The Structure of Triton X 100 and Hexadecylpyridinium Chloride in Aqueous Solutions: Fluorescence and Small-Angle X-Ray Scattering Studies in the Presence of Hg(CN)2

  • Henrich H. Paradies
Chapter

Abstract

Small-angle X-ray scattering experiments on hexadecylpyridinium chloride (CPCl) micelles and micelles of Triton X 100 in aqueous solutions were conducted in the presence and absence of Hg (CN)2 at 20°C. In addition, fluorescence measurements were performed by probing the hydrophobic nature of Hg(CN)2 in the hydrophobic core of both micelles. From fluorescence depolarisation experiments it was possible to determine the distance of Hg-(CN)2 to the pyridinium group of about 10-12 Å (20°C) from energy transfer calculations; and in Triton X 100 micelles the distance determined between Hg(CN)2 and the phenoxy group was estimated to be 16.5 Å. Smallangle X-ray scattering experiments support the spectroscopic results regarding the location of Hg(CN)2 within the hydrophobic moieties of both micelles by inspection of the radial net electron density distribution functions. Through variation of the contrast with H2 O the dependency of the apparent radius of gyration upon the density of the solvent was determined: it was discovered that the decrease of Rg with the solvent density is parabolic rather than linear, more pronounced in the presence of tightly bound Tl+ at the boundary between hydrocarbon and hydrophobic regions. In conjunction with ultracentrifugation experiments by varying the density of the solvent in addition to the molecular mass and aggregation numbers, the interaction parameter for several additives was determined.

Keywords

Radial Distribution Function Hydrophobic Core Aggregation Number High Performance Liquid Chroma Phenoxy Group 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
This is a preview of subscription content, log in to check access.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    B.J. Cabane, J. Phys. (Orsay, France) 42, 847 (1981)CrossRefGoogle Scholar
  2. 2.
    P.G. Nilson, H. Wennerström and B. Lindman, J. Phys. Chem.,87 1377 (1983); B. Lindman and H. Wennerström in“Topics in Current Chemistry: Micelles”, Springer-Verlag, Berlin (1983); F.M. Menger and J.F. Chou, J. Amer.Chem. Soc. 105, 5501 (1983)Google Scholar
  3. 3.
    K. Kalyanasundaram and J.K. Thomas, J. Phys. Chem. 80 1462 (1976)CrossRefGoogle Scholar
  4. 4.
    K. Kalyanasundaram and J.J. Thomas, in“Micellization, Solubilization and Microemulsions”, K.L. Mittal, Editor, vol 2, pp 569–588, Plenum Press, New York (1977)CrossRefGoogle Scholar
  5. 5.
    A. Ray and G. Nemethy, J. Phys. Chem. 74, 809 (1971); K.J. Kano, Y. Uena and S. Hashimoto, J. Phys. Chem. 89, 3161 (1985); K. Kano, H. Goto and T. Ogawa, Chem Lett. 653, (1981); J.C. Rüssel and D.G. Whitten, J. Amer.Chem. Soc, 104 5937 (1982)Google Scholar
  6. 6.
    C.W. Dwiggins, R.J. Bolen and H.N. Dunning, J. Phys. Chem. 64, 1175 (1960)CrossRefGoogle Scholar
  7. 7.
    D.A. Doughty, J. Phys. Chem. 83, 2621 (1979)CrossRefGoogle Scholar
  8. 8.
    J.-C. Jean, B. Djermouni and H.J. Ache, in“Solution Chemistry of Surfactants”, K.L. Mittal, Editor Vol 1, pp.129–152, Plenum Press, New York (1979)Google Scholar
  9. 9.
    D. Bendedouch, S.H. Chen and C.W. Koehler, J. Phys. Chem. 87,153 (1983)CrossRefGoogle Scholar
  10. 10.
    D. Bendedouch, S.H. Chen, W.C. Koehler and S.J. Lin, J. Chem. Phys. 76. 5022 (1982)CrossRefGoogle Scholar
  11. 11.
    J.B. Hayter and J. Penfold, J. Chem. Soc, Faraday Trans. 11, 1851 (1981); J.B. Hayter and T. Zemb, Chem. Phys. Lett. 93, 91U982)Google Scholar
  12. 12.
    F. Reiss-Husson, V. Luzzati, J. Phys. Chem. 68, 3504 (1964)CrossRefGoogle Scholar
  13. 13.
    R. Reiss-Husson, V. Luzzati, J. Colloid Interface Sci., 21, 534 (1966)CrossRefGoogle Scholar
  14. 14.
    G.W. Brady, J. Chem. Phys. 19 1547 (1951)CrossRefGoogle Scholar
  15. 15.
    A.M. Mankowich, J. Phys. Chem. 58,1027 (1954); L.M. Kushner and W.D. Hubbard, J. Phys. Chem. 58, 1163 (1954); K. Kuriyama, Kolloids-Z., l81, 144 (1962)CrossRefGoogle Scholar
  16. 16.
    M. Corti and V. Degiorgio, Opt. Commum., 14 358 (1975); M. Corti and V. Degiorgio, Phys. Rev. Lett., 45, 1045 (1980); J. Phys. Chem. 85, 1442, (1981); V. Degiorgio and M. Corti, in“Surfactants in Solution”, K.L. Mittal and M. Lindman, Editor Vol.1, pp 471-486, Plenum Press, New York (1984); V. Degiorgi, in“Physics of Amphiphiles: Micelles, Vesicles and Microemulsions”, North Holland, Amsterdam, pp. 303-332, (1985)Google Scholar
  17. 17.
    H.H. Paradies, G. Mertens, R. Schmid, E. Schneider, K. Allendorf, Biophys. J. 37, 195 (1982); H H Paradies, Biochem. Int., 3, 311 (1981)CrossRefGoogle Scholar
  18. 18.
    C. Tanford,“The Hydrophobic Effect”, Wiley, New York, 1979; J.A. Reynolds, in“Physics of Amphiphiles: Micelles, Vesicles and Micro-emulsions”, pp 553-561, North Hoiland,Amsterdam, (1985); M. Zolant, ibid, pp 663-671 (1985)Google Scholar
  19. 19.
    E.A. Dennis. A.J. Ribeiro, M.F. Roberts and R.S. Robson, in“Solution Chemistry of Surfactants” K.L. Mittal, Vol 1, pp 175–194, Plenum, New York (1979)Google Scholar
  20. 20.
    L. Cermàkowà, in“Surfactants in Solution”, K.L. Mittal and B. Lindman, Editors, Vol 2, pp. 1217-1229, Plenum Press, New York (1984)Google Scholar
  21. 21.
    L. Cantu, M. Corti, V. Degiorio, CI. Minero and K. Piazza, J. Colloid Interface Sci., 205, 628 (1985)CrossRefGoogle Scholar
  22. 22.
    Patent P 3626700.7 to Medice, Ltd. (1986) W. Germany;EP-NO.0257400,(1988)Google Scholar
  23. 23.
    F.M. Menger, J. Donohue, J. Amer.Chem.Soc. 95, 432 (1973); A. Cipicianni, P. Linda, G. Savelli, J. Heterocycl.Chem. 16, 673 (1979); A. Cipicianni, P. Linda and G. Savelli, J. Heterocycl. Chem. 16, 611 (1979)CrossRefGoogle Scholar
  24. 24.
    A. Cipicianni, P. Linda, G. Savelli, J. Heterocycl. Chem. 20, 432 (1983); A. Cipicianni, P. Linda, G. Savelli, and C.A. Bunton, J. Phys.Chem. 87, 5262 (1983)Google Scholar
  25. 25.
    A. Cipicianni, C. Ebert, R. Germani, P. Linda, M. Lovresish, F. Rubesca, G. Sacelli, J. Pharm. Sci., 74, 1184 (1985)CrossRefGoogle Scholar
  26. 26.
    K.W. Hermann, J.G. Brushmuller and W.L. Courchene, J. Phys.Chem. 70, 2909 (1966)CrossRefGoogle Scholar
  27. 27.
    H.H. Paradies, Colloids and Surfaces, 6 405 (1983)CrossRefGoogle Scholar
  28. 28.
    H.H. Paradies, J. Phys. Chem. 84, 599 (1980)CrossRefGoogle Scholar
  29. 29.
    V. Luzzati, A. Tardieu, L. Mateu and H.B. Stuhrmann, J. Mol. Biol., 101 115 (1976); H.B. Stuhrmann, J. Appl.Crystallogr.11, 325 (1978)CrossRefGoogle Scholar
  30. 30.
    O. Glatter and O. Kratky, editors,“Small-Angle X-ray Scattering”, Academic Press, New York, (1982)Google Scholar
  31. 31.
    H.H. Paradies, U.D. Schmidt and J. Zimmermann, J. Biol. Chem. 253, 8972 (1978), H.H. Paradies, ibid. 254, 7495 (1979)Google Scholar
  32. 32.
    E.F. Cassasa and H. Eisenberg, Adv. Protein Chem. 19 187–395 (1964)Google Scholar
  33. 33.
    A. Franz and H.H. Paradies; Eur. J. Biochem. 67, 23 (1976)CrossRefGoogle Scholar
  34. 34.
    H.H. Paradies and Y. Kagawa, FEBS-Lett, 136, 3 (1981)CrossRefGoogle Scholar
  35. 35.
    H.H. Paradies and H. Ziedrich, Deutsch-Österreich. Chemikertreffen, Inspruch, p 74 (1986); H.H. Paradies submitted to J. Inorg.Chem.,(1987)Google Scholar
  36. 36.
    Th. Förster, S. Volker, Chem.-Phys.Lett. 34, 1 (1975); Th. Förster, Z. Naturforsch. A, 4, 321 (1949)CrossRefGoogle Scholar
  37. 37.
    K. Kano, Y. Ueno, K. Umakoshi, S. Hashimoto, T. Ishibashi and T. Ogawa, T., J. Phys. Chem. 88, 5087 (1984)CrossRefGoogle Scholar
  38. 38.
    Binding studies indicate two binding sites with different binding constants and energies. The Scatchard Plot is nonlinear. (Paraaies, 1984, unpuoiished results)Google Scholar
  39. 39.
    H.H. Paradies, submitted to J. Amer.Chem.Soc., (1988)Google Scholar
  40. 40.
    E.W. Anacker, J. Phys.Chem. 62 41 (1958); E.W. Anacker and H.M. Ghose, J. Amer.Chem. Soc. 90, 3161 (1968)CrossRefGoogle Scholar
  41. 41.
    N. Stubicar, J. Matetas, Z. Nemet and P. Zipper, these proceedingsGoogle Scholar
  42. 42.
    M.D. Ediger and M.D. Fayer, J. Phys. Chem. 88 6108–6116 (1986); M.D. Fayer Annual, Rev.Phys. Chem. 33, 63 (1982); M.D. Ediger, R.P. Domingue and M.D. Fayer, J. Chem.Phys. 80, 1246 (1984)CrossRefGoogle Scholar
  43. 43.
    K. Sauer, Acc. Chem. Res. 7, 257 (1978)CrossRefGoogle Scholar
  44. 44.
    H.H. Paradies, J. Phys. Chem. 90, 5956 (1986)CrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1989

Authors and Affiliations

  • Henrich H. Paradies
    • 1
    • 2
  1. 1.Department Biotechnology and Physical ChemistryMärkische FachhochschuleIserlohnGermany
  2. 2.Research and DevelopmentMedice Inc.IserlohnWest Germany

Personalised recommendations