NRVS Studies of the Peroxide Shunt Intermediate in a Rieske Dioxygenase and Its Relation to the Native Fe-II O-2 Reaction

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The Rieske dioxygenases are a major subclass of mononuclear nonheme iron enzymes that play an important role in bioremediation. Recently, a high-spin Fe-III-(hydro)-peroxy intermediate (BZDOp) has been trapped in the peroxide shunt reaction of benzoate 1,2-dioxygenase. Defining the structure of this intermediate is essential to understanding the reactivity of these enzymes. Nuclear resonance vibrational spectroscopy (NRVS) is a recently developed synchrotron technique that is ideal for obtaining vibrational, and thus structural, information on Fe sites, as it gives complete information on all vibrational normal modes containing Fe displacement. In this study, we present NRVS data on BZDOp and assign its structure using these data coupled to experimentally calibrated density functional theory calculations. From this NRVS structure, we define the mechanism for the peroxide shunt reaction. The relevance of the peroxide shunt to the native Fe-II/O-2 reaction is evaluated. For the native Fe-II/O-2 reaction, an Fe-III-superoxo intermediate is found to react directly with substrate. This process, while uphill thermodynamically, is found to be driven by the highly favorable thermodynamics of proton-coupled electron transfer with an electron provided by the Rieske [2Fe-2S] center at a later step in the reaction. These results offer important insight into the relative reactivities of Fe-III-superoxo and Fe-III-hydroperoxo species in nonheme Fe biochemistry.
Publisher
AMER CHEMICAL SOC
Issue Date
2018-04
Language
English
Article Type
Article
Keywords

NUCLEAR RESONANT SCATTERING; ISOPENICILLIN N-SYNTHASE; GAUSSIAN-BASIS SETS; RING-HYDROXYLATING DIOXYGENASE; NONHEME IRON ENZYMES; NAPHTHALENE 1,2-DIOXYGENASE; CIS-DIHYDROXYLATION; HIGH-SPIN; OXYGEN ACTIVATION; NITROBENZENE DIOXYGENASE

Citation

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.140, no.16, pp.5544 - 5559

ISSN
0002-7863
DOI
10.1021/jacs.8b01822
URI
http://hdl.handle.net/10203/242254
Appears in Collection
CH-Journal Papers(저널논문)
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