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Polystyrene sulfonate - porphyrin assemblies: influence of polyelectrolyte and porphyrin structure

  • 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 inIn 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.zeige mehrzeige weniger

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Metadaten
Autor*innen:C. Ruthard, Michael Maskos, U. Kolb, F. Gröhn
Dokumenttyp:Zeitschriftenartikel
Veröffentlichungsform:Verlagsliteratur
Sprache:Deutsch
Titel des übergeordneten Werkes (Deutsch):The journal of physical chemistry / B
Jahr der Erstveröffentlichung:2011
Herausgeber (Institution):American Chemical Society
Verlag:Soc.
Verlagsort:Washington, DC
Jahrgang/Band:115
Ausgabe/Heft:19
Erste Seite:5716
Letzte Seite:5729
Freie Schlagwörter:Polyelectrolyte; Porphyrin; Self-assembly; Supramolecular nanostructures
DOI:10.1021/jp1078357
ISSN:1520-6106
ISSN:1520-5207
ISSN:1089-5647
Verfügbarkeit des Dokuments:Datei im Netzwerk der BAM verfügbar ("Closed Access")
Datum der Freischaltung:19.02.2016
Referierte Publikation:Ja
Datum der Eintragung als referierte Publikation:02.02.2012
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