Reactions of sulfoxides with reactive oxygen species to reveal the radical chemistry of pollution-derived particulate matter

The radical reactions of dimethylsulfoxide (DMSO) and tetrahydrothiophene-1-oxide (THTO) with reactive oxygen species (ROS) in the presence of a nitroxide radical scavenger have been evaluated both synthetically and in analytical practice. Fenton-mediated generation of oxygen-centred radicals produced several unusual products that reflect the fragmentation and ring-opening radical mechanisms of DMSO and THTO respectively. Addition of pollution-derived ROS to DMSO/THTO nitroxide solutions produced LC-MS detectable amounts of the same products isolated from the larger-scaled Fenton reactions. For air pollution analysis, these results highlight the complexity surrounding DMSO reactivity and fragmentation, and indicate that THTO produces simpler outcomes that should facilitate analysis of the processes involved.

Automated summary

The radical reactions of dimethylsulfoxide (DMSO) and tetrahydrothiophene-1-oxide (THTO) with reactive oxygen species (ROS) were evaluated synthetically and analytically. Fenton-mediated generation of oxygen-centred radicals produced various products, reflecting the fragmentation and ring-opening radical mechanisms of DMSO and THTO. Pollution-derived ROS added to DMSO/THTO solutions generated LC-MS detectable amounts of the same products as the larger-scaled Fenton reactions. These results highlight the complexity surrounding DMSO reactivity and fragmentation, and indicate that THTO produces simpler outcomes for easier analysis.