Mechanism of DOPA radical generation and transfer in metal-free class Ie ribonucleotide reductase based on density functional theory.

ABSTRACT: Quantum mechanical/molecular mechanical (QM/MM) calculations were carried out to investigate the mechanisms of the generation, transfer, and regeneration of the DOPA radical for metal-free class Ie ribonucleotide reductase. The crystal structure of MfR2 (Nature, 2018, 563, 416-420) was adopted for the calculations. The QM/MM calculations have revealed several key points that are vital for understanding the mechanisms. The superoxide O₂ ^•- provided by the flavoprotein NrdI cannot directly oxidize the residue Tyr126 to the DOPA radical. It should be protonated to HO₂ ^•. The calculation results suggest that the covalent modification of Tyr126 and the DOPA radical generation can be carried out with no involvement of metal cofactors. This addre

SUBMITTER: Zou J 

PROVIDER: S-EPMC8902622 | biostudies-literature | 2022

REPOSITORIES: biostudies-literature