Construction of smart glutathione s-transferase via remote optically controlled supramolecular switches

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.

提出了一种可以可逆地“打开”和“关闭”谷胱甘肽S-转移酶（GST）的超分子开关策略，为一种简单而有效的调节天然酶催化功能的方法提供了概念验证。该设计通过将基于偶氮苯/环糊精的超分子主客体系统合并到 GST 的催化口袋中得到证明。反式和顺式偶氮苯的光异构化导致环糊精的超分子络合和解离，从而通过调节底物可及性来控制 GST 的酶活性。这种光开关催化作用在多个刺激循环中是可逆的。此外，其能力还受到不同环糊精的空间尺寸和结合亲和力以及偶氮苯的修饰位点的影响。远程光调制方法可以为创造“智能”催化剂提供巨大的机会。