CC BY
21
ISSN 1998-4812
Вестник Башкирского университета. 2017. Т. 22. №1
83
УДК 544.35.03:547.458
THE INFLUENCE OF WATER-SOLUBLE POLYMER CHITOSAN SUCCINAMIDE ON SURFACE ACTIVITY OF SODIUM DODECYLSULFATE
AND TWEEN-80
© M. V. Bazunova*, I. R. Allayarov, A. A. Shulga, D. Sh. Yuzlikbaeva, E. I. Kulish
Bashkir State University 32 Zaki Validi Street, 450076 Ufa, Republic of Bashkortostan, Russia.
Phone: +7 (347) 229 97 24.
*Еmail: mbazunova@mail.ru
In the article, the effect of the water-soluble polymer chitosan succinamide on surface activity of such commonly used surfactants as anionic and non-ionic sodium dodecylsulfate TWEEN-80 was studied. It was shown that the combined use of sodium dodecylsulfate and TWEEN-80 with chitosan succinamide increases the surface activity of the studied surfactants. It was found that the association of chitosan suc-cinamide with sodium dodecylsulfate or TWEEN-80 begins at concentrations of an order of magnitude lower than the critical micelle concentration of studied surfactants. It is supposed that reduction of the dynamic viscosity ofthe solution ofchitosan succinamide in the presence of ionic and nonionic surfactants apparently is caused by formation ofpolymer-colloid complexes. The introduction ofphysiologically active polymer succinamide chitosan in a synthetic surfactant solution should lead to a decrease in irritant effect on the human skin when using this surfactant in the detergent composition.
Keywords: chitosan succinamide, sodium dodecylsulfate, TWEEN-80, surface activity, critical concentration of association.
Introduction
The systems based on surface-active substances (SAS) and water-soluble polymers have wide practical application. The use of compositions based on SAS and water-soluble polymers is dictated by the necessity of obtaining various effects: stabilization of dispersions, production of emulsions, strengthening of structure - formation processes and so on [1-5]. However, as the influence of the polymer on surface tension of SAS water solutions is ambiguous and depends on the concentration of the latter [6], it is impossible to predict beforehand the effect of the polymer on SAS surface activity, which makes it necessary to conduct special investigations.
Besides, many surface-active substances, in particular sodium dodecylsulfate (SDS), which has low cost and therefore is widely used in the production of detergents and cosmetics as a foam-forming basis, possesses an irritating action. Being gradually accumulated in internal organs, most of synthetic SAS can result in their damage [7-9]. To reduce the irritating action of SAS one can use co-SAS, like non-ionogenic SAS and polymeric additions, such as chitosan, poly-4-vinyl-N-butylpyridine bromide and others [10]. It is evident that at choosing polymers we must prefer those which are non-toxic and biocompatible, e.g. the ones chosen from polysaccharides.
The aim of this work is studying the effect of water-soluble derivative of polysaccharide chitosan-so-dium salt chitosan succinamide (ChS) on surface activity of such widespread SAS as anion-active SDS and non-ionogenic SAS-TWEEN-80. The polymer choice is conditioned by the complex of unique properties exhibited by it, among which are bio-compatibility with organism's tissues, bacteriostaticity, ability for bio-degradation and many others [11].
Experimental
In the work we used ChS with M.m. = 207 kDa and characteristic viscosity [^]= 3.60 dl/g (TU 9284-02711734126-08) produced by the company "Bioprogress" (Tchelkovo, Russia). In the used ChS, the concentration of amino-groups was 10% mol., the concentration of succinamide groups was 75% mol.
TWEEN-80 ^Across Organic brand analytical grade), a 10% solution and SDS (NPAO "Synthes SAS", Tchebkino, Russia) were used without additional purification.
Bidistilled water was used as a solvent. ChS dissolution was performed during 24 hours. The dissolution of SDS and TWEEN-80 was carried out by magnetic stirring at room temperature for 0.5 hour. SAS and ChS solutions were prepared in the concentration range of 0.3510-5 - 0.1 mol/l.
The surface tension of the investigated solutions at the liquid-gas interface was determined by the method of maximum pressure of gas bubbles at 20 °C [12].
The surface activity (g) of SDS, TWEEN-80 and ChS as well as of the SAS-polymer system at the "solution-air" boundary was determined graphically by the experimental isotherm of surface tension a=f(c), by drawing a tangent line to the curve in the point of its crossing the axis of ordinates (at c=0) and by calculating the tangent of the tangent line slope [12].
The rheological investigation of ChS solutions and ChS-SAS systems was carried out on the module dynamic rheometer Haake Mars III at 200C under the condition of constant shear deformation in the range of shear rates from 0.1 to 100 s-1.
84
ХИМИЯ
Discussion
The investigation of the surface tension of binary mixture solutions SAS-ChS was preceded by the study of the surface tension of separate components. As seen from Fig. 1, all the three substances under investigation demonstrate surface activity, the highest surface activity being exhibited by TWEEN-80 and the lowest one- by ChS. By the isotherm of surface tension, the CCMs of the studied SAS were calculated that were equal to 8.4 • 10 3 mol/l for SDS and 9.6 • 105 mol/l for TWEEN-80, as well as the values of SAS surface activity that turned out to be 0.37 (J m)/mol for SDS 2.7 (J m)/mol for TWEEN-80, which is in good agreement with literature data [12, 13, 15]. The surface activity of ChS was equal to 0.21 (Jm)/mol.
Fig. 1. The isotherm of surface tension of SDS (1), TWEEN-80 (2) and ChS (3) solutions.
The mixing of ChS solution with SDS solutions is accompanied by regular decrease in dynamic viscosity (Fig. 2), evidently due to hydrophobic interrelations of hydrocarbon radicals of SAS with hydrophobic spacers of ChS macromolecules, and by forming polymer-colloidal complexes (PPC) [6, 15, 16].
Fig. 2. The dependence of dynamic viscosity of 0.2% ChS solution on the content of SAS in the solution in semi-logarithmic coordinates
As this takes place, the mixing of SAS solutions with ChS solution is accompanied by synergetic effect
of reducing surface tension at SAS concentrations lower than CCM (Fig. 3).
Moreover, at a definite concentration a slight bend connected evidently with reaching the critical concentration of association (CCA) is observed on isotherms of surface tension. At CCA there starts the association between molecules of SAS and the polymer and SAS molecules adsorption by their hydrophobic groups on the expanded polymeric chain with forming micelle aggregates. For this reason at further increasing SAS concentration its activity doesn't increase and the surface tension remains constant. At polymer saturation with SAS molecules the concentration of the latter and its activity begin to increase again while the surface tension decreases up to reacting the CCM of SAS, after which regular SAS micelles start to form in the solution.
Fig. 3. The isotherm of surface tension for the initial SDS solution (1) and PCC ChS-SDS (2, 3). The content of ChS in the SDS solution is 510-4 mol/l (2) and 2,510-3 mol/l (3).
Analogous regularities take place for PPC ChS-TWEEN-80 solutions as well (Fig. 2 and Fig. 4). The data in Fig. 4 show that the values of surface tension of SAS-polymer mixtures are lower than the analogous isotherms of separate components.
Fig. 4. The isotherm of surface tension for the initial solution TWEEN-80(1) and PCC ChS-TWEEN (2, 3). The content of ChS in TWEEN solution is 5 10-4 mol/l (2) and 2,5 10-3 mol/l (3).
The polymer-induced micelle formation reduces the concentration of molecular- dissolved SAS, which must decrease the irritating action of SAS.
ISSN 1998-4812
BeciHHK EamKHpcKoro yHHBepcHTeTa. 2017. T. 22. №1
85
Conclusions
1. It has been demonstrated that the mixtures of SDS and TWEEN-80 with ChS are characterized by a greater value of surface activity than separate SAS.
2. It has been established that association of chitosan succinamide with SDS or TWEEN-80 starts at concentrations that are an order of magnitude lower than the critical concentration of micelle-formation of the SAS studied.
3. The fact has been established that dynamic viscosity of chitosan succinamide solutions decreases in the presence of both ionogenic SAS and non-ionogenic one due, evidently, to the formation of polymer-colloidal complex.
REFERENCES
1. Babak V. G., Colloidal chemistry in technology of microcapsu-lating. Sverdlovsk: Ural State University, 1991. 215 p.
2. Kasaykin V. A., Borodullina T. A., Kabanov N. M. // Vysoko-mol. Soed., S. A. 1987. T. 29. №11. C. 803-804.
3. S. Barany // Colloid journal. 2002. V. 64. №5. P. 533-537.
4. V. A. Kabanov // Polymer Science, Ser. A. 2004. V. 46. №5. P. 451-484.
5. Sokolovskiy M. V., Afinogenov G. E., Panarin G. N.// Chim. Pharm.Journal. 1980. №11. p. 51-56.
6. Holmberg K. Surface-active substances and polymers in water solutions. [Electronic resource]// K. Holmberg, B. Joensson, B. Kronberg et al.: 2 nd ed.(el.)-M.:BINOM. Laboratory of knowledge, 2012. P. 532.
7. Agner T. // Acta Derm. Venereol. 1991. V. 71. N 4. P. 296-300.
8. Nassif A., Chan S. C., Storrs F. J., Hanifin J. M. //Arch. Dermatol. 1994. V. 130. №11. P. 1402-1407.
9. Marrakchi S., Maibach H. I. // Skin Pharmacol. Physiol.2006. V. 19. №3. P. 177-180.
10. Barabanov V. P., Tretyakova A.Ya., Shilova S. V.// Materi-alovedeniye, 2009. №3, p. 33-40
11. Slivkin A. I., Lapenko V. L., Arzamastsev A. P. et al. // Vestnik Voronezh. Gos. Un-ta. Ser.: Chemistry. Biology. Pharmacy. 2005. №2. P. 73.
12. Ed. A. A. Abramzon, E. D. Tshukin. L// Surface phenomena and surface-active substances: Reference book.: Chemistry, 1984. 392 p.
13. Ivanova N. I. // Vestnik Mosk. Un-ta. Ser. 2. Chemistry. 2012. T. 53. №1, P. 44-49.
14. Verezhnikova V. N. // Practical studies in colloidal chemistry of surface-active substances: Textbook. Voronezh: VGU, 1984, 224 p.
15. Thunemann, A. F. // Prog. Polym.Sci. 2002.V. 27. №2. P. 14731572.
16. Langevin D. // Adv. Colloid Interface Sci. 2009. V. 147-148. P. 170-177.
nocmynma epeda^um 27.12.2016 г.
