Self-Assembly of Janus Cylinders into Hierarchical Superstructures

• Published in: Journal of the American Chemical Society 2009-04, Vol.131 (13), p.4720-4728
• Main Authors: Walther, Andreas, Drechsler, Markus, Rosenfeldt, Sabine, Harnau, Ludger, Ballauff, Matthias, Abetz, Volker, Müller, Axel H. E
• Format: Article
• Language: English
• Subjects: 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
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja808614q

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 RuO4 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.