Theoretical and Experimental Studies of the Spin Trapping of Inorganic Radicals by 5,5-Dimethyl-1-PyrrolineN-Oxide (DMPO). 2. Carbonate Radical Anion

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Abstract

Previous studies have shown that the enzyme-mediated generation of carbonate radical anion (CO(3)(.-)) may play an important role in the initiation of oxidative damage in cells. This study explored the thermodynamics of CO(3)(.-) addition to 5,5-dimethyl-1-pyrroline N-oxide (DMPO) using density functional theory at the B3LYP/6-31+G(**)//B3LYP/6-31G* and B3LYP/6-311+G* levels with the polarizable continuum model to simulate the effect of the bulk dielectric effect of water on the calculated energetics. Theoretical data reveal that the addition of CO(3)(.-) to DMPO yields an O-centered radical adduct (DMPO-OCO2) as governed by the spin (density) population on the CO(3)(.-). Electron paramagnetic resonance spin trapping with the commonly used spin trap, DMPO, has been employed in the detection of CO(3)(.-). UV photolysis of H(2)O(2) and DMPO in the presence of sodium carbonate (Na(2)CO(3)) or sodium bicarbonate (NaHCO(3)) gave two species (i.e., DMPO-OCO(2) and DMPO-OH) in which the former has hyperfine splitting constant values of a(N) = 14.32 G, a(beta)-Eta = 10.68 G, and a(gamma-H) = 1.37 G and with a shorter half-life compared to DMPO-OH. The origin of the DMPO-OH formed was experimentally confirmed using isotopically enriched H(2)(17)O(2) that indicates direct addition of HO(.) to DMPO. Theoretical studies on other possible pathways for the formation of DMPO-OH from DMPO-OCO(2) in aqueous solution and in the absence of free HO(.) such as in the case of enzymatically generated CO(3)(.-), show that the preferred pathway is via nucleophilc substitution of the carbonate moiety by H(2)O or HO(-). Nitrite formation has been observed as the end product of CO(3)(.-) trapping by DMPO and is partly dependent on the basicity of solution. The thermodynamic behavior of CO(3)(.-) in the aqueous phase is predicted to be similar to that of the hydroperoxyl (HO(2)(.)) radical.

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