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Thermodynamic and kinetic characterization of host-guest association between bolaform surfactants and alpha- and beta-cyclodextrins

Nilsson, Markus LU ; Valente, Artur J. M.; Olofsson, Gerd LU ; Söderman, Olle LU and Bonini, Massimo (2008) In The Journal of Physical Chemistry Part B 112(36). p.11310-11316
Abstract
The thermodynamics and kinetics of formation of host-guest complexes between a series of bolaform surfactants of type C(n)Me(6)(2+)2Br(-) (n = 8, 10, and 12) and alpha-cyclodextrin and beta-cyclodextrin were studied with the aid of isothermal titration calorimetry (ITC) at 298.15 and 308.20 K. The association constant, the enthalpy, and the entropy of formation were determined. The obtained thermodynamic parameters are compared with parameters for the micelle formation of a related cationic surfactant. The difference in magnitude and sign between the parameters of the alpha-CD and beta-CD complexes is discussed based on the curvature of the cavity of the CD. We suggest that. the water molecules inside the alpha-CD cavity are not able to... (More)
The thermodynamics and kinetics of formation of host-guest complexes between a series of bolaform surfactants of type C(n)Me(6)(2+)2Br(-) (n = 8, 10, and 12) and alpha-cyclodextrin and beta-cyclodextrin were studied with the aid of isothermal titration calorimetry (ITC) at 298.15 and 308.20 K. The association constant, the enthalpy, and the entropy of formation were determined. The obtained thermodynamic parameters are compared with parameters for the micelle formation of a related cationic surfactant. The difference in magnitude and sign between the parameters of the alpha-CD and beta-CD complexes is discussed based on the curvature of the cavity of the CD. We suggest that. the water molecules inside the alpha-CD cavity are not able to maintain their hydrogen bond network. Upon complex formation these water molecules are expelled and reform their hydrogen bond network. The situation is different in the larger beta-CD cavity where water has the possibility of a more extensive hydrogen bonding. The kinetics for alpha-CD is slow, associated with high activation energies for both association and dissociation of the complex. The rates increased with a decrease in the number of methylene Groups in the hydrocarbon chain. The slow kinetics is argued to originate from the fact that the charged head-roup needs to be pushed through a relative nonpolar cavity. A comparison is made with the Born energy. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part B
volume
112
issue
36
pages
11310 - 11316
publisher
The American Chemical Society
external identifiers
  • wos:000258979800019
  • scopus:52349112471
ISSN
1520-5207
DOI
10.1021/jp802963x
language
English
LU publication?
yes
id
1f34525a-f821-47a6-a743-da7df8dff913 (old id 1247718)
date added to LUP
2008-11-21 09:48:14
date last changed
2017-09-24 03:54:28
@article{1f34525a-f821-47a6-a743-da7df8dff913,
  abstract     = {The thermodynamics and kinetics of formation of host-guest complexes between a series of bolaform surfactants of type C(n)Me(6)(2+)2Br(-) (n = 8, 10, and 12) and alpha-cyclodextrin and beta-cyclodextrin were studied with the aid of isothermal titration calorimetry (ITC) at 298.15 and 308.20 K. The association constant, the enthalpy, and the entropy of formation were determined. The obtained thermodynamic parameters are compared with parameters for the micelle formation of a related cationic surfactant. The difference in magnitude and sign between the parameters of the alpha-CD and beta-CD complexes is discussed based on the curvature of the cavity of the CD. We suggest that. the water molecules inside the alpha-CD cavity are not able to maintain their hydrogen bond network. Upon complex formation these water molecules are expelled and reform their hydrogen bond network. The situation is different in the larger beta-CD cavity where water has the possibility of a more extensive hydrogen bonding. The kinetics for alpha-CD is slow, associated with high activation energies for both association and dissociation of the complex. The rates increased with a decrease in the number of methylene Groups in the hydrocarbon chain. The slow kinetics is argued to originate from the fact that the charged head-roup needs to be pushed through a relative nonpolar cavity. A comparison is made with the Born energy.},
  author       = {Nilsson, Markus and Valente, Artur J. M. and Olofsson, Gerd and Söderman, Olle and Bonini, Massimo},
  issn         = {1520-5207},
  language     = {eng},
  number       = {36},
  pages        = {11310--11316},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Thermodynamic and kinetic characterization of host-guest association between bolaform surfactants and alpha- and beta-cyclodextrins},
  url          = {http://dx.doi.org/10.1021/jp802963x},
  volume       = {112},
  year         = {2008},
}