Structure of Adenine on Metal Nanoparticles: pH Equilibria and Formation of Ag+ Complexes Detected by Surface-Enhanced Raman Spectroscopy

The SERS spectra of adenine recorded under a broad range of pH values and concentrations using both silver and gold colloids provided evidence for the existence of several distinct species. At high concentration (0.5-10 ppm), the spectra recorded between pH 1 and 11 showed only two distinct spectra, rather than the three forms that would be expected for a compound with two pK(a) values of 4.2 and 9.8. The spectra at neutral and alkaline pH were identical and assigned to the deprotonated form of adenine on the basis of DFT calculations, isotope shifts, and comparison with the normal Raman spectra of neutral and deprotonated adenine. The spectra at acidic pH were different, consistent with adenine protonation. Neutral adenine was not detected at any pH studied. At low adenine concentration (

Preferential CO oxidation over a copper-cerium oxide catalyst in a microchannel reactor

The activity of a 5-wt% Cu/CeO2-x catalyst during preferential CO oxidation in hydrogen-rich gas mixtures was studied in a microchannel reactor. The CO concentration dropped from 1 vol.% to 10 ppm at a selectivity of 60%, at a temperature of 190 degrees C, and a weight hour space velocity (WHSV) of 55,000 cm(3) g(-1) h(-1). Both the CO concentration and the temperature increased when the WHSV was increased from 50,000 to 500,000 cm(3) g(-1) h(-1). An increase of the O-2 concentration from a 1.2 to 3 fold excess reduced the CO concentration to 10 ppm in a broad temperature interval of 50 degrees C at WHSVs up to 275,000 cm(3) g(-1) h(-1). The preferential CO oxidation could be carried out at higher flow rates and at higher selectivities in the microchannel reactor compared to a fixed-bed flow reactor. (C) 2008 Elsevier B.V. All rights reserved.

Photodecomposition of ozone sensitised by a film of titanium dioxide on glass

High levels of ozone (typically 850 ppm) are readily decomposed by semiconductor photocatalysis, using a thin film of the semiconductor titanium dioxide (Degussa P25 TiO2) cast on a glass tube, and UVA light, i.e. light of energy greater than that of the bandgap of the semiconductor (ultra-bandgap light); in the absence of this light the thermal decomposition of ozone is relatively slow. The semiconductor films show no evidence of chemical or photochemical wear with repeated use. At high levels of ozone, i.e. 100 ppm less than or equal to [O-3] less than or equal to 1400 ppm, the initial rate of ozone decomposition by semiconductor photocatalysis is independent of [O-3], whereas, at lower ozone concentrations, i.e. 5 ppm less than or equal to [O-3] less than or equal to 100 ppm, the initial rate of ozone photodestruction decreases in a smooth, but non-linear, manner with decreasing [O-3]. The kinetics of ozone photodecomposition fit a Langmuir-Hinshelwood type kinetic equation and the possible mechanistic implications of these results are briefly discussed. (C) 2002 Elsevier Science B.V. All rights reserved.

Behavior-Based branch prediction by dynamically clustering branch instructions

Conditional branches frequently exhibit similar behavior (bias, time-varying behavior,...), a property that can be used to improve branch prediction accuracy. Branch clustering constructs groups or clusters of branches with similar behavior and applies different branch prediction techniques to each branch cluster. We revisit the topic of branch clustering with the aim of generalizing branch clustering. We investigate several methods to measure cluster information, with the most effective the storage of information in the branch target buffer. Also, we investigate alternative methods of using the branch cluster identification in the branch predictor. By these improvements we arrive at a branch clustering technique that obtains higher accuracy than previous approaches presented in the literature for the gshare predictor. Furthermore, we evaluate our branch clustering technique in a wide range of predictors to show the general applicability of the method. Branch clustering improves the accuracy of the local history (PAg) predictor, the path-based perceptron and the PPM-like predictor, one of the 2004 CBP finalists.

Depletion of four nitrofuran antibiotics and their tissue-bound metabolites in porcine tissues and determination using LC-MS/MS and HPLC-UV

<p>Depletion of the nitrofuran antibiotics furazolidone, furaltadone, nitrofurantoin and nitrofurazone and their tissue-bound metabolites AOZ, AMOZ, AHD and SEM from pig muscle, liver and kidney tissues is described. Groups of pigs were given feed medicated with one of the nitrofuran drugs at a therapeutic concentration (400 mg kg(-1)) for ten days. Animals were slaughtered at intervals and tissue samples collected for analysis for six weeks following withdrawal of medicated feed. These samples were analysed both for parent nitrofurans (using LC-MS/MS and HPLC-UV), and for tissue-bound metabolites (using LC-MS/MS). The parent drugs were detectable only sporadically and only in pigs subjected to no withdrawal period whatsoever. This confirms the instability of the four major nitrofuran antibiotics in edible tissues. In contrast, the metabolites accumulated to high concentrations in tissues (ppm levels) and had depletion half lives of between 5.5 and 15.5 days. The metabolites of all four drugs were still readily detectable in tissues six weeks after cessation of treatment. This emphasizes the benefits of monitoring for the stable metabolites of the nitrofurans.p>

Lead isotopes and lead shot ingestion in the globally threatened marbled teal (Marmaronetta angustirostris) and white-headed duck (Oxyura leucocephala)

Lead isotope ratios ((206)Pb/(207)Pb and (208)Pb/(207)Pb) and concentrations in the livers and bones of marbled teal and white-headed duck found dead or moribund were determined in order to establish the main lead source in these waterfowl species. Lead concentrations in bone (dry weight) and liver (wet weight) were found to be very high in many of the white-headed ducks (bone: geometric mean=88.9 ppm, maximum=419 ppm; liver: geometric mean=16.8 ppm, maximum=57.0 ppm). Some of the marbled teal had high lead levels in the bones but liver lead levels were all low (bone: geometric mean=6.13 ppm, maximum=112 ppm; liver: geometric mean=0.581 ppm, maximum=4.77 ppm). Ingested lead shot were found in 71% of the white-headed duck and 20% of the marbled teal. The (206)Pb/(207)Pb ratio in livers and bones of white-headed ducks and marbled teals showed no significant differences compared to the ratios obtained from lead shot. The (206)Pb/(207)Pb ratio in bones of marbled teal ducklings with the highest lead concentrations tended to resemble the ratios of lead shot, which supports our hypothesis that the lead was derived from the hens. We also found that the lead ratios of lead shot and lead ratios described for soils in the area overlapped, but also that the isotopic ratio (206)Pb/(207)Pb in lead shot used in Spain has a narrow range compared with those used in North America. The principal source of lead in many of these birds was, however, most likely lead shot, as supported by the similar isotopic ratios, high lead concentrations in tissues and evidence of ingested shot.

Sulfated zirconia in SBA-15 structures with strong Bronsted acidity as observed by H-1 MAS NMR spectroscopy

<p>In order to prepare high surface area highly acidic catalysts, different weight loadings of ZrO2 were incorporated in the SBA-15 structures which are subsequently sulfated by treating in 0.25 M H2SO4. The catalysts were characterized by means of TEM, XRD, N-2 adsorption, and H-1 MAS NMR. Bronsted type acidities of sulfated zirconia included SBA-15 materials were identified by a sharp H-1 MAS NMR line at 10.6 ppm. The highest acidity was obtained in the 25 mol% ZrO2 included SBA-15 catalyst with a BET surface area of 246 m(2)/g.p>

Electronic properties of interfaces and defects from many-body perturbation theory: Recent developments and applications

<p>We review some recent developments in many body perturbation theory (MBPT) calculations that have enabled the study of interfaces and defects. Starting from the theoretical basis of MBPT, Hedin's equations are presented, leading to the CW and CWI' approximations. We introduce the perturbative approach, that is the one most commonly used for obtaining quasiparticle (QP) energies. The practical strategy presented for dealing with the frequency dependence of the self energy operator is based on either plasmon-pole models (PPM) or the contour deformation technique, with the latter being more accurate. We also discuss the extrapolar method for reducing the number of unoccupied states which need to be included explicity in the calculations. The use of the PAW method in the framework of MBPT is also described. Finally, results which have been obtained using, MBPT for band offsets a interfaces and for defects presented, with companies on the main difficulties and cancels.p><p>Schematic representation of the QP corrections (marked with ) to the band edges (E and E-v) and a defect level (F) for a Si/SiO2 interface (Si and O atoms are represented in blue and red, respectively, in the ball and stick model) with an oxygen vacancy leading to a Si-Si bond (the Si atoms involved in this bond are colored light blue).p>

GSP+ and Human Rights::Is the EU's Approach the Right One?

Among the purposes of the EU’s GSP+ programme is to link human rights to trade incentives, with the idea of using such incentives to promote developing countries’ adoption of the values found in core human rights treaties. With the re-renewal of the GSP (and GSP+) programmes to take effect in January 2014, it is fruitful to examine their efficacy and consistency with WTO law. In this article, I argue the GSP+ programme is not only ineffective in obtaining an improvement in human rights conditions for the vast majority of the world’s population, but it is also incompatible with WTO law. A stick-based regime where human rights abuses are linked to trade sanctions is a better way to proceed. After outlining the GSP+ system, and its linkage of human rights and trade, I analyse its efficacy and WTO consistency. Having shown that it is ineffective and contrary to WTO law, I argue that trade sanctions based on a PPM distinction and/or GATT XX(a) may be the appropriate means of linking trade and human rights. The article ends with some concluding remarks on the need for the careful design of such a system.

Development and validation of the first high performance-lateral flow immunoassay (HP-LFIA) for the rapid screening of domoic acid from shellfish extracts

A lateral flow immunoassay (LFIA) has been developed and fully validated to detect the primary amnesic shellfish poisoning (ASP) toxin, domoic acid (DA). The performance characteristics of two versions of the test were investigated using spiked and naturally contaminated shellfish (mussels, scallops, oysters, clams, and cockles). The tests provide a qualitative result, to indicate the absence or presence of DA in extracts of shellfish tissues, at concentrations that are relevant to regulatory limits. The new rapid assay (LFIA version 2) was designed to overcome the performance limitations identified in the first version of the assay. The improved test uses an electronic reader to remove the subjective nature of the generated results, and the positive cut-off for screening of DA in shellfish was increased from 10 ppm (version 1) to 17.5 ppm (version 2). A simple extraction and test procedure was employed, which required minimal equipment and materials; results were available 15 min after sample preparation. Stability of the aqueous extracts at room temperature (22 C) at four time points (up to 245 min after extraction) and across a range of DA concentrations was 100.3±1.3% and 98.8±2.4% for pre- and post-buffered extracts, respectively. The assay can be used both within laboratory settings and in remote locations. The accuracy of the new assay, to indicate negative results at or below 10 ppm DA, and positive results at or above 17.5 ppm, was 99.5% (n=216 tests). Validation data were obtained from a 2-day, randomised, blind study consisting of multiple LFIA lots (n=3), readers (n=3) and operators (n=3), carrying out multiple extractions of mussel tissue (n=3) at each concentration (0, 10, 17.5, and 20 ppm). No matrix effects were observed on the performance of the assay with different species (mussels, scallops, oysters, clams, and cockles). There was no impact on accuracy or interference from other phycotoxins, glutamic acid or glutamine with various strip incubations (8, 10, and 12 min). The accuracy of the assay, using naturally contaminated samples to indicate negative results at or below 12.5 ppm and positive results at or above 17.5 ppm, was 100%. Variability between three LFIA lots across a range of DA concentrations, expressed as coefficient of variation (% CV), was 1.1±0.4% (n=2 days) based on quantitative readings from the electronic reader. During an 8 week stability study, accuracy of the method with test strips stored at various temperatures (6, 22, 37 and 50 C) was 100%. Validation for both versions included comparisons with results obtained using reference LC-UV methods. © 2013 Elsevier B.V.

Interacting kinetics of neutral and ionic species in an atmospheric-pressure helium-oxygen plasma with humid air impurities

We unravel the complex chemistry in both the neutral and ionic systems of a radio-frequency-driven atmospheric-pressure plasma in a helium-oxygen mixture (He-0.5% O) with air impurity levels from 0 to 500 ppm of relative humidity from 0% to 100% using a zero-dimensional, time-dependent global model. Effects of humid air impurity on absolute densities and the dominant production and destruction pathways of biologically relevant reactive neutral species are clarified. A few hundred ppm of air impurity crucially changes the plasma from a simple oxygen-dependent plasma to a complex oxygen-nitrogen-hydrogen plasma. The density of reactive oxygen species decreases from 10 to 10 cm, which in turn results in a decrease in the overall chemical reactivity. Reactive nitrogen species (10 cm ), atomic hydrogen and hydroxyl radicals (10-10 cm) are generated in the plasma. With 500 ppm of humid air impurity, the densities of positively charged ions and negatively charged ions slightly increase and the electron density slightly decreases (to the order of 10 cm). The electronegativity increases up to 2.3 compared with 1.5 without air admixture. Atomic hydrogen, hydroxyl radicals and oxygen ions significantly contribute to the production and destruction of reactive oxygen and reactive nitrogen species. © 2013 IOP Publishing Ltd.

Chemical kinetics and reactive species in atmospheric pressure helium-oxygen plasmas with humid-air impurities

In most applications helium-based plasma jets operate in an open-air environment. The presence of humid air in the plasma jet will influence the plasma chemistry and can lead to the production of a broader range of reactive species. We explore the influence of humid air on the reactive species in radio frequency (rf)-driven atmospheric-pressure helium-oxygen mixture plasmas (He-O, helium with 5000 ppm admixture of oxygen) for wide air impurity levels of 0-500 ppm with relative humidities of from 0% to 100% using a zero-dimensional, time-dependent global model. Comparisons are made with experimental measurements in an rf-driven micro-scale atmospheric pressure plasma jet and with one-dimensional semi-kinetic simulations of the same plasma jet. These suggest that the plausible air impurity level is not more than hundreds of ppm in such systems. The evolution of species concentration is described for reactive oxygen species, metastable species, radical species and positively and negatively charged ions (and their clusters). Effects of the air impurity containing water humidity on electronegativity and overall plasma reactivity are clarified with particular emphasis on reactive oxygen species. © 2013 IOP Publishing Ltd.

Antioxidant Activity of Sesame (Seasamum indicum L.) Cake Extract for the Stabilization of Olein Based Butter

This study investigated the effect of ethanolic sesame cake extract on oxidative stabilization of olein based butter. Fractionation of cream was performed by the dry fractionation technique at 10 °C, ethanolic sesame cake extract (SCE) was incorporated into olein butter at three different concentrations; 50, 100, 150 ppm (T1, T2, T3) and compared with a control. The total phenolic content of SCE was 1.72 (mg gallic acid equivalent g−1 dry weight). The HPLC characterization of ethanolic sesame cake revealed the presence of antioxidant substances viz. sesamol, sesamin and sesamolin in higher extents. The DPPH free radical scavenging activity of SCE was 83 % as compared to 64 and 75 % in BHA and BHT. Fractionation of milk fat at 10 °C significantly (p < 0.05) influenced the fatty acid profile of olein and stearin fractions from the parent milk fat. Concentration of oleic acid and linoleic acid in olein fraction was 29.62 and 33.46 % greater than the parent milk fat. The loss of C18:1 in 90 days stored control and T3 was 24.37 and 3.58 %, respectively, 58 % C18:2 was broken down into oxidation products over 8.55 % loss in T3. The peroxide value of control, T1, T2, BHT and T3 in the Schaal oven test was 8.59, 8.12, 5.34, 4.52 and 2.49 (mequiv O2/kg). The peroxide value and anisidine value of 3 months stored control and T3 were 1.21, 0.42 (mequiv O2/kg) and 27.25, 13.25, respectively. The concentration of conjugated dienes in T3 was substantially less than the control. The induction period of T3 was considerably higher than BHT with no difference in sensory characteristics (p > 0.05). Ethanolic SCE can be used for the long-term preservation of olein butter, with acceptable sensory characteristics.

Recent contribution of sediments and fluids to the mantle's volatile budget

<p>Subduction modifies the cycling of Earth's volatile elements. Fluid-rich sediments and hydrated oceanic lithosphere enter the convecting mantle at subduction zones. Some of the sediments and volatile components are released from the subducting slab, promote mantle melting and are returned to the surface by volcanism. The remainder continue into the deeper mantle. Quantification of the fate of these volatiles requires an understanding of both the nature and timing of fluid release and mantle melting(1). Here we analyse the trace element and isotopic geochemistry of fragments of upper mantle rocks that were transported to the surface by volcanic eruptions above the Batan Island subduction zone, Philippines. We find that the mantle fragments exhibit extreme disequilibrium between their U-Th-Ra isotopic ratios, which we interpret to result from the interaction of wet sediment melts and slab-derived fluids with rocks in the overlying mantle wedge. We infer that wet sediments were delivered from the slab to the mantle wedge between 8,000 and 10,000 years ago, whereas aqueous fluids were delivered separately much later. We estimate that about 625 ppm of water is retained in the wedge. A significant volume of water could therefore be delivered to the mantle transition zone at the base of the upper mantle, or even to the deeper mantle.p>

Synchronous records of pCO2 and Δ14C suggest rapid, ocean-derived pCO2 fluctuations at the onset of Younger Dryas

Just before the onset of the Younger Dryas (YD) cold event, several stomatal proxy-based pCO2 records have shown a sharp increase in atmospheric CO2 concentration (pCO2) of between ca 50 and 100 ppm, followed by a rapid decrease of similar or even larger magnitude. Here we compare one of these records, a high-resolution pCO2 record from southern Sweden, with the IntCal13 record of radiocarbon (Δ14C). The two records show broadly synchronous fluctuations at the YD onset. Specifically, the IntCal13 record documents decreasing Δ14C just before the YD onset when pCO2 peaks, consistent with a source of “old” CO2 from the deep ocean. We propose that this fluctuation occurred due to a major ocean flushing event. The cause of the flushing event remains speculative but could be related to the hypothesis of the glacial ocean as a thermobaric capacitor. We confirm that the earth system can produce such large multi-decadal timescale fluctuations in pCO2 through simulating an artificial ocean flushing event with the GENIE Earth System Model. We suggest that sharp transitions of pCO2 may have remained undetected so far in ice cores due to inter-firn gas exchange and time-averaging. The stomatal proxy record is a powerful complement to the ice core records for the study of rapid climate change.