A chemo-biocatalyst based on glutamate oxidase-integrated biomimetic trimanganese tetraoxide as cascade composite nano-catalyst for synthesis of α‑Ketoglutaric acid.

The combination of chemo- and biocatalysts to perform one-pot synthetic route has presented great challenges for decades. Herein, glutamate oxidase (GLOX) and trimanganese tetraoxide (MnO) nanocrystals were combined for the first time by one-step biomineralization to construct a mimic multi-enzyme system (GLOX@MnO) for chemoenzymatic synthesis of α‑ketoglutaric acid (α‑KG). MnO not only served as a support for the enzyme immobilization, but also contributed its catalytic activity to co-operate with natural enzymes for the cascade reactions. The as-synthesized chemo-enzyme catalysts with directly contacted catalytic sites of the enzyme and inorganic catalyst maximizes the substrate channeling effffects for in situ rapid decomposition of the oxidative intermediate, HO, during the enzymatic oxidation of sodium glutamate, thus relieving the inhibition of HO accumulation for GLOX. Benefiting from the excellent stability and reusability of GLOX@MnO, a nearly 100% conversion (99.7%) of l-glutamate to α-KG was achieved, over 4.7 times higher than that of the free GLOX system (21.2%). This work provides a feasibility for constructing a high-performance chemo-enzyme catalyst for cascade catalysis, especially for those reactions with toxic intermediates.