Reactive nitrogen species reactivities with nitrones: Theoretical and experimental studies

Kevin M. Nash, Antal Rockenbauer, Frederick A. Villamena

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

Reactive nitrogen species (RNS) such as nitrogen dioxide ( NO2), peroxynitrite (ONOO-), and nitrosoperoxycarbonate (ONOOCO2-) are among the most damaging species present in biological systems due to their ability to cause modification of key biomolecular systems through oxidation, nitrosylation, and nitration. Nitrone spin traps are known to react with free radicals and nonradicals via electrophilic and nucleophilic addition reactions and have been employed as reagents to detect radicals using electron paramagnetic resonance (EPR) spectroscopy and as pharmacological agents against oxidative stress-mediated injury. This study examines the reactivity of cyclic nitrones such as 5,5-dimethylpyrroline N-oxide (DMPO) with NO 2, ONOO-, ONOOCO2-, SNAP, and SIN-1 using EPR. The thermochemistries of nitrone reactivity with RNS and isotropic hfsc's of the addition products were also calculated at the PCM(water)/B3LYP/6- 31+G* *//B3LYP/6-31G* level of theory with and without explicit water molecules to rationalize the nature of the observed EPR spectra. Spin trapping of other RNS such as azide (N3), nitrogen trioxide (NO3), amino ( NH2) radicals and nitroxyl (HNO) were also theoretically and experimentally investigated by EPR spin trapping and mass spectrometry. This study also shows that other spin traps such as 5-carbamoyl-5-methyl-pyrroline N-oxide, 5-ethoxycarbonyl-5-methyl-pyrroline N-oxide, and 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline N-oxide can react with radical and nonradical RNS, thus making spin traps suitable probes as well as antioxidants against RNS-mediated oxidative damage.

Original languageEnglish
Pages (from-to)1581-1597
Number of pages17
JournalChemical Research in Toxicology
Volume25
Issue number8
DOIs
Publication statusPublished - Aug 20 2012

ASJC Scopus subject areas

  • Toxicology

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