Metallo-Supramolecular Block Copolymer Micelles: Improved Preparation and Characterization
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Mayer, Gottfried; Vogel, Vitali; Lohmeijer, Bas G. G.; Gohy, Jean-Francois; van den Broek, Jacomina A.; Haase, Winfried; Schubert, Ulrich S.; Schubert, Dieter
- Abstract:
- Micelles prepared from amphiphilic block copolymers in which a poly(styrene)
segment is connected to a poly(ethylene oxide) block via a bis-(2,2:6,2-terpyridine-
ruthenium) complex have been intensely studied. In most cases, the micelle
populations were found to be strongly heterogeneous in size because of massive micelle/
micelle aggregation. In the study reported in this article we tried to improve the
homogeneity of the micelle population. The variant preparation procedure developed,
which is described here, was used to prepare two “protomer”-type micelles: PS20-[Ru]-
PEO70 and PS20-[Ru]-PEO375. The dropwise addition of water to a solution of the
compounds in dimethylformamide was replaced by the controlled addition of water by
a syringe pump. The resulting micelles were characterized by sedimentation velocity
and sedimentation equilibrium analyses in an analytical ultracentrifuge and by transmission
electron microscopy of negatively stained samples. Sedimentation analysis
showed virtually unimodal size distributions, in contrast to the findings on micelles
prepared previously. PS20-[Ru]-PEO70 micelles were found to have an average molar
mass of 318,000 g/mol (corresponding to 53 protomers per micelle, which is distinctly
less than after micelle preparation by the standard method) and an average hydrodynamic
diameter (dh) of 18 nm. For PS20-[Ru]-PEO375 micelles, the corresponding values
wereM 603,000 g/mol (31 protomers per micelle) and dh 34 nm. The latter particles
were found to be identical to the “equilibrium” micelles prepared in pure water. Both
micelle types had a very narrow molar mass distribution but a much broader distribution
of s values and thus of hydrodynamic diameters. This indicates a conformational
heterogeneity that is stable on the time scale of sedimentation velocity analysis. The
findings from electron microscopy were in disagreement with those from the sedimentation
analysis both in average micelle diameter and in the width of the distributions,
apparently because of imperfections in the staining procedure. The preparation procedure described also may be useful in micelle formation from other types of protomers.
- Year:
- 2004
- Type of Publication:
- Article
- Journal:
- Journal of Polymer Science: Part A: Polymer Chemistry
- Volume:
- 42
- Pages:
- 4458 - 4465