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Controlling electron emission from the photoactive yellow protein chromophore by substitution at the coumaric acid group

Parkes, MA; Phillips, C; Porter, MJ; Fielding, HH; (2016) Controlling electron emission from the photoactive yellow protein chromophore by substitution at the coumaric acid group. Physical Chemistry Chemical Physics , 18 (15) pp. 10329-10336. 10.1039/c6cp00565a. Green open access

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Abstract

Understanding how the interactions between a chromophore and its surrounding protein control the function of a photoactive protein remains a challenge. Here, we present the results of photoelectron spectroscopy measurements and quantum chemistry calculations aimed at investigating how substitution at the coumaryl tail of the photoactive yellow protein chromophore controls competing relaxation pathways following photoexcitation of isolated chromophores in the gas phase with ultraviolet light in the range 350-315 nm. The photoelectron spectra are dominated by electrons resulting from direct detachment and fast detachment from the 2(1)ππ* state but also have a low electron kinetic energy component arising from autodetachment from lower lying electronically excited states or thermionic emission from the electronic ground state. We find that substituting the hydrogen atom of the carboxylic acid group with a methyl group lowers the threshold for electron detachment but has very little effect on the competition between the different relaxation pathways, whereas substituting with a thioester group raises the threshold for electron detachment and appears to 'turn off' the competing electron emission processes from lower lying electronically excited states. This has potential implications in terms of tuning the light-induced electron donor properties of photoactive yellow protein.

Type: Article
Title: Controlling electron emission from the photoactive yellow protein chromophore by substitution at the coumaric acid group
Location: England
Open access status: An open access version is available from UCL Discovery
DOI: 10.1039/c6cp00565a
Publisher version: http://doi.org/10.1039/c6cp00565a
Language: English
Additional information: Copyright © Royal Society of Chemistry 2016. This ia an Open Access article licensed under a Creative Commons Attribution 3.0 Unported Licence. For further information see: https://creativecommons.org/licenses/by/3.0/
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/1493603
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