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

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, Tim Brandt van Driel, Robert W. Hartsock, Kasper S. Kjaer, Clemens Weninger, Elisa Biasin, Leland B. Gee, Keith O. Hodgson, Britt Hedman, Uwe Bergmann, Edward I. Solomon () and Kelly J. Gaffney ()
Additional contact information
Marco E. Reinhard: Stanford University
Michael W. Mara: Stanford University
Thomas Kroll: Stanford University
Hyeongtaek Lim: Stanford University
Ryan G. Hadt: Stanford University
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
Britt Hedman: Stanford University
Uwe Bergmann: Stanford University
Edward I. Solomon: Stanford University
Kelly J. Gaffney: Stanford University

Nature Communications, 2021, vol. 12, issue 1, 1-8

Abstract: 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.

Date: 2021
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DOI: 10.1038/s41467-021-21423-w

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