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Tailormade Geometric Properties of Chitosan by Gamma Irradiation

Authors: F. Elashhab, L. Sheha, R. Fawzi Elsupikhe, A. E. A. Youssef, R. M. Sheltami, T. Alfazani


Chitosans, CSs, in solution are increasingly used in a range of geometric properties in various academic and industrial sectors, especially in the domain of pharmaceutical and biomedical engineering. In order to provide a tailoring guide of CSs to the applicants, gamma (γ)-irradiation technology and simple viscosity measurements have been used in this study. Accordingly, CS solid discs (0.5 cm thickness and 2.5 cm diameter) were exposed in air to Cobalt-60 (γ)-radiation, at room temperature and constant 50 kGy dose for different periods of exposer time (tγ). Diluted solutions of native and different irradiated CS were then prepared by dissolving 1.25 mg cm-3 of each polymer in 0.1 M NaCl/0.2 M CH3COOH. The single-concentration relative viscosity (ƞr) measurements were employed to obtain their intrinsic viscosity ([ƞ]) values and interrelated parameters, like: the molar mass (Mƞ), hydrodynamic radiuses (RH,ƞ), radius of gyration (RG,ƞ), and second virial coefficient (A2,ƞ) of CSs in the solution. The results show an exponential decrease of ƞr, [ƞ], Mƞ, RH,ƞ and RG,ƞ with increasing tγ. This suggests the influence of random chain-scission of CSs glycosidic bonds, with rate constant kr and kr-1 (lifetime τr ~ 0.017 min-1 and 57.14 min, respectively). The results also show an exponential decrease of A2ƞ with increasing tγ, which can be attributed to the growth of excluded volume effect in CS segments by tγ and, hence, better solution quality. The results are represented in following scaling laws as a tailoring guide to the applicants: RH,ƞ = 6.98 x 10-3 Mr0.65; RG,ƞ = 7.09 x 10-4 Mr0.83; A2,ƞ = 121.03 Mƞ,r-0.19.

Keywords: Gamma irradiation, geometric properties, kinetic model, scaling laws, viscosity measurement.

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[1] A. D. McNaught and A. Wilkinson, Compendium of chemical terminology vol. 1669: Blackwell Science Oxford, 1997
[2] A. Y. Grosberg, and A. R. Khokhlov, Giant molecules: here, there, and everywhere: World Scientific Publishing Co, 2011.
[3] H. Namazi, "Polymers in our dialy life," Biolmpacts, vol 7, no 2, pp. 73-74, 2017.
[4] P. J. Flory, Principles of polymer chemistry: Cornell University Press, 1953.
[5] P.-G. De Gennes and P.-G. Gennes, Scaling concepts in polymer physics: Cornell university press, 1979.
[6] G. Jannink, Polymers in Solution: Their Modelling and Structure: Clarendon Press, 2010.
[7] L. Figura and A. A. Teixeira, Geometric Properties: Size and Shape. Food physics: physical properties-measurement and applications: Springer Science & Business Media, 2007.
[8] L. Fetters, N. Hadjichristidis, J. Lindner, and J. Mays, "Molecular Weight Dependence of Hydrodynamic and Thermodynamic Properties for Well‐Defined Linear Polymers in Solution," J. phys. chem. Ref. data, vol. 23, pp. 619-640, July 1994.
[9] J. Lefebvre and J.-L. Doublier, "Rheological behavior of polysaccharides aqueous systems," in Polysaccharides: Structural diversity and functional versatility, 2nd ed. S. Dumitriu Ed. Marcel Dekker New York, 2005, pp. 357-394.
[10] R. Lapasin and S. Pricl, "Industrial applications of polysaccharides," in Rheology of Industrial Polysaccharides: Theory and Applications, Ed. Springer, 1995, pp. 134-161.
[11] Z. Shariatinia, "Pharmaceutical applications of natural polysaccharides," in Natural Polysaccharides in Drug Delivery and Biomedical Applications, Ed. Elsevier, 2019, pp. 15-57.
[12] L. Steffens, M. C. H. de Barros Dias, A. M. Morás, D. J. Moura, and M. Nugent, "Natural polysaccharides for the delivery of anticancer therapeutics," in Natural Polysaccharides in Drug Delivery and Biomedical Applications, Ed. Elsevier, 2019, pp. 441-470.
[13] A. K. Nayak, S. A. Ahmed, M. Tabish, and M. S. Hasnain, "Natural polysaccharides in tissue engineering applications," in Natural Polysaccharides in Drug Delivery and Biomedical Applications, Ed. Elsevier, 2019, pp. 531-548.
[14] J. Liu, S. Willför, and C. Xu, "A review of bioactive plant polysaccharides: Biological activities, functionalization, and biomedical applications," Bioact. Carbohyd. Diet. Fibr, vol. 5, pp. 31-61, Jan 2015.
[15] S. Li, Q. Xiong, X. Lai, X. Li, M. Wan, J. Zhang, et al., "Molecular modification of polysaccharides and resulting bioactivities," Compr. Rev. Food Sci. Food Saf, vol. 15, no. 2, pp. 237-250, Mar 2016.
[16] V. Soldi, "Stability and degradation of polysaccharides," in Polysaccharides: Structural diversity and functional versatility, 2nd ed. S. Dumitriu Ed. Marcel Dekker New York, 2005, pp. 395-409.
[17] S. Kumari and R. Kishor, "Chitin and chitosan: origin, properties, and applications," in Handbook of Chitin and Chitosan, Vol. 1. S. Gopi, S. Thomas, A. Pius, Eds. Elsevier, 2020, pp. 1-33.
[18] Y. Zhu, Y. Liu, and Z. Pang, "Chitosan in drug delivery applications," in Natural Polysaccharides in Drug Delivery and Biomedical Applications, M. S. Hasnain, A. K. Nayak, Eds. Elsevier, 2019, pp. 101-119.
[19] N. C. Minh, N. Van Hoa, and T. S. Trung, "Preparation, properties, and application of low-molecular-weight chitosan," in Handbook of Chitin and Chitosan, Vol. 1. S. Gopi, S. Thomas, A. Pius Eds. Elsevier, 2020, pp. 453-471.
[20] Y. Maeda and Y. Kimura, "Antitumor effects of various low-molecular-weight chitosans are due to increased natural killer activity of intestinal intraepithelial lymphocytes in sarcoma 180–bearing mice," J. Nutr., vol. 134, no. 4, pp. 945-950, Apr 2004.
[21] H. B. Moran, J. L. Turley, M. Andersson, and E. C. Lavelle, "Immunomodulatory properties of chitosan polymers," Biomaterials, vol. 184, pp. 1-9, Nov 2018.
[22] O. Ejeromedoghene, O. Oderinde, G. Egejuru, and S. Adewuyi, "Chitosan-drug encapsulation as a potential candidate for COVID-19 drug delivery systems: A review," J. Turk. Chemi. Soci. Sec. A: Chem., vol. 7, no. 3, pp. 851-864, Jan 2020.
[23] A. T. Lampe, E. J. Farris, D. M. Brown, and A. K. Pannier, "High and low molecular weight chitosan act as adjuvants during single dose influenza A virus protein vaccination through distinct mechanisms," Biotech. Bioeng., vol. 118, no. 3, pp. 1224-1243. Mar 2020.
[24] A. T. Lampe, E. J. Farris, M. D. Ballweg, A. K. Pannier, and D. M. Brown, "Chitosan adjuvantation improves protection elicited by single, low dose influenza A virus recombinant protein vaccination," J. Immnol., vol. 204, pp. 245-247, May 2020.
[25] U. Gryczka, D. Dondi, A. Chmielewski, W. Migdal, A. Buttafava, and A. Faucitano, "The mechanism of chitosan degradation by gamma and e-beam irradiation," Rad. Phys. Chem., vol. 78, no (7-8), pp. 543-548, Jul 2009.
[26] H. Kim, J. Lee, S. Oh, P. Kang, and J. Jeun, "Molecular Weight Control of Chitosan Using Gamma Ray and Electron Beam Irradiation," J. Rad. Indus., vol. 7, no. 1, pp. 51-54, Aug 2013.
[27] W.-M. Kulicke and C. Clasen, Viscosimetry of polymers and polyelectrolytes, Springer Science & Business Media, 2004.
[28] F. Elashhab, L. Sheha, T. Alfazani*, A. E. A. Youssef, and R. F. Elsupikhe, "Nanoscaled Polysaccharides in Solution: Scaling Laws of Hyaluronan," Nano. Tech. Appl., vol. 2, no. 1, pp. 1-4, May 2019.
[29] S. E. Hill, D. A. Ledward, and J. R. Mitchell, Functional properties of food macromolecules, Springer Science & Business Media, 1998.
[30] A. Krasovskii, S. Mnatsakanov, E. Guseva, A. Andreeva, E. Maryanina, and L. Ustinova, "Comparative-Study of the Structure and Relative Viscosity of Aqueous-Solutions of Commercial Photogelatin as a Function of Concentration," Russ. J. Appl. Chem., vol. 66, no. 4, pp. 671-679, Apr 1993.
[31] M. H., "Über die Entstehung und eigenschaften hochpolymer festkörper," Der FesteKörper; Sanger, R., Ed. Leipzig: Hirzel, pp. 65-104, 1938.
[32] R. Houwink, "Zusammenhang zwischen viscosimetrisch und osmotisch bestimmten Polymerisationsgraden bei Hochpolymeren," J. Prakt. Chem., vol. 157, no. 1-3, pp. 15-18, Dec 1940.
[33] G. G. Maghami and G. A. Roberts, "Evaluation of the viscometric constants for chitosan," Die Makrom. Chemi. Macrom. Chem. Phys., vol. 189, no. 1, pp. 195-200, Jan 1988.
[34] P. Flory and T. Fox, "Treatment of intrinsic viscosities," J. Am. Chem. Soc., vol. 73, no. 5, pp. 1904-1908, May 1951.
[35] P. J. Flory and M. Volkenstein, "Statistical mechanics of chain molecules," Biopolymers, vol. 8, pp. 699-700, Nov 1969.
[36] W. Krigbaum, "Relationships between
[η] or (R 2) 3/2 and the second virial coefficient," J. Polym. Sci., vol. 18, no. 88, pp. 315-320, Oct 1955.
[37] W. R. Krigbaum, "Estimating the unperturbed dimensions of polymer molecules," J. Polym. Sci., vol. 28, no. 116, pp. 213-221, Feb 1958.
[38] J. Qian and A. Rudin, "Prediction of hydrodynamic properties of polymer solutions," Eur. Polym. J., vol. 28, no. 7, pp. 733-738, Jul 1992.
[39] J. Qian, M. Wang, D. Han, and R. Cheng, "A novel method for estimating unperturbed dimension
[η] θ of polymer from the measurement of its
[η] in a non-theta solvent," Eur. Polym. J., vol. 37, no. 7, pp. 1403-1407, Jul 2001.
[40] W. W. Graessley, "Polymer chain dimensions and the dependence of viscoelastic properties on concentration, molecular weight and solvent power," Polymer, vol. 21, no. 3, pp. 258-262, Mar 1980.
[41] F. El-Ashhab, L. Sheha, M. Abdalkhalek, and H. A. Khalaf, "The influence of gamma irradiation on the intrinsic properties of cellulose acetate polymers," J. Assoc. Arab Univ. Basic Appl. Sci., vol. 14, no. 1, pp. 46-50, Oct 2013.
[42] F. Elashhab, L. Sheha, A. Youssef, H. Khalaf, and M. Salam, "Gamma Modification of Polysaccharides: Controlling of Pullulan Molar Masses," J. Pur. Appl. Sci., vol. 17, no. 1, pp. 284-288, Mar 2018.
[43] H. Yamakawa, "On the theory of the second virial coefficient for polymer chains," Macromolecules, vol. 25, no. 7, pp. 1912-1916, Mar 1992.
[44] H. Yamakawa and T. Yoshizaki, "A Monte Carlo study of effects of chain stiffness and chain ends on dilute solution behavior of polymers. II. Second virial coefficient," J. Chem. Phys., vol. 119, no. 2, pp. 1257-1270, Jul 2003.