Light-Driven Biocatalytic Oxidation

Summary

This research explores how light can be used to power enzyme-based chemical reactions that are more environmentally friendly than traditional methods. The process uses sunlight or artificial light to help enzymes perform oxidation reactions, which are important for making various chemicals and materials. Impacts on everyday life: • Enables greener production of pharmaceuticals and chemicals using sunlight instead of harsh chemicals • Reduces environmental impact of chemical manufacturing processes • Could lead to more sustainable production of everyday products like plastics and medicines • Helps advance clean energy applications in chemical synthesis • May reduce costs of producing certain chemicals through more efficient processes

Background

Enzymes are the catalyst of choice for highly selective reactions, offering nature-inspired approaches for sustainable chemical synthesis. Oxidative enzymes like monooxygenases, peroxygenases, oxidases, and dehydrogenases catalyze various enantioselective oxyfunctionalization and dehydrogenation reactions under mild conditions. These enzymes require constant supply or withdrawal of reducing equivalents (electrons) to sustain their catalytic cycles. Photocatalysis appears to be a natural choice for accomplishing this electron-relay role.

Objective

This review aims to critically summarize current developments in photoredox biocatalysis, highlight promising concepts, and discuss current limitations in light-driven enzymatic oxidation reactions.

Results

The review found that photobiocatalytic oxidation shows promise but remains in its infancy. Light-driven monooxygenase catalysis shows limited cases with low catalytic activities (TTN < 1000). For H2O2-accepting enzymes, light-driven in situ H2O2 generation proves advantageous but is limited by the small number of available UPOs and P450 peroxygenases. Current photocatalytic systems achieve total turnover numbers (TTN) up to 372,000 and space time yields (STY) up to 7.8 g/L/day for certain reactions.

Conclusion

While photobiocatalytic oxidation shows potential for sustainable chemical synthesis using solar energy, several challenges remain. These include the limited number of redox enzymes, narrow substrate range, and low stability. Future developments require genome mining for new enzymes, protein engineering, whole-cell biocatalysts, and optimized photobioreactors. The technology currently meets requirements for specialty chemicals but needs improvement for bulk chemical production.
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