title: Synthesis and spin-trapping behavior of 5-ChEPMPO, a cholesteryl ester analogue of the spin trap DEPMPO.
abstract: [structure: see text] 5-(Cholesteryloxyethoxyphosphoryl)-5-methylpyrroline N-oxide (5-ChEPMPO), a DEPMPO analogue bearing a cholesterol group on the phosphorus atom, has been prepared and used to trap peroxyl-, alkoxyl-, thiyl-, and carbon-centered radicals in organic solvent. The important steric hindrance in 5-ChEPMPO does not affect the properties of 5-ChEPMPO in comparison to DEPMPO for the spin trapping of an enantiopure linoleic acid hydroperoxide. The 5-ChEPMPO-OOL spin adduct was observed by ESR and confirmed by ESI-MS/MS experiments. The relaxation terms of the 5-ChEPMPO-lipid peroxyl spin adduct were compared with those of other peroxyl spin adducts, and it was shown that the cholesteryl group has only a weak influence on the exchange rate between adduct conformers.
authors.affiliation: Laboratoire SREP, UMR 6517 CNRS et Universités d'Aix-Marseille 1, 2 et 3, Centre de Saint Jérôme, 13397 Marseille Cedex 20, France.
authors.forename: Micaël
authors.initials: M
authors.lastname: Hardy
authors.forename: Olivier
authors.initials: O
authors.lastname: Ouari
authors.forename: Laurence
authors.initials: L
authors.lastname: Charles
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Finet
authors.forename: Gilles
authors.initials: G
authors.lastname: Iacazio
authors.forename: Valérie
authors.initials: V
authors.lastname: Monnier
authors.forename: Antal
authors.initials: A
authors.lastname: Rockenbauer
authors.forename: Paul
authors.initials: P
authors.lastname: Tordo
mesh_terms: D002784:Cholesterol / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D002788:Cholesterol Esters / Q000138:chemical synthesis*; D004578:Electron Spin Resonance Spectroscopy; D008041:Linoleic Acids; D008054:Lipid Peroxides; D013058:Mass Spectrometry; D011758:Pyrroles / Q000138:chemical synthesis* / Q000737:chemistry*; D013113:Spin Labels / Q000138:chemical synthesis*; D019097:Spin Trapping
chemical_list: C510912:(diethoxyphosphoryl)-5-methylpyrroline N-oxide; C406273:2-ethoxycarbonyl-2-methyl-3,4-dihydro-2H-pyrrole-1-oxide; C510911:5-(cholesteryloxyethoxyphosphoryl)-5-methylpyrroline N-oxide; D002788:Cholesterol Esters; D008041:Linoleic Acids; D008054:Lipid Peroxides; D011758:Pyrroles; D013113:Spin Labels; C008285:linoleic acid hydroperoxide; D002784:Cholesterol