Abstract
The formation of complexes of α-cyclodextrin with 1,2-alkanediols, α,ω-alkanediols and some cycloalkanols has been studied calorimetrically at 25 °C in water, in 7 mol kg-1 aqueous urea and in 3 mol kg-1 aqueous glucose. 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. 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. As respect to water, complexes are less stable in urea and more stable in glucose. The analysis of the data shows that this is the result of a different enthalpy-entropy balance in the two solvent media. Deaquation of the interacting substances plays a major role in determining the stability of the inclusion complexes.
Similar content being viewed by others
REFERENCES
A. Connors: Chem. Rev. 97, 1325 (1997).
W. Saenger: In J.L. Atwood, J. E. Davies, and D. MacNicol (eds.), Inclusion Compounds, Vol. 2, Academic Press, London, 1984, pp. 231–259.
W. Saenger: Angew. Chem. Int. Ed. Engl. 19, 344 (1980).
R.J. Clarke, J.H. Coates, and S.F. Lincoln: Adv. Carbohydr. Chem. Biochem. 46, 205 (1988 ).
O. Huber and J. Szejtli (eds.): Proceedings of the 4th International Symposium on Ciclodextrins, Kluwer Academic Publisher, Dordrecht (1988).
M.V. Rekharsky and Y. Inoue: Chem. Rev. 98, 1875 (1998).
P.C. Manor and W. Saenger: J. Am. Chem. Soc. 96, 3630 (1974).
W. Saenger, M. Noltemeyer, P. C. Manor, B. Hingerty, and B. Klar: Bioorg. Chem. 5, 187 (1976).
R.J. Bergeron, M.A. Channing, G.J. Gibeily, and D.M. Pillor: J. Am. Chem. Soc. 99, 5146 (1977).
R.J. Bergeron: In J.L. Atwood, J E. Davis, and D.D. MacNicol (eds.): Inclusion Compounds, Vol. 3, Academic Press, London (1984), pp. 391–443.
G. Barone, G. Castronuovo, P. Del Vecchio, V. Elia, and M. Muscetta: J. Chem. Soc. Faraday Trans. I 82, 2089 (1986).
G. Castronuovo, V. Elia, M. Niccoli, F. Velleca and G. Viscardi: Carbohydr. Res. 306, 147 (1998).
S. Andini, G. Castronuovo, V. Elia, and E. Gallotta: Carbohydr. Res. 217, 87 (1991).
G. Castronuovo, V. Elia, A. Iannone, M. Niccoli, and F. Velleca: Carbohydr. Res. 325, 278 (2000).
G. Castronuovo, V. Elia, D. Fessas, F. Velleca, and G. Viscardi: Carbohydr. Res. 287, 127 (1996).
G. Castronuovo, V. Elia, F. Velleca, and G. Viscardi: Termochim. Acta 292, 31 (1997).
G. Barone, G. Castronuovo, V. Elia, V. Di Ruocco, and C. Giancola: Carbohydr. Res. 192, 331 (1989).
G. Castronuovo, V. Elia, D. Fessas, A. Giordano and F. Velleca: Carbohyd. Res. 272, 31 (1995).
L. Paduano, R. Sartorio, V. Vitagliano, and G. Castronuovo: Termochim. Acta 162, 155 (1990).
G. Castronuovo, V. Elia, M. Niccoli, and F. Velleca: ELDATA: Int. Electron. J. Phys.-Chem. Data 3, 63 (1997).
G. Barone, G. Castronuovo, V. Elia, and M. Muscetta: J. Solution Chem. 15, 129 (1986).
G. Barone, G. Castronuovo, V. Elia, and M. Muscetta: Termochimica Acta 85, 443 (1985).
G. Barone, G. Castronuovo, P. Del Vecchio, and V. Elia: In O. Huber and J. Szejtly (eds.), Proceedings of the 4th International Symposium on Cyclodextrins, Kluwer Academic Publisher, Dordrecht (1988).
R. Lumry and Rajender: Biopolymers 9, 1125 (1970).
E.A. Lewis and L.D. Hansen: J. Chem. Soc., Perkhin Trans. II, 2081 (1973).
Y. Inoue, T. Hakushi, Y. Liu, L. Tong, B. Shen, and D. Jin: J. Am. Chem. Soc. 115, 475 (1993).
M. Eftink and R. Biltonen: In A.E. Beezer (ed.), Biological Microcalorimetry, Academic Press, London (1980).
W.G. McMillan Jr. and E. Mayer: J. Chem. Phys. 13, 276 (1945).
J.J. Kozak, W.S. Knight, and W. Kauzmann: J. Chem. Phys. 48, 675 (1945).
H.L. Friedman and V. Krishnan: J. Solution Chem. 2, 119 (1973).
I. Tabushi: In J.L. Atwood, J.E.D. Davies, and D.D. MacNicol (eds.): Inclusion Compounds, Vol. 3, Academic Press, London (1984), pp. 445–471.
M. Bastos, L.E. Briggner, I. Shehatta, and I. Wädso: J. Chem. Thermodyn. 22, 1181 (1990).
J. Li, A. Harada, and M. Kamachi: Bull. Chem. Soc, Jpn. 67, 2808, (1994).
G. Barone, P. Cacace, G. Castronuovo, and V. Elia: J. Chem. Soc. Faraday Trans. I 77, 1569 (1981).
G. Castronuovo, V. Elia, M. Niccoli, and F. Velleca: Thermochim. Acta, in press.
I. Tabuschi, Y. Kiyosuke, T. Sugimoto, and K. Yamamura: J. Am. Chem. Soc. 100, 916 (1978).
Rights and permissions
About this article
Cite this article
Castronuovo, G., Elia, V., Niccoli, M. et al. The Effects of Cosolvents on the Complexation of α-Cyclodextrin with Alkylated Substances. Calorimetric Studies at 25 °C. Journal of Inclusion Phenomena 44, 229–234 (2002). https://doi.org/10.1023/A:1023019118389
Issue Date:
DOI: https://doi.org/10.1023/A:1023019118389