Fig. 9.

Stationary points for the cleavage of the mixed disulfide intermediate by the Cys56-thiolate: (A) GSH–Cys53···Cys56, (B) TS_redox2, and (C) GSH_red···Cys53–Cys56. Distances are given in angstroms. Blue to red shades in atoms represent the variation in atomic charge relative to the GSH_red–Cys53···Cys56 state (from 0.07 to 0.30 a.u.; blue stands for decrease in atomic charge, and red stands for increase in atomic charge). (C, Right) Gibbs energy profile for the intramolecular oxidation of the a domain. All contributions are represented relative to GSH_ox–Cys53···Cys56 facing the solvent.