Magnetic ordering versus lattice distortion in very narrow bands

A simple criterion for antiferromagnetic ordering versus lattice distortion in very narrow band materials is obtained. The model describing these narrow band materials contains the Hubbard Hamiltonian, short ranged interatomic Coulomb and exchange interactions, and the electron-phonon interaction.     

Two exact models of charged dust collapse

Liang studied three classes of irrotational dust collapse models with high symmetries. Here the charged analogs of the models with spherical and plane symmetry are considered. Contrary to Liang's result that the plane-symmetric model with positive mass cannot have a static exterior we find that the corresponding charged model may have bounce and a static exterior.     

Axially symmetric stationary electrovac solutions

Perjes and Israel and Wilson have given independently a new class of solutions of the sourcefree Einstein-Maxwell equations, which can be interpreted as the external gravitational and electromagnetic fields of a spinning source with unit specific charge. Starting from Zipoy's solutions in oblate and prolate spheroidal coordinates for the source-free gravitational field we generate some axially symmetric stationary solutions of the source-free Einstein-Maxwell equations by using Perjes' method. All these solutions become Euclidean at infinity. The asymptotic behavior and the singularity of the solutions are studied in order to gain some insight into the nature of the source. The solution in prolate spheroidal coordinates is found to contain closed timelike lines.     

Kinetics and mechanism of the oxidation of substituted benzaldehydes by benzyltrimethylammonium chlorobromate

The oxidation of 35 monosubstituted benzaldehydes by benzyltrimethylammonium chlorobromate (BTMACB) in aqueous acetic acid leads to the formation of the corresponding benzoic acids. The reaction is first order with respect to both benzaldehyde and BTMACB. The reaction failed to induce the polymerization of acrylonitrile. There is no effect of benzyltrimethylammonium chloride or potassium bromide on the reaction rate. The oxidation of [(2)H]benzaldehyde (PhCDO) indicated the presence of a substantial kinetic isotope effect. The effect of solvent composition indicated that the reaction rate increases with an increase in the polarity of the solvent. The rates of oxidation of meta- and para-substituted benzaldehydes were correlated in terms of Charton's triparametric LDR equation, whereas the oxidation of ortho-substituted benzaldehydes was correlated with the tetraparametric LDRS equation. The oxidation of para-substituted benzaldehydes is more susceptible to the delocalization effect, whereas the oxidation of ortho-and meta-substituted compounds displayed a greater dependence on the field effect. The positive value of eta suggests the presence of an electron-deficient reaction center in the rate-determining step. The reaction is subjected to steric hindrance by the ortho substituents.     

A facile synthesis and crystallographic analysis of N-protected β-amino alcohols and short peptaibols

A facile, efficient and racemization-free method for the synthesis of N-protected β-amino alcohols and peptaibols using N-hydroxysuccinimide active esters is described. Using this method, dipeptide, tripeptide and pentapeptide alcohols were isolated in high yields. The conformations in crystals of β-amino alcohol, dipeptide and tripeptide alcohols were analysed, with a well-defined type III β-turn being observed in the tripeptide alcohol crystals. This method is found to be compatible with Fmoc-, Boc- and other side-chain protecting groups.     

"Directed" assembly of metallacalix[n]arenes with pyrimidine nucleobase ligands of low symmetry: metallacalix[n]arene derivatives of cis-[a2M(cytosine-N3)2]2+ (M=Pt(II), Pd(II); n=4 and 6)

Pyrimidine (pym) ligands with their two endocyclic N‐donor atoms provide 120° angles for molecular constructs, which, with the 90° angle metal fragments cis‐a₂M^II (M=Pt, Pd; a=NH₃ or a₂=diamine), form cyclic complexes known as metallacalix[n]arenes (with n=3, 4, 6, 8, …?). The number of possible isomers of these species depends on the symmetry of the pym ligand. Although highly symmetrical (C_2v) pym ligands form a single linkage isomer for any n and can adopt different conformations (e.g., cone, partial cone, 1,3‐alternate, and 1,2‐alternate in the case of n=4), low‐symmetry pym ligands (C_s) can produce a higher number of linkage isomers (e.g., four in the case of n=4) and a large number of different conformers. In the absence of any self‐sorting bias, the number of possible species derived from a self‐assembly process between cis‐a₂M^II and a C_s‐symmetrical pym ligand can thus be very high. By using the C_s‐symmetric pym nucleobase cytosine, we have demonstrated that the number of feasible isomers for n=4 can be reduced to one by applying preformed building blocks such as cis‐[a₂M(cytosine‐N3)₂]ⁿ⁺ or cis‐[a₂M(cytosinate‐N1)₂] (for the latter, see the accompanying paper: A. Khutia, P. J. Sanz Miguel, B. Lippert, Chem. Eur. J. 2011 , 17, DOI: 10.1002/chem.2010002723) and treating them with additional cis‐a₂M^II. Moreover, intramolecular hydrogen‐bonding interactions between the O2 and N4H₂ sites of the cytosine ligands reduce the number of possible rotamers to one. This approach of the “directed” assembly of a defined metallacalix[4]arene is demonstrated.     

Particle physics models of inflation and curvaton scenarios

We review the particle theory origin of inflation and curvaton mechanisms for generating large scale structures and the observed temperature anisotropy in the cosmic microwave background (CMB) radiation. Since inflaton or curvaton energy density creates all matter, it is important to understand the process of reheating and preheating into the relevant degrees of freedom required for the success of Big Bang Nucleosynthesis. We discuss two distinct classes of models, one where inflaton and curvaton belong to the hidden sector, which are coupled to the Standard Model gauge sector very weakly. There is another class of models of inflaton and curvaton, which are embedded within Minimal Supersymmetric Standard Model (MSSM) gauge group and beyond, and whose origins lie within gauge invariant combinations of supersymmetric quarks and leptons. Their masses and couplings are all well motivated from low energy physics, therefore such models provide us with a unique opportunity that they can be verified/falsified by the CMB data and also by the future collider and non-collider based experiments. We then briefly discuss the stringy origin of inflation, alternative cosmological scenarios, and bouncing universes.     

Doping dependent evolution of magnetism and superconductivity in Eu(1-x)K(x)Fe2As2 (x = 0-1) and temperature dependence of the lower critical field H(c1)

We have synthesized polycrystalline samples of Eu(1-x)K(x)Fe2As2 (x = 0-1) and carried out systematic characterization using x-ray diffraction, ac and dc magnetic susceptibility, and electrical resistivity measurements. A clear signature of the coexistence of a superconducting transition (T(c) = 5.5 K) with spin density wave (SDW) ordering is observed in our underdoped sample with x = 0.15. The SDW transition disappears completely for the x = 0.3 sample and superconductivity arises below 20 K. The superconducting transition temperature Tc increases with increase in the K content and a maximum Tc = 33 K is reached for x = 0.5, beyond which it decreases again. The doping dependent Tx phase diagram is extracted from the magnetic and electrical transport data. It is found that magnetic ordering of Eu moments coexists with the superconductivity up to x = 0.6. The isothermal magnetization data taken at 2 K for the doped samples suggest the 2+ valence state of the Eu ions. We also present the temperature dependence of the lower critical field H(c1) of the superconducting polycrystalline samples. The values of H(c1)(0) obtained for x = 0.3, 0.5, and 0.7 after taking the demagnetization factor into account are 202, 330, and 212 Oe, respectively. The London penetration depth λ(T) calculated from the lower critical field does not show exponential dependence at low temperature, as would be expected for a fully gapped clean s-wave superconductor. In contrast, it shows a T2 power law feature up to T = 0.3Tc, as observed in Ba(1-x)K(x)Fe2As2 and BaFe(2-x)Co(x)As2.     

Catalytic activity of an iron(III) Schiff base complex bound in a polymer resin

An iron(III)–ferrocene complex and its heterogeneous analogue bound in a polymer resin have been prepared and employed as catalysts for the oxidation of various organic substrates. Characterization of the heterogeneous and homogeneous complexes was done by SEM, EDAX, TGA, FT-IR, DRS-UV, and spectroscopy. The catalyst’s activity, stability, and reusability were investigated through industrially relevant oxidation reactions. The solid iron(III)–ferrocene Schiff base complex gave more effective results than the solid-supported ferrocene Schiff base ligand. The antimicrobial activities of the molecular complex and free ligand were studied for Gram-positive and Gram-negative bacteria.     

Large‐scale separation of antipsychotic alkaloids from Rauwolfia tetraphylla L. by pH‐zone‐refining fast centrifugal partition chromatography

pH‐zone‐refining centrifugal partition chromatography was successively applied in the large‐scale separation of close R_f antipsychotic indole alkaloids directly from CHCl₃ fraction of Rauwolfia tetraphylla leaves. Two experiments with increasing mass from 500 mg to 3 g of crude alkaloid extracts ( 1 C) of R. tetraphylla were carried out in normal‐displacement mode using a two‐phase solvent system composed of methyl tert‐butyl ether/ACN/water (4:1:5, v/v/v) where HCl (12 mM) was added to the lower aqueous stationary phase as a retainer and triethylamine (5 mM) to the organic mobile phase as an eluter. The two centrifugal partition chromatography separations afforded a total of 162.6 mg of 10‐methoxytetrahydroalstonine ( 1 ) and 296.5 mg of isoreserpiline ( 2 ) in 97% and 95.5% purity, respectively, along with a 400.9 mg mixture of α‐yohimbine and reserpiline ( 3 and 4 ). Further, this mixture was resolved over medium pressure LC using TLC grade silica gel H (average particle size 10 μm), which afforded 160.4 mg of α‐yohimbine ( 3) and 150.2 mg of reserpiline ( 4) in >95% purities. The purity of the isolated antipsychotic alkaloids was analyzed by high‐performance LC and their structures were characterized on the basis of their 1D, 2D NMR and electrospray ionization‐mass spectroscopic data.