Interfacial Electric Field Dynamically Confined Enzyme Self-Adaptation in Covalent Organic Framework Heterojunctions for Photoenzymatic Catalysis

Abstract Artificial photoenzymatic synthesis systems based on 1,4-NADH-dependent enzymes are challenged by unclear interfacial interactions and limited stability. Inspired by the ordered assembly and Z-scheme electron transfer mechanism in natural photosynthesis, we constructed an enzyme self-adaptive covalent organic frameworks (COFs) immobilization platform featuring a built-in electric field and a targeted Z-scheme electron transfer pathway. The CT-COF@Py-COF served as a mechanical scaffold for in situ encapsulation of reductases at the heterojunction interface, where electrostatic interactions, π–π stacking, and the ensuing formation of an interfacial electric field (IEF) collectively facilitated enzyme encapsulation. Moreover, IEF drove the conformational self-adaptation of encapsulated reductases and promoted directional charge transfer across the Z-scheme heterojunction, which synergistically enhanced catalytic activity and operational stability. The IEF-integrated system, paired with various dehydrogenases, enabled the efficient synthesis of pharmaceutical precursors under visible light. In a continuous-flow reactor, the encapsulated dehydrogenase retained approximately 88% of its initial-cycle glycine-production activity after eight cycles and exhibited a 7.18-fold increase in lactate yield when coupled with light-driven 1,4-NADH regeneration. This study provides a platform that utilizes IEF to dynamically confine enzymes’ self-adaptation in COF heterojunctions for photoenzymatic synthesis of high-value products.