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

Autor: List NH; Department of Chemistry, School of Engineering Sciences in Chemistry, Biotechnology and Health, KTH Royal Institute of Technology, SE-10044, Stockholm, Sweden. nalist@kth.se., Jones CM; Department of Chemistry and The PULSE Institute, Stanford University, Stanford, CA, 94305, USA.; SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA., Martínez TJ; Department of Chemistry and The PULSE Institute, Stanford University, Stanford, CA, 94305, USA. toddjmartinez@gmail.com.; SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA. toddjmartinez@gmail.com.
Jazyk: angličtina
Zdroj: Communications chemistry [Commun Chem] 2024 Feb 05; Vol. 7 (1), pp. 25. Date of Electronic Publication: 2024 Feb 05.
DOI: 10.1038/s42004-024-01099-1
Abstrakt: 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.
(© 2024. The Author(s).)
Databáze: MEDLINE
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