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Electrostatic hierarchical co-assembly in aqueous solutions of two oppositely charged double hydrophilic diblock copolymers |
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| Authors: | Ilja K. Voets Arie de Keizer Antoine Debuigne Christophe Detrembleur |
| Affiliation: | a Laboratory of Physical Chemistry and Colloid Science, Wageningen University, Dreijenplein 6, 6703 HB Wageningen, The Netherlands b Adolphe Merkle Institute, University of Fribourg, Route de l’ancienne Papeterie, P.O. Box 209, CH-1723 Marly 1, Switzerland c Center for Education and Research on Macromolecules, University of Liège, Sart-Tilman B6, 4000 Liege, Belgium |
| Abstract: | The formation of spherical micelles in aqueous solutions of poly(N-methyl-2-vinyl pyridinium iodide)-block-poly(ethylene oxide), P2MVP-b-PEO and poly(acrylic acid)-block-poly(vinyl alcohol), PAA-b-PVOH has been investigated with light scattering-titrations, dynamic and static light scattering, and 1H 2D Nuclear Overhauser Effect Spectroscopy. Complex coacervate core micelles, also called PIC micelles, block ionomer complexes, and interpolyelectrolyte complexes, are formed in thermodynamic equilibrium under charge neutral conditions (pH 8, 1 mM NaNO3, T = 25 °C) through electrostatic interaction between the core-forming P2MVP and PAA blocks. 2D 1H NOESY NMR experiments show no cross-correlations between PEO and PVOH blocks, indicating their segregation in the micellar corona. Self-consistent field calculations support the conclusion that these C3Ms are likely to resemble a ‘patched micelle’; that is, micelles featuring a ‘spheres-on-sphere’ morphology. |
| Keywords: | Block-copolymers Micelles Polyion complex micelles Complex coacervation Self-assembly Polyelectrolyte |
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