Reactivity Factors in Catalytic Methanogenesis and Their Tuning upon Coenzyme F430 Biosynthesis.

ABSTRACT: Methyl-coenzyme M reductase, responsible for the biological production of methane by catalyzing the reaction between coenzymes B (CoBS-H) and M (H₃C-SCoM), hosts in its core an F430 cofactor with the low-valent Ni^I ion. The critical methanogenic step involves F430-assisted reductive cleavage of the H₃C-S bond in coenzyme M, yielding the transient CH₃ radical capable of hydrogen atom abstraction from the S-H bond in coenzyme B. Here, we computationally explored whether and why F430 is unique for methanogenesis in comparison to four identified precursors formed consecutively during its biosynthesis. Indeed, all precursors are less proficient than the native F430, and catalytic competence improves at each biosynthetic step toward F430. Against the e

SUBMITTER: Bharadwaz P 

PROVIDER: S-EPMC10141249 | biostudies-literature | 2023 Apr

REPOSITORIES: biostudies-literature