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

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 am...

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Vydáno v:	Chemistry : a European journal Ročník 21; číslo 42; s. 14924 - 14930
Hlavní autoři:	Gamon, Luke F., Nathanael, Joses G., Taggert, Bethany I., Henry, Fraser A., Bogena, Jana, Wille, Uta
Médium:	Journal Article
Jazyk:	angličtina
Vydáno:	Weinheim WILEY-VCH Verlag 12.10.2015 WILEY‐VCH Verlag Wiley Wiley Subscription Services, Inc
Témata:	Air pollution Amino acids Chemistry Chemistry, Multidisciplinary Nitrogen dioxide nitrogen oxides Peptides Physical Sciences Pollutants radicals reaction mechanism rearrangement Science & Technology ACID radicals NITROSATION REACTIVITY peptides RISK MECHANISMS COMBINATION reaction mechanism nitrogen oxides KINETICS OZONE PROTEINS rearrangement NITROGEN-DIOXIDE
ISSN:	0947-6539, 1521-3765, 1521-3765
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Shrnutí:	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 nitrosation of the sterically less congested N‐terminal amide. Such backbone fragmentation–rearrangement occurs under physiologically relevant conditions and could be an important reaction pathway for peptides, in which sections without readily oxidizable side chains are exposed to the air pollutant NO2.. In addition to NO2.‐induced radical oxidation processes, this outcome shows that ionic reaction pathways, in particular nitrosation, should be factored in when assessing NO2. reactivity in biological systems. NO2. mediates the fragmentation– rearrangement of peptide backbones, which leads to shortening of the peptide chain by expulsion (see scheme) of one amino acid moiety with simultaneous fusion of the remaining ends through formation of a new peptide bond.
Bibliografie:	istex:32D5BEA71ECED0AF17B802293D89F5AD06B82413 Australian Government ArticleID:CHEM201501850 The University of Melbourne ark:/67375/WNG-SS9XV5Z4-G Australian Research Council ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23
ISSN:	0947-6539 1521-3765 1521-3765
DOI:	10.1002/chem.201501850