Deletion of the parasite-specific insertions and mutation of the catalytic triad in glutathione reductase from chloroquine-sensitive Plasmodium falciparum 3D7

Mol Biochem Parasitol. 2000 Apr 15;107(2):169-79. doi: 10.1016/s0166-6851(00)00188-2.

Abstract

The flavoenzyme glutathione reductase (GR; NADPH+glutathione disulphide+H(+)-->NADP(+)+2 glutathione-SH) of Plasmodium falciparum is a promising drug target against tropical malaria. As P. falciparum genes are assumed to be highly polymorphic we have cloned and expressed the GR cDNA of the chloroquine-sensitive strain 3D7. In comparison to the known GR of the chloroquine-resistant K1 strain there are three base exchanges all of them leading to amino acid substitutions (residues 281, 285 and 335). The catalytic efficiency k(cat)/K(m) of the 3D7 enzyme is 5-fold lower than for the K1 enzyme. In contrast, vis-à-vis the drugs carmustine, methylene blue and fluorophenyliso-alloxazine the two enzyme species exhibited identical inhibition kinetics. Two structural motifs which are specific for P. falciparum GR were studied by mutational deletion analysis of 3D7 GR. Loop 126-138 appears to be important for folding and stability of the enzyme, whereas the subdomain 318-350 was found to be involved in FAD-binding. The subdomain has no major influence on the known functions of the catalytic triad Cys-40, Cys-45 and His-485'. Flavin absorption spectroscopy of inactive point mutants showed that Cys-45 forms a thiolate charge transfer complex and Cys-40 is the interchange thiol, which reduces glutathione disulphide. The mutant His-485-->Gln had a normal K(m) for glutathione disulphide reduction but only 0.8% residual catalytic activity when compared with wild-type GR, which confirms its function as an acid/base catalyst. The parasite-specific domains in combination with the reactive catalytic residues appear to be a suitable target matrix for inhibiting GR in vivo.

MeSH terms

  • Amino Acid Sequence
  • Animals
  • Antimalarials / pharmacology*
  • Catalysis
  • Chloroquine / pharmacology*
  • Flavins / chemistry
  • Flavins / metabolism
  • Gene Deletion
  • Glutathione Reductase / chemistry
  • Glutathione Reductase / genetics*
  • Glutathione Reductase / isolation & purification
  • Glutathione Reductase / metabolism
  • Kinetics
  • Molecular Sequence Data
  • Plasmodium falciparum / drug effects*
  • Plasmodium falciparum / enzymology*
  • Plasmodium falciparum / genetics
  • Point Mutation
  • Spectrum Analysis / methods

Substances

  • Antimalarials
  • Flavins
  • Chloroquine
  • Glutathione Reductase

Associated data

  • GENBANK/X90528