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Short-lived metal-centered excited state initiates iron-methionine photodissociation in ferrous cytochrome c

Author

Listed:
  • Marco E. Reinhard

    (Stanford University
    Stanford University)

  • Michael W. Mara

    (Stanford University
    Northwestern University)

  • Thomas Kroll

    (Stanford University)

  • Hyeongtaek Lim

    (Stanford University)

  • Ryan G. Hadt

    (Stanford University
    California Institute of Technology)

  • Roberto Alonso-Mori

    (Stanford University)

  • Matthieu Chollet

    (Stanford University)

  • James M. Glownia

    (Stanford University)

  • Silke Nelson

    (Stanford University)

  • Dimosthenis Sokaras

    (Stanford University)

  • Kristjan Kunnus

    (Stanford University)

  • Tim Brandt van Driel

    (Stanford University)

  • Robert W. Hartsock

    (Stanford University)

  • Kasper S. Kjaer

    (Stanford University)

  • Clemens Weninger

    (Stanford University)

  • Elisa Biasin

    (Stanford University)

  • Leland B. Gee

    (Stanford University)

  • Keith O. Hodgson

    (Stanford University
    Stanford University)

  • Britt Hedman

    (Stanford University)

  • Uwe Bergmann

    (Stanford University)

  • Edward I. Solomon

    (Stanford University
    Stanford University)

  • Kelly J. Gaffney

    (Stanford University
    Stanford University)

Abstract

The dynamics of photodissociation and recombination in heme proteins represent an archetypical photochemical reaction widely used to understand the interplay between chemical dynamics and reaction environment. We report a study of the photodissociation mechanism for the Fe(II)-S bond between the heme iron and methionine sulfur of ferrous cytochrome c. This bond dissociation is an essential step in the conversion of cytochrome c from an electron transfer protein to a peroxidase enzyme. We use ultrafast X-ray solution scattering to follow the dynamics of Fe(II)-S bond dissociation and 1s3p (Kβ) X-ray emission spectroscopy to follow the dynamics of the iron charge and spin multiplicity during bond dissociation. From these measurements, we conclude that the formation of a triplet metal-centered excited state with anti-bonding Fe(II)-S interactions triggers the bond dissociation and precedes the formation of the metastable Fe high-spin quintet state.

Suggested Citation

  • Marco E. Reinhard & Michael W. Mara & Thomas Kroll & Hyeongtaek Lim & Ryan G. Hadt & Roberto Alonso-Mori & Matthieu Chollet & James M. Glownia & Silke Nelson & Dimosthenis Sokaras & Kristjan Kunnus & , 2021. "Short-lived metal-centered excited state initiates iron-methionine photodissociation in ferrous cytochrome c," Nature Communications, Nature, vol. 12(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:12:y:2021:i:1:d:10.1038_s41467-021-21423-w
    DOI: 10.1038/s41467-021-21423-w
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    Cited by:

    1. Marco Reinhard & Alessandro Gallo & Meiyuan Guo & Angel T. Garcia-Esparza & Elisa Biasin & Muhammad Qureshi & Alexander Britz & Kathryn Ledbetter & Kristjan Kunnus & Clemens Weninger & Tim Driel & Jos, 2023. "Ferricyanide photo-aquation pathway revealed by combined femtosecond Kβ main line and valence-to-core x-ray emission spectroscopy," Nature Communications, Nature, vol. 14(1), pages 1-11, December.

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