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How to Distinguish Isodesmic from Cooperative Supramolecular Polymerisation
Author(s) -
Smulders Maarten M. J.,
Nieuwenhuizen Marko M. L.,
de Greef Tom F. A.,
van der Schoot Paul,
Schenning Albertus P. H. J.,
Meijer E. W.
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200902415
Subject(s) - isodesmic reaction , supramolecular chemistry , polymerization , self assembly , mechanism (biology) , materials science , nanotechnology , chemistry , chemical physics , molecule , organic chemistry , polymer , physics , quantum mechanics
Abstract To study the supramolecular polymerisation mechanisms of a self‐assembling system, concentration‐ and temperature‐dependent measurements can both be used to probe the transition from the molecular dissolved state to the aggregated state. In this report, both methods are evaluated to determine their effectiveness in identifying and quantifying the self‐assembly mechanism for isodesmic and cooperative self‐assembling systems. It was found that for a rapid and unambiguous determination of the self‐assembly mechanism and its thermodynamic parameters, temperature‐dependent measurements are more appropriate. These studies allow the acquisition of a large data set leading to an accurate determination of the self‐assembly mechanism and quantification of the different thermodynamic parameters that describe the supramolecular polymerisation. For a comprehensive characterisation, additional concentration‐dependent measurements can be performed.