Colloid and Polymer Science

, Volume 297, Issue 2, pp 201–211 | Cite as

Micellization of selenium-containing cationic surfactants with different headgroups in aqueous solution

  • Zhiqiang Chen
  • Xiaofei Ren
  • Shuang Guo
  • Xiaoyi Zhang
  • Rong Zhang
  • Mingrui Zhang
  • Dongyan Li
  • Qinglin Gu
  • Yongmin ZhangEmail author
Original Contribution


Redox-responsive surfactant based on selenium atom has recently attracted considerable interests. Herein, we have designed and synthesized three selenium-containing cationic surfactants with different headgroups, including N-(benzylselanyl-undecyl)-N,N,N-trimethyl ammonium bromide (BSeTAB)/pyridinium bromide (BSePyB)/methylpyrrolidinium bromide (BSeMPB). Their micellization in dilute solution was investigated by surface tension and conductivity, and was related to redox-induced change in molecular structure. Both 1H NMR and ESI-MS spectra demonstrated that selenide in the reduced form is transformed into selenoxide after oxidation with H2O2, whatever the headgroup is. The formation of selenoxide not only increases the hydrophilicity of surfactant, resulting in a more negative \( \Delta {G}_{\mathrm{ads}}^o \), larger cmc, cmc/C20 ratio, and Gmin, compared to the reduced forms, but also provides a new polar headgroup, making it behave like bola-type structure and enhancing the hydrophilicity. The relatively smaller cmc, larger cmc/C20 ratio, and more negative \( \Delta {G}_m^o \) value all revealed that the pyridinium or pyrrolidinium polar headgroup is more favorable for the micelle formation than the trimethylammonium group. The thermodynamic parameters showed that the micellization is transformed from entropy-driven mode to enthalpy-driven mode with increasing temperature and the transition temperature at which \( \Delta {H}_m^o \) equals to \( -\mathrm{T}\Delta {S}_m^o \) is lowest for BSeMPB, and highest for BSePyB.


Aggregation Micelles Micellization Surfactants Surface tension 


Funding information

This work was financially supported by the National Natural Science Foundation of China (grant No. 21503094, 21673103), the Natural Science Foundation (BK20150128) of Jiangsu Province, PR China, and Excellence project of teacher of Jiangnan University (JC2017134).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

396_2018_4454_MOESM1_ESM.docx (451 kb)
ESM 1 (DOCX 450 kb)


  1. 1.
    Myers D (1999) Surfaces, interfaces, and colloids: principles and applications. John Wiley & Sons, Inc., HobokenCrossRefGoogle Scholar
  2. 2.
    Rosen MJ (2004) Surfactants and interfacial phenomena. John Wiley & Sons, Inc., HobokenCrossRefGoogle Scholar
  3. 3.
    Kumar D, Rub MA (2018) Interaction of ninhydrin with chromium-glycylglycine complex in the presence of dimeric gemini surfactants. J Mol Liq 250:329–334CrossRefGoogle Scholar
  4. 4.
    Kumar D, Rub MA (2018) Studies of interaction between ninhydrin and Gly-Leu dipeptide: influence of cationic surfactants (m-s-m type Gemini). J Mol Liq 269:1–7CrossRefGoogle Scholar
  5. 5.
    Kumar D, Rub MA (2017) Effect of anionic surfactant and temperature on micellization behavior of promethazine hydrochloride drug in absence and presence of urea. J Mol Liq 238:389–396CrossRefGoogle Scholar
  6. 6.
    Arnould A, Gaillard C, Fameau A-L (2015) pH-responsive fatty acid self-assembly transition induced by UV light. J Colloid Interface Sci 458:147–154CrossRefGoogle Scholar
  7. 7.
    Ren G, Wang L, Chen Q, Xu Z, Xu J, Sun D (2017) pH switchable emulsions based on dynamic covalent surfactants. Langmuir 33:3040–3046CrossRefGoogle Scholar
  8. 8.
    Zhang Y, An P, Liu X (2015) Bell-shaped sol-gel-sol conversions in pH-responsive worm-based nanostructured fluid. Soft Matter 11:2080–2084CrossRefGoogle Scholar
  9. 9.
    Zhang Y, Han Y, Chu Z, He S, Zhang J, Feng Y (2013) Thermally induced structural transitions from fluids to hydrogels with pH-switchable anionic wormlike micelles. J Colloid Interface Sci 394:319–328CrossRefGoogle Scholar
  10. 10.
    Zhao W, Wang H, Wang Y (2018) Coacervation of dynamic covalent surfactants with polyacrylamides: properties and applications. Soft Matter 14:4178–4184CrossRefGoogle Scholar
  11. 11.
    Singh VK, Ramesh S, Pal K, Anis A, Pradhan DK, Pramanik K (2014) Olive oil based novel thermo-reversible emulsion hydrogels for controlled delivery applications. J Mater Sci-Mater Med 25:703–721CrossRefGoogle Scholar
  12. 12.
    Zhang Y, An P, Liu X (2015) “Worm”-containing viscoelastic fluid based on single amine oxide surfactant with an unsaturated C22-tail. RSC Adv 5:19135–19144CrossRefGoogle Scholar
  13. 13.
    Fameau A-L, Cousin F, Derrien R, Saint-Jalmes A (2018) Design of responsive foams with an adjustable temperature threshold of destabilization. Soft Matter 14:2578–2581CrossRefGoogle Scholar
  14. 14.
    Lei L, Xie D, Song B, Jiang J, Pei X, Cui Z (2017) Photoresponsive foams generated by a rigid surfactant derived from dehydroabietic acid. Langmuir 33:7908–7916CrossRefGoogle Scholar
  15. 15.
    Fameau AL, Arnould A, Lehmann M, von Klitzing R (2015) Photoresponsive self-assemblies based on fatty acids. Chem Commun 51:2907–2910CrossRefGoogle Scholar
  16. 16.
    Yang D, Zhao J (2016) A light-responsive organofluid based on reverse worm-like micelles formed from an equi-charged, mixed, anionic gemini surfactant with an azobenzene spacer and a cationic conventional surfactant. Soft Matter 12:4044–4051CrossRefGoogle Scholar
  17. 17.
    Schnurbus M, Stricker L, Ravoo BJ, Braunschweig B (2018) Smart air–water interfaces with arylazopyrazole surfactants and their role in photoresponsive aqueous foam. Langmuir 34:6028–6035CrossRefGoogle Scholar
  18. 18.
    Liu Y, Jessop PG, Cunningham M, Eckert CA, Liotta CL (2006) Switchable surfactants. Soft Matter 313:958–960Google Scholar
  19. 19.
    Ceschia E, Harjani JR, Liang C, Ghoshouni Z, Andrea T, Brown RS, Jessop PG (2014) Switchable anionic surfactants for the remediation of oil-contaminated sand by soil washing. RSC Adv 4:4638–4645CrossRefGoogle Scholar
  20. 20.
    Zhang Y, Feng Y, Wang J, He S, Guo Z, Chu Z, Dreiss CA (2013) CO2-switchable wormlike micelles. Chem Commun 49:4902–4904CrossRefGoogle Scholar
  21. 21.
    Zhang Y, Chu Z, Dreiss CA, Wang Y, Fei C, Feng Y (2013) Smart wormlike micelles switched by CO2 and air. Soft Matter 9:6217–6221CrossRefGoogle Scholar
  22. 22.
    Zhang Y, Zhang Y, Wang C, Liu X, Fang Y, Feng Y (2016) CO2-responsive microemulsion: reversible switching from an apparent single phase to near-complete phase separation. Green Chem 18:392–396CrossRefGoogle Scholar
  23. 23.
    Baumgartner E, F J H (1980) Vesicles with a monolayer, redox-active membrane. Angew Chem Inter Edit. 19:550–551CrossRefGoogle Scholar
  24. 24.
    Tsuchiya K, Sakai H, Saji T, Abe M (2003) Electrochemical reaction in an aqueous solution of a ferrocene-modified cationic surfactant mixed with an anionic surfactant. Langmuir 19:9343–9350CrossRefGoogle Scholar
  25. 25.
    Noyhouzer T, L’Homme C, Beaulieu I, Mazurkiewicz S, Kuss S, Kraatz H-B, Canesi S, Mauzeroll J (2016) Ferrocene-modified phospholipid: an innovative precursor for redox-triggered drug delivery vesicles selective to cancer cells. Langmuir 32:4169–4178CrossRefGoogle Scholar
  26. 26.
    Aydogan N, Abbott NL (2002) Effect of electrolyte concentration on interfacial and bulk solution properties of ferrocenyl surfactants with anionic Headgroups. Langmuir 18:7826–7830CrossRefGoogle Scholar
  27. 27.
    Fan HM, Han F, Liu Z, Qin L, Li ZC, Liang DH, Ke FY, Huang JB, Fu HL (2008) Active control of surface properties and aggregation behavior in amino acid-based Gemini surfactant systems. J Colloid Interface Sci 321:227–234CrossRefGoogle Scholar
  28. 28.
    Brown P, Bushmelev A, Butts CP, Cheng J, Eastoe J, Grillo I, Heenan RK, Schmidt AM (2012) Magnetic control over liquid surface properties with responsive surfactants. Angew Chem Inter Edit 51:2414–2416CrossRefGoogle Scholar
  29. 29.
    Kim S, Bellouard C, Eastoe J, Canilho N, Rogers SE, Ihiawakrim D, Ersen O, Pasc A (2016) Spin state as a probe of vesicle self-assembly. J Am Chem Soc 138:2552–2555CrossRefGoogle Scholar
  30. 30.
    Winterbourn CC (2008) Reconciling the chemistry and biology of reactive oxygen species. Nat Chem Biol 4:278–286CrossRefGoogle Scholar
  31. 31.
    Trachootham D, Alexandre J, Huang P (2009) Targeting cancer cells by ROS-mediated mechanisms: a radical therapeutic approach? Nat Rev Drug Discov 8:579–591CrossRefGoogle Scholar
  32. 32.
    Deng Z, Qian Y, Yu Y, Liu G, Hu J, Zhang G, Liu S (2016) Engineering intracellular delivery nanocarriers and nanoreactors from oxidation-responsive polymersomes via synchronized bilayer cross-linking and permeabilizing inside live cells. J Am Chem Soc 138:10452–10466CrossRefGoogle Scholar
  33. 33.
    Yao J, Cheng Y, Zhou M, Zhao S, Lin S, Wang X, Wu J, Li S, Wei H (2018) ROS scavenging Mn3O4 nanozymes for in vivo anti-inflammation. Chem Sci 9:2927–2933CrossRefGoogle Scholar
  34. 34.
    Zhang HC, An W, Liu ZN, Hao AY, Hao JC, Shen J, Zhao XH, Sun HY, Sun LZ (2010) Redox-responsive vesicles prepared from supramolecular cyclodextrin amphiphiles. Carbohydr Res 345:87–96CrossRefGoogle Scholar
  35. 35.
    Aydogan N, Abbott NL (2001) Comparison of the surface activity and bulk aggregation of ferrocenyl surfactants with cationic and anionic headgroups. Langmuir 17:5703–5706CrossRefGoogle Scholar
  36. 36.
    Anton P, Heinze J, Laschewsky A (1993) Redox-active monomeric and polymeric surfactants. Langmuir 9:77–85CrossRefGoogle Scholar
  37. 37.
    Susan MABH, Begum M, Takeoka Y, Watanabe M (2000) Study of the correlation of the cyclic voltammetric responses of a nonionic surfactant containing an anthraquinone group with the dissolved states. Langmuir 16:3509–3516CrossRefGoogle Scholar
  38. 38.
    Ghosh S, Irvin K, Thayumanavan S (2007) Tunable disassembly of micelles using a redox trigger. Langmuir 23:7916–7919CrossRefGoogle Scholar
  39. 39.
    Metanis N, Hilvert D (2014) Natural and synthetic selenoproteins. Curr Opin Chem Biol 22:27–34CrossRefGoogle Scholar
  40. 40.
    Reich HJ, Hondal RJ (2016) Why nature chose selenium. ACS Chem Biol 11:821–841CrossRefGoogle Scholar
  41. 41.
    Wang YP, Xu HP, Ma N, Wang ZQ, Zhang X, Liu JQ, Shen JC (2006) Block copolymer micelles as matrixes for incorporating diselenide compounds: a model system for a water-soluble glutathione peroxidase mimic fine-tuned by ionic strength. Langmuir 22:5552–5555CrossRefGoogle Scholar
  42. 42.
    Xu H, Cao W, Zhang X (2013) Selenium-containing polymers: promising biomaterials for controlled release and enzyme mimics. Accounts Chem Res 46:1647–1658CrossRefGoogle Scholar
  43. 43.
    Zhang Y, Chen H, Liu X, Zhang Y, Fang Y, Qin Z (2016) Effective and reversible switching of emulsions by an acid/base-mediated redox reaction. Langmuir 32:13728–13735CrossRefGoogle Scholar
  44. 44.
    Kong WW, Guo S, Zhang YM, Liu XF (2017) Redox-responsive interfacial properties of Se-containing sulfobetaine surfactant. Acta Phys -Chim Sin 33:1205–1213Google Scholar
  45. 45.
    Kong W, Guo S, Wu S, Liu X, Zhang Y (2016) Redox-controllable interfacial properties of zwitterionic surfactant featuring selenium atoms. Langmuir 32:9846–9853CrossRefGoogle Scholar
  46. 46.
    Zhang Y, Kong W, Wang C, An P, Fang Y, Feng Y, Qin Z, Liu X (2015) Switching wormlike micelles of selenium-containing surfactant using redox reaction. Soft Matter 11:7469–7473CrossRefGoogle Scholar
  47. 47.
    Zhang Y, Qin F, Liu X, Fang Y (2018) Switching worm-based viscoelastic fluid by pH and redox. J Colloid Interface Sci 514:554–564CrossRefGoogle Scholar
  48. 48.
    Zhang Y, Liu L, Liu X, Fang Y (2018) Reversibly switching wormlike micelles formed by selenium-containing surfactant and benzyl tertiary amine using CO2/N2 and redox reaction. Langmuir 34:2302–2311CrossRefGoogle Scholar
  49. 49.
    Zhang Y, Yang C, Guo S, Chen H, Liu X (2016) Tandem triggering of wormlike micelles using CO2 and redox. Chem Commun 52:12717–12720CrossRefGoogle Scholar
  50. 50.
    Zhang Y, Kong W, An P, He S, Liu X (2016) CO2/pH-controllable viscoelastic nanostructured fluid based on stearic acid soap and bola-type quaternary ammonium salt. Langmuir 32:2311–2320CrossRefGoogle Scholar
  51. 51.
    Meguro K, Ikeda K, Otsuji A, Taya M, Yasuda M, Esumi K (1987) Physicochemical properties of the α,ω-type surfactant in aqueous solution. J Colloid Interface Sci 118:372–378CrossRefGoogle Scholar
  52. 52.
    Zhao M, Zheng L (2011) Micelle formation by N-alkyl-N-methylpyrrolidinium bromide in aqueous solution. Phys Chem Chem Phys 13:1332–1337CrossRefGoogle Scholar
  53. 53.
    Rub MA, Azum N, Khan F, Asiri AM (2018) Aggregation of sodium salt of ibuprofen and sodium taurocholate mixture in different media: a tensiometry and fluorometry study. J Chem Thermodyn 121:199–210CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Materials EngineeringJiangnan UniversityWuxiPeople’s Republic of China

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