A single amino acid replacement results in the Ca2+-induced self-assembly of a helical conantokin-based peptide

Biochemistry. 2004 Oct 19;43(41):13225-32. doi: 10.1021/bi048796s.

Abstract

Conantokins are short (17-27 amino acid residues), gamma-carboxyglutamate (Gla)-rich peptide components of the venoms of marine snails of the genus Conus. They display high apo and/or Ca(2+)-induced helicity and act as potent and selective inhibitors of the N-methyl-d-aspartate receptor (NMDAR). We have previously established that one of the conantokins, conantokin-G (con-G), self-associates in the presence of Ca(2+) with high specificity for antiparallel chain orientation [Dai, Q., Prorok, M., and Castellino, F. J. (2004) J. Mol. Biol. 336, 731-744]. The dimerization appears to be driven by interhelical Ca(2+) coordination between the following residue pairings: Gla(3)-Gla(14)('), Gla(7)-Gla(10)('), Gla(10)-Gla(7)('), and Gla(14)-Gla(3)('). A second member of the conantokin family, conantokin-T (con-T), shares sequence identity with con-G at 8 of 21 amino acids, including 4 Gla residues. These similarities notwithstanding, several primary and secondary structural differences exist between con-T and con-G. Particularly notable is that con-T contains a Lys, rather than a Gla, at position 7. Moreover, unlike con-G, con-T does not undergo Ca(2+)-triggered self-assembly. In the present study, sedimentation equilibrium ultracentrifugation is employed to demonstrate that a single amino acid replacement analogue of con-T, con-T[K7gamma], assumes a dimeric superstructure in the presence of Ca(2+) at pH values consistent with the ionization of Gla carboxylate groups. Furthermore, HPLC-monitored thiol-disulfide folding and rearrangement assays with Cys-containing con-T variants suggest that the relative chain alignment preference in the noncovalent complex is antiparallel. Our results suggest that interchain Ca(2+) coordination in con-T[K7gamma] is incumbent upon an "i, i + 4, i +7, i +11" arrangement of Gla residues, as occurs in native con-G.

Publication types

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

MeSH terms

  • 1-Carboxyglutamic Acid / chemistry
  • Amino Acid Sequence
  • Amino Acid Substitution*
  • Calcium / chemistry*
  • Centrifugation, Density Gradient
  • Circular Dichroism
  • Conotoxins / chemistry*
  • Conotoxins / metabolism*
  • Intercellular Signaling Peptides and Proteins
  • Lysine / chemistry
  • Molecular Sequence Data
  • Mollusk Venoms / chemistry*
  • Mollusk Venoms / metabolism*
  • Peptides / chemistry*
  • Peptides / metabolism*
  • Protein Processing, Post-Translational*
  • Protein Structure, Secondary

Substances

  • Conotoxins
  • Intercellular Signaling Peptides and Proteins
  • Mollusk Venoms
  • Peptides
  • conantokin-T
  • 1-Carboxyglutamic Acid
  • conotoxin GV
  • Lysine
  • Calcium