Selective photo labeling of tryptophan in N ‐acetyl‐L‐tryptophan ethyl ester and peptide WWCNDGR with a diaryl nitrenium ion

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Autores principales: Edward S. Chinn, Yue Li, Abigail M. Joyce, Daniel E. Falvey
Formato: Artículo Open Access
Publicado: Wiley 2026
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author Edward S. Chinn
Yue Li
Abigail M. Joyce
Daniel E. Falvey
author_facet Edward S. Chinn
Yue Li
Abigail M. Joyce
Daniel E. Falvey
Edward S. Chinn
Yue Li
Abigail M. Joyce
Daniel E. Falvey
collection Wiley Open Access
contents Selective photo labeling of tryptophan in N ‐acetyl‐L‐tryptophan ethyl ester and peptide WWCNDGR with a diaryl nitrenium ion Edward S. Chinn Yue Li Abigail M. Joyce Daniel E. Falvey Photochemistry and Photobiology Abstract Diaryl nitrenium ions are short‐lived electrophiles that have been shown to react rapidly with various nucleic and amino acids. To determine whether these species could be used to covalently photomodify proteins or peptides, a diarylnitrenium ion precursor, N ‐(4,4′‐dibromodiphenylamino)‐2,4,6‐trimethylpyridinium ion, was photolyzed in the presence of tryptophan as well as a tryptophan‐containing peptide (WWCNDGR). It is shown that the resulting diarylnitrenium ion, N ‐(4,4′‐dibromodiphenyl)nitrenium ion, forms two covalent adducts with tryptophan, the first where the ortho‐ring carbon of the nitrenium ion couples to the C‐2 of the tryptophan and a second isomer where the indole N‐1 nitrogen of tryptophan couples to the ortho‐ring carbon of the nitrenium ion. When photolyzed in the presence of the peptide, tandem mass spectrometry demonstrates selective formation of adducts on the tryptophan residues. Laser flash photolysis experiments verify that trapping occurs via a nitrenium ion intermediate. 10.1111/php.70109 http://creativecommons.org/licenses/by/4.0/
doi_str_mv 10.1111/php.70109
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spellingShingle Selective photo labeling of tryptophan in N ‐acetyl‐L‐tryptophan ethyl ester and peptide WWCNDGR with a diaryl nitrenium ion
Edward S. Chinn
Yue Li
Abigail M. Joyce
Daniel E. Falvey
Photochemistry and Photobiology
Selective photo labeling of tryptophan in N ‐acetyl‐L‐tryptophan ethyl ester and peptide WWCNDGR with a diaryl nitrenium ion Edward S. Chinn Yue Li Abigail M. Joyce Daniel E. Falvey Photochemistry and Photobiology Abstract Diaryl nitrenium ions are short‐lived electrophiles that have been shown to react rapidly with various nucleic and amino acids. To determine whether these species could be used to covalently photomodify proteins or peptides, a diarylnitrenium ion precursor, N ‐(4,4′‐dibromodiphenylamino)‐2,4,6‐trimethylpyridinium ion, was photolyzed in the presence of tryptophan as well as a tryptophan‐containing peptide (WWCNDGR). It is shown that the resulting diarylnitrenium ion, N ‐(4,4′‐dibromodiphenyl)nitrenium ion, forms two covalent adducts with tryptophan, the first where the ortho‐ring carbon of the nitrenium ion couples to the C‐2 of the tryptophan and a second isomer where the indole N‐1 nitrogen of tryptophan couples to the ortho‐ring carbon of the nitrenium ion. When photolyzed in the presence of the peptide, tandem mass spectrometry demonstrates selective formation of adducts on the tryptophan residues. Laser flash photolysis experiments verify that trapping occurs via a nitrenium ion intermediate. 10.1111/php.70109 http://creativecommons.org/licenses/by/4.0/
title Selective photo labeling of tryptophan in N ‐acetyl‐L‐tryptophan ethyl ester and peptide WWCNDGR with a diaryl nitrenium ion
topic Photochemistry and Photobiology
url https://onlinelibrary.wiley.com/doi/10.1111/php.70109