Chemical control of excited-state reactivity of the anionic green fluorescent protein chromophore

List, Nanna H.; Jones, Chey M.; Martínez, Todd J.

doi:10.1038/s42004-024-01099-1

Title: Chemical control of excited-state reactivity of the anionic green fluorescent protein chromophore

Journal Article · Sun Feb 04 23:00:00 EST 2024 · Communications Chemistry

DOI: https://doi.org/10.1038/s42004-024-01099-1 · OSTI ID:2322463

^[1]; Jones, Chey M. ^[2];

^[2]

KTH Royal Institute of Technology, Stockholm (Sweden); SLAC
Stanford University, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE)

Controlling excited-state reactivity is a long-standing challenge in photochemistry, as a desired pathway may be inaccessible or compete with other unwanted channels. An important example is internal conversion of the anionic green fluorescent protein (GFP) chromophore where non-selective progress along two competing torsional modes (P: phenolate and I: imidazolinone) impairs and enables Z-to-E photoisomerization, respectively. Developing strategies to promote photoisomerization could drive new areas of applications of GFP-like proteins. Motivated by the charge-transfer dichotomy of the torsional modes, we explore chemical substitution on the P-ring of the chromophore as a way to control excited-state pathways and improve photoisomerization. As demonstrated by methoxylation, selective P-twisting appears difficult to achieve because the electron-donating potential effects of the substituents are counteracted by inertial effects that directly retard the motion. Conversely, these effects act in concert to promote I-twisting when introducing electron-withdrawing groups. Specifically, 2,3,5-trifluorination leads to both pathway selectivity and a more direct approach to the I-twisted intersection which, in turn, doubles the photoisomerization quantum yield. Our results suggest P-ring engineering as an effective approach to boost photoisomerization of the anionic GFP chromophore.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); Villum Foundation; KTH Royal Institute of Technology; National Science Foundation (NSF); Swedish Research Council

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 2322463

Journal Information:: Communications Chemistry, Journal Name: Communications Chemistry Journal Issue: 1 Vol. 7; ISSN 2399-3669

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

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