Quaternized and Unmodified Chitosans: Hydrodynamic Properties
DOI:
https://doi.org/10.6000/1929-5995.2015.04.01.4Keywords:
Polysaccharides, chitosan, quaternization, hydrodynamic behavior.Abstract
Molecular properties of N-[(2-hydroxy-3-trimethylammonium)propyl]chitosan (modified chitosan) series with the averaged quaternization degree 90% have been studied in comparison with the unmodified chitosan series by the method of translation isothermal diffusion, viscometry and static light scattering in dilute solutions in 0.33М СН3СООН+0.2М CH3СООNa at pH 3.54. Molecular mass, translation diffusion coefficient, and hydrodynamic size of the homologues samples in the modified/unnmodified series have been determined as well as their chain rigidity and Mark-Kuhn-Houwink equations at acidic pH. It was established that the size of modified chitosan molecules might be smaller than the initial polysaccharide of an equal polymerization degree in the same solvent, which was explained by the change of thermodynamic conditions and the change of the ratio of thermodynamic/electrostatic contributions to the total chain rigidity. Quaternized chitosan molecules displayed the different hydrodynamic behavior in 0.33М СН3СООН+0.2М CH3СООNa and in 0.2M NaCl (neutral pH). Solution properties of quaternized chitosan at neutral pH had been identified as the concentration dependent. The threshold influence of the secondary amino group protonation on the hydrodynamic properties of modified chitosan molecules was detected in 0.2M NaCl at the solute concentration range 0.001-0.004 g/cm3.
References
Muzarelli RAA, Muzarelli C. Chitosan chemistry: relevance to the biomedical sciences. Adv Polym Sci 2005; 186: 151-209. http://dx.doi.org/10.1007/b136820 DOI: https://doi.org/10.1007/b136820
Runarsson OV, Holappa J, Nevalainen T, et al. Antibacterial activity of methylated chitosan and chitooligomers: sythesis and structure activity relationships. Eur Polym J 2007; 43: 2660-71. http://dx.doi.org/10.1016/j.eurpolymj.2007.03.046 DOI: https://doi.org/10.1016/j.eurpolymj.2007.03.046
Jia ZS, Shen DF, Xu WL. Synthesis and antibacterial activities of quaternary ammonium salt of chitosan. Carbohydr Res 2001; 333: 1-6. http://dx.doi.org/10.1016/S0008-6215(01)00112-4 DOI: https://doi.org/10.1016/S0008-6215(01)00112-4
Xu T, Xin M, Li M, Huang H, Zho S, Liu J. Synthesis, characterization and antibacterial activity of N,O-quaternary ammonium chitosan. Carbohydr Res 2011; 346: 2445-50. http://dx.doi.org/10.1016/j.carres.2011.08.002 DOI: https://doi.org/10.1016/j.carres.2011.08.002
Avadi MR, Sadeghi AMM, Tahzibi A, et al. Diethylmethyl chitosan as an antimicrobial agent: Synthesis, characterization and antibacterial effects. Eur Polym J 2004; 40: 1355-61. http://dx.doi.org/10.1016/j.eurpolymj.2004.02.015 DOI: https://doi.org/10.1016/j.eurpolymj.2004.02.015
Wang JJ, Zeng ZW, Xiao RZ, et al. Recent advances of chitosan nanoparticles as drug carriers. Int J Nanomedicine 2011; 6: 765-74. DOI: https://doi.org/10.2147/IJN.S17296
Mao S, Sun W, Kissel T. Chitosan-based formulations for delivery of DNA and siRNA. Adv Drug Del Rev 2010; 62: 12-27. http://dx.doi.org/10.1016/j.addr.2009.08.004 DOI: https://doi.org/10.1016/j.addr.2009.08.004
Tong H, Qin S, Fernandes JC, Li L, Dai K, Zhang X. Progress and prospects of chitosan and its derivatives as nonviral gene vector in gene therapy. Current Gene Therapy 2009; 9: 495-502. http://dx.doi.org/10.2174/156652309790031111 DOI: https://doi.org/10.2174/156652309790031111
Belatia R, Grelier S, Benassia M, Coma V. New bioactive biomaterials based on quaternized chitosan. J Agric Food Chem 2008; 56: 1582-8. http://dx.doi.org/10.1021/jf071717+ DOI: https://doi.org/10.1021/jf071717+
Lim SH, Hudson SM. Application of fiber-reactive chitosan derivative to cotton fabric as an antimicrobial textile finish. Carbohydr Polym 2004; 56: 227-34. http://dx.doi.org/10.1016/j.carbpol.2004.02.005 DOI: https://doi.org/10.1016/j.carbpol.2004.02.005
Sieval AB, Thanou M, Kotze AF, Verhoef JC, Brussee J, Junginger HE. Preparation and NMR characterization of highly substituted N-trimethylchitosan chloride. Carbohydr Polym 1998; 36: 157-65. http://dx.doi.org/10.1016/S0144-8617(98)00009-5 DOI: https://doi.org/10.1016/S0144-8617(98)00009-5
Muzarelli RAA. In: Aspinall GO, editor. The Polysaccharides. NY: Academic Press 1985; p.3.
Gamzazade AI, Shlimak VM, Sklyar AM, Stykova EV, Pavlova SSA,Rogozhin SV. Investigation of the hydrodynamic properties of chitosan solutions. Acta Polymerica 1985; 36: 420-4. http://dx.doi.org/10.1002/actp.1985.010360805 DOI: https://doi.org/10.1002/actp.1985.010360805
Pogodina NV, Pavlov GМ, Bushin SV, et al. Conformational characteristics of chitosan molecules according to diffusion-sedimentation and viscometry data. Polym Sci Ser A 1986; 28: 232-9. DOI: https://doi.org/10.1016/0032-3950(86)90076-6
Rinaudo M, Domard A. In: Chitin and chitosan. London: Elsevier Applied Sciences 1989; p.71-86.
Buhler E, Rinaudo M. Structural and dynamical properties of semirigid polyelectrolyte solution: a light scattering study. Macromolecules 2000; 33: 2098-106. http://dx.doi.org/10.1021/ma991309+ DOI: https://doi.org/10.1021/ma991309+
Kim YH, Nam CW, Choi JW, Jang J. Durable antimicrobial treatment of cotton fabrics using N-(2-hydroxy)propyl-3-trimethylammonium chitosan chloride and polycarboxylic acids. J Appl Polym Sci 2003; 88: 1567-72. http://dx.doi.org/10.1002/app.11845 DOI: https://doi.org/10.1002/app.11845
Qin CQ, Xiao Q, Li HR, et al. Calorimetric studies of the action of chitosan-N-2-hydroxypropyltrimethyl ammonium chloride on the growth of microorganisms. Int J Biol Macromol 2004; 34: 121-6. http://dx.doi.org/10.1016/j.ijbiomac.2004.03.009 DOI: https://doi.org/10.1016/j.ijbiomac.2004.03.009
Faizuloev EB, Marova AA, Nikonova AA, Volkova IF, Gorshkova M Yu, Izumrudov VA. Water-soluble N-[(2-hydroxy)propyl-3-trimethylammonium)propyl]chitosan chloride as nucleic acid vector for cell transfection. Carbohydr Polym 2012; 89: 1088-94. http://dx.doi.org/10.1016/j.carbpol.2012.03.071 DOI: https://doi.org/10.1016/j.carbpol.2012.03.071
Huang M, Khor E, Lim LY. Uptake and cytotoxicity of chitosan molecules and nanoparticles: effect of molecular weight and degree of deacetylation. J Pharm Res 2004; 21: 344-53. http://dx.doi.org/10.1023/B:PHAM.0000016249.52831.a5 DOI: https://doi.org/10.1023/B:PHAM.0000016249.52831.a5
Gorshkova МYu, Volkova IF, Alexeeva SG, Molotkova NN, Skorikova ЕЕ, Izumrudov VА. Water-soluble modified chitosan and its interaction with polystyrenesulfonate anion. Polym Sci Ser A 2011; 53: 67-74. DOI: https://doi.org/10.1134/S0965545X11010019
Lim SH, Hudson SM. Synthesis and antimicrobial activity of water-soluble chitosan derivative with a fiber-reactive group. Carbohydr Res 2004; 339: 313-9. http://dx.doi.org/10.1016/j.carres.2003.10.024 DOI: https://doi.org/10.1016/j.carres.2003.10.024
Tsvetkov VN. Rigid-chain polymers. New York: Plenum, Consultans Bureau 1989.
Lam L, Lee SW, Suen CY. IEEE transactions on pattern analysis and machine intelligence. Thinning Methodologies. A Comprehensive Survey 1992; 14: 879-85. DOI: https://doi.org/10.1109/34.161346
Chu B. Laser Light Scattering - Basic principles and Practice. New York: Dover Publication 2007.
Yevlampieva NP, Gorshkova МYu, Volkova IF, Grigorjan ES, Khurchak АP, Rjumtsev ЕI. Molecular properties of modified chitosan containing quaternary amino groups. Polym Sci Ser A 2011; 53: 124-32. http://dx.doi.org/10.1134/S0965545X11020039 DOI: https://doi.org/10.1134/S0965545X11020039
Rinaudo M, Pavlov G, Desbrieres J. Influenece of acetic acid concentration on solubilization of chitosan. Polymer 1999; 40: 7029-32. http://dx.doi.org/10.1016/S0032-3861(99)00056-7 DOI: https://doi.org/10.1016/S0032-3861(99)00056-7
Flory PJ. Statistical Mechanics of Chain Molecules. New York: Interscience 1989.
Yamakawa H, Fujii M. Translation friction coefficient of wormlike chains. Macromolecules 1973; 6: 407-15. http://dx.doi.org/10.1021/ma60033a018 DOI: https://doi.org/10.1021/ma60033a018
de Oliveira VAV, de Morais WA, Pereira MR, Fonseca JLC. Dynamic light scattering in semidilute and concentrated chitosan solutions. Eur Pol J 2012; 48: 1932-9. http://dx.doi.org/10.1016/j.eurpolymj.2012.07.017 DOI: https://doi.org/10.1016/j.eurpolymj.2012.07.017
Philippova OE, Korchagina EV, Volkov EV, Smirnov VA, Khokhlov AR, Rinaudo M. Aggregation of some water-soluble derivetives of chitin in aqueous solutions: role of the degree of acetylation and effect of hydrogen bond breaker. Carbohydr Polym 2012; 87: 687-94. http://dx.doi.org/10.1016/j.carbpol.2011.08.043 DOI: https://doi.org/10.1016/j.carbpol.2011.08.043
Esquenet C, Buhler E. Phase behavior of associating polyelectrolyte polysaccharides. Aggregation process in dilute solution. Macromolecules 2001; 34: 5287-94. http://dx.doi.org/10.1021/ma010451j DOI: https://doi.org/10.1021/ma010451j
Downloads
Published
How to Cite
Issue
Section
License
Copyright (c) 2015 Journal of Research Updates in Polymer Science
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
Policy for Journals/Articles with Open Access
Authors who publish with this journal agree to the following terms:
- Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License that allows others to share the work with an acknowledgement of the work's authorship and initial publication in this journal.
- Authors are permitted and encouraged to post links to their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work
Policy for Journals / Manuscript with Paid Access
Authors who publish with this journal agree to the following terms:
- Publisher retain copyright .
- Authors are permitted and encouraged to post links to their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work .
