Synthesis, theoretical studies, antibacterial, and antibiofilm activities of novel azo-azomethine chelates against the pathogenic bacterium Proteus mirabilis.

2-((1-(4-((2,4,6-trioxohexahydropyrimidin-5-yl)diazenyl) phenyl) ethylidene) amino) benzoic acid (H3L), and its V(IV), Co(II), Ni(II), Cu(II), Pd(II) and Ag(I) chelates were synthesized. They were defined using multiple spectral and analytical techniques. With the exception of Ag(I) chelate, all chelates possessed non-electrolytic character. Square pyramidal shape was proposed for V(IV) chelate and Square planar for the other chelates. The analysis of functional group bands of H3L and its coordination compounds alludes that H3L chelated as neutral tetradentate via nitrogen atoms of azo and azomethine groups, oxygen atom of carbonyl of barbituric acid and OH of the carboxylic group. TG/DTG predicted the thermal behaviors of all compounds. The antibacterial activity of H3L and its coordination compounds was conducted against Proteus mirabilis at concentrations of 250, 500, and 1000 µg/mL. Ag(I) at 1000 µg/mL, showed the most inhibiting potency against P. mirabilis and registered zone of inhibition of 28.33 ± 0.84 mm and highest biofilm inhibition of 70.31%. At 50 Gy of gamma irradiation, the reducing effect of Ag(I) chelate was improved. The protein interruption of P. mirabilis was greatly interrupted by increasing the concentration of the chaletes. Also, Ag(I) showed the highest cytotoxicity with IC50 value of 11.5 µg/ mL. The novelty of this study is the synthesis of a new azo-Schiff base and this is almost the first publication of the effect of azo-Schiff ligands against that bacterial strain P. mirabilis.

Bivalent Metal Chelates with Pentadentate Azo-Schiff Base Derived from Nicotinic Hydrazide: Preparation, Structural Elucidation, and Pharmacological Activity.

Azo-Schiff base ligand (N'-((E)-2-hydroxy-5-((E)-(2-hydroxyphenyl)diazenyl)benzylidene)nicotinohydrazide) and its Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Pd(II) chelates were prepared and elucidated. The geometrical structures of the prepared chelates were characterized by several spectroanalytical techniques and thermogravimetric analysis. The obtained data revealed that the chelates have (1M:1L), (1M:2L), (1M:3L), and (1M:4L) molar ratios. The infrared spectra displayed that the H2 L ligand behaves in a pentacoordinate fashion in chelates of Mn(II), Ni(II), and Cu(II) ions. However, in Zn(II) and Pd(II) chelates, the ligand is coordinated as a tetradentate species (NONO) through nitrogen atoms of azomethine and azo groups as well as oxygen atoms of phenolic hydroxy, and carbonyl groups. Besides, it was concluded that the oxygen atoms of carbonyl and hydroxy groups along with the azomethine nitrogen atom of the ligand are bounded with Co(II) ion in metal chelate (2). According to the measured molar conductance values, the chelates of Cu(II), Zn(II), and Pd(II) are weak electrolytes, but Mn(II), Co(II), and Ni(II) chelates are ionic. The azo-Schiff base ligand and its prepared metal chelates were tested for their antioxidant and antibacterial properties. The Ni(II) chelate was found to be considered an effective antioxidant agent. In addition, the available antibacterial data suggest that the Ni(II) and Co(II) chelates may be employed as inhibitor agents against Proteus vulgaris, Escherichia coli, and Bacillus subtilis bacteria. Furthermore, the data showed that, in comparison to the ligand and other metal chelates, copper(II) chelate (4) exhibited higher action against Bacillus subtilis bacteria.

Electrochemical and computational evaluation of hydrazide derivative for mild steel corrosion inhibition and anticancer study.

In the present study the authors' main goal is to avoid the corrosive attack of the chloride ions of 3.5% NaCl solution in saline medium on the mild steel (MS), by addition of small amount of a new derivative of the hydrazide called ligand (HL), as a corrosion inhibitor. This study had been achieved by employing different electrochemical measurements such as, open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentio-dynamic polarization (PDP) methods. The results of the electrochemical test (OCP), showed that, the open circuit potential of the mild steel in saline solution, was guided to more positive direction in presence of the ligand (HL), at its ideal concentration (1 × 10-3 M), compared to the (OCP), of the mild steel in absence of (HL). The results of the electrochemical methods, EIS and PDP presented that, the ligand (HL), was acted as a good corrosion inhibitor for hindering the corrosion process of the mild steel in 3.5% sodium chloride, as it was recorded a good percentage of the inhibition efficiency (77.45%, 53.41%, by EIS and PDP techniques respectively), at its optimum concentration (1 × 10-3 M). Also, the corrosion rate of the mild steel in the saline medium without (HL), was listed about (0.0017 mm/year), while in existence of (HL), was decreased to a value about (0.00061 mm/year). As well, some of electrical properties of (HL), and its derivative [Pd(II), Cr(III), and Ru(III)], complexes were investigated such as; the activation energy (Ea(ac)), which recorded values in the range of 0.02-0.44 (eV) range and electrical conductivity which listed values at room temperature in the range of 10-5-10-8 S.cm-1. The results of the AC and DC electrical conductivity measurements for (HL), and its derivative [Pd(II), Cr(III) and Ru(III)] complexes indicate semiconducting nature which suggests that these compounds could be used in electronic devices. Also, the complexes exhibited higher conductivity values than (HL). Photophysical studies showed good florescence properties of HL that indicated that it can be used to determine most of the drugs with no fluorescence properties by quenching and calculating quantum yield. Moreover, the hydrazide ligand (HL), has shown selectivity as an active anticancer candidate drug for both breast and colon cancer in humans. Density function theory demonstrated that, the frontier molecular orbital HOMOs of the complexes have exhibited similar behavior and the charge density has localized in the metallic region of all the studied complexes. Also, the values of the energy gap of the ligand (HL), and its complexes Pd(II), Cr(III) and Ru(III), had been arranged in this order HL > Cr(III) > Ru(III) > Pd(II). All characterization using different spectroscopic techniques were reported to elucidate the proposed structures such as; thermal analysis, elemental analysis of C, H, and N atoms, spectral analysis using IR, UV, 1H NMR techniques, scanning electron microscopy and energy dispersive X-ray analyses.

Synthesis of Some Novel Nanosized Chelates of Anchoring Bisazo Dye 5-[5-(4,6-Dioxo-2-thioxo-hexahydro-pyrimidin-5-ylazo)-naphthalen-1-ylazo]-2-mercapto-1H-pyrimidine-4,6-dione and Their Applications as Antioxidant and Antitumor Agents.

A novel bisazo 5-[5-(4,6-dioxo-2-thioxo-hexahydro-pyrimidin-5-ylazo)-naphthalen-1-ylazo]-2-mercapto-1H-pyrimidine-4,6-dione (H4L) ligand has been synthesized from diazotization coupling between naphthalene-1,5-diamine and 2-thiobarbituric acid. Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Fe(III) chelates were prepared. All prepared compounds were characterized by different techniques. The azo groups did not participate in chelation according to the infrared spectra, whereas the thioamide group did participate. The azo dye ligand coordinated with all metallic ions in a neutral-keto-thiol structure and behaved as a bi- and tridentate moiety. Zinc, manganese, and iron chelates had an octahedral structure, while nickel and cobalt chelates had a tetrahedral structure, but the copper chelate had a square pyramidal geometry. The thermal behavior of all prepared compounds was investigated and thermokinetic parameters were also discussed. X-ray diffraction (XRD) data reflected that Fe(III) and Zn(II) complexes were crystalline while the Cu(II) complex was amorphous. Calcination of the Fe(III) complex at 600 °C yielded a nanosized Fe2O3 crystalline phase, elucidated by XRD and transmission electron microscope. The novel azo dye and some of its chelates were tested against HepG-2. The Fe2O3 nanooxide showed remarkable activity against the HepG-2 cell line rather than its precursor Fe(III) complex. Co(II) had a higher antioxidant activity than the other investigated complexes. In both activities, the Cu(II) complex did not show any activity. Molecular modeling and some theoretical studies were validated, and the experimental results were interpreted.