Interpenetrated Chitosan-Poly(Acrylic Acid-Co-Acrylamide) Hydrogels. Synthesis, Characterization and Sustained Protein Release Studies


Interpenetrated polymer networks of chitosan (CHI), polyacrylic acid (PAA) and polyacrylamide (PAM) were prepared by free radical polymerization. These hydrogels were either washed with double distilled water (CHI/PAA/PAM) A or hydrolyzed with 1M sodium hydroxide (NaOH), (CHI/PAA/PAM) S. Both types of hydrogels were characterized by infrared spectroscopy, microstructural techniques and compressive mechanical testing. Finally, hydrogels were loaded with bovine serum albumin (BSA) and release followed at different pHs. Infrared spectra analysis showed correspondence between hydrogels and monomer feed compositions. Hydrolyzed hydrogels, had increased water content and pH swelling dependence. Compression modulus of swelled hydrolyzed hydrogels decreased with increasing equilibrium water content. Higher BSA loadings were achieved on hydrolyzed hydrogels due to their high water content and porosity. Protein release from hydrogels was low (≤ 20% after 10 hours) at pH 1.2, but sustained release was observed at pH 6.8 and 7.4. The integrity of the protein released at 6.8 and 7.4 by hydrolyzed hydrogels was unaffected. The hydrogles showed no cytotoxic effects on human skin dermal fibroblasts as determined by MTT assay except for two compositions of (CHI/PAA/PAM) A samples, which after seven days presented a viability lower than 80% respect to the control.

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M. Povea, W. Monal, J. Cauich-Rodríguez, A. Pat, N. Rivero and C. Covas, "Interpenetrated Chitosan-Poly(Acrylic Acid-Co-Acrylamide) Hydrogels. Synthesis, Characterization and Sustained Protein Release Studies," Materials Sciences and Applications, Vol. 2 No. 6, 2011, pp. 509-520. doi: 10.4236/msa.2011.26069.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] A. Singh, S. S. Narvi, P. K. Dutta and N. D. Pandey, “External stimuli response on a novel chitosan hydrogel crosslinked with formaldehyde,” Bulletin of Materials Science, Vol. 29, No. 3, June 2006, pp. 233-238.
[2] C. C. Lin and K. Anseth, “PEG hydrogels for the controlled release of biomolecules in regenerative medicine.,”Pharmaceutical Research,Vol. 26, No. 3, March 2009, pp. 631-643.
[3] J. Kope?ek, “Hydrogel from soft contact lenses and implants to self-assembled nanomaterials,”Journal of Polymer Science Part A: Polymer Chemistry, Vol. 47, No. 22, November 2009, pp. 5929-5946.
[4] K. Murota, S. Sakamoto and K. Kudo, “Reversible immobilization of protein into hydrogel using designed coiled-coil peptides,” Chemistry Letters, Vol. 36, No. 11, September 2007, pp. 132-137.
[5] E. Fonseca, F. Campos, A. Pereira, R. Cerqueira, L. Guilherme, W. L. Vasconcelos, Z. I. Portela and H. Sander, “Synthesis and characterization of poly(vinyl alcohol) hydrogels and hybrids for rMPB70 protein adsorption,” Journal of Materials Research, Vol. 9, No. 2, June 2006, pp. 185-190.
[6] P. M. Torre, Y. Enobakhare, G. Torrado and S. Torrados, “Release of amoxicillin from polyionic complexs of chitosan and poly(acrylic acid), study of polymer/polymer and polymer/drug interactions within the network structure.,” Biomaterials, Vol. 24, No. 8, April 2003, pp. 1499-1509.
[7] L. I. Yang, J. S. Chu and J. A. Fix, “Colon-specific drug delivery: new approaches and in vitro/in vivo evaluation.,” International Journal of Pharmaceutics, Vol. 235, No. 1, March 2000, pp. 1 -15.
[8] Y. Qui and K. Park, “Environment-sensitive hydrogels for drug delivery,” Advanced Drug Delivery Reviews, Vol. 53, No. 3, December 2001, pp. 321-339.
[9] S. Torrado, P. Prada, M. Paloma and S. Torrado, “Chitosan-poly(acrylic) acid polyionic complex: in vivo study to demostrate prolonged gastric retention.,” Biomaterials., Vol. 25, No. 5, July 2003, pp. 917-923.
[10] S. Jeong, S. Jun and S. I. Kim, “Swelling behavior of interpenetrating polymer network hydrogels composed of poly(vinyl alcohol) and chitosan,” Reactive and Functional Polymers, Vol. 55, No. 1, February 2003, pp. 53- 59.
[11] A. Borzacchielo, L. Ambrosio, P. A. Netti, L. Nicolais, C. Peniche, A. Gallardo and J. S. Román, “Chitosan-based hydrogels: synthesis and characterization,” Journal of Materials Science: Materials in Medicine, Vol. 12, No. 10, May 2001, pp. 861-864.
[12] T. R. Singh, G. Indu, S. Reena and A. K. Nagpal, “Synthesis of Poly (Acrylamide-co-Acrylic Acid) based Superabsorbent Hydrogels: Study of Network Parameters and Swelling Behaviour “Polymer-Plastics Technology and Engineering Vol.46, No. 5, May 2007, pp. 481-488.
[13] A. Gemeinhart, A. Richard, Chen J, Park H and Park K, “pH-sensitivity of fast responsive superporous hydrogels “Journal of Biomaterials Science, Polymer Edition Vol. 11, No. 12, December 2000, pp. 1371-1380.
[14] Y. Shen, X. Zhang, J. Lu, A. Zhang, K. Chen and A. Li, “Effect of chemical composition on properties of pH-responsive poly(acrylamide-co-acrylic acid) microgels prepared by inverse microemulsion polymerization.,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 350, No. 1, October 2009, pp. 87-90.
[15] S. Duran, D. Olpan and O. Güven, “Synthesis and characterization of acrylamide–acrylic acid hydrogels and adsorption of some textile dyes.,” Nuclear Instruments and Methods in Physics Research Section B, Vol. 151, No. 1, May 1999, pp. 196-199.
[16] A. Li and A. Wang, “Synthesis and properties of clay-based superabsorbent composite,”European Polymer Journal, Vol. 41, No. 7, May 2005, pp. 1630-1637.
[17] A. Fiumefreddo and M. Utz, “Bulk streaming potential in poly(acrylic acid)/poly(acrylamide) hydrogels,” Macromolecules, Vol. 43, No. 13, January 2010, pp. 5814-5819.
[18] M. V. Risbud and R. R. Bhonde, “Polyacrylamide-chitosan hydrogel: In vitro biocompatibility and sustained antibiotic release studies,” Drug Delivery, Vol. 7, No. 2, January 2000, pp. 69-75.
[19] C. Peniche, W. Arguelles-Monal, N. Davidenko, R. Sastre, A. Gallardo and J. S. Roman, “Self-curing membranes of chitosan/PAA IPNs obtained by radical polymerization: preparation, characterization and interpolymer complexation,” Biomaterials, Vol. 20, No. 20, October 1999, pp. 1869-1878.
[20] M. Recillas, L. L. Silva, C. Peniche, F. M. Goycoolea, M. Rinaudo and W. M. Argüelles-Monal, “Thermo-responsive behavior of chitosan-g-Nisopropylacrylamide copolymer solutions,” Biomacromolecules, Vol. 10, No. 6, April 2009, pp. 1633-1641.
[21] A. Srivastava, D. K. Mishra and K. Behari, “Graft copolymerization of N-vinyl-2-pyrrolidone onto chitosan: Synthesis, characterization and study of physicochemical properties.,” Carbohydrate Polymers, Vol. 80, No. 3, May 2010, pp. 790-798.
[22] F. Long, Y. Chiun, H. Fa and H. Wen, “In vivo biocompatibility and degradability of a novel injectable chitosan-bead implant,” Biomaterials, Vol. 23, No. 1, January 2002, pp. 181-191.
[23] M. Rinaudo, “Chitin and chitosan: Chemistry, properties and applications,”Progress in Polymer Science Vol. 31, No. 7, January 2006, pp. 603-632.
[24] G. R. Mahdavinia, A. Pourjavadi, H. Hosseinzadeh and M. J. Zohuriaan, “Modified chitosan 4. Superabsorbent hydrogels from poly(acrylic acid-co-acrylamide) grafted chitosan with salt- and pH- responsiveness properties,” European Polymer Journal, Vol. 40, No. 7, July 2004, pp. 1399-1407.
[25] Bio-Rad protein assay kit manual. Bio-Rad Laboratories. Hercules, CA, Printed in USA, 1998.
[26] U. K. Laemmli, “Cleavage of structural proteins during the assembly of the head of bacteriophage T4,” Nature, Vol. 227, No., August 1970, pp. 680-685.
[27] H. Wan, R. L. Williams, P. J. Doherty and D. F. Williams, “The cytotoxicity evaluation of Kevlar and silicon carbide by MTT assay,” Journal of Materials Science: Materials in Medicine, Vol. 5, No. 6, December 1994, pp. 441-445.
[28] X. Z. Zhang, D. Q. Wu and C. Chu, “Synthesis, characterization and controlled drug release of thermosensitive IPN-PNIPAM hydrogels,” Biomaterials, Vol. 25, No. 17, August 2004, pp. 3793-3805.
[29] W. Argüelles-Monal and C. Peniche-Covas, “Study of the interpolyelectrolyte reaction between chitosan and carboxymethyl cellulose,” Makromol Chem, Rapid Commun, Vol. 9, No. 10, June 1988, pp. 693-697.
[30] M. Bocourt, N. Bada, W. Argüelles-Monal and C. Peniche, “Síntesis y caracterización de redes poliméricas interpenetradas de quitosana-poli(ácido acrílico-co-acrilamida),” Revista CENIC Ciencias Químicas, Vol. 40, No. 2, February 2009, pp. 81-88.
[31] H. Schott, “Swelling kinetics of polymers,”Journal of Macromolecular Science, Vol. 31, No. 1, March 1992, pp. 1-9.
[32] K. Sivadasan, P. Somasundaran and N. J. Turro, “Fluorescence and viscometry study of complexation of poly(acrylic acid) with poly(acrylamide) and hydrolysed poly(acrylamide),” Colloid Polymer Sci., Vol. 269, April 1991, pp. 131-113.
[33] C. L. Bell and N. A. Peppas, in Advances in Polymer Science 122, Biopolymer II, eds., N. A. Peppas and R. S. Langer, Springer-Verlag, Berlin, 1995, pp. 125-175.
[34] Q. Tang, S. X., Q. Li, J. Wu and J. Lin, “A simple route to interpenetrating network hydrogel with high mechanical strength,” Journal of Colloid Science, Vol. 339, No., July 2009, pp. 45-52.
[35] W. Gombotz and A. S. Hoffman, “Medicine and Pharmacy,” In: N. A. Peppas, Ed., Hydrogels in Medicine and Pharmacy, Vol. 1, T. A. Horbett, CRC Press, Florida, 1986, pp. 95-126.
[36] E. Karadag, D. Saraydin, H. Nursevin and O. Guven, “Adsorption of bovine serum albumin to acrylamide-itaconic acid hydrogels,” Polymers for Advanced Technologies, Vol. 5, No., April 1994, pp. 664-668.

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