Autonomous viscosity oscillation via metallo-supramolecular terpyridine chemistry of branched poly(ethylene glycol) driven by the Belousov-Zhabotinsky reaction.

Soft Matter. 2014 Mar 7;10(9):1349-55.

Ueki T, Takasaki Y, Bundo K, Ueno T, Sakai T, Akagi Y, Yoshida R.

Department of Materials Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan. [email protected] [email protected] &

Department of Bioengineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Japan &

Green Mobility Collaborative Research Center, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Japan.

 

ABSTRACT

We report an autonomous viscosity oscillation of polymer solutions coupled with the metal-ligand association/dissociation between Ru and terpyridine (tpy), driven by the Belousov-Zhabotinsky (BZ) reaction. The tpy ligand for the Ru catalyst was attached to the terminals of poly(ethylene glycol) (PEG) with different numbers of branches (linear-, tetra-, and octa-PEG). It is well known that mono-tpy coordination is stable when Ru is oxidized (Ru(tpy)(3+)), whereas bis-tpy coordination is stable when the Ru centre is reduced (Ru(tpy)2(2+)). In the oxidized state, the three different polymers existed as solutions. In contrast, when the Ru centre was reduced, gels were obtained for the tetra- and octa-PEG owing to the formation of a three-dimensional polymer network through Ru-tpy coordination. Rheological measurements confirmed that the sol-gel transition occurred much more quickly in the octa-PEG system than in the tetra-PEG system, because of the requirement of fewer crosslinking points. The polymer solutions exhibited self-oscillation of absorbance and viscosity when BZ substrates were added to the solutions of Ru(2+)-tpy-modified tetra-/octa-PEG. This indicated that the Ru(tpy)2(2+) attached to the polymer ends could work as a metal catalyst for the BZ reaction. By increasing the number of branches from 4 to 8, the amount of crosslinking changed more remarkably during the oscillation, with a maximum value closer to that necessary for gelation. Thus, viscosity oscillation with a larger amplitude in the region of higher viscosity was achieved by using octa-PEG.

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Autonomous viscosity oscillation via metallo-supramolecular terpyridine chemistry of branched poly(ethylene glycol) driven by Belousov-Zhabotinsky reaction.