Chemical control of excited-state reactivity of the anionic green fluorescent protein chromophore
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 p...
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-02-01
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| Series: | Communications Chemistry |
| Online Access: | https://doi.org/10.1038/s42004-024-01099-1 |
| _version_ | 1797275540004012032 |
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| author | Nanna H. List Chey M. Jones Todd J. Martínez |
| author_facet | Nanna H. List Chey M. Jones Todd J. Martínez |
| author_sort | Nanna H. List |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-03-07T15:15:56Z |
| format | Article |
| id | doaj.art-40dc5e29d2d2424d9d6d248235722dc8 |
| institution | Directory Open Access Journal |
| issn | 2399-3669 |
| language | English |
| last_indexed | 2024-03-07T15:15:56Z |
| publishDate | 2024-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Communications Chemistry |
| spelling | doaj.art-40dc5e29d2d2424d9d6d248235722dc82024-03-05T17:55:41ZengNature PortfolioCommunications Chemistry2399-36692024-02-017111010.1038/s42004-024-01099-1Chemical control of excited-state reactivity of the anionic green fluorescent protein chromophoreNanna H. List0Chey M. Jones1Todd J. Martínez2Department of Chemistry, School of Engineering Sciences in Chemistry, Biotechnology and Health, KTH Royal Institute of TechnologyDepartment of Chemistry and The PULSE Institute, Stanford UniversityDepartment of Chemistry and The PULSE Institute, Stanford UniversityAbstract 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.https://doi.org/10.1038/s42004-024-01099-1 |
| spellingShingle | Nanna H. List Chey M. Jones Todd J. Martínez Chemical control of excited-state reactivity of the anionic green fluorescent protein chromophore Communications Chemistry |
| title | Chemical control of excited-state reactivity of the anionic green fluorescent protein chromophore |
| title_full | Chemical control of excited-state reactivity of the anionic green fluorescent protein chromophore |
| title_fullStr | Chemical control of excited-state reactivity of the anionic green fluorescent protein chromophore |
| title_full_unstemmed | Chemical control of excited-state reactivity of the anionic green fluorescent protein chromophore |
| title_short | Chemical control of excited-state reactivity of the anionic green fluorescent protein chromophore |
| title_sort | chemical control of excited state reactivity of the anionic green fluorescent protein chromophore |
| url | https://doi.org/10.1038/s42004-024-01099-1 |
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