Allylic amination of unfunctionalyzed olefins by nitroarenes and CO, catalyzed by Ru3(CO)12/Ph-BIAN (Ph-BIAN=bis(phenylimino)acenaphthenequinone): extension to the synthesis of allylic amines with strongly electron-withdrawing or electron-donating groups on the aryl ring

The allylic amination of unfunctionalyzed olefins by nitroarenes under CO pressure, catalyzed by Ru₃(CO)₁₂/Ph-BIAN (Ph-BIAN=bis(phenylimino)acenaphthenequinone) has been extended to some substrates with strongly electron-withdrawing groups on the nitroarene. Reaction of 1,4-dinitrobenzene selectively affords functionalization of only one nitro group, the other remaining unreacted. However, the second nitro group can be reduced in one pot by CO/H₂O in the presence of the same catalytic system employed in the amination reaction, to afford the corresponding 4-amino derivative. Some attempts to render the reaction enantioselective by employing chiral bis-oxazolines as ligands in place of Ph-BIAN are described. Bis-oxazolines are suitable ligands for the reaction, although not as efficient as Ph-BIAN, but the allylic amine obtained was found to be racemic.     

Twin-hollow-core optical fibres

Twin-hollow-core microstructured optical fibres have been fabricated and characterised for the first time. The fibre cladding structure results in guidance by the inhibited coupling mechanism, in which there is a low overlap between the core modes and surrounding structure. This results in minimal interaction between the modes of each core in the transmission bands of the fibre and hence minimal coupling between the cores. It is shown that light is able to couple between the cores via coupling to cladding struts in the high loss wavelength bands.     

Packing items to feed assembly lines

We treat a practical application of packing problems in feeding assembly lines. This study was motivated by a real situation encountered in the shop floor of a major automobile industry plant in Brazil. The assembly line feed problem (LFP) consists in how pack the items in the available containers to meet the line work centers’ requirements with a minimum total cost over the planning horizon. LFP is a variable-sized bin packing problem that has two special features: (i) a cardinality constraint on each bin’s size; and, (ii) a cost structure such that each bin’s cost varies according to the items that are packed in it. We propose an integer programming model and a GRASP heuristic for LFP. Numerical results on real-life test instances are reported.     

Bis(pyrrol-2-yl)arylenes from the tandem bidirectional addition of vinyl Grignard reagent to aryl diesters

[Chemical reaction: See text] A practical three-step synthesis of bis(pyrrol-2-yl)arylenes has been accomplished, featuring a copper-catalyzed tandem bidirectional addition of vinylmagnesium bromide to aryldicarboxylates. Spectroscopic and cyclic voltammetric analyses revealed the influence of the central aromatic core and pyrrole substitution pattern on the electrochemical properties of these comonomers.     

Mechanochemical Route for the Synthesis of Cobalt Ferrite–Silica and Iron–Cobalt Alloy–Silica Nanocomposites

CoFe₂O₄–SiO₂ and Fe–Co alloy–SiO₂ nanocomposites were prepared by high energy ball milling of Si, -Fe₂O₃, Co₃O₄ and SiO₂ mixtures, followed by thermal treatment under appropriate oxidative/reductive conditions. XRD and TEM measurements carried out after 50 h of milling show highly dispersed unidentified reaction products. Further thermal treatment at 900°C in air leads to spherical CoFe₂O₄ nanocrystals (NCs) with a narrow size distribution centered around 2.5 nm, uniformly dispersed in the amorphous SiO₂ matrix. Reduction of this sample in a H₂ flow at 800°C produces a mixture of dispersed metallic cobalt and iron silicate with traces of Fe–Co alloy NCs. Reduction of the as-milled sample, on the contrary, leads almost completely to Fe–Co alloy NCs uniformly dispersed in the SiO₂ matrix and with an average particles size around 11.2 nm.     

Oxide/metal interface distance and epitaxial strain in the NiO/Ag(001) system

Geometric parameters of NiO films epitaxially grown on Ag(001) were determined using two independent experimental techniques and ab initio simulations. Primary beam diffraction modulated electron emission experiments determined that the NiO films grow with O on top of Ag and that the oxide/metal interface distance is d=2.3+/-0.1 A. Polarization-dependent x-ray absorption, at the Ni-K edge, determined the tetragonal strain (r( parallel )=2.046+/-0.009 A, r( perpendicular )=2.12+/-0.02 A) and d=2.37+/-0.05 A. Periodic slab model results agree with the experiments (d=2.40, r( parallel )=2.07, r( perpendicular )=2.10 A; the O-on-top configuration is the most stable).     

Nonlinear dynamics of inviscid reduced MHD plasmas: the appearance of Quasi-Single-helicity states

The nonlinear dynamics of an inviscid magnetohydrodynamic system in a low-beta plasma is investigated through a simplified model obtained by a Galerkin projection. We show that a single Fourier mode dominates over the whole energy spectrum, a self-organization mechanism of turbulence being responsible for this nonlinear effect. Our results are in agreement with observations of an analogous phenomenon, say, the emergence of a quasi-single-helicity state both in numerical simulations and real experiments in reversed field pinch laboratory plasmas.