title: Nuclear magnetic resonance analysis of the solution and solvolysis of sulfur mustard in deuterium oxide.
abstract: Our laboratory performs in vitro experiments in which cell cultures are exposed to sulfur mustard (HD) to investigate the toxicity of this agent of chemical warfare. To perform these experiments, it is important to know the rate of hydrolysis of HD in order to calculate the concentrations of HD and its hydrolysis products during the experiment. Researchers have previously investigated the kinetics and mechanism of the hydrolysis of HD using a variety of methods. In the present study, we used nuclear magnetic resonance (NMR) spectroscopy and gas chromatography/mass spectrometry (GC/MS) to investigate HD's dissolution and solvolysis in deuterium oxide (D 2 O) at 2 mM. We followed activity in proton spectrums and determined the half-life (t 1/2) of HD to be 7.0 +/- 0.5 min in four experiments performed at 22 degrees C. In addition, we determined the t 1/2 of HD in D 2 O containing 0.17 M sodium chloride to be 24 +/- 1 min in three experiments performed at 22 degrees C. As further proof of the existence of HD dissolved into D 2 O, deutero-hexane was used to extract the D 2 O HD solution. The resulting deutero-hexane solution was studied by 1 H NMR and GC/MS. The results obtained match those received from a standard deutero-hexane HD solution. These results demonstrate that HD can be identified in D 2 O with proton NMR and that proton NMR data can be used to monitor the subsequent solvolysis of HD.
authors.affiliation: Drug Assessment Division, US Army Medical Institute of Chemical Defense, Aberdeen Proving Ground, Maryland, USA.
authors.forename: Thomas P
authors.initials: TP
authors.lastname: Logan
authors.forename: David A
authors.initials: DA
authors.lastname: Sartori