Novel Cβ–Cγ Bond Cleavages of Tryptophan-Containing Peptide Radical Cations
In this study, we observed unprecedented cleavages of the C β –C γ bonds of tryptophan residue side chains in a series of hydrogen-deficient tryptophan-containing peptide radical cations (M •+ ) during low-energy collision-induced dissociation (CID). We used CID experiments and theoretical density f...
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Veröffentlicht in: | Journal of the American Society for Mass Spectrometry 2012-02, Vol.23 (2), p.264-273 |
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Sprache: | eng |
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Zusammenfassung: | In this study, we observed unprecedented cleavages of the C
β
–C
γ
bonds of tryptophan residue side chains in a series of hydrogen-deficient tryptophan-containing peptide radical cations (M
•+
) during low-energy collision-induced dissociation (CID). We used CID experiments and theoretical density functional theory (DFT) calculations to study the mechanism of this bond cleavage, which forms [M – 116]
+
ions. The formation of an α-carbon radical intermediate at the tryptophan residue for the subsequent C
β
–C
γ
bond cleavage is analogous to that occurring at leucine residues, producing the same product ions; this hypothesis was supported by the identical product ion spectra of [LGGGH – 43]
+
and [WGGGH – 116]
+
, obtained from the CID of [LGGGH]
•+
and [WGGGH]
•+
, respectively. Elimination of the neutral 116-Da radical requires inevitable dehydrogenation of the indole nitrogen atom, leaving the radical centered formally on the indole nitrogen atom ([Ind]
•
-2), in agreement with the CID data for [WGGGH]
•+
and [W
1-CH3
GGGH]
•+
; replacing the tryptophan residue with a 1-methyltryptophan residue results in a change of the base peak from that arising from a neutral radical loss (116 Da) to that arising from a molecule loss (131 Da), both originating from C
β
–C
γ
bond cleavage. Hydrogen atom transfer or proton transfer to the γ-carbon atom of the tryptophan residue weakens the C
β
–C
γ
bond and, therefore, decreases the dissociation energy barrier dramatically. |
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ISSN: | 1044-0305 1879-1123 |
DOI: | 10.1007/s13361-011-0295-5 |