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Gas-Phase Reactivity of Peptide Thiyl (RS•), Perthiyl (RSS•), and Sulfinyl (RSO•) Radical Ions Formed from Atmospheric Pressure Ion/Radical Reactions

  • Focus: Distonic Ions: Research Article
  • Published:
Journal of The American Society for Mass Spectrometry

Abstract

In this study, we demonstrated the formation of gas-phase peptide perthiyl (RSS•) and thiyl (RS•) radical ions besides sulfinyl radical (RSO•) ions from atmospheric pressure (AP) ion/radical reactions of peptides containing inter-chain disulfide bonds. The identity of perthiyl radical was verified from characteristic 65 Da (•SSH) loss in collision-induced dissociation (CID). This signature loss was further used to assess the purity of peptide perthiyl radical ions formed from AP ion/radical reactions. Ion/molecule reactions combined with CID were carried out to confirm the formation of thiyl radical. Transmission mode ion/molecule reactions in collision cell (q2) were developed as a fast means to estimate the population of peptide thiyl radical ions. The reactivity of peptide thiyl, perthiyl, and sulfinyl radical ions was evaluated based on ion/molecule reactions toward organic disulfides, allyl iodide, organic thiol, and oxygen, which followed in order of thiyl (RS•) > perthiyl (RSS•) > sulfinyl (RSO•). The gas-phase reactivity of these three types of sulfur-based radicals is consistent with literature reports from solution studies.

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Acknowledgments

The authors acknowledge Purdue Research Fund and NSF CHE-1248613 for financial support. The authors thank Dr. J. L. Campbell from AB SCIEX for helpful suggestions on setting up ion/molecule reactions on 4000 QTRAP and Professor R. G. Cooks for the use of LTQ Orbitrap.

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  1. Department of Chemistry, Purdue University, West Lafayette, IN, USA

    Lei Tan & Yu Xia

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Correspondence to Yu Xia.

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Tan, L., Xia, Y. Gas-Phase Reactivity of Peptide Thiyl (RS•), Perthiyl (RSS•), and Sulfinyl (RSO•) Radical Ions Formed from Atmospheric Pressure Ion/Radical Reactions. J. Am. Soc. Mass Spectrom. 24, 534–542 (2013). https://doi.org/10.1007/s13361-012-0548-y

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  • DOI: https://doi.org/10.1007/s13361-012-0548-y

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