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

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. As a result, this activation of peroxide by protonation is likely also relevant to the reactive peroxo intermediates in other binuclear non-heme iron enzymes.
Authors:
 [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)
Publication Date:
Grant/Contract Number:
AC02-76SF00515; CHE-1058931; MCB1404866; 24221005; GM40392; AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 20; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Institutes of Health (NIH); National Science Foundation (NSF); Japan Society for the Promotion of Science (JSPS) - KAKENHI
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; O2 activation; diiron site; peroxo intermediate; nuclear resonance vibrational spectroscopy; O2; activation
OSTI Identifier:
1369431
Alternate Identifier(s):
OSTI ID: 1377396