The last step in cephalosporin C formation revealed: crystal structures of deacetylcephalosporin C acetyltransferase from Acremonium chrysogenum in complexes with reaction intermediates

J Mol Biol. 2008 Mar 28;377(3):935-44. doi: 10.1016/j.jmb.2008.01.047. Epub 2008 Jan 30.

Abstract

Deacetylcephalosporin C acetyltransferase (DAC-AT) catalyses the last step in the biosynthesis of cephalosporin C, a broad-spectrum beta-lactam antibiotic of large clinical importance. The acetyl transfer step has been suggested to be limiting for cephalosporin C biosynthesis, but has so far escaped detailed structural analysis. We present here the crystal structures of DAC-AT in complexes with reaction intermediates, providing crystallographic snapshots of the reaction mechanism. The enzyme is found to belong to the alpha/beta hydrolase class of acetyltransferases, and the structures support previous observations of a double displacement mechanism for the acetyl transfer reaction in other members of this class of enzymes. The structures of DAC-AT reported here provide evidence of a stable acyl-enzyme complex, thus underpinning a mechanism involving acetylation of a catalytic serine residue by acetyl coenzyme A, followed by transfer of the acetyl group to deacetylcephalosporin C through a suggested tetrahedral transition state.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acetylation
  • Acetyltransferases / chemistry*
  • Acremonium / enzymology*
  • Binding Sites
  • Cephalosporins / biosynthesis
  • Cephalosporins / chemistry*
  • Crystallography, X-Ray
  • Fungal Proteins / chemistry*
  • Models, Molecular*
  • Protein Conformation
  • Protein Subunits / chemistry

Substances

  • Cephalosporins
  • Fungal Proteins
  • Protein Subunits
  • cephalosporin C
  • Acetyltransferases
  • acetyl CoA-deacetylcephalosporin C acetyltransferase

Associated data

  • PDB/2VAT
  • PDB/2VAV
  • PDB/2VAX