Biofunctionalized “Kiwifruit‐Assembly” of Oxidoreductases in Mesoporous ZnO/Carbon Nanoparticles for Efficient Asymmetric Catalysis

A mesoporous ZnO/carbon composite is designed for coimmobilization of two oxidoreductases involving a novel “kiwifruit‐assembly” pattern. The coimmobilization of (S)‐carbonyl reductase II‐glucose dehydrogenase on nanoparticles (SCRII–GDHnano) exhibits 40–50% higher specific activity than the free enzyme and significantly improves stabilities of enzymes to heat, pH and solvents. It performs asymmetric catalysis of 75 × 10−3m substrate with a perfect yield of 100% and an excellent enantioselectivity of 99.9% within 1 h. SCRII–GDHnano gives an over 72% yield and 99.9% enantioselectivity after it is reused for ten times. Even with a highly concentrated (400 × 10−3m) substrate, it shows about 60% yield and 99.9% enantioselectivity within 4 h. SCRII–GDHnano presents 4.5–8.0‐fold higher productivity in 2.0–8.0‐fold shorter reaction time than the free enzyme. This work provides a general, facile, and unique approach for the immobilization of two oxidoreductases and gives high catalytic efficiency, long‐term and good recycling stabilities by triggering radical proton‐coupled electron transfer.