Synthesis, spectroscopic characterization and antibacterial activity of new cobalt(II) complexes of unsymmetrical tetradentate (OSN2) Schiff base ligands.

Cobalt ion complexes with the Schiff bases, (4-X-2-{[2-(2-pyridine-2-yl-ethylsulfanyl)ethylimino]methyl}phenol (X=methoxy (OMe), phenylazo (N(2)Ph), bromo (Br), nitro (NO(2))),were synthesized and investigated by several techniques using elemental analysis (C, H, N), FTIR, electronic spectra and molar conductivity. The thermal stability of free ligands and related cobalt complexes were studied by using differential scanning calorimetry (DSC) and thermogravimetric analyses (TGA). Cyclic voltammetry indicates that the investigated cobalt complexes, under the experimental conditions, have irreversible redox behavior. The synthesized compounds have antibacterial activity against the four Gram-positive bacteria: Streptococcus pyogenes, Streptococcus agalactiae, Staphylococcus aureus and Bacillus anthracis and also against the two Gram-negative bacteria: Klebsiella pneumoniae and Pseudomonas aeruginosa. The activity data show that the parent Schiff bases are more potent antibacterials than the cobalt complexes.

A selective optical chemosensor based on a thia-containing Schiff-base iron(III) complex for thiocyanate ion.

A new optode membrane for the sensitive and selective determination of thiocyanate ion, based on a change in the absorption spectrum of a polymer film, is proposed. A membrane composed of plasticized poly vinyl chloride (PVC), an Fe(III) Schiff-base complex as a chromoionophore and hexadecyl trimethyl ammonium bromide (HDTMABr) as a cationic additive was prepared. The influence of different plasticizers was studied concerning the sensitivity, linear range and selectivity of the membrane film. Satisfactory analytical sensing characteristics for determining thiocyanate ion were obtained in terms of the selectivity, reversibility and reproducibility with a good detecting range. In addition, the optical film responds to thiocyanate ion reversibly over a wide dynamic range 1.0 x 10(-8) to 1.0 x 10(-3) M with fast response and recovery times. The optode membrane has been applied to determine the thiocyanate ion in urine samples.

Cobalt hydroxide nanoparticles modified glassy carbon electrode as a biosensor for electrooxidation and determination of some amino acids.

The electrochemical behavior of some amino acids was investigated on cobalt hydroxide nanoparticles modified glassy carbon (CHM-GC) electrode in alkaline solution. The process of oxidation and its kinetics were established by using cyclic voltammetry, chronoamperometry techniques, and steady-state polarization measurements. The results revealed that cobalt hydroxide promotes the rate of oxidation by increasing the peak current, so these bimolecular reactions are oxidized at lower potentials. Cyclic voltammograms and chronoamperometry indicate a catalytic EC' mechanism to be operative with electrogeneration of Co(IV) as the electrochemical process. Also, the process is diffusion controlled and the current-time responses follow Cottrellian behavior. This result was confirmed by steady-state measurements. The rate constants of the catalytic oxidation of amino acids and the electron transfer coefficients are reported.

Preparation of Zinc (II) and cadmium (II) complexes of the tetradentate Schiff base ligand 2-((E)-(2-(2-(pyridine-2-yl)- ethylthio)ethylimino)methyl)-4-bromophenol (PytBrsalH).

We describe the synthesis and characterization of two new zinc (II) and cadmium (II) complexes of the tetradentate dissymmetric Schiff base ligand 2-((E)-(2-(2-(pyridine-2-yl)ethylthio)ethylimino)methyl)-4-bromophenol (PytBrsalH), prepared from 1-(2-pyridyl)-3-thia-5-aminopentane (pyta) and 5-bromosalicylaldehyde. The complexes were synthesized by treating an ethanolic solution of the ligand with equimolar amounts of appropriate metal salts in 1 M methanolic solution of NaOH or alternatively, by a more direct route in which the two reactants are added to a solution of the ligand immediately after formation of the latter and prior to any isolation. The complexes were characterized by elemental analysis, FTIR, (1)H-NMR, electronic spectra and molar conductivity. According to obtained data, the probable coordination geometries of zinc and cadmium in these complexes with mixed N, S and O donor atoms are tetrahedral- and octahedral-like,respectively. Both complexes were found to be 1:1 electrolyte systems in acetonitrile.

Preparation of a diclofenac potentiometric sensor and its application to pharmaceutical analysis and to drug recovery from biological fluids.

A novel diclofenac ion-selective electrode is prepared, characterized and used in pharmaceutical analysis. The diclofenac complex with hexadecylpyridinium bromide is obtained in situ by soaking the PVC-membranes in a 1x10(-2) M diclofenac solution. Among four different solvent mediators tested, dibutyl phthalate (DBP) exhibited a proper behavior including Nernstian slope of the calibration curve, fast response time and good reproducibility of the emf values. The electrode exhibits a Nernstian slope of -59+/-1 mV decade(-1) for diclofenac in the concentration range 1.0x10(-5) to 1.0x10(-2) M with a limit of detection of 4.0x10(-6) M. The electrode displays a good selectivity for diclofenac with respect to a number of common inorganic and organic species. It can be used in a pH range of 6.0-9.0. The membrane sensor was successfully applied to the determination of diclofenac in its tablets as well as for its recovery from blood serum and urine samples.

The first use of a Rh(III) complex as a novel ionophore for thiocyanate-selective polymeric membrane electrodes.

The feasibility of a newly synthesized Rh(III) complex, Rh[(trpy)(bpy)Cl](PF(6))(2), as a novel ionophore for the preparation of anion-selective polymeric membrane electrodes was tested. The ionophore exhibited anti-Hofmeister behavior with enhanced potentiometric selectivity toward thiocyanate ion compared to other anions. The influence of some experimental parameters such as membrane composition, nature and amount of plasticizer and additive and concentration of internal solution on the potential response of the SCN(-) sensor were investigated. The electrode exhibits a Nernstian response for SCN(-) over a wide concentration range (1.0 x 10(-5) to 1.0 x 10(-1)M) with a slope -58.7 +/- 0.5mV per decade and a detection limit of 4.0 x 10(-6)M (0.23ppm). It could be used in a pH range of 3.0-8.0 and has a fast response time of about 15s. The proposed sensor was used for the determination of thiocyanate ions in real samples such as urine and saliva of smokers and nonsmokers and, as an indicator electrode, in potentiometric titrations of SCN(-) ion.

Hydroxy-thioxanthones as suitable neutral ionophores for the preparation of PVC-membrane potentiometric sensors for Al(III) ion.

The complexation of five recently synthesized hydroxy-thioxanthone derivatives with Al3+ ion was studied in a methanol solution spectrophotometrically, and the stepwise formation constants of the resulting 1:1 and 2:1 (ligand-to-metal) complexes were evaluated. The suitability of the thioxanthone derivatives as neutral ionophores for the preparation of a new Al3+ ion-selective PVC-membrane electrode was investigated, and 1-hydroxy-3-methyl-thiocanthone was selected as the best compound for this purpose. The prepared electrode exhibits a Nernstian response for Al3+ ions over a wide concentration range (2.0 x 10(-2) to 2.0 x 10(-6) M), with a limit of detection of 1.0 x 10(-6) M. It has a very fast response time of about 5 s and can be used for at least 3 months without any considerable divergence in the potentials. The proposed membrane sensor revealed very good selectivities for Al3+ over a wide variety of other metal ions, and could be used at a working pH range of 3.4 - 5.0. It was used as an indicator electrode in potentiometric titration of aluminum ions with EDTA, and in the determination of Al3+ in different real samples.