title: Dimethylthioarsinic anhydride: a standard for arsenic speciation.
abstract: Dimethylthioarsinic acid (DMTA(V)) has recently been identified in biological, dietary and environmental matrices. The relevance of this compound to the toxicity of arsenic in humans is unknown and further exposure assessment and metabolic studies are difficult to conduct because of the unavailability of a well characterized standard. The synthesis of DMTA(V) was accomplished by the reaction of dimethylarsinic acid (DMA(V)) with hydrogen sulfide. The initial reaction product produced is DMTA(V) but multiple products over the course of the reaction are also observed. Therefore, a chromatographic separation was developed to monitor the reaction progress via LC-ICP-MS. In this synthesis, conversion of DMA(V) to DMTA(V) was not taken to completion to avoid the production of side products. The product was isolated from the starting material by standard organic techniques. Single crystal diffraction demonstrated that solid DMTA(V) is present in the form of the oxygen-bridged dimethylthioarsinic anhydride. Dissolution of the anhydride in water produces the acid form of DMTA(V) and the aqueous phase DMTA(V) provided a characteristic molecular ion of m/z 155 by LC-ESI-MS. The synthesis and isolation of dimethylthioarsinic anhydride provides a stable crystalline standard suitable for identification, toxicological study and exposure assessment of dimethylthioarsinic acid.
authors: United States Environmental Protection Agency, National Exposure Research Laboratory, Microbiological and Chemical Exposure Assessment Research Division, 26 W. Martin Luther King Drive, Cincinnati, OH 45268, USA.
authors: Michael
authors: M
authors: Fricke
authors: Matthias
authors: M
authors: Zeller
authors: William
authors: W
authors: Cullen
authors: Mark
authors: M
authors: Witkowski
authors: John
authors: J
authors: Creed
mesh_terms: D000812:Anhydrides / Q000032:analysis*; D001151:Arsenic / Q000032:analysis; D001152:Arsenicals / Q000032:analysis* / Q000138:chemical synthesis; D002853:Chromatography, Liquid / Q000379:methods; D006801:Humans; D007202:Indicators and Reagents; D021241:Spectrometry, Mass, Electrospray Ionization
chemical_list: D000812:Anhydrides; D001152:Arsenicals; D007202:Indicators and Reagents; C520159:dimethylthioarsinic anhydride; D001151:Arsenic