Selective NOx Reduction During the H2 + NO + O2 Reaction Under Oxygen-Rich Conditions Over Pd/V2O5/Al2O3: Evidence for In Situ Ammonia Generation

Under oxygen-rich conditions in H₂ + NO + O₂ mixtures, Pd/V₂O₅/Al₂O₃ catalysts are active and highly selective (～80%) for NO_x reduction to N₂. In situ DRIFT spectroscopy and reactor data show that the system operates via formation of NH_x species on the highly dispersed V₂O₅ component. Both NH₃ and NH₄ ⁺ are formed, with the latter dominant. The role of the palladium component is also discussed.     

Regulation of polyisoprenylated methylated protein methyl esterase by polyunsaturated fatty acids and prostaglandins

Polyisoprenylation is a set of secondary modifications involving proteins whose aberrant activities are implicated in cancers and degenerative disorders. The last step of the pathway involves an ester‐forming polyisoprenylated protein methyl transferase‐ and hydrolytic polyisoprenylated methylated protein methyl esterase (PMPMEase)‐catalyzed reactions. Omega‐3 and omega‐6 PUFAs have been linked with antitumorigeneis and tumorigenesis, respectively. PUFAs are structurally similar to the polyisoprenyl groups and may interfere with polyisoprenylated protein metabolism. It was hypothesized that PUFAs may be more potent inhibitors of PMPMEase than their more polar oxidative metabolites, the prostaglandins. As such, the relative effects of PUFAs and prostaglandins on PMPMEase could explain the association between cyclooxygenase‐2 (COX‐2) expression in tumors, the chemopreventive effects of the non‐steroidal anti‐inflammatory (NSAIDs) COX‐2 inhibitors and PUFAs. PUFAs such as AA, EPA, and DHA inhibited PMPMEase activity with K_i values of 0.12–3.7 µM. The most potent prostaglandin was 63‐fold less potent than AA. The PUFAs were also more effective at inducing neuroblastoma cell death at physiologically equivalent concentrations. The lost PMPMEase activity in AA‐treated degenerating cells was restored by incubating the lysates with COX‐1 or COX‐2. PUFAs may thus be physiological regulators of cell growth and could owe these effects to PMPMEase inhibition. Practical applications: Some PUFAs have been widely reported to have anticancer benefits. However, the molecular mechanisms for these effects are not well understood. The findings in the current paper appear to suggest that inhibition of PMPMEase may underlie their effects. They also imply that the expression of COX‐2 in various tumors may serve to convert the PUFAs into significantly less inhibitory prostaglandins. From these findings, AA and the other PUFAs, rather than being substrates for the synthesis of tumorigenic agents may actually contribute in suppressing cell proliferation. This being congruent with the lower cancer risks associated with long term use of anti‐inflammatory agents, the practical implications will likely include the nutritional and/or therapeutic management of cancer with the goal of maintaining suitable levels of the fatty acids in tissues.     

Characterization of the Polishing‐Induced Contamination of Fused Silica Optics

In this work, the polishing‐induced contamination layer at the fused silica optics surface was studied with various interface analysis techniques: Secondary Ion Mass Spectroscopy (SIMS), Electron Probe Microanalysis (EPMA), X‐Ray Photoelectron Spectroscopy (XPS), and Inductively Coupled Plasma—Optical Emission Spectroscopy (ICP‐OES). Samples were prepared using an MRF polishing machine and cerium‐based slurry. The cerium and iron penetration and concentration were measured in the surface out of defects. Cerium is embedded at the surface in a 60 nm layer and concentrated at 1200 ppmw in this layer while iron concentration falls down at 30 nm. Spatial distribution and homogeneity of the pollution were also studied in the scratches and bevel using SIMS and EPMA techniques. We saw evidence that surface defects, such as scratches, are specific places that hold the pollutants. This overconcentration is also observed in the chamfer. These new insights into the polishing‐induced contamination of fused silica optics and it repartition have been obtained using various characterization methods. Advantages and disadvantages of each one are discussed.     

Ultra‐selective epoxidation of styrene on pure Cu{111} and the effects of Cs promotion

Styrene undergoes efficient epoxidation to styrene epoxide on the Cu{111} surface. At the optimum condition (Θ_o = 0.03 ML) ∼20% of the styrene is converted to the epoxide with almost 100% selectivity. Comparison with Ag{111} shows that the epoxidation activity and selectivity of Cu greatly exceed those of Ag. Incipient oxidation of the Cu{111} surface does not suppress the adsorption of styrene, but the oxidised metal is catalytically inert. Submonolayer amounts of Cs enhance styrene uptake and increase conversion to the epoxide without adversely affecting epoxidation selectivity. This effect is due to inhibition of Cu oxidation by Cs. Our findings are discussed in the light of current understanding of Ag‐catalysed alkene epoxidation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Activity and selectivity of a {\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}} catalytic membrane in the partial hydrogenation reactions of acetylene and 1,3-butadiene

A ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ membrane supported on a macroporous $\alpha {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ tube was prepared by sol–gel processing and used in the partial hydrogenation of acetylene and 1,3-butadiene. The average pore diameter of the ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ membrane was 3.6 nm. The gases were separated by Knudsen diffusion. The activity and selectivity of the ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ membrane was compared to that of ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ catalysts used in a conventional packed bed reactor. The highest selectivity to the partially hydrogenated products occurred when the reactant was premixed with H₂ and was passed through the membrane wall.     

Crystal Structure of the Human Monoacylglycerol Lipase,a Key Actor in Endocannabinoid Signaling

2‐Arachidonoylglycerol plays a major role in endocannabinoid signaling, and is tightly regulated by the monoacylglycerol lipase (MAGL). Here we report the crystal structure of human MAGL. The protein crystallizes as a dimer, and despite structural homologies to haloperoxidases and esterases, it distinguishes itself by a wide and hydrophobic access to the catalytic site. An apolar helix covering the active site also gives structural insight into the amphitropic character of MAGL, and likely explains how MAGL interacts with membranes to recruit its substrate. Docking of 2‐arachidonoylglycerol highlights a hydrophobic and a hydrophilic cavity that accommodate the lipid into the catalytic site. Moreover, we identified Cys201 as the crucial residue in MAGL inhibition by N‐arachidonylmaleimide, a sulfhydryl‐reactive compound. Beside the advance in the knowledge of endocannabinoids degradation routes, the structure of MAGL paves the way for future medicinal chemistry works aimed at the design of new drugs exploiting 2‐arachidonoylglycerol transmission.     

Proxies and measurement techniques for mineral dust in Antarctic ice cores

To improve quantitative interpretation of ice core aeolian dust records, a systematic methodological comparison was made. This involved methods for water-insoluble particle counting (Coulter counter and laser-sensing particle detector), soluble ion analysis (ion chromatography and continuous flow analysis), elemental analysis (inductively coupled plasma mass spectroscopy at pH 1 and after full acid digestion), and water-insoluble elemental analysis (proton induced X-ray emission). Antarctic ice core samples covering the last deglaciation from the EPICA Dome C (EDC) and the EPICA Dronning Maud Land (EDML) cores were used. All methods correlate very well among each other, but the ratios of glacial age to Holocene concentrations, which are typically a factor approximately 100, differ between the methods by up to a factor of 2 with insoluble particles showing the largest variability. The recovery of ICP-MS measurements depends on the digestion method and is differentfor different elements and during different climatic periods. EDC and EDML samples have similar dust composition, which suggests a common dust source or a common mixture of sources for the two sites. The analyzed samples further reveal a change of dust composition during the last deglaciation.     

An explanation for the effect of inoculum size on MIC and the growth/no growth interface

The inoculum effect (IE) is the phenomenon observed where changes in the inoculum size used in an experiment alters the outcome with respect to, for example, the minimum inhibitory concentration of an antimicrobial or the growth/no growth boundary for a given set of environmental conditions. Various hypotheses exist as to the cause of the IE such as population heterogeneity and quorum sensing, as well as the null hypothesis - that it is artefactual. Time to detection experiments (TTD) were carried out on different initial inoculum sizes of several bacterial species (Aeromonas hydrophila, Enterobacter sakazakii, Salmonella Poona, Escherichia coli and Listeria innocua) when challenged with different pH and with combined pH and sodium acetate. Data were modelled using a modification to a Gamma model (Lambert and Bidlas 2007, Int. J. Food Microbiology 115, 204-213), taking into account the inoculum size dependency on the TTD obtained under ideal conditions. The model suggests that changes in minimum inhibitory concentration (MIC) or in the growth-no growth boundary with respect to inoculum size are due to using a smaller or larger inoculum (i.e. is directly related to microbial number) and is not due to other, suggested, phenomena. The model used further suggests that the effect of a changing inoculum size can be modelled independently of any other factor, which implies that a simple 1 to 2-day experiment measuring the TTD of various initial inocula can be used as an adjunct to currently available models.