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Ultrafast Energy Transfer from Photoexcited Tryptophan to the Haem in Cytochrome c

Bacellar, Camila; Rouxel, Jérémy R; Ingle, Rebecca A; Mancini, Giulia F; Kinschel, Dominik; Cannelli, Oliviero; Zhao, Yang; ... Chergui, Majed; + view all (2023) Ultrafast Energy Transfer from Photoexcited Tryptophan to the Haem in Cytochrome c. Journal of Physical Chemistry Letters , 14 (9) pp. 2425-2432. 10.1021/acs.jpclett.3c00218. Green open access

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Abstract

We report femtosecond Fe K-edge absorption (XAS) and nonresonant X-ray emission (XES) spectra of ferric cytochrome C (Cyt c) upon excitation of the haem (>300 nm) or mixed excitation of the haem and tryptophan (<300 nm). The XAS and XES transients obtained in both excitation energy ranges show no evidence for electron transfer processes between photoexcited tryptophan (Trp) and the haem, but rather an ultrafast energy transfer, in agreement with previous ultrafast optical fluorescence and transient absorption studies. The reported (J. Phys. Chem. B 2011, 115 (46), 13723-13730) decay times of Trp fluorescence in ferrous (∼350 fs) and ferric (∼700 fs) Cyt c are among the shortest ever reported for Trp in a protein. The observed time scales cannot be rationalized in terms of Förster or Dexter energy transfer mechanisms and call for a more thorough theoretical investigation.

Type: Article
Title: Ultrafast Energy Transfer from Photoexcited Tryptophan to the Haem in Cytochrome c
Location: United States
Open access status: An open access version is available from UCL Discovery
DOI: 10.1021/acs.jpclett.3c00218
Publisher version: https://doi.org/10.1021/acs.jpclett.3c00218
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions.
Keywords: Bioinorganic chemistry, Charge transfer, Fluorescence, Fluorescence resonance energy transfer, Peptides and proteins
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10168557
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