Filtern
Erscheinungsjahr
- 2011 (2)
Dokumenttyp
Referierte Publikation
- ja (2)
Schlagworte
- Self-assembly (2)
- Bottle-brush (1)
- Electrostatic interaction (1)
- Macromonomers (1)
- Polyelectrolyte (1)
- Polyelectrolytes (1)
- Porphyrin (1)
- Supramolecular nanostructures (1)
Cylindrical poly(styrene sulfonate) brushes were combined with a tetravalent double-DABCO based counterion. With increasing addition of counterion, hydrodynamic radius and radius of gyration decrease and AFM reveals a conformation change from wormlike to curled structures. Rg/Rh changes from 1.3 to 0.9. Above charge stoichiometry, brushes become interconnected into finite size assemblies, which are stable in aqueous solution for charge ratios (ratio of the molar concentration of charged counterion groups to the molar concentration of charged monomer units of the polymer brush) 1 < Ι < 1.2. They are compact and consist of the brushes in curled (bent) conformation, which is in difference to network-like aggregates from cylindrical poly(styrene sulfonate) brushes with tetravalent porphyrin counterions (Gröhn et al. Macromolecules 2009) and to a wormlike — bent conformation — helix transition found for another brush counterion system (Müller et al. Soft Matter 2009).
Polystyrene sulfonate - porphyrin assemblies: influence of polyelectrolyte and porphyrin structure
(2011)
In this study, electrostatic self-assembly of different polystyrene sulfonates and a set of tetravalent cationic porphyrins is investigated. It is shown that association of linear polystyrene sulfonates of different molar masses yields finite size nanoscale assemblies that are stable in aqueous solution. Aggregates are compared to the ones of cylindrical brushes, revealing that both form assemblies in the 100 nm range with the charge ratio (molar ratio of porphyrin charges to polyelectrolyte charges) being determining, while the morphology of the resulting network-like assemblies is different for both polyelectrolyte architectures. For the smallest 8k polystyrene sulfonate, in addition, stoichiometric conditions differ. The influence of the molecular porphyrin structure was investigated by comparing meso-tetrakis(4-(trimethyl-ammonium)phenyl)porphyrin (TAPP) with its Cu(II) and Zn(II) loaded analogues and meso-tetrakis(4-N-methylpyridinium)porphyrin (TMPyP), revealing differences in stacking tendency and geometry. Additionally, the TMPyP accumulates more in the inside of the brush than the other porphyrins, likely due to the different position of its charged groups. The supramolecular nanostructures formed were characterized by UV–vis spectroscopy, light scattering, atomic force microscopy, cryo transmission electron microscopy, and small-angle neutron scattering. Results may build a valuable basis for the use of polyelectrolyte–porphyrin assemblies in medicine, catalysis, or energy conversion.