Zeotype SAPO-34 Synthesized by Combination of Templates for the Gasification of Biomass

SAPO-34 is a crystalline microporous material, the characteristics of which are greatly influenced by synthetic parameters, especially the silica precursors and templates. In this study, the combination of templates and silica sources was optimized to obtain SAPO-34 phases in the purest form. The physicochemical properties of the thus-synthesized catalysts were characterized, and the Si environment in the SAPO-34 framework was analyzed. The catalytic performance in biomass gasification was investigated in a fixed-bed flow reactor. SAPO-34 synthesized with triethylamine/morpholine/tetraethylammonium hydroxide templates exhibited the highest total acidity, the smallest particle size, and high surface area, and produced a large amount of light hydrocarbons in biomass gasification.     

Bulk Micromachining of Si by Metal‐assisted Chemical Etching

Bulk micromachining of Si is demonstrated by the well‐known metal‐assisted chemical etching (MaCE). Si microstructures, having lateral dimension from 5 μm up to millimeters, are successfully sculpted deeply into Si substrate, as deep as >100 μm. The key ingredient of this success is found to be the optimizations of catalyst metal type and its morphology. Combining the respective advantages of Ag and Au in the MaCE as a Ag/Au bilayer configuration leads to quite stable etch reaction upon a prolonged etch duration up to >5 h. Further, the permeable nature of the optimized Ag/Au bilayer metal catalyst enables the etching of pattern features having very large lateral dimension. Problems such as the generation of micro/nanostructures and chemical attacks on the top of pattern surface are successfully overcome by process optimizations such as post‐partum sonication treatment and etchant formulation control. The method can also be successful to vertical micromachining of Si substrate having other crystal orientations than Si(100), such as Si(110) and Si(111). The simple, easy, and low‐cost nature of present approach may be a great help in bulk micromachining of Si for various applications such as microelectromechanical system (MEMS), micro total analysis system (μTAS), and so forth.     

The determinants of pKas in proteins

Although validation studies show that theoretical models for predicting the pKas of ionizable groups in proteins are increasingly accurate, a number of important questions remain: (1) What factors limit the accuracy of current models? (2) How can conformational flexibility of proteins best be accounted for? (3) Will use of solution structures in the calculations, rather than crystal structures, improve the accuracy of the computed pKas? and (4) Why does accurate prediction of protein pKas seem to require that a high dielectric constant be assigned to the protein interior? This paper addresses these and related issues. Among the conclusions are the following: (1) computed pKas averaged over NMR structure sets are more accurate than those based upon single crystal structures; (2) use of atomic parameters optimized to reproduce hydration energies of small molecules improves agreement with experiment when a low protein dielectric constant is assumed; (3) despite use of NMR structures and optimized atomic parameters, pKas computed with a protein dielectric constant of 20 are more accurate than those computed with a low protein dielectric constant; (4) the pKa shifts in ribonuclease A that result from phosphate binding are reproduced reasonably well by calculations; (5) the substantial pKa shifts observed in turkey ovomucoid third domain result largely from interactions among ionized groups; and (6) both experimental data and calculations indicate that proteins tend to lower the pKas of Asp side chains but have little overall effect upon the pKas of other ionizable groups.     

Mechanical Buckling: Mechanics,Metrology, and Stretchable Electronics

Mechanical buckling usually means catastrophic failure in structural mechanics systems. However, controlled buckling of thin films on compliant substrates has been used to advantage in diverse fields such as micro‐/nanofabrication, optics, bioengineering, and metrology as well as fundamental mechanics studies. In this Feature Article, a mechanical buckling model is presented, which sprang, in part, from the buckling study of high‐quality, single‐crystalline nanomaterials. To check the mechanical‐buckling phenomenon down to the nano‐/molecular scale, well‐aligned single‐walled carbon nanotube arrays and cross linked carbon‐based monolayers are transferred from growth substrate onto elastomeric substrate and then they are buckled into well‐defined shapes that are amenable to quantitative analysis. From this nano‐ or molecular‐scale buckling, it is shown that the mechanical moduli of nanoscale materials can easily be determined, even using a model based on continuum mechanics. In addition, buckling phenomena can be utilized for the determination of mechanical moduli of organic functional materials such as poly(3‐hexylthiophene) (P3HT) and P3HT/6,6‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) composite, which are widely used for organic transistors and organic photovoltaics. The results provide useful information for the realization of flexible and/or stretchable organic electronics. Finally, the fabrication and applications of “wavy, stretchable” single‐crystal Si electronics on elastomeric substrates are demonstrated.     

Worm population characteristics and pathological changes in lambs after a single or trickle infection with Teladorsagia circumcincta

The regulation of the worm population and of its pathological effects was studied after a single or trickle infection with T. circumcincta. One hundred and twenty lambs, 60 Romanov and 60 Mérinos d'Arles, 3 months old, were distributed in four balanced groups: non-infected (G0), infected with 7000 L3 per animal once and slaughtered after 4 weeks (G14) or 8 weeks (G18), and infected 8 times and slaughtered after 8 weeks (G88). Parasitological, histological, haematological parameters and weight gains were recorded on each animal. Female and artificially nursed lambs had lower worm burdens and egg counts (epg) than males and naturally suckled lambs. No difference in parasitological parameters was seen between the two breeds, but Mérinos lambs infected once, had a higher increase in pepsinogen concentrations than Romanov lambs. In the infected animals, a significant proliferation of mast and eosinophil cells was observed in the abomasum wall. Serum pepsinogen concentrations were significantly higher 3 weeks p.i. and the weight gain was depressed during the first month p.i. The worm population was more numerous and younger in group G14 compared with G18 in which 24% of the worms had been expelled during the second month p.i. The female worms in G18 were longer and had more eggs in utero and higher egg output. After the trickle infection (G88) the take was reduced, female worms were longer with more eggs in vagina (pars ejectrix) and there was a higher variability in the number of eggs (compared with G18 data). The pepsinogen rise was smaller but no specific effect was seen on histological and haematological parameters.(ABSTRACT TRUNCATED AT 250 WORDS)     

New scale-up and design method for stirrer agitated batch mixing vessels

Residence time distribution theory and probability conditions predict that the infusion rate of a slug of tracer into a batch mixer can be characterized by a single quantity, a decay rate constant. This constant is then used to define a dimensionless mixing-rate number.Experiments in turbine-agitated and propeller-agitated fully-baffled tanks verify the theory, and relate this mixing-rate number to the stirrer Reynolds number and to the Power number for mixing. These new correlationships allow calculation of time needed or energy input needed to achieve any desired degree of uniformity of the mixture.     

Investigation of multilayer silicon structures with buried iron silicide nanocrystallites: growth, structure, and properties

The growth of nanosize islands of iron silicides on Si(100) substrates and epitaxial silicon overgrowth atop them have been studied by low energy electron diffraction and reflectance high energy electron diffraction methods. The near optimal formation conditions of iron silicide islands with high density and minimal sizes have been determined by using of atomic force microscopy. Multilayer (8-10) monolithic structures with buried iron silicide nanocrystallites have been grown after the definition of monocrystalline burying conditions of iron silicides nanocrystallites in silicon lattice. The structure of buried nanocrystallites has been studied in multilayer monolithic heterostructures by high resolution transmission electron microscopy. It was established that in multilayer samples the majority of nanocrystallites have beta-FeSi2 structure, but some of them have gamma-FeSi2 structure. It was observed an influence of additional annealing at 850 degrees C on the morphology and structure of nanocrystallites. By means of deep level transient spectroscopy data one and two trap levels have been observed in multilayer structures (without and with additional annealing, respectively). Photoluminescence spectra have been studied at 4.2 K and the causes of its absence from buried beta-FeSi, NC have been analyzed.     

Iron‐Promoted Tandem Cyclization of 1,3‐Diynyl Chalcogen Derivatives with Diorganyl Dichalcogenides for the Synthesis of Benzo[b]furan‐Fused Selenophenes

A double intramolecular 5‐endo‐dig cyclization of butyl[2‐(phenylbuta‐1,3‐diynyl)phenyl]chalcogens has been employed in a selective preparation of benzo[b]chalcogenopheno[2,3‐d]furans. Several reaction parameters were studied to determine the best reaction conditions and we observed that the reaction of butyl[2‐(phenylbuta‐1,3‐diynyl)phenyl]chalcogens (0.25 mmol) with iron(III) chloride hexahydrate (2.0 equiv.) and diorganyl diselenides (1.75 equiv.) at reflux of dichloromethane was the most appropriate to give the products in 35–89% yields. These standard reaction conditions were compatible with many functional groups in the substrates, such as methyl, chlorine, fluorine, methoxy and heteroaryl. This protocol was also efficient for diorganyl diselenides but it was ineffective with diorganyl disulfides and ditellurides. In a competition among selenium, sulfur and oxygen nucleophiles we observed that the nucleophilicity and steric effects of the competing functional groups were determinant factors for the selectivity of the cyclization. The benzo[b]chalcogenopheno[2,3‐d]furans had absorptions in the UV region (300–350 nm range) with molar absorptivity coefficient values ascribed to spin and symmetry allowed π–π* electronic transitions. An emission located in the purple region (380–440 nm range), with a Stokes shift of between 65–100 nm, is probably associated to the charge transfer character of the excited state.