Factors determining the formation of complexes between alpha-cyclodextrin and alkylated substances in aqueous solutions: a calorimetric study at 25 degrees C.
The formation of complexes of alpha-cyclodextrin with cycloalkanediols, monoalkylamines and 1-alkanols has been studied calorimetrically at 25 degrees C in water, in phosphoric acid, pH 1.3, and in phosphate buffer, pH 5.5, respectively. When a complex is formed, calorimetry enables the calculation of both the enthalpy and the association constant, from which the free energy and the entropy of the process can be obtained. A model is proposed to explain the unusual trend of the association parameters for substances having alkyl chains longer than six-seven carbon atoms. The main role played by the different functional groups, and the forces involved in the association process, are discussed in the light of the signs and values of the thermodynamic parameters obtained. The effect of the variation of the aqueous medium on the hydration of the interacting substances and the consequent changes in the association parameters have been investigated. To this end, the thermodynamic parameters for the formation of the complexes between the cyclodextrin and 1-pentanol were determined at increasing concentrations of phosphate buffer. There is an increase in the association constant due to a positive entropy contribution originating from the relaxation of water molecules from the hydrophobic hydration cosphere of the alkanol to an increasingly disordered bulk. Deaquation of the interacting substances is the main factor determining the stability of the inclusion complex.
Castronuovo
G
G
Department of Chemistry, University Federico II of Naples, Italy. castronuovo@chemna.dichi.unina.it
Elia
V
V
Iannone
A
A
Niccoli
M
M
Velleca
F
F
D000478:Alkylation; D002151:Calorimetry; D003505:Cyclodextrins / Q000378:metabolism*; D004305:Dose-Response Relationship, Drug; D000431:Ethanol / Q000737:chemistry; D006860:Hydrogen Bonding; D006863:Hydrogen-Ion Concentration; D008956:Models, Chemical; D000439:Pentanols / Q000737:chemistry; D010710:Phosphates / Q000737:chemistry; D011485:Protein Binding; D013696:Temperature; D013816:Thermodynamics; D014867:Water / Q000378:metabolism*; D047391:alpha-Cyclodextrins
D003505:Cyclodextrins; D000439:Pentanols; D010710:Phosphates; D047391:alpha-Cyclodextrins; D014867:Water; D000431:Ethanol; C024999:n-pentanol; C032613:alpha-cyclodextrin