Factor analysis of transient spectra. Free radicals in cyclic dipeptides containing methionine

Factor analysis of transient spectra. Free radicals in cyclic dipeptides containing methionine Factor analysis is introduced and applied to resolving puzzling behavior in the free-radical chemistry of the cyclic dipeptide cyclo-(D-Met-L-Met). Previously, spectral analysis of the transient absorption spectra, following the hydroxyl radical-induced oxidation of cyclo-(D-Met-L-Met), failed to match expectations seen when transient conductivity was used to monitor the same reaction sequence. In the current work, factor analysis is used to show that a radical cation is formed via the stabilization of the oxidized sulfur through the formation of two-centered three-electron bonds with the lone pairs on oxygen. This previously undetected radical resolves the discrepancy between transient absorption and transient conductivity observations. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Factor analysis of transient spectra. Free radicals in cyclic dipeptides containing methionine

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Publisher
Springer Netherlands
Copyright
Copyright © 2009 by Springer Science+Business Media BV
Subject
Chemistry; Inorganic Chemistry ; Physical Chemistry ; Catalysis
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1007/s11164-009-0044-6
Publisher site
See Article on Publisher Site

Abstract

Factor analysis is introduced and applied to resolving puzzling behavior in the free-radical chemistry of the cyclic dipeptide cyclo-(D-Met-L-Met). Previously, spectral analysis of the transient absorption spectra, following the hydroxyl radical-induced oxidation of cyclo-(D-Met-L-Met), failed to match expectations seen when transient conductivity was used to monitor the same reaction sequence. In the current work, factor analysis is used to show that a radical cation is formed via the stabilization of the oxidized sulfur through the formation of two-centered three-electron bonds with the lone pairs on oxygen. This previously undetected radical resolves the discrepancy between transient absorption and transient conductivity observations.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Jun 19, 2009

References

  • Molecular mechanisms of late life dementias
    Martin, GM
  • Mechanism of 4-carboxybenzophenone-sensitized photooxidation of methionine-containing dipeptides and tripeptides in aqueous solution
    Marciniak, B; Hug, GL; Bobrowski, K; Kozubek, H
  • Competitive photosensitized oxidation of tyrosine and methionine residues in enkephalins and their model peptides
    Wojcik, A; Lukaszewicz, A; Brede, O; Marciniak, B

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