Izvestiya of Saratov University.

Chemistry. Biology. Ecology

ISSN 1816-9775 (Print)
ISSN 2541-8971 (Online)

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Atomic Force Microscopy Study of the Surface of Films of Chitosan and Its Salts with Organic Acids

Rudenko Darya A., Saratov State University
Bratashov Daniil N., Saratov State University
Shipovskaya Anna B., Saratov State University

The results of the study of the morphology and surface topography of chitosan films of the salt (S-) and basic (B-) chemical form by atomic force microscopy are presented. The films were cast from polymer solutions in acetic, lactic, citric and succinic acid. NaOH and triethanolamine were used for the salt > chitosan base reaction. Surface tomograms were obtained; the main morphological characteristics and roughness parameters of the film samples were estimated. It was found that the morphology, the degree of order, root-mean-square roughness and the height of the surface roughness were determined by the polymer chemical form, the nature of the acid used and the reagent of the polymer-like conversion reaction. The surface of the S-form chitosan films is characterized by fibrillar structural ordering (also dendritic for chitosan succinate), and that of the B-form is globular. The smallest size of surface supramolecular elements was observed for the S-form chitosan films, while the greatest roughness was for the B-form ones. Changing the reagent of the chitosan S > B reaction did not affect the morphological characteristics of the films; however, it affected the microrelief roughness. A more uniform basic chitosan film is formed in an organic base environment. It was suggested that the formation of fibrillar supramolecular structures was due to the unfolding and straightening of macrochains because of the repulsion of the same charged monomer units, while the globular ones were formed due to the folding and densification of macrocoils after neutralizing the total charge of the macrochain.

  1. Slivkin D. A., Lapenko V. L., Safonova O. A., Suslina S. N., Belenova A. S. Chitosan for pharmacy and medicine. Proceedings of Voronezh State University. Series: Chemistry. Biology. Pharmacy, 2011, iss. 2, pp. 214–232 (in Russian).
  2. Dutta P. K., Tripathi S., Mehrotra G. K., Dutta J. Perspectives for chitosan based antimicrobial fi lms in food applications. Food Chemistry, 2009, vol. 114, iss. 4, pp. 1173–1182.
  3. Muthusankar E., Ragupathy D. Chitosan Based Nanocomposite Biosensors: A Recent Review. Sensor Letters, 2018, vol. 16, iss. 2, pp. 81–91.
  4. Chudinova Yu. V., Konovalova M. V., Il’ina A. V., Varlamov V. P. Infl uence of the chitosan physical and chemical characteristics on the thin fi lms structure. Procceding of the RAS Ufa Scientifi c Center, 2016, iss. 3, pp. 103–106 (in Russian).
  5. Zhuykova Yu. V. Puti formirovaniya i molekulyarnaya struktura tonkikh plenok na osnove prirodnykh polisakharidov [Formation pathways and molecular structure of thin fi lms based on natural polysaccharides]. Thesis Dis. Cand. Sci. (Biol.). Moscow, 2018. 162 p. (in Russian).
  6. Zhong Y., Zhuang C., Gu W., Zhao Y. Effect of molecular weight on the properties of chitosan fi lms prepared using electrostatic spraying technique. Corb. Pol., 2019, vol. 212, pp. 197–205.
  7. Zhuang C., Zhong Y., Zhao Y. Effect of deacetylation degree on properties of Chitosan fi lms using electrostatic spraying technique. Food Control, 2019, vol. 97, pp. 25–31.
  8. Wang Z., Fei S., Kong W., Xiao Q., Zhu J. Effects of metal ions on the self-assembly of chitosan molecules investigated with atomic force microscopy. International Journal of Food Properties, 2018, vol. 21, iss. 1, pp. 1986–1994.
  9. Lewandowska K., Sionkowska A., Kaczmarek B., Furtos G. Characterization of chitosan composites with various clays. Intern. J. Biol. Macromol., 2014, vol. 65, pp. 534–541.
  10. Li J., Zivanovic S., Davidson P. M., Kit K. Production and characterization of thick, thin and ultra-thin chitosan/PEO fi lms. Corb. Pol., 2014, vol. 83, iss. 2, pp. 375–382.
  11. Ferreira A. S., Nunes C., Castro A., Ferreira P., Coimbra M. A. Infl uence of grape pomace extract incorporation on chitosan fi lms properties. Corb. Pol., 2014, vol. 113, pp. 490–499.
  12. Kara F., Aksoy E. A., Yuksekdag Z., Hasirci N., Aksoy S. Synthesis and surface modifi cation of polyurethanes with chitosan forantibacterial properties. Corb. Pol., 2014, vol. 112, pp. 39–47.
  13. Ko Y. G., Yu S. M., Park S. J. Chun H. J., Kim C. H. Characterization of surface properties and cytocompatibility of ionetched chitosan fi lms. Langmuir, 2012, vol. 28, iss. 18, pp. 7223?7232.
  14. Karakecili A. G., Satriano C., Gumusderelioglu M., Marletta G. Surface characteristics of ionically crosslinked chitosan membranes. J. Appl. Surf. Sci., 2007, vol. 106, pp. 3884–3888.
  15. Arzate-Vbzquez I., Chanona-Pйrez J. J., CalderуnDomнnguez G., Terres-Rojas E., Garibay-Febles V., Martнnez-Rivas A., Gutiйrrez-Lуpez G. F. Microstructural characterization of chitosan and alginate fi lms by microscopy techniques and texture image analysis. Carbohydr. Polym., 2012, vol. 87, iss. 1, pp. 289–299.
  16. Lei J., Yang L., Zhan Y., Wang Y., Ye T., Li Y., Deng H., Li B. Polyethylene terephthalate/polypropylene fi lmsassembled with chitosan and various preservatives for antimicrobialfood packaging. Colloids and Surfaces B: Biointerfaces, 2014, vol. 114, pp. 60–66.
  17. Morgado D. L., Frollini E., Castellan A., Rosa D. S., Coma V. Biobased fi lms prepared from NaOH/thiourea aqueous solution of chitosan and linter cellulose. Cellulose, 2011, vol. 18, iss. 3. pp. 699–712.
  18. Mathew S., Abraham T. E. Characterisation of ferulic acid incorporated starch–chitosan blend fi lms. Food Hydrocoll, 2008, vol. 2, pp. 826–835.
  19. Zheng Z., Zhang L., Kong L., Wang A., Gong Y., Zhang X. The behavior of MC3T3-E1 cells on chitosan/ poly-L-lysine composite fi lms: Effect of nanotopography, surface chemistry, and wettability. J. Biomed. Mater. Res. A, 2008, vol. 89, iss. 2, pp. 453–465.
  20. Lewandowska K. Surface studies of microcrystalline chitosan/poly(vinyl alcohol) mixtures. Appl. Surf. Sci., 2012, vol. 263, iss. 15, pp. 115–123.
  21. Xu H., Ma L., Shi H., Gao C., Han G. Chitosan-hyaluronic acid hybrid fi lm as a novel wound dressing: in vitro and in vivo studies. Polym. Adv. Technol., 2007, vol. 18, pp. 869–875.
  22. Yan X.-L., Khor E., Lim L.-Y. Chitosan-Alginate Films Prepared with Chitosans of Different Molecular Weights. J. Biomed. Mater. Res., 2001, vol. 58, iss. 4, pp. 358–365.
  23. Mazaheri M., Akhavan O., Simchi A. Flexible bactericidal graphene oxide–chitosan layers for stemcell proliferation. Applied Surface Science, 2014, vol. 301, pp. 456–462.
  24. Xu Y., Ren X., Hanna M. A. Chitosan/clay nanocomposite fi lm preparation and characterization. J. Appl. Surf. Sci., 2006, vol. 99, pp. 1684–1691.
  25. Wang S., Jing Y. Effects of formation and penetration properties of biodegradable montmorillonite/chitosan nanocomposite fi lm on the barrier of package paper. Applied Clay Science, 2017, vol. 138, pp. 74–80.
  26. Cardenas G., Anaya P., Rio R. D., Schrebler R., Plessing C., Schneider M. Scanning electron microscopy and atomic force microscopy of chitosan composite fi lms. J. Chil. Chem. Soc., 2010, vol. 55, iss. 3, pp. 352–358.
  27. Bogomolova T. B., Kozlova N. V., Chvalun S. N. Modifi cation of chitosan via grafting of glycolic acid followed by polycondensation during heat treatment. Polymer Science. Series B, 2009, vol. 51, iss. 9, pp. 1695–1703 (in Russian).
  28. Ghosh A., Ali M. A. Studies on physicochemical characteristics of chitosan derivatives with dicarboxylic acids. J. Mater. Sci., 2012, vol. 47. pp. 1196–1204.
  29. Necas D., Klapetek P. Gwyddion: an open-source software for SPM data analysis. Cent. Eur. J. Phys., 2012, vol. 10, iss. 1, pp. 181–188.
  30. Aksenova N. A., Timofeeva V. A., Rogovina S. Z., Timashev P. S., Glagolev N. N., Solov’eva A. B. Photocatalytic properties and structure of chitosan-based porphyrincontaining systems. Polymer Science. Series B, 2010, vol. 52, iss. 2, pp. 314–320 (in Russian).
  31. Shatalova О. V., Aksenova N. А., Solov’eva А. B., Кrivandin А. V., Rogovina S. Z., Sidokhin F. А. Crystallization peculiarities of chitosan with different molecular mass and its mixtures with pluronic F-127 according to atomic force microscopy and X-ray diffraction data. Journal of Surface Investigation X-ray, Synchrotron and Neutron Techniques, 2011, iss. 5, pp. 50–56 (in Russian).
  32. Fedoseeva Е. N., Fedoseev V. B. Interaction of chitosan with benzoic acid in solution and fi lms. Polymer Science. Series A, 2011, vol. 53, iss. 11, pp. 1900–1907 (in Russian).