5 years ago

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

Peroxide Activation for Electrophilic Reactivity by the Binuclear Non-heme Iron Enzyme AurF
Kiyoung Park, Yoshitaka Yoda, J. Martin Bollinger, Carsten Krebs, Ning Li, Shinji Kitao, Michael Hu, Shaun D. Wong, Jiyong Zhao, Caleb B. Bell, Martin Srnec, Yeonju Kwak, Edward I. Solomon, Makoto Seto, Lei V. Liu
Binuclear non-heme iron enzymes activate O2 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 O2. 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.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b02997

DOI: 10.1021/jacs.7b02997

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