ABSTRACT
Although the crystals of coordination polymer {[CuCl(µ-O,O'-L-Br2Tyr)]}n (1) (L-Br2Tyr = 3,5-dibromo-L-tyrosine) were formed under basic conditions, crystallographic studies revealed that the OH group of the ligand remained protonated. Two adjacent [CuCl(L-Br2Tyr)] monomers, bridged by the carboxylate group of the ligand in the syn-anti bidentate bridging mode, are differently oriented to form a polymeric chain; this specific bridging was detected also by FT-IR and EPR spectroscopy. Each Cu(II) ion in polymeric compound 1 is coordinated in the xy plane by the amino nitrogen and carboxyl oxygen of the parent ligand and the oxygen of the carboxyl group from the symmetry related ligand of the adjacent [Cu(L-Br2Tyr)Cl] monomer, as well as an independent chlorine ion. In addition, the Cu(II) ion in the polymer chain participates in long-distance intermolecular contacts with the oxygen and bromine atoms of the ligands located in the adjacent chains; these intramolecular contacts were also supported by NCI and NBO quantum chemical calculations and Hirshfeld surface analysis. The resulting elongated octahedral geometry based on the [CuCl(L-Br2Tyr)] monomer has a lower than axial symmetry, which is also reflected in the symmetry of the calculated molecular EPR g tensor. Consequently, the components of the d-d band obtained by analysis of the NIR-VIS-UV spectrum were assigned to the corresponding electronic transitions.
ABSTRACT
This study investigated the sorption of Ni(ii) ions from an aqueous solution using novel, synthetic amino-hypophosphite polyampholyte resin (AHP) in a batch adsorption system. The removal of Ni(ii) ions was determined as a function of pH (2.0-8.0), initial concentration of Ni(ii) ions (2.0-20.0 mM), resin dosage (1.0-10.0 g dm-3), contact time (0.04-24 h), and temperature (298-318 K). Moreover, continuous fixed-bed column sorption was also studied using model solutions and actual wastewater from the galvanising plant. The batch sorption experimental data showed that the maximum pH for efficient Ni(ii) ion removal was about 5.0. An equilibrium was reached after about 24 hours. The kinetics results were fitted using pseudo-first-order (PFO), pseudo-second-order (PSO), liquid film (LFD), and intraparticle diffusion (IPD) models. Freundlich and Langmuir isotherm models were applied for sorption equilibrium data. The maximum sorption capacity was obtained from the Langmuir equation to be 2.39, 2.52, and 2.62 mmol g-1 at 298, 308, and 318 K, respectively. The thermodynamic parameters for the sorption of Ni(ii) ions on AHP imply the endothermic and spontaneous character of the process. The experimental results demonstrated that amino-hypophosphite polyampholyte resin could be used to effectively remove Ni(ii) ions from model solutions and real wastewater.
ABSTRACT
The encapsulation of a set of small molecules, H2, CO, CO2, SO2, and SO3, by a circular C18 ring is investigated by quantum calculations. These ligands lie near the center of the ring but, with the exception of H2, are disposed roughly perpendicular to the ring plane. Their binding energies with the C18 vary from 1.5 kcal/mol for H2 up to 5.7 kcal/mol for SO2, and the bonding is dominated by dispersive interactions spread over the entire ring. The binding of these ligands on the outside of the ring is weaker but allows the opportunity for each to bond covalently with the ring. A pair of C18 units lie parallel to one another. This pair can bind each of these ligands in the area between them with only small perturbations of the double ring geometry. The binding energies of these ligands to this double ring configuration are amplified by some 50% compared to the single ring systems. The presented data concerning the trapping of small molecules may have larger implications regarding hydrogen storage or air pollution reduction.
