Membrane binding properties of the factor IX gamma-carboxyglutamic acid-rich domain prepared by chemical synthesis

J Biol Chem. 1994 Oct 14;269(41):25494-501.

Abstract

The fully gamma-carboxylated peptides based upon the complete and truncated Gla/aromatic amino acid stack domains of human Factor IX were prepared by solid phase peptide synthesis using Fmoc (N-(9-fluorenyl)methoxycarbonyl) chemistry. A 47-residue peptide Factor IX-(1-47) and a 42-residue peptide Factor IX-(1-42), both containing 12 residues of L-gamma-carboxyglutamic acid, were purified by high performance liquid chromatography and oxidized to form the disulfide bond. Quantitative gamma-carboxyglutamic acid analysis of Factor IX-(1-47) and Factor IX-(1-42) indicated the presence of 12.1 and 11.2 gamma-carboxyglutamic acid residues/mol of peptide, respectively; no glutamic acid was detected. As monitored by fluorescence quenching, calcium ions induced the prototypical conformational transition in Factor IX-(1-47), but not in Factor IX-(1-42), that is observed with Factor IX. Half-maximal quenching of the intrinsic fluorescence of Factor IX-(1-47) was observed at Ca(II) concentrations of about 50 microM. Factor IX-(1-47) bound to the conformation-specific antibodies, anti-Factor IX:Mg(II) and anti-Factor IX:Ca(II)-specific in the presence of metal ions. Factor IX-(1-47) bound to phospholipid membranes, as monitored by energy transfer from intrinsic fluorophores to dansyl (5-dimethylaminonaphthalene-1-sulfonyl)-phosphatidylethanolamine incorporated into a lipid bilayer composed of phosphatidylserine:phosphatidylcholine. In contrast, Factor IX-(1-42) bound poorly to these same membranes. Factor IX-(1-47) did not inhibit Factor XIa activation of Factor IX but did inhibit the activation of Factor X by Factor IXa bound to Factor VIII in the presence of calcium ions and phospholipid. These results show that phospholipid membrane binding is a property of the Gla/aromatic amino acid stack domain and that the Factor IX-(1-47) peptide, prepared by chemical synthesis, preserves the membrane binding properties and the metal-induced conformational transitions observed in native Factor IX. These results indicate that Factor IX-(1-47) but not Factor IX-(1-42) is a suitable model for structural studies of Factor IX-membrane interaction.

Publication types

  • Comparative Study
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • 1-Carboxyglutamic Acid / metabolism*
  • Amino Acid Sequence
  • Amino Acids / analysis
  • Calcium / metabolism
  • Factor IX / chemical synthesis
  • Factor IX / immunology
  • Factor IX / metabolism*
  • Factor VIII / metabolism
  • Factor X / metabolism
  • Factor XIa / metabolism
  • Fluorometry
  • Humans
  • Lipid Bilayers / metabolism*
  • Molecular Probes
  • Molecular Sequence Data
  • Peptide Fragments / chemical synthesis
  • Peptide Fragments / immunology
  • Peptide Fragments / metabolism*
  • Protein Binding
  • Protein Structure, Tertiary
  • Structure-Activity Relationship

Substances

  • Amino Acids
  • Lipid Bilayers
  • Molecular Probes
  • Peptide Fragments
  • factor IX (1-47)
  • 1-Carboxyglutamic Acid
  • Factor VIII
  • Factor IX
  • Factor X
  • Factor XIa
  • Calcium