Cuticular oxidases

Teal P. E. A. and Tumlinson J. H. (1988) Properties of cuticular oxidases used for sex pheromone biosynthesis by Heliothis zea. J. Chem. Ecol. 14, 2131-2145. 

Hurst (19) discusses the similarity in action of the pyrethrins and of DDT as indicated by a dispersant action on the lipids of insect cuticle and internal tissue. He has developed an elaborate theory of contact insecticidal action but provides no experimental data. Hurst believes that the susceptibility to insecticides depends partially on the cuticular permeability, but more fundamentally on the effects on internal tissue receptors which control oxidative metabolism or oxidative enzyme systems. The access of pyrethrins to insects, for example, is facilitated by adsorption and storage in the lipophilic layers of the epicuticle. The epicuticle is to be regarded as a lipoprotein mosaic consisting of alternating patches of lipid and protein receptors which are sites of oxidase activity. Such a condition exists in both the hydrophilic type of cuticle found in larvae of Calliphora and Phormia and in the waxy cuticle of Tenebrio larvae. Hurst explains pyrethrinization as a preliminary narcosis or knockdown phase in which oxidase action is blocked by adsorption of the insecticide on the lipoprotein tissue components, followed by death when further dispersant action of the insecticide results in an irreversible increase in the phenoloxidase activity as a result of the displacement of protective lipids. This increase in phenoloxidase activity is accompanied by the accumulation of toxic quinoid metabolites in the blood and tissues—for example, O-quinones which would block substrate access to normal enzyme systems. The varying degrees of susceptibility shown by different insect species to an insecticide may be explainable not only in terms of differences in cuticle make-up but also as internal factors associated with the stability of oxidase systems. 

A few facts are also known concerning the metabolism of alkanes by plants. Cuticular waxes typically contain secondary alcohols, ketones and ) -diketones in addition to alkanes and the former have the skeletons as in Figure 8, where functionalization is near the centre of the molecule and the chain lengths of the alcohols and ketones are closely similar to those of the major n-alkanes present in any particular species. Tracer evidence indicates that the secondary alcohol and ketone are formed in sequence by oxidation of the corresponding n-alkane by a mixed function oxidase which is inhibited by chelating agents. Thus in Brassica species, the 14- or 15-hydroxy- and oxo-derivatives of the n-C29 alkane were thus formed both in vivo and in cell-free extracts ". ... 

---