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Issue 8, 2009
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Gas-phase peptide sequencing by TEMPO-mediated radical generation

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Abstract

Collisional activation of 2-[(2,2,6,6-tetramethylpiperidin-1-yloxy)methyl]benzoic acid (TEMPO-Bz)-conjugated peptide cations, prepared by attaching a TEMPO-derived precursor 1 to an N-terminal amino group or a lysine side chain, resulted in the formation of radical species. The subsequent tandem mass spectrometry on the radical cations exhibited odd-electron peptide backbone dissociations in the same manner as that observed by electron capture dissociation (ECD) or electron transfer dissociation (ETD). For example, a-, x-, or z-types of ions were major fragments and the disulfide bond was readily cleaved. The TEMPO-FRIPS (free radical initiated peptide sequencing) was also applicable to characterizing even singly protonated peptides, in contrast to ECD or ETD in which only doubly or highly protonated cations are responsive. The TEMPO-FRIPS approach also has universality in that it can be used in any type of a tandem mass spectrometer.

Graphical abstract: Gas-phase peptide sequencing by TEMPO-mediated radical generation

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Article information


Submitted
27 Feb 2009
Accepted
01 Jun 2009
First published
12 Jun 2009

Analyst, 2009,134, 1706-1712
Article type
Paper

Gas-phase peptide sequencing by TEMPO-mediated radical generation

M. Lee, M. Kang, B. Moon and H. B. Oh, Analyst, 2009, 134, 1706
DOI: 10.1039/B904115J

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