Journal article

Fragmentation-Rearrangement of Peptide Backbones Mediated by the Air Pollutant NO2 center dot

Luke F Gamon, Joses G Nathanael, Bethany I Taggert, Fraser A Henry, Jana Bogena, Uta Wille

Chemistry - A European Journal | WILEY-V C H VERLAG GMBH | Published : 2015


The fragmentation-rearrangement of peptide backbones mediated by nitrogen dioxide, NO2 (.) , was explored using di-, tri-, and tetrapeptides 8-18 as model systems. The reaction, which is initiated through nonradical N-nitrosation of the peptide bond, shortens the peptide chain by the expulsion of one amino acid moiety with simultaneous fusion of the remaining molecular termini through formation of a new peptide bond. The relative rate of the fragmentation-rearrangement depends on the nature of the amino acids and decreases with increasing steric bulk at the α carbon in the order Gly>Ala>Val. Peptides that possessed consecutive aromatic side chains only gave products that resulted from nitros..

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Funding Acknowledgements

Financial support by the Australian Research Council (Centre of Excellence Scheme) and The University of Melbourne is gratefully acknowledged. We thank the Australian Government for an Australian Postgraduate Award (LFG) and an International Postgraduate Research Scholarship (JGN).