Identification of the peroxidation products of 13-hydroxy-gamma-linolenate and 15-hydroxyarachidonate: mechanistic studies on the formation of leukotriene-like diols.
Monohydroxy-gamma-linolenates and arachidonates were oxidized in the presence of alpha-tocopherol and free radical initiators at 37 degrees C. The dihydroxylinolenate products were analyzed and identified by use of a combination of liquid chromatography, mass spectrometry, and NMR techniques. A mechanism for the formation of the dihydroxylinolenates is proposed based on product analysis of oxidations using varied concentrations of alpha-tocopherol. The mechanism for monohydroxyarachidonate oxidation is the same as that of monohydroxylinolenates. However, arachidonate diol analysis is more complicated because of the formation of additional regioisomers that are a result of the parent arachidonate possessing multiple bisallylic hydrogens.
Rector
Christopher L
CL
Department of Chemistry and Center in Molecular Toxicology, Vanderbilt University, Nashville, Tennessee 37235, USA.
Stec
Donald F
DF
Brash
Alan R
AR
Porter
Ned A
NA
D001095:Arachidonic Acids / Q000378:metabolism*; D002851:Chromatography, High Pressure Liquid; D015289:Leukotrienes / Q000378:metabolism; D008041:Linoleic Acids / Q000378:metabolism*; D015227:Lipid Peroxidation; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D010084:Oxidation-Reduction
D001095:Arachidonic Acids; D015289:Leukotrienes; D008041:Linoleic Acids