X-ray Induced Fragmentation of Protonated Cystine

Overview

Journal J Phys Chem A

Publisher American Chemical Society

Specialty Chemistry

Date 2022 Feb 25

PMID 35213156

Authors

Geethanjali Gopakumar

Pamela H W Svensson

Oscar Granas

Barbara Brena

Lucas Schwob

Isaak Unger

Clara-Magdalena Saak

Martin Timm

Christine Bulow

Markus Kubin

Vicente Zamudio-Bayer

J Tobias Lau

Bernd von Issendorff

Abdul R Abid

Andreas Lindblad

Emma Danielsson

Ebba Koerfer

Carl Caleman

Olle Bjorneholm

Rebecka Lindblad

Affiliations

Soon will be listed here.

Abstract

We demonstrate site-specific X-ray induced fragmentation across the sulfur L-edge of protonated cystine, the dimer of the amino acid cysteine. Ion yield NEXAFS were performed in the gas phase using electrospray ionization (ESI) in combination with an ion trap. The interpretation of the sulfur L-edge NEXAFS spectrum is supported by Restricted Open-Shell Configuration Interaction (ROCIS) calculations. The fragmentation pathway of triply charged cystine ions was modeled by Molecular Dynamics (MD) simulations. We have deduced a possible pathway of fragmentation upon excitation and ionization of S 2p electrons. The disulfide bridge breaks for resonant excitation at lower photon energies but remains intact upon higher energy resonant excitation and upon ionization of S 2p. The larger fragments initially formed subsequently break into smaller fragments.

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