title: Radical mechanisms of the decomposition of peroxynitrite and the peroxynitrite-CO(2) adduct and of reactions with L-tyrosine and related compounds as studied by (15)N chemically induced dynamic nuclear polarization.
abstract: Enhanced absorption is observed in the (15)N NMR spectra of (15)NO(-)(3) during decomposition of peroxynitrite and the peroxynitrite-CO(2) adduct at pH 5.25, indicating the formation of (15)NO(-)(3) in radical pairs [(15)NO(*)(2), HO(*)] and [(15)NO(*)(2), CO(*-)(3)]. During the reaction of peroxynitrite and the peroxynitrite-CO(2) adduct with L-tyrosine, the (15)N NMR signal of the nitration product 3-nitrotyrosine exhibits emission showing a radical pathway of its formation. The nuclear polarization is built up in radical pairs [(15)NO(*)(2), tyr(*)] generated by free radical encounters of nitrogen dioxide and tyrosinyl radicals. The (15)N NMR signal of (15)NO(-)(2) formed during reaction of peroxynitrite with L-tyrosine appears in emission. It is concluded that tyrosinyl radicals are generated by reaction of nitrogen dioxide with L-tyrosine. In contrast to this, (15)NO(-)(2) does not show (15)N chemically induced dynamic nuclear polarization (CIDNP) during reaction of the peroxynitrite-CO(2) adduct with L-tyrosine, indicating a different reaction mechanism, which is assumed to be a hydrogen transfer between CO(*-)(3) and L-tyrosine. Emission is also observed in the (15)N NMR signals of 2-nitro-4-fluorophenol, 3-nitro-4-hydroxyphenylacetic acid, 2-nitrophenol, and 4-nitrophenol during reaction of 4-fluorophenol, 4-hydroxyphenylacetic acid, and phenol with peroxynitrite and the peroxynitrite-CO(2) adduct. 3-Nitro-4-hydroxyphenylacetic acid is also observed in emission during reaction of phenylacetic acid with peroxynitrite, but is not formed with the peroxynitrite-CO(2) adduct. The magnitude of the (15)N CIDNP effect during reaction of peroxynitrite with 4-fluorophenol and of the peroxynitrite-CO(2) adduct with 4-fluorophenol and phenol is determined. It excludes the occurrence of nonradical reactions. Only weak emission signals are observed during the reaction of peroxynitrite with phenol in (15)NO(-)(2), 2-nitrophenol, and 4-nitrophenol. 2-Nitrophenol is only formed in traces, and 4-nitrophenol is only formed in higher yields. The latter might be generated in part via a nonradical pathway.
authors.affiliation: Fachbereich Chemie, Universität Dortmund, Dortmund, D-44221, Germany. lehnig@citrin.chemie.uni-dortmund.de
authors.forename: M
authors.initials: M
authors.lastname: Lehnig
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry*; D005609:Free Radicals; D009682:Magnetic Resonance Spectroscopy; D009566:Nitrates / Q000737:chemistry*; D014443:Tyrosine / Q000737:chemistry*
chemical_list: D005609:Free Radicals; D009566:Nitrates; D002245:Carbon Dioxide; C039642:peroxynitric acid; D014443:Tyrosine