Angewandte Chemie International Edition
10.1002/anie.202107917
RESEARCH ARTICLE
As can be observed from Fig. 5a, the gel acted as a D-glucose
sensor[40] and autonomously transformed from gel to sol state
vice-versa, and only refueling the system with D-glucose (not
Keywords: enzyme catalysis • non-equilibrium systems •
hydrogels • self-regulating behaviour • cyclodextrin
2 2
H O ) was required after every cycle. Large amounts of D-
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glucose could not be added in the beginning as it could lead to
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release. 0.8 mM Carboxyfluorescein dye was added while
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2 2
much faster than the control hydrogel. The formation of H O in
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Conclusion
We present a fuel driven and enzyme regulated supramolecular
hydrogel capable of showing redox responsive as well as
emerging self-regulating behavior depending on the
concentration of fuel (D-glucose) provided to the chemical
reaction network. While as responsive network the hydrogel
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reduction fuel D-glucose and catalyst GOx acting orthogonally to
each other by initiating oxidation of Fc or reduction of Fc+,
respectively. At higher D-glucose concentrations, the enzyme
catalyzed reaction network generates the oxidation fuel H
This negative feedback leads to a transition from the equilibrium
responsive network into non-equilibrium self-regulating
network with autonomous assembly and disassembly of the
hydrogel. Our results show that the kinetics of biocatalytic
reaction networks can be orchestrated inside a hydrogel to
design synthetic soft matter with self-regulating properties.
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Acknowledgements
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The project was funded by CiM IMPRS Graduate School
doctoral fellowship at the University of Münster. We are very
grateful for inspiring discussions within the CRC 1459 “Intelligent
Matter”.
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Conflict of Interest
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The authors declare no conflict of interests.
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6
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