Colloid and Polymer Science

, Volume 282, Issue 1, pp 21–31 | Cite as

2-(Acylaminoethyl)trimethylammonium chloride surfactants: synthesis and properties of aqueous solutions

  • Susana Shimizu
  • Omar A. El Seoud
Original Contribution


The title cationic surfactants have been synthesized by reaction of carboxylic acids with N,N-dimethylethylenediamine to give an intermediate amidoamine. The latter was quaternized with methyl iodide; the product was transformed into the corresponding chloride surfactant by ion-exchange on a macroporous resin. Adsorption and aggregation of these surfactants in H2O have been studied by surface tension measurement. Additionally, solution conductivity, electromotive force (H2O), and Fourier transform IR spectroscopy (D2O) have been employed to investigate micelle formation. Increasing the length of R resulted in the following changes: an increase in the micelle aggregation number; a decrease in the minimum area per surfactant at the solution/air interface, the critical micelle concentration, and the degree of counterion dissociation. Gibbs free energies of adsorption at the solution/air interface and micelle formation in water were calculated and compared to those of alkyltrimethylammonium chlorides. The contribution to these free energies from surfactant methylene groups (in the hydrophobic tail) and the head group was calculated. The former are similar to those of other cationic surfactants. The corresponding free-energy contributions of head groups are smaller (i.e., more negative), indicating that the transfer of this group from bulk water to the interface (for adsorption) and/or to the micelle (aggregate formation) is more favorable. This is attributed to intermolecular hydrogen bonding of monomers at the interface, and/or in the aggregate, via the amide group, in agreement with our Fourier transform IR data. Our results are compatible with a micellar interface closer to the amide nitrogen than to the quaternary ammonium ion.


2-(Acylaminoethyl)trimethylammonium chloride surfactants Properties of cationic surfactants Critical micelle concentration Counterion dissociation Aggregation number 



We thank the FAPESP for financial support and for a predoctoral fellowship to S.S., the CNPq for a research productivity fellowship to O.A.ES, Paulo A.R. Pires for his help with calculations, and H. Chaimovich and I.M. Cuccovia for making the chloride-ion-selective electrode available to us.


  1. 1.
    Hiemenz PC, Rajagopalan R (1997) Principles of colloid and surface chemistry. Dekker, New York, pp 297, 355Google Scholar
  2. 2.
    Rosen MJ (1989) Surfactants and interfacial phenomena. Wiley, New York, pp 33, 108Google Scholar
  3. 3.
    (a) Kahlweit M, Strey R, Haase D, Firman P (1988) Langmuir 4785; (b) Evans DF, Wennerström H (1994) The colloidal domain. VCH, New York, pp 451Google Scholar
  4. 4.
    Bazito RC, El Seoud OA, Barlow GK, Halstead TK (1997) Ber Bunsenges Phys Chem 101:1933Google Scholar
  5. 5.
    Tada EB, Novaki LP, El Seoud OA (2001) Langmuir 17:652CrossRefGoogle Scholar
  6. 6.
    (a) Lacko I, Mlynarcik D, Jadronova M, Karoskova J (1987) CS 237747, Chem Abstr 108:186165; (b) Devinky F, Masarova L, Lacko I (1987) CS 240390, Chem Abstr 108:221286; (c) Login RB, Chaudhuri RK, Tracy DJ, Helioff MW (1989) US 4837013A, Chem Abstr 111:201398; (d) Oshima T (1989) JP 01006210, Chem Abstr 111:20620; (e) Oshima T (1990) JP 02160714, Chem Abstr 113:217792; (f) Iwai H, Nomura T, Shiraiwa T, Mori S, DaihoY (1996) JP 08206581, Chem Abstr 125:250488; (g) Kaneda E, Ohtaki H, Oka S (1994) JP 54043731, Chem Abstr 91:99908; (h) Bailey AV et al (1974) US 473477, Chem Abstr 84:79590Google Scholar
  7. 7.
    (a) Mod RR, Magne FC, Skau EL, Sumrell GJ (1971) Med Chem 14:558; (b) Bailey AV, Sumrell G, Gurtner TE (1974) J Am Oil Chem Soc 51:515Google Scholar
  8. 8.
    (a) Bazito RC, El Seoud OA (2001) Carbohyd Res 323:95; (b) Bazito RC, El Seoud OA (2001) J Surfactant Deterg 4:395; (c) Bazito RC, El Seoud OA (2002) Langmuir 18:4362CrossRefGoogle Scholar
  9. 9.
    Shimizu S, El Seoud OA (2003) Langmuir 19:238CrossRefGoogle Scholar
  10. 10.
    (a) Kollman P (1993) Chem Rev 93:2395; (b) Ludwig RO, Winter R, Weinhold F, Farrar TC (1998) J Phys Chem B 102:9312Google Scholar
  11. 11.
    Huelsekopf M, Ludwig R (2001) Mag Res Chem 39:127CrossRefGoogle Scholar
  12. 12.
    (a) Solans C, Infante R, Azemar N, Wärnheim T (1989) Prog Colloid Polym Sci 79:70; (b) Kunieda H, Nakamura K, Infante R, Solans C (1992) Adv Mater 4:291Google Scholar
  13. 13.
    Eastoe J, Nave S, Downer A, Paul A, Rankin A, Tribe K (2000) Langmuir 16:4511CrossRefGoogle Scholar
  14. 14.
    Tanford C (1991) The hydrophobic effect: formation of micelles and biological membranes. Krieger, FLGoogle Scholar
  15. 15.
    Rosen MJ, Li F (2002) Environ Sci Technol 35:954CrossRefGoogle Scholar
  16. 16.
    Blois DW, Swarbrick J (1971) J Colloid Interface Sci 36:227Google Scholar
  17. 17.
    Frahm J, Diekmann S, Haase A (1980) Ber Bunsenges Phys Chem 84:566Google Scholar
  18. 18.
    Evans HC (1956) J Chem Soc 579Google Scholar
  19. 19.
    Evans DF, Allen M, Ninham BW and Fouda A (1984) J Sol Chem 13:87Google Scholar
  20. 20.
    Gaillon L, Hamidi M, Lelièvre J, Gaboriaud R (1997) J Chim Phys 94:707Google Scholar
  21. 21.
    Umemura J, Mantsch HH, Cameron DG (1981) J Colloid Interface Sci 83:558Google Scholar
  22. 22.
    Yang PW, Mantsch HH (1986) J Colloid Interface Sci 113:218; (c) Etori F, Yamada H, Taga Y, Okabayashi K, Ohshima HK, O'Connor CJ (1997) Vib Spectrosc 14:133CrossRefGoogle Scholar
  23. 23.
    (a) Lafrance D, Marion D, Pézolet (1990) M Biochem 29:4592Google Scholar
  24. 24.
    (a) Nilsson A, Holmgren A, Lindblom G (1994) Chem Phys Lipids 69:219; (b) Domingo JC, Mora M, de Madariaga MA (1994) Chem Phys Lipids 69:229; (c) Domingo JC, de Madariaga MA Chem Phys Lipids 84:147Google Scholar
  25. 25.
    (a) Sasaki T, Hattori M, Sasaki J, Nukina K (1975) Bull Chem Soc Jpn 48:1397; (b) Moroi Y (1988) J Colloid Interface Sci 122:308.Google Scholar
  26. 26.
    Eaton G, Symons MCR, Rastogi PP (1989) J Chem Soc Farday Trans 1 85:3257Google Scholar
  27. 27.
    Miyazawa T, Shimanouchi T, Mizushima S (1958) J Chem Phys 29:611Google Scholar
  28. 28.
    (a) Chen CYS, Swenson CA (1969) J Phys Chem 73:2999; (b) Symons MCR (1993) J Mol Struct 297:133; (c) Schweitzer-Stenner R, Sieler G, Mirkin NG, Krimm S (1998) J Phys Chem A 102:118CrossRefGoogle Scholar
  29. 29.
    Hioka T, Morohara K, Meguro K (1970) Bull Chem Soc Jpn 43:3913Google Scholar
  30. 30.
    Leo A (1993) J Chem Rev 93:1281Google Scholar
  31. 31.
    Shah SS, Jamroz NV, Sharif Q M (2001) Colloids Surf A 178:199CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2003

Authors and Affiliations

  1. 1.Instituto de QuímicaUniversidade de São PauloSão PauloBrazil

Personalised recommendations