Electron spin echo modulation and electron spin resonance studies of sodium dodecylsulfate and dodecyltrimethylammonium bromide micellar solutions: Effect of urea addition

  • P. Baglioni
  • L. Dei
  • E. Ferroni
  • L. Kevan
Part of the Progress in Colloid & Polymer Science book series (PROGCOLLOID, volume 84)


Electron spin echo modulation (ESEM) and electron spin resonance (ESR) studies have been carried out for a series of x-doxylstearic acids (x-DSA, x=5, 7, 10, 12 and 16) and 4-octanoyl-2,2,6,6-tetramethylpiperidinyl-1-oxy (C8-TEMPO) spin probes in micellar solutions of sodium dodecylsulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) in H2O, D2O, and in presence of 2 M or 6 M urea and urea-d4. The analysis of the nitrogen hyperfine coupling constant, 〈A N 〉, and of the correlation time for the probe motion τ indicates that urea slightly decreases the polarity and strongly increases (from 20% to 100% depending on the surfactant and urea concentration) the microviscosity of the micellar interface. Modulation effects due to the interaction of the unpaired electron with urea and water deuteriums show that urea does not affect the U-bent conformation of the x-DSA probe in the micelle. The analysis of the deuterium modulation depth and the Fourier transformation of the two-pulse spectra show that urea interacts with the surfactant polar headgroups at the micelle surface. It is also found that the interaction of urea is greater with DTAB than SDS surfactant. These results support recent molecular dynamics and Monte Carlo calculations, and are in agreement with a direct mechanism of action in which urea replaces some water molecules that solvate the hydrophobic chain and the polar headgroups of the amphiphile.

Key words

Micelle sodium dodecylsulfate dodecyltrimethylammonium bromide urea electron spin resonance electron spin echo 


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  1. 1.
    Israelachvili JN (1985) Intermolecular and Surface Forces. Academic, New YorkGoogle Scholar
  2. 2.
    Tanford C (1980) The Hydrophobic Effect. Wiley, New YorkGoogle Scholar
  3. 3.
    Israelachvili JN, Mitchell DJ, Ninham BW (1976) J Chem Soc Faraday Trans 2:72, 1525Google Scholar
  4. 4.
    Schick MJ (1964) J Phys Chem 68:3585CrossRefGoogle Scholar
  5. 5.
    Emerson MF, Holtzer AJ (1967) J Phys Chem 71:3320CrossRefGoogle Scholar
  6. 6.
    Franks F (1978) Water: A Comprehensive Treatise, Plenum, New York, Vol 4Google Scholar
  7. 7.
    Wetlaufer DB, Malik SK, Stoller L, Coffin RI (1977) J Am Chem Soc 69:2898Google Scholar
  8. 8.
    Nozaki Y, Tanford C (1963) J Biol Chem 238:4074Google Scholar
  9. 9.
    Enea O, Jolicoeur CJ (1982) J Phys Chem 86:3370CrossRefGoogle Scholar
  10. 10.
    Kresheck GC, Scheraga HA (1965) J Phys Chem 69:1704CrossRefGoogle Scholar
  11. 11.
    MacDonald JC, Serpillis J, Guerreva JJ (1973) J Phys Chem 77:370CrossRefGoogle Scholar
  12. 12.
    Bonner OD, Dednarek JM, Arisman Rk (1977) J Am Chem Soc 99:2848CrossRefGoogle Scholar
  13. 13.
    Finer EG, Franks F, Tait M (1972) J Am Chem Soc 94:4424CrossRefGoogle Scholar
  14. 14.
    Herskovits TT, Kelly TM (1973) J Phys Chem 77:381CrossRefGoogle Scholar
  15. 15.
    Lang J, Tondre C, Zana R (1971) J Phys Chem 75:374CrossRefGoogle Scholar
  16. 16.
    Manabe M, Koda M, Shirahama K (1980) J Colloid Interface Sci 77:189CrossRefGoogle Scholar
  17. 17.
    Philip PR, Perron G, Desnoyer JE (1974) Can J Chem 52:1079CrossRefGoogle Scholar
  18. 18.
    Rupley JA (1964) J Phys Chem 68:2002CrossRefGoogle Scholar
  19. 19.
    Kuharski RA, Rossky PJ (1984) J Am Chem Soc 106:5786CrossRefGoogle Scholar
  20. 20.
    Kuharski RA, Rossky PJ (1984) J Am Chem Soc 106:5794CrossRefGoogle Scholar
  21. 21.
    Tanaka H, Nakanishi K, Touhara H (1985) J Chem Phys 82:5184CrossRefGoogle Scholar
  22. 22.
    Tanaka H, Touhara H, Nakanishi K, Watanabe N (1984) J Chem Phys 80:5170CrossRefGoogle Scholar
  23. 23.
    Marchese RA, Mehrota PK, Beveridge DL (1984) 88:5692Google Scholar
  24. 24.
    Ottaviani MF, Baglioni P, Martini G (1983) 87:3146Google Scholar
  25. 25.
    Baglioni P, Ferroni E, Martini G, Ottaviani MF (1984) J Phys Chem 88:5107CrossRefGoogle Scholar
  26. 26.
    Baglioni P, Cocciaro R, Dei L (1987) J Phys Chem 91:4020CrossRefGoogle Scholar
  27. 27.
    Baglioni P, Ottaviani MF, Martini G, Ferroni E (1984) In: Mittal KL, Lindman B (eds) Surfactants in Solution. Plenum, New York, vol 1, pp 541–557CrossRefGoogle Scholar
  28. 28.
    Kevan L, Bowman MK (1990) Modern Pulsed and Continuous-Wave Electron Spin Resonance. Wiley, New YorkGoogle Scholar
  29. 29.
    Baglioni P, Ferroni E, Kevan L (1990) J Phys Chem 4:4290; Baglioni P, Rivara-Minten E, Dei L, Ferroni E (1990) J Phys Chem 94, in pressGoogle Scholar
  30. 30.
    Ramachandran C, Pyter RA, Mukerjee P (1982) J Phys Chem 86:3198; ibidem (1982) 86:3206CrossRefGoogle Scholar
  31. 31.
    Janzen EG (1971) Top Stereochem 6:117Google Scholar
  32. 32.
    Stout G, Engberts JBNF (1974) J Org Chem 39:3800CrossRefGoogle Scholar
  33. 33.
    Knauer BR, Napier JJ (1976) J Am Chem Soc 98:4395CrossRefGoogle Scholar
  34. 34.
    Abe BR, Tero-Kubata S, Ikegami Y (1982) J Phys Chem 86:1358CrossRefGoogle Scholar
  35. 35.
    Berliner LJ (ed) (1976) Spin Labelling. Theory and Applications. Academic, New York, vols I and IIGoogle Scholar
  36. 36.
    Burning W, Holtzer A (1961) J Am Chem Soc 83:4865CrossRefGoogle Scholar
  37. 37.
    Baglioni P, Ottaviani MF, Martini G (1986) J Phys Chem 90:1022CrossRefGoogle Scholar
  38. 38.
    Lindman B, Wennerström H (1980) Topics in Current Chemistry, vol 87. Springer-Verlag, Berlin, pp 329–324Google Scholar
  39. 39.
    Kevan L (1988) In: Fox MA, Chanon M (eds) Photoinduced Electron Transfer, Part B. Elsevier, Amsterdam, pp 329–394Google Scholar
  40. 40.
    Szajdzinska-Pietek E, Maldonado R, Kevan L, Jones RRM (1986) J Colloid Interface Sci 110:514CrossRefGoogle Scholar
  41. 41.
    Szajdzinska-Pietek E, Maldonado R, Kevan L, Jone RRM, Coleman MJ (1985) J Am Chem Soc 107:784CrossRefGoogle Scholar
  42. 42.
    Baglioni P, Rivara-Minten E, Kevan L (1988) J Phys Chem 92:4726CrossRefGoogle Scholar
  43. 43.
    Baglioni P, Bongiovanni R, Rivara-Minten E, Kevan L (1989) J Phys Chem 93:5574CrossRefGoogle Scholar
  44. 44.
    Baglioni P, Kevan L (1987) J Phys Chem 91:1850CrossRefGoogle Scholar

Copyright information

© Dr. Dietrich Steinkopff Verlag GmbH & Co. KG 1991

Authors and Affiliations

  • P. Baglioni
    • 2
  • L. Dei
    • 2
  • E. Ferroni
    • 1
  • L. Kevan
    • 1
  1. 1.Department of ChemistryUniversity of HoustonHoustonUSA
  2. 2.Department of ChemistryUniversity of FlorenceFlorenceItaly

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