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Title: Peroxide Activation for Electrophilic Reactivity by the Binuclear Non-heme Iron Enzyme AurF

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b02997· OSTI ID:1369431
 [1];  [2];  [3]; ORCiD logo [3];  [3];  [3];  [3];  [4];  [5];  [5];  [6];  [6]; ORCiD logo [2];  [2]; ORCiD logo [7]
  1. Stanford Univ., Stanford, CA (United States); KAIST, Daejeon (Republic of Korea)
  2. Pennsylvania State Univ., University Park, PA (United States)
  3. Stanford Univ., Stanford, CA (United States)
  4. SPring-8/JASRO, Hyogo (Japan)
  5. Kyoto Univ., Osaka (Japan)
  6. Argonne National Lab. (ANL), Lemont, IL (United States)
  7. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
+ Show Author Affiliations

Binuclear non-heme iron enzymes activate O-2 for diverse chemistries that include oxygenation of organic substrates and hydrogen atom abstraction. This process often involves the formation of peroxo-bridged biferric intermediates, only some of which can perform electrophilic reactions. To elucidate the geometric and electronic structural requirements to activate peroxo reactivity, the active peroxo intermediate in 4-aminobenzoate N-oxygenase (AurF) has been characterized spectroscopically and computationally. A magnetic circular dichroism study of reduced AurF shows that its electronic and geometric structures are poised to react rapidly with O-2. Nuclear resonance vibrational spectroscopic definition of the peroxo intermediate formed in this reaction shows that the active intermediate has a protonated peroxo bridge. Density functional theory computations on the structure established here show that the protonation activates peroxide for electrophilic/single-electron-transfer reactivity. This activation of peroxide by protonation is likely also relevant to the reactive peroxo intermediates in other binuclear non-heme iron enzymes.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH); National Science Foundation (NSF); Japan Society for the Promotion of Science (JSPS) - KAKENHI
Grant/Contract Number:
AC02-76SF00515; CHE-1058931; MCB1404866; 24221005; GM40392; AC02-06CH11357
OSTI ID:
1369431
Alternate ID(s):
OSTI ID: 1377396
Journal Information:
Journal of the American Chemical Society, Vol. 139, Issue 20; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 38 works
Citation information provided by
Web of Science

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Cited By (3)

Origin of Nitric Oxide Reduction Activity in Flavo–Diiron NO Reductase: Key Roles of the Second Coordination Sphere journal February 2019
Mechanism of the Dinuclear Iron Enzyme p ‐Aminobenzoate N‐oxygenase from Density Functional Calculations journal October 2018
Origin of Nitric Oxide Reduction Activity in Flavo–Diiron NO Reductase: Key Roles of the Second Coordination Sphere journal March 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
O2 activation
diiron site
peroxo intermediate
nuclear resonance vibrational spectroscopy
O2
activation