Colloid and Polymer Science

, Volume 296, Issue 9, pp 1599–1608 | Cite as

Preparation of multifunctional poly(acrylic acid)-poly(ethylene oxide) nanogels from their interpolymer complexes by radiation-induced intramolecular crosslinking

  • Thitirat Rattanawongwiboon
  • Mohammadreza Ghaffarlou
  • S. Duygu Sütekin
  • Wanvimol PasanphanEmail author
  • Olgun GüvenEmail author
Original Contribution


Poly(acrylic acid)-poly(ethylene oxide) (PAA-PEO) interpolymer complexes (IPC)s were prepared with equimolar stoichiometric ratio of repeating units and converted to crosslinked nanogels via γ-ray irradiation of aqueous acetone solutions. The effect of acetone concentration on the coil size of nanogels was investigated by dynamic light scattering (DLS). pH and temperature effects on the size and surface charge of nanogels were studied by using DLS. Zeta potentials of the PAA-PEO nanogels were between − 5.31 mV (pH = 2) and − 45.00 mV (pH = 11) depending on dissociation of PAA. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) pictures showed that dry PAA-PEO nanogels are spherical with diameters of ~ 100 and ~ 240 nm in the swollen state as determined by DLS. PAA-PEO nanogels synthesized in 25% (v/v) acetone/water mixture exhibited size stability over a period of 2 months. This simple method of preparing nanogels from polymer pairs avoids tiresome synthesis of corresponding block copolymers as precursors of functional nanogels.

Graphical abstract

Formation of poly(acrylic acid)-poly(ethylene oxide) (PAA-PEO) nanogels from interpolymer complexes and radiation-induced crosslinking


Poly(acrylic acid) Poly(ethylene oxide) Nanogels Interpolymer complexes Radiation-induced crosslinking 


Funding information

This study is financially supported by the Bilateral Research Cooperation (BRC), Faculty of Science, Kasetsart University, the Synchrotron Light Research Institute (Public Organization), Thailand and Kasetsart University Research and Development Institute (KURDI 26.59). The authors also acknowledge the research funds and technical activities provided via Coordinated Research project (CRP No. 18316) and Technical Cooperation project (THA1010) of the International Atomic Energy Agency (IAEA), Vienna, Austria.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Jayakumar R, Nair A, Rejinold NS, Maya S, Nair S (2012) Doxorubicin-loaded pH-responsive chitin nanogels for drug delivery to cancer cells. Carbohydr Polym 87:2352–2356CrossRefGoogle Scholar
  2. 2.
    Ahn H-J, Kang E-C, Jang C-H, Song K-W, Lee J-O (2000) Complexation behavior of poly(acrylic acid) and poly(ethylene oxide) in water and water-methanol. J Macromol Sci, Pure Appl Chem 37:573–590CrossRefGoogle Scholar
  3. 3.
    Khutoryanskiy VV, Dubolazov AV, Nurkeeva ZS, Mun GA (2004) pH effects in the complex formation and blending of poly(acrylic acid) with poly(ethylene oxide). Langmuir 20:3785–3790CrossRefPubMedGoogle Scholar
  4. 4.
    Atchison JS, Schauer CL (2011) Fabrication and characterization of electrospun semiconductor nanoparticle-polyelectrolyte ultra-fine fiber composites for sensing applications. Sensors 11:10372–10387CrossRefPubMedGoogle Scholar
  5. 5.
    Nurkeeva ZS, Mun GA, Khutoryanskiy VV (2003) Interpolymer complexes of water soluble nonionic polysaccharides with polycarboxylic acids and their applications. Macromol Biosci 3:283–295CrossRefGoogle Scholar
  6. 6.
    Liao Q, Shao Q, Wang H, Qiu G, Lu X (2012) Hydroxypropylcellulose templated synthesis of surfactant-free poly(acrylic acid) nanogels in aqueous media. Carbohydr Polym 87:2648–2654CrossRefGoogle Scholar
  7. 7.
    Lu X, Hu Z, Schwartz J (2002) Phase transition behavior of hydroxypropylcellulose under interpolymer complexation with poly(acrylic acid). Macromolecules 35:9164–9168CrossRefGoogle Scholar
  8. 8.
    Nurkeeva ZS, Khutoryanskiy VV, Mun GA, Bitekenova AB, Kadlubowski S, Shilina YA, Ulanski P, Rosiak JM (2004) Interpolymer complexes of poly(acrylic acid) nanogels with some non-ionic polymers in aqueous solutions. Colloids Surf A Physicochem Eng Asp 236:141–146CrossRefGoogle Scholar
  9. 9.
    Maitra J, Shukla VK (2014) Cross-linking in hydrogels—a review. Am J Polym Sci 4:25Google Scholar
  10. 10.
    Güven O (2016) Ionizing radiation: a versatile tool for nanostructuring of polymers. Pure Appl Chem 88:1049CrossRefGoogle Scholar
  11. 11.
    Henke A, Kadlubowski S, Ulanski P, Rosiak JM, Arndt K-F (2005) Radiation-induced cross-linking of polyvinylpyrrolidone-poly(acrylic acid) complexes. Nucl Instr Meth Phys Res 236:391–398CrossRefGoogle Scholar
  12. 12.
    El-Rehim HAA, Hegazy E-SA, Hamed AA, Swilem AE (2013) Controlling the size and swellability of stimuli-responsive polyvinylpyrrolidone–poly(acrylic acid) nanogels synthesized by gamma radiation-induced template polymerization. Eur Polym J 49:601–612CrossRefGoogle Scholar
  13. 13.
    Ghaffarlou M, Sütekin SD, Güven O (2018) Preparation of nanogels by radiation-induced crosslinking of interpolymer complexes of poly(acrylic acid) with poly(N-vinyl pyrrolidone) in aqueous medium. Radiat Phys Chem 142:130–136CrossRefGoogle Scholar
  14. 14.
    Zhang L, Jeong Y-I, Zheng S, Jang SI, Suh H, Kang DH, Kim I (2013) Biocompatible and pH-sensitive PEG hydrogels with degradable phosphoester and phosphoamide linkers end-capped with amine for controlled drug delivery. Polym Chem 4:1084–1094CrossRefGoogle Scholar
  15. 15.
    Tsuchida E, Abe K (1982) Interactions between macromolecules in solution and intermacromolecular complexes. In: Interactions between macromolecules in solution and intermacromolecular complexes. SpringerGoogle Scholar
  16. 16.
    Bastakoti BP, Wu KCW, Inoue M, Yusa SI, Nakashima K, Yamauchi Y (2013) Multifunctional core-shell-corona-type polymeric micelles for anticancer drug-delivery and imaging. Chem Eur J 19:4812–4817CrossRefPubMedGoogle Scholar
  17. 17.
    Liu Q, Chen J, Du J (2014) Asymmetrical polymer vesicles with a “stealthy” outer corona and an endosomal-escape-accelerating inner corona for efficient intracellular anticancer drug delivery. Biomacromolecules 15:3072–3082CrossRefPubMedGoogle Scholar
  18. 18.
    Gu Y, Zhong Y, Meng F, Cheng R, Deng C, Zhong Z (2013) Acetal-linked paclitaxel prodrug micellar nanoparticles as a versatile and potent platform for cancer therapy. Biomacromolecules 14:2772–2780CrossRefPubMedGoogle Scholar
  19. 19.
    Bourganis V, Karamanidou T, Samaridou E, Karidi K, Kammona O, Kiparissides C (2015) On the synthesis of mucus permeating nanocarriers. Eur J Pharm Biopharm 97:239–249CrossRefPubMedGoogle Scholar
  20. 20.
    Vasi AM, Popa MI, Tanase EC, Butnaru M, Verestiuc L (2014) Poly(acrylic acid)–poly(ethylene glycol) nanoparticles designed for ophthalmic drug delivery. J Pharm Sci 103:676–686CrossRefPubMedGoogle Scholar
  21. 21.
    Brandrup J, Immergut EH (1989) Polymer handbook3rd edn. Wiley, CanadaGoogle Scholar
  22. 22.
    Khutoryanskiy VV, Nurkeeva ZS, Mun GA, Dubolazov AV (2004) Effect of temperature on aggregation/dissociation behavior of interpolymer complexes stabilized by hydrogen bonds. J Appl Polym Sci 93:1946–1950CrossRefGoogle Scholar
  23. 23.
    Hart EJ, Gordon S, Thomas J (1964) Rate constants of hydrated electrons with organic compounds. J Phys Chem 68:1271–1274CrossRefGoogle Scholar
  24. 24.
    Zhunuspayev DE, Mun GA, Hole P, Khutoryanskiy VV (2008) Solvent effects on the formation of nanoparticles and multilayered coatings based on hydrogen-bonded interpolymer complexes of poly(acrylic acid) with homo-and copolymers of N-vinyl pyrrolidone. Langmuir 24:13742–13747CrossRefPubMedGoogle Scholar
  25. 25.
    Nurkeeva ZS, Mun GA, Khutoryanskiy VV, Kan VA, Zotov AA, Shaikhutdinov EM (2000) Interactions of linear and cross-linked polyacrylic acid with polyvinyl ether of ethyleneglycol in some aliphatic alcohols. Polym Bull 44:563–568CrossRefGoogle Scholar
  26. 26.
    Ward MA, Georgiou TK (2011) Thermoresponsive polymers for biomedical applications. Polymers 3:1215–1242CrossRefGoogle Scholar
  27. 27.
    Gebhardt J, Fuerstenau D (1983) Adsorption of PAA at oxide/water interfaces. Colloids Surf 7:221–231CrossRefGoogle Scholar
  28. 28.
    Henke A, Kadlubowski S, Wolszczak M, Ulanski P, Boyko V, Schmidt T, Arndt K-F, Rosiak JM (2011) The structure and aggregation of hydrogen-bonded interpolymer complexes of PAA with PVP in dilute aqueous solution. Macromol Chem Phys 212:2529–2540CrossRefGoogle Scholar
  29. 29.
    ASTM D4187-82 (1985) Methods of test for zeta potential of colloids in water and waste waterGoogle Scholar

Copyright information

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

Authors and Affiliations

  • Thitirat Rattanawongwiboon
    • 1
    • 2
    • 3
  • Mohammadreza Ghaffarlou
    • 4
  • S. Duygu Sütekin
    • 4
  • Wanvimol Pasanphan
    • 1
    • 2
    Email author
  • Olgun Güven
    • 4
    Email author
  1. 1.Department of Materials Science, Faculty of ScienceKasetsart UniversityBangkokThailand
  2. 2.Center of Radiation Processing for Polymer Modification and Nanotechnology (CRPN), Department of Materials Science, Faculty of ScienceKasetsart UniversityBangkokThailand
  3. 3.Nuclear Research and Development GroupThailand Institute of Nuclear Technology (Public Organization)Nakorn NayokThailand
  4. 4.Department of ChemistryHacettepe UniversityAnkaraTurkey

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