Structural insights into the cofactor-assisted substrate recognition of yeast methylglyoxal/isovaleraldehyde reductase Gre2

Biochim Biophys Acta. 2014 Sep;1844(9):1486-92. doi: 10.1016/j.bbapap.2014.05.008. Epub 2014 May 27.

Abstract

Saccharomyces cerevisiae Gre2 (EC1.1.1.283) serves as a versatile enzyme that catalyzes the stereoselective reduction of a broad range of substrates including aliphatic and aromatic ketones, diketones, as well as aldehydes, using NADPH as the cofactor. Here we present the crystal structures of Gre2 from S. cerevisiae in an apo-form at 2.00Å and NADPH-complexed form at 2.40Å resolution. Gre2 forms a homodimer, each subunit of which contains an N-terminal Rossmann-fold domain and a variable C-terminal domain, which participates in substrate recognition. The induced fit upon binding to the cofactor NADPH makes the two domains shift toward each other, producing an interdomain cleft that better fits the substrate. Computational simulation combined with site-directed mutagenesis and enzymatic activity analysis enabled us to define a potential substrate-binding pocket that determines the stringent substrate stereoselectivity for catalysis.

Keywords: Crystal structure; Enzymatic kinetics; Methylglyoxal/isovaleraldehyde reductase; Saccharomyces cerevisiae; Substrate-binding pocket.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amino Acid Sequence
  • Apoenzymes / chemistry*
  • Apoenzymes / genetics
  • Apoenzymes / metabolism
  • Coenzymes / chemistry*
  • Coenzymes / metabolism
  • Crystallography, X-Ray
  • Kinetics
  • Molecular Docking Simulation
  • Molecular Sequence Data
  • Mutagenesis, Site-Directed
  • NADP / chemistry*
  • NADP / metabolism
  • Oxidoreductases / chemistry*
  • Oxidoreductases / genetics
  • Oxidoreductases / metabolism
  • Protein Binding
  • Protein Multimerization
  • Protein Subunits / chemistry*
  • Protein Subunits / genetics
  • Protein Subunits / metabolism
  • Recombinant Proteins / chemistry
  • Recombinant Proteins / genetics
  • Recombinant Proteins / metabolism
  • Saccharomyces cerevisiae / chemistry*
  • Saccharomyces cerevisiae / enzymology
  • Saccharomyces cerevisiae Proteins / chemistry*
  • Saccharomyces cerevisiae Proteins / genetics
  • Saccharomyces cerevisiae Proteins / metabolism
  • Sequence Alignment
  • Substrate Specificity
  • Thermodynamics

Substances

  • Apoenzymes
  • Coenzymes
  • Protein Subunits
  • Recombinant Proteins
  • Saccharomyces cerevisiae Proteins
  • NADP
  • Oxidoreductases
  • GRE2 protein, S cerevisiae