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The ability of the acetylcholinesterase reactivator obidoxime (H2L2+) to bind palladium(II) cations was evaluated spectrophotometrically at different reaction conditions (pH, reaction time, metal-to-ligand molar ratio). The results showed that immediately after mixing the reagents, pH 7.4, complex species of composition [PdHL]3+ existed predominantly with a value of conditional stability constant lgβ‘=6.52. The reaction was completed within 24 hours affording the formation of species [Pd2L]4+ with significantly increased stability (lgβ‘=9.34). The spectral data suggest that obidoxime coordinates metal(II) ions through the oximate functional groups. The in vitro reactivation assay of paraoxon-inhibited rat brain acetylcholinesterase revealed that the new complex species were much less active than the non-coordinated obidoxime. The lack of reactivation ability could be explained by the considerable stability of complexes in solution as well as by the deprotonation of oxime groups essential for recovery of the enzymatic activity.

Monensin is a natural antibiotic that exhibits high affinity to certain metal ions. In order to explore its potential in coordination chemistry, circular dichroism (CD) spectra of monensic acid A (MonH) and its derivatives containing monovalent cations (Li(+) , Na(+) , K(+) , Rb(+) , Ag(+) , and Et4 N(+) ) in methanolic solutions were measured and compared to computational models. Whereas the conventional CD spectroscopy allowed recording of the transitions down to 192 nm, synchrotron radiation circular dichroism (SRCD) revealed other bands in the 178-192 nm wavelength range. CD signs and intensities significantly varied in the studied compounds, in spite of their similar crystal structure. Computational modeling based on the Density Functional Theory (DFT) and continuum solvent model suggests that the solid state monensin structure is largely conserved in the solutions as well. Time-dependent Density Functional Theory (TDDFT) simulations did not allow band-to-band comparison with experimental spectra due to their limited precision, but indicated that the spectral changes were caused by a combination of minor conformational changes upon the monovalent cation binding and a direct involvement of the metal electrons in monensin electronic transitions. Both the experiment and simulations thus show that the CD spectra of monensin complexes are very sensitive to the captured ions and can be used for their discrimination. Chirality 28:420-428, 2016. © 2016 Wiley Periodicals, Inc.

The present research is focused on evaluation of complexation ability of Monensic acid (MonH) towards La3+ and Nd3+ ions.Changes in the SRCD spectrum of Monensinate anion were monitored upon addition of lanthanide(III) ions. The antibiotic undergoes formation of one neutral ([Ln(Mon)3(H2O)3]) and two positively charged complex species of composition [Ln(Mon)2(H2O)2]+ and [Ln(Mon) (H2O)]2+, respectively (Ln = La3+, Nd3+). Neutral complexes were isolated as fine powders and were characterized by IR, FAB-MS and ESI-MS. It is assumed that Monensin acts in bidentate coordination mode via monodentate carboxylate moiety and hydroxyl group, both located at the opposite ends of antibiotic molecule.Activity of Monensic acid and [Ln(Mon)3(H2O)3] to decrease visible bacteria growth of B. subtilis, S. Lutea and B. mycoides was evaluated by agar hole diffusion method. Results showed that complexation of lanthanide(III) ions to Monensin enhances the activity of non-coordinated ligand.Antitumor efficacy of compounds was assayed on human triple negative breast cancer and transplantable sarcoma in rat. The cytotoxicity was accessed by MTT test, NR uptake, CV assay and double AO/PI staining. Experimental data revealed that Monensic acid and [Ln(Mon)3(H2O)3] possess concentration- and time-dependent activity, and express promising cytotoxic properties against human and rat permanent cancer cell lines.