Bromine isotopic signature facilitates de novo sequencing of peptides in free-radical-initiated peptide sequencing (FRIPS) mass spectrometry
- Authors
- Nam, Jungjoo; Kwon, Hyuksu; Jang, Inae; Jeon, Aeran; Moon, Jingyu; Lee, Sun Young; Kang, Dukjin; Han, Sang Yun; Moon, Bongjin; Oh, Han Bin
- Issue Date
- Feb-2015
- Publisher
- WILEY
- Keywords
- free-radical-initiated peptide sequencing (FRIPS); bromine signature; isotopic pattern; de novo sequencing; radical-based tandem mass spectrometry
- Citation
- JOURNAL OF MASS SPECTROMETRY, v.50, no.2, pp.378 - 387
- Journal Title
- JOURNAL OF MASS SPECTROMETRY
- Volume
- 50
- Number
- 2
- Start Page
- 378
- End Page
- 387
- URI
- https://scholarworks.bwise.kr/gachon/handle/2020.sw.gachon/10842
- DOI
- 10.1002/jms.3539
- ISSN
- 1076-5174
- Abstract
- We recently showed that free-radical-initiated peptide sequencing mass spectrometry (FRIPS MS) assisted by the remarkable thermochemical stability of (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO) is another attractive radical-driven peptide fragmentation MS tool. Facile homolytic cleavage of the bond between the benzylic carbon and the oxygen of the TEMPO moiety in o-TEMPO-Bz-C(O)-peptide and the high reactivity of the benzylic radical species generated in center dot Bz-C(O)-peptide are key elements leading to extensive radical-driven peptide backbone fragmentation. In the present study, we demonstrate that the incorporation of bromine into the benzene ring, i.e. o-TEMPO-Bz(Br)-C(O)-peptide, allows unambiguous distinction of the N-terminal peptide fragments from the C-terminal fragments through the unique bromine doublet isotopic signature. Furthermore, bromine substitution does not alter the overall radical-driven peptide backbone dissociation pathways of o-TEMPO-Bz-C(O)-peptide. From a practical perspective, the presence of the bromine isotopic signature in the N-terminal peptide fragments in TEMPO-assisted FRIPS MS represents a useful and cost-effective opportunity for de novo peptide sequencing. Copyright (c) 2015 John Wiley & Sons, Ltd.
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