COMPARATIVE STUDY OF CELLULOSE AND ITS NITROGENATED DERIVATIVES

Volume 1, Issue 1, October 2016     |     PP. 1-15      |     PDF (671 K)    |     Pub. Date: October 13, 2016
DOI:    569 Downloads     7553 Views  

Author(s)

Michael Ioelovich, Designer Energy Ltd, 2 Bergman Str., Rehovot 7670504 (ISRAEL)

Abstract
In this paper structural characteristics and properties of cellulose and its nitrogenated derivatives – chitin and chitosan, have been studied. The obtained results showed that substitution of hydroxyl group in C2 of anhydroglucose unit of cellulose on nitrogen-containing groups leads to transformation of crystalline unit cell, increasing of interplanar distances and cell volume, and reduction of packing density of crystallites. Since cellulose contains lesser amounts of atoms C and H, the combustion of this polysaccharide requires lower oxygen amount than of nitrogenated derivatives; as a result, the exothermic value of combustion enthalpy increases when going from cellulose to chitosan and chitin. Study of hydrophilic properties revealed that wetting enthalpy and sorption of water vapor depend on the degree of amorphicity (Y) of the biopolymers. At the same Y-value the hydrophilic properties of cellulose and chitosan containing hydroxyl or amino groups were higher than of chitin containing hydrophobic acetyl groups. In the sequence: cellulose-chitin-chitosan, an increase in hydrolyzability of the biopolymer samples was observed. Furthermore, three methods for determination of degree of crystallinity and amorphicity such as X-ray, calorimetry and sorption, were discussed.

Keywords
Cellulose, Chitosan, Chitin, Structure, Crystallinity, Amorphicity, Thermodynamic properties, Hydrophility, Hydrolyzability

Cite this paper
Michael Ioelovich, COMPARATIVE STUDY OF CELLULOSE AND ITS NITROGENATED DERIVATIVES , SCIREA Journal of Chemistry. Volume 1, Issue 1, October 2016 | PP. 1-15.

References

[ 1 ] Klemm, D., Heublein, B., Fink, H.-P., Bohn, A. Cellulose: fascinating biopolymer and sustainable raw material. Angew. Chem. 2005, 44, 2-37.
[ 2 ] Roberts, G. Chitin Chemistry; MacMillan: London, 1998.
[ 3 ] Ioelovich, M. Recent findings and the energetic potential of plant biomass as a renewable source of biofuels – a review. Bioresources 2015, 10, 1879-1914.
[ 4 ] Ioelovich, M. Cellulose Nanostructured Natural Polymer; LAP: Saarbrücken, 2014.
[ 5 ] Younes, I., and Rinaudo, M. Chitin and chitosan preparation from marine sources: structure, properties and applications. Mar. Drugs 2015, 13, 1133-1174.
[ 6 ] Zelencova, L., Erdogan, S., Baran, T, Kaya, M. Chitin extraction and chitosan production from chilopoda (Scolopendra cingulata) with identification of physicochemical properties. J. Polym. Sci. Ser. A. 2015, 57, 437- 444.
[ 7 ] Aranaz, I., Mengibar, M., Harris, R., Panos, I., Miralles, B., Acosta, N. Functional characterization of chitin and chitosan. Current Chem. Biol. 2009, 3, 203-230.
[ 8 ] Rinaudo, M. Chitin and chitosan: properties and applications. Progr. Polym. Sci. 2006, 31, 603-632.
[ 9 ] Rudall, K.M., and Kenchington W. The α-chitin system. Biol. Rev. 1973, 48, 597-633.
[ 10 ] Gardner, K.H., and Blackwell, J. Refinement of the structure of β-chitin. Biopolymers 1975, 14, 1581-1595.
[ 11 ] Al Sagheer, F.A. Al-Sughayer, M.A., Muslim, S., Elsabee, M.Z. Extraction and characterization of chitin and chitosan from marine sources in Arabian Gulf. Carbohyd. Polym. 2009, 77, 410-419.
[ 12 ] Ioelovich, M., Leykin, A., Figovsky, O. Study of cellulose paracrystallinity. Bioresources 2010, 5, 1393-1407.
[ 13 ] Ioelovich, M. Structure and physicochemical properties of nitrogenated derivatives of cellulose. Amer. J. Biosci. 2014, 2, 6-12.
[ 14 ] Ioelovich, M. Study of thermodynamic stability of various allomorphs of cellulose. J. Basic Appl. Res. Int. 2016, 16, 96-103.
[ 15 ] Ioelovich, M. Physicochemical methods for determination of cellulose crystallinity. ChemXpress 2016, 9, 245-251.
[ 16 ] Ioelovich, M., and Leykin, A. Study of sorption properties of cellulose and its derivatives. Bioresources 2011, 6, 178-195.
[ 17 ] Slonimsky, G.L., Askadsky, A.A., Kitaigorodsky, A.I. About packing of macromolecules in polymers. J. Polym Sci. Part A. 1970, 12, 494-506.
[ 18 ] Krässig, H. Cellulose: Structure, Accessibility and Reactivity; Gordon and Breach Publ.: Yverdon, 1993.
[ 19 ] Cartier, N, Domard, A, Chanzy, H. Single crystals of chitosan. Int. J. Biol. Macromol. 1990, 12, 289-294.
[ 20 ] Mazeau, K., William, W.T., Chanzy, H. Molecular and crystal structure of a high-temperature polymorph of chitosan from electron diffraction data. Macromolecul. 1994, 27, 7606-7612.
[ 21 ] Nishino, T., Matsui, R., Nakamae, K. Elastic modulus of the crystalline regions of chitin and chitosan. J. Polym. Sci. Part B. 1999, 37, 1191-1196.
[ 22 ] Dong, Y., Ruan, Y., Wang, H., Zhao, Y., Bi, D. Studies on glass transition temperature of chitosan with four techniques. J. Appl. Polym. Sci. 2004, 93, 1553-1558.
[ 23 ] Uryash,V.F., Kokurina, N.Y., Larina, V.N., Varlamov, P.V., Ilyina, A.V., Grishatova, N.V., Gruzdeva, A.E. Effect of acid hydrolysis on specific heat capacity and physical translations of chitin and chitosan. News of NN University 2007, 3, 98-104.
[ 24 ] Van Krevelen, D.W. Properties of polymers and correlation with chemical structure; Elsevier Publ.: Amsterdam, 1972.