Counterion-mediated hierarchical self-assembly of an ABC miktoarm star terpolymer

Andreas Hanisch, André H. Gröschel, Melanie Förtsch, Markus Drechsler, Hiroshi Jinnai, Thomas M. Ruhland, Felix H. Schacher, Axel H.E. Müller

Research output: Contribution to journalArticlepeer-review

81 Citations (Scopus)


Directed self-assembly processes of polymeric systems represent a powerful approach for the generation of structural hierarchy in analogy to biological systems. Herein, we utilize triiodide as a strongly polarizable counterion to induce hierarchical self-assembly of an ABC miktoarm star terpolymer comprising a polybutadiene (PB), a poly(tert-butyl methacrylate) (PtBMA), and a poly(N-methyl-2-vinylpyridinium) (P2VPq) segment. Hereby, the miktoarm architecture in conjunction with an increasing ratio of triiodide versus iodide counterions allows for a stepwise assembly of spherical micelles as initial building blocks into cylindrical structures and superstructures thereof. Finally, micrometer-sized multicompartment particles with a periodic lamellar fine structure are observed, for which we introduce the term "woodlouse". The counterion-mediated decrease in hydrophilicity of the corona-forming P2VPq block is the underlying trigger to induce this hierarchical structure formation. All individual steps and the corresponding intermediates toward these well-defined superstructures were intensively studied by scattering and electron microscopic techniques, including transmission electron microtomography.

Original languageEnglish
Pages (from-to)4030-4041
Number of pages12
JournalACS Nano
Issue number5
Publication statusPublished - 2013 May 28


  • ABC miktoarm star terpolymer
  • hierarchical self-assembly
  • multicompartment micelles
  • poly(2-vinylpyridine)
  • polyelectrolytes


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