Transformation of [M + 2H](2+) Peptide Cations to [M - H](+), [M + H + O](+), and M(+•) Cations Via Ion/Ion Reactions: Reagent Anions Derived from Persulfate

Overview

Journal J Am Soc Mass Spectrom

Specialty Chemistry

Date 2015 May 7

PMID 25944366

Citations 9

Authors

Alice L Pilo

Jiexun Bu

Scott A McLuckey

Affiliations

Soon will be listed here.

Abstract

The gas-phase oxidation of doubly protonated peptides is demonstrated here using ion/ion reactions with a suite of reagents derived from persulfate. Intact persulfate anion (HS2O8(-)), peroxymonosulfate anion (HSO5(-)), and sulfate radical anion (SO4(-•)) are all either observed directly upon negative nanoelectrospray ionization (nESI) or easily obtained via beam-type collisional activation of persulfate into the mass spectrometer. Ion/ion reactions between each of these reagents and doubly protonated peptides result in the formation of a long-lived complex. Collisional activation of the complex containing a peroxymonosulfate anion results in oxygen transfer from the reagent to the peptide to generate the [M + H + O](+) species. Activation of the complex containing intact persulfate anion either results in oxygen transfer to generate the [M + H + O](+) species or abstraction of two hydrogen atoms and a proton to generate the [M - H](+) species. Activation of the complex containing sulfate radical anion results in abstraction of one hydrogen atom and a proton to form the peptide radical cation, [M](+•). This suite of reagents allows for the facile transformation of the multiply protonated peptides obtained via nESI into a variety of oxidized species capable of providing complementary information about the sequence and structure of the peptide.

Citing Articles

Exploring the Potential of Bioactive Peptides: From Natural Sources to Therapeutics.

Purohit K, Reddy N, Sunna A Int J Mol Sci. 2024; 25(3).

PMID: 38338676 PMC: 10855437. DOI: 10.3390/ijms25031391.

Recent Developments in Gas-Phase Ion/Ion Reactions for Analytical Mass Spectrometry.

Foreman D, McLuckey S Anal Chem. 2019; 92(1):252-266.

PMID: 31693342 PMC: 6949396. DOI: 10.1021/acs.analchem.9b05014.

Gas-phase rearrangement reaction of Schiff-base-modified peptide ions.

Wang N, Pilo A, Zhao F, Bu J, McLuckey S Rapid Commun Mass Spectrom. 2018; 32(24):2166-2173.

PMID: 30280440 PMC: 6657513. DOI: 10.1002/rcm.8298.

The Generation of Dehydroalanine Residues in Protonated Polypeptides: Ion/Ion Reactions for Introducing Selective Cleavages.

Peng Z, Bu J, McLuckey S J Am Soc Mass Spectrom. 2017; 28(9):1765-1774.

PMID: 28497355 PMC: 5681889. DOI: 10.1007/s13361-017-1672-5.

Gas-Phase Oxidation via Ion/Ion Reactions: Pathways and Applications.

Pilo A, Zhao F, McLuckey S J Am Soc Mass Spectrom. 2017; 28(6):991-1004.

PMID: 28050870 PMC: 5438755. DOI: 10.1007/s13361-016-1554-2.

References

Sohn C, Chung C, Yin S, Ramachandran P, Loo J, Beauchamp J . Probing the mechanism of electron capture and electron transfer dissociation using tags with variable electron affinity. J Am Chem Soc. 2009; 131(15):5444-59. PMC: 2765496. DOI: 10.1021/ja806534r. View

Hopkinson A . Radical cations of amino acids and peptides: structures and stabilities. Mass Spectrom Rev. 2009; 28(4):655-71. DOI: 10.1002/mas.20229. View

Oh H, Moon B . Radical-driven peptide backbone dissociation tandem mass spectrometry. Mass Spectrom Rev. 2014; 34(2):116-32. DOI: 10.1002/mas.21426. View

Hassell K, Stutzman J, McLuckey S . Gas-phase bioconjugation of peptides via ion/ion charge inversion: Schiff base formation on the conversion of cations to anions. Anal Chem. 2010; 82(5):1594-7. PMC: 2834292. DOI: 10.1021/ac902732v. View

Good D, Wirtala M, McAlister G, Coon J . Performance characteristics of electron transfer dissociation mass spectrometry. Mol Cell Proteomics. 2007; 6(11):1942-51. DOI: 10.1074/mcp.M700073-MCP200. View

Ly T, Julian R . Residue-specific radical-directed dissociation of whole proteins in the gas phase. J Am Chem Soc. 2007; 130(1):351-8. DOI: 10.1021/ja076535a. View

Chu I, Laskin J . Formation of peptide radical ions through dissociative electron transfer in ternary metal-ligand-peptide complexes. Eur J Mass Spectrom (Chichester). 2012; 17(6):543-56. DOI: 10.1255/ejms.1156. View

Blanksby S, Ellison G . Bond dissociation energies of organic molecules. Acc Chem Res. 2003; 36(4):255-63. DOI: 10.1021/ar020230d. View

Liang X, Xia Y, McLuckey S . Alternately pulsed nanoelectrospray ionization/atmospheric pressure chemical ionization for ion/ion reactions in an electrodynamic ion trap. Anal Chem. 2006; 78(9):3208-12. PMC: 2575744. DOI: 10.1021/ac052288m. View

10.

Laskin J, Yang Z, Chu I . Energetics and dynamics of electron transfer and proton transfer in dissociation of metal(III)(salen)-peptide complexes in the gas phase. J Am Chem Soc. 2008; 130(10):3218-30. DOI: 10.1021/ja077690s. View

11.

Schey K, Finley E . Identification of peptide oxidation by tandem mass spectrometry. Acc Chem Res. 2000; 33(5):299-306. DOI: 10.1021/ar9800744. View

12.

Masterson D, Yin H, Chacon A, Hachey D, Norris J, Porter N . Lysine peroxycarbamates: free radical-promoted peptide cleavage. J Am Chem Soc. 2004; 126(3):720-1. DOI: 10.1021/ja038615u. View

13.

Pilo A, McLuckey S . Oxidation of methionine residues in polypeptide ions via gas-phase ion/ion chemistry. J Am Soc Mass Spectrom. 2014; 25(6):1049-57. PMC: 4020970. DOI: 10.1007/s13361-014-0861-8. View

14.

Sun Q, Nelson H, Ly T, Stoltz B, Julian R . Side chain chemistry mediates backbone fragmentation in hydrogen deficient peptide radicals. J Proteome Res. 2008; 8(2):958-66. DOI: 10.1021/pr800592t. View

15.

Gilbert J, Fisher C, Bu J, Prentice B, Redwine J, McLuckey S . Strategies for generating peptide radical cations via ion/ion reactions. J Mass Spectrom. 2015; 50(2):418-26. PMC: 4372815. DOI: 10.1002/jms.3548. View

16.

Mentinova M, McLuckey S . Intra- and inter-molecular cross-linking of peptide ions in the gas phase: reagents and conditions. J Am Soc Mass Spectrom. 2011; 22(5):912-21. PMC: 3241442. DOI: 10.1007/s13361-011-0103-2. View

17.

McGee W, Mentinova M, McLuckey S . Gas-phase conjugation to arginine residues in polypeptide ions via N-hydroxysuccinimide ester-based reagent ions. J Am Chem Soc. 2012; 134(28):11412-4. PMC: 3404623. DOI: 10.1021/ja304778j. View

18.

Reid G, Roberts K, Kapp E, Simpson R . Statistical and mechanistic approaches to understanding the gas-phase fragmentation behavior of methionine sulfoxide containing peptides. J Proteome Res. 2004; 3(4):751-9. DOI: 10.1021/pr0499646. View

19.

Barlow C, McFadyen W, OHair R . Formation of cationic peptide radicals by gas-phase redox reactions with trivalent chromium, manganese, iron, and cobalt complexes. J Am Chem Soc. 2005; 127(16):6109-15. DOI: 10.1021/ja043088f. View

20.

Turecek F, Julian R . Peptide radicals and cation radicals in the gas phase. Chem Rev. 2013; 113(8):6691-733. DOI: 10.1021/cr400043s. View