Enhanced Photocatalytic Efficiency in Visible-Light-Induced NADH Regeneration by Intramolecular Electron Transfer

Inspired by natural photosynthesis, photocatalytic NADH regeneration has drawn increasing interest in the recent decade as it provides a perfect approach for NAD⁺ reduction into NADH, which can be further consumed by oxidordeuctase for enzymatic redox reactions. However, two issues still remain unsolved in this procedure. First, the photocatalytic efficiency in NAD⁺ hydrogenation requires further improvement. Second, the rhodium electron mediator [Cp*Rh(bpy)H₂O]²⁺ (M), which is always required for selective 1,4-NADH regeneration, is difficult to recover because of its good solubility in aqueous solution. Given the high price of M, it is highly wasteful and inefficient if it only spends once. Here, we report a Cp*Rh(bpy)Cl implanted conjugated microporous polymer DTS/Rh@CMPs which can be employed as a highly effective visible light photocatalysts for in situ NADH regeneration without using additional M. In addition, the insertion of Rh complex into a polymer skeleton, as demonstrated in UV-vis, fluorescence, photocurrent and electrochemical impedance, dramatically improves the light absorption capacity and the electron separation and transfer efficiency. Compared with that of DTS@CMP-1 with M, an enhanced reaction yield of 33% was determined in DTS/Rh@CMP-1 suggesting that intramolecular electron transfer has a better activity than that of intermolecular electron transfer in photocatalytic NAD⁺ reduction. Moreover, as the Rh complex is rooted firmly in a polymer framework, negligible Rh loss and conversion decrease in NADH regeneration are observed. When the DTS/Rh@CMP-1 was coupled with yeast alcohol dehydrogenase (YADH, from Saccharomyces cerevisiae), 1.36 mM of methanol was accumulated, implying an excellent biocompatibility of DTS/Rh@CMP-1 and a high feasibility of photobiocatalysis for formaldehyde hydrogenation.