High Throughput Screening of Low Temperature SCR and SCD De-NOx Catalysts in Scanning Mass Spectrometer

High-throughput synthesis and screening methods have been developed for the discovery of highly active lead compounds for the selective catalytic reduction as well as direct decomposition of NO in the temperature range 200–300 °C. The discovery libraries for primary screening consisted of 16 × 16 catalyst arrays on 4in. square quartz wafers. Catalysts were prepared by robotic liquid dispensing techniques and screened for catalytic activity in Symyx' scanning mass spectrometer. The scanning mass spectrometer is a fast serial screening tool that uses flat wafer catalyst surfaces, local laser heating, a scanning/sniffing nozzle and a quadrupolar mass spectrometer to compare relative catalytic activities. The feed consisted of NO/NH₃ mixtures with optional O₂ cofeed and Kr as the internal standard in Ar carrier gas. QMS detection allowed for tracking of H₂O, N₂, NO, O₂, N₂O and Kr. Screening protocols for catalytic materials encompassed metal precursors and carriers for supported vanadia systems, extensive doping of V₂O₅/TiO₂, and broad screening of mixed redox metal oxides and supported base and noble metal systems. More than 500 samples could be screened in a single day. Active hits (high NO consumption accompanied by corresponding N₂ production) identified in discovery libraries were re-synthesized as focus libraries for lead confirmation and further optimization. These libraries used shallower compositional gradients, for example 56 points (compositions) per ternary, with four 56-point ternaries per 4in. wafer. Broad screening ternaries were generally 8 or 15 points. The focus libraries more clearly reveal the trends and provide guidelines for secondary screening and scale-up. High conversions were achieved in scanning mass spectrometer so the scalability risk is small for the short contact time reactions.     

Effect of early postnatal dietary sterculate on the fatty acid composition of rat liver and brain lipids

Pregnant rats were fed a high carbohydrate diet containing either 1% trilinolein or 1% trilinolein with 0.2% methyl sterculate from 18 day gestation to 21 day postpartum. The pups were weaned at 21 days and continued on the same diet for an additional 10 days. The microsomal stearyl CoA desaturase activities of the liver were effectively inhibited. Liver triglycerides showed increases in the saturated fatty acids concentrations at the expense of the corresponding monoenes. The concentration ofcis 6–7 octadecenoic acid was elevated. In liver phospholipids, the concentration of stearic acid was increased without a corresponding decrease in the oleic acid content. A drastic decrease in the nervonic acid (24∶1, n−9) concentration of liver sphingomyelin was observed. The lipids of the brain did not contain sterculic acid, and brain desaturase activity was unaffected. There was no significant change in the concentration of monoenoic acids from 16∶1 to 22∶1. However, nervonic acid was decreased by 32%. These results suggest that brain nervonic acid may be derived from a precursor other than oleic acid.     

Lipid hydrolysis and oxidation on the surface of milled rice

The changes in milled rice FFA content and composition and in conjugated diene (CD) content and bacterial, yeast, and mold counts were determined at 24, 37, and 50°C and 70% RH over 50 d. There was a rapid rate of FFA formation during the first few days of storage, which was optimal at 37°C, but that slowed after 2, 4, and 5 d at 37, 24, and 50°C, respectively. There was a second increase in FFA after about day 12 that increased with increasing temperature, indicating nonlipase hydrolysis. Linoleic and oleic acids were the main components of the total FFA produced on the surface of milled rice. The pattern of CD development followed that of FFA increase. Bacterial growth correlated with increased FFA levels after 12 d of storage, suggesting that bacterial lipase rather than bran lipase may be responsible for rice lipid hydrolysis     

ON GENERALIZED FRACTIONAL PROCESSES

Abstract. A class of stationary long-memory processes is proposed which is an extension of the fractional autoregressive moving-average (FARMA) model. The FARMA model is limited by the fact that it does not allow data with persistent cyclic (or seasonal) behavior to be considered. Our extension, which includes the FARMA model as a special case, makes use of the properties of the generating function of the Gegenbauer polynomials, and we refer to these models as Gegenbauer autoregressive moving-average (GARMA) models. While the FARMA model has a peak in the spectrum at f = 0, the GARMA process can model long-term periodic behavior for any frequency 0 f 0.5. Properties of the GARMA process are examined and techniques for generation of realizations, model identification and parameter estimation are proposed. The use of the GARMA model is illustrated through simulated examples as well as with classical sunspot data.     

Microenvironmental engineering: An effective strategy for tailoring enzymatic activities

Rationally, engineering a favorable physicochemical microenvironment for enzymes has recently emerged as an effective strategy to improve their catalytic performance. In this review, we discuss four microenvironmental effects according to the mechanism of action: localizing and excluding reactants and regulators, regulating microenvironmental pH, creating a water-like microenvironment, and increasing the local temperature. These mechanisms are enzyme-independent and can in principle be used in combination to tailor enzyme behaviors, offering new approaches to enabling, enhancing, and regulating enzyme catalysis in diverse applications without the need for genetic engineering.     

Stereospecific synthesis ofcis andtrans fatty esters

Theerythro andthreo isomers of methyl 9,10-dihydroxyoctadecanoate and thethreo isomer of methyl 12,13-dihydroxy-cis-9-octadecenoate were converted into methylcis- andtrans-9-octadecenoate and methylcis-9,rans-12-octadecadienoate, respectively, by reaction of the dihydroxy ester with triethyl orthoformate to give the 2-ethoxy-1,3-dioxolane which was thermally decomposed to the unsaturated ester.     

A review of the unique features of HDL apoproteins

The human plasma high density lipoproteins (HDL) are a heterogeneous ensemble of five proteins associated with both neutral and polar lipids. The sequences of all five proteins are known. ApoA-I and apoA-II are the major protein components; apoC-I, apoC-II and apoC-III are the minor protein components. All these apoproteins spontaneously recombine with phospholipids to give stable lipid-protein complexes and freely exchange between the two major HDL subclasses, HDL₂ and HDL₃. In addition, ApoC-I, apoC-II, and apoC-III exchange between HDL and very low density lipoproteins. Furthermore, certain HDL apoproteins are activators for plasma enzymes that are important in lipid metabolism. ApoA-I and apoC-I activate lecithin/cholesterol acyltransferase; apoC-II is an activator of lipoprotein lipase. The regions of apoC-I and apoC-II that are involved in the activation of these enzymes have been localized with synthetic peptides. Studies of synthetic and native fragments of apoA-II, apoC-I, apoC-II, and apoC-III as well as model lipid-binding peptides have identified specific regions with structural features common to lipid-binding proteins. These special properties, which include helical potential, sequences with a critical amphipathic length, and high hydrophobicity of the nonpolar side of the amphipathic helix, are the determinants of HDL structure and metabolism.     

Effect of Microstructure on the Tribological and Mechanical Properties of CuO-Doped 3Y-TZP Ceramics

Dense 8 mol% CuO-doped 3Y-TZP ceramics were prepared by pressureless sintering for 8 h at 1500° and 1550°C, respectively. Transmission electron spectroscopy revealed that the ceramic sintered at 1500°C exhibits grain boundaries free of any amorphous phase, while crystalline copper-oxide grains were found in the zirconia matrix, whereas the sample sintered at 1550°C contains a Cu-rich amorphous grain boundary layer. The tribological behavior of these materials was tested under dry-sliding conditions using a pin-on-disk tribometer. The material sintered at 1500°C showed self-lubrication resulting in a low coefficient of friction ( f ) of 0.2–0.3 and a low specific wear rate ( k ) ≪ 10⁻⁶ mm³·(N·m)⁻¹. In contrast, the material sintered at 1550°C showed poor tribological behavior ( f =0.8–0.9; k ≫ 10⁻⁶ mm³·(N·m)⁻¹ under the same conditions. The difference in the tribological behavior of these two materials was interpreted on the basis of mechanical properties and microstructural characteristics.     

Isosteric heat of sorption of CO2 in poly(ethylene terephthalate)

Sorption isotherms for carbon dioxide in poly(ethylene terephthalate) have been measured at 35–55°C. The isotherms were measured gravimetrically on a Mettler Thermoanalyzer-1 from vacuum to 1 atmosphere. The sorption data were used to generate sorption isotherms from which the isosteric heat of sorption of CO₂ in PET was determined. At 45°C the isosteric heat of sorption increases from −10 kcal/mole at a concentration of 0.5 cm³ (STP)/cm³ (polymer) to −8 kcal mole⁻¹ at a concentration of 1.5 cm³ (STP)/cm³ (polymer). It has been reported in the literature that the isosteric heat of sorption for this system decreased through a minimum before increasing with increasing concentration. Our measurement of the low-pressure sorption isotherms shows that this is not the case.     

Microstructure and tensile properties of squeeze cast magnesium alloy AM50

High-pressure die cast magnesium alloy AM50 is currently used extensively in large and complex shaped thin-wall automotive components. For further expansion of the alloy usage in automobiles, novelmanufacturing processes need to be developed. In this study, squeeze casting of AM50 alloy with a relatively thick cross section was carried out using a hydraulic press with an applied pressure of 70 MPa. Microstructure and mechanical properties of the squeeze cast AM50 with a cross-section thickness of 10 mm were characterized in comparison with the die cast counterpart. The squeeze cast AM50 alloy exhibits virtually no porosity in the microstructure as evaluated by both optical microscopy and the density measurement technique. The results of tensile testing indicate the improved tensile properties, specifically ultimate tensile strength and elongation, for the squeeze cast samples over the conventional high-pressure die cast parts. The analysis of tensile behavior show that the strain-hardening rate during the plastic deformation of the squeeze cast specimens is constantly higher than that of the die cast specimens. The scanning electron microscopy fractography evidently reveals the ductile fracture features of the squeeze cast alloy AM50.