Recognition of ionic guests by ionic beta-cyclodextrin derivatives.
Inclusion compounds of cationic, anionic, and neutral p-substituted derivatives of tert-butylbenzene complexed in beta-cyclodextrin and its ionic 6-mono and 6-hepta derivatives were systematically investigated by isothermal titration calorimetry (ITC). All inclusion compounds showed 1:1 stoichiometry with binding constants ranging from 10 to 3 x 10(6) M(-1). The binding free energies could be subdivided into apolar and electrostatic contributions. The electrostatic interactions could be quantitatively described by Coulomb's law by taking into account the degree of protonation of hosts and guests, the orientations of the guests within the hosts, and ion shielding as described by the Debye-Hückel-Onsager theory. The orientations of the guests within the cyclodextrin cavities were determined by ROESY NMR spectroscopy.
Wenz
Gerhard
G
Organische Makromolekulare Chemie, Saarland University, Saarbrücken, Germany. g.wenz@mx.uni-saarland.de
Strassnig
Christian
C
Thiele
Carolin
C
Engelke
Annegret
A
Morgenstern
Bernd
B
Hegetschweiler
Kaspar
K
D002151:Calorimetry; D009682:Magnetic Resonance Spectroscopy; D021241:Spectrometry, Mass, Electrospray Ionization; D013816:Thermodynamics; D047392:beta-Cyclodextrins / Q000737:chemistry*
D047392:beta-Cyclodextrins; C031215:betadex