Computational Investigation of the Role of Metal Center Identity in Cytochrome P450 Enzyme Model Reactivity

Biochemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 21, 2025

Mononuclear Fe enzymes such as heme-containing cytochrome P450 catalyze a variety of C-H activation reactions under ambient conditions, and they represent an attractive platform for engineering reactivity through changes to the native enzyme. Using density functional theory, we study both non-native group 8 (Ru, Os) 9 (Ir) metal centers in active site model P450. We quantify how changing spin state preferences throughout catalytic cycle. Our calculations reveal intermediate-spin ground all intermediates while heavier metals prefer low-spin states across most reaction also rate-determining hydrogen atom transfer (HAT) step subsequent rebound step. observe comparable HAT barriers Ru, much higher barrier Os, lowest Ir. Rebound steps are barrierless metals, intermediate is significantly stabilized. Examination cycle reveals spin-allowed pathways spin-forbidden energetics Ir with potential two-state reactivity. work highlights differences between Ir, it suggests that engineered Ru particular result improved enzyme toward hydroxylation.

Язык: Английский

Computational Exploration of Codoped Fe and Ru Single-Atom Catalysts for the Oxygen Reduction Reaction

Опубликована: Янв. 1, 2025

Язык: Английский

Computational exploration of codoped Fe and Ru single-atom catalysts for the oxygen reduction reaction

Journal of Catalysis, Год журнала: 2025, Номер unknown, С. 116163 - 116163

Опубликована: Май 1, 2025

Язык: Английский