Radicals in ‘biologically relevant’ concentrations behave differently: Uncovering new radical reactions following the reaction of hydroxyl radicals with DMSO

Methyl radicals play key roles in various chemical and biological processes. Mechanistic studies of methyl radicals with their precursor, Dimethyl Sulfoxide (DMSO), were extensively studied. Though the involved mechanisms seemed to be clarified, essentially none of the studies have been performed at conditions relevant to both biological and catalytic systems, i.e. low steady state radical concentrations. A chain-like reaction, as an inverse function of the radicals concentrations ([^•CH₃]_ss), increases the methyl radical yields. The nature of the additional products obtained differs from those commonly observed. Furthermore it is shown that methyl radicals abstract a methyl group from DMSO to yield ethane. Herein we report a novel mechanism relevant mainly at low steady state radical concentrations, which may change the understanding of certain reaction routes present in both biological systems and catalytic chemical systems. Thus the results point out that mechanistic studies have to be carried out at dose rates forming radicals at analogous concentrations to those present in the process of interest.