In situ XAFS investigation of palladium species present during the Heck reaction in room temperature ionic liquids

The Heck reaction, performed in room temperature ionic liquids, has been studied by in situ XAFS, which indicates that palladium clusters of 0.8-1.6 nm diameter are the main species present during reaction.

Room Temperature, Electrochemical Generation of Ozone with 50% Current Efficiency in 0.5M Sulfuric Acid at Cell Voltages <3V.

The electrochemical generation of ozone by Ni/Sb-SnO2 anodes immersed in 0.5M H2SO4 was assessed in both flow and recycle systems using the same electrochemical cell. The anodes were found to exhibit current efficiencies of up to 50% for ozone generation under flow conditions at room temperature, with an optimum mole ratio in the precursor solutions of ca. 500:8:3 Sn:Sb:Ni and optimum cell voltage of 2.7V. A comparison of the data obtained under flow and recycle conditions suggests that the presence of ozone in the anolyte inhibits its formation. The minimum electrical energy cost achieved, of 18 kWh kg1 compares favorably with estimated costs for Cold Corona Discharge generally reported in the literature, especially when the very significant advantages of electrochemical ozone generation are taken into account.

Green synthesis of ZnO nanoparticles in a room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Nanoparticles of ZnO with the wurtzite structure have been successfully synthesized via a microwave through the decomposition of zinc acetate dihydrate in an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, as a solvent. Fundamental characterizations including X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were conducted for the ZnO nanostructures.

Dissolved Argon Changes the Rate of Diffusion in Room Temperature Ionic Liquids: Effect of the Presence and Absence of Argon and Nitrogen on the Voltammetry of Ferrocene

This work explores the effects of argon and nitrogen, two electrochemically and chemically inert gases frequently used in sample preparation of room temperature ionic liquid (RTIL) solutions, on the eelectrochemical characterization of ferrocene (Fc) dissolved in the RTIL 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C(2)mim][NTf2]). Remarkably, chronoamperometrically determined diffusion coefficients of Fc in [C(2)mim][NTf2] are found to increase from 4.8 (+/- 0.2) x 10(-11) m(2) s(-1) under vacuum conditions to 6.6 (+/- 0.5) x 10(-11) m(2) s(-1) in an atmosphere of 1 atm Ar. In contrast, exposing a vacuum-purified sample to an atmosphere of 1 atm N-2 resulted in no significant change in the measured diffusion coefficient of Fc. The effect of dissolved argon on diffusion transport is unexpected and has implications in electrochemistry and elsewhere. Fc was found to volatilize under vacuum conditions. We propose, however, that evacuation of the cell by vacuum prior to electrochemical measurements being carried out is the only way to ensure that no contamination of the sample occurs, and use of an in situ method of determining the diffusion coefficient and concentration of Fc dispells,any ambiguity associated with Fc depletion by vacuum.

Channel characterization for single- and multiple-antenna wearable systems used for indoor body-to-body communications

In this paper, an analysis of radio channel characteristics for single- and multiple-antenna bodyworn systems for use in body-to-body communications is presented. The work was based on an extensive measurement campaign conducted at 2.45 GHz representative of an indoor sweep and search scenario for fire and rescue personnel. Using maximum-likelihood estimation in conjunction with the Akaike information criterion (AIC), five candidate probability distributions were investigated and from these the kappa - mu distribution was found to best describe small-scale fading observed in the body-to-body channels. Additional channel parameters such as autocorrelation and the cross-correlation coefficient between fading signal envelopes were also analyzed. Low cross correlation and small differences in mean signal levels between potential dual-branch diversity receivers suggested that the prospect of successfully implementing diversity in this type application is extremely good. Moreover, using selection combination, maximal ratio, and equal gain combining, up to 8.69-dB diversity gain can be made available when four spatially separated antennas are used at the receiver. Additional improvements in the combined envelopes through lower level crossing rates and fade durations at low signal levels were also observed.

Non-invasive VHF monitoring of low-temperature atmospheric pressure plasma

A real-time VHF swept frequency (20–300 MHz) reflectometry measurement for radio-frequency capacitive-coupled atmospheric pressure plasmas is described. The measurement is scalar, non-invasive and deployed on the main power line of the plasma chamber. The purpose of this VHF signal injection is to remotely interrogate in real-time the frequency reflection properties of plasma. The information obtained is used for remote monitoring of high-value atmospheric plasma processing. Measurements are performed under varying gas feed (helium mixed with 0–2% oxygen) and power conditions (0–40 W) on two contrasting reactors. The first is a classical parallel-plate chamber driven at 16 MHz with well-defined electrical grounding but limited optical access and the second is a cross-field plasma jet driven at 13.56 MHz with open optical access but with poor electrical shielding of the driven electrode. The electrical measurements are modelled using a lumped element electrical circuit to provide an estimate of power dissipated in the plasma as a function of gas and applied power. The performances of both reactors are evaluated against each other. The scalar measurements reveal that 0.1% oxygen admixture in helium plasma can be detected. The equivalent electrical model indicates that the current density between the parallel-plate reactor is of the order of 8–20 mA cm-2 . This value is in accord with 0.03 A cm-2 values reported by Park et al (2001 J. Appl. Phys. 89 20–8). The current density of the cross-field plasma jet electrodes is found to be 20 times higher. When the cross-field plasma jet unshielded electrode area is factored into the current density estimation, the resultant current density agrees with the parallel-plate reactor. This indicates that the unshielded reactor radiates electromagnetic energy into free space and so acts as a plasma antenna.

Isotopic composition of inorganic carbon as an indicator of benzoate degradation by Pseudomonas putida: temperature, growth rate and pH effects.

Degradation experiments of benzoate by Pseudomonas putida resulted in enzymatic carbon isotope fractionations. However, isotopic temperature effects between experiments at 20 and 30 °C were minor. Averages of the last three values of the CO2 isotopic composition (δ13CCO2(g)) were more negative than the initial benzoate δ13C value (−26.2‰ Vienna Pee Dee Belenite (VPDB)) by 3.8, 3.4 and 3.2‰ at 20, 25 and 30 °C, respectively. Although the maximum isotopic temperature difference found was only 0.6‰, more extreme temperature variations may cause larger isotope effects. In order to understand the isotope effects on the total inorganic carbon (TIC), a better measure is to calculate the proportions of the inorganic carbon species (CO2(g), CO2(aq) and HCO3−) and to determine their cumulative δ13CTIC. In all three experiments δ13CTIC was more positive than the initial isotopic composition of the benzoate at a pH of 7. This suggests an uptake of 12C in the biomass in order to match the carbon balance of these closed system experiments.

Protracted rainfall decreases temperature within leatherback turtle (Dermochelys coriacea) clutches in Grenada, West Indies: Ecological implications for a species displaying temperature dependent sex determination

Protracted or intense rainfall may affect the reproductive success of reptilian species on a number of levels ranging from the availability of prey, the integrity of the nesting site and the subsequent survivability of offspring. For sea turtles (a species displaying temperature sex determination) nesting throughout the tropics and subtropics, rainfall has previously been shown to influence the development environment of clutches; in its extreme resulting in high levels of egg or hatchling mortality. Yet when compared to other abiotic variables affecting clutch success, rainfall has received relatively little attention. We therefore examined how fluctuations in local rainfall at a tropical nesting site for leatherback turtles (Dermochelys coriacea) affected the nest environment. Temperature data loggers placed within clutches (n = 8) revealed that protracted rainfall had a marked cooling effect on nests, so that seasonally improbable male-producing temperatures (

On the function of the internal cavity of histone deacetylase protein 8: R37 is a crucial residue for catalysis

Biochemical studies reveal that a conserved arginine residue (R37) at the centre of the 14 angstrom internal cavity of histone deacetylase (HDAC) 8 is important for catalysis and acetate affinity. Computational studies indicate that R37 forms multiple hydrogen bonding interactions with the backbone carbonyl oxygen atoms of two conserved glycine residues, G303 and G305, resulting in a 'closed' form of the channel. One possible rationale for these data is that water or product (acetate) transit through the catalytically crucial internal channel of HDAC8 is regulated by a gating interaction between G139 and G303 tethered in position by the conserved R37. (C) 2011 Elsevier Ltd. All rights reserved.

Characterization of Nickel Germanide Schottky Contacts for the Fabrication of Germanium p-channel MOSFETs

Nickel germanide Schottky contacts, formed by rapid thermal annealing of thin nickel films, have been characterized on n-type germanium wafers for a range of RTA temperatures. The highest Schottky barrier heights for electrons (= 0.6-0.7 eV) were obtained for RTA temperatures of approximately 300°C. For this RTA schedule, the corresponding barrier height for holes is close to zero, ideal for Schottky contacted p-channel germanium MOSFETs. When the RTA temperature was increased to 400oC, a dramatic reduction in electron barrier height (< 0.1 eV) was observed. This RTA schedule, therefore, appears ideal for ohmic source/drain contacts to n channel germanium MOSFETs. From sheet resistance measurements and XRD characterization, nickel germanide formation was found to occur at 300oC and above. The NiGe phase was dominant for RTA temperatures up to at least 435oC.

Microstructure evolution of a 10Cr heat-resistant steel during high temperature creep

The microstructure evolution of a 10Cr ferritic/martensitic heat-resistant steel during creep at 600°C was investigated in this work. Creep tests demonstrated that the 10Cr steel had higher creep strength than conventional ASME-P92 steel at 600°C. The microstructure after creep was studied by transmission electron microscopy, scanning electron microscopy and electron probe microanalysis. It was revealed that the martensitic laths were coarsened with time and eventually developed into subgrains after 8354 h. Laves phase was observed to grow and cluster along the prior austenite grain boundaries during creep and caused the fluctuation of solution and precipitation strengthening effects, which was responsible for the two slope changes on the creep rupture strength vs rupture time curve. It was also revealed that the microstructure evolution could be accelerated by stress, which resulted in the lower hardness in the deformed part of the creep specimen, compared with the aging part.

Temperature, predator-prey interaction strength and population stability

Warming could strongly stabilize or destabilize populations and food webs by changing the interaction strengths between predators and their prey. Predicting the consequences of warming requires understanding how temperature affects ingestion (energy gain) and metabolism (energy loss). Here, we studied the temperature dependence of metabolism and ingestion in laboratory experiments with terrestrial arthropods (beetles and spiders). From this data, we calculated ingestion efficiencies (ingestion/metabolism) and per capita interaction strengths in the short and long term. Additionally, we investigated if and how body mass changes these temperature dependencies. For both predator groups, warming increased metabolic rates substantially, whereas temperature effects on ingestion rates were weak. Accordingly, the ingestion efficiency (the ratio of ingestion to metabolism) decreased in all treatments. This result has two possible consequences: on the one hand, it suggests that warming of natural ecosystems could increase intrinsic population stability, meaning less fluctuations in population density; on the other hand, decreasing ingestion efficiencies may also lead to higher extinction risks because of starvation. Additionally, predicted long-term per capita interaction strengths decreased with warming, which suggests an increase in perturbation stability of populations, i.e., a higher probability of returning to the same equilibrium density after a small perturbation. Together, these results suggest that warming has complex and potentially profound effects on predator-prey interactions and food-web stability.

Short Isoforms of the Cold Receptor TRPM8 Inhibit Channel Gating by Mimicking Heat Action Rather than Chemical Inhibitors

Transient receptor potential (TRP) channels couple various environmental factors to changes in membrane potential, calcium influx, and cell signaling. They also integrate multiple stimuli through their typically polymodal activation. Thus, although the TRPM8 channel has been extensively investigated as the major neuronal cold sensor, it is also regulated by various chemicals, as well as by several short channel isoforms. Mechanistic understanding of such complex regulation is facilitated by quantitative single-channel analysis. We have recently proposed a single-channel mechanism of TRPM8 regulation by voltage and temperature. Using this gating mechanism, we now investigate TRPM8 inhibition in cell-attached patches using HEK293 cells expressing TRPM8 alone or coexpressed with its short sM8-6 isoform. This is compared with inhibition by the chemicals N-(4-tert-butylphenyl)-4-(3-chloropyridin-2-yl)piperazine-1-carboxamide (BCTC) and clotrimazole or by elevated temperature. We found that within the seven-state single-channel gating mechanism, inhibition of TRPM8 by short sM8-6 isoforms closely resembles inhibition by increased temperature. In contrast, inhibition by BCTC and that by clotrimazole share a different set of common features. © 2012 by The American Society for Biochemistry and Molecular Biology, Inc.

Emission lines of Fe XI in the 257-407 A wavelength region observed in solar spectra from EIS/Hinode and SERTS

Theoretical emission-line ratios involving Fe xi transitions in the 257-407 A wavelength range are derived using fully relativistic calculations of radiative rates and electron impact excitation cross-sections. These are subsequently compared with both long wavelength channel Extreme-Ultraviolet Imaging Spectrometer (EIS) spectra from the Hinode satellite (covering 245-291 A) and first-order observations (similar to 235-449 A) obtained by the Solar Extreme-ultraviolet Research Telescope and Spectrograph (SERTS). The 266.39, 266.60 and 276.36 A lines of Fe xi are detected in two EIS spectra, confirming earlier identifications of these features, and 276.36 A is found to provide an electron density (N-e) diagnostic when ratioed against the 257.55 A transition. Agreement between theory and observation is found to be generally good for the SERTS data sets, with discrepancies normally being due to known line blends, while the 257.55 A feature is detected for the first time in SERTS spectra. The most useful Fe xi electron density diagnostic is found to be the 308.54/352.67 intensity ratio, which varies by a factor of 8.4 between N-e = 108 and 1011 cm-3, while showing little temperature sensitivity. However, the 349.04/352.67 ratio potentially provides a superior diagnostic, as it involves lines which are closer in wavelength, and varies by a factor of 14.7 between N-e = 108 and 1011 cm-3. Unfortunately, the 349.04 A line is relatively weak, and also blended with the second-order Fe x 174.52 A feature, unless the first-order instrument response is enhanced.