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.
Research on Chemical Intermediates – Springer Journals
Published: Jun 19, 2009
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