Concerted Chemoenzymatic Synthesis of α-Keto Acid through Compartmentalizing and Channeling of Metal-Organic Frameworks

Chemoenzymatic catalysis inherits the attributes of enzymatic catalysis and chemical catalysis, where the efficiency is usually governed by the synergy of the two catalytic modules, particularly, the compatibility between two catalysts and the mass transfer between two catalytic processes. To achieve a high photosynthesis efficiency, green plants compartmentalize water oxidation and NADPH regeneration modules on two sides of the thylakoid membrane while conveying electron transfer and proton transport via the channeling of the electron transfer chain and ATP synthase, respectively. Herein, we demonstrate this principle in vitro by using UiO-66 to confine platinum nanoparticles (Pt NPs) inside and immobilize L-amino acid oxidase (LAAO) outside for the chemoenzymatic synthesis of a-keto acid. The framework structure of UiO-66 affords the compartmentalization of LAAO and Pt NPs to avoid the deactivation of LAAO by Pt NPs, while its angstrom-scale pore size ensures channeling of the byproduct, H2O2, from LAAO to Pt NPs for instant elimination. A 99.7% yield of alpha-keto acid is achieved, far surpassing that enabled by free LAAO (41.2%). The compartmentalization-channeling strategy offers a generic platform to coordinate reactions and mass transfer in complex catalytic processes beyond chemoenzymatic catalysis.