Ziyad A. Taha

Syntheses, characterization, biological activity and fluorescence properties of bis-(salicylaldehyde)-1,3-propylenediimine Schiff base ligand and its lanthanide complexes.

Eight new lanthanide metal complexes [LnL(NO(3))(2)]NO(3) {Ln(III) = Nd, Dy, Sm, Pr, Gd, Tb, La and Er, L = bis-(salicyladehyde)-1,3-propylenediimine Schiff base ligand} were prepared. These complexes were characterized by elemental analysis, thermogravimetric analysis (TGA), molar conductivity measurements and spectral studies ((1)H NMR, FT-IR, UV-vis, and luminescence). The Schiff base ligand coordinates to Ln(III) ion in a tetra-dentate manner through the phenolic oxygen and azomethine nitrogen atoms. The coordination number of eight is achieved by involving two bi-dentate nitrate groups in the coordination sphere. Sm, Tb and Dy complexes exhibit the characteristic luminescence emissions of the central metal ions attributed to efficient energy transfer from the ligand to the metal center. Most of the complexes exhibit antibacterial activity against a number of pathogenic bacteria.

Thermal decomposition of lanthanide(III) complexes of bis-(salicylaldehyde)-1,3-propylenediimine Schiff base ligand

The thermal decomposition of lanthanide complexes, with a general formula: [LnL(NO3)2](NO3), where Ln = La, Pr, Nd, Sm, Gd, Tb, Dy, and Er; and L = bis-(salicyladehyde)-1,3-propylenediimine Schiff base ligand, was studied by thermogravimetric (TG) and derivative thermogravimetric (DTG) techniques. The TG and DTG data indicated that all complexes are thermostable up to 398 K. The thermal decomposition of all Ln(III) complexes was a two-stage process and the final residues were Ln2O3 (Ln = La, Nd, Sm, Gd, Dy, Er), Tb4O7, and Pr6 O11. The activation energies of thermal decomposition of the complexes were calculated from analysis of the TG-DTG curves using the Kissinger, Friedman, and Flynn-Well-Ozawa methods.

Synthesis, characterization, biological activities and luminescent properties of lanthanide complexes with [2-thiophenecarboxylic acid, 2-(2-pyridinylmethylene)hydrazide] Schiff bases ligand

Abstract A Schiff base L [2-thiophenecarboxylic acid, 2-(2-pyridinylmethylene)hydrazide] with its lanthanide metal complexes was synthesized. These complexes were characterized by elemental analysis, molar conductivity measurements, spectral analysis (NMR, FT-IR, and UV-Vis), luminescence and thermal gravimetric analysis. The Schiff base ligand was a tridentate chelate and coordinates to the central lanthanide ion with 1:2 metal:ligand ratio. The conductivity data showed a 1:1 electrolytic nature with a general formula [LnL2(NO3)2]NO3. The luminescence emission properties for Sm, Tb, and Eu complexes were observed and showed that the ligand L could absorb and transfer energy to Sm(III), Tb(III) and Eu(III) ions. The complexes possessed a good antibacterial activity against different bacterial strains. In addition, the scavenging activity of the Ln(III) complexes on DPPH was concentration dependant and the complexes were significantly more efficient in quenching DPPH than the free Schiff base ligand.

CONDUCTANCE AND THERMODYNAMIC STUDY OF THALLIUM AND SILVER ION COMPLEXES WITH CROWN ETHERS IN DIFFERENT BINARY ACETONITRILE-WATER SOLVENT MIXTURES

The complexation reactions between Ag+ andTl+ ions with 15-crown-5 (15C5) and phenyl-aza-15-crown-5(PhA15C5) have been studied conductometrically in 90%acetonitrile-water and 50% acetonitrile - water mixed solvents attemperatures of 293, 298, 303 and 308 K. The stability constants of theresulting 1 : 1 complexes were determined, indicating that theTl+ complexes are more stable than the Ag+complexes. The enthalpy and entropy of crown complexation reactions were determined from the temperature dependence of the complexation constants.The enthalpy and entropy changes depend on solvent composition and the TΔ S0o–ΔH0 plotshows a good linear correlation, indicating the existence of entropy –enthalpy compensation in the crown complexation reactions.

Synthesis and Biological Activities of Lanthanide (III) Nitrate Complexes with N-(2-hydroxynaphthalen-1-yl) methylene) Nicotinohydrazide Schiff Base

BACKGROUND The field of coordination chemistry has registered a phenomenal growth during the last few decades. It is well known that precious metals have been used for medicinal purposes for at least 3500 years. At that time, precious metals were believed to benefit health because of their rarity, but research has now well established the link between medicinal properties of inorganic drugs and specific biological properties. METHODS The current study was designed to explain the synthesis and characterization of the lanthanide (III) nitrate complexes with N-(2-hydroxynaphthalen-1-yl) methylene) nicotinohydrazide schiff base and to evaluate the antibacterial and the antioxidant activities of the schiff base and its lanthanide ion complexes. Antimicrobial activity of the Lanthanide (III) nitrate complexes with N-(2- hydroxynaphthalen-1-yl) methylene) nicotinohydrazide schiff base was estimated by minimum inhibitory concentration (MIC, µg/mL) using a micro-broth dilution method for different clinical isolates such as Eschereshia coli and Enterococcus faecalis. The antioxidant activities of the ligand and its lanthanide complexes were tested using a UV-Visible spectrophotometer by preparing 5x10-4M of all tested samples and DPPH in Dimethyl sulphoxide (DMSO). RESULTS Our present study has shown that moderate antimicrobial activity exists against both ligand and its complexes. There was no significant difference between Gram-positive and Gram-negative bacteria towards the tested ligand and its complexes. The free ligand has scavenging activity between 13-21 % while all complexes are more efficient in quenching DPPH than free ligand. CONCLUSION The results obtained herein indicate that the ligand and its complexes have a considerable antibacterial activity as well as antioxidant activity in quenching DPPH.

Conductance and Thermodynamic Study of the Interaction of Mixed Oxygen–N2–Donor Macrocycles with Ag(I), Ni(II) and Fe(III) in Acetonitrile Solutions

The thermodynamic stabilities of Ag+, Ni2+ and Fe3+with diaza-crown ethers have been determinedconductometrically in acetonitrile at temperatures of 293, 298, 303 and 308 K.Both the size of the macrocyclic ring and the hard and soft acidand base (HSAB) character of the metal ions influence the relative stabilities of the complexes. For the metal ions with diazacrown ethers the values of log Kf for the 1 : 1 complexesfollow the order Ag+ > Ni2+ > Fe3+in accordance with Pearsons principle of HSAB character. The enthalpy and entropy of complexation were determined from the temperature dependence of the complexationconstants. The complexation process is entropy governed.

A Thermodynamic Study of Complexation of Iron Ions with Clarithromycin and Roxithromycin in Methanol Using a Conductometric Method

The formation constants KML of Clarithromycin (CLA) and Roxithromycin (ROX) with Fe(III) and Fe(II) ions in methanol have been determined at various temperatures using a conductometric technique. The interaction yields complexes with metal-to-ligand compositions of 1:1. The conductivity data were analyzed using a computer program based on 1:1 stoichiometry from which the stability constants and the limiting molar conductance were obtained. The stability of these complexes was found to increase with temperature. Compared with Fe(II), Fe(III) forms more stable complexes with ROX and CLA. The values of the thermodynamic parameters enthalpies (ΔH∘), entropies (ΔS∘), and the derived Gibbs energies (ΔG∘) were deduced from the dependence of the formation constants on temperature. The positive values of ΔH∘ and ΔS∘ indicate that the complexation processes is enthalpically unfavorable but entropically favored. The negative values of ΔG∘ show the ability of the studied ligand to form stable complexes and that the complexation process is favorable.

Conductance Study and Thermodynamics of Some Substituted Ammonium Salts with Crown Ethers in Aqueous Solution

A conductance study of the interaction between substituted ammonium ions with three crown ethers in aqueous solution has been carried out at different temperatures. The formation constants of the 1 : 1 complexes at various temperatures were determined from the molar conductance-mole ratio data and found to vary in the order 18C6 > 15C5 > 12C4 for the same salt and with the same crown, the formation constants vary in the order (C2H5)3NHCl > (C2H5)4NBr > (CH3)3NPhI.The enthalpy and entropy of complexation were determined from the temperature dependence of the formation constants. The results indicate that the complexation process is enthalpy unfavored and entropy favored. The influence on the thermodynamic data for different parameters such as cavity size of crown ethers and nature of salt are discussed.

DFT computational studies, biological and antioxidant activities, and kinetic of thermal decomposition of 1,10-phenanthroline lanthanide complexes

Abstract[Ln (phen)2(NO3)3] complexes were synthesized by interaction of lanthanide nitrate {Ln (NO3)3.xH2O where Ln = Tb, Eu, Sm, Dy, and La} with 1,10-phenanthroline {phen} in ethylacetate. The complexes were characterized by several analytical and spectroscopic techniques. Density functional theory (DFT) calculations were carried out to optimize the geometries of all prepared complexes at the B3LYP/6-31G(d) level of theory. Vibrational frequencies of the complexes theoretically calculated were in good agreement with experimentally determined values. Most of the complexes exhibited high to moderate antibacterial and antifungal activities in vitro against seven different clinical isolates. The complexes were tested for their antioxidant activity toward 1,1-diphenyl-2-picryl-hydrazyl (DPPH) radical. Dy(III) complex showed the highest activity. Thermal degradation of complexes at different heating rates was investigated by thermogravimetric analysis (TGA). The complexes had high thermal stability. The activation energies (Ea) of the degradation were calculated by Kissinger and Flynn-Wall-Ozawa methods.

Redetermination of [Gd(NO3)3(H2O)4]·2H2O

The crystal structure of the title compound, tetraaquatris(nitrato-κ2 O,O′)gadolinium(III) dihydrate, was redetermined from single-crystal X-ray data. In comparison with the first determination [Ma et al. (1991 ▶). Wuji Huaxue Xuebao, 7, 351–353], all H atoms could be located, accompanied with higher accuracy and precision. The GdIII atom shows a ten-coordination with three nitrate ligands behaving in a bidentate manner and the other positions being occupied by four water molecules, forming a distorted bicapped square antiprism. Two nitrate ions coordinate to the metal atom with similar bond lengths while the third shows a more asymmetric bonding behaviour. An intricate network of O—H⋯O hydrogen bonds, including the lattice water molecules, stabilizes the crystal packing.