Impairment of lipoylation mediated by bromooctanoate targets eukaryotic
amidotransferases
Abstract
Lipoylation is a post-translational modification in which lipoic acid is
attached to specific apoproteins of enzyme complexes, like E2 subunits
of dehydrogenases or GcvH of the glycine cleavage system. A defining
feature of organisms with a lipoyl-relay system is the presence of
amidotransferase activity, which enables the transfer of lipoyl groups
attached to intermediary proteins to the E2 subunits. In this study, we
characterized the lipoate metabolism of Capsaspora owczarzaki and
Plasmodium falciparum. Both organisms utilize amidotransferases
in their lipoylation pathways, with the filasterian enzyme playing a key
role in lipoate synthesis, while the apicomplexan counterpart,
previously considered a lipoyltransferase, is essential in its lipoate
salvage pathway. We also discovered that specific structural features
and certain conserved domains in eukaryotic amidotransferases can
significantly influence their mechanism of action and susceptibility to
the lipoate analog bromooctanoate. Overall, this study highlights the
metabolic strategies of C. owczarzaki and emphasizes the critical
role of amidotransferases as ancestral enzymes in the evolution of
lipoate metabolism, suggesting that the lipoyl relay may represent a
universal pathway across diverse clades.