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Relevant academic research and scientific papers

A Bis(μ-phenoxo)-bridged dizinc complex with hydrolytic activity

The dinuclear complex [Zn2(papy)2]·2CH 3OH [H2papy = N-(2-hydroxybenzyl)-N-(2-picolyl)glycine] was synthesized and characterized. The crystal structure of the complex reveals that both ZnII ions are pentacoordinate with distorted pentagonal bipyramidal coordination arrangements. The phenoxyl groups of each ligand bridge the two metal atoms, whereas each carboxylate of the ligand is terminally bound to one ZnII ion. Potentiometric studies of the Zn II:H2papy system in a methanol/water mixture show the existence of a mononuclear species at lower pH; but at a pH above 5, a dimeric species starts to dominate and transforms further into a bis(μ-phenoxo) bridged dizinc complex by deprotonation of phenolic hydrogen. A kinetic study of the hydrolysis of bis(2, 4-dinitrophenyl)phosphate at different pH, catalyzed by complex 1, indicates a maximum rate at pH 9, where the bis(μ-phenoxo)- bridged dizinc species corresponding to 1 dominates in solution. Copyright

Phosphorylimidazole derivatives: Potentially biosignaling molecules

The phosphorylation of imidazole by two activated phosphate diesters and a triester gives phosphorylimidazole derivatives that are stable enough in aqueous solution to be observed and identified by ESI-MS/MS and NMR. Half-lives ranging from hours to days (in the case of the monoethyl ester) show that it is possible to design molecules with variable half-lives with potential to be used for biological intervention experiments as possible inhibitors of biosignaling processes or as haptens for the generation of antibodies.

A heterobimetallic FeIIIMnII complex of an unsymmetrical dinucleating ligand: A structural and functional model complex for the active site of purple acid phosphatase of sweet potato

The heterodinuclear mixed-valence complex [FeMn(ICIMP)(OAc)2Cl] (1) {H2ICIMP = 2-(N-carboxylmethyl)-[N-(N-methylimidazolyl-2-methyl) aminomethyl]-[6-(N-isopropylmethyl)-[N-(N-methylimidazolyl-2-methyl)] aminomethyl-4-methylphenol], an unsymmetrical N4O2 donor ligand} has been synthesized and fully characterized by several spectroscopic techniques as well as by X-ray crystallography. The crystal structure of the complex reveals that both metal centers in 1 are six-coordinate with the chloride ion occupying the sixth coordination site of the MnII ion. The phenoxide moiety of the ICIMP ligand and both acetate ligands bridge the two metal ions of the complex. M?ssbauer spectroscopy shows that the iron ion in 1 is high-spin FeIII. Two quasi-reversible redox reactions for the complex, attributed to the FeIIIMnII/Fe IIMnII (at -0.67 V versus Fc/Fc+) and Fe IIIMnII/FeIIIMnIII (at 0.84 V), were observed by means of cyclic voltammetry. Complex 1, with an Fe III-MnII distance of 3.58 ?, may serve as a model for the mixed-valence oxidation state of purple acid phosphatase from sweet potato. The capability of the complex to effect organophosphate hydrolysis (phosphatase activity) has been investigated at different pH levels (5.5-11) by using bis(2,4-dinitrophenyl)phosphate (BDNPP) as the substrate. Density functional theory calculations indicate that the substrate coordinates to the MnII ion. In the transition state, a hydroxide ion that bridges the two metal ions becomes terminally coordinated to the FeIII ion and acts as a nucleophile, attacking the phosphorus center of BDNPP with the concomitant dissociation of the leaving group. Copyright

A heterobimetallic Feiiimnii complex of an unsymmetrical dinucleating ligand: A structural and functional model complex for the active site of purple acid phosphatase of sweet potato

The heterodinuclear mixed-valence complex [FeMn(ICIMP)(OAc)2Cl] (1) {H2ICIMP = 2-(N-carboxylmethyl)-[N-(N-methylimidazolyl-2-methyl)aminomethyl]-[6-(N-isopropylmethyl)-[N-(N-methylimidazolyl-2-methyl)]aminomethyl-4-methylphenol], an unsymmetrical N4O2 donor ligand} has been synthesized and fully characterized by several spectroscopic techniques as well as by X-ray crystallography. The crystal structure of the complex reveals that both metal centers in 1 are six-coordinate with the chloride ion occupying the sixth coordination site of the MnII ion. The phenoxide moiety of the ICIMP ligand and both acetate ligands bridge the two metal ions of the complex. M?ssbauer spectroscopy shows that the iron ion in 1 is high-spin FeIII. Two quasi-reversible redox reactions for the complex, attributed to the FeIIIMnII/FeIIMnII (at -0.67 V versus Fc/Fc+) and FeIIIMnII/FeIIIMnIII (at 0.84 V), were observed by means of cyclic voltammetry. Complex 1, with an FeIII-MnII distance of 3.58 ?, may serve as a model for the mixed-valence oxidation state of purple acid phosphatase from sweet potato. The capability of the complex to effect organophosphate hydrolysis (phosphatase activity) has been investigated at different pH levels (5.5-11) by using bis(2,4-dinitrophenyl)phosphate (BDNPP) as the substrate. Density functional theory calculations indicate that the substrate coordinates to the MnII ion. In the transition state, a hydroxide ion that bridges the two metal ions becomes terminally coordinated to the FeIII ion and acts as a nucleophile, attacking the phosphorus center of BDNPP with the concomitant dissociation of the leaving group.