Physical Properties of Chitosan Films Obtained after Neutralization of Polycation by Slow Drip Method
Affiliation(s)
Basic Sciences Department, Faculty of Animal Science and Food Engineering, University of S?o Paulo, Pirassununga, S?o Paulo, Brazil .
Basic Sciences Department, Faculty of Animal Science and Food Engineering, University of S?o Paulo, Pirassununga, S?o Paulo, Brazil .
ABSTRACT
The development of new materials from biodegradable constituents is enticing for applications in bioelectronics and biomedicine, due to their considerable durability, versatility and biodegrada-bility. The present work aims to determine the chemical and physical properties of chitosan membranes after neutralization of the polycation solution. This work was divided into two stages: solubilization and neutralization. In the first stage, the chitosan was solubilized with three different concentrations of acetic acid (1%, 0.8% and 0.5%) in order to evaluate whether the acid affected the physical-chemical properties of the films. In the second stage, the chitosan polycation was neutralized with two strong bases (NaOH and KOH) using three different molar concentrations, by the slow drip method for obtaining films with pH values close to neutrality. The characterization of the membranes obtained from casting method showed that the different concentrations of acetic acid did not affect the physical-chemical properties of the films. In contrast, the neutralization process did affect their properties, and in particular, different behaviors were observed depending on the type of base used for neutralization. More ductile and plasticity were obtained in the films when the polycation was neutralized with KOH, whereas the films neutralized with NaOH exhibited a more fragile behavior.
The development of new materials from biodegradable constituents is enticing for applications in bioelectronics and biomedicine, due to their considerable durability, versatility and biodegrada-bility. The present work aims to determine the chemical and physical properties of chitosan membranes after neutralization of the polycation solution. This work was divided into two stages: solubilization and neutralization. In the first stage, the chitosan was solubilized with three different concentrations of acetic acid (1%, 0.8% and 0.5%) in order to evaluate whether the acid affected the physical-chemical properties of the films. In the second stage, the chitosan polycation was neutralized with two strong bases (NaOH and KOH) using three different molar concentrations, by the slow drip method for obtaining films with pH values close to neutrality. The characterization of the membranes obtained from casting method showed that the different concentrations of acetic acid did not affect the physical-chemical properties of the films. In contrast, the neutralization process did affect their properties, and in particular, different behaviors were observed depending on the type of base used for neutralization. More ductile and plasticity were obtained in the films when the polycation was neutralized with KOH, whereas the films neutralized with NaOH exhibited a more fragile behavior.
Cite this paper
Llanos, J. , Vercik, L. and Vercik, A. (2015) Physical Properties of Chitosan Films Obtained after Neutralization of Polycation by Slow Drip Method. Journal of Biomaterials and Nanobiotechnology, 6, 276-291. doi: 10.4236/jbnb.2015.64026.
Llanos, J. , Vercik, L. and Vercik, A. (2015) Physical Properties of Chitosan Films Obtained after Neutralization of Polycation by Slow Drip Method. Journal of Biomaterials and Nanobiotechnology, 6, 276-291. doi: 10.4236/jbnb.2015.64026.
References
[1] Akkilic, K., Uzun, I. and Kilicoglu, T. (2007) The Calculation of Electronic Properties of an Ag/chitosan/n-Si Schottky Barrier Diode. Synthetic Metals, 157, 297-302.
http://dx.doi.org/10.1016/j.synthmet.2007.03.009 [2] Croisier, F. and Jérome C. (2013) Chitosan-Based Biomaterials for Tissue Engineering. European Polymer Journal, 49, 780-792.
http://dx.doi.org/10.1016/j.eurpolymj.2012.12.009 [3] Giri, T.K., Thakur, A., Alexander, A., Badwaik, H. and Tripathi, D.K. (2012) Modified Chitosan Hydrogels as Drug Delivery and Tissue Engineering Systems: Present Status and Applications. Acta Pharmaceutica Sinica B, 2, 439-449.
http://dx.doi.org/10.1016/j.apsb.2012.07.004 [4] Park, J.H., Saravanakumar, G., Kim, K. and Kwon, I.C. (2010) Targeted Delivery of Low Molecular Drugs Using Chitosan and Its Derivatives. Advanced Drug Delivery Reviews, 62, 28-41.
http://dx.doi.org/10.1016/j.addr.2009.10.003 [5] Bernkop-Schnürch, A. and Dünnhaupt, S. (2012) Chitosan-Based Drug Delivery Systems. European Journal of Pharmaceutics and Biopharmaceutics, 81, 463-469.
http://dx.doi.org/10.1016/j.ejpb.2012.04.007 [6] Rinaudo, M. (2006) Chitin and Chitosan: Properties and Applications. Progress in Polymer Science, 31, 603-632.
http://dx.doi.org/10.1016/j.progpolymsci.2006.06.001 [7] Schmidt, T.F., Caseli, L., dos Santos, D.S. and Oliveira, O.N. (2009) Enzyme Activity of Horseradish Peroxidase Immobilized in Chitosan Matrices in Alternated Layers. Materials Science and Engineering: C, 29, 1889-1892.
http://dx.doi.org/10.1016/j.msec.2009.02.020 [8] Valencia, G.A. (2013) Transporte eletronico em biofilmes nanoestruturados para biossensores a base de enzimas. Universidade de Sao Paulo, 122.
http://www.teses.usp.br/teses/disponiveis/74/74132/tde-10072013-095546/pt-br.php [9] Noriega, S.E. and Subramanian, A. (2011) Consequences of Neutralization on the Proliferation and Cytoskeletal Organization of Chondrocytes on Chitosan-Based Matrices. International Journal of Carbohydrate Chemistry, 2011, Article ID: 809743.
http://dx.doi.org/10.1155/2011/809743 [10] Tanuma, H., Saito, T., Nishikawa, K., Dong, T., Yazawa, K. and Inoue, Y. (2010) Preparation and Characterization of PEG-Cross-Linked Chitosan Hydrogel Films with Controllable Swelling and Enzymatic Degradation Behavior. Carbohydrate Polymers, 80, 260-265.
http://dx.doi.org/10.1016/j.carbpol.2009.11.022 [11] Boeris, V., Micheletto, Y., Lionzo, M., Da Silveira, N.P. and Picó, G. (2011) Interaction Behavior between Chitosan and Pepsin. Carbohydrate Polymers, 84, 459-464.
http://dx.doi.org/10.1016/j.carbpol.2010.12.008 [12] Vicentini, N.M., Dupuy, N., Leitzelman, M., Cereda, M.P. and Sobral, P.J.A. (2005) Prediction of Cassava Starch Edible Film Properties by Chemometric Analysis of Infrared Spectra. Spectroscopy Letters, 38, 749-767.
http://dx.doi.org/10.1080/00387010500316080 [13] Bonilla, J., Fortunati, E., Atarés, L., Chiralt, A. and Kenny, J.M. (2014) Physical, Structural and Antimicrobial Properties of Poly Vinyl Alcohol-Chitosan Biodegradable Films. Food Hydrocolloids, 35, 463-470.
http://dx.doi.org/10.1016/j.foodhyd.2013.07.002 [14] Abdelrazek, E.M., Elashmawi, I.S. and Labeeb, S. (2010) Chitosan Filler Effects on the Experimental Characterization, Spectroscopic Investigation and Thermal Studies of PVA/PVP Blend Films. Physica B: Condensed Matter, 405, 2021- 2027.
http://dx.doi.org/10.1016/j.physb.2010.01.095 [15] Singh, J. and Dutta, P.K. (2009) Preparation, Circular Di-chroism Induced Helical Conformation and Optical Property of Chitosan Acid Salt Complexes for Biomedical Applications. International Journal of Biological Macromolecules, 45, 384-392.
http://dx.doi.org/10.1016/j.ijbiomac.2009.07.004 [16] He, Q., Ao, Q., Gong, Y. and Zhang, X. (2011) Preparation of Chitosan Films Using Different Neutralizing Solutions to Improve Endothelial Cell Compatibility. Journal of Materials Science: Materials in Medicine, 22, 2791-2802.
http://dx.doi.org/10.1007/s10856-011-4444-y [17] Pucic, I. and Jurkin, T. (2012) FTIR Assessment of Poly(ethylene oxide) Irradiated in Solid State, Melt and Aqeuous Solution. Radiation Physics and Chemistry, 81, 1426-1429.
http://dx.doi.org/10.1016/j.radphyschem.2011.12.005 [18] Wan, Y., Creber, K.A.M., Peppley, B. and Tam Bui, V. (2006) Chitosan-Based Solid Electrolyte Composite Membranes: I. Preparation and Characterization. Journal of Membrane Science, 280, 666-674.
http://dx.doi.org/10.1016/j.memsci.2006.02.024 [19] Lima, C.G.A., de Oliveira, R.S., Figueiró, S.D., Wehmann, C.F., Góes, J.C. and Sombra, A.S.B. (2006) DC Conductivity and Dielectric Permittivity of Collagen-Chitosan Films. Materials Chemistry and Physics, 99, 284-288.
http://dx.doi.org/10.1016/j.matchemphys.2005.10.027 [20] Zong, Z., Kimura, Y., Takahashi, M. and Yamane, H. (2000) Characterization of Chemical and Solid State Structures of Acylated Chitosans. Polymer, 41, 899-906.
http://dx.doi.org/10.1016/S0032-3861(99)00270-0 [21] Thakhiew, W., Devahastin, S. and Soponronnarit, S. (2013) Physical and Mechanical Properties of Chitosan Films as Affected by Drying Methods and Addition of Antimicrobial Agent. Journal of Food Engineering, 119, 140-149.
http://dx.doi.org/10.1016/j.jfoodeng.2013.05.020 [22] Khoshgozaran-Abras, S., Azizi, M.H., Hamidy, Z. and Bagheripoor-Fallah, N. (2012) Mechanical, Physicochemical and Color Properties of Chitosan Based-Films as a Function of Aloe Vera Gel Incorporation. Carbohydrate Polymers, 87, 2058-2062.
http://dx.doi.org/10.1016/j.carbpol.2011.10.020 [23] Campos, M.G.N., Grosso, C.R.F., Cárdenas, G. and Mei, L.H.I. (2005) Effects of Neutralization Process on Preparation and Characterization of Chitosan Membranes for Wound Dressing. Macromolecular Symposia, 229, 253-257.
http://dx.doi.org/10.1002/masy.200551131 [24] Tasselli, F., Mirmohseni, A., Seyed Dorraji, M.S. and Figoli, A. (2013) Mechanical, Swelling and Adsorptive Properties of Dry-Wet Spun Chitosan Hollow Fibers Crosslinked with Glutaraldehyde. Reactive and Functional Polymers, 73, 218-223.
http://dx.doi.org/10.1016/j.reactfunctpolym.2012.08.007 [25] Bonilla, J., Atarés, L., Vargas, M. and Chiralt, A. (2013) Properties of Wheat Starch Film-Forming Dispersions and Films as Affected by Chitosan Addition. Journal of Food Engineering, 114, 303-312.
http://dx.doi.org/10.1016/j.jfoodeng.2012.08.005 [26] Wan, Y., Creber, K.A.M., Peppley, B. and Bui, V.T. (2006) Chitosan-Based Electrolyte Composite Membranes II. Mechanical Properties and Ionic Conductivity. Journal of Membrane Science, 284, 331-338.
http://dx.doi.org/10.1016/j.memsci.2006.07.046 [27] Azevedo, E.P., Saldanha, T.D.P., Navarro, M.V.M., Medeiros, A.C., Ginani, M.F. and Raffin, F.N. (2006) Mechanical Properties and Release Studies of Chitosan Films Impregnated with Silver Sulfadiazine. Journal of Applied Polymer Science, 102, 3462-3470.
http://dx.doi.org/10.1002/app.24537
[1] Akkilic, K., Uzun, I. and Kilicoglu, T. (2007) The Calculation of Electronic Properties of an Ag/chitosan/n-Si Schottky Barrier Diode. Synthetic Metals, 157, 297-302.
http://dx.doi.org/10.1016/j.synthmet.2007.03.009 [2] Croisier, F. and Jérome C. (2013) Chitosan-Based Biomaterials for Tissue Engineering. European Polymer Journal, 49, 780-792.
http://dx.doi.org/10.1016/j.eurpolymj.2012.12.009 [3] Giri, T.K., Thakur, A., Alexander, A., Badwaik, H. and Tripathi, D.K. (2012) Modified Chitosan Hydrogels as Drug Delivery and Tissue Engineering Systems: Present Status and Applications. Acta Pharmaceutica Sinica B, 2, 439-449.
http://dx.doi.org/10.1016/j.apsb.2012.07.004 [4] Park, J.H., Saravanakumar, G., Kim, K. and Kwon, I.C. (2010) Targeted Delivery of Low Molecular Drugs Using Chitosan and Its Derivatives. Advanced Drug Delivery Reviews, 62, 28-41.
http://dx.doi.org/10.1016/j.addr.2009.10.003 [5] Bernkop-Schnürch, A. and Dünnhaupt, S. (2012) Chitosan-Based Drug Delivery Systems. European Journal of Pharmaceutics and Biopharmaceutics, 81, 463-469.
http://dx.doi.org/10.1016/j.ejpb.2012.04.007 [6] Rinaudo, M. (2006) Chitin and Chitosan: Properties and Applications. Progress in Polymer Science, 31, 603-632.
http://dx.doi.org/10.1016/j.progpolymsci.2006.06.001 [7] Schmidt, T.F., Caseli, L., dos Santos, D.S. and Oliveira, O.N. (2009) Enzyme Activity of Horseradish Peroxidase Immobilized in Chitosan Matrices in Alternated Layers. Materials Science and Engineering: C, 29, 1889-1892.
http://dx.doi.org/10.1016/j.msec.2009.02.020 [8] Valencia, G.A. (2013) Transporte eletronico em biofilmes nanoestruturados para biossensores a base de enzimas. Universidade de Sao Paulo, 122.
http://www.teses.usp.br/teses/disponiveis/74/74132/tde-10072013-095546/pt-br.php [9] Noriega, S.E. and Subramanian, A. (2011) Consequences of Neutralization on the Proliferation and Cytoskeletal Organization of Chondrocytes on Chitosan-Based Matrices. International Journal of Carbohydrate Chemistry, 2011, Article ID: 809743.
http://dx.doi.org/10.1155/2011/809743 [10] Tanuma, H., Saito, T., Nishikawa, K., Dong, T., Yazawa, K. and Inoue, Y. (2010) Preparation and Characterization of PEG-Cross-Linked Chitosan Hydrogel Films with Controllable Swelling and Enzymatic Degradation Behavior. Carbohydrate Polymers, 80, 260-265.
http://dx.doi.org/10.1016/j.carbpol.2009.11.022 [11] Boeris, V., Micheletto, Y., Lionzo, M., Da Silveira, N.P. and Picó, G. (2011) Interaction Behavior between Chitosan and Pepsin. Carbohydrate Polymers, 84, 459-464.
http://dx.doi.org/10.1016/j.carbpol.2010.12.008 [12] Vicentini, N.M., Dupuy, N., Leitzelman, M., Cereda, M.P. and Sobral, P.J.A. (2005) Prediction of Cassava Starch Edible Film Properties by Chemometric Analysis of Infrared Spectra. Spectroscopy Letters, 38, 749-767.
http://dx.doi.org/10.1080/00387010500316080 [13] Bonilla, J., Fortunati, E., Atarés, L., Chiralt, A. and Kenny, J.M. (2014) Physical, Structural and Antimicrobial Properties of Poly Vinyl Alcohol-Chitosan Biodegradable Films. Food Hydrocolloids, 35, 463-470.
http://dx.doi.org/10.1016/j.foodhyd.2013.07.002 [14] Abdelrazek, E.M., Elashmawi, I.S. and Labeeb, S. (2010) Chitosan Filler Effects on the Experimental Characterization, Spectroscopic Investigation and Thermal Studies of PVA/PVP Blend Films. Physica B: Condensed Matter, 405, 2021- 2027.
http://dx.doi.org/10.1016/j.physb.2010.01.095 [15] Singh, J. and Dutta, P.K. (2009) Preparation, Circular Di-chroism Induced Helical Conformation and Optical Property of Chitosan Acid Salt Complexes for Biomedical Applications. International Journal of Biological Macromolecules, 45, 384-392.
http://dx.doi.org/10.1016/j.ijbiomac.2009.07.004 [16] He, Q., Ao, Q., Gong, Y. and Zhang, X. (2011) Preparation of Chitosan Films Using Different Neutralizing Solutions to Improve Endothelial Cell Compatibility. Journal of Materials Science: Materials in Medicine, 22, 2791-2802.
http://dx.doi.org/10.1007/s10856-011-4444-y [17] Pucic, I. and Jurkin, T. (2012) FTIR Assessment of Poly(ethylene oxide) Irradiated in Solid State, Melt and Aqeuous Solution. Radiation Physics and Chemistry, 81, 1426-1429.
http://dx.doi.org/10.1016/j.radphyschem.2011.12.005 [18] Wan, Y., Creber, K.A.M., Peppley, B. and Tam Bui, V. (2006) Chitosan-Based Solid Electrolyte Composite Membranes: I. Preparation and Characterization. Journal of Membrane Science, 280, 666-674.
http://dx.doi.org/10.1016/j.memsci.2006.02.024 [19] Lima, C.G.A., de Oliveira, R.S., Figueiró, S.D., Wehmann, C.F., Góes, J.C. and Sombra, A.S.B. (2006) DC Conductivity and Dielectric Permittivity of Collagen-Chitosan Films. Materials Chemistry and Physics, 99, 284-288.
http://dx.doi.org/10.1016/j.matchemphys.2005.10.027 [20] Zong, Z., Kimura, Y., Takahashi, M. and Yamane, H. (2000) Characterization of Chemical and Solid State Structures of Acylated Chitosans. Polymer, 41, 899-906.
http://dx.doi.org/10.1016/S0032-3861(99)00270-0 [21] Thakhiew, W., Devahastin, S. and Soponronnarit, S. (2013) Physical and Mechanical Properties of Chitosan Films as Affected by Drying Methods and Addition of Antimicrobial Agent. Journal of Food Engineering, 119, 140-149.
http://dx.doi.org/10.1016/j.jfoodeng.2013.05.020 [22] Khoshgozaran-Abras, S., Azizi, M.H., Hamidy, Z. and Bagheripoor-Fallah, N. (2012) Mechanical, Physicochemical and Color Properties of Chitosan Based-Films as a Function of Aloe Vera Gel Incorporation. Carbohydrate Polymers, 87, 2058-2062.
http://dx.doi.org/10.1016/j.carbpol.2011.10.020 [23] Campos, M.G.N., Grosso, C.R.F., Cárdenas, G. and Mei, L.H.I. (2005) Effects of Neutralization Process on Preparation and Characterization of Chitosan Membranes for Wound Dressing. Macromolecular Symposia, 229, 253-257.
http://dx.doi.org/10.1002/masy.200551131 [24] Tasselli, F., Mirmohseni, A., Seyed Dorraji, M.S. and Figoli, A. (2013) Mechanical, Swelling and Adsorptive Properties of Dry-Wet Spun Chitosan Hollow Fibers Crosslinked with Glutaraldehyde. Reactive and Functional Polymers, 73, 218-223.
http://dx.doi.org/10.1016/j.reactfunctpolym.2012.08.007 [25] Bonilla, J., Atarés, L., Vargas, M. and Chiralt, A. (2013) Properties of Wheat Starch Film-Forming Dispersions and Films as Affected by Chitosan Addition. Journal of Food Engineering, 114, 303-312.
http://dx.doi.org/10.1016/j.jfoodeng.2012.08.005 [26] Wan, Y., Creber, K.A.M., Peppley, B. and Bui, V.T. (2006) Chitosan-Based Electrolyte Composite Membranes II. Mechanical Properties and Ionic Conductivity. Journal of Membrane Science, 284, 331-338.
http://dx.doi.org/10.1016/j.memsci.2006.07.046 [27] Azevedo, E.P., Saldanha, T.D.P., Navarro, M.V.M., Medeiros, A.C., Ginani, M.F. and Raffin, F.N. (2006) Mechanical Properties and Release Studies of Chitosan Films Impregnated with Silver Sulfadiazine. Journal of Applied Polymer Science, 102, 3462-3470.
http://dx.doi.org/10.1002/app.24537