Boosting LPMO-driven lignocellulose degradation by polyphenol oxidase-activated lignin building blocks.

Background: Many fungi boost the deconstruction of lignocellulosic plant biomass via oxidation using lytic polysaccharide monooxygenases (LPMOs). The application of LPMOs is expected to contribute to ecologically friendly conversion of biomass into fuels and chemicals. Moreover, applications of LPMO-modified cellulose-based products may be envisaged within the food or material industry.

Results: Here, we show an up to 75-fold improvement in LPMO-driven cellulose degradation using polyphenol oxidase-activated lignin building blocks. This concerted enzymatic process involves the initial conversion of monophenols into diphenols by the polyphenol oxidase PPO7 from C1 and the subsequent oxidation of cellulose by LPMO9B. Interestingly, PPO7 shows preference towards lignin-derived methoxylated monophenols. Sequence analysis of genomes of 336 Ascomycota and 208 Basidiomycota reveals a high correlation between PPO7 and AA9 LPMO genes.

Conclusions: The activity towards methoxylated phenolic compounds distinguishes PPO7 from well-known PPOs, such as tyrosinases, and ensures that PPO7 is an excellent redox partner of LPMOs. The correlation between PPO7 and AA9 LPMO genes is indicative for the importance of the coupled action of different monooxygenases in the concerted degradation of lignocellulosic biomass. These results will contribute to a better understanding in both lignin deconstruction and enzymatic lignocellulose oxidation and potentially improve the exploration of eco-friendly routes for biomass utilization in a circular economy.