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Femtosecond X-ray emission study of the spin cross-over dynamics in haem proteins

Dominik Kinschel, Camila Bacellar, Oliviero Cannelli, Boris Sorokin, Tetsuo Katayama, Giulia F. Mancini, Jérémy R. Rouxel, Yuki Obara, Junichi Nishitani, Hironori Ito, Terumasa Ito, Naoya Kurahashi, Chika Higashimura, Shotaro Kudo, Theo Keane, Frederico A. Lima, Wojciech Gawelda, Peter Zalden, Sebastian Schulz, James M. Budarz, Dmitry Khakhulin, Andreas Galler, Christian Bressler, Christopher J. Milne, Thomas Penfold, Makina Yabashi, Toshinori Suzuki, Kazuhiko Misawa and Majed Chergui ()
Additional contact information
Dominik Kinschel: Ecole Polytechnique Fédérale de Lausanne (EPFL)
Camila Bacellar: Ecole Polytechnique Fédérale de Lausanne (EPFL)
Oliviero Cannelli: Ecole Polytechnique Fédérale de Lausanne (EPFL)
Boris Sorokin: Ecole Polytechnique Fédérale de Lausanne (EPFL)
Tetsuo Katayama: Japan Synchrotron Radiation Research Institute (JASRI)
Giulia F. Mancini: Ecole Polytechnique Fédérale de Lausanne (EPFL)
Jérémy R. Rouxel: Ecole Polytechnique Fédérale de Lausanne (EPFL)
Yuki Obara: Tokyo University of Agriculture and Technology (TUAT)
Junichi Nishitani: Kyoto University
Hironori Ito: Tokyo University of Agriculture and Technology (TUAT)
Terumasa Ito: Tokyo University of Agriculture and Technology (TUAT)
Naoya Kurahashi: Sofia University
Chika Higashimura: Kyoto University
Shotaro Kudo: Kyoto University
Theo Keane: Newcastle University
Frederico A. Lima: European XFEL
Wojciech Gawelda: European XFEL
Peter Zalden: European XFEL
Sebastian Schulz: European XFEL
James M. Budarz: Ecole Polytechnique Fédérale de Lausanne (EPFL)
Dmitry Khakhulin: European XFEL
Andreas Galler: European XFEL
Christian Bressler: European XFEL
Christopher J. Milne: Paul-Scherrer-Institut (PSI)
Thomas Penfold: Newcastle University
Makina Yabashi: Japan Synchrotron Radiation Research Institute (JASRI)
Toshinori Suzuki: Kyoto University
Kazuhiko Misawa: Tokyo University of Agriculture and Technology (TUAT)
Majed Chergui: Ecole Polytechnique Fédérale de Lausanne (EPFL)

Nature Communications, 2020, vol. 11, issue 1, 1-8

Abstract: Abstract In haemoglobin the change from the low-spin (LS) hexacoordinated haem to the high spin (HS, S = 2) pentacoordinated domed deoxy-myoglobin (deoxyMb) form upon ligand detachment from the haem and the reverse process upon ligand binding are what ultimately drives the respiratory function. Here we probe them in the case of Myoglobin-NO (MbNO) using element- and spin-sensitive femtosecond Fe Kα and Kβ X-ray emission spectroscopy at an X-ray free-electron laser (FEL). We find that the change from the LS (S = 1/2) MbNO to the HS haem occurs in ~800 fs, and that it proceeds via an intermediate (S = 1) spin state. We also show that upon NO recombination, the return to the planar MbNO ground state is an electronic relaxation from HS to LS taking place in ~30 ps. Thus, the entire ligand dissociation-recombination cycle in MbNO is a spin cross-over followed by a reverse spin cross-over process.

Date: 2020
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Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:11:y:2020:i:1:d:10.1038_s41467-020-17923-w

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DOI: 10.1038/s41467-020-17923-w

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