Unprecedented Fe(IV) Species in a Diheme Protein MauG: A Quantum Chemical Investigation on the Unusual Mossbauer Spectroscopic Properties

Document Type

Article

Publication Date

10-7-2010

Department

Chemistry and Biochemistry

School

Mathematics and Natural Sciences

Abstract

Ferryl species are important catalytic intermediates in heme enzymes. A recent experimental investigation of a diheme protein MauG reported the first case of using two Fe(IV) species as an alternative to compound I in catalysis. Both Fe(IV) species have unusual Mössbauer properties, which was found to originate from novel structural features based on a quantum chemical investigation. With comparison with the previously reported FeIV═O and FeIV−OH species, results here provide evidence of new mechanisms by which proteins influence the properties of ferryl species by directly providing the O via Tyr or stabilizing exogenous O via hydrogen bonding interaction. These results expand our ability to identify and evaluate high-valent heme proteins and models.

Publication Title

Journal of Physical Chemistry Letters

Volume

1

Issue

19

First Page

2936

Last Page

2939

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