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Molybdenum and Diabetes，2013 - II

Molybdenum have anti-diabetic properties.Each molybdenum complex was applied mixed with chemically inert boron nitride to simulate an oral pharmaceutical preparation. They were subjected under physiological conditions (37 °C) to: artificial gastric and intestinal digestion with semi-synthetic meal; simulated gastric juice (pH = 1.2); simulated intestinal fluid (pH = 7.5); cell culture medium (DMEM) with 10% fetal calf serum; and horse serum, heat-inactivated.

Sodium molybdate was added to intact human blood then plasma separated and intact human blood then red blood cells separated. Molybdenum concentrations were 1.0 mM (100 ppm).The compounds and their speciation were studied by Mo K-edge XANES (X-ray absorption near-edge structure) spectroscopy. The XANES spectra enable one to distinguish beween tetrahedral molybdenum(VI) (as in the molybdate anion) and octahedral molybdenum(VI) (as in the complexes) and to deduce the ligand envirionment of the molybdenum atom (2O + 4O or 2N and 2S or 4S) and hence the speciation of molybdenum(VI) under the conditions employed.

The [MoO2L2] complexes decomposed under simulated gastric and intestinal digestion conditions (3 h at 37 °C), and in blood plasma and cell culture medium (24 h at 37 °C). The dithiocarbamato complex (D) was less reactive than the other complexes, decomposing in the meal but not in the gastric and intestinal liquids.

The reaction products of [MoO4]2- and [MoO2L2] with the biological fluids were modelled as mixtures of tetrahedral and octahedral Mo(VI) oxo-species (i.e. having molybdenum ligated only with oxygen atoms) in various ratios depending on the nature of the medium. Red blood cells took up Mo(VI) predominantly as the [MoO4]2- ion.

The octahedral oxo-Mo(VI) species were formed in more acidic media ([H+] = 2–6 M) as the monomeric [MoO2(OH2)4]2+ ion or as polynuclear molybdophosphates, e.g. [Mo5O15(PO3OR)2]2−, where R is the nucleoside residue (known to be formed in solutions of molybdate and nucleosides at pH = 4–5)..

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