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Photo-isomerization of the isolated photoactive yellow protein chromophore: what comes before the primary step?

Anstöter, Cate S. and Curchod, Basile F. E. and Verlet, Jan R. R. (2022) 'Photo-isomerization of the isolated photoactive yellow protein chromophore: what comes before the primary step?', Physical chemistry chemical physics., 24 (3). pp. 1305-1309.

Abstract

Photoactive proteins typically rely on structural changes in a small chromophore to initiate a biological response. While these changes often involve isomerization as the “primary step”, preceding this is an ultrafast relaxation of the molecular framework caused by the sudden change in electronic structure upon photoexcitation. Here, we capture this motion for an isolated model chromophore of the photoactive yellow protein using time-resolved photoelectron imaging. It occurs in <150 fs and is apparent from a spectral shift of ∼70 meV and a change in photoelectron anisotropy. Electronic structure calculations enable the quantitative assignment of the geometric and electronic structure changes to a planar intermediate from which the primary step can then proceed.

Item Type:Article
Full text:(AM) Accepted Manuscript
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Status:Peer-reviewed
Publisher Web site:https://doi.org/10.1039/D1CP05259D
Date accepted:23 December 2021
Date deposited:16 March 2022
Date of first online publication:23 December 2021
Date first made open access:23 December 2022

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