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@ARTICLE{Kwon:826420,
author = {Kwon, Hanna and Basran, Jaswir and Casadei, Cecilia M. and
Fielding, Alistair J. and Schrader, Tobias E. and Ostermann,
Andreas and Devos, Juliette M. and Aller, Pierre and
Blakeley, Matthew P. and Moody, Peter C. E. and Raven, Emma
L.},
title = {{D}irect visualization of a {F}e({IV})–{OH} intermediate
in a heme enzyme},
journal = {Nature Communications},
volume = {7},
issn = {2041-1723},
address = {London},
publisher = {Nature Publishing Group},
reportid = {FZJ-2017-00648},
pages = {13445 -},
year = {2016},
abstract = {Catalytic heme enzymes carry out a wide range of oxidations
in biology. They have in common a mechanism that requires
formation of highly oxidized ferryl intermediates. It is
these ferryl intermediates that provide the catalytic engine
to drive the biological activity. Unravelling the nature of
the ferryl species is of fundamental and widespread
importance. The essential question is whether the ferryl is
best described as a Fe(IV)=O or a Fe(IV)–OH species, but
previous spectroscopic and X-ray crystallographic studies
have not been able to unambiguously differentiate between
the two species. Here we use a different approach. We report
a neutron crystal structure of the ferryl intermediate in
Compound II of a heme peroxidase; the structure allows the
protonation states of the ferryl heme to be directly
observed. This, together with pre-steady state kinetic
analyses, electron paramagnetic resonance spectroscopy and
single crystal X-ray fluorescence, identifies a Fe(IV)–OH
species as the reactive intermediate. The structure
establishes a precedent for the formation of Fe(IV)–OH in
a peroxidase.},
cin = {JCNS (München) ; Jülich Centre for Neutron Science JCNS
(München) ; JCNS-FRM-II / Neutronenstreuung ; JCNS-1},
ddc = {500},
cid = {I:(DE-Juel1)JCNS-FRM-II-20110218 /
I:(DE-Juel1)JCNS-1-20110106},
pnm = {6G15 - FRM II / MLZ (POF3-6G15) / 6G4 - Jülich Centre for
Neutron Research (JCNS) (POF3-623)},
pid = {G:(DE-HGF)POF3-6G15 / G:(DE-HGF)POF3-6G4},
experiment = {EXP:(DE-MLZ)BIODIFF-20140101},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000388990900001},
pubmed = {pmid:27897163},
doi = {10.1038/ncomms13445},
url = {https://juser.fz-juelich.de/record/826420},
}