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Tetrathiomolybdate and Wilson’s disease,2013 - IV

Ammonium tetrathiomolybdate treats chronic Cu poisoning in sheep and is recommended for Wilson's disease in humans (congenital inability to excrete copper resulting in its accumulation).

Although addition of mineral acids to WS42- in water is known to lead to aggregation and formation of various polynuclear thiotungstate anions, acid hydrolysis of the MoS42- anion is reported to give mainly MoS3 or MoS2 as hydrolysis products. knowledge of the resulting product(s) from such reactions has implications on the use of  tetrathiomolybdate (MOS42-) as both a potential anti-tumour drug and for the treatment of Wilson's disease.

In this investigation, reaction of HCl with MOS42- in water was monitored as a function of time. Reaction mixtures of both 1:1 and 2:1 mole ratios of the acid to MOS42- were examined, as well as MOS42- reactions in simulated human stomach fluids at pH ca 2 and 3. Monitoring by electrospray mass spectrometry (ESMS), Fourier transform infrared (FTIR), and UV-visible spectroscopy clearly has revealed the formation of complex mixtures of polynuclear thiomolybdates.

Generally, a two-stage consecutive reaction sequence occurs. A faster stage (k = 7.0-7.9 x 10-2 min-1), which seems to extend to trinuclear thiomolybdate species, followed by a slower second stage (k = 5.4-15.2 x 10-4 min-1) to higher polynuclear thiomolybdates. Under acidic conditions (e.g. pH ca 3) that could also mimic some human stomach fluids, and under anaerobic atmosphere where the generated hydrogen sulfide is prevented from escaping from the reaction vessel, Mo3 S92- predominates over an extended reaction period. In similar reactions under aerobic conditions and where the hydrogen sulfide is irretrievably lost from the reaction mixture the binuclear (Mo2OaS10-a2-; a = 0-3) and trinuclear (Mo3ObS9-b2-; b = 1-3) anions predominate.

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