Are dioxetanes chemiluminescent intermediates in lipoperoxidation?
Ultraweak chemiluminescence arising from lipoperoxidation has been attributed by several authors to the radiative deactivation of singlet oxygen and triplet carbonyl products. The latter emitters have been suggested to come from annihilation of RO. and ROO. radicals as well as from the thermolysis of dioxetane intermediates formed by (2 + 2) cycloaddition of 1O2 to polyunsaturated fatty acids. This article questions possible dioxetane intermediacy in lipoperoxidation, as the literature clearly states that addition of 1O2 to alpha-hydrogen-containing alyphatic olefins yields only the corresponding allylic hydroperoxides. These compounds may undergo dark thermal or Lewis acid-assisted decomposition to the same product obtained from dioxetane cleavage. Here, reexamining the chemiluminescence properties of dioxygenated tetramethylethylene and linoleic acid and comparing them with those of tetraethyldioxetane, a hindered dioxetane, we corroborate the literature information that only steric hindrance leads to dioxetane formation upon singlet oxygen addition to electron-poor olefins, albeit in very low yields. Proton nuclear magnetic resonance (1H-NMR) analysis, quenching by dioxygen and energy transfer studies to 9,10-dibromoanthracene, as well as gas chromatography (GC) analysis of triphenylphosphine-treated and untreated photo- and chemically dioxygenated olefins support our final conclusion that dioxetane formation during lipoperoxidation can be safely excluded on the basis of the data presently available.
Di Mascio
P
P
Instituto de Química, Universidade de São Paulo, Brazil.
Catalani
L H
LH
Bechara
E J
EJ
D000438:Alcohols / Q000737:chemistry; D000447:Aldehydes / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry; D002849:Chromatography, Gas; D005609:Free Radicals; D006571:Heterocyclic Compounds / Q000737:chemistry*; D019787:Linoleic Acid; D008041:Linoleic Acids / Q000737:chemistry; D015227:Lipid Peroxidation; D008163:Luminescent Measurements; D009682:Magnetic Resonance Spectroscopy; D010100:Oxygen / Q000737:chemistry*; D010777:Photochemistry; D026082:Singlet Oxygen
D000438:Alcohols; D000447:Aldehydes; D000475:Alkenes; D005609:Free Radicals; D006571:Heterocyclic Compounds; D008041:Linoleic Acids; C059688:alkoxyl radical; D026082:Singlet Oxygen; C040216:2,3-dimethyl-2-butene; D019787:Linoleic Acid; D010100:Oxygen