A Molecular Mechanism for the Reduction of the Cu Site in Lytic Polysaccharide Monooxygenases by Phenol Reductants.

ABSTRACT: Lytic polysaccharide monooxygenases (LPMOs) play a pivotal role in the degradation of recalcitrant polysaccharides. As abundant reductants in nature, phenolic compounds may serve as sustainable reducing agents for LPMO reactions. However, the mechanism by which phenolic compounds drive the LPMO reactions remains elusive. In this study, we propose a molecular mechanism for the reduction of LPMO-Cu-(II) by phenolic reductants. Among the mechanisms that we investigated, the most favorable one involves the coordination replacement of water by the phenolic reductant. The coordination of phenols to LPMO-Cu-(II) significantly enhances the proton-coupled electron transfer process for the LPMO-Cu-(II) reduction. The proposed mechanism has been cross-validated by MD, QM/MM and QM/MM-MD studies, EPR

SUBMITTER: Liao L 

PROVIDER: S-EPMC12458002 | biostudies-literature | 2025 Sep

REPOSITORIES: biostudies-literature