Mechanochemical Encapsulation of Enzymes into MOFs for Photoenzymatic Enantioselective Catalysis

The combination of photocatalysis and biocatalysis in a heterogeneous fashion for enantioselective catalysis is of great importance but is still underexplored. Herein, we rationally design and construct a heterogeneous photoenzymatic platform for enantioselective catalysis, by a mechanochemical synthesis strategy to simultaneously encapsulate a photocatalyst and WGL into a robust Zr-based MOF. Due to the rapid synthesis and minimizing the use of organic solvents and strong acid, the fabricated photobiocatalysts show high photobiological activity and operational stability, hence affording good performance and reusability in asymmetric Mannich reactions. These photobiocatalysts show a wide substrate scope (up to 12 substrates) and are first used for asymmetric N-aryl-substituted tetrahydroisoquinoline substrates, which have not yet been achieved by photobiocatalysis yet. Furthermore, various characterization techniques unveil superoxide anions and singlet oxygen as the main active substances of asymmetric catalysis. This research marks a pivotal step toward crafting a range of enzyme-MOF photobiocatalysts tailored for diverse applications across industrial processes.