Oxylipins in the spikemoss Selaginella martensii: Detection of divinyl ethers, 12-oxophytodienoic acid and related cyclopentenones.
Green tissues of spikemoss Selaginella martensii Spring possessed the complex oxylipins patterns. Major oxylipins were the products of linoleic and α-linolenic acids metabolism via the sequential action of 13-lipoxygenase and divinyl ether synthase (DES) or allene oxide synthase (AOS). AOS products were represented by 12-oxophytodienoic acid (12-oxo-PDA) isomers. Exceptionally, S. martensii possesses high level of 12-oxo-9(13),15-PDA, which is very uncommon in flowering plants. Separate divinyl ethers were purified after micro-preparative incubations of linoleic or α-linolenic acids with homogenate of S. martensii aerial parts. The NMR data allowed us to identify all geometric isomers of divinyl ethers. Linoleic acid was converted to divinyl ethers etheroleic acid, (11Z)-etheroleic acid and a minority of (ω5Z)-etheroleic acid. With α-linolenate precursor, the specificity of divinyl ether biosynthesis was distinct. Etherolenic and (ω5Z)-etherolenic acids were the prevailing products while (11Z)-etherolenic acid was a minor one. Divinyl ethers are detected first time in non-flowering land plant. These are the first observations of fatty acid metabolism through the lipoxygenase pathway in spikemosses (Lycopodiophyta).
Kazan Institute of Biochemistry and Biophysics, Russian Academy of Sciences, P.O. Box 30, Kazan 420111, Russia.
Anna V
AV
Ogorodnikova
Kazan Institute of Biochemistry and Biophysics, Russian Academy of Sciences, P.O. Box 30, Kazan 420111, Russia.
Fakhima K
FK
Mukhitova
Kazan Institute of Biochemistry and Biophysics, Russian Academy of Sciences, P.O. Box 30, Kazan 420111, Russia. Electronic address: grechkin@kibb.knc.ru.
Alexander N
AN
Grechkin
D003517:Cyclopentanes / Q000032:analysis*; D003577:Cytochrome P-450 Enzyme System / Q000378:metabolism; D005231:Fatty Acids, Unsaturated / Q000032:analysis* / Q000737:chemistry; D019746:Intramolecular Oxidoreductases / Q000378:metabolism; D019787:Linoleic Acid / Q000032:analysis; D008084:Lipoxygenase; D019906:Nuclear Magnetic Resonance, Biomolecular; D054883:Oxylipins / Q000032:analysis / Q000737:chemistry / Q000378:metabolism; D010940:Plant Proteins / Q000378:metabolism; D032503:Selaginellaceae / Q000737:chemistry* / Q000378:metabolism; D014753:Vinyl Compounds / Q000032:analysis; D017962:alpha-Linolenic Acid / Q000378:metabolism
D003517:Cyclopentanes; D005231:Fatty Acids, Unsaturated; D054883:Oxylipins; D010940:Plant Proteins; D014753:Vinyl Compounds; C095608:etheroleic acid; D017962:alpha-Linolenic Acid; C100195:vinyl ether; C025999:12-oxophytodienoic acid; D003577:Cytochrome P-450 Enzyme System; D019787:Linoleic Acid; C100485:divinyl ether synthase; C117433:13-lipoxygenase; D008084:Lipoxygenase; D019746:Intramolecular Oxidoreductases; C021377:hydroperoxide isomerase; C013905:cyclopentenone
12-Oxophytodienoic acid; Divinyl ethers; Lipoxygenase pathway; Oxylipins; Selaginella martensii Spring