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. Author manuscript; available in PMC: 2010 Jun 10.
Published in final edited form as: J Am Chem Soc. 2009 Jun 10;131(22):7685–7698. doi: 10.1021/ja810080c

Table 4.

Rate constants for the reactions of WT and E332A TH complexes with O2 at 5 °C.

FeIITH + O2 →FeIIITH(mM−1s−1)

FeIITH-[ ] 0.037

FeIITH + O2 ⇔ FeIITH:O2 FeIITH:O2 → FeIIITH (s−1) 6MPH4 → q-6MPH2 (mM−1s−1)
kon (mM−1s−1) koff (s−1)
FeIITH-[6MPH4] 1.5 0.5 0.16 40
apoTH-[6MPH4] 0.00017
FeIITH-[5-deaza-6MPH4] No reaction
FeIITH-[6MPH2] 2.0 0.5 0.032
FeIITH-[L-tyr] 2.0 0.5 0.040
FeIITH-[5-deaza-6MPH4, L-tyr] 2.0 0.4 0.026
FeIITH-[6MPH2, L-tyr] 6.0 0.5 0.050

FeIITH:O2 → FeIV=O + 4a-HO-6MPH3

FeIITH-[L-tyr, 6MPH4] 300 50 24 s−1

FeIITH:O2 → FeII+ HOO-6MPH3

E332A-[L-tyr, 6MPH4] 10 3 0.3 s−1