Reductase specificity and the ratio regulation of E/Z isomers in pheromone biosynthesis of the European corn borer, Ostrinia nubilalis (Lepidoptera Pyralidae)

Species specificity of moth sex pheromones is in many cases achieved by means of specific blends rather than by specific components. Two pheromone strains of the European corn borer, Ostrinia nubilalis, use (E)- and (Z)-11-tetradecenyl acetate in different ratios as their pheromone, but show the same ratio of the pheromone precursors (70:30 E/Z-11-tetradecenoic acid). The hypothesis that the ratio of the pheromone components in the two strains and their hybrids is controlled by the specificity of the reductase system, responsible for conversion of acid to the corresponding alcohol precursors, was tested. Deuterium-labeled alcohols, aldehydes and fatty acids corresponding to the two pheromone components were topically applied to the pheromone glands in different ratios and their selective incorporation into pheromone components was determined by gas chromatography with mass selective detection. Acetylation of the (E)- and (Z)-11-tetradecenols was unselective, whereas the corresponding aldehydes and acids were selectively incorporated into the pheromone components. Z strain females selectively metabolized the Z-isomers whereas E strain females converted the E-isomers. The E strain being the most selective of the two strains. Hybrids converted both geometric isomers. The relative conversion rate of both E- and Z-isomers of all tetradecenoic acids with the double bond in positions from 7-12, was also determined. In addition to the Δ11-isomers, the E strain females converted (E)-8-tetradecenoic acid into acetate and the Z strain females converted (E)-12-tetradecenoic acid. None of these substrates occur naturally in the pheromone gland, but (E)-12-tetradecenyl acetate is a pheromone component of the Asian corn borer O. furnacalis. Thus the possibility for conversion of (E)-12-tetradecenoic acid to acetate in the Z strain, as well as the earlier reported conversion of (Z)-11-tetradecenoic acid to acetate in O. furnacalis, suggests that O. furnacalis is closest related to the Z strain of O. nubilalis.