Mechanistic Insights into the electron-transfer driven substrate activation by [4Fe-4S]-dependent Enzymes

[4Fe-4S]-dependent enzymes catalyze many different types of biological reactions. The quantum chemical cluster approach and the combined quantum mechanics/molecular mechanics approach, with the broken symmetry approach, are powerful tools for understanding the reaction mechanism in enzymes. This review discusses examples of the computational studies on [4Fe-4S]-dependent enzymes, focusing on the electron-transfer driven substrate activation. This review summarizes the computational insights into the mechanisms of six different types of [4Fe-4S] cluster-containing enzymes. The [4Fe-4S] cluster serves as catalytic centers and adopts either a one-electron or two-electron transfer process for substrate activation. image