陕西师范大学陈煜团队报道了生物杂化物上的电酶级联反应促进手性环氧化反应。相关研究成果于2023年12月12日发表在《科学通报》。

苯乙烯及其衍生物的手性环氧化反应是化学工业中一个重要的转化过程，引起了人们极大的科学兴趣。

该文中，研究人员将酶催化和电催化相结合，提出了苯乙烯及其衍生物手性环氧化的新途径。用1-乙基-3-甲基咪唑溴化物（IL_EMB）功能化的氯过氧化物酶（CPO）负载在钴氮掺杂的碳纳米管上(CoN@CNT)形成生物杂交体（CPO-IL_EMB/CoN@CNT)。H₂O₂物种通过双电子氧还原反应（2e^–ORR）在CoN@CNT以通过CPO引发苯乙烯的后续酶促环氧化。

CoN@CNT具有高的电活性，使ORR在更正的电势下产生H₂O₂，禁止CPO的血红素中Fe^III转化为Fe^II以维持酶活性。同时CoN@CNT可作为CPO-IL_EMB固定化的理想载体。因此，CPO-IL_EMB和CoN@CNT可以促进中间体H₂O₂的扩散，这实现了比本体溶液中等量的游离CPO-IL_EMB高17倍的苯乙烯环氧化效率。值得注意的是，苯乙烯环氧化的手性选择性提高了（～45%）。

附：英文原文 

Title: Electroenzymatic cascade reaction on a biohybrid boosts the chiral epoxidation reaction

Author: anonymous

Issue&Volume: 2023/12/12

Abstract: The chiral epoxidation of styrene and its derivatives is an important transformation that has attracted considerable scientific interest in the chemical industry. Herein, we integrate enzymatic catalysis and electrocatalysis to propose a new route for the chiral epoxidation of styrene and its derivatives. Chloroperoxidase (CPO) functionalized with 1-ethyl-3-methylimidazolium bromide (ILEMB) was loaded onto cobalt nitrogen-doped carbon nanotubes (CoN@CNT) to form a biohybrid (CPO-ILEMB/CoN@CNT). H2O2 species were generated in situ through a two-electron oxygen reduction reaction (2e–ORR) at CoN@CNT to initiate the following enzymatic epoxidation of styrene by CPO. CoN@CNT had high electroactivity for the ORR to produce H2O2 at a more positive potential, prohibiting the conversion of FeIII to FeII in the heme of CPO to maintain enzymatic activity. Meanwhile, CoN@CNT could serve as an ideal carrier for the immobilization of CPO-ILEMB. Hence, the coimmobilization of CPO-ILEMB and CoN@CNT could facilitate the diffusion of intermediate H2O2, which achieved 17 times higher efficiency than the equivalent amounts of free CPO-ILEMB in bulk solution for styrene epoxidation. Notably, an enhancement (～45%) of chiral selectivity for the epoxidation of styrene was achieved.

DOI: 10.1016/j.scib.2023.12.025

Source: https://www.sciencedirect.com/science/article/abs/pii/S2095927323008812