{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["List NH"],"funding":["Svenska Forskningsrådet Formas","Villum Fonden","National Science Foundation (NSF)","Villum Fonden (Villum Foundation)","Svenska Forskningsrådet Formas (Swedish Research Council Formas)","National Science Foundation"],"pagination":["25"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC10844232"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["7(1)"],"pubmed_abstract":["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."],"journal":["Communications chemistry"],"pubmed_title":["Chemical control of excited-state reactivity of the anionic green fluorescent protein chromophore."],"pmcid":["PMC10844232"],"funding_grant_id":["2018-05973","Graduate Research Fellow","VKR023371"],"pubmed_authors":["Jones CM","List NH","Martinez TJ"],"additional_accession":[]},"is_claimable":false,"name":"Chemical control of excited-state reactivity of the anionic green fluorescent protein chromophore.","description":"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.","dates":{"release":"2024-01-01T00:00:00Z","publication":"2024 Feb","modification":"2025-04-22T05:37:21.46Z","creation":"2025-04-05T21:23:40.305Z"},"accession":"S-EPMC10844232","cross_references":{"pubmed":["38316834"],"doi":["10.1038/s42004-024-01099-1"]}}