Chirality Enhancement of Porphyrin Supramolecular Assembly Driven by a Template Preorganization Effect

Cationic polylysine promotes, under neutral conditions, the spontaneous aggregation of opposite charged ZnTPPS in water. Spectroscopic investigations evidence a different preorganization of ZnTPPS onto the polypeptide matrix depending on the chain length. Spinodal decomposition theory in confined ge...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-08, Vol.57 (33), p.10656-10660
Main Authors: Gaeta, Massimiliano, Raciti, Domenica, Randazzo, Rosalba, Gangemi, Chiara M. A., Raudino, Antonio, D'Urso, Alessandro, Fragalà, Maria E., Purrello, Roberto
Format: Article
Language:English
Subjects:
Chirality
circular dichroism
Polyelectrolytes
Polylysine
porphyrinoids
Porphyrins
self-assembly
Spinodal decomposition
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Summary:Cationic polylysine promotes, under neutral conditions, the spontaneous aggregation of opposite charged ZnTPPS in water. Spectroscopic investigations evidence a different preorganization of ZnTPPS onto the polypeptide matrix depending on the chain length. Spinodal decomposition theory in confined geometry is used to model this mechanism by considering the time evolution of a homogeneous distribution of randomly adsorbed particles (porphyrins) onto a rodlike polyelectrolyte (polymer) of variable length L. The matrix is everywhere: Different modes of preorganization of ZnTPPS [zinc(II) meso‐tetrakis‐(4‐sulfonatophenyl)porphyrin] onto a polypeptide matrix affects the porphyrin demetalation/protonation kinetics at acidic pH. The process results in templating the formation of highly ordered J‐aggregates (J‐Agg) on longer polylysine chains.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201806192