Preparation of Chitosan Copper Complexes: Molecular Dynamic Studies of Chitosan and Chitosan Copper Complexes
Affiliation(s)
Biological Advanced Materials, Department of Physics, Faculty of Science, Mansoura University, Mansoura, Egypt.
Biological Advanced Materials, Department of Physics, Faculty of Science, Mansoura University, Mansoura, Egypt.
ABSTRACT
This work studied the effect of copper ions concentration chelated by functional groups in chitosan on its molecular dynamic. Chitosan Copper complexes prepared having different copper concentrations by the electrochemical oxidation technique in aqueous-acetic acid medium. It was carried out at constant voltage (2 volt.) at room temperature at different electro-oxidation time. The result of partial elemental analysis and XRD studies of chitosan copper complexes compared with chitosan confirmed that the percentage composition of the complexes were found to be depend on the time of electrolysis which is in good agreement with our previous work. Interpretation of the effect of copper ions concentration on molecular motion of chitosan studied using dielectric spectroscopy, the results showed that dielectric constant of chitosan is higher than that of chitosan copper complexes. This may be attributed to the relatively fast segmental motion of chitosan chain slowed down by complexation with copper ions of all complex samples. Calculated activation energy from Arrhenius variation showed increase in value with increasing the copper concentration and all in the range that required for ionic conduction. Temperature dependence part of dielectric parameters gives very useful representation in the glass transition temperature determination.
This work studied the effect of copper ions concentration chelated by functional groups in chitosan on its molecular dynamic. Chitosan Copper complexes prepared having different copper concentrations by the electrochemical oxidation technique in aqueous-acetic acid medium. It was carried out at constant voltage (2 volt.) at room temperature at different electro-oxidation time. The result of partial elemental analysis and XRD studies of chitosan copper complexes compared with chitosan confirmed that the percentage composition of the complexes were found to be depend on the time of electrolysis which is in good agreement with our previous work. Interpretation of the effect of copper ions concentration on molecular motion of chitosan studied using dielectric spectroscopy, the results showed that dielectric constant of chitosan is higher than that of chitosan copper complexes. This may be attributed to the relatively fast segmental motion of chitosan chain slowed down by complexation with copper ions of all complex samples. Calculated activation energy from Arrhenius variation showed increase in value with increasing the copper concentration and all in the range that required for ionic conduction. Temperature dependence part of dielectric parameters gives very useful representation in the glass transition temperature determination.
Cite this paper
ELmezayyen, A. and Reicha, F. (2015) Preparation of Chitosan Copper Complexes: Molecular Dynamic Studies of Chitosan and Chitosan Copper Complexes. Open Journal of Applied Sciences, 5, 415-427. doi: 10.4236/ojapps.2015.58041.
ELmezayyen, A. and Reicha, F. (2015) Preparation of Chitosan Copper Complexes: Molecular Dynamic Studies of Chitosan and Chitosan Copper Complexes. Open Journal of Applied Sciences, 5, 415-427. doi: 10.4236/ojapps.2015.58041.
References
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[1] Guibal, E. (2004) Interactions of Metal Ions with Chitosan-Based Sorbents: A Review. Separation Science and Technology, 38, 43-47.
http://dx.doi.org/10.1016/j.seppur.2003.10.004 [2] Juang, R., Tseng, R., Wu, F. and Lee, S.(1997) Adsorption Behavior of Reactive Dyes from Aqueous Solutions on Chitosan. Journal of Chemical Technology & Biotechnology, 70, 391-399.
http://dx.doi.org/10.1002/(SICI)1097-4660(199712)70:4<391::AID-JCTB792>3.0.CO;2-V [3] Vold, I., Varum,K., Guibal, E. and Smidsrod, O. (2003) Binding of Ions to Chitosan—Selectivity Studies. Carbohydrate Polymers, 54, 471-477.
http://dx.doi.org/10.1016/j.carbpol.2003.07.001 [4] Zheng, Y., Wang, Y., Zhang, W. and Du, M. (2006) Preparation of Chitosan—Copper Complexes and Their Antitumor Activity. Bioorganic & Medicinal Chemistry Letters, 16, 4127-4129. http://dx.doi.org/10.1016/j.bmcl.2006.04.077 [5] Coleman, N., Bishop, A., Booth, S. and Nicholoson, J. (2009) Ag+- and Zn2+-Exchange Kinetics and Antimicrobial Properties of 11Å Tobermorites. Journal of the European Ceramic Society, 29, 1109-1117. http://dx.doi.org/10.1016/j.jeurceramsoc.2008.08.015 [6] Reicha, F., Shebl, A., Badria, F. and EL-Asmy, A. (2012) Electrochemical Synthesis, Characterization and Biological Activity of Chitosan Metal Complexes. International Journal of Basic and Applied Chemical Sciences, 2, 7-22. [7] Webster, A., Halling, M. and Grant, D. (2007) Metal Complexation of Chitosan and Its Glutaraldehyde Cross-Linked Derivative. Carbohydrate Research, 342, 1189-1201.
http://dx.doi.org/10.1016/j.carres.2007.03.008 [8] Yin, X., Zhang, X., Lin, Q., Feng, Y. and Zhang, Q. (2004) Metal-Coordinating Controlled Oxidative Degradation of Chitosan and Antioxidant Activity of Chitosan-Metal Complex. ARKIVOC, 2004, 66-78. http://dx.doi.org/10.3998/ark.5550190.0005.910 [9] Trimukhe, K. and Varma, A.(2008) A Morphological Study of Heavy Metal Complexes of Chitosan and Crosslinkedchitosans by SEM and WAXRD. Carbohydrate Polymers, 71, 698-702. http://dx.doi.org/10.1016/j.carbpol.2007.07.010 [10] Ogawa, K. (1991) Effect of Heating and Aqueous Suspension of Chitosan on the Crystallinity and Polymorphs. Agricultural and Biological Chemistry, 55, 2375-2379.
http://dx.doi.org/10.1271/bbb1961.55.2375 [11] Schmuhl, R., Kreig, H. and Kiezer, K. (2001) Adsorption of Cu (II) and Cr (VI) Ions by Chitosan: Kinetics and Equilibrium Studies. Water, 27, 1-8. [12] Scott, A., Curtis, D. and Auritzenandj, A.D. (1962) Dielectric Properties of Semicrystalline Polychlorotrifluoroethylene. Journal of Research of the National Bureau of Standard, 66, 269-305. http://dx.doi.org/10.6028/jres.066A.028 [13] Qian, X., Gu, N., Cheng, Z., Yang, X., Wang, E. and Dong, S. (2001) Impedance Study of (PEO)10LiCIO4-Al2o3 Co- mpsite Polymer Electrolyte with Blocking Electrodes. Electrochimica Acta, 46, 1829-1836. http://dx.doi.org/10.1016/S0013-4686(00)00723-4 [14] Govindaraj, G., Baskaran, N., Shahi, K. and Monoravi, P. (1995) Preparation, Conductivity, Complex Permittivity and Electric Modulus in AgI-Ag2O-SeO3-MoO3. Solid State Ionics, 76, 47-55. http://dx.doi.org/10.1016/0167-2738(94)00204-6 [15] Howell, F.S., Bose, R.A., Macedo, P.B. and Moynihan, C.T. (1974) Electrical Relaxation in a Glass Forming Molten Salt. The Journal of Physical Chemistry, 78, 639-648. [16] Angell, C. (1990) Dynamic Process in Ionic Glass. Chemical Reviews, 90, 523-542.
http://dx.doi.org/10.1021/cr00101a006 [17] Pradhan, D., Choudhary, R. and Samantaray, B. (2008) Studies of Structural, Thermal and Electrical Behavior of Polymer Nanocomposite Electrolytes. Express Polymer Letters, 2, 630-638. [18] Yakuphanoglu, F. (2007) Electrical Conductivity and Electrical Modulus Properties of α, ω-Dihexylsexithiophene Organic Semiconductor. Physica B: Condensed Matter, 393, 139-142. http://dx.doi.org/10.1016/j.physb.2006.12.075 [19] Dutta, A., Sinha, T., Jena, P. and Adak, S. (2008) AC Conductivity and Dielectric Relaxation in Ionically Conducting Soda-Lime-Silicate Glasses. Journal of Non-Crystalline Solids, 354, 3952-3957. http://dx.doi.org/10.1016/j.jnoncrysol.2008.05.028 [20] Patro, L. and Hariharan, K. (2009) AC Conductivity and Scaling Studies of Polycrystalline SnF2. Materials Chemistry and Physics, 116, 81-87. [21] Patro, L. and Hariharan, K. (2009) Frequency Dependent Conduction Characteristics of Mechanochemically Synthesized NaSn2F5. Materials Science and Engineering: B, 162, 173-178. http://dx.doi.org/10.1016/j.mseb.2009.04.003 [22] Blythe, T. and Bloor, D. (1979) Electrical Properties of Polymers. 2nd Edition, Cambridge University Press, Cambridge. [23] Kwan, K. (2004) Dielectric Phenomena in Solids. Academic Press, New York.