Journal Article

FZJ-2017-00648

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Direct visualization of a Fe(IV)–OH intermediate in a heme enzyme

Kwon, H. ; Basran, J. ; Casadei, C. M. ; Fielding, A. J. ; Schrader, T. E.FZJ* ; Ostermann, A. ; Devos, J. M. ; Aller, P. ; Blakeley, M. P. ; Moody, P. C. E. (Corresponding author) ; Raven, E. L. (Corresponding author)

2016
Nature Publishing Group London

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Please use a persistent id in citations: http://hdl.handle.net/2128/13579  doi:10.1038/ncomms13445

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.

Keyword(s): Health and Life (1st) ; Biology (2nd)

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Contributing Institute(s):

1. JCNS-FRM-II (JCNS (München) ; Jülich Centre for Neutron Science JCNS (München) ; JCNS-FRM-II)
2. Neutronenstreuung (Neutronenstreuung ; JCNS-1)

Research Program(s):

1. 6G15 - FRM II / MLZ (POF3-6G15) (POF3-6G15)
2. 6G4 - Jülich Centre for Neutron Research (JCNS) (POF3-623) (POF3-623)

Experiment(s):

1. BIODIFF: Diffractometer for large unit cells (NL1)

Appears in the scientific report 2016

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