Linda Vogt, University of Saskatchewan

Abstract

The sulfones are a very widespread group of organo-sulfur compounds that contain the sulfonyl SO2 group attached to two carbons, and have a formal sulfur oxidation state of +2. Sulfones find a range of uses in industry, as a number of drugs, and as versatile reagents in chemical syntheses. They also play roles in the environment, both within the sulfur biogeochemical cycle and in metabolic processes. We have examined both the sulfur K near-edge X-ray absorption spectroscopy (XAS) and the sulfur Kβ X-ray emission spectroscopy (XES) of a range of sulfones and find substantial spectroscopic variability depending upon the nature of the coordination to the sulfonyl group. Density functional theory simulations of both XAS and XES enable assignment of the various transitions comprising the spectra, and show promise for ab initio prediction of sulfur XAS and XES of sulfones with any substituents. Sulfones are also in-vivo oxidation products of the amino acid L-methionine, which can be oxidized to sulfones via the sulfoxide; while the conversion to the sulfoxide is at least in part reversible the conversion of sulfoxide to sulfone is not. We hypothesize that the in-situ presence of sulfones may be a biomarker for the presence of redox dyshomeostasis, and we present some preliminary results demonstrating this in equine blood serum.