand this and many other phenomena related to O2' activity (e.g., nucleophilicity and basicity [vide infra]), we must recall that OZ' is a small, hard, nonpolarizable anion. In aqueous/protic media it w~ll be highly and tightly solvated and hence thermodynamically more stable than in aprotic media in which such solvat~ mechanisms are generally absent. Superoxide plays the role of reductant with metals. 37 For example, in the extremely important metal catalyzed Haber-Weiss reaction38 (equation 6; R = H). F +3 ° .+ ROOH _e __ > O2 + RO' + HO (6) 2 O2 + Fe+ 3 ---> Fe+2 + O2 (7) Fe+2 + ROOH ---> Fe+3 + RO + HO (8) Superoxide2serves to reduce the metal cation (Fe+ 3) to a lower oxidation state (Fe+ ; equation 7), which in turn oxidizes the peroxide linkage in a Fenton reaction (equation 8). Hence, the metal-catalyzed Haber-Weiss reaction is, in fact, a superoxide-driven Fenton process. Superoxide will not reduce peroxides directly,31,32,39 nor does it interact with simple olefins (including arachadonic acid and other PUFA) or aromatic compounds. It will, however, transfer electrons to ¥ood electron acceptors 31 ,32,40 such as quinones, 31, 32 diketones,31,3 ,41,42 chalcones,40,43 nitrobenzenes,40,44 as well as electron-poor cyanoand nitroolefins40 (equation 9-13). Recently Gibian and Russo 45 have demonstrated that the rapid superoxide-mediated cis-trans isomerization of l,3-di-t-butylpropenone occurs via electron transfer as well (equation 14). ..:. 0=0=0 'o-@-o+ °2 (9) "°2 CPCCCP --'" --> ..:.

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