Spectroscopic Evidence for Peptide-Bond-Selective Ultraviolet Photodissociation

Aleksandr Y. Pereverzev; Zsuzsanna Koczor-Benda; Erik Saparbaev; Vladimir N. Kopysov; Edina Rosta; Oleg V. Boyarkin

doi:10.1021/acs.jpclett.9b03221

Spectroscopic Evidence for Peptide-Bond-Selective Ultraviolet Photodissociation

Aleksandr Y. Pereverzev, Zsuzsanna Koczor-Benda, Erik Saparbaev, Vladimir N. Kopysov, Edina Rosta, Oleg V. Boyarkin

Chemistry

Research output: Contribution to journal › Letter › peer-review

8 Citations (Scopus)

Abstract

We study the photodissociation induced by ultraviolet excitation of amide bonds in gas-phase protonated peptides. Jointly, mass spectrometry and cold ion spectroscopy provide evidence for a selective nonstatistical dissociation of specific peptide bonds in the spectral region of the formally forbidden n → π* transition of amide groups. Structural analysis reveals that the activation of this transition, peaked at 226 nm, originates from the nonplanar geometry of the bond. In contrast, the statistical dissociation in the electronic ground state appears to be the main outcome of the π → π* excitation of the peptide bonds at 193 nm. We propose a tentative model that explains the difference in the fragmentation mechanisms by the difference in localization of the electronic transitions and the higher amount of vibrational energy released in the electronic excited state upon absorption at 193 nm.

Original language	English
Pages (from-to)	206-209
Number of pages	4
Journal	Journal of physical chemistry letters
Volume	11
Issue number	1
DOIs	https://doi.org/10.1021/acs.jpclett.9b03221
Publication status	Published - 2 Jan 2020

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10.1021/acs.jpclett.9b03221

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title = "Spectroscopic Evidence for Peptide-Bond-Selective Ultraviolet Photodissociation",

abstract = "We study the photodissociation induced by ultraviolet excitation of amide bonds in gas-phase protonated peptides. Jointly, mass spectrometry and cold ion spectroscopy provide evidence for a selective nonstatistical dissociation of specific peptide bonds in the spectral region of the formally forbidden n → π* transition of amide groups. Structural analysis reveals that the activation of this transition, peaked at 226 nm, originates from the nonplanar geometry of the bond. In contrast, the statistical dissociation in the electronic ground state appears to be the main outcome of the π → π* excitation of the peptide bonds at 193 nm. We propose a tentative model that explains the difference in the fragmentation mechanisms by the difference in localization of the electronic transitions and the higher amount of vibrational energy released in the electronic excited state upon absorption at 193 nm.",

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T1 - Spectroscopic Evidence for Peptide-Bond-Selective Ultraviolet Photodissociation

AU - Pereverzev, Aleksandr Y.

AU - Koczor-Benda, Zsuzsanna

AU - Saparbaev, Erik

AU - N. Kopysov, Vladimir

AU - Rosta, Edina

AU - Boyarkin, Oleg V.

PY - 2020/1/2

Y1 - 2020/1/2

N2 - We study the photodissociation induced by ultraviolet excitation of amide bonds in gas-phase protonated peptides. Jointly, mass spectrometry and cold ion spectroscopy provide evidence for a selective nonstatistical dissociation of specific peptide bonds in the spectral region of the formally forbidden n → π* transition of amide groups. Structural analysis reveals that the activation of this transition, peaked at 226 nm, originates from the nonplanar geometry of the bond. In contrast, the statistical dissociation in the electronic ground state appears to be the main outcome of the π → π* excitation of the peptide bonds at 193 nm. We propose a tentative model that explains the difference in the fragmentation mechanisms by the difference in localization of the electronic transitions and the higher amount of vibrational energy released in the electronic excited state upon absorption at 193 nm.

AB - We study the photodissociation induced by ultraviolet excitation of amide bonds in gas-phase protonated peptides. Jointly, mass spectrometry and cold ion spectroscopy provide evidence for a selective nonstatistical dissociation of specific peptide bonds in the spectral region of the formally forbidden n → π* transition of amide groups. Structural analysis reveals that the activation of this transition, peaked at 226 nm, originates from the nonplanar geometry of the bond. In contrast, the statistical dissociation in the electronic ground state appears to be the main outcome of the π → π* excitation of the peptide bonds at 193 nm. We propose a tentative model that explains the difference in the fragmentation mechanisms by the difference in localization of the electronic transitions and the higher amount of vibrational energy released in the electronic excited state upon absorption at 193 nm.

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DO - 10.1021/acs.jpclett.9b03221

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JO - Journal of physical chemistry letters

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ER -

Spectroscopic Evidence for Peptide-Bond-Selective Ultraviolet Photodissociation

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