Engineering cell membranes for catalysis is challenging due to their inherent complexity. Here we introduce a polymeric strategy to overcome these challenges by chemically modifying cell membranes with catalytic polymers, enabling robust, recyclable and photoenzymatic catalysis. Through a one-step in situ atom transfer radical polymerization on living Escherichia coli cells, polymers are generated to protect the cells from environmental stressors while facilitating chemoenzymatic synthesis by integrating catalytic polymers with intracellular enzymes. As a proof of concept, a photoenzymatic cascade with an anthraquinone-based polymer and benzaldehyde lyase is demonstrated, converting benzyl alcohol into benzoin and achieving bioconversion yields that are 15 times higher than controls. Additionally, cells serve as large biological scaffolds for polymers, enabling recycling of macromolecular catalysts. A recyclable chemoenzymatic system incorporating an organometallic polymer with intracellular enzymes is also presented. Our versatile, straightforward approach offers a technology platform for engineering cell membranes for cascade synthesis, with broad implications for synthetic chemistry, polymer chemistry and biotechnology.

由于其固有的复杂性，设计用于催化的细胞膜具有挑战性。在这里，我们介绍了一种聚合物策略，通过用催化聚合物对细胞膜进行化学修饰来克服这些挑战，从而实现稳健、可回收和光酶催化。通过在活大肠杆菌细胞上进行一步原位原子转移自由基聚合，生成聚合物以保护细胞免受环境压力，同时通过将催化聚合物与细胞内酶整合来促进化学酶合成。作为概念验证，证明了具有基于蒽醌的聚合物和苯甲醛裂解酶的光酶级联反应，将苯甲醇转化为安息香，并实现了比对照高 15 倍的生物转化产率。此外，细胞还充当聚合物的大型生物支架，能够回收大分子催化剂。还提出了一种可回收的化学酶系统，该系统结合了有机金属聚合物和细胞内酶。我们通用、直接的方法为用于级联合成的细胞膜工程提供了一个技术平台，对合成化学、聚合物化学和生物技术具有广泛的影响。