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Chimera spectrum diagnostics for peptides using two-dimensional partial covariance mass spectrometry

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Title: Chimera spectrum diagnostics for peptides using two-dimensional partial covariance mass spectrometry
Authors: Driver, T
Bachhawat, N
Frasinski, L
Marangos, J
Averbukh, V
Edelson-Averbukh, M
Item Type: Journal Article
Abstract: The rate of successful identification of peptide sequences by tandem mass spectrometry (MS/MS) is adversely affected by the common occurrence of co-isolation and co-fragmentation of two or more isobaric or isomeric parent ions. This results in so-called `chimera spectra’, which feature peaks of the fragment ions from more than a single precursor ion. The totality of the fragment ion peaks in chimera spectra cannot be assigned to a single peptide sequence, which contradicts a fundamental assumption of the standard automated MS/MS spectra analysis tools, such as protein database search engines. This calls for a diagnostic method able to identify chimera spectra to single out the cases where this assumption is not valid. Here, we demonstrate that, within the recently developed two-dimensional partial covariance mass spectrometry (2D-PC-MS), it is possible to reliably identify chimera spectra directly from the two-dimensional fragment ion spectrum, irrespective of whether the co-isolated peptide ions are isobaric up to a finite mass accuracy or isomeric. We introduce ‘3-57 chimera tag’ technique for chimera spectrum diagnostics based on 2D-PC-MS and perform numerical simulations to examine its efficiency. We experimentally demonstrate the detection of a mixture of two isomeric parent ions, even under conditions when one isomeric peptide is at one five-hundredth of the molar concentration of the second isomer.
Issue Date: 18-Jun-2021
Date of Acceptance: 2-Jun-2021
URI: http://hdl.handle.net/10044/1/90259
DOI: 10.3390/molecules26123728
ISSN: 1420-3049
Publisher: MDPI AG
Journal / Book Title: Molecules
Volume: 26
Issue: 12
Copyright Statement: © 2021 by the authors.Licensee MDPI, Basel, Switzerland.This article is an open access articledistributed under the terms andconditions of the Creative CommonsAttribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Sponsor/Funder: Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (E
EPSRC/DSTL
Funder's Grant Number: EP/I032517/1
EP/R511547/1
EPSRC/DSTL MURI grant EP/N018680/1.
Keywords: 0304 Medicinal and Biomolecular Chemistry
0305 Organic Chemistry
0307 Theoretical and Computational Chemistry
Organic Chemistry
Publication Status: Published
Article Number: ARTN 3728
Appears in Collections:Quantum Optics and Laser Science
Physics



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