A new strategy to induce gamma-turns: peptides composed of alternating alpha-aminoxy acids and alpha-amino acids

J Am Chem Soc. 2003 Oct 29;125(43):13018-9. doi: 10.1021/ja036136p.

Abstract

It is known that the seven-membered-ring intramolecular hydrogen bond (gamma-turn) is seldom formed in naturally occurring peptides composed of alpha-amino acids. Here we report a new strategy to induce gamma-turns in short linear peptides. We designed and synthesized several peptides (1-5) containing alternating alpha-l-aminoxy acids and alpha-d-amino acids. 1H NMR studies revealed that the gamma-turn could be initiated by the following N-O turn, an eight-membered-ring intramolecular hydrogen bond induced by an alpha-aminoxy acid. Moreover, NOESY and CD studies suggested peptides 4 and 5 form a novel secondary structure, a mixed 7-8 helix. Theoretical calculations on several di-, tri-, and tetrapeptide models provided strong support to the above conclusions.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amides / chemistry
  • Amino Acids / chemistry*
  • Circular Dichroism
  • Models, Molecular
  • Nuclear Magnetic Resonance, Biomolecular
  • Peptides / chemistry*
  • Protein Conformation
  • Protein Structure, Secondary

Substances

  • Amides
  • Amino Acids
  • Peptides