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N-Terminal Peptide Sequence Repetition Influences the Kinetics of Backbone Fragmentation: A Manifestation of the Jahn-Teller Effect?

  • Focus: Electron Transfer Dissociation: Research Article
  • Published:
Journal of The American Society for Mass Spectrometry

Abstract

Analysis of large (>10,000 entries) databases consisting of high-resolution tandem mass spectra of peptide dications revealed with high statistical significance (P < 1⋅10–3) that peptides with non-identical first two N-terminal amino acids undergo cleavages of the second peptide bond at higher rates than repetitive sequences composed of the same amino acids (i.e., in general AB- and BA- bonds cleave more often than AA- and BB- bonds). This effect seems to depend upon the collisional energy, being stronger at lower energies. The phenomenon is likely to indicate the presence of the diketopiperazine structure for at least some b2 + ions. When consisting of two identical amino acids, these species should form through intermediates that have a symmetric geometry and, thus, must be subject to the Jahn-Teller effect that reduces the stability of such systems.

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Acknowledgment

This work was supported by the Wallenberg Foundation and the Swedish Research Council (grants 2007–4410 and 2011–3726 to RAZ). D.M.G. is grateful for a post-doctoral fellowship from the Wenner-Gren Foundation.

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Author notes

  1. David M. Good

    Present address: Department of Medicine, University of Wisconsin-Madison, Madison, WI, 53706, USA

Authors and Affiliations

  1. Division of Physiological Chemistry I, Department of Medical Biochemistry and Biophysics, Karolinska Institutet, Stockholm, Sweden

    David M. Good, Hongqian Yang & Roman A. Zubarev

  2. SciLifeLab, Stockholm, Sweden

    Roman A. Zubarev

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  1. David M. Good
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  2. Hongqian Yang
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  3. Roman A. Zubarev
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Correspondence to Roman A. Zubarev.

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Good, D.M., Yang, H. & Zubarev, R.A. N-Terminal Peptide Sequence Repetition Influences the Kinetics of Backbone Fragmentation: A Manifestation of the Jahn-Teller Effect?. J. Am. Soc. Mass Spectrom. 24, 1671–1675 (2013). https://doi.org/10.1007/s13361-013-0628-7

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  • DOI: https://doi.org/10.1007/s13361-013-0628-7

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