The combination of heterogeneous catalysts and enzymes, in so-called hybrid catalysts, is an attractive strategy to effectively run chemoenzymatic reactions. Yet, the preparation of such bifunctional materials remains challenging because both the inorganic and the biological moieties must be integrated in the same solid, while preserving their intrinsic activity. Combining an enzyme and a zeolite, for example, is complicated because the pores of the zeolite are too small to accommodate the enzyme and a covalent anchorage on the surface is often ineffective. Herein, we developed a new pathway to prepare a hybrid catalyst built from glucose oxidase and TS-1 zeolite. Such hybrid material can catalyze the in situ formation of H2O2, which is subsequently used by the zeolite to trigger the epoxidation of allylic alcohol. Starting from an enzymatic solution and a suspension of zeolite nanocrystals, the hybrid catalyst is obtained in one step, using a continuous spray drying method. While enzymes are expectedly unable to resist the conditions used in spray drying (temperature, shear stress, etc.), we leverage on the preparation of “enzyme-polyelectrolyte complexes” (EPCs) to increase the enzyme stability. Importantly, the use of EPCs also appears to prevent enzyme leaching and to stabilize the enzyme against pH changes. We show that the one-pot preparation by spray drying gives access to hybrid catalysts with unprecedented performance in the targeted chemoenzymatic reaction. Interestingly, the hybrid catalyst performs much better than the two catalysts operating as separate entities. We anticipate that this strategy could be used as an adaptable method to prepare other types of multifunctional materials.


中文翻译：

---

一步法从沸石纳米晶体和酶-聚合物复合物制备的混合化学生物催化剂

在所谓的杂化催化剂中，非均相催化剂和酶的结合是有效进行化学酶反应的有吸引力的策略。然而，此类双功能材料的制备仍然具有挑战性，因为无机和生物部分都必须整合在同一固体中，同时保留其固有活性。例如，将酶和沸石结合是复杂的，因为沸石的孔太小而不能容纳酶，并且共价锚定在表面上通常是无效的。在本文中，我们开发了一条新的途径来制备由葡萄糖氧化酶和TS-1沸石构建的杂化催化剂。这种杂化材料可以催化H2O2的原位形成，H2O2随后被沸石用于引发烯丙基醇的环氧化。从酶溶液和沸石纳米晶体的悬浮液开始，使用连续喷雾干燥法一步获得杂化催化剂。虽然预期酶不能抵抗喷雾干燥中使用的条件（温度，剪切应力等），但我们利用“酶-聚电解质复合物”（EPC）的制备来提高酶的稳定性。重要的是，使用EPC似乎还可以防止酶的浸出并稳定酶抵抗pH的变化。我们表明，通过喷雾干燥的一锅法制备可以在目标化学酶反应中获得具有空前性能的杂化催化剂。有趣的是，杂化催化剂的性能要比作为独立实体运行的两种催化剂好得多。