(a) Prx1 catalytic cycle. The Prx1 peroxidase cycle and
hyperoxidation
mechanism are shown at the level of the Prx1 dimeric unit to highlight
the conformational state [fully folded (FF) and locally unfolded (LU)]
of the active site identified by the peroxidatic Cys CP and C-terminal tail identified by resolving Cys CR. The
rate constants of peroxide reduction kSOH, sulfinylation kSO2, resolution kSS, and FF–LU transition kFF and kLU are indicated.
(b) Zoom into the catalytic site of Tsa1. The subunit containing the
CP is shown in blue, and the subunit containing the CR is shown in yellow (PDB code 3SBC). Residues CP and CR are shown in yellow, W83 and W173 in orange, and W161 in red. Within
the C-terminal tail, residues A177 and A178 are highlighted in green
and the Y190-F191 motif in purple.