Injectable ultra soft hydrogel with natural nanoclay
https://doi.org/10.17586/2220-8054-2019-10-1-76-85
Abstract
Soft hydrogels based on a transient network of wormlike surfactant micelles containing bentonite nanoclay tactoids as physical cross-links were developed. The network was composed of mixed micelles of nontoxic zwitterionic surfactant oleylamidopropyldimethylcarboxybetaine and an anionic surfactant sodium dodecyl sulfate. It was demonstrated that before nanoclay addition the solution has pronounced viscoelastic properties with zero-shear viscosity of 100 Pa s and plateau modulus around 7 Pa, which were attributed to the formation of an entangled micellar network. The solution demonstrated pronounced shear thinning behavior provided by the elongation of wormlike micellar chains in flow direction. Upon addition of non-exfoliated nanoclay particles, the zero-shear viscosity increases by an order of magnitude, while the useful property of shear-induced thinning is retained. Oscillation amplitude tests show that viscoelastic fluid becomes hydrogel upon addition of nanoclay, because elastic response was observed even at large stress amplitudes. This behavior was attributed to the formation of nanoclaywormlike micelles junctions. Prepared soft hydrogel is a promising candidate for injection applications, because of its self-assembled structure providing pronounced shear-thinning behavior and fast recovery of rheological properties at rest. In this nanocomposite material, nanoclay tactoids strengthen the hydrogels and can serve as reservoirs for the delivery of various substances.
Supporting agencies: This work was supported by the Russian Science Foundation (project No. 17-13-01535).
About the Authors
V. S. Molchanov
Department of Physics, Lomonosov Moscow State University
Russian Federation
Russian Federation
Leninskie Gory, 1, bld. 2, Moscow, 119991
M. A. Efremova
Department of Physics, Lomonosov Moscow State University
Russian Federation
Russian Federation
Leninskie Gory, 1, bld. 2, Moscow, 119991
T. Yu. Kiseleva
Department of Physics, Lomonosov Moscow State University
Russian Federation
Russian Federation
Leninskie Gory, 1, bld. 2, Moscow, 119991
O. E. Philippova
Department of Physics, Lomonosov Moscow State University
Russian Federation
Russian Federation
Leninskie Gory, 1, bld. 2, Moscow, 119991
References
1. Philippova O.E., Khokhlov A.R. Polymer gels. In Polymer Science: A Comprehensive reference, vol. 1, Elsevier B.V., USA, 2012, P. 339–366.
2. Philippova O.E., Chtcheglova L.A., Karybiants N.S., Khokhlov A.R. Two mechanisms of gel/surfactant binding. Polymer Gels and Networks, 1998, 6, P. 409–421.
3. Sharifi S., Blanquer S.B.G., Van Kooten T.G., Grijpma D.W. Biodegradable nanocomposite hydrogel structures with enhanced mechanical properties prepared by photo-crosslinking solutions of poly(trimethylene carbonate)-poly(ethylene glycol)-poly(trimethylene carbonate) macromonomers and nanoclay particles. Acta Biomater., 2012, 8 (12), P. 4233–4243.
4. Li C., Shi G. Functional gels based on chemically modified graphenes. Advanced Materials, 2014, 26 (24), P. 3992–4012.
5. Lokhande G., Carrow J.K., et al. Nanoengineered injectable hydrogels from kappa-carrageenan and two-dimensional nanosilicates for wound healing application. Acta Biomater., 2018, 70 (1), P. 35–47.
6. Rehage H., Hoffmann H. Rheological properties of viscoelastic surfactant systems. J. Phys. Chem., 1988, 92 (16), P. 4712–4719.
7. Granek R., Cates M.E. Stress relaxation in living polymers: Results from a Poisson renewal model. J. Chem. Phys., 1992, 96 (6), P. 4758–4767.
8. Philippova O.E. Self-assembled networks formed by wormlike micelles and nanoparticles. In Wormlike Micelles: Advances in Systems, Characterisation and Applications, Soft Matter Series, 2017, 6, P. 103–120.
9. Shibaev A.V., Philippova O.E. Viscoelastic properties of new mixed wormlike micelles formed by a fatty acid salt and alkylpyridinium surfactant. Nanosystems: Physics, Chemistry, Mathematics, 2017, 8 (6), P. 732–739.
10. Berret J.-F., Appell J., Porte G. Linear rheology of entangled wormlike micelles. Langmuir, 1993, 9 (11), P. 2851–2854.
11. Dreiss C.A. Wormlike micelles: Where do we stand? Recent developments, linear rheology and scattering techniques. Soft Matter, 2007, 3 (8), P. 956–970.
12. Chu Z., Dreiss C.A., Feng Y. Smart wormlike micelles. Chem. Soc. Rev., 2013, 42 (17), P. 7174–7203.
13. Khatory A., Lequeux F., Kern F., Candau S.J. Linear and nonlinear viscoelasticity of semidilute solutions of wormlike micelles at high salt content. Langmuir, 1993, 9 (6), P. 1456–1464.
14. Bandyopadhyay R., Sood A.K. Effect of silica colloids on the rheology of viscoelastic gels formed by the surfactant cetyl trimethylammonium tosylate. J. Colloid Interface Sci., 2005, 283, P. 585–591.
15. Helgeson M.E., Hodgdon T.K., Kaler E.W., Wagner N.J. Formation and rheology of viscoelastic “double networks” in wormlike micellenanoparticle mixtures. Langmuir, 2010, 26 (11), P. 8049–8060.
16. Luo M., Jia Z., et al. Rheological behavior and microstructure of an anionic surfactant micelle solution with pyroelectric nanoparticle. Colloids and Surfaces A: Physicochem. Eng. Aspects, 2012, 395, P. 267–275.
17. Pletneva V.A., Molchanov V.S., Philippova O.E. Viscoelasticity of smart fluids wormlike micelles and oppositely charged magnetic particles. Langmuir, 2015, 31, P. 110–119.
18. Fan Q., Li W., et al. Nanoparticles induced micellar growth in sodium oleate wormlike micelles solutions. Colloid. Polym. Sci., 2015, 293 (9), P. 2507–2513.
19. Molchanov V.S., Pletneva V.A., et al. Soft magnetic nanocomposites based on adaptive matrix of wormlike surfactant micelles. RSC Adv., 2018, 8 (21), P. 11589–11597.
20. Molchanov V.S., Klepikov I.A., Razumovskaya I.V., Philippova O.E. Magnetically tunable viscoelastic response of soft magnetic nanocomposites with wormlike surfactant micellar matrix. Nanosystems: Physics, Chemistry, Mathematics, 2018, 9 (3), P. 335–341.
21. Hosseini F., Hosseini F., Jafari S.M., Taheri A. Bentonite nanoclay-based drug-delivery systems for treating melanoma. Clay Minerals, 2018, 53 (1), P. 53–63.
22. Zhang Y., Peng M.L., et al. Emerging integrated nanoclay-facilitated drug delivery system for papillary thyroid cancer therapy. Scientific Reports, 2016, 6, AN33335.
23. Kelleppan V.T., Moore J.E., et al. Self-Assembly of long-chain betaine surfactants: effect of tail group structure on wormlike micelle formation. Langmuir, 2018, 34 (3), P. 970–977.
24. McCoy T.M., King J.P., et al. The effects of small molecule organic additives on the self-assembly and rheology of betaine wormlike micellar fluids. J Colloid Interface Sci., 2019, 534, P. 518–532.
25. Kuryashov D.A., Philippova O.E., et al. Temperature effect on the viscoelastic properties of solutions of cylindrical mixed micelles of zwitterionic and anionic surfactants. Colloid J., 2010, 72, P. 230–235.
26. Christov N.C., Denkov N.D., et al. Synergistic sphere-to-rod micelle transition in mixed solutions of sodium dodecyl sulfate and cocoamidopropyl betaine. Langmuir, 2004, 20, P. 565–571.
27. Weers J.G, Rathman J.F., et al. Effect of the intramolecular charge separation distance on the solution properties of betaines and sulfobetaines. Langmuir, 1991, 7, P. 854–867.
28. Tayebee R., Mazruy V. Acid-thermal activated nanobentonite as an economic industrial adsorbent for malachite green from aqueous solutions. Optimization, isotherm, and thermodynamic studies. J. Water Environ. Nanotechnol., 2018, 3 (1), P. 40–50.
29. Baik M.H., Lee S.Y. Colloidal stability of bentonite clay considering surface charge properties as a function of pH and ionic strength. J. Ind. Eng. Chem., 2010, 16, P. 837–841.
30. Yao M., Zhang X., Lei L. Removal of reactive Blue 13 from dyeing wastewater by self-assembled organobentonite in a one-step process. J. Chem. Eng. Data, 2012, 57 (7), P. 1915–1922.
31. Zhu J., Qing Y., et al. Preparation and characterization of zwitterionic surfactant-modified montmorillonites. J. Colloid Interface Sci., 2011, 360 (2), P. 386–392.
32. Belova V., Mohwald H., Shchukin D.G. Ultrasonic intercalation of gold nanoparticles into a clay matrix in the presence of surface-active materials. Part II: negative sodium dodecylsulfate and positive cetyltrimethylammonium bromide. J. Phys. Chem., 2009, 113, P. 6721–6760.
33. Yalc¸in T., Alemdar A., Ece O.I., G¨ung ¨ or N. The viscosity and zeta potential of bentonite dispersions in presence of anionic surfactants. ¨ Materials Letters, 2002, 57, P. 420–424.
34. Kooli F. Exfoliation properties of acid-activated montmorillonites and their resulting organoclay. Langmuir, 2009, 25 (2), P. 724–730.
35. Molchanov V.S., Shashkina Y.A., Philippova O.E., Khokhlov A.R. Viscoelastic properties of aqueous anionic surfactant (potassium oleate) solutions. Colloid J., 2005, 67 (5), P. 606–609.
36. Lerouge S., Berret J.-F. Shear-induced transitions and instabilities in surfactant wormlike micelles. Adv. Polym. Sci., 2009, 230, P. 1–71.
37. Molchanov V.S., Philippova O.E. Dominant role of wormlike micelles in temperature-responsive viscoelastic properties of their mixtures with polymeric chains. J. Colloid Interface Sci., 2013, 394, P. 353–359.
38. Hyun K., Kim S.H., Ahn K.H., Lee S.J. Large amplitude oscillatory shear as a way to classify the complex fluids. J. Non-Newtonian Fluid Mech., 2005, 107, P. 51–65.
39. Zhao Y. Rheological characterizations of wormlike micellar solutions containing cationic surfactant and anionic hydrotropic salt. J. Rheology, 2015, 59 (5), P. 1229–1259.
Review
For citations:
Molchanov V.S., Efremova M.A., Kiseleva T.Yu., Philippova O.E. Injectable ultra soft hydrogel with natural nanoclay. Nanosystems: Physics, Chemistry, Mathematics. 2019;10(1):76-85. https://doi.org/10.17586/2220-8054-2019-10-1-76-85
Views:
1
Email this article 