Cyclodextrin-based [2]pseudorotaxane formation studied by probe displacement assay

In the present manuscript, we use a guest displacement assay as a methodological tool to study the [2]pseudorotaxane formation between a bolaform surfactant and α‐cyclodextrin. The displacement assay has several advantages in comparison with the most used NMR spectroscopy because its larger availabi...

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Bibliographic Details
Published in:Journal of physical organic chemistry 2016-11, Vol.29 (11), p.574-579
Main Authors: Quiroga, Miguel, Pessêgo, Marcia, Parajo, Mercedes, Rodriguez-Dafonte, Pedro, Garcia-Rio, Luis
Format: Article
Language:English
Subjects:
cyclodextrin
kinetic
mechanism
pseudorotaxane
supramolecular
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Summary:In the present manuscript, we use a guest displacement assay as a methodological tool to study the [2]pseudorotaxane formation between a bolaform surfactant and α‐cyclodextrin. The displacement assay has several advantages in comparison with the most used NMR spectroscopy because its larger availability and mainly the possibility to study inclusion processes taking place in the millisecond time scale. Application to rotaxane formation between bolaform surfactants, B10 or B12, and α‐CD allows us to obtain the activation parameters for this reaction. Activation enthalpy for the dissociation step is larger, more positive, than for the inclusion one according to the [2]pseudorotaxane formation being an exothermic process. Activation entropy is negative reflecting the loss of movement freedom on going from reactants to the transition state with the dissociation step being more negative than the inclusion one. Copyright © 2015 John Wiley & Sons, Ltd. Displacement assays from the CD cavity allow kinetic studies on inclusion of added guests.
ISSN:0894-3230
1099-1395
DOI:10.1002/poc.3518