Aerobic Photobiocatalysis Enabled by Combining Core–Shell Nanophotoreactors and Native Enzymes

Abstract

Biocatalysis has become a powerful tool in synthetic chemistry, where enzymes are used to produce highly selective products under mild conditions. Using photocatalytically regenerated cofactors in synergistic combination with enzymes in a cascade fashion offers an efficient synthetic route to produce specific compounds. However, the combination of enzymes and photocatalysts has been limited due to the rapid degradation of the biomaterials by photogenerated reactive oxygen species, which denature and deactivate the enzymatic material. Here, we design core–shell structured porous nano-photoreactors for highly stable and recyclable photobiocatalysis under aerobic conditions. The enzymatic cofactor NAD + from NADH can be efficiently regenerated by the photoactive organosilica core, while photogenerated active oxygen species are trapped and deactivated through the non-photoactive shell, protecting the enzymatic material. The versatility of these photocatalytic core–shell nanoreactors was demonstrated in tandem with two different enzymatic systems, glycerol dehydrogenase and glucose 1-dehydrogenase, where long-term enzyme stability was observed for the core–shell photocatalytic system.

Direct Z-Scheme Polymer/Polymer Double-Shell Hollow Nanostructures for Efficient NADH Regeneration and Biocatalytic Artificial Photosynthesis under Visible Light

“…The covalent combination makes the electron transfer more feasible and convenient between those two polymer layers. It is noteworthy that the hollow structure of PCN@PDBTS-HN can also help to improve energy utilization efficiency due to the multiple light reflections and scattering occurring in the interior of cavities, which contributes greatly to light-harvesting. , In accordance with the Kubelka–Munk equation, , the optical band gap of PDBTS and PCN are calculated to be 2.93 and 2.88 eV, respectively (Figure S9). Furthermore, the Mott–Schottky analysis was performed to study the band structures of polymers (Figure S10).…”

Carbazolic Conjugated Microporous Polymers for Photocatalytic Organic Transformations

“…[1][2][3][4] Among all kinds of projects, those of visible-light driven photocatalysis, which directly converts photon to chemical energy, are DOI: 10.1002/marc.202300012 appealing and highly promising due to environmental-friendly advantages. [5][6][7][8][9][10][11][12][13] In view that the vast majority of chemical transformations require energy and account for a large proportion of the world's energy consumption, the research into a stable, recyclable, and efficient catalyst is gaining traction in the chemical fields. Traditionally, homogeneous photocatalysts, such as transition metal complexes [14,15] and organic dyes, [16] have been explored, exhibiting excellent photocatalytic performance in various chemical reactions.…”

Cr3+-ZnGa2O4@Pt for Light-Triggered Dark Catalytic Regeneration of Nicotinamide Coenzymes without Other Electron Mediators

“…To date, numerous approaches for NADH regeneration have been developed, such as biological enzymatic catalysis, , chemical reduction, electrochemical method, , and photocatalysis. ,,− Among these, photocatalysis has the characteristics of mild reaction conditions and good biocompatibility and thereby has attracted growing attention. The photocatalysts used for NADH regeneration include titanium dioxide, , carbon nitride, − precious metals (especially platinum , and gold − ), organic conjugated polymer, − cadmium sulfide quantum dot, , etc.…”