Separation and pre-concentration of palladium(II) from environmental and industrial samples by formation of a derivative of 1,2,4-triazole complex on Amberlite XAD–2010 resin

A simple separation/pre-concentration method was developed for extraction of Pd(II) in various environmental samples, based on its adsorption of 4–phenyl–5–{[(4–phenyl–5–pyridin–4–yl–4H–1,2,4–triazole–3–yl)thio]methyl}–4H–1,2,4–triazole–3–thyol (PPTTMET) complex on Amberlite XAD–2010 resin in a mini column. The ligand has high affinity for Pd(II) among many other metals that are taken into consideration. The flame atomic absorption spectrometry is employed to determine the concentration of Pd(II). The optimum working conditions which were determined are as follows: 0.05?mol?L^?1 HNO₃ as working medium, 1.0?mol?L^?1 HCI in acetone as elution solvent, 0.75?mg of PPTTMET amount and 750?mL of sample volume. The system was independent from the flow rates between 3.1 and 23.1?mL?min^?1. The Pd(II) adsorption capacity of Amberlite XAD–2010 resin was found to be 12.8?mg?g^?1 and the enrichment factor was calculated as 375. The method was successfully applied for the determination of Pd(II) in motorway dust samples, anodic sludge, gold ore, industrial electronic waste materials and various water samples.     

Copper (II)-Surfactant Complex and Its Nano Analog as Potential Antitumor Agents

The in vitro anticancer activity of copper cetyl trimethyl ammonium bromide (Cu-CTAB)-loaded cyclodextrin nanoparticles on Ehrlich ascites carcinoma (EAC), colon cancer cells (HCT 116), liver cancer cells (HepG-2), breast cancer cells (MCF-7), and cervix cancer cells (Hela) was investigated using MTT due assay. Cyclodextrin nanoparticles loaded with Cu-CTAB exerted in vitro anticancer activity against the previous human cancer cell lines comparable to the activity of free non-entrapped in nanoparticles macro-particle Cu-CTAB. The nano analog was synthesized by physical loading using grinding with ball mill. The ratio between Cu-CTAB and cyclodextrin oligosaccharide was 1 Cu-CTAB: 3 cyclodextrin. The particle size of the nano derivative was determined using the transmitted electron microscope (TEM).     

Anomeric effect and theoretical vibrational spectra compared to the experiment in 2-chloro-1,3,2-dioxaphosphorinane-2-oxide, -sulfide,and -selenide. I. Anomeric effect and structures

2-Chloro-1,3,2-dioxaphosphorinane-2-oxide, -sulfide, and -selenide are studied at the DFT/B3LYP level and several ab initio methods using a 6-311G** basis set. Our energy optimizations by all these methods show that for oxide DFT and ab initio methods are not much different, while for the sulfide and the selenide the DFT relative energies are higher by about a kcal/mol as compared to those of MP2, MP3, MP4(SDTQ)//MP2, and CCSD(T)//MP2 (//MP2 indicates that a single-point calculation based on the MP2 optimized geometry is performed). However, regardless of rather large relative energies, that does not change the fact that in all three cases the conformational equilibrium mixture contains more than 95% of the lowest, chair-equatorial conformer (this indicates that the P=X bond is in equatorial position). This one and the next higher conformer (chair-axial) are confirmed to be real conformers (energy minima) in all cases. The energetically much higher twist and boat forms are probably just stationary states and local maxima because in many cases, geometry optimizations do not converge to them. Only for MP2 and the selenide do all optimizations converge to the desired stationary state. The relative energies could all be explained in terms of anomeric effects and ring strains. The decreasing covalent character of the P=X bond, with X changing from O to S and to Se, shows itself in the increasing bond lengths and the decreasing strength of anomeric effects.     

Stereoelectronic requirements for optimal hydrogen-bond-catalyzed enolization

Protein crystallographic analysis of the active sites of enolizing enzymes and structural analysis of hydrogen-bonded carbonyl compounds in small molecule crystal structures, complemented by quantum chemical calculations on related model enolization reactions, suggest a new stereoelectronic model that accounts for the observed out-of-plane orientation of hydrogen-bond donors (HBDs) in the oxyanion holes of enolizing enzymes. The computational results reveal that the lone-pair directionality of HBDs characteristic for hydrogen-bonded carbonyls is reduced upon enolization, and the enolate displays almost no directional preference for hydrogen bonding. Positioning the HBDs perpendicular to the carbonyl plane induces strain in the catalyst-substrate complex, which is released upon enolization, resulting in more favorable kinetics and thermodynamics than the in-plane arrangement of HBDs.     

An introduced effective-field theory study of spin-1 transverse Ising model with crystal field anisotropy in a longitudinal magnetic field

A spin-1 transverse Ising model with longitudinal crystal field in a longitudinal magnetic field is examined by introducing an effective field approximation (IEFT) which includes the correlations between different spins that emerge when expanding the identities. The effects of the crystal field as well as the transverse and longitudinal magnetic fields on the thermal and magnetic properties of the spin system are discussed in detail. The order parameters, Helmholtz free energy, entropy and specific heat curves are calculated numerically as functions of the temperature and Hamiltonian parameters. A number of interesting phenomena such as reentrant phenomena originating from the temperature, crystal field, transverse and longitudinal magnetic fields have been found.