RRC ID 11416
Author Hamberg M, Chechetkin IR, Grechkin AN, Ponce de León I, Castresana C, Bannenberg G.
Title Synthesis of 3-oxalinolenic acid and beta-oxidation-resistant 3-oxa-oxylipins.
Journal Lipids
Abstract 99%-pure 3-oxalinolenic acid in 10-15% overall yield. 3-Oxalinolenic acid was efficiently oxygenated by soybean lipoxygenase-1 into 3-oxa-13(S)-hydroperoxy-9(Z),11(E),15(Z)-octadecatrienoic acid, and this hydroperoxide could be further converted chemically into 3-oxa-13(S)-hydroxy-9(Z),11 (E),15(Z)-octadecatrienoic acid and 3-oxa-13-oxo-9(Z),11 (E),15(Z)-octadecatrienoic acid. The 3-oxa-hydroperoxide also served as the substrate for the plant enzymes allene oxide synthase, divinyl ether synthase, and hydroperoxide lyase to produce 3-oxa-12-oxo-10,15(Z)-phytodienoic acid and other 3-oxa-oxylipins that were characterized by MS. 3-Oxalinolenic acid was not oxygenated by 9-lipoxygenase from tomato but was converted at a slow rate into 3-oxa-9(S)-hydroperoxy-10(E),12(Z),15(Z)-octadecatrienoic acid by recombinant maize 9-lipoxygenase. Recombinant alpha-dioxygenase-1 from Arabidopsis thaliana catalyzed the conversion of 3-oxalinolenic acid into a 2-hydroperoxide, which underwent spontaneous degradation into a mixture of 6,9,12-pentadecatrienol and 6,9,12-pentadecatrienyl formate. A novel alpha-dioxygenase from the moss Physcomitrella patens was cloned and expressed and was found to display the same activity with 3-oxalinolenic acid as Arabidopsis thaliana alpha-dioxygenase-1. Lipoxygenase-generated 3-oxa-oxylipins are resistant toward beta-oxidation and have the potential for displaying enhanced biological activity in situations where activity is limited by metabolic degradation.
Volume 41(5)
Pages 499-506
Published 2006-5
PMID 16933794
MeSH Chromatography, High Pressure Liquid Dioxygenases / metabolism Electrophoresis, Polyacrylamide Gel Gas Chromatography-Mass Spectrometry Linolenic Acids / chemical synthesis Linolenic Acids / chemistry* Linolenic Acids / metabolism Lipoxygenase / metabolism Models, Chemical Molecular Structure Oxidation-Reduction Plants / enzymology
IF 1.936
Times Cited 9
WOS Category NUTRITION & DIETETICS BIOCHEMISTRY & MOLECULAR BIOLOGY
Resource
Arabidopsis / Cultured plant cells, genes pdp14290