Preview

Fine Chemical Technologies

Advanced search

Obtaining chitosan sulfate nanoparticles in an aqueous medium and their colloidal protection with polysaccharides

https://doi.org/10.32362/2410-6593-2024-19-2-111-126

Abstract

Objectives. To develop a method to obtain a hydrosol of the salt of chitosan with sulfuric acid—chitosanium sulfate (ChS) hydrosol—and to study the effect of various water-soluble polysaccharides on its stability over time, as well as its resistance to indifferent and non-indifferent electrolytes.

Methods. κ-Carrageenan, sodium alginate (SA), and xanthan were used as polymers which perform the function of colloidal protection for ChS nanoparticles. Capillary viscometry was used to study the viscosity of polymer solutions, their molecular weight, and their adsorption on ChS. The stability of the sols over time and their resistance to indifferent and non-indifferent electrolytes were evaluated photometrically. The hydrosol particle size was determined by means of dynamic light scattering.

Results. On the surface of ChS, κ-carrageenan is adsorbed most strongly over a wide range of concentrations. The graphs of the dependencies of the relative change in the turbidity of sols with the addition of various polysaccharides on their weight concentration at a sol lifetime of 2 days have the shape of curves with a maximum. Sols with the addition of 0.0125% SA and κ-carrageenan in the range of 0.04% have the greatest stability over time. According to dynamic light scattering data, the average particle size of freshly prepared sols with the addition of the polymers to ensure their greatest stability over time are 10.8 nm and 14.6 nm, respectively. For freshly prepared sols without polysaccharides, this size is 24.8 nm. The hydrosol coagulation threshold with an indifferent electrolyte (NaCl) is 9.3 times higher than that with a non-indifferent electrolyte (Na2SO4). κ-Carrageenan and SA protect the hydrosol from coagulation with an indifferent electrolyte (NaCl) at all their used amounts. At the same polymer concentrations, no protection from coagulation with a non-indifferent electrolyte (Na2SO4) was observed.

Conclusions. A method was developed to obtain ChS hydrosol with a positive particle charge. The stability of ChS sols over time was studied both without and with the addition of SA, κ-carrageenan, and xanthan. Sol coagulation thresholds with indifferent and non-indifferent electrolytes, as well as the protective numbers for κ-carrageenan and SA against the coagulation of hydrosols with these electrolytes, were established. The mechanism of stability of sols at certain concentrations of water-soluble polysaccharides was explained using data on the adsorption of these polysaccharides on the surface of chitosan treated with a solution of sulfuric acid. Based on the results of the work, it can be concluded that SA and κ-carrageenan can be used for the efficient stabilization of ChS hydrosols over time and for the colloidal protection of ChS from coagulation with sodium chloride.

About the Authors

V. S. Erasov
MIREA — Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)
Russian Federation

Vadim S. Erasov, Cand. Sci. (Eng.), Senior Lecturer, S.S. Voyutsky Department of Nanoscale Systems and Surface Phenomena, M.V. Lomonosov Institute of Fine Chemical Technologies

Scopus Author ID 57484351900

86, Vernadskogo pr., Moscow, 119571, Russia



Yu. O. Maltseva
MIREA — Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)
Russian Federation

Yuliya O. Mal’tseva, Student, M.V. Lomonosov Institute of Fine Chemical Technologies

86, Vernadskogo pr., Moscow, 119571, Russia



References

1. Varlamov V.P., Il’ina A.V., Shagdarova B.T., et al. Chitin/chitosan and its derivatives: Fundamental problems and practical approaches. Biochemistry Moscow. 2020; 85(Suppl. 1):154–176. https://doi.org/10.1134/S0006297920140084 [Original Russian Text: Varlamov V.P., Il’ina A.V., Shagdarova B.Ts., Lun’kov A.P., Mysyakina I.S. Chitin/chitosan and its derivatives: Fundamental problems and practical approaches. Uspekhi Biologicheskoi Khimii. 2020;60:317–368 (in Russ.).]

2. Skryabin K.G., Mihajlov S.N., Varlamov V.P. (Eds.). Khitozan (Chitosan). Moscow: Bioinzheneriya; 2013. 591 p. (in Russ.). ISBN 978-5-4253-0596-1

3. Samujlenko A.Ya. (Ed.). Biologicheski aktivnye veshchestva (khitozan i ego proizvodnye) (Biologically active substances (Chitosan and its derivatives)). Krasnodar: KubGAU; 2018. 329 p. (in Russ.). ISBN 978-5-00097-319-6

4. Khvostov M.V., Tolstikova T.G., Borisov S.A., Dushkin A.V. Application of natural polysaccharides in pharmaceutics. Russ. J. Bioorg. Chem. 2019; 45(6):438–450. https://doi.org/10.1134/S1068162019060219 [Original Russian Text: Khvostov M.V., Tolstikova T.G., Borisov S.A., Dushkin A.V. Application of natural polysaccharides in pharmaceutics. Bioorganicheskaya Khimiya. 2019;45(6): 563–575 (in Russ.). https://doi.org/10.1134/S0132342319060241 ]

5. Garg U., Chauhan S., Nagaich U., Jain N. Current advances in chitosan nanoparticles based drug delivery and targeting. Adv. Pharm. Bull. 2019;9(2):195–204. https://doi.org/10.15171/apb.2019.023

6. Li J., Cai Ch., Li J., Li J., Li J., Sun T., Wang L., Wu H., Yu G. Chitosan-Based Nanomaterials for Drug Delivery. Molecules. 2018;23(10):2661. https://doi.org/10.3390/molecules23102661

7. Bernkop-Schnürch A., Dünnhaupt S. Chitosan-based drug delivery systems. Europ. J. Pharm. Biopharm. 2012;81(3): 463–469. https://doi.org/10.1016/j.ejpb.2012.04.007

8. Hasnain M.S., Sarwar B., Nayak A.K. (Eds.). Chitosan in Drug Delivery. USA: Academic Press (Elsevier); 2021. 556 p. ISBN 978 0128-1933-65

9. Parhi R. Drug delivery applications of chitin and chitosan: a review. Environ. Chem. Lett. 2020;18(2):577–594. https://doi.org/10.1007/s10311-020-00963-5

10. Mikušová V., Mikuš P. Advances in chitosan-based nanoparticles for drug delivery. Int. J. Mol. Sci. 2021;22(17):9652. https://doi.org/10.3390/ijms22179652

11. Ghosh R., Mondal S., Mukherjee D., Adhikari A., Saleh A.A., Alsantali I., Khder A.S., Altass H.M., Moussa Z., Das R., Bhattacharyya M., Pal S.K. Oral drug delivery using a polymeric nanocarrier: chitosan nanoparticles in the delivery of rifampicin. Mater. Adv. 2022;3(11):4622–4628. https://doi.org/10.1039/D2MA00295G

12. Radha D., Lal J.S., Devaky K.S. Chitosan‐based films in drug delivery applications. Starch-Starke. 2022;74(7–8):2100237. https://doi.org/10.1002/star.202100237

13. Herdiana Y., Wathoni N., Shamsuddin Sh., Muchtaridi M. Drug release study of the chitosan-based nanoparticles. Heliyon. 2022;8(1):e08674. https://doi.org/10.1016/j.heliyon.2021.e08674

14. Lau A. K.-T., Hussain F., Dafdie H. (Eds.). Nanoi biokompozity (Nanoand Biocomposites): transl. from Engl. Moscow: BINOM. Laboratoriya znanii; 2020. 390 p. (in Russ.). ISBN 978-00101-727-1 [Lau A.K.-T., Hussain F., Dafdie H. (Eds.). Nano and Biocomposites. Boca Raton: CRC Press; 2010. 408 p.]

15. Munawar A.M., Syeda J.T.M., Wasan K.M., Wasan E.K. An overview of chitosan nanoparticles and its application in non-parenteral drug delivery. Pharmaceutichs. 2017;9(4):53. https://doi.org/10.3390/pharmaceutics9040053

16. Azimov Zh.T., Oksengendler B.L., Turaeva N.N., et al. Effect of the structure of the biopolymer chitosan on its bactericidal activity. Polym. Sci. Ser. A. 2013;55(2):98–101. https://doi.org/10.1134/S0965545X13020028 [Original Russian Text: Azimov Zh.T., Oksengendler B.L., Turaeva N.N., Rashidova S.Sh. Eff of the structure of the biopolymer chitosan on its bactericidal activity. Vysokomolekulyarnye Soedineniya. Ser. A. 2013;55(2):165–101 (in Russ.). https://doi.org/10.7868/S0507547513020025 ]

17. Kritchenkov A.S., Andranovitšc S., Skorik Yu.A. Chitosan and its derivatives: vectors in gene therapy. Russ. Chem. Rev. 2017;86(3):231–239. https://doi.org/10.1070/rcr4636 [Original Russian Text: Kritchenkov A.S., Andranovitšc S., Skorik Yu.A. Chitosan and its derivatives: vectors in gene therapy. Uspekhi Khimii. 2017;86(3):231–239 (in Russ.).]

18. Povernov P.A., Shibryaeva L.S., Lusova L.R., Popov A.A. Modern polymer composite materials for bone surgery: Problems and prospects. Tonk. Khim. Tekhnol. = Fine Chem. Technol. 2022;17(6):514–536 (Russ., Eng.). https://doi.org/10.32362/2410-6593-2022-17-6-514-536

19. Lykoshin D.D., Zaitsev V.V., Kostromina M.A., Esipov R.S. New-generation osteoplastic materials based on biological and synthetic matrices. Tonk. Khim. Tekhnol. = Fine Chem. Technol. 2021;16(1):36–54 (Russ., Eng.). https://doi.org/10.32362/2410-6593-2021-16-1-36-54

20. Ignatieva P.E., Zhavoronok E.S., Legonkova O.A., Kedik S.A. Compositions based on aqueous solutions of chitosan and glutar aldehyde for embolization of blood vessels. Tonk. Khim. Tekhnol. = Fine Chem. Technol. 2019;14(1):25–31 (Russ., Eng.). https://doi.org/10.32362/2410-6593-2019-14-1-25-31

21. Al-Remawi M.M. Properties of Chitosan Nanoparticles Formed Using Sulfate Anions as Crosslinking Bridges. Am. J. Applied Sci. 2012;9(7):1091–1100. https://doi.org/10.3844/AJASSP.2012.1091.1100

22. Mezina E.A., Lipatova I.M. Formation of the dispersed phase in mixed solutions of chitosan and magnesium sulfate. Russ. J. Appl. Chem. 2014;87(6):830–835. https://doi.org/10.1134/S1070427214060275 [Original Russian Text: Mezina E.A., Lipatova I.M. Formation of the dispersed phase in mixed solutions of chitosan and magnesium sulfate. Zhurnal Prikladnoi Khimii. 2014;87(6):821–827 (in Russ.).]

23. Mezina E.A., Lipatova I.M. Eff of peroxide depolymerization of chitosan on properties of chitosan sulfate particles produced from this substance. Russ. J. Appl. Chem. 2015;88(10):1576–1581. https://doi.org/10.1134/S1070427215100031 [Original Russian Text: Mezina E.A., Lipatova I.M. Effekt of peroxide depolymerization of chitosan on properties of chitosan sulfate particles produced from this substance. Zhurnal Prikladnoi Khimii. 2015;88(10):1390–1395 (in Russ.).]

24. Gordienko M.G., Somov T.N., Yusupova Y.S., Chupikova N.I., Menshutina N.V. Preparation of spherical microparticles from biodegradable natural and synthetic polymers for their application in regenerative medicine. Fine Chem. Technol. 2015;10(5):66–76 (in Russ.).

25. Zhang С., Zhang H., Li R., Xing Y. Morphology and adsorption properties of chitosan sulfate salt microspheres prepared by a microwave-assisted method. RSC Adv. 2017;7(76): 48189–48198. https://doi.org/10.1039/C7RA09867G

26. Apryatina K.V., Mochalova A.E., Gracheva T.A., et al. Influence of the molecular mass of chitosan on the dimensional characteristics of silver nanoparticles. Polymer Sci. Ser. B. 2015;57(2):145–149. https://doi.org/10.1134/S1560090415020013 [Original Russian Text: Apryatina K.V., Mochalova A.E., Gracheva T.A., Kuz’micheva T.A., Smirnova L.A., Smirnova O.N. Infl of the molecular mass of chitosan on the dimensional characteristics of silver nanoparticles. Vysokomolekulyarnye Soedineniya. Ser. B. 2015;57(2):154–1158 (in Russ.). https://doi.org/10.7868/S2308113915020011 ]

27. Tyukova I.S., Safronov A.P., Kotel’nikova A.P., et al. Electrostatic and steric mechanisms of iron oxide nanoparticle sol stabilization by chitosan. Polymer Sci. Ser. А. 2014;56(4):498–504. https://doi.org/10.1134/S0965545X14040178 [Original Russian Text: Tyukova I.S., Safronov A.P., Kotel’nikova A.P., Agalakova D.Yu. Electrostatic and steric mechanisms of iron oxide nanoparticle sol stabilization by chitosan. Vysokomolekulyarnye Soedineniya. Ser. А. 2014;56(4):419–426 (in Russ.). https://doi.org/10.7868/S2308112014040178 ]

28. Bochek A.M., Vokhidova N., Saprykina N.N., et al. The properties of chitosan-cobalt nanoparticle solutions and related composite films. Polymer Sci. Ser. А. 2015;57(4): 460–466. https://doi.org/10.1134/S0965545X15040033 [Original Russian Text: Bochek A.M., Vokhidova N., Saprykina N.N., Ashurov N.S., Yugai S.M., Rashidova S.S. The properties of chitosan-cobalt nanoparticle solutions and related composite films. Vysokomolekulyarnye Soedineniya. Ser. А. 2015;57(4):354–360 (in Russ.). https://doi.org/10.7868/S2308112015040033 ]

29. Wilson B.K., Prud’homme R.K. Processing Chitosan for Preparing Chitosan-Functionalized Nanoparticles by Polyelectrolyte Adsorption. Langmuir. 2021;37(28):8517–8524. https://doi.org/10.1021/acs.langmuir.1c00990

30. Czechowska-Biskup R., Jarosińska D., Rokita B., et al. Determination of degree of deacetylation of chitosan – Comparison of methods. Progress on Chemistry and Application of Chitin and its Derivatives. 2012;17:5–20.

31. Wang W., Bo Sh., Li S., Qin W. Detrmination of the Mark– Houwink equation for chitosans with different degrees of deacetylation. Int. J. Biol. Macromol. 1991;13(5):281–285. https://doi.org/10.1016/0141-8130(91)90027-R

32. Belalia F., Djelali N.-E. Rheological properties of sodium alginate solutions. Revue Roumaine de Chimie. 2014;59(2):135–145.

33. Distantina S., Wiratni, Fahrurrozi M., Rochmadi. Carrageenan properties extracted from Eucheuma cottonii, Indonesia. Int. J. Chem. Mol. Eng. 2011;5(6):501–505.

34. Masuelli M.A. Mark–Houwink parameters for aqueoussoluble polymers and biopolymers at various temperatures. J. Polymer Biopolymer Phys. Chem. 2014;2(2):37–43.


Supplementary files

1. Cross-linking of protonated chitosan with sulfate anions
Subject
Type Исследовательские инструменты
View (35KB)    
Indexing metadata ▾
  • A method was developed to obtain chitosanium sulfate (ChS) hydrosol with a positive particle charge.
  • The stability of ChS sols over time was studied both without and with the addition of sodium alginate (SA), κ-carrageenan, and xanthan. Sol coagulation thresholds with indifferent and non-indifferent electrolytes, as well as the protective numbers for κ-carrageenan and SA against the coagulation of hydrosols with these electrolytes, were established.
  • The mechanism of stability of sols at certain concentrations of water-soluble polysaccharides was explained using data on the adsorption of these polysaccharides on the surface of chitosan treated with a solution of sulfuric acid.
  • Based on the results of the work, it can be concluded that SA and κ-carrageenan can be used for the efficient stabilization of ChS hydrosols over time and for the colloidal protection of ChS from coagulation with sodium chloride.

Review

For citations:


Erasov V.S., Maltseva Yu.O. Obtaining chitosan sulfate nanoparticles in an aqueous medium and their colloidal protection with polysaccharides. Fine Chemical Technologies. 2024;19(2):111-126. https://doi.org/10.32362/2410-6593-2024-19-2-111-126

Views: 508


ISSN 2410-6593 (Print)
ISSN 2686-7575 (Online)