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Title: Radiation chemical studies of Gly-Met-Gly in aqueous solution

Abstract

Important biological consequences are related to the reaction of HO radicals with methionine (Met). Several fundamental aspects remain to be defined when Met is an amino acid residue incorporated in the interior of peptides and proteins. The present study focuses on Gly-Met-Gly, the simplest peptide where Met is not a terminal residue. The reactions of HO with Gly-Met-Gly and its N-acetyl derivative were studied by pulse radiolysis technique. The transient absorption spectra were resolved into contributions from specific components of radical intermediates. Moreover, a detailed product analysis is provided for the first time for Met-containing peptides in radiolytic studies to support the mechanistic proposal. By parallel radiolytical and electrochemical reactions and consequent product identification, the formation of sulfoxide attributed to the direct HO radical attack on the sulfide functionality of the Met residue could be excluded, with the in situ generated hydrogen peroxide responsible for this oxidation. LC–MS and high resolution MS/MS were powerful analytical tools to envisage the structures of five products, thus allowing to complete the mechanistic picture of the overall Met-containing peptide reactivity.

Authors:
 [1];  [1];  [2];  [2];  [2];  [3];  [4]
+ Show Author Affiliations
  1. Consiglio Nazionale delle Ricerche (CNR), Bologna (Italy)
  2. Univ. of Groningen (The Netherlands)
  3. Univ. of Notre Dame, IN (United States)
  4. Consiglio Nazionale delle Ricerche (CNR), Bologna (Italy); NCSR Demokritos, Athens (Greece)
Publication Date:
Research Org.:
University of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1438192
Grant/Contract Number:  
FC02-04ER15533
Resource Type:
Accepted Manuscript
Journal Name:
Free Radical Research
Additional Journal Information:
Journal Volume: 50; Journal Issue: sup1; Journal ID: ISSN 1071-5762
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Methionine; free radicals; peptide; ionizing radiation; electrochemistry; EC-MS; LC–MS/MS; reaction mechanism

Citation Formats

Barata-Vallejo, Sebastian, Ferreri, Carla, Zhang, Tao, Permentier, Hjalmar, Bischoff, Rainer, Bobrowski, Krzysztof, and Chatgilialoglu, Chryssostomos. Radiation chemical studies of Gly-Met-Gly in aqueous solution. United States: N. p., 2016. Web. doi:10.1080/10715762.2016.1231402.
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Barata-Vallejo, Sebastian, Ferreri, Carla, Zhang, Tao, Permentier, Hjalmar, Bischoff, Rainer, Bobrowski, Krzysztof, & Chatgilialoglu, Chryssostomos. Radiation chemical studies of Gly-Met-Gly in aqueous solution. United States. https://doi.org/10.1080/10715762.2016.1231402
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Barata-Vallejo, Sebastian, Ferreri, Carla, Zhang, Tao, Permentier, Hjalmar, Bischoff, Rainer, Bobrowski, Krzysztof, and Chatgilialoglu, Chryssostomos. Tue . "Radiation chemical studies of Gly-Met-Gly in aqueous solution". United States. https://doi.org/10.1080/10715762.2016.1231402. https://www.osti.gov/servlets/purl/1438192.
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@article{osti_1438192,
title = {Radiation chemical studies of Gly-Met-Gly in aqueous solution},
author = {Barata-Vallejo, Sebastian and Ferreri, Carla and Zhang, Tao and Permentier, Hjalmar and Bischoff, Rainer and Bobrowski, Krzysztof and Chatgilialoglu, Chryssostomos},
abstractNote = {Important biological consequences are related to the reaction of HO radicals with methionine (Met). Several fundamental aspects remain to be defined when Met is an amino acid residue incorporated in the interior of peptides and proteins. The present study focuses on Gly-Met-Gly, the simplest peptide where Met is not a terminal residue. The reactions of HO with Gly-Met-Gly and its N-acetyl derivative were studied by pulse radiolysis technique. The transient absorption spectra were resolved into contributions from specific components of radical intermediates. Moreover, a detailed product analysis is provided for the first time for Met-containing peptides in radiolytic studies to support the mechanistic proposal. By parallel radiolytical and electrochemical reactions and consequent product identification, the formation of sulfoxide attributed to the direct HO radical attack on the sulfide functionality of the Met residue could be excluded, with the in situ generated hydrogen peroxide responsible for this oxidation. LC–MS and high resolution MS/MS were powerful analytical tools to envisage the structures of five products, thus allowing to complete the mechanistic picture of the overall Met-containing peptide reactivity.},
doi = {10.1080/10715762.2016.1231402},
journal = {Free Radical Research},
number = sup1,
volume = 50,
place = {United States},
year = {Tue Oct 25 00:00:00 EDT 2016},
month = {Tue Oct 25 00:00:00 EDT 2016}
}
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https://doi.org/10.1080/10715762.2016.1231402
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Free Radical Reactions of Methionine in Peptides:  Mechanisms Relevant to β-Amyloid Oxidation and Alzheimer's Disease
journal, November 2003

  • Schöneich, Christian; Pogocki, Dariusz; Hug, Gordon L.
  • Journal of the American Chemical Society, Vol. 125, Issue 45
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Stabilization of Sulfide Radical Cations through Complexation with the Peptide Bond:  Mechanisms Relevant to Oxidation of Proteins Containing Multiple Methionine Residues
journal, August 2007

  • Bobrowski, Krzysztof; Hug, Gordon L.; Pogocki, Dariusz
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Electrochemical strategies for the label-free detection of amino acids, peptides and proteins
journal, January 2007

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  • The Analyst, Vol. 132, Issue 7
  • DOI: 10.1039/b701472d

P ROTEIN S ULFENIC A CIDS IN R EDOX S IGNALING
journal, February 2004

On the Radiolysis of Methionine in Aqueous Solution by Gamma Irradiation
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journal, June 2012

  • Chatgilialoglu, Chryssostomos; Ferreri, Carla; Masi, Annalisa
  • CHIMIA International Journal for Chemistry, Vol. 66, Issue 6
  • DOI: 10.2533/chimia.2012.368
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