Control of swelling–deswelling behavior of a self-oscillating gel by designing the chemical structure

Masuda, Tsukuru; Terasaki, Ayako; Akimoto, Aya Mizutani; Nagase, Kenichi; Okano, Teruo; Yoshida, Ryo

doi:10.1039/c4ra10675j

Cited by 47 publications

(65 citation statements)

References 27 publications

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“…Compared with NIPAAm-based LCST-type self-oscillating polymers, [21] the transmittance amplitudes of the Ru-PAUs were smaller. This is because Ru-PAUsdonot become completely soluble during the oxidization process,because of strong polymer-polymer interaction derived from hydrogen bonding.T he UCST-type polymer system oscillated at higher temperature than did the LCST-type self-oscillating polymers.…”

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confidence: 88%

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Design of a Tunable Self‐Oscillating Polymer with Ureido and Ru(bpy)₃ Moieties

et al. 2017

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An upper critical solution temperature (UCST)-type self-oscillating polymer was designed that exhibited rhythmic soluble-insoluble changes induced by the Belousov-Zhabotinsky (BZ) reaction. The target polymers were prepared by conjugating Ru(bpy) 3 ,acatalyst for the BZ reaction, to ureidocontaining poly(allylamine-co-allylurea) (PAU)c opolymers. The Ru(bpy) 3 -conjugated PAUs exhibited aUCST-type phasetransition behavior,and the solubility of the polymer changed in response to the alternation in the valency of Ru(bpy) 3 .T he ureido content influences the temperature range of selfoscillation, and the oscillation occurred at higher temperatures than conventional LCST-type self-oscillating polymers.F urthermore,the self-oscillating behavior of the Ru-PAU could be regulated by addition of urea, which is aunique tuning strategy. We envision that novel self-oscillating polymers with widely tunable soluble-insoluble behaviors can be rationally designed based these UCST-type polymers.Stimuli-responsive polymer materials are of interest owing to their ability to change their physicochemical properties in response to external stimuli (temperature,p H, light, and specific chemicals). These polymers have applications as smart materials,i ncluding soft actuators,b iosensors,d rug delivery systems,a nd cell culture materials. [1][2][3][4][5][6][7] Our research group has developed another class of smart materials known as "self-oscillating" polymers that autonomously undergo periodic soluble-insoluble or swelling-deswelling changes driven by an oscillating chemical reaction referred to as the Belousov-Zhabotinsky (BZ) reaction. [8,9] We have demonstrated the utility of self-oscillating materials as autonomous biomimetic materials,such as autonomous transport tubes, [10] artificial cells and amoeba composed of block copolymers, [11,12] and autonomous functional surfaces composed of polymer brushes. [13,14] Theb asic chemical structure of the self-oscillating polymer is ar andom copolymer composed of N-isopropylacrylamide (NIPAAm) and tris(2,2'-bipyridine) [Ru(bpy) 3 ]a s ac atalyst for the BZ reaction. Poly(NIPAAm) is one of the most widely studied thermoresponsive polymers;i te xhibits aphase transition from the soluble state to the insoluble state at the lower critical solution temperature (LCST). The poly(NIPAAm-co-Ru(bpy) 3 )a lso shows LCST-type phasetransition behavior and the LCST shifts to the higher temperature upon oxidation of the copolymerized Ru(bpy) 3 moiety.T he BZ reaction spontaneously generates periodic redox changes in the catalyst, and periodic hydrationdehydration of the polymer chain is induced at ac onstant temperature.A utonomous smart materials have been developed by functionalizing the LCST-type thermoresponsive poly(NIPAAm-co-Ru(bpy) 3 ).Fewp olymers show ap hase transition behavior at the upper critical solution temperature (UCST) in aqueous media. To induce UCST-type behavior in aqueous solutions, polymer-polymer interactions must be stronger than polymer-solvent interactions at lower temperatures....

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“…Next, the N-hydroxysuccinimidyl ester of Ru(bpy) 3 ,Ru(bpy) 3 -NHS,was introduced into the PAUb yt he reaction with the amino group of PAU. [21] Thus,t he compositions of Ru-PAUc opolymer were determined (Table 1). [21] Thus,t he compositions of Ru-PAUc opolymer were determined (Table 1).…”

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Design of a Tunable Self‐Oscillating Polymer with Ureido and Ru(bpy)₃ Moieties

et al. 2017

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“…For future applications of self‐oscillating gels in biomedical fields, self‐oscillating behavior must be observable at a physiological temperature. For this purpose, we recently developed post‐modification methods for the preparation of self‐oscillating polymers and gels 48. First, the copolymer of NIPAAm and N ‐(3‐aminopropyl)methacrylamide (NAPMAm) was synthesized by atom transfer radical polymerization (ATRP).…”

Section: Development Of Self‐oscillating Gel Systemsmentioning

confidence: 99%

Recent Advances in Self‐Oscillating Polymer Material Systems

Tamate¹,

Akimoto²,

Yoshida

2016

The Chemical Record

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In 1996, we first reported self-oscillating polymer gels exhibiting autonomous swelling-deswelling oscillations driven by the Belousov-Zhabotinsky reaction. In contrast to conventional stimuli-responsive gels, the self-oscillating gel can autonomously and periodically change its volume in a closed solution without any external stimuli. Since the first report, the novel concept of self-oscillating gels has been expanded into various polymer and gel systems. Herein, we summarize recent advances in self-oscillating polymers and gels.

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“…[1][2][3][4][5][6] In the past few decades, various gel functions, including stimuli response, self-oscillation, self-healing, high mechanical strength, and biomolecular recognition, have been developed. [7][8][9][10][11][12][13] Moreover, researchers have attempted strategic control of the gel structure, [14][15][16][17][18] because the molecular design of polymer networks plays a significant role in the development of various gel functionalities. www.advancedsciencenews.com www.mcp-journal.de…”

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Strong Cationic Radical Initiator‐Based Design of a Thermoresponsive Hydrogel Showing Drastic Volume Transition

Masuda

Tsuji

Koizumi

et al. 2020

Macro Chemistry & Physics

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In this study, a millimeter‐sized thermoresponsive poly(N‐isopropylacrylamide) (PNIPAAm) gel is prepared by free radical polymerization using 2,2′‐azobis‐[2‐(1,3‐dimethyl‐4,5‐dihydro‐1H‐imidazol‐3‐ium‐2‐yl)]propane triflate (ADIP), a radical initiator possessing a strong cationic group that is newly developed. By comparing this gel with a PNIPAAm gel prepared using a conventional radical initiator, 2,2′‐azobisisobutyronitrile, the following properties are found: 1) the cationic residue of ADIP is introduced in the gel, and 2) the PNIPAAm gel prepared using ADIP exhibits a discontinuous volume transition as a function of temperature and rapid shrinking in response to temperature jump. This thermoresponsive behavior is attributed to the low polymer fraction in the gel prepared using ADIP. The ADIP‐based design of the thermoresponsive hydrogel investigated herein may contribute to the design of functional soft materials.

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Control of swelling–deswelling behavior of a self-oscillating gel by designing the chemical structure

Cited by 47 publications

References 27 publications

Design of a Tunable Self‐Oscillating Polymer with Ureido and Ru(bpy)₃ Moieties

Design of a Tunable Self‐Oscillating Polymer with Ureido and Ru(bpy)₃ Moieties

Recent Advances in Self‐Oscillating Polymer Material Systems

Strong Cationic Radical Initiator‐Based Design of a Thermoresponsive Hydrogel Showing Drastic Volume Transition

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Control of swelling–deswelling behavior of a self-oscillating gel by designing the chemical structure

Cited by 47 publications

References 27 publications

Design of a Tunable Self‐Oscillating Polymer with Ureido and Ru(bpy)3 Moieties

Design of a Tunable Self‐Oscillating Polymer with Ureido and Ru(bpy)3 Moieties

Recent Advances in Self‐Oscillating Polymer Material Systems

Strong Cationic Radical Initiator‐Based Design of a Thermoresponsive Hydrogel Showing Drastic Volume Transition

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Design of a Tunable Self‐Oscillating Polymer with Ureido and Ru(bpy)₃ Moieties

Design of a Tunable Self‐Oscillating Polymer with Ureido and Ru(bpy)₃ Moieties