Self-assembly of Janus cylinders into hierarchical superstructures.
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.
Walther
Andreas
A
Makromolekulare Chemie II, Bayreuther Zentrum für Kolloide and Grenzflächen, Universität Bayreuth, D-95440 Bayreuth, Germany. andreas.walther@hut.fi
Drechsler
Markus
M
Rosenfeldt
Sabine
S
Harnau
Ludger
L
Ballauff
Matthias
M
Abetz
Volker
V
Müller
Axel H E
AH
D002070:Butadienes / Q000138:chemical synthesis / Q000737:chemistry*; D003432:Cross-Linking Reagents / Q000737:chemistry; D020724:Elastomers / Q000138:chemical synthesis / Q000737:chemistry*; D008027:Light; D049329:Nanostructures / Q000737:chemistry* / Q000648:ultrastructure; D033363:Neutron Diffraction; D010316:Particle Size; D019904:Polymethyl Methacrylate / Q000138:chemical synthesis / Q000737:chemistry*; D011137:Polystyrenes / Q000138:chemical synthesis / Q000737:chemistry*; D012542:Scattering, Radiation; D053838:Scattering, Small Angle; D013499:Surface Properties
D002070:Butadienes; D003432:Cross-Linking Reagents; D020724:Elastomers; D011137:Polystyrenes; C028834:polybutadiene; D019904:Polymethyl Methacrylate