Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts

To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions.     

Impact of the North Dakota Growing Location on Canola Biodiesel Quality

Canola biodiesel (fatty acid methyl esters, FAME) may have superior cold flow properties when compared to other biodiesel feedstocks, which is attributed to canola’s high unsaturated and low saturated fat content. The objective of this study was to evaluate canola biodiesel fatty acid composition, cloud point (CP) and oil stability index (OSI) among several ND locations and production years. In Experiment 1, bulked canola varieties from seven growing seasons (2003–2009) were analyzed and in Experiment 2 a single canola variety (Interstate Hyola 357RR) harvested at two locations (2003–2005, and 2007) were analyzed. FAME was produced directly from seed via in situ alkaline transesterification methods. CP ranged from −0.1 to −2.4 °C and was significantly impacted by year and location. FAME generally met the ASTM B100 specification for OSI (3 h), but increased seed storage decreased stability. No significant differences were detected in FAME composition, and iodine value ranged from 108 to 123 g I₂/100 g. A significant relationship between fat saturation and location with CP and stability was not detected among the samples in this study. Variation in fatty acid composition was small; thus, the significant variability in CP and OSI suggests either differences in minor constituents (antioxidants, waxes) or environmental seed stress impacted biodiesel quality. Our study supports the value of examining biodiesel quality in a canola breeding program.     

Syntheses of nano-multilayered TiN/TiSiN and CrN/CrSiN hard coatings

Nano-structured superhard coatings represent the state-of-the-art in the rapidly increasing worldwide market for protective coatings. In this study, the combination of nano-composite and nano-multilayered structures into the same coating was attempted. Nano-multilayered coatings of TiN/TiSiN and CrN/CrSiN were deposited on tool steel substrates by closed-magnetic-field unbalanced DC magnetron sputter ion plating. The coating structures were characterized using X-ray diffraction, atomic force microscopy, and scanning electron microscopy. Mechanical characterizations were performed including nano-hardness measurement, progressively-increasing-load scratch test, and wear test. TiN/TiSiN coatings have a nano-hardness of 40.2 GPa, whereas CrN/CrSiN coatings have a hardness of 30.9 GPa. TiN/TiSiN coatings also showed a higher critical failure force and scratch fracture toughness as well as better wear resistance and lower acoustic emission signal, indicating less total damage to the coatings.     

Field response of Ips paraconfusus,Dendroctonus brevicomis,and their predators to 2-methyl-3-buten-2-ol,a novel alcohol emitted by ponderosa pine

Methylbutenol (MBO) is a major component of the aggregation pheromone of the European spruce beetle Ips typographus and also has been found to be emitted in large amounts by several species of pine native to western North America. This study investigates the influence this signal may have on the behavior of North American bark beetles and examines whether MBO functions as a defensive compound for emitting pines. The response of two North American bark beetles (Ips paraconfusus and Dendroctonus brevicomis) and their predaceous beetles (Trogositidae and Cleridae) to MBO, pheromone, and monoterpenes in varying release rates was investigated in the field using Lindgren funnel traps. MBO exhibited no repellent properties when tested alone, nor did MBO appear to have any effect on the aggregation response of these bark beetles and their predators to their pheromones. These results provide no support for a defensive function of MBO.     

Proton Conductivity Measurements in Yttrium Barium Cerate by Impedance Spectroscopy

Proton-conducting solid-electrolyte perovskite ceramics based on acceptor-doped barium and strontium cerates have become the focus of extensive investigations as candidate materials for fuel cells that operate at moderate temperatures. To assess the suitability of a material for this application, it is necessary that bulk electrolyte conductivity be measured at the operating temperature. However, very little reliable published conductivity data exist above 600°C. Protonic conductivity in yttrium-doped barium cerate has been observed to be less at high temperatures than would be expected, based on the activation energy and preexponential for hydrogen transport at temperatures <300°C. Conductivity data obtained from impedance spectroscopy on BaCe_0.9Y_0.1O_3–α over the extended temperature range of 100°–900°C are presented. An Arrhenius plot of the data shows two distinct linear regions, suggesting that two different rate-limiting processes occur in series with a break-over transition at ∼250°C. The decrease in conductivity is apparently not due to dehydration. An activation energy for protonic transport of 0.26 eV, about one-half of the low-temperature value, is proposed, based on curve fitting of the high-temperature data.     

Development and Scale-up of Aqueous Surfactant-Assisted Extraction of Canola Oil for Use as Biodiesel Feedstock

Aqueous surfactant-assisted extraction (ASE) has been proposed as an alternative to n-hexane for extraction of vegetable oil; however, the use of inexpensive surfactants such as sodium dodecyl sulfate (SDS) and the effect of ASE on the quality of biodiesel from the oil are not well understood. Therefore, the effects on total oil extraction efficiency of surfactant concentration, extraction time, oilseed to liquid ratio and other parameters were evaluated using ASE with ground canola and SDS in aqueous solution. The highest total oil extraction efficiency was 80 %, and was achieved using 0.02 M SDS at 20 °C, solid–liquid ratio 1:10 (g:mL), 1,000 rpm stirring speed and 45 min contact time. Applying triple extraction with three stages reduced the amount of SDS solution needed by 50 %. The ASE method was scaled up to extract 300 g of ground canola using the best combination of extraction conditions as described above. The extracted oil from the scale-up of the ASE method passed the recommendation for biodiesel feedstock quality with respect to water content, acid value and phosphorous content. Water content, kinematic viscosity, acid value and oxidative stability index of ASE biodiesel were within the ASTM D6751 biodiesel standards.     

VISUALIZING THE ENTRAPMENT OF AIR POCKETS IN THE SHELL OF A HEMODIALYZER DURING WET-OUT

An experimental study of the wet-out of the shell-side of a commercial hollow fiber hemodialyzer is presented. Using X-ray Computed Tomography, we followed the movement of water into the shell of an initially dry unit. Local values of fiber packing fraction were also determined from the dry images. During wet-out, water moved preferentially through regions of lower fiber packing. Additionally, air pockets were observed in regions of higher fiber packing that were bordered by regions of lower fiber packing. Thus, hydraulic permeability differences, due to non-uniform fiber packing, provide one mechanism for air entrapment.     

The Critical Role of Passive Permeability in Designing Successful Drugs

Passive permeability is a key property in drug disposition and delivery. It is critical for gastrointestinal absorption, brain penetration, renal reabsorption, defining clearance mechanisms and drug-drug interactions. Passive diffusion rate is translatable across tissues and animal species, while the extent of absorption is dependent on drug properties, as well as in vivo physiology/pathophysiology. Design principles have been developed to guide medicinal chemistry to enhance absorption, which combine the balance of aqueous solubility, permeability and the sometimes unfavorable compound characteristic demanded by the target. Permeability assays have been implemented that enable rapid development of structure-permeability relationships for absorption improvement. Future advances in assay development to reduce nonspecific binding and improve mass balance will enable more accurately measurement of passive permeability. Design principles that integrate potency, selectivity, passive permeability and other ADMET properties facilitate rapid advancement of successful drug candidates to patients.     

Entwicklung eines Transformationsmodells – Modularisierung schrittweise gedacht

For some years now, the process industry has been meeting the challenges of the markets with modular production and logistics concepts. This article presents this development process in the form of a four-stage transformation model. It is shown that the path towards modular production environments can be taken step by step. The motto is “evolution instead of revolution”. First, an overview of the state of the art of modularized production and logistics systems is given. Based on this, the article describes and classifies the four different stages of modularization.     

Heat Killed Lactobacillus reuteri GMNL-263 Reduces Fibrosis Effects on the Liver and Heart in High Fat Diet-Hamsters via TGF-β Suppression

Obesity is one of the major risk factors for nonalcoholic fatty liver disease (NAFLD), and NAFLD is highly associated with an increased risk of cardiovascular disease (CVD). Scholars have suggested that certain probiotics may significantly impact cardiovascular health, particularly certain Lactobacillus species, such as Lactobacillus reuteri GMNL-263 (Lr263) probiotics, which have been shown to reduce obesity and arteriosclerosis in vivo. In the present study, we examined the potential of heat-killed bacteria to attenuate high fat diet (HFD)-induced hepatic and cardiac damages and the possible underlying mechanism of the positive effects of heat-killed Lr263 oral supplements. Heat-killed Lr263 treatments (625 and 3125 mg/kg-hamster/day) were provided as a daily supplement by oral gavage to HFD-fed hamsters for eight weeks. The results show that heat-killed Lr263 treatments reduce fatty liver syndrome. Moreover, heat-killed Lactobacillus reuteri GMNL-263 supplementation in HFD hamsters also reduced fibrosis in the liver and heart by reducing transforming growth factor β (TGF-β) expression levels. In conclusion, heat-killed Lr263 can reduce lipid metabolic stress in HFD hamsters and decrease the risk of fatty liver and cardiovascular disease.