Atmospheric-pressure ionization and fragmentation of peptides by solution-cathode glow discharge

Schwartz, Andrew J.; Shelley, Jacob T.; Walton, Courtney L.; Williams, Kelsey L.; Hieftje, Gary M.

doi:10.1039/c6sc02032a

Title: Atmospheric-pressure ionization and fragmentation of peptides by solution-cathode glow discharge

Journal Article · Mon Jun 27 00:00:00 EDT 2016 · Chemical Science

DOI:https://doi.org/10.1039/c6sc02032a· OSTI ID:1421367

Schwartz, Andrew J. ^[1]; Shelley, Jacob T. ^[2]; Walton, Courtney L. ^[2]; Williams, Kelsey L. ^[2]; Hieftje, Gary M. ^[1]

Indiana Univ., Bloomington, IN (United States). Dept. of Chemistry
Kent State Univ., Kent, OH (United States). Dept. of Chemistry and Biochemistry

Modern “-omics” (e.g., proteomics, glycomics, metabolomics, etc.) analyses rely heavily on electrospray ionization and tandem mass spectrometry to determine the structural identity of target species. Unfortunately, these methods are limited to specialized mass spectrometry instrumentation. Here in this paper, a novel approach is described that enables ionization and controlled, tunable fragmentation of peptides at atmospheric pressure. In the new source, a direct-current plasma is sustained between a tapered metal rod and a flowing sample-containing solution. As the liquid stream contacts the electrical discharge, peptides from the solution are volatilized, ionized, and fragmented. At high discharge currents (e.g., 70 mA), electrospray-like spectra are observed, dominated by singly and doubly protonated molecular ions. At lower currents (35 mA), many peptides exhibit extensive fragmentation, with a-, b-, c-, x-, and y-type ion series present as well as complex fragments, such as d-type ions, not previously observed with atmospheric-pressure dissociation. Though the mechanism of fragmentation is currently unclear, observations indicate it could result from the interaction of peptides with gas-phase radicals or ultraviolet radiation generated within the plasma.

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Research Organization:: Indiana Univ., Bloomington, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: FG02-98ER14890

OSTI ID:: 1421367

Journal Information:: Chemical Science, Vol. 7, Issue 10; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 24 works

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