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Fundamental Study of Hydrogen-Attachment-Induced Peptide Fragmentation Occurring in the Gas Phase and during Matrix-Assisted Laser Desorption/Ionization process

Abstract

Mass spectrometry with hydrogen-radical-mediated fragmentation techniques has been used for sequencing of proteins/peptides. The two methods, matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) and hydrogen attachment/abstraction (HAD) are known as the hydrogen-radical-mediated fragmentation techniques. MALDI-ISD occurs during laser induced desorption processes, whereas HAD utilizes the association of hydrogen with peptide ions in the gas phase. In this study, the general mechanism of MALDI-ISD and HAD of peptides was investigated. We demonstrated the fragmentation of four model peptides and investigated the fragment formation pathways using density functional theory (DFT) calculations. The current experimental and computational joint study indicated that MALDI-ISD and HAD produce aminoketyl radical intermediates, which immediately undergo radical-induced cleavage on the N–Cα bond located on the C-terminal side of the radical site, leading to the c'/z• fragment pair. In the case of MALDI-ISD, the z• fragments undergo subsequent reaction with the matrix to give z' and matrix adducts on z fragments. In contrast, c' and z• fragments react with hydrogen atoms during HAD processes, and various fragment species, such as c•, c', z• and z', were observed in the HAD-MS/MS mass spectrum.

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Publication details

The article was received on 01 Feb 2018, accepted on 09 Apr 2018 and first published on 09 Apr 2018


Article type: Paper
DOI: 10.1039/C8CP00733K
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    Fundamental Study of Hydrogen-Attachment-Induced Peptide Fragmentation Occurring in the Gas Phase and during Matrix-Assisted Laser Desorption/Ionization process

    D. Asakawa, H. Takahashi, S. Iwamoto and K. Tanaka, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C8CP00733K

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