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157 nm Photodissociation of a Complete Set of Dipeptide Ions Containing C-Terminal Arginine

  • Focus: Development and Application of TOF and TOF/TOF MS: Research Article
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Journal of The American Society for Mass Spectrometry

Abstract

Twenty singly-charged dipeptide ions with C-terminal arginine were photodissociated with 157 nm light and their tandem mass spectra recorded. Many of the small product ions that were observed are standard peptide fragments that have been commonly seen in VUV photodissociation studies. However, the study of a library of dipeptides containing all 20 N-terminal amino acids enabled the recognition of trends associated with the occurrence of w-, v-, and immonium ions, the observation of competition between forming N- and C-terminal fragments in dipeptide RR, and the identification of some unusual fragment ions appearing at masses of 183, 187, 196, and 197 Da. A highly accurate internal calibration of the photodissociation TOF-TOF data enabled molecular formulae for these four product ions to be derived. Their proposed structures reflect the rather high-energy nature of this fragmentation phenomenon.

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Acknowledgments

The authors acknowledge support for this work by grant CHE-1012855 from the National Science Foundation.

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Correspondence to James P. Reilly.

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He, Y., Webber, N. & Reilly, J.P. 157 nm Photodissociation of a Complete Set of Dipeptide Ions Containing C-Terminal Arginine. J. Am. Soc. Mass Spectrom. 24, 675–683 (2013). https://doi.org/10.1007/s13361-012-0514-8

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  • DOI: https://doi.org/10.1007/s13361-012-0514-8

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