An organic semiconducting polymer nanobiocatalyst (SPNB) composed of a semiconducting polymer core conjugated with microsomal cytochrome P450 (CYP) has been developed for photoactivation of intracellular redox. The core serves as the light-harvesting unit to initiate photoinduced electron transfer (PET) and facilitate the regeneration of dihydronicotinamide adenine dinucleotide phosphate (NADPH), while CYP is the catalytic center for intracellular redox. Under light irradiation, the semiconducting core can efficiently catalyze the generation of NADPH with a turnover frequency (TOF) 75 times higher than the reported nanosystems, ensuring the supply of the cofactor for intracellular redox. SPNB-mediated intracellular redox thus can be efficiently activated by light in living cells to convert the model substrate and also to trigger the bioactivation of anticancer drugs. This study provides an organic nanobiocatalytic system that allows light to remotely control intracellular redox in living systems.
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