Hao Liqin, Zhu Qianqian, Qiao Xueling, Shi Qiongyu, Liu Yujie, Wang Tonghai, Lin En, Cheng Peng, Zhang Zhenjie, Chen Yao
State Key Laboratory of Medicinal Chemical Biology, College of Chemistry, Nankai University, Tianjin, 300071, China.
Frontiers Science Center for New Organic Matter, Renewable Energy Conversion and Storage Center, Nankai University, Tianjin, 300071, China.
Angew Chem Int Ed Engl. 2025 Jan 21;64(4):e202416550. doi: 10.1002/anie.202416550. Epub 2024 Nov 6.
Developing new enzyme-immobilization systems to stabilize their dynamic structures and meanwhile enhance their catalytic activity is of great significance but very challenging. Herein, we design and fabricate a class of robust mesoporous covalent organic frameworks (COFs) via Michael addition-elimination reaction. It is found that highly crystalline COFs can be produced in 10 min, which is attributed to the promoting effect of the intramolecular hydrogen bond activation. The COFs rich in hydroxyl groups can be facilely post-modified by epibromohydrin to covalently immobilize enzymes with both high loading and activity. Furthermore, we create a solar-driven photothermal-promoted strategy by introducing photoactive azo groups to COF carriers, which can boost the enzyme catalytic performance (lipase) with much higher conversion of various racemic substrates and chiral resolution upon solar light irradiation. The heterogeneous biocatalysts also demonstrate exceptional reusability and stability. This work provides a green and energy-efficient approach to facilitate the scale application of enzyme-immobilized biocatalysts.
开发新的酶固定化系统以稳定其动态结构并同时提高其催化活性具有重要意义，但极具挑战性。在此，我们通过迈克尔加成-消除反应设计并制备了一类坚固的介孔共价有机框架（COF）。发现可在10分钟内制备出高度结晶的COF，这归因于分子内氢键活化的促进作用。富含羟基的COF可通过环氧溴丙烷轻松进行后修饰，以高负载量和活性共价固定酶。此外，我们通过将光活性偶氮基团引入COF载体，创建了一种太阳能驱动的光热促进策略，该策略在太阳光照射下可提高酶催化性能（脂肪酶），实现各种外消旋底物的更高转化率和手性拆分。这种非均相生物催化剂还表现出出色的可重复使用性和稳定性。这项工作提供了一种绿色且节能的方法，以促进固定化酶生物催化剂的规模化应用。
