Fig. 3.
4.2-K/40-mT Mössbauer spectra of selected samples of P4H. (Left) O2-free P4H·Fe(II)·αKG·(Pro-Ala-Pro-Lys)3 complex (Top) and 20-ms freeze-quenched samples from the reaction of this complex with O2 at 5°C [Middle, deuteriated (d7-Pro-Ala-d7-Pro-Lys)3; Bottom, unlabeled (Pro-Ala-Pro-Lys)3]. The solid line in the middle spectrum is the contribution of the Fe(IV) intermediate (38%) simulated according to the parameters quoted in the text. The solid line in Bottom is the contribution of the P4H·Fe(II)·αKG·(Pro-Ala-Pro-Lys)3 complex (62%). (Right) Comparison of derived spectra of the three accumulating states from the P4H (vertical lines) and TauD (solid lines) catalytic cycles: quaternary complex (Top), Fe(IV) intermediate (Middle), and product(s) complex (Bottom). For the 20-ms samples, the concentrations after mixing were 1.4 mM P4H, 1.25 mM Fe(II), 5 mM αKG, 5 mM ascorbate, 3.3 mM (Pro-Ala-Pro-Lys)3 (unlabeled or deuteriated), and 1.2 mM O2.