Complexation of adamantane-ammonium substrates by beta-cyclodextrin and itsO-methylated derivatives

  • Robert I. Gelb
  • Lowell M. Schwartz
Article

Abstract

A spectrophotometric method is used to determine formation constants of complexes ofβ-cyclodextrin, the 2,6-di-O-methylated and 2,3,6-tri-O-methylated derivatives ofβ-cyclodextrin as hosts with adamantan-1-ylammonium, adamantan-2-ylammonium and adamantan-1-ylmethylammonium as substrate species. The spectrophotometric method uses methyl orange anion and acid forms as indicator species. Complexes of the cyclodextrins with these species are determined as well as with the adamantane derivatives. Standard enthalpies and entropies of formation of all complexes are calculated from the temperature variation of the equilibrium constants.β-Cyclodextrin and its 2,6-O-methyl derivative have comparable complex strengths with adamantaneammonium substrates and these strengths are about two orders of magnitude stronger than the corresponding complexes of the permethylated derivative. Thermodynamic parameters are interpreted in terms of differing intramolecular properties of the cyclodextrin complexes.

Key words

Cyclodextrin formation constant uv-visible spectrophotometry cationic guests 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    M. L. Bender and M. Komiyama:Cyclodextrin Chemistry, Springer-Verlag: New York (1978) and references therein.Google Scholar
  2. 2.
    K. Takeo and T. Kuge:Stärke 24, 331 (1972).Google Scholar
  3. 3.
    E. A. Lewis and L. D. Hansen:J. Chem. Soc., Perkin Trans. 2, 2081 (1973).Google Scholar
  4. 4.
    M. R. Eftink and J. C. Harrison:Bioorg. Chem. 10, 388 (1981).Google Scholar
  5. 5.
    L. A. Selvidge and M. R. Eftink:Anal. Biochem. 154, 400 (1986).PubMedGoogle Scholar
  6. 6.
    T. Matsui, D. H. Evans, T. Osa, and N. Kabayashi:J. Am. Chem. Soc. 107, 3411 (1985).Google Scholar
  7. 7.
    R. I. Gelb, L. M. Schwartz, B. Cardelino, H. Fuhrman, R. F. Johnson, and D. A. Laufer:J. Am. Chem. Soc. 103, 1750 (1981).Google Scholar
  8. 8.
    R. I. Gelb, L. M. Schwartz, B. Cardelino, and D. A. Laufer:Anal. Biochem. 103, 362 (1980).PubMedGoogle Scholar
  9. 9.
    R. A. Robinson and R. H. Stokes:Electrolyte Solutions, 2nd ed., Butterworths: London (1965).Google Scholar
  10. 10.
    B. Casu, M. Reggiani, G. G. Gallo, and A. Vigevani:Tetrahedron 24, 803 (1968).Google Scholar
  11. 11.
    B. Casu, M. Reggiani, G. G. Gallo, and A. Vigevani:Carbohyd. Res. 12, 157 (1970).Google Scholar
  12. 12.
    B. Casu, M. Reggiani, G. G. Gallo, and A. Vigevani:Tetrahedron 22, 3061 (1966).Google Scholar
  13. 13.
    M. St. Jaques, P. R. Sundarrajan, K. J. Taylor, and R. H. Marchessault:J. Am. Chem. Soc. 98, 4386 (1976).Google Scholar

Copyright information

© Kluwer Academic Publishers 1989

Authors and Affiliations

  • Robert I. Gelb
    • 1
  • Lowell M. Schwartz
    • 1
  1. 1.Department of ChemistryUniversity of MassachusettsBostonUSA

Personalised recommendations