Substrate-Triggered
Formation of a Peroxo-Fe2(III/III) Intermediate during
Fatty Acid Decarboxylation by UndA
Version 2 2019-09-10, 16:39Version 2 2019-09-10, 16:39
Version 1 2019-09-10, 16:36Version 1 2019-09-10, 16:36
Posted on 2019-09-10 - 16:39
The iron-dependent oxidase UndA cleaves
one C3–H bond and
the C1–C2 bond of dodecanoic acid to produce 1-undecene and
CO2. A published X-ray crystal structure showed that UndA
has a heme-oxygenase-like fold, thus associating it with a structural
superfamily that includes known and postulated non-heme diiron proteins,
but revealed only a single iron ion in the active site. Mechanisms
proposed for initiation of decarboxylation by cleavage of the C3–H
bond using a monoiron cofactor to activate O2 necessarily
invoked unusual or potentially unfeasible steps. Here we present spectroscopic,
crystallographic, and biochemical evidence that the cofactor of Pseudomonas fluorescens Pf-5 UndA is actually a diiron
cluster and show that binding of the substrate triggers rapid addition
of O2 to the Fe2(II/II) cofactor to produce
a transient peroxo-Fe2(III/III) intermediate. The observations
of a diiron cofactor and substrate-triggered formation of a peroxo-Fe2(III/III) intermediate suggest a small set of possible mechanisms
for O2, C3–H and C1–C2 activation by UndA;
these routes obviate the problematic steps of the earlier hypotheses
that invoked a single iron.
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Zhang, Bo; Rajakovich, Lauren J.; Van Cura, Devon; Blaesi, Elizabeth J.; Mitchell, Andrew J.; Tysoe, Christina R.; et al. (2019). Substrate-Triggered
Formation of a Peroxo-Fe2(III/III) Intermediate during
Fatty Acid Decarboxylation by UndA. ACS Publications. Collection. https://doi.org/10.1021/jacs.9b06093