Assembling a single active pocket from enzyme and metal modules for simultaneously catalyzing oxidation-reduction cascades

Chemoenzymatic cascades, which combine the merits of enzymatic catalysis and chemical catalysis, have blossomed into a powerful technology for new-to-nature reactions. The diffusion resistance of reaction intermediates is a major rate-limiting factor in cascade reactions, which can be reduced by integrating metal catalytic modules and enzymes in a single catalyst due to the proximity effect. Here we assemble enzymatic and dual metal-single-atom photocatalytic modules in a single active pocket for “one binding two reactions” catalysis, which can eliminate the diffusion resistance of reaction intermediates. The enzyme-metal hybrid active pocket exhibits excellent activity in simultaneously catalyzing transfer hydrogenation and oxidation reactions under visible light. The diffusion and rebinding of intermediates between the multiple catalytic modules are eliminated in the artificial active pocket, achieving efficient oxidation-reduction cascades for the directed detoxification of low-concentration mycotoxins, which is not reachable through engineered enzymes or photocatalysts alone. This work proposes an innovative type of cascade process and establishes a powerful tool for editing enzyme active pockets with metal catalytic modules. The diffusion resistance of reaction intermediates is a major rate-limiting factor in chemoenzymatic cascades and can be reduced by integrating metal catalytic modules and enzymes in a single catalyst due to the proximity effect. Here, the authors assemble enzymatic and dual metal-single-atom photocatalytic modules in a single active pocket for “one binding two reactions” catalysis, which can eliminate the diffusion resistance of reaction intermediates, and catalyze transfer hydrogenation and oxidation reactions under visible light.