Colloid and Polymer Science

, Volume 297, Issue 2, pp 183–189 | Cite as

Interfacial behavior of gemini surfactants with different spacer lengths in aqueous medium

  • Hiromichi Nakahara
  • Ayami Nishino
  • Ayaka Tanaka
  • Yoshika Fujita
  • Osamu ShibataEmail author
Original Contribution


A series of alkanediyl-1-s-bis(dimethyltetradecylammonium bromide) (abbr. 14-s-14,2Br) has been characterized in an aqueous medium at temperatures of 288.2, 298.2, and 308.2 K. Critical micelle concentration (cmc) of the surfactants was determined by measuring the surface tension and electrical conductivity as a function of concentrations. The micelle formation was elucidated thermodynamically from the results of electrical conductivity measurement. A steady-state fluorescence quenching and dynamic light scattering were performed to determine the aggregation number and the size of micelles, respectively. Furthermore, the surface potential (ΔV) was measured against surfactant concentrations to understand the condensing state of the adsorbed layer located at the air–water interface. The ΔV value directly can catch a vertical unequal shift of electric charges in the surface region above the bulk where the ΔV value is zero or electroneutrality is held. The results of ΔV measurements indicated that the adsorbed surfactants in the surface region were saturated in terms of amounts far below the cmc and that the vertical orientation of tetradecyl chains of 14-s-14,2Br was improved by the longer spacers in a bending conformation towards the air.


Gemini surfactant Surface potential Surface tension Conductivity Steady-state fluorescence quenching Dynamic light scattering 



This work was supported by a Grant-in-Aid for Scientific Research 16K08216 from the Japan Society for the Promotion of Science (JSPS).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

396_2018_4459_MOESM1_ESM.doc (145 kb)
ESM 1 (DOC 145 kb)


  1. 1.
    Menger FM, Littau CA (1991) Gemini-surfactants: synthesis and properties. J Am Chem Soc 113(4):1451–1452CrossRefGoogle Scholar
  2. 2.
    Zana R, Benrraou M, Rueff R (1991) Alkanediyl-α,ω-bis(dimethylalkylammonium bromide) surfactants. 1. Effect of the spacer chain length on the critical micelle concentration and micelle ionization degree. Langmuir 7(6):1072–1075CrossRefGoogle Scholar
  3. 3.
    Alami E, Beinert G, Marie P, Zana R (1993) Alkanediyl-α,ω-bis(dimethylalkylammonium bromide) surfactants. 3. Behavior at the air-water interface. Langmuir 9(6):1465–1467CrossRefGoogle Scholar
  4. 4.
    Alami E, Levy H, Zana R, Skoulios A (1993) Alkanediyl-α,ω-bis(dimethylalkylammonium bromide) surfactants. 2. Structure of the lyotropic mesophases in the presence of water. Langmuir 9(4):940–944CrossRefGoogle Scholar
  5. 5.
    Menger FM, Littau CA (1993) Gemini surfactants: a new class of self-assembling molecules. J Am Chem Soc 115(22):10083–10090CrossRefGoogle Scholar
  6. 6.
    Zana R, Talmon Y (1993) Dependence of aggregate morphology on structure of dimeric surfactants. Nature 362(6417):228–230CrossRefGoogle Scholar
  7. 7.
    Zana R (1996) Gemini (dimeric) surfactants. Curr Opin Colloid Interface Sci 1(5):566–571CrossRefGoogle Scholar
  8. 8.
    Danino D, Talmon Y, Zana R (1995) Alkanediyl-α,ω-bis(dimethylalkylammonium bromide) surfactants (dimeric surfactants). 5. Aggregation and microstructure in aqueous solutions. Langmuir 11(5):1448–1456CrossRefGoogle Scholar
  9. 9.
    Chen X, Wang J, Shen N, Luo Y, Li L, Liu M, Thomas RK (2002) Gemini surfactant/DNA complex monolayers at the air-water interface: effect of surfactant structure on the assembly, stability, and topography of monolayers. Langmuir 18(16):6222–6228CrossRefGoogle Scholar
  10. 10.
    Karlsson L, van Eijk MCP, Söderman O (2002) Compaction of DNA by gemini surfactants: effects of surfactant architecture. J Colloid Interface Sci 252(2):290–296CrossRefGoogle Scholar
  11. 11.
    Nakahara H, Nishizaka H, Iwasaki K, Otsuji Y, Sato M, Matsuoka K, Shibata O (2017) Role of the spacer of gemini surfactants in solubilization into their micelles. J Mol Liq 244:499–505CrossRefGoogle Scholar
  12. 12.
    Nakahara H, Krafft MP, Shibata A, Shibata O (2011) Interaction of a partially fluorinated alcohol (F8H11OH) with biomembrane constituents in two-component monolayers. Soft Matter 7(16):7325–7333CrossRefGoogle Scholar
  13. 13.
    Nakahara H, Lee S, Shibata O (2009) Pulmonary surfactant model systems catch the specific interaction of an amphiphilic peptide with anionic phospholipid. Biophys J 96(4):1415–1429CrossRefGoogle Scholar
  14. 14.
    Orbulescu J, Micic M, Ensor M, Trajkovic S, Daunert S, Leblanc RM (2010) Human cardiac troponin I: a Langmuir monolayer study. Langmuir 26(5):3268–3274CrossRefGoogle Scholar
  15. 15.
    Nakahara H, Hasegawa A, Uehara S, Akisada H, Shibata O (2013) Solution properties of gemini surfactant of decanediyl-1-10-bis (dimethyltetradecylammonium bromide) in aqueous medium. J Oleo Sci 62(11):905–912CrossRefGoogle Scholar
  16. 16.
    Nakahara H, Shibata O, Moroi Y (2011) Examination of surface adsorption of cetyltrimethylammonium bromide and sodium dodecyl sulfate. J Phys Chem B 115(29):9077–9086CrossRefGoogle Scholar
  17. 17.
    Infelta PP, Grätzel M (1979) Statistics of solubilizate distribution and its application to pyrene fluorescence in micellar systems. A concise kinetic model. J Chem Phys 70(1):179–190CrossRefGoogle Scholar
  18. 18.
    Tachiya M (1975) Application of a generating function to reaction kinetics in micelles. Kinetics of quenching of luminescent probes in micelles. Chem Phys Lett 33(2):289–292CrossRefGoogle Scholar
  19. 19.
    Turro NJ, Yekta A (1978) Luminescent probes for detergent solutions. A simple procedure for determination of the mean aggregation number of micelles. J Am Chem Soc 100(18):5951–5952CrossRefGoogle Scholar
  20. 20.
    Nakahara H, Shibata O, Rusdi M, Moroi Y (2008) Examination of surface adsorption of soluble surfactants by surface potential measurement at the air/solution interface. J Phys Chem C 112:6398–6403CrossRefGoogle Scholar
  21. 21.
    Nakahara H, Shibata O, Moroi Y (2005) Examination of surface adsorption of sodium chloride and sodium dodecyl sulfate by surface potential measurement at the air/solution interface. Langmuir 21(20):9020–9022CrossRefGoogle Scholar
  22. 22.
    Matsuoka K, Chiba N, Yoshimura T, Takeuchi E (2011) Effect of double quaternary ammonium groups on micelle formation of partially fluorinated surfactant. J Colloid Interface Sci 356(2):624–629CrossRefGoogle Scholar
  23. 23.
    Faustino CMC, Calado ART, Garcia-Rio L (2010) Dimeric and monomeric surfactants derived from sulfur-containing amino acids. J Colloid Interface Sci 351(2):472–477CrossRefGoogle Scholar
  24. 24.
    Tsubone K, Arakawa Y, Rosen MJ (2003) Structural effects on surface and micellar properties of alkanediyl-α, ω-bis(sodium N-acyl-β-alaninate) gemini surfactants. J Colloid Interface Sci 262(2):516–524CrossRefGoogle Scholar
  25. 25.
    Zana R (1996) Critical micellization concentration of surfactants in aqueous solution and free energy of micellization. Langmuir 12(5):1208–1211CrossRefGoogle Scholar
  26. 26.
    Moroi Y, Humphry-Baker R, Gratzel M (1987) Determination of micellar aggregation number of alkylsulfonic acids by fluorescence quenching method. J Colloid Interface Sci 119(2):588–591CrossRefGoogle Scholar
  27. 27.
    Alargova RG, Kochijashky II, Sierra ML, Zana R (1998) Micelle aggregation numbers of surfactants in aqueous solutions: a comparison between the results from steady-state and time-resolved fluorescence quenching. Langmuir 14(19):5412–5418CrossRefGoogle Scholar
  28. 28.
    Carnero Ruiz C, Díaz-López L, Aguiar J (2007) Self-assembly of tetradecyltrimethylammonium bromide in glycerol aqueous mixtures: a thermodynamic and structural study. J Colloid Interface Sci 305(2):293–300CrossRefGoogle Scholar
  29. 29.
    Zhao J, Christian SD, Fung BM (1998) Mixtures of monomeric and dimeric cationic surfactants. J Phys Chem B 102(39):7613–7618CrossRefGoogle Scholar
  30. 30.
    Zana R (1980) Ionization of cationic micelles: effect of the detergent structure. J Colloid Interface Sci 78(2):330–337CrossRefGoogle Scholar
  31. 31.
    Davis JT, Rideal EK (1963) Interfacial phenomena. Academic, New YorkGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Hiromichi Nakahara
    • 1
  • Ayami Nishino
    • 1
  • Ayaka Tanaka
    • 2
  • Yoshika Fujita
    • 2
  • Osamu Shibata
    • 2
    Email author
  1. 1.Department of Industrial PharmacyDaiichi University of PharmacyFukuokaJapan
  2. 2.Department of Biophysical Chemistry, Graduate School of Pharmaceutical Sciences, Faculty of Pharmaceutical SciencesNagasaki International UniversitySaseboJapan

Personalised recommendations