PEROXYGENASE-CATALYZED FATTY ACID EPOXIDATION IN CEREAL SEEDS - SEQUENTIAL OXIDATION OF LINOLEIC ACID INTO 9(S),12(S),13(S)-TRIHYDROXY-10(E)-OCTADECENOIC ACID

摘要

Peroxygenase-catalyzed epoxidation of oleic acid in preparations of cereal seeds was investigated. The 105,000 g particle fraction of oat (Avena sativa) seed homogenate showed high peroxygenase activity, i.e. 3034 +/- 288 and 2441 +/- 168 nmol (10 min)(-1) mg(-1) protein in two cultivars, whereas the corresponding fraction obtained from barley (Hordeum vulgare and Hordeum distichum), rye (Secale cereale), and wheat (Triticum aestivum) showed only weak activity, i.e. 13 to 138 nmol (10 min)(-1) mg(-1) protein. In subcellular fractions of oat seed homogenate, peroxygenase specific activity was highest in the 105,000 g particle fraction, whereas lipoxygenase activity was more evenly distributed and highest in the 105,000 g supernatant fraction. Incubation of [1-C-14]linoleic acid with the 105,000 g supernatant of oat seed homogenate led to the formation of several metabolites, i.e. in order of decreasing abundance, 9(S)hydroxy-10(E),12(Z)-octadecadienoic acid, 9(S),12(S),13(S)-trihydroxy-10(E)-octadecenoic acid, cis-9,10-epoxy-12(Z)-octadecenoic acid [mainly the 9(R),10(S) enantiomer], cis-12,13-epoxy-9(Z)-octadecenoic acid [mainly the 12(R),13(S) enantiomer], threo-12,13-dihydroxy-9(Z)-octadecenoic acid, and 12(R),13(S)-epoxy-9(S)-hydroxy-10(E)-octadecenoic acid. Incubation of linoleic acid with the 105,000 g particle fraction gave a similar, but not identical, pattern of metabolites. Conversion of linoleic acid into 9(S),12(S),13(S)trihydroxy-10(E)-octadecenoic acid, a naturally occurring oxylipin with antifungal properties, took place by a pathway involving sequential catalysis by lipoxygenase, peroxygenase, and epoxide hydrolase. [References: 34]