Email the author Interfacial properties of chitosan lactate at the liquid/air interface
DOI: https://doi.org/10.15407/hftp12.04.374
Abstract
The interfacial properties (dynamic and equilibrium surface tension, viscosity and elasticity moduli) of chitosan lactate have been studied at the liquid/air interface by the oscillating drop shape method. Isotherms of dynamic surface tension of chitosan lactate are similar to dependences for other polyelectrolyte solutions, in particular for proteins. Chitosan is a weak cationic polyelectrolyte which can change its conformation from a linear rod to a chaotic and compacted coil. Therefore, the experimental dependence of the equilibrium surface tension on concentration of chitosan lactate was analyzed with the adsorption model proposed earlier for proteins. This model accounts the possibility of polyelectrolyte molecules existence in surface layer in n states with different molar surface varying from the maximum value at very low surface coverage by polyelectrolyte molecules to a minimum value at high surface coverage. Good agreement between the calculated and experimental values of surface tension was observed. The dependences of the elasticity and viscosity moduli of chitosan lactate solutions on the drop oscillations frequency are conditioned by the influence of exchange processes both between the surface layer and the bulk solution and in the surface layer itself. An increase of the solution concentration intensifies the exchange processes, and an increase of the oscillation frequency suppresses them. It is shown that the dependence of the surface viscoelasticity modulus of chitosan lactate is extreme in nature with a pronounced maximum. The reason for such behavior is the possibility of changing the molar surface area of the polyelectrolyte at the interface dependent on the amount of adsorption and its structural properties. Attempt of theoretical description of the viscoelasticity modulus within the framework of model accounting mono- or bilayer adsorption did not lead to a satisfactory result, possibly due to barrier adsorption mechanism of chitosan. But bilayer model provide qualitative description of extreme behavior of surface viscoelasticity on concentration. The values of the surface viscoelasticity modulus of chitosan lactate occupy an intermediate position in comparison with the data available in the literature for globular and flexible-chain proteins, that is consistent with their molecular structure. In addition, the work shows the applicability of the adsorption model, developed earlier for proteins in the framework of a nonideal two-dimensional solution theory, for describing the surface properties of other polyelectrolytes. This makes it possible to obtain qualitative and quantitative information about the processes occurring in the systems under study.
Keywords
Full Text:
References
1. Negi P., Sharma G., Verma C., Garg P., Rathore Ch., Kulshrestha S., Lal U.R., Gupta B., Pathania D. Novel thymoquinone loaded chitosan-lecithin micelles for effective wound healing: Development, characterization, and preclinical evaluation. Carbohydr. Polym. 2020. 230: 115659. https://doi.org/10.1016/j.carbpol.2019.115659
2. Ullah F., Javed F., Kudus M.H.A., Khan A.N., Akil H.Md. Determining the molecular-weight and interfacial properties of chitosan built nanohydrogel for controlled drug delivery applications. Biointerface Res. Appl. Chem. 2019. 9(6): 4452. https://doi.org/10.33263/BRIAC96.452457
3. Zinoviadou K.G., Scholten E., Moschakis T., Biliaderis C.G. Engineering interfacial properties by anionic surfactant-chitosan complexes to improve stability of oil-in-water emulsions. Food Funct. 2012. 3(3): 312. https://doi.org/10.1039/c2fo10197a
4. Santini E., Jarek E., Ravera F., Liggieri L., Warszynski P., Krzan M. Surface properties and foamability of saponin and saponin-chitosan systems. Colloids Surf., B. 2019. 181: 198. https://doi.org/10.1016/j.colsurfb.2019.05.035
5. Wang X.-Y., Wang J., Rousseau D., Tan Ch.-H. Chitosan-stabilized emulsion gels via pH-induced droplet flocculation. Food Hydrocolloids. 2020. 105: 105811. https://doi.org/10.1016/j.foodhyd.2020.105811
6. Liu M.M., Zhou Y., Zhang Y., Yu Ch., Cao Sh. Preparation and structural analysis of chitosan films with and without sorbitol. Food Hydrocolloids. 2013. 33(2): 186. https://doi.org/10.1016/j.foodhyd.2013.03.003
7. Poshina D.N., Kryzhanovskaya V.S., Torkunova E.A., Sukhova A.A., Skorik Y.A. Influence of the composition of water chitosan lactate solutions on their properties and electrospinning. Izvestia Ufimskogo Nauchnogo Tsentra RAN. 2018. 3(3): 90. [in Russian]. https://doi.org/10.31040/2222-8349-2018-3-3-90-94
8. Monroy F., Ortega F., Rubio R.G., Noskov B.A. Surface rheology studies of spread and adsorbed polymer layers. In: Progress in Colloid and Interface Science, Interfacial Rheology. V. 1. (Leiden: Brill, 2009). P. 178. https://doi.org/10.1163/ej.9789004175860.i-684.41
9. Debrier J., Babak V.G. Interfacial properties of amphiphilic systems on the basis of natural polymers-chitin derivatives. Russ. J. Gen. Chem. 2008. 78(11): 2230. https://doi.org/10.1134/S1070363208110443
10. Fricke N., Keul H., Moller M. Synthesis of Chitosan Surfactants. Macromol. Chem. Phys. 2009. 21(9): 752. https://doi.org/10.1002/macp.200800622
11. Vikhoreva G.A., Chernukhina A.I., Strokova N.G., Gal'braikh L.S. Preparation and investigation of solutions of chitosan derivatives with long-chain hydrophilic substituents. Polym. Sci. Ser. B. 2007. 49(5-6): 131. https://doi.org/10.1134/S1560090407050065
12. Babak V.G., Desbrieres J. Dynamic surface tension of hydrophobically modified chitosans. Mendeleev Commun. 2004. 14(2): 66. https://doi.org/10.1070/MC2004v014n02ABEH001824
13. Pérez-Gramatges A., Matheus C.R.V., Lopes G., da Silva J.C. Surface and interfacial tension study of interactions between water-soluble cationic and hydrophobically modified chitosans and nonylphenolethoxylate. Colloids and Surfaces A: Physicochem. Eng. Aspects. 2013. 418: 124. https://doi.org/10.1016/j.colsurfa.2012.11.035
14. Babak V.G., Baros F., Boury F., Desbrieres J. Dilational viscoelasticity and relaxation properties of interfacial electrostatic complexes between oppositely charged hydrophobic and hydrophilic polyelectrolytes. Colloids Surf. B. 2008. 65: 43. https://doi.org/10.1016/j.colsurfb.2008.02.019
15. Babak V.G., Auzely R., Rinaudo M. Effect of electrolyte concentration on the dynamic surface tension and dilational viscoelasticity of adsorption layers of chitosan and dodecyl chitosan. J. Phys. Chem. B. 2007. 111(32): 9519. https://doi.org/10.1021/jp0718653
16. Zholob S.A., Kovalchuk V.I., Makievski A.V., Krägel J. Determination of the dilational elasticity and viscosity from the surface tension response to harmonic area perturbations. In: Progress in Colloid and Interface Science, Interfacial Rheology. V. 1. (Leiden: Brill, 2009). P. 77.
17. Zholob S.A., Makievski A.V., Miller R., Fainerman V.B. Optimization of calculation methods for determination of surface tensions by drop profile analysis tensiometry. Adv. Colloid Interface Sci. 2007. 134-135: 322. https://doi.org/10.1016/j.cis.2007.04.011
18. Fainerman V.B., Miller R. Equilibrium and Dynamic Characteristics of Protein Adsorption Layers at Gas-Liquid Interfaces: Theoretical and Experimental Data. Colloid J. 2005. 67: 393. https://doi.org/10.1007/s10595-005-0110-8
19. Babak V.G., Desbrieres J. Dynamic surface tension and dilational viscoelasticity of adsorption layers of alkylated chitosans and surfactant-chitosan complexes. Colloid Polym. Sci. 2006. 284: 745. https://doi.org/10.1007/s00396-005-1427-x
20. Davydova V.N., Yermak I.M. The Conformation of Chitosan Molecules in Aqueous Solutions. Biophysics. 2008. 63: 501. https://doi.org/10.1134/S000635091804005X
21. Cunha R.A., Soares Th.A., Rusu V.H., Pontes F.J.S., Franca E.F., Lins R.D. The molecular structure and conformational dynamics of chitosan polymers: an integrated perspective from experiments and computational simulations. In: The Complex World of Polysaccharides. Ch. 9. (Intech Open, 2012). P. 229.
22. Fainerman V.B., Lucassen-Reynders E.H., Miller R. Description of the adsorption behaviour of proteins at water/fluid interfaces in the framework of a two-dimensional solution model. Adv. Colloid Interface Sci. 2003. 106: 237. https://doi.org/10.1016/S0001-8686(03)00112-X
23. Tiraferri A., Maroni P., Caro Rodríguez D., Borkovec M. Mechanism of chitosan adsorption on silica from aqueous Solutions. Langmuir. 2014. 30: 4980. https://doi.org/10.1021/la500680g
24. Fainerman V.B., Aksenenko E.V., Makievski A.V. Trukhin D.V., Yeganehzad S., Gochev G., Miller R. Surface tension and dilational rheology of mixed β-casein - β-lactoglobulin aqueous solutions at the water/air interface. Food Hydrocolloids. 2020. 106: 1. https://doi.org/10.1016/j.foodhyd.2020.105883
25. Lucassen-Reynders E.H., Fainerman V.B., Miller R. Surface dilational modulus or Gibbs elasticity of protein adsorption layers. J. Phys. Chem. B. 2004. 108: 9173. https://doi.org/10.1021/jp049682t
26. Noskov B.A., Latnikova A.V., Lin S.-Y., Loglio G., Miller R. Dynamic surface elasticity of β-casein solutions during adsorption. J. Phys. Chem. C. 2007. 111(45): 16895. https://doi.org/10.1021/jp073813j
27. Benjamins J., Lyklema J., Lucassen-Reynders E.H. Compression/expansion rheology of oil/water interfaces with adsorbed proteins. Comparison with the air/water surface. Langmuir. 2006. 22: 6181. https://doi.org/10.1021/la060441h
DOI: https://doi.org/10.15407/hftp12.04.374
Copyright (©) 2021 G. I. Kovtun
This work is licensed under a Creative Commons Attribution 4.0 International License.