Theoretical and experimental studies of the spin trapping of inorganic radicals by 5,5-dimethyl-1-pyrroline N-oxide (DMPO). 2. Carbonate radical anion

Frederick A. Villamena, Edward J. Locigno, Antal Rockenbauer, Christopher M. Hadad, Jay L. Zweier

Research output: Contribution to journalArticle

Abstract

Previous studies have shown that the enzyme-mediated generation of carbonate radical anion (CO3̇-) may play an important role in the initiation of oxidative damage in cells. This study explored the thermodynamics of CO3̇- 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 CO3̇- to DMPO yields an O-centered radical adduct (DMPO-OCO2) as governed by the spin (density) population on the CO3̇-. Electron paramagnetic resonance spin trapping with the commonly used spin trap, DMPO, has been employed in the detection of CO3̇-. UV photolysis of H2O2 and DMPO in the presence of sodium carbonate (Na2CO3) or sodium bicarbonate (NaHCO 3) gave two species (i.e., DMPO-OCO2 and DMPO-OH) in which the former has hyperfine splitting constant values of aN = 14.32 G, aβ-H = 10.68 G, and aγ-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 H2 17O2 that indicates direct addition of HȮ to DMPO. Theoretical studies on other possible pathways for the formation of DMPO-OH from DMPO-OCO2 in aqueous solution and in the absence of free HȮ such as in the case of enzymatically generated CO 3̇- show that the preferred pathway is via nucleophilc substitution of the carbonate moiety by H2O or HO-. Nitrite formation has been observed as the end product of CO3 ̇- trapping by DMPO and is partly dependent on the basicity of solution. The thermodynamic behavior of CO3̇- in the aqueous phase is predicted to be similar to that of the hydroperoxyl (HO 2̇) radical.

Original languageEnglish (US)
Pages (from-to)384-391
Number of pages8
JournalJournal of Physical Chemistry A
Volume111
Issue number2
DOIs
StatePublished - Jan 18 2007
Externally publishedYes

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Carbonates
Anions
carbonates
trapping
anions
oxides
5,5-dimethyl-1-pyrroline-1-oxide
Thermodynamics
sodium carbonates
thermodynamics
Sodium Bicarbonate
nitrites
Photolysis
Carbon Monoxide
Alkalinity
Nitrites
half life
adducts
Density functional theory
Paramagnetic resonance

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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Theoretical and experimental studies of the spin trapping of inorganic radicals by 5,5-dimethyl-1-pyrroline N-oxide (DMPO). 2. Carbonate radical anion. / Villamena, Frederick A.; Locigno, Edward J.; Rockenbauer, Antal; Hadad, Christopher M.; Zweier, Jay L.

In: Journal of Physical Chemistry A, Vol. 111, No. 2, 18.01.2007, p. 384-391.

Research output: Contribution to journalArticle

Villamena, Frederick A. ; Locigno, Edward J. ; Rockenbauer, Antal ; Hadad, Christopher M. ; Zweier, Jay L. / Theoretical and experimental studies of the spin trapping of inorganic radicals by 5,5-dimethyl-1-pyrroline N-oxide (DMPO). 2. Carbonate radical anion. In: Journal of Physical Chemistry A. 2007 ; Vol. 111, No. 2. pp. 384-391.
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abstract = "Previous studies have shown that the enzyme-mediated generation of carbonate radical anion (CO3̇-) may play an important role in the initiation of oxidative damage in cells. This study explored the thermodynamics of CO3̇- 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 CO3̇- to DMPO yields an O-centered radical adduct (DMPO-OCO2) as governed by the spin (density) population on the CO3̇-. Electron paramagnetic resonance spin trapping with the commonly used spin trap, DMPO, has been employed in the detection of CO3̇-. UV photolysis of H2O2 and DMPO in the presence of sodium carbonate (Na2CO3) or sodium bicarbonate (NaHCO 3) gave two species (i.e., DMPO-OCO2 and DMPO-OH) in which the former has hyperfine splitting constant values of aN = 14.32 G, aβ-H = 10.68 G, and aγ-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 H2 17O2 that indicates direct addition of HȮ to DMPO. Theoretical studies on other possible pathways for the formation of DMPO-OH from DMPO-OCO2 in aqueous solution and in the absence of free HȮ such as in the case of enzymatically generated CO 3̇- show that the preferred pathway is via nucleophilc substitution of the carbonate moiety by H2O or HO-. Nitrite formation has been observed as the end product of CO3 ̇- trapping by DMPO and is partly dependent on the basicity of solution. The thermodynamic behavior of CO3̇- in the aqueous phase is predicted to be similar to that of the hydroperoxyl (HO 2̇) radical.",
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AU - Hadad, Christopher M.

AU - Zweier, Jay L.

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