Supramolecular Domains in Mixed Peptide Self-Assembled Monolayers on Gold Nanoparticles

Authors

  • Laurence Duchesne Dr.,

    1. School of Biological Sciences and Liverpool Institute of Nanoscale Science, Engineering and Technology, University of Liverpool, Biosciences Building, Crown Street, Liverpool L69 7ZB (UK), Fax: (+44) 151-795-4406
    Search for more papers by this author
  • Geoff Wells Dr.,

    1. Department of Pharmaceutical and Biological Chemistry, The School of Pharmacy, University of London, 29–39 Brunswick Square, London, WC1N 1AX (UK)
    Search for more papers by this author
  • David G. Fernig Prof.,

    1. School of Biological Sciences and Liverpool Institute of Nanoscale Science, Engineering and Technology, University of Liverpool, Biosciences Building, Crown Street, Liverpool L69 7ZB (UK), Fax: (+44) 151-795-4406
    Search for more papers by this author
  • Sarah A. Harris Dr.,

    1. School of Physics and Astronomy, University of Leeds, Leeds LS2 9JT (UK)
    Search for more papers by this author
  • Raphaël Lévy Dr.

    1. School of Biological Sciences and Liverpool Institute of Nanoscale Science, Engineering and Technology, University of Liverpool, Biosciences Building, Crown Street, Liverpool L69 7ZB (UK), Fax: (+44) 151-795-4406
    Search for more papers by this author

Abstract

Self-organization in mixed self-assembled monolayers of small molecules provides a route towards nanoparticles with complex molecular structures. Inspired by structural biology, a strategy based on chemical cross-linking is introduced to probe proximity between functional peptides embedded in a mixed self-assembled monolayer at the surface of a nanoparticle. The physical basis of the proximity measurement is a transition from intramolecular to intermolecular cross-linking as the functional peptides get closer. Experimental investigations of a binary peptide self-assembled monolayer show that this transition happens at an extremely low molar ratio of the functional versus matrix peptide. Molecular dynamics simulations of the peptide self-assembled monolayer are used to calculate the volume explored by the reactive groups. Comparison of the experimental results with a probabilistic model demonstrates that the peptides are not randomly distributed at the surface of the nanoparticle, but rather self-organize into supramolecular domains.

Ancillary