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Tuning artificial oxidase catalysis by cavity modification
1Department of Chemistry, University of Copenhagen, Denmark. bols@chem.ku.dk.
None:
Previously, the ketone-bridged α-cyclodextrin derivative 6A,6D-di-O-propan-2-on-1,3-diyl α-cyclodextrin-6A,6D-dicarboxylate (2) was shown to be a potent artificial oxidase. In this work, a new isomer of this compound 6A,6D-di-O-propan-2-on-1,3-diyl 3A,3D-diepi-α-cyclodextrin-6A,6D-dicarboxylate 12 was synthesized and its catalytic properties were investigated and compared to those of 2. The catalyst 12 was also an excellent artificial enzyme exhibiting kcat values 0.2 to 1.1 times and Km values 0.1 to 4 times higher than those of 2. The reduced cavity size and the formation of a hydrogen bond are the primary factors affecting the catalytic performance.
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