Stability in solution and chemoprotection by octadecavanadates(IV/V) in E. coli cultures

Abstract

Two mixed-valence octadecavanadates, (NH₄)₂(Me₄N)₅[V^IV₁₂V^V₆O₄₂I]·Me₄NI·5H₂O (V₁₈I) and [{K₆(OH₂)₁₂V^IV₁₁V^V₇O₄₁(PO₄)·4H₂O}_n] (V₁₈P), were synthesized and characterized by single-crystal X-ray diffraction analysis and FTIR, Raman, ⁵¹V NMR, EPR and UV/Vis/NIR spectroscopies. The chemoprotective activity of V₁₈I and V₁₈P towards the alkylating agent diethyl sulfate was assessed in E. coli cultures. The complex V₁₈I was nontoxic in concentrations up to 5.0 mmol L^-1, while V₁₈P presented moderate toxicity in the concentration range 0.10 - 10 mmol L^-1. Conversely, a ca. 35% enhancement in culture growth as compared to cells treated only with diethyl sulfate was observed upon addition of V₁₈I (0.10 to 2.5 mmol L^-1), while the combination of diethyl sulfate with V₁₈P increased the cytotoxicity presented by diethyl sulfate alone. ⁵¹V NMR and EPR speciation studies showed that V₁₈I is stable in solution, while V₁₈P suffers partial breakage to give low nuclearity oxidometalates of vanadium(V) and (IV). According to the results, the chemoprotective effect depends strongly on the direct reactivity of the polyoxidovanadates (POV) towards the alkylating agent. The reaction of diethyl sulfate with V₁₈I apparently produces a new, rearranged POV instead of poorly-reactive breakage products, while V₁₈P shows the formation and subsequent consumption of low-nuclearity species. The correlation of this chemistry with that of other mixed-valence polyoxidovanadates, [H₆V^IV₂V^V₁₂O₃₈PO₄]^5- (V₁₄) and [V^IV₈V^V₇O₃₆Cl]^6- (V₁₅), suggests a relationship between stability in solution and chemoprotective performance.

Keywords: Alkylation; Chemoprotection; Diethyl sulfate; Polyoxidovanadates; Speciation.