Polyoxometalate oxidation of chemical warfare agent simulants in fluorinated media

The aim of this research is to determine if appropriate polyoxometalates (POMs) could be added to perfluoropolyether topical skin protectants (TSPs) currently available or under development to give these TSPs the additional capability of detecting and in some cases catalytically decontaminating sulfur mustard (HD) and perhaps other chemical warfare agents (CWAs) at ambient temperatures. Detection would be based on significant color changes in the POM upon reduction by the CWA whereas catalytic decontamination would be based on the ability of some families of POMs to catalyze O(2)-based oxidations by more than one mechanism. Five POMs (10-25% by weight) were each suspended in ca. 5 g of the perfluoropolyether (PFPE, CF(3)O[-CF(CF(3))CF(2)O-](x)(-CF(2)O-)(y)CF(3)) 'barrier' cream. A stoichiometric amount of HD sulfide simulant was layered on top of each POM-cream mixture. The short reaction times were recorded for each system. Mechanistic studies were conducted using an PFPE oil analog of the barrier cream in a microemulsion with the sulfide simulant, POM, PFPE surfactant and 2,2,2-trifluoroethanol co-surfactant.