Reduction of nitrobenzene derivatives using sodium borohydride and transition metal sulfides

Reported here is the reduction of aromatic nitro compounds using sodium borohydride and transition metal sulfides as catalysts. The reaction conditions were optimized using the reduction of nitrobenzene as a model reaction. The catalysts studied were iron sulfide (Fe₃S₄), copper sulfide (CuS), zinc sulfide (ZnS), cobalt sulfide (Co₃S₄), and nickel sulfide (NiS). The reduction was monitored using gas chromatography. Quantitative conversions were achieved using Co₃S₄ and NiS, representing a ten-fold increase in reactivity compared to the non-catalyzed reaction. Fe₃S₄ and ZnS had no apparent effect on the reduction of nitrobenzene while the reduction using CuS showed a marginal increase. The reduction method was applied to several aryl-nitro derivatives containing either electron-withdrawing or electron-donating groups. Halogen containing aryl-nitro compounds were reduced without dehalogenation. The reduction had no effect on other functional groups such as carboxylic acids, esters, amides, or alkenes, indicating that the reduction is highly chemoselective.     

Palladium nanoparticles on modified cellulose as a novel catalyst for low temperature gas reactions

Cellulose - Palladium was incorporated into carboxymethylated cellulose fibers as a support, thereby becoming an efficient and stable catalyst for low temperature gas phase reaction. Thus, NO was...     

Nickel‐Catalyzed Mizoroki–Heck Reaction of Aryl Sulfonates and Chlorides with Electronically Unbiased Terminal Olefins: High Selectivity for Branched Products

Achieving high selectivity in the Heck reaction of electronically unbiased alkenes has been a longstanding challenge. Using a nickel‐catalyzed cationic Heck reaction, we were able to achieve excellent selectivity for branched products (≥19:1 in all cases) over a wide range of aryl electrophiles and aliphatic olefins. A bidentate ligand with a suitable bite angle and steric profile was key to obtaining high branched/linear selectivity, whereas the appropriate base suppressed alkene isomerization of the product. Although aryl triflates are traditionally used to access the cationic Heck pathway, we have shown that, by using triethylsilyl trifluoromethanesulfonate, we can effect a counterion exchange of the catalytic nickel complex, such that cheaper and more stable aryl chlorides, mesylates, tosylates, and sulfamates can be used to yield the same branched products with high selectivity.     

Study of medieval enamelling on gilded objects combining SEM-EDAX and PIXE

A set of fragments of metallic artefacts from the medieval period excavated from Ciudad Real in Spain has been studied. The objects are gilded copper buckles with a champlevé enamelling decoration. The composition of predominantly blue-coloured enamels has been analysed using three non-destructive techniques, SEM-EDAX (scanning electron microscopy coupled with energy-dispersive X-ray analysis), X-ray fluorescence (XRF) and PIXE (particle-induced X-ray emission). Analyses show that Co is responsible for the blue colour. The results of the two techniques are compared, as well as the main components which constitute the enamel. Analyses suggest that Cu is responsible for red colour.     

A relativistic quark-diquark model for the nucleon

We developed a constituent quark-diquark model for the nucleon and its resonances using a harmonic oscillator potential for the interaction. The effects due to relativistic kinetic energy correction are studied. Finally, charge form factor of the model is calculated and compared with experimental data.      

Phenylpropanoids from Umbilicus pendulinus

Phytochemical investigation of the leaves of Umbilicus pendulinus afforded in addition to 2-O-caffeoyl malate, isoquercitrin and Z-venusol, the new isomer E-venusol. Special NMR experiments were carried out to elucidate the configuration of the two latter compounds.     

Search for exotic baryons in 800 GeV pp-->pXi+/-piX reactions

We report the results of a high-statistics, sensitive search for narrow baryon resonances decaying to Xi-pi-, Xi-pi+, Xi+pi-, and Xi+pi+. The only resonances observed are the well known Xi0(1530) and Xi0(1530). No evidence is found for the states near 1862 MeV, previously reported by NA49 [Phys. Rev. Lett. 92, 042003 (2003)]. At the 95% confidence level, we find the upper limit for the production of a Gaussian enhancement with sigma=7.6 MeV in the Xi-pi- effective mass spectrum to be 0.3% of the number of observed Xi0(1530)-->Xi-pi+. We find similarly restrictive upper limits for an enhancement at 1862 MeV in the Xi-pi+, Xi+pi-, and Xi+pi+ mass spectra.     

FEM simulation of the Nitinol wire

In recent years, one of the most promising new actuator technologies is based on the use of Shape Memory Alloys (SMA). The main challenge for the application of devices that use these materials is the hysteresis in the phase transition they suffer during actuation. Finite element analysis (FEA) is an important aid in the simulation of mechanical properties and thermal fields in actuators. Dynamic simulations give in many cases enough information without the necessity of building a prototype. We have used ABAQUS to simulate a Nitinol wire used in a micropositioning actuator. The model parameters, not given by the supplier but required by the FEA program, have been obtained by thermal and mechanical characterization of the material used. The output force is computed and compared with the measurements.     

Survivable capacitated network design problem: new formulation and Lagrangean relaxation

This work is focused on the analysis of the survivable capacitated network design problem. This problem can be stated as follows: Given a supply network with point-to-point traffic demands, specific survivability requirements, a set of available capacity ranges and their corresponding discrete costs for each arc, find minimum cost capacity expansions such that these demands can be met even if a network component fails. Solving this problem consists of selecting the links and their capacity, as well as the routings for each demand in every failure situation. This type of problem can be shown to be NP-hard. A new linear mixed-integer mathematical programming formulation is presented. An effective solution procedure based on Lagrangean relaxation is developed. Comparison heuristics and improvement heuristics are also described. Computational results using these procedures on different sizes of randomly generated networks are reported.