Copper(II) complexes containing pyridine-based and phenolate-based systems: Synthesis,characterization, DFT study,biomimetic catalytic activity of catechol oxidase and phenoxazinone synthase

A template Schiff condensation of 2,6-pyridine dicarbaldehyde or 2,6-diformyl-4- bromophenol and 1,3–diamino-2-hydroxy propane or 3,4-diaminotoluene in the presence of copper(II) salts (CuX₂) (X = Cl, Br, CH₃COO, or ClO₄) affords different types of copper(II) complexes. Depending on the employed molar ratio of the dicarbonyl compounds and diamines, different types of copper(II) complexes formed during the template condensation reaction. Structural formulation of the complexes was confirmed by elemental analysis (C, H, N, and M), physical measurements such as thermal analysis (TAG & DTG), molar conductivity, and magnetic moments in addition to spectral studies (UV–Vis, IR, and ESR). Homobinuclear in a four-coordinate square planar and five-coordinate square pyramidal and trigonal bipyramidal in monomeric structures are proposed. A mononuclear hexa-coordinate in an octahedral geometry is suggested as well. Oxidase biomimetic catalytic activity of these newly synthesized copper(II) complexes was examined toward the aerobic oxidation of 4-tert-butylcatechol (4-TBCH₂) and o-aminophenol under catalytic conditions. Both catalytic and kinetic investigations demonstrate promising oxidase catalytic activity and based on the kinetic results, probable mechanistic catalytic implications are discussed. Geometrical structures of representative copper(II) complexes were determined by optimizing their bond lengths, bond angles, dihedral angles, and the structural index (τ).     

N,N'-dipyridoxyl Schiff bases: synthesis, experimental and theoretical characterization

Three N,N'-dipyridoxyl Schiff bases (L1, L2 and L3) have been newly synthesized and characterized by IR, (1)H NMR, mass spectrometry and elemental analysis. Their optimized geometries together with the theoretical assignment of the vibrational frequencies and the (1)H NMR chemical shifts of them have been computed by using density functional theory (DFT) method. In the optimized structures of the Schiff bases, two pyridine rings are not in a same plane; however the substitutions are essentially in the same plane with the pyridine rings. Also, the benzene ring(s) in the bridge region is (are) not in the same plane with the pyridine rings and azomethine moieties. In all the species, engagement in intramolecular-hydrogen bonds causes to weakness of the phenolic O-H bonds. Consistency between the theoretical results and experimental evidence confirms suitability of the optimized geometries for the synthesized Schiff bases.     

Biosorption of beryllium from aqueous solutions onto modified chitosan resin: Equilibrium,kinetic and thermodynamic study

The goal of the present work is the recovery of beryllium ion from their solution by modified chitosan hydrogel. Chitosan was chemically cross-linked with glutaraldehyde to prevent its dissolution in aqueous acidic solutions. The obtained chitosan/glutaraldehyde adsorbent was reacted with chloroacetic acid to produce carboxymethyl chitosan (CMC), which was converted into sodium form by reaction with sodium hydroxide solution to increase its hydrophilic properties. The chemically synthesized chitosan adsorbent contains carboxylate group that expected to have a strong affinity to beryllium ions according to the hard-soft acid-base concept by Pearson because that beryllium ion is a hard acid and has smaller ionic radii. The synthesized adsorbent was characterized and its affinity towards beryllium ions was tested. The different experimental parameters including pH, beryllium concentration, agitation period and temperature were studied to optimize the biosorption process. The maximum biosorption values of beryllium species on the investigated biosorbent are 44.96 and 36.72?mg/g at pH 1 and 5, respectively. Kinetics and thermodynamic parameters of the biosorption process were evaluated from kinetic and biosorption experiments. The adsorbed beryllium species were eluted with a 3?M H₂SO₄ solution.     

Asymmetric effects of polymers in finite thermoviscoplasticity

Glassy polymers such as polycarbonate exhibit different behaviours in different loading scenarios, such as tension and compression. For the simulation of these asymmetric effects we present a framework for thermoviscoplastic modelling of polymers at large strains. To this end a flow rule is postulated within a thermodynamic consistent framework in a mixed variant formulation which is decomposed into a sum of weighted stress mode related quantities. The different stress modes are chosen such that they are accessible to individual examination in the laboratory, where tension and compression are typical examples. The characterisation of the stress modes is obtained in the octahedral plane of the deviatoric stress space in terms of the Lode angle, such that stress mode dependent scalar weighting functions can be constructed. Furthermore the numerical implementation of the resulting set of constitutive equations is used in the finite element program ABAQUS to simulate the laser transmission welding process. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)