Journal of Polymer Research

, 20:285 | Cite as

Morphogical and swelling properties of porous hydrogels based on poly(hydroxyethyl methacrylate) and chitosan modulated by ice-templating process and porogen leaching

  • Maria Valentina Dinu
  • Martin Přádný
  • Ecaterina Stela Drăgan
  • Jiří Michálek
Original Paper


A comparative evaluation of the morphological and swelling properties corresponding to the porous poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogels and to the chitosan (CS) hydrogels was developed in this paper. The porous structure of hydrogels based on PHEMA or CS was tailored by ice-templating process and porogen leaching. Poly(methylmethacrylate) (PMMA), as fractionated particles, was used as polymer porogen. The influence of the average size of the fractionated PMMA particles on the internal morphology and swelling properties of the hydrogels was followed. The average pore diameter of PHEMA cryogels increased from 10 ± 2 μm up to 22 ± 5 μm with the increase of the size of the fractionated PMMA particles from below 32 μm up to 50–90 μm. On the other hand, in the case of CS cryogels prepared in the presence of the PMMA particles with different sizes, pores with an average size of 74 ± 6 μm, irrespective of the size of PMMA particles were formed, strong changes being observed in the morphology of the pore walls, these being less compact and, therefore, more accessible for the diffusion of low molecular weight species. Hydrogels based on PHEMA or CS with microchanneled structures arranged along the freezing direction, were generated by unidirectional freezing. The swelling measurements showed that the cryogels prepared in the presence of PMMA particles attained the equilibrium swelling much faster than those prepared without PMMA.


Chitosan Morphology Poly(hydroxyethyl methacrylate) Porous hydrogels Swelling 



This work was supported by CNCSIS-UEFISCSU by the project PN-II385 ID-PCE-2011-3-0300 and Grant Agency of the Czech Republic, projects No. 108/12/1538.


  1. 1.
    Peppas NA, Hilt JZ, Khademhosseini A, Langer R (2006) Hydrogels in biology and medicine: from molecular principles to bionanotechnology. Adv Mater 18:1345–1360CrossRefGoogle Scholar
  2. 2.
    Wichterle O, Lim D (1960) Hydrophilic gels for biological use. Nature 185:117–118CrossRefGoogle Scholar
  3. 3.
    McMahon TT, Zadnik K (2000) Twenty-five years of contact lenses. Cornea 19:730–740CrossRefGoogle Scholar
  4. 4.
    Orienti I, Bertasi V, Zecchi V (1992) Loading level influence on drug release from ethylene glycol dimethacrylate crosslinked poly(2-hydroxyethyl methacrylate) microspheres. J Control Release 22:159–165CrossRefGoogle Scholar
  5. 5.
    Michalek J, Pradny M, Artyukhov A, Slouf M, Smetana K Jr (2005) Macroporous hydrogels based on 2-hydroxyethyl methacrylate. Part III. Hydrogels as carriers for immobilization of proteins. J Mater Sci Mater Med 16:783–786CrossRefGoogle Scholar
  6. 6.
    Pradny M, Slouf M, Martinova L, Michalek J (2010) Macroporous hydrogels based on 2-hydroxyethyl metacrylate. Part 7: Methods of preparation and comparison of resulting physical properties. e-Polymers 10:1–12Google Scholar
  7. 7.
    Yuna J, Jespersena GR, Kirsebom H, Gustavsson PE, Mattiasson B, Galaev IY (2011) An improved capillary model for describing the microstructure characteristics, fluid hydrodynamics and breakthrough performance of proteins in cryogel beds. J Chromatogr 1218:5487–5497CrossRefGoogle Scholar
  8. 8.
    Yavuz M, Baysal Z (2013) Preparation and use of poly(hydroxyethyl methacrylate) cryogels containing l-histidine for β-casein adsorption. J Food Sci 78:238–243CrossRefGoogle Scholar
  9. 9.
    Pradny M, Lesny P, Fiala J, Vacik J, Slouf M, Michalek J, Sykova E (2003) Macroporous hydrogels based on 2-hydroxyethyl metacrylate. Part 1. Copolymers of 2-hydroxyethyl metacrylate with methacrylic acid. Collect Czech Chem Commun 68:812–822CrossRefGoogle Scholar
  10. 10.
    Pradny M, Michalek J, Lesny P, Hejcl A, Vacik J, Slouf M, Sykova E (2006) Macroporous hydrogels based on 2-hydroxyethyl methacrylate. Part 5: hydrolytically degradable materials. J Mater Sci Mater Med 17:1357–1364CrossRefGoogle Scholar
  11. 11.
    Singh D, Nayak V, Kumar A (2010) Proliferation of myoblast skeletal cells on three dimensional supermacropous cryogel. Int J Biol Sci 6:371–381CrossRefGoogle Scholar
  12. 12.
    Savina IN, Cnudde V, D’Hollander S, Van Hoorebeke L, Mattiasson B, Galaev IY, Du Prez F (2007) Cryogels from poly(hydroxyethyl methacrylate): macroporous, interconnected materials with potential as cell scaffolds. Soft Matter 3:1176–1184CrossRefGoogle Scholar
  13. 13.
    Ji C, Annabi N, Khademhosseini A, Dehghani F (2011) Fabrication of porous chitosan scaffolds for soft tissue engineering using dense gas CO2. Acta Biomater 7:1653–1664CrossRefGoogle Scholar
  14. 14.
    Kathuria N, Tripathi A, Kar KK, Kumar A (2009) Elastic and macroporous chitosan-gelatin cryogels: a new material for tissue engineering. Acta Biomater 5:406–418CrossRefGoogle Scholar
  15. 15.
    Sayil C, Okay O (2001) Macroporous poly(N-isopropyl)acrylamide networks: formation conditions. Polymer 42:7639–7652CrossRefGoogle Scholar
  16. 16.
    Kim D, Park K (2004) Swelling and mechanical properties of superporous hydrogels of poly(acrylamide-co-acrylic acid)/polyethylenimine interpenetrating polymer networks. Polymer 45:189–196CrossRefGoogle Scholar
  17. 17.
    Drăgan ES, Cazacu M, Nistor A (2009) Ionic organic/inorganic materials. III. Stimuli responsive hybrid hydrogels based on oligo(N, N-dimethylaminoethylmethacrylate) and chloroalkyl-functionalized siloxanes. J Polym Sci Part A Polym Chem 47:6801–6813CrossRefGoogle Scholar
  18. 18.
    Lozinsky VI (2002) Cryogels on the basis of natural and synthetic polymers: preparation, properties and application. Russ Chem Rev 71:489–511CrossRefGoogle Scholar
  19. 19.
    Dinu MV, Perju MM, Drăgan ES (2011) Porous semi-interpenetrating hydrogel networks based on dextran and polyacrylamide with superfast responsiveness. Macromol Chem Phys 212:240–251CrossRefGoogle Scholar
  20. 20.
    Wu J, Zhao Q, Sun J, Zhou Q (2012) Preparation of poly(ethylene glycol) aligned porous cryogels using a unidirectional freezing technique. Soft Matter 8:3620–3626CrossRefGoogle Scholar
  21. 21.
    Dinu MV, Ozmen MM, Drăgan ES, Okay O (2007) Freezing as a path to build macroporous structures: superfast responsive polyacrylamide hydrogels. Polymer 48:195–204CrossRefGoogle Scholar
  22. 22.
    Drăgan ES, Lazar MM, Dinu MV, Doroftei F (2012) Macroporous composite IPN hydrogels based on poly(acrylamide) and chitosan with tuned swelling and sorption of cationic dyes. Chem Eng J 204–206:198–209CrossRefGoogle Scholar
  23. 23.
    Drăgan ES, Apopei DF (2013) Multiresponsive macroporous semi-IPN composite hydrogels based on native or anionically modified potato starch. Carbohydr Polym 92:23–32CrossRefGoogle Scholar
  24. 24.
    Artyukhov AA, Shtilman MI, Kuskov AN, Fomina AP, Lisovyy DE, Golunova AS, Tsatsakis AM (2011) Macroporous polymeric hydrogels formed from acrylate modified polyvinyl alcohol macromers. J Polym Res 18:667–673CrossRefGoogle Scholar
  25. 25.
    Lozinsky VL, Plieva FM, Galaev IY, Mattiasson B (2001) The potential of polymeric cryogels in bioseparation. Bioseparation 10:163–188CrossRefGoogle Scholar
  26. 26.
    Dispinar T, Van Camp W, De Cock LJ, De Geest BG, Du Prez FE (2012) Redox-responsive degradable PEG cryogels as potential cell scaffolds in tissue engineering. Macromol Biosci 12:383–394CrossRefGoogle Scholar
  27. 27.
    Dinu MV, Perju MM, Drăgan ES (2011) Composite IPN ionic hydrogels based on polyacrylamide and dextran sulfate. React Funct Polym 71:881–890CrossRefGoogle Scholar
  28. 28.
    Dinu MV, Schwarz S, Dinu IA, Drăgan ES (2012) The rheological behavior of ionic semi-IPN composite hydrogels based on polyacrylamide and dextran sulfate. Colloid Polym Sci 290:1647–1657CrossRefGoogle Scholar
  29. 29.
    Apopei DF, Dinu MV, Trochimczuk AW, Dragan ES (2012) Sorption isotherms of heavy metal ions onto semi-IPN cryogels based on polyacrylamide and anionically modified potatoes starch. Ind Eng Chem Res 51:10462–10471CrossRefGoogle Scholar
  30. 30.
    Perju MM, Dinu MV, Drăgan ES (2012) Sorption of Methylene Blue onto ionic composite hydrogels based on polyacrylamide and dextran sulfate: Kinetics, isotherms and thermodynamics. Sep Sci Technol 47:1322–1333CrossRefGoogle Scholar
  31. 31.
    Rodriguez-Felix DE, Perez-Martinez CJ, Castillo-Ortega MM, Perez-Tello M, Romero-Garcia J, Ledezma-Perez AS, Del Castillo-Castro T, Rodriguez-Felix F (2012) pH- and temperature-sensitive semi-interpenetrating network hydrogels composed of poly(acrylamide) and poly(γ-glutamic acid) as amoxicillin controlled-release system. Polym Bull 68:197–207CrossRefGoogle Scholar
  32. 32.
    Drăgan ES, Dinu MV, Timpu D (2010) Preparation and characterization of novel composites based on chitosan and clinoptilolite with enhanced adsorption properties for Cu2+. Bioresour Technol 101:812–817CrossRefGoogle Scholar
  33. 33.
    Aranaz I, Mengibar M, Harris R, Paños I, Miralles B, Acosta N, Galed G, Heras Á (2009) Functional characterization of chitin and chitosan. Curr Chem Biol 3:203–230Google Scholar
  34. 34.
    Chauhan GS, Chauhan S, Sen U, Garg D (2009) Synthesis and characterization of acrylamide and 2-hydroxyethyl methacrylate hydrogels for use in metal ion uptake studies. Desalination 243:95–108CrossRefGoogle Scholar
  35. 35.
    Podkocielna B, Bartnicki A, Gawdzik B (2012) New crosslinked hydrogels derivatives of 2-hydroxyethyl methacrylate: synthesis, modifications and properties. eXPRESS Polym Lett 6:759–771CrossRefGoogle Scholar
  36. 36.
    Gutiérrez MC, Ferrer ML, del Monte F (2008) Ice-templated materials: sophisticated structures exhibiting enhanced functionalities obtained after unidirectional freezing and ice-segregation-induced self-assembly. Chem Mater 20:634–648CrossRefGoogle Scholar
  37. 37.
    Dinu MV, Prádny M, Drăgan ES, Michálek J (2013) Ice-templated hydrogels based on chitosan with tailored porous morphology. Carbohydr Polym 94:170–178CrossRefGoogle Scholar
  38. 38.
    Dogu Y, Okay O (2006) Swelling-deswelling kinetics of poly(N-isopropylacrylamide) hydrogels formed in PEG solutions. J Appl Polym Sci 99:37–44CrossRefGoogle Scholar
  39. 39.
    Zhao Q, Sun J, Ling Q, Zhou Q (2009) Synthesis of macroporous thermosensitive hydrogels: a novel method of controlling pore size. Langmuir 25:3249–3254CrossRefGoogle Scholar
  40. 40.
    Nistor MT, Chiriac AP, Nita LE, Vasile C, Bercea M (2013) Semi-interpenetrated polymer networks of hyaluronic acid modified with poly(aspartic acid). J Polym Res 20:86CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2013

Authors and Affiliations

  • Maria Valentina Dinu
    • 1
  • Martin Přádný
    • 2
  • Ecaterina Stela Drăgan
    • 1
  • Jiří Michálek
    • 2
  1. 1.„Petru Poni“ Institute of Macromolecular Chemistry of Romanian AcademyIasiRomania
  2. 2.Institute of Macromolecular ChemistryAcademy of Sciences of the Czech RepublicPrague 6Czech Republic

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