Construction of Smart Glutathione S-Transferase via Remote Optically Controlled Supramolecular Switches
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Abstract
A supramolecular switch strategy that can reversibly “turn-on” and “turn-off” glutathione S-transferase (GST) is presented, which provides a proof-of-concept for a simple but efficient way to regulate the catalytic function of natural enzymes. This design is demonstrated by incorporating azobenzene/cyclodextrin-based supramolecular host–guest systems into the catalytic pocket of GST. The photoisomerization of trans- and cis-azobenzene leads to supramolecular complexation and dissociation of cyclodextrin, and thereby controls the enzymatic activity of GST by tuning substrate accessibility. This photoswitchable catalysis is reversible over multiple stimulus cycles. Furthermore, its capability is affected by the spatial size and binding affinity of different cyclodextrins, as well as the modification sites of azobenzene. The remote optical modulation method could offer great opportunities in the effort to create “smart” catalysts.
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