Probing the structure of hirudin from Hirudinaria manillensis by limited proteolysis. Isolation, characterization and thrombin-inhibitory properties of N-terminal fragments

Eur J Biochem. 1994 Dec 1;226(2):323-33. doi: 10.1111/j.1432-1033.1994.tb20056.x.

Abstract

Hirudin is the most potent and specific inhibitor of the blood-clotting enzyme thrombin so far known. Several hirudin variants were isolated mostly from Hirudo medicinalis and shown to be polypeptide chains of approximately 7 kDa with three internal disulfide bridges. In this study, limited proteolysis has been used to probe aspects of the structure and dynamics of a hirudin variant HM2 isolated from Hirudinaria manillensis. Proteolysis of the polypeptide chain of 64-amino-acid residues of hirudin HM2 by protease from Staphylococcus aureus V8, trypsin, thermolysin and subtilisin occurs at region 41-49 of the chain. The N-terminal fragments 1-41 and 1-47 were isolated to homogeneity and shown to maintain inhibitory action on thrombin, though much lower than the intact protein. The results were interpreted on the basis of a proposed three-dimensional structure of hirudin HM2 deduced by protein modelling the known structure of hirudin variant HV1 from Hirudo medicinalis (75% sequence similarity between HM2 and HV1). Both proteolysis experiments and protein modelling provide evidence for the existence in hirudin HM2 of a N-terminal well-structured domain (core) and a C-terminal flexible polypeptide segment. Determination of the accessible surface area of the three-dimensional model of hirudin HM2 showed that the sites of preferential cleavages are at the surface of the polypeptide molecule.

MeSH terms

  • Amino Acid Sequence
  • Animals
  • Chromatography, High Pressure Liquid
  • Disulfides / chemistry
  • Endopeptidases / metabolism*
  • Hirudins / chemistry*
  • Hirudins / metabolism
  • Hirudins / pharmacology
  • Leeches / chemistry*
  • Magnetic Resonance Spectroscopy
  • Models, Molecular
  • Molecular Sequence Data
  • Peptide Fragments / chemistry*
  • Peptide Fragments / isolation & purification
  • Peptide Fragments / pharmacology
  • Protein Structure, Secondary
  • Serine Endopeptidases / metabolism
  • Subtilisins / metabolism
  • Thermolysin / metabolism
  • Thrombin / antagonists & inhibitors*
  • Trypsin / metabolism

Substances

  • Disulfides
  • Hirudins
  • Peptide Fragments
  • Endopeptidases
  • Serine Endopeptidases
  • Subtilisins
  • glutamyl endopeptidase
  • Trypsin
  • Thrombin
  • Thermolysin