Biosynthetic pathways of the sex pheromone components and substrate selectivity of the oxidation enzymes working in pheromone glands of the fall webworm, Hyphantria cunea

Abstract

The fall webworm, Hyphantria cunea Drury (Lepidoptera: Arctiidae), is a harmful polyphagous defoliator. Female moths produce the following four pheromone components in a ratio of about 5:4:10:2; (9 Z,12 Z)-9,12-octadecadienal ( I), (9 Z,12 Z,15 Z)-9,12,15-octadecatrienal ( II), cis-9,10-epoxy-(3 Z,6 Z)-3,6-henicosadiene ( III), and cis-9,10-epoxy-(3 Z,6 Z)-1,3,6-henicosatriene ( IV). Although 13C-labeled linolenic acid was not converted into trienal II at the pheromone glands of H. cunea females, GC–MS analysis of an extract of the pheromone gland treated topically with 13C-labeled linolenyl alcohol showed the aldehyde incorporating the isotope. Other C 18 and C 19 fatty alcohols were also oxidized to the corresponding aldehydes in the pheromone gland, indicating a biosynthetic pathway of II via linolenyl alcohol and low substrate selectivity of the alcohol oxidase in the pheromone gland. On the other hand, epoxydiene III was expected to be produced by specific 9,10-epoxidation of the corresponding C 21 trienyl hydrocarbon, which might be biosynthesized from dietary linolenic acid in oenocytes and transported to the pheromone gland. The final biosynthetic step in the pheromone gland was confirmed by an experiment using deuterated C 21 triene, which was synthesized by the chain elongation of linolenic acid and LiAlD 4 reduction as key reactions. When the labeled triene was administered to the female by topical application at the pheromone gland or injection into the abdomen, deuterated III was detected in a pheromone extract by GC–MS analysis. Furthermore, the substrate selectivity of epoxidase and selective incorporation by the pheromone glands were examined by treatments with mixtures of the deuterated precursor and other hydrocarbons such as C 19–C 23 trienyl, C 21 dienyl, and C 21 monoenyl hydrocarbons. The 9,10-epoxy derivative of each alkene was produced, while the epoxidation of the C 21 monoene was poorer than those of the trienes and diene. The low selectivity indicated that the species-specific pheromone of the H. cunea female was mainly due to the critical formation of the precursor of each component.