Damage of aromatic amino acids by the atmospheric free radical oxidant NO3˙ in the presence of NO2˙, N2O4, O3 and O2

Catrin Goeschen; Natalia Wibowo; Jonathan M. White; Uta Wille

doi:10.1039/C0OB01186J

Damage of aromatic amino acids by the atmospheric free radical oxidant NO₃˙ in the presence of NO₂˙, N₂O₄, O₃ and O₂†

Catrin Goeschen,^a Natalia Wibowo,^a Jonathan M. White^b and Uta Wille*^a

* Corresponding authors

^a ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, School of Chemistry and BIO21 Molecular Science and Biotechnology Institute, The University of Melbourne, 30 Flemington Road, Parkville, Australia
E-mail: uwille@unimelb.edu.au
Fax: +61 3 9347 8189
Tel: +61 3 8344 2425

^b School of Chemistry and BIO21 Molecular Science and Biotechnology Institute, The University of Melbourne, 30 Flemington Road, Parkville, Australia

Abstract

Analysis of the products formed in the reaction of NO₃˙ with the N- and C-protected aromatic amino acids 1–5, which was performed under conditions that simulate exposure of biosurfaces to environmental pollutants, revealed insight how this important atmospheric free-radical oxidant can cause irreversible damage. In general, NO₃˙ induced electron transfer at the aromatic ring is the exclusive initial pathway in a multi-step sequence, which ultimately leads to nitroaromatic compounds. In the reaction of NO₃˙ with tryptophan 5 tricyclic products 12 and 13 are formed through an intramolecular, oxidative cyclization involving the amide moiety. In addition to this, strong indication for formation of N-nitrosamides was obtained, which likely result from reaction with N₂O₄ through an independent non-radical pathway.

This article is part of the themed collection: Free Radical Chemistry special themed issue in memory of Athel Beckwith

Supplementary files

Article information

DOI: https://doi.org/10.1039/C0OB01186J
Article type: Paper
Submitted: 16 Dec 2010
Accepted: 07 Feb 2011
First published: 16 Mar 2011

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Org. Biomol. Chem., 2011,9, 3380-3385

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Damage of aromatic amino acids by the atmospheric free radical oxidant NO₃˙ in the presence of NO₂˙, N₂O₄, O₃ and O₂

C. Goeschen, N. Wibowo, J. M. White and U. Wille, Org. Biomol. Chem., 2011, 9, 3380 DOI: 10.1039/C0OB01186J

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Organic & Biomolecular Chemistry