Synthetic rates of key stored fatty acids in the biosynthesis of sex pheromone in the moth Heliothis virescens.

Using a tracer-tracee approach, we fed 1-d-old virgin Heliothis virescens U-(13)C-glucose and analyzed the key labeled fatty acids, (Z)-11-hexadecenoate, hexadecanoate and octadecanoate, known to be intermediates in pheromone biosynthesis, by mass isotopomer distribution analysis. This method allowed determination of enrichment, and fractional (FSR) and absolute (ASR) synthetic rates. As expected, FSRs and ASRs for all three moieties were greater in the scotophase than photophase. However, in whole gland extracts, FSRs and ASRs of (Z)-11-hexadecenoate and hexadecanoate were much lower than those of the major pheromone component, (Z)-11-hexadecenal, determined previously. Since pheromone is made via these acids, we postulated that pheromone was produced directly and very rapidly via a small pool of acyl CoA thioesters of these acids and that the pool of acids we analyzed in our whole gland extract was largely a 'dead end' pool of excess acids (i.e., not converted directly to pheromone) stored in glycerolipids. We tested this by fractionating the whole glandular extract and analyzing the glycerolipid fraction. FSRs and ASRs for the two acids in the glycerolipid fraction were similar to those for the whole gland extract, confirming our postulate. Thus, most acetate produced in the pheromone gland is converted rapidly and directly to pheromone, while excess fatty acids are stored in glycerolipids and remain relatively inaccessible for pheromone production, at least over the two periods studied. Precursor enrichment of octadecanoate was substantially lower than that determined for the two 16-carbon acids and pheromone component. This suggests that hexadecanoate is the principal product of the multi-enzyme complex fatty acid synthase in the gland, and that octadecanoate is formed by subsequent chain elongation of hexadecanoate.