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Combined Raman and IR spectroscopic study on the radical-based modifications of methionine

  • A. TorreggianiEmail author
  • S. Barata-Vallejo
  • C. Chatgilialoglu
Original Paper

Abstract

Among damages reported to occur on proteins, radical-based changes of methionine (Met) residues are one of the most important convalent post-translational modifications. The combined application of Raman and infrared (IR) spectroscopies for the characterisation of the radical-induced modifications of Met is described here. Gamma-irradiation was used to simulate the endogenous formation of reactive species such as hydrogen atoms (H), hydroxyl radicals (OH) and hydrogen peroxide (H2O2). These spectroscopic techniques coupled to mass experiments are suitable tools in detecting almost all the main radical-induced degradation products of Met that depend on the nature of the reactive species. In particular, Raman spectroscopy is useful in revealing the radical-induced modifications in the sulphur-containing moiety, whereas the IR spectra allow decarboxylation and deamination processes to be detected, as well as the formation of other degradation products. Thus, some band patterns useful for building a library of spectra–structure correlation for radical-based degradation of Met were identified. In particular, the bands due to the formation of methionine sulfoxide, the main oxidation product of Met, have been identified. All together, these results combine to produce a set of spectroscopic markers of the main processes occurring as a consequence of radical stress exposure, which can be used in a spectroscopic protocol for providing a first assessment of Met modifications in more complex systems such as peptides and proteins, and monitoring their impact on protein structure.

Figure

The combined use of Raman and IR spectroscopy allows to monitor the formation of the main degradation products of amino acids like methionine after radical stress exposure. In particular, Raman spectra are useful for revealing the occurrence of modifications in sulphur-containing moiety, whereas IR spectroscopy is able to detect decarboxylation and deamination processes, as well as the formation of new products

Keywords

Methionine Radical stress Raman spectroscopy IR spectroscopy Gamma-radiolysis 

Abbreviations

Aba

α-Aminobutyric acid

ESI

Electron spray ionisation

GC/MS

Gas chromatography/mass spectrometry

HomoSer

Homoserine

IR

Infrared

Met

Methionine

Met(O)

Methionine sulfoxide

MTPA

3-(Methylthio)-propionaldeide

MTPNH2

3-(Methylthio)-propionamine

Notes

Acknowledgements

The support and sponsorship concerned by CNR-CONICET joint research project 2009–2010 and COST Action CM0603 on “Free Radicals in Chemical Biology (CHEMBIORADICAL)” are kindly acknowledged.

Supplementary material

216_2011_5203_MOESM1_ESM.pdf (52 kb)
ESM 1 (PDF 51 kb)

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Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • A. Torreggiani
    • 1
    Email author
  • S. Barata-Vallejo
    • 1
    • 2
  • C. Chatgilialoglu
    • 1
  1. 1.I.S.O.F., Consiglio Nazionale delle RicercheBolognaItaly
  2. 2.Faculty of Pharmacy and BiochemistryUniversity of Buenos AiresBuenos AiresArgentina

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