Kinetic analysis of the three-substrate reaction mechanism of an NRPS-independent siderophore (NIS) synthetase

Methods Enzymol. 2024:702:1-19. doi: 10.1016/bs.mie.2024.06.012. Epub 2024 Jul 3.

Abstract

The biosynthesis of many bacterial siderophores employs a member of a family of ligases that have been defined as NRPS-independent siderophore (NIS) synthetases. These NIS synthetases use a molecule of ATP to produce an amide linkage between a carboxylate and an amine. Commonly used carboxylate substrates include citrate or α-ketoglutarate, or derivatives thereof, while the amines are often hydroxamate derivatives of lysine or ornithine, or their decarboxylated forms cadaverine and putrescine. Enzymes that employ three substrates to catalyze a reaction may proceed through alternate mechanisms. Some enzymes use sequential mechanisms in which all three substrates bind prior to any chemical steps. In such mechanisms, substrates can bind in a random, ordered, or mixed fashion. Alternately, other enzymes employ a ping-pong mechanism in which a chemical step occurs prior to the binding of all three substrates. Here we describe an enzyme assay that will distinguish among these different mechanisms for the NIS synthetase, using IucA, an enzyme involved in the production of aerobactin, as the model system.

Keywords: Aerobactin; Mechanistic enzymology; NIS syntheses; NRPS-independent siderophores; Siderophore biosynthesis.

MeSH terms

  • Bacterial Proteins / chemistry
  • Bacterial Proteins / metabolism
  • Enzyme Assays / methods
  • Ketoglutaric Acids / metabolism
  • Kinetics
  • Ligases / chemistry
  • Ligases / metabolism
  • Peptide Synthases* / chemistry
  • Peptide Synthases* / metabolism
  • Siderophores* / chemistry
  • Siderophores* / metabolism
  • Substrate Specificity

Substances

  • Siderophores
  • Peptide Synthases
  • non-ribosomal peptide synthase
  • Bacterial Proteins
  • Ketoglutaric Acids
  • Ligases