Unexpected Reaction Pathway of the Alpha-Aminoalkyl Radical Derived from One-Electron Oxidation of S-Alkylglutathiones

Tomasz Pedzinski; Krzysztof Bobrowski; Bronislaw Marciniak; Piotr Filipiak

doi:10.3390/molecules25040877

Unexpected Reaction Pathway of the Alpha-Aminoalkyl Radical Derived from One-Electron Oxidation of S-Alkylglutathiones

Molecules. 2020 Feb 17;25(4):877. doi: 10.3390/molecules25040877.

Authors

Tomasz Pedzinski^{1

2}, Krzysztof Bobrowski^{3

4}, Bronislaw Marciniak^{1

2}, Piotr Filipiak^{1

2}

Affiliations

¹ Faculty of Chemistry, Adam Mickiewicz University, 61-614 Poznan, Poland.
² Center for Advanced Technology, Adam Mickiewicz University, 61-614 Poznan, Poland.
³ Centre of Radiation Research and Technology, Institute of Nuclear Chemistry and Technology, 03-195 Warsaw, Poland.
⁴ Notre Dame Radiation Laboratory, University of Notre Dame, Notre Dame, IN 46556, USA.

Abstract

Laser flash photolysis and high-resolution mass spectrometry were used to investigate the mechanism of one-electron oxidation of two S-alkylglutathiones using 3-carboxybenzophenone (3CB) as a photosensitizer. This report indicates an unexpected reaction pathway of the α-aminoalkyl radical cation (αN⁺) derived from the oxidation of S-alkylglutathiones. Instead of a common hydrolysis reaction of αN⁺ reported earlier for methionine and other sulfur-containing aminoacids and peptides, an intramolecular ring-closure reaction was found for S-alkylglutathiones.

Keywords: S-alkylglutathiones; decarboxylation; laser flash photolysis; one-electron oxidation.

MeSH terms

Alkylation
Electrons*
Glutathione / chemistry*
Lasers
Oxidation-Reduction
Photolysis

Substances

Glutathione

Abstract

MeSH terms

Substances

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