Max Planck institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
Department of Materials Science, Fudan University, 200433 Shanghai, People's Republic of China.
J Am Chem Soc. 2022 Apr 27;144(16):7320-7326. doi: 10.1021/jacs.2c00576. Epub 2022 Apr 1.
Biocatalysis has become a powerful tool in synthetic chemistry, where enzymes are used to produce highly selective products under mild conditions. Using photocatalytically regenerated cofactors in synergistic combination with enzymes in a cascade fashion offers an efficient synthetic route to produce specific compounds. However, the combination of enzymes and photocatalysts has been limited due to the rapid degradation of the biomaterials by photogenerated reactive oxygen species, which denature and deactivate the enzymatic material. Here, we design core-shell structured porous nano-photoreactors for highly stable and recyclable photobiocatalysis under aerobic conditions. The enzymatic cofactor NAD from NADH can be efficiently regenerated by the photoactive organosilica core, while photogenerated active oxygen species are trapped and deactivated through the non-photoactive shell, protecting the enzymatic material. The versatility of these photocatalytic core-shell nanoreactors was demonstrated in tandem with two different enzymatic systems, glycerol dehydrogenase and glucose 1-dehydrogenase, where long-term enzyme stability was observed for the core-shell photocatalytic system.
生物催化已成为合成化学中的有力工具，其中酶被用于在温和条件下生产高选择性的产物。在级联方式中，用光催化再生的辅助因子与酶协同组合，提供了一种生产特定化合物的有效合成途径。然而，由于光生反应性氧物种快速降解生物材料，使酶材料变性和失活，因此酶和光催化剂的组合受到限制。在这里，我们设计了核壳结构的多孔纳米光反应器，用于在有氧条件下进行高度稳定和可回收的光生物催化。来自 NADH 的酶辅助因子 NAD 可以被光活性有机硅核有效地再生，而光生活性氧物种则通过非光活性壳被捕获和失活，从而保护酶材料。这些光催化核壳纳米反应器的多功能性在与两种不同的酶系统甘油脱氢酶和葡萄糖 1-脱氢酶的串联反应中得到了证明，其中观察到核壳光催化体系中酶的长期稳定性。
