The interaction between peracetylated beta-cyclodextrin and several triphenyl phosphine derivatives was studied in supercritical carbon dioxide (scCO2) by UV-visible spectroscopy. The equilibrium constant for a 1:1 complexation reaction was obtained from titration spectra and calculated using two established mathematical models. The values of the equilibrium constants are 1-3 orders of magnitude smaller than those obtained in aqueous solution with analogous phosphines. This is likely due to the absence in scCO2 of the hydrophobic effect, which is replaced by a corresponding, but weaker, CO2-phobic effect. The largest value of Kf was found for complexes of diphenyl(4-adamantylphenyl)phosphine, which is rationalized on the basis of the excellent fit of the phosphine in the cyclodextrin cavity, leading to enhanced host-guest van der Waals interactions. This study can be considered the first step toward the comprehension of the complexation thermodynamics of modified cyclodextrins soluble in scCO2.

GALIA, A., NAVARRE, E.C., SCIALDONE, O., MICHEL FERREIRA, FILARDO, G., SEBASTIEN TILLOY, et al. (2007). Complexation of phosphine ligands with peracetylated β-cyclodextrin in supercritical carbon dioxide: spectroscopic determination of equilibrium constants. JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL, 111, 2573-2578 [10.1021/jp0673112].

Complexation of phosphine ligands with peracetylated β-cyclodextrin in supercritical carbon dioxide: spectroscopic determination of equilibrium constants

GALIA, Alessandro;NAVARRE, Edward Charles;SCIALDONE, Onofrio;FILARDO, Giuseppe;
2007-01-01

Abstract

The interaction between peracetylated beta-cyclodextrin and several triphenyl phosphine derivatives was studied in supercritical carbon dioxide (scCO2) by UV-visible spectroscopy. The equilibrium constant for a 1:1 complexation reaction was obtained from titration spectra and calculated using two established mathematical models. The values of the equilibrium constants are 1-3 orders of magnitude smaller than those obtained in aqueous solution with analogous phosphines. This is likely due to the absence in scCO2 of the hydrophobic effect, which is replaced by a corresponding, but weaker, CO2-phobic effect. The largest value of Kf was found for complexes of diphenyl(4-adamantylphenyl)phosphine, which is rationalized on the basis of the excellent fit of the phosphine in the cyclodextrin cavity, leading to enhanced host-guest van der Waals interactions. This study can be considered the first step toward the comprehension of the complexation thermodynamics of modified cyclodextrins soluble in scCO2.
GALIA, A., NAVARRE, E.C., SCIALDONE, O., MICHEL FERREIRA, FILARDO, G., SEBASTIEN TILLOY, et al. (2007). Complexation of phosphine ligands with peracetylated β-cyclodextrin in supercritical carbon dioxide: spectroscopic determination of equilibrium constants. JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL, 111, 2573-2578 [10.1021/jp0673112].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10447/7927
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