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Angew Chem Int Ed Engl. 2016 Aug 26;55(36):10741-5. doi: 10.1002/anie.201605335. Epub 2016 Jul 25.

Multiple Ionization of Free Ubiquitin Molecular Ions in Extreme Ultraviolet Free-Electron Laser Pulses.

Angewandte Chemie (International ed. in English)

Thomas Schlathölter, Geert Reitsma, Dmitrii Egorov, Olmo Gonzalez-Magaña, Sadia Bari, Leon Boschman, Erwin Bodewits, Kirsten Schnorr, Georg Schmid, Claus Dieter Schröter, Robert Moshammer, Ronnie Hoekstra

Affiliations

  1. Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747, AG, Groningen, The Netherlands. [email protected].
  2. Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747, AG, Groningen, The Netherlands.
  3. Max-Born-Institute, Max Born Strasse 2A, 12489, Berlin, Germany.
  4. European XFEL GmbH, Holzkoppel 4, 22869, Schenefeld, Germany.
  5. DESY, Notkestraße 85, 22607, Hamburg, Germany.
  6. Kapteyn Institute, Landleven 12, 9747, AD, Groningen, The Netherlands.
  7. Max-Planck-Institut für Kernphysik, Saupfercheckweg 1, 69117, Heidelberg, Germany.

PMID: 27453360 DOI: 10.1002/anie.201605335

Abstract

The fragmentation of free tenfold protonated ubiquitin in intense 70 femtosecond pulses of 90 eV photons from the FLASH facility was investigated. Mass spectrometric investigation of the fragment cations produced after removal of many electrons revealed fragmentation predominantly into immonium ions and related ions, with yields increasing linearly with intensity. Ionization clearly triggers a localized molecular response that occurs before the excitation energy equilibrates. Consistent with this interpretation, the effect is almost unaffected by the charge state, as fragmentation of sixfold deprotonated ubiquitin leads to a very similar fragmentation pattern. Ubiquitin responds to EUV multiphoton ionization as an ensemble of small peptides.

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: free-electron lasers; mass spectrometry; multiphoton ionization; photoionization; proteins

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