Figure 4.
Stopped-flow analysis of intermediate species generated upon oxidation of CcP W191F and CcP S-Trp W191F. (a) The Trp51S-Trp substitution in CcP W191F stabilizes the CpdI state but leads to a faster decay of CpdII. (b,c) Oxidation of the ferric states of CcP W191F (a, black line) and CcP S-Trp W191F (b, dark blue line) leads to the generation of a transient porphyrin π-cation radical in both variants (dotted line), which decays to a CpdII state (gray line in CcP W191F (Soret maximum 423 nm) and pale blue line in CcP S-Trp W191F (Soret maximum 414 nm)). Concentration profiles are indicated in insets. (d) The CpdII state of CcP S-Trp W191F decays to the ferric enzyme (dark blue line) over 60 s, whereas CpdII of CcP W191F is stable for >5 min (inset).
