Substrate-Triggered
Formation of a Peroxo-Fe2(III/III) Intermediate during
Fatty Acid Decarboxylation by UndA
Version 2 2019-09-10, 16:39
Version 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
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AUTHORS (13)
BZ
Bo Zhang
LR
Lauren J. Rajakovich
DV
Devon Van Cura
EB
Elizabeth J. Blaesi
AM
Andrew J. Mitchell
CT
Christina R. Tysoe
XZ
Xuejun Zhu
BS
Bennett R. Streit
ZR
Zhe Rui
WZ
Wenjun Zhang
AB
Amie K. Boal
CK
Carsten Krebs
JB
J. Martin Bollinger