View PDF Version
 
DOI: 10.1039/A806488A (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1999, 1257-1264

Host–guest complexation of aromatic carboxylic acids and their conjugate bases by 6A-(ω-aminoalkylamino)-6A-deoxy-β-cyclodextrins[hair space]† in aqueous solution

(Note: The full text of this document is currently only available in the PDF Version )

Suzanna D. Kean, Bruce L. May, Philip Clements, Stephen F. Lincoln and Christopher J. Easton

Abstract

A potentiometric titration study of the complexation of the guests benzoic acid, 4-methylbenzoic acid and (RS)-2-phenylpropanoic acid and their conjugate bases by host 6A-(ω-aminoalkylamino)-6A-deoxy-β-cyclodextrins, where the ω-aminoalkylamino groups are -NH(CH2)nNH2 (n = 2, 3, 4 and 6), is reported. Of the 64 host–guest complexes whose formation is statistically possible over the pH range 2.0–12.0 studied, 35 were detected. Their stability constants range from 140 ± 35 dm3 mol–1 for the [βCDNH(CH2)2NH3·4-methylbenzoate] complex to 1760 ± 150 dm3 mol–1 for the [βCDNH(CH2)6NH2·(S[hair space])-2-phenylpropanoate]– complex at 298.2 K and I = 0.10 mol dm–3 (NaClO4). The charge and hydrophobicity of both host and guest appear to be significant factors in the variation of host–guest complex stability. Qualitative structural information on the host–guest complexes obtained from 600 MHz 1H NMR ROESY spectroscopy is generally consistent with the structures generated by molecular modelling.

References

  1. R. J. Clarke, J. H. Coates and S. F. Lincoln, Adv. Carbohydr. Chem. Biochem., 1988, 46, 205 Search PubMed.
  2. S. E. Brown, J. H. Coates, P. A. Duckworth, S. F. Lincoln, C. J. Easton and B. L. May, J. Chem. Soc., Faraday Trans., 1993, 89, 1035 RSC.
  3. Y. Inoue, T. Hakushi, Y. Liu, L.-H. Tong, B.-J. Shen and D.-S. Jin, J. Am. Chem. Soc., 1993, 115, 475 CrossRef CAS.
  4. S. E. Brown, J. H. Coates, C. J. Easton and S. F. Lincoln, J. Chem. Soc., Faraday Trans., 1994, 90, 739 RSC.
  5. R. Dhillon, C. J. Easton, S. F. Lincoln and J. Papageorgiou, Aust. J. Chem., 1995, 48, 1117 CAS.
  6. K. A. Connors, J. Pharm. Sci., 1995, 84, 843 CAS.
  7. C. J. Easton and S. F. Lincoln, Chem. Soc. Rev., 1996, 25, 163 RSC.
  8. J. Szejtli, in Comprehensive Supramolecular Chemistry, J. L. Atwood, J. E. D. Davies, D. D. MacNicol and F. Vögtle, eds., vol. 3, 1996, p. 189, Elsevier Science, Oxford Search PubMed.
  9. E. Fenyvesi, L. Szente, N. R. Russell and M. McNamara, in Comprehensive Supramolecular Chemistry, J. L. Atwood, J. E. D. Davies, D. D. MacNicol and F. Vögtle, eds., vol. 3, 1996, p. 305, Elsevier Science, Oxford Search PubMed.
  10. V. Rüdiger, A. Eliseev, S. Simonova, H.-J. Schneider, M. J. Blandamer, P. M. Cullis and A. J. Meyer, J. Chem. Soc., Perkin Trans. 2, 1996, 2119 RSC.
  11. A. Gadre, V. Rüdiger, H.-J. Schneider and K. A. Connors, J. Pharm. Sci., 1997, 86, 236 CrossRef CAS.
  12. K. Kano, T. Kitae, H. Takashima and Y. Shimofuri, Chem. Lett., 1997, 899 CrossRef CAS.
  13. K. A. Connors, Chem. Rev., 1997, 97, 1325 CrossRef CAS.
  14. T. Kitae, T. Nakayama and K. Kano, J. Chem. Soc., Perkin Trans. 2, 1998, 207 RSC.
  15. M. V. Rekharsky and Y. Inoue, Chem. Rev., 1998, 98, 1875 CrossRef CAS.
  16. C. J. Easton and S. F. Lincoln, Modified Cyclodextrins: Templates and Scaffolds for Supramolecular Chemistry, 1999, Imperial College Press, London Search PubMed.
  17. B. L. May, S. D. Kean, C. J. Easton and S. F. Lincoln, J. Chem. Soc., Perkin Trans. 1, 1997, 3157 RSC.
  18. P. Gans, A. Sabatini and A. Vacca, J. Chem. Soc., Dalton Trans., 1985, 1195 RSC.
  19. J. N. S. Evans, Biomolecular NMR Spectroscopy, Oxford University Press, Oxford, 1995 Search PubMed.
  20. Biosym/MSI of San Diego.
  21. D. Mentzafos, A. Terzis, A. W. Coleman and C. de Rango, Carbohydr. Res., 1996, 282, 125 CrossRef CAS X-Ray crystallography shows βCDNH(CH2)6NH2 molecules align head to tail in a zig-zag array in the crystal. The -NH(CH2)6NH2 substituent of each βCDNH(CH2)6NH2 enters the annulus of an adjacent βCDNH(CH2)6NH2 from the secondary face so that the -(CH2)6- chain is largely within the hydrophobic annulus region with the -NH2 group protruding from the primary face. This solid state interm olecular complexation contrasts with the intramolecular complexation proposed in the present solution study in which no evidence for other than monomeric βCDNH(CH2)6NH2 was found.
  22. R. Corradini, A. Dossena, R. Marchelli, A. Panagia, G. Sartor, M. Saviano, A. Lombardi and V. Pavone, Chem. Eur. J., 1996, 2, 373 CrossRef CAS.
  23. R. Corradini, A. Dossena, G. Galaverna, R. Marchelli, A. Panagia and G. Sartor, J. Org. Chem., 1997, 62, 6283 CrossRef CAS.
  24. K. Lindner and W. Saenger, Angew. Chem., Int. Ed. Engl., 1978, 17, 694 CrossRef.
  25. C. Betzel, W. Saenger, B. E. Hingerty and G. M. Brown, J. Am. Chem. Soc., 1984, 106, 7545 CrossRef CAS.
  26. V. Zabel, W. Saenger and S. A. Mason, J. Am. Chem. Soc., 1986, 108, 3664 CrossRef CAS.
  27. T. Steiner, W. Saenger and R. E. Lechner, Mol. Phys., 1991, 72, 1211 CAS.
Click here to see how this site uses Cookies. View our privacy policy here.