Rapid enzymatic isomerization of 12-oxophytodienoic acid in the gut of lepidopteran larvae

In response to feeding larvae of the Mediterranean climbing cut-worm (Spodoptera littoralis), leaves of the lima bean (Phaseolus lunatus) produce fatty acid-derived signaling compounds (oxylipins). The major products are the phytohormones jasmonic acid and its biosynthetic precursor 12-oxophytodienoic acid (OPDA), along with 13-hydroxy-12-oxooctadeco-9,15-dienoic acid, 9-hydroxy-12-oxooctadeca-70,15-dienoic acid (alpha- and gamma-ketol), as well as unsaturated aldehydes. Oxylipin production is highest at the feeding zone of the insect and decreases with distance from the damaged area. Accordingly, the feeding insect experiences high local concentrations of oxylipins, which are taken up into the alimentary canal and are finally excreted with the feces. In contrast to most other oxylipins, OPDA was not detectable in the insect's gut; instead the structurally related tetrohydrodicranenone B (iso-OPDA) was identified. Feeding experiments with deuterium-labeled OPDA proved that the isomerization is catalyzed by an enzyme from the insect's gut tissue. The phenomenon appears to be widespread among Lepidopteran larvae.