Biofunctionalized “Kiwifruit‐Assembly” of Oxidoreductases in Mesoporous ZnO/Carbon Nanoparticles for Efficient Asymmetric Catalysis
Biofunctionalized “Kiwifruit‐Assembly” of Oxidoreductases in Mesoporous ZnO/Carbon Nanoparticles for Efficient Asymmetric Catalysis
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DOI：
10.1002/adma.201705443
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发表时间：
2018-03
影响因子：
29.4
通讯作者：
Rongzhen Zhang;Jiawei Jiang;Junping Zhou;Yan Xu;R. Xiao;X. Xia;Z. Rao
中科院分区：
文献类型：
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作者：
Rongzhen Zhang;Jiawei Jiang;Junping Zhou;Yan Xu;R. Xiao;X. Xia;Z. Rao
介孔 ZnO/碳复合材料设计用于共固定两种氧化还原酶，涉及一种新颖的“猕猴桃组装”模式。 (S)-羰基还原酶 II-葡萄糖脱氢酶在纳米粒子 (SCRII-GDHnano) 上的共固定化表现出比游离酶高 40-50% 的比活性，并显着提高了酶对热、pH 和溶剂的稳定性。它对 75 × 10−3m 底物进行不对称催化，1 小时内收率达到 100%，对映选择性达到 99.9%。 SCRII-GDHnano重复使用10次后，收率超过72%，对映选择性高达99.9%。即使使用高浓度 (400 × 10−3m) 的底物，它也能在 4 小时内显示出约 60% 的产率和 99.9% 的对映选择性。 SCRII-GDHnano 的生产率比游离酶高 4.5-8.0 倍，反应时间短 2.0-8.0 倍。这项工作为两种氧化还原酶的固定化提供了一种通用、简便且独特的方法，并通过触发自由基质子耦合电子转移而提供高催化效率、长期和良好的回收稳定性。
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.