title: How to distinguish isodesmic from cooperative supramolecular polymerisation.
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.
authors.affiliation: Laboratory of Macromolecular and Organic Chemistry and Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
authors.forename: Maarten M J
authors.initials: MM
authors.lastname: Smulders
authors.forename: Marko M L
authors.initials: MM
authors.lastname: Nieuwenhuizen
authors.forename: Tom F A
authors.initials: TF
authors.lastname: de Greef
authors.forename: Paul
authors.initials: P
authors.lastname: van der Schoot
authors.forename: Albertus P H J
authors.initials: AP
authors.lastname: Schenning
authors.forename: E W
authors.initials: EW
authors.lastname: Meijer