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Radiation- and Photo-Induced Oxidation Pathways of Methionine in Model Peptide Backbone under Anoxic Conditions.


ABSTRACT: Within the reactive oxygen species (ROS) generated by cellular metabolisms, hydroxyl radicals (HO•) play an important role, being the most aggressive towards biomolecules. The reactions of HO• with methionine residues (Met) in peptides and proteins have been intensively studied, but some fundamental aspects remain unsolved. In the present study we examined the biomimetic model made of Ac-Met-OMe, as the simplest model peptide backbone, and of HO• generated by ionizing radiation in aqueous solutions under anoxic conditions. We performed the identification and quantification of transient species by pulse radiolysis and of final products by LC-MS and high-resolution MS/MS after γ-radiolysis. By parallel photochemical experiments, using 3-carboxybenzophenone (CB) triplet with the model peptide, we compared the outcomes in terms of short-lived intermediates and stable product identification. The result is a detailed mechanistic scheme of Met oxidation by HO•, and by CB triplets allowed for assigning transient species to the pathways of products formation.

SUBMITTER: Pedzinski T 

PROVIDER: S-EPMC8125225 | biostudies-literature | 2021 Apr

REPOSITORIES: biostudies-literature

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Radiation- and Photo-Induced Oxidation Pathways of Methionine in Model Peptide Backbone under Anoxic Conditions.

Pędzinski Tomasz T   Grzyb Katarzyna K   Skotnicki Konrad K   Filipiak Piotr P   Bobrowski Krzysztof K   Chatgilialoglu Chryssostomos C   Marciniak Bronislaw B  

International journal of molecular sciences 20210430 9


Within the reactive oxygen species (ROS) generated by cellular metabolisms, hydroxyl radicals (HO<sup>•</sup>) play an important role, being the most aggressive towards biomolecules. The reactions of HO<sup>•</sup> with methionine residues (Met) in peptides and proteins have been intensively studied, but some fundamental aspects remain unsolved. In the present study we examined the biomimetic model made of Ac-Met-OMe, as the simplest model peptide backbone, and of HO<sup>•</sup> generated by ion  ...[more]

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