Stereospecific biosynthesis of (9S,13S)-10-oxo-phytoenoic acid in young maize roots.
Profiling of oxylipins from young maize roots revealed complex patterns of products mainly originating from the combined actions of 9- and 13-lipoxygenases and allene oxide synthase (AOS). A distinctive feature was the high content of the cyclopentenone 10-oxo-11-phytoenoic acid (10-oxo-PEA). Incubations with [1-14C]linoleic acid led to the formation of the α-ketols 13-hydroxy-12-oxo-9-octadecenoic acid and 9-hydroxy-10-oxo-12-octadecenoic acid as well as the cyclopentenones 12-oxo-10-phytoenoic acid (12-oxo-PEA) and 10-oxo-PEA in a ratio of 10:2:1:3. Chiral phase radio-HPLC showed that the labeled 10-oxo-PEA was mainly (93%) due to the 9S,13S-enantiomer, whereas 12-oxo-PEA was racemic. Recombinant maize AOS CYP74A19 (ZmAOS2) converted linoleic acid 9(S)-hydroperoxide (9-HPOD) into an allene oxide, 9,10-epoxy-10,12-octadecadienoic acid (9,10-EOD), which did not undergo cyclization but was solely hydrolyzed into the α-ketol. A cyclase activity promoting the conversion of 9,10-EOD into (9S,13S)-10-oxo-PEA was detected in the 10(5)×g supernatant prepared by differential centrifugation of the maize root homogenate. The data obtained suggested the existence of a new type of allene oxide cyclase, which is active towards an allene oxide formed from a 9-lipoxygenase-derived hydroperoxide.
['Ogorodnikova|Anna V|AV|', 'Gorina|Svetlana S|SS|', 'Mukhtarova|Lucia S|LS|', 'Mukhitova|Fakhima K|FK|', 'Toporkova|Yana Y|YY|', 'Hamberg|Mats|M|', 'Grechkin|Alexander N|AN|']
D002851:Chromatography, High Pressure Liquid D003517:Cyclopentanes D005231:Fatty Acids, Unsaturated D018507:Gene Expression Regulation, Developmental D018506:Gene Expression Regulation, Plant D019746:Intramolecular Oxidoreductases D007527:Isoenzymes D008041:Linoleic Acids D050356:Lipid Metabolism D008054:Lipid Peroxides D008084:Lipoxygenase D010940:Plant Proteins D018517:Plant Roots D013237:Stereoisomerism D003313:Zea mays
Oxylipins Allene oxide synthase Cyclopentenone Cyclase (9S,13S)-10-oxo-11-phytoenoic acid Maize (Zea mays L.) roots