Aqueous hydrogen peroxide is widely used as an oxidizing agent in industry and academia. Herein, the hydrogen peroxide adducts of phosphine oxides, [tBu3PO⋅H2O2]2 and [Ph3PO⋅H2O2]2⋅H2O2, are described. Additionally, the corresponding di(hydroperoxy)propane adducts R3PO⋅(HOO)2CMe2 (R=Cy, Ph) were synthesized and characterized. All adducts could be obtained as large single crystals suitable for structural characterization by X-ray crystallography and solid-state NMR spectroscopy. The di(hydroperoxy)propane adducts are soluble in organic solvents which enables oxidation reactions in one phase. As the adducts are solid and molecular, they can easily be applied stoichiometrically. No loss of oxidizing power occurs upon long-term storage of the single crystals at room temperature or the powders at -20 °C.
Pathogenic bacteria scavenge ferric iron from the host for survival and proliferation using smallmolecular chelators, siderophores. Here, we introduce and assess the gallium(III) complex of ciprofloxacin-functionalized desferrichrome (D2) as a potential therapeutic for bacterial infection using an in vitro assay and radiochemical, tracer-based approach. Ga-D2 exhibits a minimum inhibitory concentration of 0.23 μM in Escherichia coli, in line with the parent fluoroquinolone antibiotic. Competitive and mutant strain assays show that Ga-D2 relies on FhuA-mediated transport for internalization. Ga-D2 is potent against Pseudomonas aeruginosa (3.8 μM), Staphylococcus aureus (0.94 μM), and Klebsiella pneumoniae (12.5 μM), while Fe-D2 is inactive in these strains. Radiochemical experiments with E. coli reveal that 67 Ga-D2 is taken up more efficiently than 67 Ga-citrate. In naive mice, 67 Ga-D2 clears renally and is excreted 13% intact in the urine. These pharmacokinetic and bacterial growth inhibitory properties qualify Ga-D2 for future investigations as a diagnosis and treatment tool for infection.
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