Ab initio investigation of the structural and unusual electronic properties of α-CuSe （klockmannite）

In this article, a computational analysis has been performed on the structural properties and predominantly on the electronic properties of the α-CuSe （klockmannite） using density functional theory. The studies in this work show that the best structural results, in comparison to the experimental values, belong to the PBEsol-GGA and WC-GGA functionals. However, the best results for the bulk modulus and density of states （DOSs） are related to the local density approximation （LDA） functional. Through utilized approaches, the LDA is chosen to investigate the electronic structure. The results of the electronic properties and geometric optimization of α-CuSe respectively show that this compound is conductive and non-magnetic. The curvatures of the energy bands crossing the Fermi level explicitly reveal that major charge carriers in CuSe are holes, whose density is estimated to be 0.86×1022 hole/cm3. In particular, the Fermi surfaces in the first Brillouin zone demonstrate interplane conductivity between （001） planes. Moreover, the charge carriers among them are electrons and holes simultaneously. The conductivity in CuSe is mainly due to the hybridization between the d orbitals of Cu atoms and the p orbitals of Se atoms. The former orbitals have the dual nature of localization and itinerancy.     

Molecular complexation of free base meso-tetraarylporphyrins with antimony(III) chloride in free solvent media

The reaction of meso-tetraarylporphyrins (H₂t(Xp)p) with SbCl₃ under free solvent conditions affords green complexes with a 1:1 H₂t(X)pp:SbCl₃ ratio. These complexes have dimeric structures with a (μ-Cl)₂bridge. UV–VIS, ¹H NMR and ¹³C NMR spectra data show that the porphyrin core of [(H₂t(Xp)p)₂Sb₂Cl₆], similar to 1:2 (donor:acceptor) molecular complexes of meso-tetraarylporphyrins and porphyrin diacid, is distorted, thus two nitrogen atoms of pyrrolenine in a side of the porphyrin plane act as electron donors to an antimony atom of SbCl₃. Molecular complexation of meso-tetraarylporphyrins with SbCl₃ produces a large downfield shift for the NH signal, although there is no hydrogen bonding present.     

Synthesis,characterization, anticancer activity,thermal and electrochemical studies of some novel uranyl Schiff base complexes

Some tetradentate N₂O₂ Schiff base ligands, such as N,N′-bis(naphtalidene)-1,2-phenylenediamine, N,N′-bis(naphtalidene)-4-methyl-1,2-phenylenediamine, N,N′-bis(naphtalidene)-4-chloro-1,2-phenylenediamine, N,N′-bis(naphtalidene)-4-nitro-1,2-phenylenediamine, N,N′-bis(naphtalidene)-4-carboxyl-1,2-phenylenediamine, and their uranyl complexes were synthesized and characterized by ¹H NMR, IR, UV–Vis spectroscopy, TG (thermogravimetry), and elemental analysis (C.H.N.). Thermogravimetric analysis shows that uranyl complexes have very different thermal stabilities. This method is used also to establish that only one solvent molecule is coordinated to the central uranium ion and this solvent molecule does not coordinate strongly and is removed easier than the tetradentate ligand and also trans oxides. The electrochemical properties of the uranyl complexes were investigated by cyclic voltammetry. Electrochemistry of these complexes showed a quasireversible redox reaction without any successive reactions. Also, the kinetic parameters of thermal decomposition were calculated using Coats–Redfern equation. According to Coats–Redfern plots the kinetics of thermal decomposition of the studied complexes is first-order in all stages. Anticancer activity of the uranyl Schiff base complexes against cancer cell lines (Jurkat) was studied and determined by MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazoliumbromide) assay.     

Vector Product Approach of Producing Non-Gaussian States

International Journal of Theoretical Physics - Two new configurations of superposition of quantum states corresponding to the angular momentum of spin-1 quantum system is proposed in this article....     

Proton radioactivity half-lives with nuclear asymmetry factor

The dependence of proton emission half-lives on the nuclear asymmetry parameter is investigated using the WKB method and two types of empirical formula.Using the single-folding formalism with asymmetry-depend-ent nuclear radius and surface diffuseness of nuclear matter,the nuclear potential and consequently the half-life are functions of the asymmetry factor.Despite small values of asymmetry in neutron-deficient proton emitters,notice-able changes in the half-lives are observed.The addition of an asymmetry parameter term to the two forms of empir-ical formulas leads to a reduction in the rms error for ground state and isomeric transitions.A noticeable reduction of about 43%is obtained for isomeric transitions in the second form of the empirical formula.Considering ground state transitions in two categories,odd-even and odd-odd emitters,and adopting deformation and asymmetry-dependent empirical formulas,the rms decreases remarkably.The low est values of rms errors,viz.0.1492,0.2312,and 0.1999,are obtained for the aforementioned empirical formulas for ground state transitions of odd-even and odd-odd emit-ters and for all isomeric transitions,respectively.     

Determination of haloperidol in biological samples with the aid of ultrasound‐assisted emulsification microextraction followed by HPLC‐DAD

A rapid and simple quantitative method for preconcentration and determination of haloperidol in biological samples was developed using ultrasound‐assisted emulsification microextraction, based on the solidification of floating organic droplet combined with HPLC‐DAD. The effects of several factors were investigated. A total of 30 μL of 1‐undecanol as an extraction solvent was injected slowly into a glass‐centrifuge tube containing 4 mL alkaline sample solution that was located inside the ultrasonic water bath. The formed emulsion was centrifuged and the fine droplets of solvent were floated at the top of the test tube, then it was cooled in an ice bath and the solidified solvent was transferred into a conical vial, after melt, the analysis of the extract was carried out by HPLC. Under the optimal conditions, the extraction efficiencies were more than 90% and the preconcentration factors were obtained between 119–122. The LOQs were obtained between 4–8 μg/L and the calibration curves were linear within the range of 4–1000 μg/L. Finally this method was applied to the determination of haloperidol in plasma and urine samples in the range of μg/L and satisfactory results were achieved (RSDs <7%).     

Towards click chemistry: Multicomponent reactions via combinations of name reactions

In this report, we try to show the importance of incorporation of name reactions in the sequential cascade reaction in which significantly decreasing the number of steps towards an ideal and practical multi-step synthesis of natural products as well showing virtually all the advantages already mentioned for “Click Chemistry”. In addition, since the chiral inductions are desired for most of these sequential name reactions, their asymmetric catalyzed reactions were also described.     

Study of the effect of the ligand structure on the catalytic activity of Pd@ ligand decorated halloysite: Combination of experimental and computational studies

Taking advantage of computational chemistry, the best diamine for the synthesis of a multi‐dentate ligand from the reaction with 3‐(trimethoxysilyl) propylisocyanate (TEPI) was selected. Actually, predictive Density Functional Theory (DFT) calculations provided the right diamino chain, i.e. ethylenediamine, capable to sequester a palladium atom, together with the relatively polar solvent toluene, and then undergo the experiments as a selective catalytic agent. The ligand was then prepared and applied for the decoration of the halloysite (Hal) outer surface to furnish an efficient support for the immobilization of Pd nanoparticles. The resulting catalyst exhibited high catalytic activity for hydrogenation of nitroarenes. Moreover, it showed high selectivity towards nitro functional group. The study of the catalyst recyclability confirmed that the catalyst could be recycled for several reaction runs with only slight loss of the catalytic activity and Pd leaching. Hot filtration test also proved the heterogeneous nature of the catalysis.