Abstract
A chain transfer agent was immobilized onto the surface of 11-μm diameter silica particles (CPD-SiO2) for use in reversible addition-fragmentation chain transfer (RAFT)-controlled radical polymerization. pH-responsive poly(6-(acrylamido)hexanoic acid) (PAaH)-grafted silica particles (PAaH-SiO2) were prepared via RAFT-controlled radical polymerization using CPD-SiO2. Immobilization of the PAaH chains onto the surface of silica particles was confirmed by thermogravimetric analysis, attenuated total reflection-Fourier transfer infrared and scanning electron microscopy measurements. The solubility of PAaH in water is strongly dependent on the pH of the solution. PAaH-SiO2 was flocculated at pH 3 because of the hydrophobic interaction of the grafted PAaH chains with protonated carboxyl pendant groups. In contrast, PAaH-SiO2 was dispersed at pH 10 because of electrostatic repulsion between the grafted PAaH chains with pendant carboxylate ions. Millimeter-sized ‘liquid marbles’ can be prepared using the pH-responsive PAaH-SiO2 particles. The ‘liquid marble’ can be transferred intact onto the surface of a neutral or acidic water pool and exhibit long-term stability. When the pH of the water pool becomes alkaline, the ‘liquid marble’ immediately bursts on the surface of the water pool.
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
Ramsden, W. Separation of solids in the surface-layers of solutions and ‘suspensions’ (observations on surface-membranes, bubbles, emulsions, and mechanical coagulation). Proc. R. Soc. London 72, 156–164 (1903).
Pickering, S. U. CXCVI.-emulsions. J. Chem. Soc. Trans. 91, 2001–2021 (1907).
Amalvy, J. I., Armes, S. P., Binks, B. P., Rodrigues, J. A. & Unali, G.- F. Use of sterically-stabilised polystyrene latex particles as a pH-responsive particulate emulsifier to prepare surfactant-free oil-in-water emulsions. Chem. Commun. 1826–1827 (2003).
Binks, B. P. & Lumsdon, S. O. Pickering emulsions stabilized by monodisperse latex particles: effects of particle size. Langmuir 17, 4540–4547 (2001).
Li, J. & Stöver, H. D. H. Doubly pH-responsive pickering emulsion. Langmuir 24, 13237–13240 (2008).
Aussilious, P. & Quere, D. Properties of liquid marbles. Proc. R. Soc. London Ser. A 426, 973–999 (2006).
Fujii, S. & Murakami, R. Microparticles as foam and liquid marble stabilizers. KONA 26, 153–166 (2008).
Binks, B. P. & Murakami, R. Phase inversion of particle-stabilized materials from foams to dry water. Nat. Mater. 5, 865–869 (2006).
Mahadevan, L. & Pomeau, Y. Rolling droplets. Phys. Fluids 11, 2449–2454 (1999).
Aussillous, P. & Quéré, D. Liquid marbles. Nature 411, 924–927 (2001).
Rao, A. V., Kulkarni, M. M. & Bhagat, S. D. Transport of liquids using superhydrophobic aerogels. J. Colloid Interface Sci. 285, 413–418 (2005).
Wang, W., Bray, C. L., Adams, D. J. & Cooper, A. I. Methane storage in dry water gas hydrates. J. Am. Chem. Soc. 130, 11608–11609 (2008).
Bhosale, P. S., Panchagnula, M. V. & Stretz, H. A. Mechanically robust nanoparticle stabilized transparent liquid marbles. Appl. Phys. Lett. 93, 034109-1-3 (2008).
Dandan, M. & Erbil, H. Y. Evaporation rate of graphite liquid marbles: comparison with water droplets. Langmuir 25, 8362–8367 (2009).
Bormashenko, E., Pogreb, R., Bormashenko, Y., Musin, A. & Stein, T. New investigations on ferrofluidics: ferrofluidic marbles and magnetic-field-driven drops on superhydrophobic surfaces. Langmuir 24, 12119–12122 (2008).
Bormashenko, E., Pogreb, R., Whyman, G., Musin, A., Bormashenko, Y. & Barkay, Z. Shape, vibrations, and effective surface tension of water marbles. Langmuir 25, 1893–1896 (2009).
Gao, L. & McCarthy, T. J. Ionic liquid marbles. Langmuir 23, 10445–10447 (2007).
Matsukuma, D., Watanabe, H., Yamaguchi, H. & Takahara, A. Preparation of low-surface-energy poly[2-(perfluorooctyl)ethyl acrylate] microparticles and its application to liquid marble formation. Langmuir 27, 1269–1274 (2011).
McHale, G., Herbertson, D. L., Elliott, S. J., Shirtcliffe, N. J. & Newton, M. I. Electrowetting of nonwetting liquids and liquid marbles. Langmuir 23, 918–924 (2007).
Dupin, D., Armes, S. P. & Fujii, S. Stimulus-responsive liquid marbles. J. Am. Chem. Soc. 131, 5386–5387 (2009).
Fujii, S., Kameyama, S., Armes, S. P., Dupin, D., Suzaki, M. & Nakamura, Y. pH-responsive liquid marbles stabilized with poly(2-vinylpyridine) particles. Soft Matter 6, 635–640 (2010).
Lattuada, M. & Hatton, T. A. Preparation and controlled self-assembly of Janus magnetic nanoparticles. J. Am. Chem. Soc. 129, 12878–12889 (2007).
Zhao, Y. & Perrier, S. Reversible addition-fragmentation chain transfer graft polymerization mediated by fumed silica supported chain transfer agents. Macromolecules 40, 9116–9124 (2007).
Mitsukami, Y., Donovan, M. S., Lowe, A. B. & McCormick, C. L. Water-soluble polymers. 81. Direct synthesis of hydrophilic styrenic-based homopolymers and block copolymers in aqueous solution via RAFT. Macromolecules 34, 2248–2256 (2001).
Shibaev, V. P., Platé, N. A. & Freidzon, Y. S. Thermotropic liquid crystalline polymers. I. Cholesterol-containing polymers and copolymers. J. Polym. Sci. Chem. Ed. 17, 1655–1670 (1979).
Li, C., Han, J., Ryu, C. Y. & Benicewicz, B. C. A versatile method to prepare RAFT agent anchored substrates and the preparation of PMMA grafted nanoparticles. Macromolecules 39, 3175–3183 (2006).
Li, C. & Benicewicz, B. C. RAFT polymerization of methyl methacrylate from silica nanoparticles. Polym. Prep. 46, 459–460 (2005).
Newton, M. I., Herbertson, D. L., Elliott, S. J., Shirtcliffe, N. J. & McHale, G. Electrowetting of liquid marbles. J. Phys. D. Appl. Phys. 40, 20–24 (2007).
Berger, S., Synytska, A., Ionov, L., Eichhorn, K. J. & Stamm, M. Stimuli-responsive bicomponent polymer Janus particles by ‘grafting from’/’grafting to’ approaches. Macromolecules 41, 9669–9676 (2008).
Ionov, L., Zdyrko, B., Sidorenko, A., Minko, S., Klep, V., Luzinov, I. & Stamm, M. Gradient polymer layers by ‘grafting to’ approach. Macromol. Rapid Commun. 25, 360–365 (2004).
Zhao, Y. & Perrier, S. Synthesis of well-defined homopolymer and diblock copolymer grafted onto silica particles by z-supported RAFT polymerization. Macromolecules 39, 8603–8608 (2006).
Acknowledgements
We are grateful to Dr H Kawasaki (Kansai University) for ATR-FTIR investigations. This work was supported by a Grant-in-Aid (No. 21106518) for Scientific Research on Innovative Areas, ‘Molecular Soft-Interface Science,’ from the Ministry of Education, Culture, Sports, Science and Technology of Japan.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Competing interests
The authors declare no conflict of interest.
Additional information
Supplementary Information accompanies the paper on Polymer Journal website
Supplementary information
Rights and permissions
About this article
Cite this article
Inoue, M., Fujii, S., Nakamura, Y. et al. pH-responsive disruption of ‘liquid marbles’ prepared from water and poly(6-(acrylamido) hexanoic acid)-grafted silica particles. Polym J 43, 778–784 (2011). https://doi.org/10.1038/pj.2011.55
Received:
Revised:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1038/pj.2011.55
Keywords
This article is cited by
-
Stimulus-responsive soft dispersed systems developed based on functional polymer particles: bubbles and liquid marbles
Polymer Journal (2019)
-
Dynamic behaviour of a magnetically actuated floating liquid marble
Microfluidics and Nanofluidics (2017)
-
Manipulation of liquid marbles
Microfluidics and Nanofluidics (2015)


