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Metalloporphyrin–polyelectrolyte assemblies in aqueous solution: Influence of the metal center and the polyelectrolyte architecture

ABSTRACT

This study investigates the influence of different metal centers in porphyrins and of different polyelectrolyte architectures on the formation of supramolecular metalloporphyrin–polyelectrolyte assemblies in aqueous solution via electrostatic self‐assembly. Metal‐analogues of the tetravalent anionic meso‐tetrakis(4‐sulfonatophenyl)‐porphyrin (with Zn2+, Co2+, Ni2+, Mn3+, and Fe3+) are combined with the cationic dendrimer of generation 4 or with the linear polydiallyldimethyl‐ammoniumchloride. Dynamic light scattering and atomic force microscopy reveal that the different molecular geometries of the metalloporphyrins resulting from axial ligands determine the size and the stability of the aggregates. A thermodynamic study elucidates the importance of the polymer architecture in controlling the size of the assembly and the role of the metal center. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017

Electrostatic interactions have been exploited for the supramolecular structure formation of ionic porphyrins with polyelectrolytes in aqueous solution. The role of different metal centers in the porphyrins and different polyelectrolyte architectures has been investigated systematically via DLS, AFM, ITC, and spectroscopy techniques. A thermodynamic study revealed the importance of the polymer architecture in determining the size of the complex and the central role of the metal center for the affinity and the stoichiometry.

Authors:   Sabine Frühbeißer, Juan Pablo Fuenzalida Werner, Franziska Gröhn
Journal:   Journal of Polymer Science Part B: Polymer Physics
Year:   2017
Pages:   n/a
DOI:   10.1002/polb.24557
Publication date:   22-Dec-2017
Facts, background information, dossiers
  • metal centers
  • ITC
  • interactions
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