Spin trapping of superoxide, alkyl- and lipid-derived radicals with derivatives of the spin trap EPPN.
The N-t-butyl-alpha-phenylnitrone derivative N-2-(2-ethoxycarbonyl-propyl)-alpha-phenylnitrone (EPPN) has recently been reported to form a superoxide spin adduct (t(1/2)=5.25 min at pH 7.0), which is considerably more stable than the respective N-t-butyl-alpha-phenylnitrone or 5,5-dimethylpyrroline N-oxide adducts (t(1/2) approximately 10 and 45s, respectively). In continuation of our previous studies on structure optimization of 5-(ethoxycarbonyl)-5-methyl-1-pyrroline N-oxide derivatives, a series of six different EPPN derivatives was synthesized and characterized by 1H NMR, 13C NMR and IR spectroscopy. The ethoxy group of EPPN was replaced by a propoxy, iso-propoxy, n-butoxy, sec-butoxy, and tert-butoxy moiety, as well as the phenyl by a pyridyl ring. Electron spin resonance spectra and stabilities of the superoxide adducts of the propoxy derivatives were found to be similar to those of the respective EPPN adduct, whereas the electron spin resonance spectra of the superoxide adducts of N-2-(2-ethoxycarbonyl-propyl)-alpha-(4-pyridyl) nitrone and the butoxy derivatives were accompanied by decomposition products. In contrast to the 5-(ethoxycarbonyl)-5-methyl-1-pyrroline N-oxide series, no significant improvement of the superoxide adduct stability could be obtained when the ethoxy group was replaced by other substituents. Carbon centered radical adducts derived from methanol, ethanol, formic acid and linoleic acid hydroperoxide were more stable than those of 5,5-dimethylpyrroline N-oxide, whereas among the alkoxyl radicals only the methoxyl radical adduct could be detected.
Stolze
Klaus
K
Basic Pharmacology and Toxicology, Institute of Applied Botany, University of Veterinary Medicine Vienna, Veterinärplatz 1, A-1210 Vienna, Austria.
Udilova
Natascha
N
Rosenau
Thomas
T
Hofinger
Andreas
A
Nohl
Hans
H
D001555:Benzene Derivatives; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods*; D005609:Free Radicals / Q000737:chemistry*; D008041:Linoleic Acids / Q000737:chemistry; D008054:Lipid Peroxides / Q000737:chemistry; D008055:Lipids / Q000737:chemistry; D009589:Nitrogen Oxides / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D013113:Spin Labels / Q000138:chemical synthesis; D019097:Spin Trapping; D013481:Superoxides / Q000737:chemistry
D001555:Benzene Derivatives; D005609:Free Radicals; D008041:Linoleic Acids; D008054:Lipid Peroxides; D008055:Lipids; C447030:N-2-(2-ethoxycarbonylpropyl)phenylnitrone; D009589:Nitrogen Oxides; D013113:Spin Labels; D013481:Superoxides; C008285:linoleic acid hydroperoxide; D010100:Oxygen