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The rate-limiting step of sulfiredoxin is associated with the transfer of the γ-phosphate of ATP to the sulfinic acid of overoxidized typical 2-Cys peroxiredoxins

Abstract : Sulfiredoxin Rate-limiting step Peroxiredoxin ATP Sulfinic acid Phosphoryl anhydride intermediate a b s t r a c t The eukaryotic sulfiredoxin (Srx) catalyzes the reduction of overoxidized typical 2-Cys peroxiredox-ins PrxSO 2 via ATP/Mg 2+-dependent phosphorylation of the sulfinic acid group, followed by formation of a PrxSO-SSrx thiolsulfinate intermediate. Using real-time kinetics of wild-type and C84A Srxs, and pH-rate profiles with ATP/Mg 2+ analogues, we show that the rate-limiting step of the reaction is associated with the chemical process of transfer of the c-phosphate of ATP to the sulfinic acid, in contrast to that described by Jönsson et al. [7]. Two pK apps of 6.2 and 7.5 were extracted from the bell-shaped pH-rate profile, corresponding to the c-phosphate of ATP, and to an acid–base catalyst, respectively.
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Xavier Roussel, Samia Boukhenouna, Sophie Rahuel-Clermont, Guy Branlant. The rate-limiting step of sulfiredoxin is associated with the transfer of the γ-phosphate of ATP to the sulfinic acid of overoxidized typical 2-Cys peroxiredoxins. FEBS Letters, Wiley, 2011, 585 (3), pp.574 - 578. ⟨10.1016/j.febslet.2011.01.012⟩. ⟨hal-01682359⟩

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