Uranium(VI) Complexes of Glutathione Disulfide Forming in Aqueous Solution

The interactions between glutathione disulfide, GSSG, the redox partner and dimer of the intracellular detoxification agent glutathione, GSH, and hexavalent uranium, U(VI), were extensively studied by solution NMR (in D₂O), complemented by time-resolved laser-induced fluorescence and IR spectroscopies. As expected for the hard Lewis acid U(VI), coordination facilitates by the ligands' O-donor carboxyl groups. However, owing to the adjacent cationic α-amino group, the glutamyl-COO reveal monodentate binding, while the COO of the glycyl residues show bidentate coordination. The log K value for the reaction UO₂²⁺ + H₃GSSG^- → UO₂(H₃GSSG)⁺ (pH 3, 0.1 M NaClO₄) was determined for the first time, being 4.81 ± 0.08; extrapolation to infinite dilution gave log K^⊖ = 5.24 ± 0.08. U(VI) and GSSG form precipitates in the whole pD range studied (2-8), showing least solubility for 4 < pD < 6.5. Thus, particularly GSSG, hereby representing also other peptides and small proteins, affects the mobility of U(VI), strongly depending on the speciation of either component.