Evaluation of Kinetic Data to Discern Stereospecific Reactions of ToxicOrganophosphorus Fluorides

摘要

Neurotoxins, such as soman, sarin, or tabun, contain a chiral phosphorus centerproducing stereoisomers, which have been shown to have marked differences in toxicity or the rate at which the isomers inhibit acetylcholinesterase. The neurotoxins are detoxified with strong caustic or bleach; research is underway to find novel catalysts or other reagents that are less deleterious to skin or material. One frequently overlooked aspect of such research is to test whether the catalysts or novel reagents react equally well with the agents enantiomers. It is shown that careful treatment of kinetic data with nonlinear, least-squares programs can detect differences in reaction rates of isomers in racemic mixtures. It is recommended that the kinetic data can be screened with nonlinear, least-squares programs to look for deviations from first-order kinetic behavior before one attempts to perform experiments with optically resolved samples of agent. These results are applicable to studies with commercial organophosphorus pesticides, which also frequently possess chiral centers. Decontamination, Soman, Nerve agents, Catalysis, Hydrolysis, Kinetics, Enzymes.