Evolution of self-oscillating polymer gels as autonomous polymer systems
Source abstract
Abstract
We have developed ‘self-oscillating’ gels that undergo spontaneous cyclic swelling–deswelling changes without any on–off switching of external stimuli, as with heart muscle. The self-oscillating gels were designed by utilizing the Belousov–Zhabotinsky (BZ) reaction, an oscillating reaction, as a chemical model of the tricarboxylic acid cycle. We have systematically studied these polymer gels since they were first reported in 1996. Our studies represent innovative research, creating new concepts of functional gels and expanding their potential, and they have attracted attention in many research fields and have inspired related studies. Here, our recent progress on self-oscillating polymer gels is summarized. We developed ‘self-oscillating’ polymer gels that undergo spontaneous cyclic swelling–deswelling changes without any on–off switching of external stimuli like a heart muscle. Here, our recent progress on the self-oscillating polymer gels was summarized. Muscles and other soft tissues in the body experience spontaneous rhythmic changes, such as a heartbeat, hormonal secretion and the cell cycle, without requiring external stimulation. Ryo Yoshida and Takeshi Ueki from the University of Tokyo, Japan, review their team's progress to develop polymer gels that freely undergo cyclic swelling and shrinking. Although tremendous efforts to mimic biological systems have generated numerous synthetic responsive materials for smart tissue engineering and therapeutic applications, these existing systems lack autonomy and depend on induced pH, temperature and other environmental fluctuations to operate. In contrast, the team's gels rely on the oscillating Belousov–Zhabotinsky reaction — a metal-catalyzed oxidation reaction that exhibits spontaneous periodic temporal and spatial patterns. The self-oscillating gels have applications that include biomimetic actuators and tubular intestine-like mass transport systems, providing new perspectives for materials science, robotics and biophysics.
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Research context
OpenAlex topics: Hydrogels: synthesis, properties, applications · Advanced Materials and Mechanics · Advanced Sensor and Energy Harvesting Materials
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (72)
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1. Tanaka, T. Gels. Sci. Am. 244, 124–136 (1981).10.1038/scientificamerican0181-124 ↗
2. Schild, H. G. Poly(N-isopropylacrylamide): experiment, theory and application. Prog. Polym. Sci. 17, 163–249 (1992).10.1016/0079-6700(92)90023-R ↗
3. Yoshida, R. Design of functional polymer gels and their application to biomimetic materials. Curr. Org. Chem. 9, 1617–1641 (2005).10.2174/138527205774610949 ↗
4. Lendlein, A. & Shastri, V. P. Stimuli-sensitive polymers. Adv. Mater. 22, 3344–3347 (2010).10.1002/adma.201002520 ↗
5. Urban, M. W. (ed.) Handbook of stimuli-responsive materials (Wiley-VCH, Weinheim, 2011).10.1002/9783527633739 ↗
6. Bhattacharyya, D. & Schafer, T. (eds) Responsive membranes and materials (John Wiley & Sons, Ltd., West Sussex, UK, 2013).
7. Ottenbrite, R. M., Park, K., Okano, T. & Peppas, N. A. (eds) Biomedical Applications of Hydrogels Handbook (Springer, New York, 2010).10.1007/978-1-4419-5919-5 ↗
8. Yang, J., Yamato, M., Sekine, H., Sekiya, S., Tsuda, Y., Ohashi, K., Shimizu, T. & Okano, T. Tissue engineering using laminar cellular assemblies. Adv. Mater. 21, 3404–3409 (2009).10.1002/adma.200801990 ↗
9. Miyata, T. In Supramolecular Design for Biological Applications (ed. Yui, N.) pp 191–225 (CRC Press, Boca Raton, 2002).
10. Hoffman, A. S. Stumuli-responsive polymers: biomedical applications and challenges for clinical translation. Adv. Drug. Deliv. Rev. 65, 10–16 (2013).10.1016/j.addr.2012.11.004 ↗
11. Yoshida, R., Uchida, K., Kaneko, Y., Sakai, K., Kikuchi, A., Sakurai, Y. & Okano, T. Comb-type grafted hydrogels with rapid de-swelling response to temperature changes. Nature 374, 240–242 (1995).10.1038/374240a0 ↗
12. Kaneko, Y., Sakai, K., Kikuchi, A., Yoshida, R., Sakurai, Y. & Okano, T. Influence of freely mobile grafted chain length on dynamic properties of comb-type grafted poly(N-isopropylacrylamide) hydrogels. Macromolecules 28, 7717–7723 (1995).10.1021/ma00127a018 ↗
13. Gong, J. P., Katsuyama, Y., Kurosawa, T. & Osada, Y. Double-network hydrogels with extremely high mechanical strength. Adv. Mater. 15, 1155–1158 (2003).10.1002/adma.200304907 ↗
14. Okumura, Y. & Ito, K. The polyrotaxane gel: a topological gel by figure-of–eight cross-links. Adv. Mater. 13, 485–487 (2001).10.1002/1521-4095(200104)13:7<485::AID-ADMA485>3.0.CO;2-T ↗
15. Haraguchi, K. & Takehisa, T. Nanocomposite hydrogels: a unique organic-inorganic network structure with extraordinary mechanical, optical, and swelling/de-swelling properties. Adv. Mater. 14, 1120–1124 (2002).10.1002/1521-4095(20020816)14:16<1120::AID-ADMA1120>3.0.CO;2-9 ↗
16. Sakai, T., Akagi, Y., Matsunaga, T., Kurakazu, M., Chung, U. & Shibayama, M. Highly elastic and deformable hydrogel formed from tetra-arm polymers. Macromol. Rapid Commun. 31, 1954–1959 (2010).10.1002/marc.201000286 ↗
17. Wang, Q., Mynar, J. L., Yoshida, M., Lee, E., Lee, M., Okuro, K., Kinbara, K. & Aida, T. High-water-content mouldable hydrogels by mixing clay and a dendritic molecular binder. Nature 463, 339–343 (2010).10.1038/nature08693 ↗
18. Harada, A. & Takashima, Y. Macromolecular recognition and macroscopic interactions by cyclodextrins. Chem. Rec. 13, 420–431 (2013).10.1002/tcr.201300006 ↗
19. Rabai, G., Kustin, K. & Epstein, I. R. A systematically designed pH oscillatior: the hydrogen peroxide-sulfite-ferrocyanide reaction in a continuous-flow stirred tank reactor. J. Am. Chem. Soc. 111, 3870–3874 (1989).10.1021/ja00193a018 ↗
20. Yoshida, R., Ichijo, H., Hakuta, T. & Yamaguchi, T. Self-oscillating swelling and deswelling of polymer gels. Macromol. Rapid Commun. 16, 305–310 (1995).10.1002/marc.1995.030160412 ↗
21. Yoshida, R., Yamaguchi, T. & Ichijo, H. Novel oscillating swelling-deswelling dynamic behaviour for pH-sensitive polymer gels. Mater. Sci. Eng. C 4, 107–113 (1996).10.1016/0928-4931(96)00138-5 ↗
22. Yoshida, R., Takahashi, T., Yamaguchi, T. & Ichijo, H. Self-oscillating gel. J. Am. Chem. Soc. 118, 5134–5135 (1996).10.1021/ja9602511 ↗
23. Field, R. J. & Burger, M. (eds) Oscillations and Traveling Waves in Chemical Systems (John Wiley & Sons, New York, 1985).
24. Epstein, I. R. & Pojman, J. A. An Introduction to Nonlinear Chemical Dynamics: Oscillations, Waves, Patterns, and Chaos (Oxford University Press, New York, 1998).10.1093/oso/9780195096705.001.0001 ↗
25. Field, R. J., Körös, E. & Noyes, R. M. Oscillations in chemical systems. II. Through analysis of temporal oscillation in the bromate-cerium-malonic acid system. J. Am. Chem. Soc. 94, 8649–8664 (1972).10.1021/ja00780a001 ↗
26. Amemiya, T., Ohmori, T. & Yamaguchi, T. An Oregonator-class model for photoinduced behavior in the Ru(bpy)32+-catalyzed Belousov-Zhabotinsky reaction. J. Phys. Chem. A 104, 336–344 (2000).10.1021/jp9929317 ↗
27. Yoshida, R. Self-oscillating gels driven by the Belousov-Zhabotinsky reaction as novel smart materials. Adv. Mater. 22, 3463–3483 (2010).10.1002/adma.200904075 ↗
28. Yoshida, R., Tanaka, T., Onodera, S., Yamaguchi, T. & Kokufuta, E. In-phase synchronization of chemical and mechanical oscillations in self-oscillating gels. J. Phys. Chem. A 104, 7549–7555 (2000).10.1021/jp0011600 ↗
29. Maeda, S., Hara, Y., Yoshida, R. & Hashimoto, S. Peristaltic motion of polymer gels. Angew. Chem. Int. Ed. 47, 6690–6693 (2008).10.1002/anie.200801347 ↗
30. Takeoka, Y., Watanabe, M. & Yoshida, R. Self-sustaining peristaltic motion on the surface of a porous gel. J. Am. Chem. Soc. 125, 13320–13321 (2003).10.1021/ja036904c ↗
31. Sasaki, S., Koga, S., Yoshida, R. & Yamaguchi, T. Mechanical oscillation coupled with the Belousov-Zhabotinsky reaction in gel. Langmuir 19, 5595–5600 (2003).10.1021/la0270035 ↗
32. Murase, Y., Maeda, S., Hashimoto, S. & Yoshida, R. Design of a mass transport surface utilizing peristaltic motion of a self-oscillating gel. Langmuir 25, 483–489 (2009).10.1021/la8029006 ↗
33. Hara, Y. & Yoshida, R. Self-oscillating polymer fueled by organic acid. J. Phys. Chem. B 112, 8427–8429 (2008).10.1021/jp802014d ↗
34. Hidaka, M. & Yoshida, R. Self-oscillating gel composed of thermosensitive polymer exhibiting higher LCST. J. Controlled Release 150, 171–176 (2011).10.1016/j.jconrel.2010.11.026 ↗
35. Suzuki, D., Kobayashi, T., Yoshida, R. & Hirai, T. Soft actuators of organized self-oscillating microgels. Soft Matter 8, 11447–11449 (2012).10.1039/c2sm26477c ↗
36. Mitsunaga, R., Okeyoshi, K. & Yoshida, R. Design of comb-type self-oscillating gel. Chem. Comm. 49, 4935–4937 (2013).10.1039/c3cc42054j ↗
37. Ito, Y., Nogawa, N. & Yoshida, R. Temperature control of the Belousov-Zhabotinsky reaction using a thermo-responsive polymer. Langmuir 19, 9577–9579 (2003).10.1021/la0355242 ↗
38. Yoshida, R., Takei, K. & Yamaguchi, T. Self-beating motion of gels and modulation of oscillation rhythm synchronized with organic acid. Macromolecules 36, 1759–1761 (2003).10.1021/ma0259618 ↗
39. Shinohara, S., Seki, T., Sakai, T., Yoshida, R. & Takeoka, Y. Chemical and optical control of peristaltic actuator based on self-oscillating porous gel. Chem. Commun. 39, 4735–4737 (2008).10.1039/b808427k ↗
40. Shinohara, S., Seki, T., Sakai, T., Yoshida, R. & Takeoka, Y. Photoregulated wormlike motion of a gel. Angew. Chem. Int. Ed. 47, 9039–9043 (2008).10.1002/anie.200803046 ↗
41. Yamamoto, T. & Yoshida, R. Self-oscillation of polymer and photo-regulation by introducing photochromic site to induce LCST changes. React. Func. Polym. 73, 945–950 (2013).10.1016/j.reactfunctpolym.2013.02.015 ↗
42. Tabata, O., Kojima, H., Kasatani, T., Isono, Y. & Yoshida, R. Chemo-mechanical actuator using self-oscillating gel for artificial cilia. Proceedings of the International Conference on MEMS 2003, pp 12–15 (2003).10.1109/MEMSYS.2003.1189675 ↗
43. Tabata, O., Hirasawa, H., Aoki, S., Yoshida, R. & Kokufuta, E. Ciliary motion actuator using self-oscillating gel. Sens. Actuat. A 95, 234–238 (2002).10.1016/S0924-4247(01)00731-2 ↗
44. Maeda, S., Hara, Y., Sakai, T., Yoshida, R. & Hashimoto, S. Self-walking gel. Adv. Mater. 19, 3480–3484 (2007).10.1002/adma.200700625 ↗
45. Kuksenok, O., Yashin, V. V., Kinoshita, M., Sakai, T., Yoshida, R. & Balazs, A. C. Exploiting gradients in cross-link density to control the bending and self-propelled motion of active gels. J. Mater. Chem. 21, 8360–8371 (2011).10.1039/c0jm03426f ↗
46. Yashin, V. V., Suzuki, S., Yoshida, R. & Balazs, A. C. Controlling the dynamic behavior of heterogeneous self-oscillating gels. J. Mater. Chem. 22, 13625–13636 (2012).10.1039/c2jm32065g ↗
47. Murase, Y., Hidaka, M. & Yoshida, R. Self-driven gel conveyer: Autonomous transportation by peristaltic motion of self-oscillating gel. Sens. Actuat. B 149, 272–283 (2010).10.1016/j.snb.2010.06.017 ↗
48. Murase, Y., Takeshima, R. & Yoshida, R. Self-driven gel conveyer: effect of interactions between loaded cargo and self-oscillating gel surface. Macromol. Bioscience 11, 1713–1721 (2011).10.1002/mabi.201100184 ↗
49. Yoshida, R. & Murase, Y. Self-oscillating surface of gel for autonomous mass transport. Colloids Surf. B Biointerfaces 99, 60–66 (2012).10.1016/j.colsurfb.2011.09.036 ↗
50. Shiraki, Y. & Yoshida, R. Autonomous intestine-like motion of tubular self-oscillating gel. Angew. Chem. Int. Ed. 51, 6112–6116 (2012).10.1002/anie.201202028 ↗
51. Masuda, T., Hidaka, M., Murase, Y., Akimoto, A. M., Nagase, K., Okano, T. & Yoshida, R. Self-oscillating polymer brushes. Angew. Chem. Int. Ed. 52, 7468–7471 (2013).10.1002/anie.201301988 ↗
52. Yoshida, R., Sakai, T., Ito, S. & Yamaguchi, T. Self-oscillation of polymer chains with rhythmical soluble-insoluble changes. J. Am. Chem. Soc. 124, 8095–8098 (2002).10.1021/ja012584q ↗
53. Suzuki, D., Sakai, T. & Yoshida, R. Self-flocculating/self-dispersing oscillation of microgels. Angew. Chem. Int. Ed. 47, 917–920 (2008).10.1002/anie.200703953 ↗
54. Suzuki, D. & Yoshida, R. Temporal control of self-oscillation for microgels by cross-linking network structure. Macromolecules 41, 5830–5838 (2008).10.1021/ma800684d ↗
55. Suzuki, D. & Yoshida, R. Effect of initial substrate concentration of the Belousov-Zhabotinsky reaction on self-oscillation for microgel system. J. Phys. Chem. B 112, 12618–12624 (2008).10.1021/jp8037973 ↗
56. Suzuki, D. & Yoshida, R. Self-oscillating core/shell microgels. Polymer J. 42, 501–508 (2010).10.1038/pj.2010.28 ↗
57. Hara, Y. & Yoshida, R. A viscosity self-oscillation of polymer solution induced by the BZ reaction under acid-free condition. J. Chem. Phys. 128, 224904 (2008).10.1063/1.2931543 ↗
58. Suzuki, D., Taniguchi, H. & Yoshida, R. Autonomously oscillating viscosity in microgel dispersions. J. Am. Chem. Soc. 131, 12058–12059 (2009).10.1021/ja904677g ↗
59. Taniguchi, H., Suzuki, D. & Yoshida, R. Characterization of autonomously oscillating viscosity induced by swelling/deswelling oscillation of the microgels. J. Phys. Chem. B 114, 2405–2410 (2010).10.1021/jp911779j ↗
60. Ueno, T., Bundo, K., Akagi, Y., Sakai, T. & Yoshida, R. Autonomous viscosity oscillation by reversible complex formation of terpyridine-terminated poly(ethylene glycol) in the BZ reaction. Soft Matter 6, 6072–6074 (2010).10.1039/c0sm00788a ↗
61. Ueki, T., Takasaki, Y., Bundo, K., Ueno, T., Sakai, T., Akagi, Y. & Yoshida, R. Autonomous viscosity oscillation via metallo-supramolecular terpyridine chemistry of branched poly(ethylene glycol) driven by the Belousov-Zhabotinsky reaction. Soft Matter 10, 1349–1355 (2014).10.1039/C3SM51537K ↗
62. Ueki, T. & Yoshida, R. Self-oscillating micelles. Chem. Comm. 49, 6947–6949 (2013).10.1039/c3cc38432b ↗
63. Dayal, P., Kuksenok, O. & Balazs, A. C. Designing autonomously motile gels that follow complex paths. Soft Matter 6, 768–773 (2010).10.1039/B918434A ↗
64. Dayal, P., Kuksenok, O. & Balazs, A. C. Using light guide the self-sustained motion of active gels. Langmiur 25, 4298–4301 (2009).10.1021/la900051b ↗
65. Kuksenok, O. & Balazs, A. C. Modeling the photoinduced reconfiguration and directed motion of polymer gels. Adv. Funct. Mater. 23, 4601–4610 (2013).10.1002/adfm.201203876 ↗
66. Yashin, V. V. & Balazs, A. C. Pattern formation and shape changes in self-oscillating polymer gels. Science 314, 798–801 (2006).10.1126/science.1132412 ↗
67. Yashin, V. V., Kuksenok, O. & Balazs, A. C. Modeling autonomously oscillating chemo-responsive gels. Prog. Polym. Sci. 35, 155–173 (2010).10.1016/j.progpolymsci.2009.10.003 ↗
68. Yashin, V. V., Kuksenok, O., Dayal, P. & Balazs, A. C. Mechano-chemical oscillations and waves in reactive gels. Rep. Prog. Phys. 75, 066601 (2012).10.1088/0034-4885/75/6/066601 ↗
69. Yashin, V. V., Kuksenok, O. & Balazs, A. C. Computational design of active, self-reinforcing gels. J. Phys. Chem. B 114, 6316–6322 (2010).10.1021/jp101009h ↗
70. Lohmeijer, B. G. G. & Schubert, U. S. Supramolecular engineering with macromolecules: An alternative concept for block copolymers. Angew. Chem. Int. Ed. 41, 3825–3829 (2002).10.1002/1521-3773(20021018)41:20<3825::AID-ANIE3825>3.0.CO;2-6 ↗
71. Ueki, T., Watanabe, M. & Yoshida, R. Belousov-Zhabotinsky reaction in protic ionic liquids. Angew. Chem. Int. Ed. 51, 11991–11994 (2012).10.1002/anie.201205061 ↗
72. Zhou, H., Ding, X., Zheng, Z. & Peng, Y. Self-regulated intelligent systems: where adaptive entities meet chemical oscillators. Soft Matter 9, 4956–4968 (2013).10.1039/c3sm00021d ↗