Self-assembly of Janus cylinders into hierarchical superstructures

J Am Chem Soc. 2009 Apr 8;131(13):4720-8. doi: 10.1021/ja808614q.

Abstract

We present in-depth studies of the size tunability and the self-assembly behavior of Janus cylinders possessing a phase segregation into two hemicylinders. The cylinders are prepared by cross-linking the lamella-cylinder morphology of a polystyrene-block-polybutadiene-block-poly(methyl methacrylate) block terpolymer. The length of the Janus cylinders can be adjusted by both the amplitude and the duration of a sonication treatment from the micro- to the nanometer length. The corona segregation into a biphasic particle is evidenced by selective staining of the PS domains with RuO(4) and subsequent imaging. The self-assembly behavior of these facial amphiphiles on different length scales is investigated combining dynamic light scattering (DLS), small-angle neutron scattering (SANS), and imaging procedures. Cryogenic transmission electron microscopy images of the Janus cylinders in THF, which is a good solvent for both blocks, exhibit unimolecularly dissolved Janus cylinders with a core-corona structure. These results are corroborated by SANS measurements. Supramolecular aggregation takes place in acetone, which is a nonsolvent for polystyrene, leading to the observation of fiber-like aggregates. The length of these fibers depends on the concentration of the solution. A critical aggregation concentration is found, under which unimolecularly dissolved Janus cylinders exist. The fibers are composed of 2-4 Janus cylinders, shielding the inner insoluble polystyrene hemicylinder against the solvent. Herein, the SANS data reveal a core-shell structure of the aggregates. Upon deposition of the Janus cylinders from more concentrated solution, a second type of superstructure is formed on a significantly larger length scale. The Janus cylinders form fibrillar networks, in which the pore size depends on the concentration and deposition time of the sample.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Butadienes / chemical synthesis
  • Butadienes / chemistry*
  • Cross-Linking Reagents / chemistry
  • Elastomers / chemical synthesis
  • Elastomers / chemistry*
  • Light
  • Nanostructures / chemistry*
  • Nanostructures / ultrastructure
  • Neutron Diffraction
  • Particle Size
  • Polymethyl Methacrylate / chemical synthesis
  • Polymethyl Methacrylate / chemistry*
  • Polystyrenes / chemical synthesis
  • Polystyrenes / chemistry*
  • Scattering, Radiation
  • Scattering, Small Angle
  • Surface Properties

Substances

  • Butadienes
  • Cross-Linking Reagents
  • Elastomers
  • Polystyrenes
  • polybutadiene
  • Polymethyl Methacrylate