Electrochemical reduction of benzyl halides at a silver electrode

The electrochemical reduction of benzyl halides PhCH₂X (X = Cl, Br and I) has been investigated at Ag and glassy carbon (GC) electrodes in CH₃CN + 0.1 M Et₄NClO₄. At both electrodes reduction of PhCH₂X involves irreversible electron transfer concerted with breaking of the carbon-halogen bond. All three halides exhibit a single 2e⁻ reduction peak at GC, whereas up to three peaks can be observed at the Ag electrode. Silver exhibits remarkable catalytic properties for the reduction process, which is positively shifted by 0.45-0.72 V with respect to GC. The mechanism of reduction of the organic halides at Ag involves adsorption of both the starting reagents and their reduction products. Adsorption of PhCH₂Cl and PhCH₂Br is weak and slow, whereas PhCH₂I is more rapidly and strongly adsorbed, so that two distinct peaks can be observed for the reduction of the dissolved and adsorbed molecules. Controlled-potential electrolyses at Ag have shown that the process may be directed to the production of bibenzyl or toluene, depending on the applied potential.     

Biological Removal of High Loads of Thiosulfate Using a Trickling Filter Under Alkaline Conditions

Uncontrolled release of thiosulfate can cause high oxygen demand, or generate toxic compounds under anaerobic scenarios. Biooxidation of thiosulfate in a biotrickling filter (BTF) colonized by an alkaliphilic sulfide-oxidizing bacterial consortium was studied at pH ≈10. Inlet thiosulfate concentrations were varied from 3.5 to 21.3 g L^?1, with a residence time of 216 s, emulating conditions encountered in wastewater from mining processes. Sulfate production, oxygen concentration, and biomass in both packing and effluent were periodically analyzed to characterize bioreactor performance. Removal efficiencies near 100 % were obtained during the entire experimental period, with a maximum elimination capacity of 242 g thiosulfate m^?3 h^?1. Although the BTF was able to transfer large amounts of oxygen to biooxidize thiosulfate to sulfate, under high initial thiosulfate loads, thiosulfate was not completely oxidized to sulfate, since biooxidation was conditioned to oxygen supply. Respirometric tests performed to investigate biomass adaptation and activity revealed oxygen consumption values of 0.5 mmol O₂ (g protein)^?1 min^?1 for the period with the highest thiosulfate inlet load.     

Automated decomposition of intramuscular electromyographic signals

We present a novel method for extracting and classifying motor unit action potentials (MUAPs) from one-channel electromyographic recordings. The extraction of MUAP templates is carried out using a symbolic representation of waveforms, a common technique in signature verification applications. The assignment of MUAPs to their specific trains is achieved by means of repeated template matching passes using pseudocorrelation, a new matched-filter-based similarity measure. Identified MUAPs are peeled off and the residual signal is analyzed using shortened templates to facilitate the resolution of superimpositions. The program was tested with simulated data and with experimental signals obtained using fine-wire electrodes in the biceps brachii during isometric contractions ranging from 5% to 30% of the maximum voluntary contraction. Analyzed signals were made of up to 14 MUAP trains. Most templates were extracted automatically, but complex signals sometimes required the adjustment of 2 parameters to account for all the MUAP trains present. Classification accuracy rates for simulations ranged from an average of 96.3% +/- 0.9% (4 trains) to 75.6% +/- 11.0% (12 trains). The classification portion of the program never required user intervention. Decomposition of most 10-s-long signals required less than 10 s using a conventional desktop computer, thus showing capabilities for real-time applications.     

Methane reforming with carbon dioxide over a Ni/ZiO2–SiO2 catalyst: Influence of pretreatment gas atmospheres

Carbon dioxide reforming of methane to synthesis gas was studied over Ni/ZrO₂–SiO₂ catalyst under different pretreatment atmospheres. Characterization using powder X-ray diffraction, H₂ temperature-programmed reduction, H₂ temperature-programmed hydrogenation, TG/DTA, XPS, Raman spectra and transmission electron microscopy techniques revealed that gas atmospheres employed in the catalyst pretreatment have a significant influence on the catalytic performance. The helium-pretreated catalyst was found to be the most suitable catalyst for this application, showing the improved catalytic performance. More specifically, helium pretreatment facilitated the generation of well-distributed active metal sites while the heterogeneity of Ni components upon H₂ pretreatment degraded catalytic activity of metal sites considerably. Pretreatment under CO atmosphere resulted in the formation of carbon encapsulated metal species thus causing catalyst deactivation severely. Inefficient reduction under CH₄ activation and the presence of a great amount of carbonaceous species, disfavor the production of synthesis gas during the dry reforming.     

Effect of wood species on property and weathering performance of wood plastic composites

The effects of wood species on mechanical, thermal and accelerated weathering behaviors of high-density polyethylene based wood plastic composites (WPC) were investigated. The selected wood species are poplar, Douglas-fir, black locust, white oak, and ponderosa pine. Hybrid poplar and Douglas-fir based composite ranked highly in flexural properties. Thermogravimetric analysis indicated that thermal stability of the WPC is species dependent. The final decomposition of hemicelluloses in the hardwoods occurred at higher temperatures compared to that of softwoods. Color and chemical changes that occurred due to accelerated weathering were monitored using colorimetry and Fourier transform infrared spectroscopy. Weathered WPCs showed that color change and lightness increased with exposure time; degree of increase depends on wood species. WPC oxidation by weathering was assessed by carbonyl group concentration and was shown to increase with exposure. Hybrid poplar and ponderosa pine were shown to have good color stability among the wood species examined for WPC.     

Synthesis and biological evaluation of isosteric analogues of FK866, an inhibitor of NAD salvage

One of the great challenges of medicinal chemistry is to create novel, effective, chemotherapeutic agents that show specificity for cancer cells combined with low systemic toxicity. A novel idea is to target the enzymes of the NAD biosynthesis and recycling pathways given that cancer cells display a higher NAD turnover rate than healthy cells. To this end, the compound FK866 (APO866; (E)-N-[4-(1-benzoylpiperidin-4-yl) butyl]-3-(pyridin-3-yl) acrylamide), which blocks nicotinamide phosphoribosyltransferase (NMPRTase) has entered clinical trials as a potential chemotherapeutic agent. Here we report the synthesis of analogues of FK866 synthesized by click chemistry.     

Electrodeposition growth of nanowire arrays with height gradient profiles for microwave device applications

A simple and nonexpensive adapted dip-coating technique is presented and used to fabricate arrays of magnetic nanowires with a linear varying height profile. This approach allows controlling the wire height from tenths of nanometers up to several micrometers. Furthermore, the main parameters of this height gradient can be controlled, such as the maximum wire height and the lateral span of the wire array, which can be predicted with excellent accuracy using a proposed analytical model. Moreover, we show that by sequential electrodeposition with dip-coating, arrays of these height varying wires can be grown. This technique represents a novel method to fill porous templates with controlled spatial growth, leading to the fabrication of novel structures and providing control over structural features on the nanoscale level. In particular, the use of these asymmetrically loaded magnetic nanowired substrates to obtain improved microwave nonreciprocal behavior is shown for a microwave phase shifter.     

Condensation Reactions of Lignin During Oxygen Delignification Under Acidic Conditions

Spruce wood (Picea abies) has been subjected to delignification by oxygen under acidic conditions using different solvent media. The residual and removed lignins were submitted to permanganate oxidation and the products analyzed by GC and GC-MS. Results from the analysis of the residual lignins indicate that lignin “condensation” depends on the nature of oxidation medium. It was found that the addition of acetone to the aqueous liquor decreases both acid catalyzed and radical side reactions. Lignin “condensation” in water containing media is dominated by radical reactions. Results from the analysis of the lignin removed during oxygen delignification in an acetone/water medium indicate that significant amounts of “condensed” structures are present, which are relatively stable towards oxidation. The presence of diphenylmethane, diarylether and biphenyl type structures in the removed lignin was confirmed by CP-MAS ¹³C NMR spectroscopy.     

Analysis of the conjugate heat transfer in a multi-layer wall including an air layer

Analysis of the conjugate heat transfer in a multi-layer furnace wall including an air layer, using computational fluid dynamics (CFD), is presented. The analysis consists of the study of the heat transfer in the air layer to determine the heat flow that passes through the wall of the furnace. In the study, the natural convection effect on the insulating capacity of the wall was determined. The multi-layer wall is found in industrial furnaces used in the baking process of ceramics. In this study a critical thickness of the air layer was determined, identifying the beginning of natural convection, which represents a reduction in the insulating effect of the wall. In addition, different combinations of air layer thickness with vertical partitions were analyzed in order to increase the total thickness of the multi-layer wall and to improve the insulating capacity of the wall. An air layer with 10 cm of thickness and four parallel partitions presents the best insulating capacity, reducing by 44% the heat losses through the multi-layer wall.