title: 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; (9Z,12Z)-9,12-octadecadienal (I), (9Z,12Z,15Z)-9,12,15-octadecatrienal (II), cis-9,10-epoxy-(3Z,6Z)-3,6-henicosadiene (III), and cis-9,10-epoxy-(3Z,6Z)-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 C₁₈ and C₁₉ fatty alcohols were also oxidized to the corresponding aldehydes in the pheromone gland, indicating a biosynthetic pathway of IIvia 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 C₂₁ 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 C₂₁ triene, which was synthesized by the chain elongation of linolenic acid and LiAlD₄ 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 C₁₉-C₂₃ trienyl, C₂₁ dienyl, and C₂₁ monoenyl hydrocarbons. The 9,10-epoxy derivative of each alkene was produced, while the epoxidation of the C₂₁ 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.
authors.affiliation: Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan.
authors.forename: Ryutaro
authors.initials: R
authors.lastname: Kiyota
authors.forename: Maki
authors.initials: M
authors.lastname: Arakawa
authors.forename: Rei
authors.initials: R
authors.lastname: Yamakawa
authors.forename: Abeda
authors.initials: A
authors.lastname: Yasmin
authors.forename: Tetsu
authors.initials: T
authors.lastname: Ando
mesh_terms: D000429:Alcohol Oxidoreductases / Q000378:metabolism*; D000447:Aldehydes / Q000378:metabolism; D000475:Alkenes / Q000378:metabolism; D000818:Animals; D053898:Biosynthetic Pathways; D002247:Carbon Isotopes / Q000032:analysis; D003903:Deuterium / Q000378:metabolism; D005233:Fatty Alcohols / Q000378:metabolism; D005260:Female; D008401:Gas Chromatography-Mass Spectrometry; D009682:Magnetic Resonance Spectroscopy; D008845:Microinjections; D009036:Moths / Q000201:enzymology*; D010084:Oxidation-Reduction; D010088:Oxidoreductases / Q000378:metabolism*; D011090:Polyenes / Q000378:metabolism; D011679:Pupa / Q000378:metabolism; D012543:Scent Glands / Q000201:enzymology*; D012724:Sex Attractants / Q000096:biosynthesis*; D013379:Substrate Specificity; D017962:alpha-Linolenic Acid / Q000378:metabolism
chemical_list: D000447:Aldehydes; D000475:Alkenes; D002247:Carbon Isotopes; D005233:Fatty Alcohols; D011090:Polyenes; D012724:Sex Attractants; D017962:alpha-Linolenic Acid; D003903:Deuterium; D010088:Oxidoreductases; C023111:epoxidase; D000429:Alcohol Oxidoreductases; C019643:alcohol oxidase; C037936:linolenyl alcohol