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Chromatographic separation and identification of products from the reaction of dimethylarsinic acid with hydrogen sulfide

TitleChromatographic separation and identification of products from the reaction of dimethylarsinic acid with hydrogen sulfide
Publication TypeJournal Article
Year of Publication2005
AuthorsFricke, MW, Zeller, M, Sun, H, Lai, VWM, Cullen, WR, Shoemaker, JA, Witkowski, MR, Creed, JT
JournalChemical Research in Toxicology
Volume18
Pagination1821-1829
Date PublishedDec
Type of ArticleArticle
ISBN Number0893-228X
KeywordsCRYSTAL-STRUCTURE, DIMETHYLDITHIOARSINATE, GLUTATHIONE, METABOLITE, ORGANIC ARSENIC COMPOUNDS, RATS, REARRANGEMENT, TOXICITY, TRIMETHYLARSINE OXIDE, urine
Abstract

The reaction of dimethylarsinic acid (DMA(V)) with hydrogen sulfide (H2S) is of biological significance and may be implicated in the overall toxicity and carcinogenicity of arsenic. The course of the reaction in aqueous phase was monitored, and an initial product, dimethylthioarsinic acid, was observed by using LC-ICP-MS and LC-ESI-MS. Dimethylarsinous acid was observed as a minor product. A second slower-forming product was identified, and the electrospray mass chromatograms for this species produced ions at m/z 275, 171, and 137 in positive mode. To aid in the identification of this slower-forming product, crystalline standards of sodium dimethyldithioarsinate and dimethylarsino dimethyldithioarsinate were prepared and re-characterized by using improved spectroscopic and structural analysis techniques. An aqueous solution of sodium dimethyldithioarsinate produced a single major chromatographic peak that matched the retention time (7.6 min) of the slower-forming product and contained similar molecular ions at m/z 275, 171, and 137 via LC-ESI-MS. The dimethylarsino dimethyldithioarsinate standard produced four aqueous phase species one of which coeluted with the slower forming product. This coeluting peak also produced the identical ESI-MS ions as the slower-forming product of DMA(V) + H2S. ESI-MS/MS experiments conducted on sodium dimethyldithioarsinate in deuterated water produced molecular ions at m/z 276, 173, and 137. Subsequent collisionally activated dissociation (CAD) experiments on m/z 276 did not produce a product ion at m/z 173. These data indicate that two different species are present in solution, while NMR data indicate that only dimethyldithioarsinic acid exists in aqueous solutions. This discrepancy was investigated by conducting NMR studies on the acidic solution of sodium dimethyldithioarsinate after taking this solution to dryness. The resolubilized solution produced a proton NMR signal characteristic of dimethylarsino dimethyldithioarsinate. Therefore, it was concluded that the ESI-MS ion at m/z 275 associated with the slowly forming second reaction product and the sodium dimethyldithioarsinate compound is a product of the ESI desolvation process.

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