Straightforward and Highly Diastereoselective Synthesis of a New Set of Functionalized Dispiropyrrolidines Involving Multicomponent 1,3‐Dipolar Cycloaddition with Azomethine Ylides

The diastereoselective synthesis of novel series of dispiropyrrolidines has been achieved by a one‐pot three‐component [3 + 2] cycloaddition reaction of (E)‐2‐arylideneindanones, glycine ethyl ester, and the cyclic diketones 1H‐indole‐2,3‐dione (isatin) or acenaphthenequinone. Moreover, we disclose an unprecedented epimerization of spiroadducts leading to a new family of dispiropyrrolidines with an unusual relative stereochemistry.     

Existence and Asymptotic Behavior of Boundary Blow-up Weak Solutions for Problems Involving the p-Laplacian

Let D⊂R^N(N ≥ 3), be a smooth bounded domain with smooth boundary ∂D. In this paper, the existence of boundary blow-upweak solutions for the quasilinear elliptic equation Δ_pu=λk(x) f (u) in D(λ > 0 and 1 < p < N), is obtained under new conditions on k. We give also asymptotic behavior near the boundary of such solutions.     

Random crystal field effect on hysteresis loops and compensation behavior of mixed spin-(1, 3/2) Ising system

Magnetic hysteresis and compensation behavior of a mixed spin-(1, 3/2) Ising model on a square lattice are investigated in the framework of effective field theory based on a probability distribution technique. The effect of random crystal field, ferromagnetic and ferrimagnetic exchange interaction on hysteresis loops and compensation phenomenon are discussed. A number of characteristic phenomena have been reported such as the observation of triple hysteresis loops at low temperatures and for negative values of random crystal field. Critical and double compensation temperatures have been also found. The obtained results are also compared to some previous works.     

Role of Basic Surface Groups of Activated Carbon in Chlordecone and β-Hexachlorocyclohexane Adsorption: A Molecular Modelling Study

The influence of nitrogen-containing surface groups (SGs) onto activated carbon (AC) over the adsorption of chlordecone (CLD) and β-hexachlorocyclohexane (β-HCH) was characterized by a molecular modelling study, considering pH (single protonated SGs) and hydration effect (up to three water molecules). The interactions of both pollutants with amines and pyridine as basic SGs of AC were studied, applying the multiple minima hypersurface (MMH) methodology and using PM7 semiempirical Hamiltonian. Representative structures from MMH were reoptimized using the M06-2X density functional theory. The quantum theory of atoms in molecules (QTAIM) was used to characterize the interaction types in order understanding the adsorption process. A favorable association of both pesticides with the amines and pyridine SGs onto AC was observed at all pH ranges, both in the absence and presence of water molecules. However, a greater association of both pollutants with the primary amine was found under an acidic pH condition. QTAIM results show that the interactions of CLD and β-HCH with the SGs onto AC are governed by Cl···C interactions of chlorine atoms of both pesticides with the graphitic surface. Electrostatic interactions (H-bonds) were observed when water molecules were added to the systems. A physisorption mechanism is suggested for CLD and β-HCH adsorption on nitrogen-containing SGs of AC.     

First-principles study of rocksalt MgxZn1− xO: band structure and optical spectra

ABSTRACT

The present work deals with electronic band structure and derived optical spectra of Mg_xZn_1?xO in the hypothetical rocksalt structure. The computations are performed using full-potential linearised augmented plane wave method. The exchange–correlation potential is described using the Wu-Cohen and Tran-Blaha modified Becke–Johnson generalised gradient approximation (TB-mBJ-GGA). The calculated lattice parameter deviates by less than 1% from experiment showing a net improvement when compared with previous calculations. Moreover, its variation with respect to x does not violate Vegard's law. The TB-mBJ-GGA approach improves the magnitude of the fundamental band gap with respect to experiment. The rocksalt Mg_xZn_1?xO is found to be an indirect gap semiconductor for x?=?0, 0.25, 0.50 and 0.75 and a direct gap semiconductor for x?=?1. The nature of the gap for rocksalt Mg_xZn_1?xO is still in controversy and further investigations are required in this respect. The optical spectra of Mg_xZn_1?xO are analysed and discussed. Our findings yield values of 1.55 and 1.25 for the static refractive index and 2.4 and 1.55 for the static dielectric constant for rocksalt ZnO and rocksalt MgO, respectively.     

S(N)Ar-based, facile synthesis of a library of benzothiaoxazepine-1,1'-dioxides

The construction of a library of benzothiaoxazepine-1,1'-dioxides utilizing a one-pot, S(N)Ar diversification-ODCT(50) scavenging protocol is reported. This protocol combines microwave irradiation to facilitate the reaction, in conjunction with a soluble ROMP-derived scavenger (ODCT) to afford the desired products in good overall purity. Utilizing this protocol, a 78-member library was successfully synthesized and submitted for biological evaluation.     

The oxidation of Fe(OH)2 in the presence of carbonate ions: Structure of carbonate green rust one

Sodium carbonate Na₂CO₃ is added to a solution containing an Fe(OH)₂ precipitate in order to study the influence of CO ₃ ^2– ions on the oxidation of ferrous hydroxide. The first stage of the reaction leads to a ferrous-ferric compound, the carbonate green rust one (GR1), identified by its X-ray diffraction pattern. The Mössbauer spectrum at 78 K of this GR1 displays two ferrous doublets and one ferric doublet in the 312 abundance ratio. The quadrupole splittingsQS are 2.91, 2.58 and 0.42 mm/s, respectively, and the isomer shifts 75 are 1.25, 1.25 and 0.47 mm/s respectively. These values are very close to those of the three doublets of the chloride GR1, 3Fe(OH)₂Cl·Fe(OH)₂Cl·nH₂O. This fact confirms that the crystallographic structures of these two GR1s are similar, formed by the stacking of hydroxide layers and interlayers containing the considered anions (Cl^– or CO ₃ ^2– ) and water molecules. The chemical formula of carbonate GR1 is Fe ₄ ^(II) Fe ₂ ^(III) (OH)₁₂CO₃·nH₂O, and its standard chemical potential -853 900 cal/mol ifn=0. The second stage of the reaction is the oxidation of GR1, which leads to -FeOOH goethite.