Colloid and Polymer Science

, Volume 296, Issue 5, pp 941–949 | Cite as

Self-assembly behavior of amphiphilic polyelectrolyte with ultrahigh charge density

  • Rongqiang Li
  • Junli Zhang
  • Yu Han
  • Jinlian Zhao
Original Contribution


A series of novel amphiphilic polyelectrolytes with ultrahigh charge density were synthesized by copolymerization of monomers with double-quaternary ammonium groups. The self-assembly properties of the amphiphilic polyelectrolyte with ultrahigh charge density in aqueous solutions have been investigated by means of steady-state fluorescence, dynamic light scattering (DLS), transmission electric microscopy (TEM), and zeta potential measurements. The critical aggregation concentrations (cac) of the polyelectrolytes decreased as the molar content of hydrophobic segments and the length of hydrophobic carbon chains increased. The sizes of the aggregates in the polyelectrolyte solution increased as the concentration of the solution and the molar content of hydrophobic units increased. Compared with the counterparts of the single quaternized ammonium groups in hydrophilic units, the values of cac of the novel ultrahigh charge density polyelectrolytes were larger; however, the size and the zeta potential of aggregates in aqueous solutions were smaller than that of the former. These phenomena were ascribed to the strong hydrophilic capacity and electrostatic repulsions existed in the double quaternized groups of polyelectrolytes.


Self-assembly Amphiphilic Polyelectrolyte Ultrahigh charge density 


Funding information

This research was funded by the National Natural Science Foundation of China (NSFC U1204210).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interest.

Supplementary material

396_2018_4313_MOESM1_ESM.docx (1.2 mb)
ESM 1 (DOCX 1201 kb)


  1. 1.
    Rasteiro MG, Garcia FAP, Ferreira PJ, Antunes E, Hunkeler D, Wandrey C (2010) Flocculation by cationic polyelectrolytes: relating efficiency with polyelectrolyte characteristics. J Appl Polym Sci 116(6):3603–3612Google Scholar
  2. 2.
    Boudou T, Crouzier T, Ren K, Blin G, Picart C (2010) Multiple functionalities of polyelectrolyte multilayer films: new biomedical applications. Adv Mater 22(4):441–467CrossRefGoogle Scholar
  3. 3.
    De G, McClements DJ (2006) Formation, stability and properties of multilayer emulsions for application in the food industry. Adv Colloid Interf Sci 128-130:227–248CrossRefGoogle Scholar
  4. 4.
    Llamas S, Guzman E, Ortega F, Baghdadli N, Cazeneuve C, Rubio RG, Luengo GS (2015) Adsorption of polyelectrolytes and polyelectrolytes-surfactant mixtures at surfaces: a physico-chemical approach to a cosmetic challenge. Adv Colloid Interf Sci 222:461–487CrossRefGoogle Scholar
  5. 5.
    Dutertre F, Gaillard C, Chassenieux C, Nicolai T (2015) Branched wormlike micelles formed by self-assembled comblike amphiphilic copolyelectrolytes. Macromolecules 48(20):7604–7612CrossRefGoogle Scholar
  6. 6.
    Schott MA, Domurado M, Leclercq L, Barbaud C, Domurado D (2013) Solubilization of water-insoluble drugs due to random amphiphilic and degradable poly (dimethylmalic acid) derivatives. Biomacromolecules 14(6):1936–1944CrossRefGoogle Scholar
  7. 7.
    Zhou Y, Yan D (2009) Supramolecular self-assembly of amphiphilic hyperbranched polymers at all scales and dimensions: progress, characteristics and perspectives. Chem Commun 10(10):1172–1188CrossRefGoogle Scholar
  8. 8.
    Kötz J, Kosmella S, Beitz T (2001) Self-assembled polyelectrolyte systems. Prog Polym Sci 26(8):1147–1336CrossRefGoogle Scholar
  9. 9.
    Zhou W, An X, Gong J, Shen W, Chen Z, Wang X (2011) Synthesis, characteristics, and phase behavior of a thermosensitive and pH-sensitive polyelectrolyte. J Appli Polym Sci 121(4):2089–2097CrossRefGoogle Scholar
  10. 10.
    Akbay C, Agbaria RA, Warner IM (2005) Monomeric and polymeric anionic gemini surfactants and mixed surfactant systems in micellar electrokinetic chromatography. Part II: characterization of chemical selectivity using two linear solvation energy relationship models. Electrophoresis 26(2):426–445CrossRefGoogle Scholar
  11. 11.
    Hajduova J, Prochazka K, Slouf M, Angelov B, Mountrichas G, Pispas S, Stepanek M (2013) Polyelectrolyte–surfactant complexes of poly [3, 5-bis (dimethylaminomethyl)-4-hydroxystyrene]-block-poly (ethylene oxide) and sodium dodecyl sulfate: anomalous self-assembly behavior. Langmuir 29(18):5443–5449CrossRefGoogle Scholar
  12. 12.
    Losada R, Wandrey C (2008) Non-ideal polymerization kinetics of a cationic double charged acryl monomer and solution behavior of the resulting polyelectrolytes. Macromol Rapid Commun 29(3):252–257CrossRefGoogle Scholar
  13. 13.
    Losada R, Wandrey C (2009) Copolymerization of a cationic double-charged monomer and electrochemical properties of the copolymers. Macromolecules 42(9):3285–3293CrossRefGoogle Scholar
  14. 14.
    Mantzaridis C, Mountrichas G, Pispas S (2009) Complexes between high charge density cationic polyelectrolytes and anionic single-and double-tail surfactants. J Phys Chem B 113(20):7064–7070CrossRefGoogle Scholar
  15. 15.
    Abe M, Tsubone K, Koike T, Tsuchiya K, Ohkubo T, Sakai H (2006) Polymerizable cationic gemini surfactant. Langmuir 22(20):8293–8297CrossRefGoogle Scholar
  16. 16.
    Abe M, Koike T, Nishiyama H, Sharma SC, Tsubone K, Tsuchiya K, Sakai K, Sakai H, Shchipunov YA, Schmidt J, Talmon Y (2009) Polymerized assemblies of cationic gemini surfactants in aqueous solution. J Colloid Interface Sci 330(1):250–253CrossRefGoogle Scholar
  17. 17.
    Wang H, Shi X, Yu D, Zhang J, Yang G, Cui Y, Sun K, Wang J, Yan H (2015) Antibacterial activity of geminized amphiphilic cationic homopolymers. Langmuir 31(50):13469–13477CrossRefGoogle Scholar
  18. 18.
    Wang H, Zhang P, Shi X, Yu D, Wang J, Yan H, Ji G (2014) Environmentally responsive polymeric materials: effect of the topological structure on self-assembly. Soft Matter 10(35):6749–6757CrossRefGoogle Scholar
  19. 19.
    Yu D, Yang H, Wang H, Cui Y, Yang G, Zhang J, Wang J (2014) Interactions between colloidal particles in the presence of an ultrahighly charged amphiphilic polyelectrolyte. Langmuir 30(48):14512–14521CrossRefGoogle Scholar
  20. 20.
    Yang H, Duan H, Wu X, Wang M, Chen T, Liu F, Wang J (2016) Self-assembly behavior of ultrahighly charged amphiphilic polyelectrolyte on solid surfaces. Langmuir 32(44):11485–11491CrossRefGoogle Scholar
  21. 21.
    Li R, Wei L, Hu C, Xu C, Wang J (2010) Aggregation properties of a novel class of amphiphilic cationic polyelectrolytes containing Gemini surfactant segments. J Phys Chem B 114(39):12448–12454CrossRefGoogle Scholar
  22. 22.
    Li R, Xu C, Wei L, Wang J (2010) Synthesis and self-aggregation behaviors of novel amphiphilic polyelectrolytes containing Gemini surfactant units. Chem J Chinese U 31(10):2024–2029Google Scholar
  23. 23.
    Provencher SW (1982) CONTIN: a general purpose constrained regularization program for inverting noisy linear algebraic and integral equations. Comput Phys Commun 27(3):229–242CrossRefGoogle Scholar
  24. 24.
    Binana-Limbele W, Zana R (1987) Fluorescence probing of microdomains in aqueous solutions of polysoaps. 1. Use of pyrene to study the conformational state of polysoaps and their comicellization with cationic surfactants. Macromolecules 20(6):1331–1335CrossRefGoogle Scholar
  25. 25.
    Wilhelm M, Zhao CL, Wang Y, Xu R, Winnik MA, Mura JL, Croucher MD (1991) Poly (styrene-ethylene oxide) block copolymer micelle formation in water: a fluorescence probe study. Macromolecules 24(5):1033–1040CrossRefGoogle Scholar
  26. 26.
    Zhao CL, Winnik MA, Riess G, Croucher MD (1990) Fluorescence probe techniques used to study micelle formation in water-soluble block copolymers. Langmuir 6(2):514–516CrossRefGoogle Scholar
  27. 27.
    Fetsch C, Flecks S, Gieseler D, Marschelke C, Ulbricht J, Pée KH, Luxenhofer R (2015) Self-assembly of amphiphilic block copolypeptoids with C2-C5 cide chains in aqueous solution. Macromol Chem Phys 216(5):547–560CrossRefGoogle Scholar
  28. 28.
    Chang Y, McCormick CL (1993) Water-soluble copolymers. 49. Effect of the distribution of the hydrophobic cationic monomer dimethyldodecyl(2-acrylamidoethy1)ammonium bromide on the solution behavior of associating acrylamide copolymers. Macromolecules 26(22):6121–6126CrossRefGoogle Scholar
  29. 29.
    Esquenet C, Buhler E (2001) Phase behavior of associating polyelectrolyte polysaccharides. 1. Aggregation process in dilute solution. Macromolecules 34(15):5287–5294CrossRefGoogle Scholar
  30. 30.
    Koromilas ND, Lainioti GC, Oikonomou EK, Bokias G, Kallitsis JK (2014) Synthesis and self-association in dilute aqueous solution of hydrophobically modified polycations and polyampholytes based on 4-vinylbenzyl chloride. Eur Polym J 54(1):39–51CrossRefGoogle Scholar
  31. 31.
    Philippova O (2016) Solution properties of associating polymers. In: Billon L, Borisov O (eds) Macromolecular self-assembly. John Wiley & Sons, Inc., Hoboken, New Jersey, pp 141–158CrossRefGoogle Scholar
  32. 32.
    Adamson AW, Gast AP (1990) Physical chemistry of surfaces, 5th ed. Wiley Interscience, New York Chapter VGoogle Scholar
  33. 33.
    Riemer S, Prévost S, Dzionara M, Appavou MS, Schweins R, Gradzielski M (2015) Aggregation behaviour of hydrophobically modified polyacrylate-variation of alkyl chain length. Polymer 70:194–206CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.College of Chemistry and Pharmaceutical EngineeringHuanghuai UniversityZhumadianPeople’s Republic of China

Personalised recommendations