Splitting of Surface-Immobilized Multicompartment Micelles into Clusters upon Charge Inversion.
We investigate a morphological transition of surface-immobilized triblock terpolymer micelles: the splitting into well-defined clusters of satellite micelles upon pH changes. The multicompartment micelles are formed in aqueous solution of ABC triblock terpolymers consisting of a hydrophobic polybutadiene block, a weak polyanionic poly(methacrylic acid) block, and a weak polycationic poly(2-(dimethylamino)ethyl methacrylate) block. They are subsequently immobilized on silicon wafer surfaces by dip-coating. The splitting process is triggered by a pH change to strongly basic pH, which goes along with a charge reversal of the micelles. We find that the aggregation number of the submicelles is well-defined and that larger micelles have a tendency to split into a larger number of submicelles. Furthermore, there is a clear preference for clusters consisting of doublets and triplets of submicelles. The morphology of surface-immobilized clusters can be "quenched" by returning to the original pH. Thus, such well-defined micellar clusters can be stabilized and are available as colloidal building blocks for the formation of hierarchical surface structures. We discuss the underlying physicochemical principles of the splitting process considering changes in charge and total free energy of the micelles upon pH change.
Department of Physical Chemistry II, University of Bayreuth , Universitätsstrasse 30, 95440 Bayreuth, Germany.
Inna
I
Dewald
Department of Physical Chemistry II, University of Bayreuth , Universitätsstrasse 30, 95440 Bayreuth, Germany.
Julia
J
Gensel
Department of Macromolecular Chemistry II, University of Bayreuth , Universitätsstrasse 30, 95440 Bayreuth, Germany.
Eva
E
Betthausen
Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux, UMR 5254 CNRS/UPPA , 2 av. P. Angot, 64053 Pau, France.|Saint-Petersburg State Polytechnic University , 195251 St. Petersburg, Russia.
Oleg V
OV
Borisov
Department of Macromolecular Chemistry II, University of Bayreuth , Universitätsstrasse 30, 95440 Bayreuth, Germany.|Institut für Organische Chemie, Johannes Gutenberg Universität Mainz , Duesbergweg 10-14, 55128 Mainz, Germany.
Axel H E
AH
Müller
Institut für Organische Chemie und Makromolekulare Chemie, Friedrich-Schiller-Universität Jena , Lessingstrasse 8, 07743 Jena, Germany.|Jena Center for Soft Matter (JCSM), Friedrich-Schiller-Universität Jena , Philosophenweg 7, 07743 Jena, Germany.
Felix H
FH
Schacher
Department of Physical Chemistry II, University of Bayreuth , Universitätsstrasse 30, 95440 Bayreuth, Germany.|Leibniz-Institut für Polymerforschung Dresden e.V. , Hohe Strasse 6, 01069 Dresden, Germany.|Cluster of Excellence Centre for Advancing Electronics Dresden (cfaed), Technische Universität Dresden , 01062 Dresden, Germany.
Andreas
A
Fery
ABC triblock terpolymer; atomic force microscopy; cluster formation; micelle splitting; multicompartment micelles; smart coatings; surface immobilization