Synthesis and spin-trapping behavior of 5-ChEPMPO, a cholesteryl ester analogue of the spin trap DEPMPO.
[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.
Hardy
Micaël
M
Laboratoire SREP, UMR 6517 CNRS et Universités d'Aix-Marseille 1, 2 et 3, Centre de Saint Jérôme, 13397 Marseille Cedex 20, France.
Ouari
Olivier
O
Charles
Laurence
L
Finet
Jean-Pierre
JP
Iacazio
Gilles
G
Monnier
Valérie
V
Rockenbauer
Antal
A
Tordo
Paul
P
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
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