Gopakumar, G.; Svensson, P.H. W.; Granas, O.; Brena, B.; Schwob, L.; Unger, I.; Saak, C.-M.; Timm, M.; Buelow, C.; Kubin, M.; Zamudio-Bayer, V.; Lau, J. T.; von Issendorff, B.; Abid, A.R.; Lindblad, A.; Danielsson, E.; Koerfer, E.; Caleman, C.; Bjorneholm, O.; Lindblad, R.: X-ray Induced Fragmentation of Protonated Cystine. The Journal of Physical Chemistry A 126 (2022), p. 1496–1503
10.1021/acs.jpca.1c10158
Open Access Version
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.