Between peptides and bile acids: self-assembly of phenylalanine substituted cholic acids

J Phys Chem B. 2013 Aug 8;117(31):9248-57. doi: 10.1021/jp405342v. Epub 2013 Jul 25.

Abstract

Biocompatible molecules that undergo self-assembly are of high importance in biological and medical applications of nanoscience. Peptides and bile acids are among the most investigated due to their ability to self-organize into many different, often stimuli-sensitive, supramolecular structures. With the aim of preparing molecules mixing the aggregation properties of bile acid and amino acid-based molecules, we report on the synthesis and self-association behavior of two diastereomers obtained by substituting a hydroxyl group of cholic acid with a l-phenylalanine residue. The obtained molecules are amphoteric, and we demonstrate that they show a pH-dependent self-assembly. Both molecules aggregate in globular micelles at high pH, whereas they form tubular superstructures under acid conditions. Unusual narrow nanotubes with outer and inner cross-section diameters of about 6 and 3 nm are formed by the derivatives. The diasteroisomer with α orientation of the substituent forms in addition a wider tubule (17 nm cross-section diameter). The ability to pack in supramolecular tubules is explained in terms of a wedge-shaped bola-form structure of the derivatives. Parallel or antiparallel face-to-face dimers are hypothesized as fundamental building blocks for the formation of the narrow and wide nanotubes, respectively.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bile Acids and Salts / chemistry*
  • Cholic Acids / chemistry*
  • Circular Dichroism
  • Hydrogen-Ion Concentration
  • Micelles
  • Microscopy, Atomic Force
  • Peptides / chemistry*
  • Peptides / metabolism
  • Phenylalanine / chemistry*
  • Surface Tension
  • Temperature

Substances

  • Bile Acids and Salts
  • Cholic Acids
  • Micelles
  • Peptides
  • Phenylalanine