Dr Jemma Gibbard jemma.gibbard@durham.ac.uk
Royal Society University Research Fellow
Photoelectron spectroscopy of the deprotonated tryptophan anion: the contribution of deprotomers to its photodetachment channels
Gibbard, Jemma A.; Kellow, Catherine S.; Verlet, Jan. R. R.
Authors
Catherine S. Kellow
Jan. R. R. Verlet
Abstract
Photoelectron spectroscopy and electronic structure calculations are used to investigate the electronic structure of the deprotonated anionic form of the aromatic amino acid tryptophan, and its chromophore, indole. The photoelectron spectra of tryptophan, recorded at different wavelengths across the UV, consist of two direct detachment channels and thermionic emission, whereas the hν = 4.66 eV spectrum of indole consists of two direct detachment features. Electronic structure calculations indicate that two deprotomers of tryptophan are present in the ion beam; deprotonation of the carboxylic acid group (Trp(i)−) or the N atom on the indole ring (Trp(ii)−). Strong similarities are observed between the direct detachment channels in the photoelectron spectra of tryptophan and indole, which in conjunction with electronic structure calculations, indicate that electron loss from Trp(ii)− dominates this portion of the spectra. However, there is some evidence that direct detachment of Trp(i)− is also observed. Thermionic emission is determined to predominantly arise from the decarboxylation of Trp(i)−, mediated by the ππ* excited state near λ = 300 nm, which results in an anionic fragment with a negative electron affinity that readily autodetaches.
Citation
Gibbard, J. A., Kellow, C. S., & Verlet, J. R. R. (2024). Photoelectron spectroscopy of the deprotonated tryptophan anion: the contribution of deprotomers to its photodetachment channels. Physical Chemistry Chemical Physics, 26(15), 12053-12059. https://doi.org/10.1039/d4cp00309h
Journal Article Type | Article |
---|---|
Acceptance Date | Mar 27, 2024 |
Online Publication Date | Apr 5, 2024 |
Publication Date | Apr 21, 2024 |
Deposit Date | Apr 23, 2024 |
Publicly Available Date | Apr 24, 2024 |
Journal | Physical Chemistry Chemical Physics |
Print ISSN | 1463-9076 |
Electronic ISSN | 1463-9084 |
Publisher | Royal Society of Chemistry |
Peer Reviewed | Peer Reviewed |
Volume | 26 |
Issue | 15 |
Pages | 12053-12059 |
DOI | https://doi.org/10.1039/d4cp00309h |
Public URL | https://durham-repository.worktribe.com/output/2378867 |
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