The fate of topically applied fatty acids in the sex pheromone gland of the moth Heliothis virescens

Abstract

Deuterium-labeled hexadecanoic acid (D4–16:COOH), a sex pheromone biosynthetic intermediate, and heptadecanoic acid (D3–17:COOH), an acid that cannot be converted to sex pheromone, were topically applied to the pheromone gland of female Heliothis virescens, and the fate of the label determined. Both acids were incorporated similarly into the glycerolipids, with by far the greatest amount found in the triacylglycerols (TGs), and relatively small amounts found in other neutral and polar classes. For D4–16:COOH, the labeled pheromone precursor, ( Z)-11-hexadecenoate, was also found predominantly in the TGs but relatively (compared to labeled hexadecanoate) high amounts were also found in the phospholipids. Within the TGs, both acids, as well as the pheromone precursor, were found almost exclusively on the sn-3 position of the glycerol backbone. This demonstrates that the major fate, in the glycerolipids, of free fatty acids is addition to 1,2-diacylglycerols. A relatively large amount of the applied acid was also found in the gland in the form of the acyl-CoA thioester. In a 24-h time–course study, this form remained at a relatively high level for the duration of the assay, and decreased at a rate comparable to the titer of this acid in the TGs, suggesting that titers of fatty acids in the glycerolipids and acyl-CoA thioesters may be in equilibrium. A time–course assay with D4–16:COOH demonstrated that peak pheromone titer after application was reached before peak titers of both total hexadecanoate and hexadecanoyl-CoA. Combined with a dose–response experiment, which showed that labeled pheromone titer did not increase above an applied concentration of 20 mg/ml, these data suggest that the final step in pheromone biosynthesis, reduction of Z11–16:Acyl-CoA, may be inhibited by increased acyl-CoA titers in the gland. Overall, our data are consistent with the glycerolipids modulating acyl-CoA concentrations in the pheromone gland.