Preferential sites for InAsP/InP quantum wire nucleation using molecular dynamics

In this paper, stress fields at the surface of the capping layer of self-assembled InAsP quantum wires grown on an InP (001) substrate have been determined from atomistic models using molecular dynamics and Stillinger-Weber potentials. To carry out these calculations, the quantum wire compositional distribution was extracted from previous works, where the As and P distributions were determined by electron energy loss spectroscopy and high-resolution aberration-corrected Z-contrast imaging. Preferential sites for the nucleation of wires on the surface of the capping layer were studied and compared with (i) previous simulations using finite element analysis to solve anisotropic elastic theory equations and (ii) experimentally measured locations of stacked wires. Preferential nucleation sites of stacked wires were determined by the maximum stress location at the MD model surface in good agreement with experimental results and those derived from finite element analysis. This indicates that MD simulations based on empirical potentials provide a suitable and flexible tool to study strain dependent atom processes.     

Complex response function of magnetic resonance spectrometers

A vectorial analysis of magnetic resonance spectrometers, based on traveling wave resonators and including the reference arm and the automatic control of frequency, has been developed. The proposed model, valid also for stationary wave resonators, gives the response function of the spectrometer for any working condition, including scalar detectors with arbitrary response law and arbitrary excitation frequency. The purely dispersive and purely absorptive linear responses are discussed in detail for different scalar detectors. The developed approach allows for optimizing the performances of the spectrometer and for obtaining the intrinsic lineshape of the sample in a very broad range of working conditions. More complex setups can be modeled following the proposed scheme.     

High frequency single-mode resonators for EPR spectroscopy enabling rotations of the sample about two orthogonal axes

A novel single-mode resonant structure which enables the rotation of the sample about two orthogonal axes is investigated in view of electron paramagnetic resonance applications. The proposed solution is based on cylindrical non-radiative resonators laterally loaded by the sample holder. The resulting structure can still operate in non-radiative regime, although no longer rotationally invariant. These theoretical predictions, based on symmetry considerations, are confirmed by means of a finite element numerical modelling. Theoretical and computational results are then substantiated by experimental investigations at millimeter wavelengths. As a result, a single-mode resonator which enables all the relevant rotations of the sample is demonstrated at millimeter wavelengths for the first time. In this resonator the intensity of the microwave field on the sample and its orientation with respect to the static magnetic field can be kept constant during the rotations. Therefore, a complete characterization of anisotropic systems is possible at the highest sensitivity, without the need of split-coil magnets. Possible applications at very high frequencies are discussed.     

A Schiff base expanded porphyrin macrocycle that acts as a versatile binucleating ligand for late first-row transition metals

The coordination chemistry of the Schiff base polypyrrolic octaaza macrocycle 1 toward late first-row transition metals was investigated. Binuclear complexes with the divalent cations Ni(II), Cu(II), and Zn(II) and with the monovalent cation Cu(I) were prepared and characterized. Air oxidation of the Cu(I) ions in the latter complex to their divalent oxidation state resulted in a change in the coordination mode relative to the macrocycle.     

Acetone powder from dormant seeds of Ricinus communis L

The influence of several factors on the hydrolytic activity of lipase, present in the acetone powder from dormant castor seeds (Ricinus communis) was evaluated. The enzyme showed a marked specificity for short-chain substrates. The best reaction conditions were an acid medium, Triton X-100 as the emulsifying agent and a temperature of 30 degrees C. The lipase activity of the acetone powder of different castor oil genotypes showed great variability and storage stability of up to 90%. The toxicology analysis of the acetone powder from genotype Nordestina BRS 149 showed a higher ricin (toxic component) content, a lower 2S albumin (allergenic compound) content, and similar allergenic potential compared with untreated seeds.     

Photochemistry of Hantzsch 1,4-dihydropyridines and pyridines

The photochemistry of some Hantzsch 4-phenyl-1,4-dihydropyridines bearing a substituent on the phenyl ring (the three isomeric chloro derivatives and the 4′-nitro derivative) has been studied. All of these compounds underwent inefficient aromatization to the corresponding pyridines (quantum yield <10⁻⁴ at 366 nm, <10⁻² at 254 nm). This process is scarcely affected by molecular oxygen and is initiated by proton transfer (from C₄-H), probably to the solvent, from the excited singlet. In turn, the thus formed pyridines were photoreactive with comparable or higher efficiency. Thus, the 4-(3′-chlorophenyl) and 4-(4′-chlorophenyl) Hantzsch pyridines underwent positional rearrangement to form two isomers each. The reaction occurs via Dewar benzene--prismane path. In the case of the minor isomer a further 1,3-shift take place at the Dewar benzene level. The 4-(2′-chlorophenyl) derivative underwent C-Cl bond homolysis, which led to cyclization of the phenyl group onto one of the ester groups forming a pyrane ring.     

Mechanism insights into an unexpected isomerisation reaction observed during conversion of N-benzyl piperazinones to corresponding N-benzyl thio-piperazinones

An interesting and surprising rearrangement was observed during the reaction of 4-N-benzyl piperazinone derivatives with Lawesson’s reagent as a thionating agent. Investigation into the possible mechanism responsible for these results is reported herein.