2604 A. K. Y. Lam, C. A. Hutton and R. A. J. O’Hair
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Introduction of an oxygen or sulfur atom onto the side chain
of histidine was found to have a significant effect on the gas-
phase properties of the amino acid, altering the preferred
tautomer to the keto, 2c, and thioketo, 3c, forms, thereby
lowering their proton affinities. These changes in turn influ-
ence the fragmentation chemistry of the modified histidine
residues. The change in fragmentation for the protonated
amino acids is subtle, with protonated 2 and 3 undergoing
additional minor losses of NH3 and the imine HN¼
CHCO2H. Introduction of a methyl ester enhances the diffe-
rence in fragmentation chemistry, which appears to be
amplified in larger peptides whereby the preferential clea-
vage C-terminal to the histidine residue18 is suppressed for 2-
oxo-histidine residues. Since recent studies have indicated
that oxidised histidine residues can be correctly assigned
using electron-transfer dissociation, ETD,50 future studies
will explore the gas-phase chemistry of 2-oxo- and 2-thioxo-
histidine radical cations.
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SUPPORTING INFORMATION
Additional supporting information may be found in the
online version of this article.
Acknowledgements
We thank the ARC for financial support via the ARC Centre
of Excellence in Free Radical Chemistry and Biotechnology.
The authors gratefully acknowledge the generous allocation
of computing time from both the Victorian Partnership for
Advanced Computing and the NCI National Facility. The
authors would also like to thank the ARC and VICS for
funding of the LTQ FT hybrid mass spectrometer instrument.
AKYL acknowledges the award of a Melbourne Research
Scholarship from The University of Melbourne. The authors
would also like to acknowledge discussions with Christo-
pher K. Barlow and Brett Paterson, and Barbara Li for advice
on the synthesis of 2-oxo-histidine.
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Copyright # 2010 John Wiley & Sons, Ltd.
Rapid Commun. Mass Spectrom. 2010; 24: 2591–2604
DOI: 10.1002/rcm