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Chemoenzymatic catalysis of tert-butyl 6-cyano-(3R,5R)-dihydroxyhexanoate by aldo-keto reductase coupled with composite Fe3O4 nanozyme scaffold
Chemical Engineering Science ( IF 4.7 ) Pub Date : 2022-07-22 , DOI: 10.1016/j.ces.2022.117935
Shuai Qiu , Shen-Yuan Xu , Ya-Jun Wang , Yu-Guo Zheng

Cofactor NADPH is widely used in enzymatic redox reactions, however, its regeneration by glucose dehydrogenase (GDH) suffers from massive glucose consumption, costly wastewater treatment, and low atom efficiency. Herein, Fe3O4 nanoparticles supported on helical multi-walled carbon nanotubes (Fe3O4@HMWCNTs) was prepared and displayed comparable transfer hydrogenation activity to Exiguobacterium sibiricum GDH (EsGDH). We developed a chemoenzymatic catalysis based on a combination of an aldo–keto reductase KmAKR with Fe3O4@HMWCNTs scaffold, which asymmetrically synthesized optically pure tert-butyl 6-cyano-(3R,5R)-dihydroxyhexanoate ((3R,5R)-2, > 99.5 % dep). Under the optimized conditions, 10 mM NADP+ was converted to NADPH by 5.0 mg Fe3O4@HMWCNTs, in a yield of > 80.0 %. The combination of Fe3O4@HMWCNTs with KmAKRM7 completely reduced 10 mM tert-butyl 6-cyano-(5R)-hydroxy-3-oxohexanoate ((5R)-1) to (3R,5R)-2, in a conversion of > 99.0 % and dep > 99.5 %. Contrast to the previous developed biocatalytic approach with KmAKR and EsGDH, this efficient and compatible nanozyme-enzyme process required neither glucose/alcohols as co-substrate nor a glucose dehydrogenase/alcohol dehydrogenase for NADPH regeneration.



中文翻译:

醛酮还原酶与复合Fe3O4纳米酶支架的化学酶催化6-氰基-(3R,5R)-二羟基己酸叔丁酯

辅因子 NADPH 广泛用于酶促氧化还原反应,但其通过葡萄糖脱氢酶 (GDH) 再生存在大量葡萄糖消耗、废水处理成本高和原子效率低等问题。在此,制备了负载在螺旋状多壁碳纳米管(Fe 3 O 4 @HMWCNTs)上的 Fe 3 O 4纳米颗粒,并显示出与 Exiguobacterium sibiricum GDH ( Es GDH) 相当的转移氢化活性。我们开发了一种基于醛酮还原酶Km AKR 与 Fe 3 O 4 @HMWCNTs 支架组合的化学酶催化,该支架不对称地合成了光学纯-6-氰基-(3 R ,5 R )-二羟基己酸丁酯 ((3 R ,5 R )- 2 , > 99.5 % de p )。在优化条件下,10 mM NADP +通过 5.0 mg Fe 3 O 4 @HMWCNTs 转化为 NADPH,产率 > 80.0 %。Fe 3 O 4 @HMWCNTs 与Km AKR M7的组合将 10 mM 6-氰基-(5 R )-羟基-3-氧代己酸叔丁酯 ((5 R )- 1 ) 完全还原为 (3 R ,5 R ) - 2, 转化率 > 99.0 % 和de p  > 99.5 % 与之前开发的Km AKR 和Es GDH 生物催化方法相比,这种高效且相容的纳米酶-酶过程既不需要葡萄糖/醇作为共底物,也不需要葡萄糖脱氢酶/醇脱氢酶来再生 NADPH。

更新日期:2022-07-22
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