Theoretical and experimental correlations of gas dissolution, diffusion, and thermodynamic properties in determination of gas permeability and selectivity in supported ionic liquid membranes

Supported ionic liquid membranes (SILMs) has the potential to be a new technological platform for gas/organic vapour separation because of the unique non-volatile nature and discriminating gas dissolution properties of room temperature ionic liquids (ILs). This work starts with an examination of gas dissolution and transport properties in bulk imidazulium cation based ionic liquids [C_nmim][NTf2] (n = 2.4, 6, 8.10) from simple gas H₂, N₂, to polar CO₂, and C₂H₆, leading to a further analysis of how gas dissolution and diffusion are influenced by molecular specific gas-SILMs interactions, reflected by differences in gas dissolution enthalpy and entropy. These effects were elucidated again during gas permeation studies by examining how changes in these properties and molecular specific interactions work together to cause deviations from conventional solution–diffusion theory and their impact on some remarkably contrasting gas perm-selectivity performance. The experimental perm-selectivity for all tested gases showed varied and contrasting deviation from the solution–diffusion, depending on specific gas-IL combinations. It transpires permeation for simpler non-polar gases (H₂, N₂) is diffusion controlled, but strong molecular specific gas-ILs interactions led to a different permeation and selectivity performance for C₂H₆ and CO₂. With exothermic dissolution enthalpy and large order disruptive entropy, C₂H₆ displayed the fastest permeation rate at increased gas phase pressure in spite of its smallest diffusivity among the tested gases. The C₂H₆ gas molecules “peg” on the side alkyl chain on the imidazulium cation at low concentration, and are well dispersed in the ionic liquids phase at high concentration. On the other hand strong CO₂-ILs affinity resulted in a more prolonged “residence time” for the gas molecule, typified by reversed CO₂/N₂ selectivity and slowest CO₂ transport despite CO₂ possess the highest solubility and comparable diffusivity in the ionic liquids. The unique transport and dissolution behaviour of CO₂ are further exploited by examining the residing state of CO₂ molecules in the ionic liquid phase, which leads to a hypothesis of a condensing and holding capacity of ILs towards CO₂, which provide an explanation to slower CO₂ transport through the SILMs. The pressure related exponential increase in permeations rate is also analysed which suggests a typical concentration dependent diffusion rate at high gas concentration under increased gas feed pressure. Finally the strong influence of discriminating and molecular specific gas-ILs interactions on gas perm-selectivity performance points to future specific design of ionic liquids for targeted gas separations.

Study of structural change in Wyodak coal in high pressure CO2 by small-angle neutron scattering

Small angle neutron scattering (SANS) has been applied to examine the effect of high pressure CO2 on the structure of Wyodak coal. Significant decrease in the scattering intensities upon exposure of the coal to high pressure CO2 showed that high pressure CO2 rapidly adsorbs on the coal and reaches to all pores in the structure. This is confirmed by strong and steep exothermic peaks observed on DSC scans during coal/ CO2 interactions. In situ small angle neutron scattering on coal at high pressure CO2 atmosphere showed an increase in scattering intensities with time suggesting that after adsorption, high pressure CO2 immediately begins to diffuse into the coal matrix, changes the macromolecular structure of the coal, swells the matrix and probably creates microporosity in coal structure by extraction of volatile components from coal. Significant decrease in the glass transition temperature of coal caused by high pressure CO2 also confirms that CO2 at elevated pressures dissolve in the coal matrix, results in significant plasticization and physical rearrangement of the coal’s macromolecular structure.

Hydrogen peroxide vapour indicator

A hydrogen peroxide vapour indicator is described comprising a triarylmethane dye, lissamine green (LG), dissolved in a polymer, polyvinyl alcohol (PVA). The indicator is green/blue in the absence of hydrogen peroxide vapour but is rapidly bleached in the presence of hydrogen peroxide vapour. The kinetics of LG bleaching appear approximately first order with respect [LG] and the concentration of H2O2, which, in turn, is proportional to the partial pressure of H2O2. However, the kinetics also appear to depend directly upon the reciprocal of the film thickness, implying some dependence upon the diffusion of the H2O2 vapour through the indicator film. Like most other H2O2 indicator films (such as starch-iodide paper), the LG/PVA indicator is not particularly selective and responds to most other volatile strong oxidising agents, such as ozone and chlorine. However, it is rapid in response (

Platinum and Palladium in Semiconductor Photocatalytic Systems FACTORS AFFECTING THE PURIFICATION OF WATER AND AIR

A wide range of organic pollutants can be destroyed by semiconductor photocatalysis using titania. The purification of water and air contaminated with organic pollutants has been investigated by semiconductor photocatalysis for many years and in attempts to improve the purification rate platinum and palladium have been deposited, usually as fine particles, on the titania surface. Such deposits are expected to improve the rate of reduction of oxygen and so reduce the probability of electron-hole recombination and increase the overall rate of the reaction. The effectiveness of the deposits is reviewed here and appears very variable with reported rate enhancement factors ranging from 8 to 0.1. Semiconductor photocatalysis can be used to purify air (at temperatures > 100 degrees C) and Pt deposits can markedly improve the overall rate of mineralisation. However, volatile organic compounds containing an heteroatom can deactivate the photocatalyst completely and irreversibly. Factors contributing to the success of the processes are considered. The use of chloro-Pt(IV)-titania and other chloro-platinum group metals-titania complexes as possible visible light sensitisers for water and air purification is briefly reviewed.

Observational and Dynamical Characterization of Main-belt Comet P/2010 R2 (La Sagra)

We present observations of the recently discovered comet-like main-belt object P/2010 R2 (La Sagra) obtained by Pan-STARRS1 and the Faulkes Telescope-North on Haleakala in Hawaii, the University of Hawaii 2.2 m, Gemini-North, and Keck I telescopes on Mauna Kea, the Danish 1.54 m telescope (operated by the MiNDSTEp consortium) at La Silla, and the Isaac Newton Telescope on La Palma. An antisolar dust tail is observed to be present from 2010 August through 2011 February, while a dust trail aligned with the object's orbit plane is also observed from 2010 December through 2011 August. Assuming typical phase darkening behavior, P/La Sagra is seen to increase in brightness by >1 mag between 2010 August and December, suggesting that dust production is ongoing over this period. These results strongly suggest that the observed activity is cometary in nature (i.e., driven by the sublimation of volatile material), and that P/La Sagra is therefore the most recent main-belt comet to be discovered. We find an approximate absolute magnitude for the nucleus of HR = 17.9 ± 0.2 mag, corresponding to a nucleus radius of ~0.7 km, assuming an albedo of p = 0.05. Comparing the observed scattering surface areas of the dust coma to that of the nucleus when P/La Sagra was active, we find dust-to-nucleus area ratios of Ad /AN = 30-60, comparable to those computed for fellow main-belt comets 238P/Read and P/2008 R1 (Garradd), and one to two orders of magnitude larger than for two other main-belt comets (133P/Elst-Pizarro and 176P/LINEAR). Using optical spectroscopy to search for CN emission, we do not detect any conclusive evidence of sublimation products (i.e., gas emission), finding an upper limit CN production rate of Q CN 100 Myr, suggesting that it is likely native to its current location and that its composition is likely representative of other objects in the same region of the main belt, though the relatively close proximity of the 13:6 mean-motion resonance with Jupiter and the (3,-2,-1) three-body mean-motion resonance with Jupiter and Saturn mean that dynamical instability on larger timescales cannot be ruled out.

Why and how FDI stocks are a biased measure of MNE affiliate activity

Many international business (IB) studies have used foreign direct investment (FDI) stocks to measure the aggregate value-adding activity of multinational enterprises (MNE) affiliates in host countries. We argue that FDI stocks are a biased measure of that activity, because the degree to which they overestimate or underestimate affiliate activity varies systematically with host-country characteristics. First, most FDI into countries that serve as tax havens generate no actual productive activity; thus FDI stocks in such countries overestimate affiliate activity. Second, FDI stocks do not include locally raised external funds, funds widely used in countries with well-developed financial markets or volatile exchange rates, resulting in an underestimation of affiliate activity in such countries. Finally, the extent to which FDI translates into affiliate activity increases with affiliate labor productivity, so in countries where labor is more productive, FDI stocks also result in an underestimation of affiliate activity. We test these hypotheses by first regressing affiliate value-added and affiliate sales on FDI stocks to calculate a country-specific mismatch, and then by regressing this mismatch on a host country's tax haven status, level of financial market development, exchange rate volatility, and affiliate labor productivity. All hypotheses are supported, implying that FDI stocks are a biased measure of MNE affiliate activity, and hence that the results of FDI-data-based studies of such activity need to be reconsidered. [ABSTRACT FROM AUTHOR]

Interface mediated resistive switching in epitaxial NiO nanostructures

We report on the non-volatile resistive switching properties of epitaxial nickel oxide (NiO) nanostructures, 10-100 nm wide and up to 30 nm high grown on (001)-Nb:SrTiO3 substrates. Conducting-atomic force microscopy on individual nano-islands confirms prominent bipolar switching with a maximum ON/OFF ratio of similar to 10(3) at a read voltage of similar to+0.4V. This ratio is found to decrease with increasing height of the nanostructure. Linear fittings of I-V loops reveal that low and high resistance states follow Ohmic-conduction and Schottky-emission mechanism, respectively. The switching behavior (dependence on height) is attributed to the modulation of the carrier density at the nanostructure-substrate interface due to the applied electric field.

Investigation of organic xenobiotic transfers, partitioning and processing in air-soil-plant systems using a microcosm apparatus. Part II:comparing the fate of chlorobenzenes in grass planted soil

A microcosm system was used to investigate and compare transfers of 14C labeled-1,2-dichlorobenzene (DCB), 1,2,4-trichlorobenzene (TCB) and hexachlorobenzene (HCB) in an air-soil-plant system using single grass tillers planted into spiked soil. This study was the second phase of a development investigation for eventual study of a range of xenobiotic pollutants. Recoveries from the system were excellent at >90%. The predominant loss pathway for 14C labeled-1,2-DCB and 1,2,4-TCB was volatilisation with 85% and 76% volatilisation of parent compound and volatile metabolites over 5 weeks respectively. Most of the added label in the hexachlorobenzene spiked system remained in soil. Mineralisation was

Toxicity assessment of xenobiotic contaminated groundwater using lux modified Pseudomonas fluorescens

A bacterial bioassay, suitable for rapid screening to assess the relative toxicity of xenobiotic contaminated groundwater has been developed. The quantitative bioassay utilizes a decline in luminescence of the lux marked soil bacterium Pseudomonas fluorescens on exposure to contaminated groundwaters from which effective concentration (EC) values can be assessed and compared. P. fluorescens was most sensitive to semi-volatile organics in groundwaters but there was no correlation between EC value and chemical content. The sensitivity and reproducibility of the P. fluorescens bioassay was compared with that of Microtox and results showed that mean EC₅₀ values for diluted ground water replicate samples were 20% and 18% respectively. This suggested that the P. fluorescens bioassay was as applicable to groundwater screening as the widely used Microtox bioassay.

Molecular line emission from a protoplanetary disk irradiated externally by a nearby massive star

Star formation often occurs within or nearby stellar clusters. Irradiation by nearby massive stars can photoevaporate protoplanetary disks around young stars (so-called proplyds) which raises questions regarding the ability of planet formation to take place in these environments. We investigate the two-dimensional physical and chemical structure of a protoplanetary disk surrounding a low-mass (T Tauri) star which is irradiated by a nearby massive O-type star to determine the survivability and observability of molecules in proplyds. Compared with an isolated star-disk system, the gas temperature ranges from a factor of a few (in the disk midplane) to around two orders of magnitude (in the disk surface) higher in the irradiated disk. Although the UV flux in the outer disk, in particular, is several orders of magnitude higher, the surface density of the disk is sufficient for effective shielding of the disk midplane so that the disk remains predominantly molecular in nature. We also find that non-volatile molecules, such as HCN and H2O, are able to freeze out onto dust grains in the disk midplane so that the formation of icy planetesimals, e.g., comets, may also be possible in proplyds. We have calculated the molecular line emission from the disk assuming LTE and determined that multiple transitions of atomic carbon, CO (and isotopologues, 13CO and C18O), HCO+, CN, and HCN may be observable with ALMA, allowing characterization of the gas column density, temperature, and optical depth in proplyds at the distance of Orion (˜400 pc).

The biology of habitat dominance; can microbes behave as weeds?

Competition between microbial species is a product of, yet can lead to a reduction in, the microbial diversity of specific habitats. Microbial habitats can resemble ecological battlefields where microbial cells struggle to dominate and/or annihilate each other and we explore the hypothesis that (like plant weeds) some microbes are genetically hard-wired to behave in a vigorous and ecologically aggressive manner. These 'microbial weeds' are able to dominate the communities that develop in fertile but uncolonized - or at least partially vacant - habitats via traits enabling them to out-grow competitors; robust tolerances to habitat-relevant stress parameters and highly efficient energy-generation systems; avoidance of or resistance to viral infection, predation and grazers; potent antimicrobial systems; and exceptional abilities to sequester and store resources. In addition, those associated with nutritionally complex habitats are extraordinarily versatile in their utilization of diverse substrates. Weed species typically deploy multiple types of antimicrobial including toxins; volatile organic compounds that act as either hydrophobic or highly chaotropic stressors; biosurfactants; organic acids; and moderately chaotropic solutes that are produced in bulk quantities (e.g. acetone, ethanol). Whereas ability to dominate communities is habitat-specific we suggest that some microbial species are archetypal weeds including generalists such as: Pichia anomala, Acinetobacter spp. and Pseudomonas putida; specialists such as Dunaliella salina, Saccharomyces cerevisiae, Lactobacillus spp. and other lactic acid bacteria; freshwater autotrophs Gonyostomum semen and Microcystis aeruginosa; obligate anaerobes such as Clostridium acetobutylicum; facultative pathogens such as Rhodotorula mucilaginosa, Pantoea ananatis and Pseudomonas aeruginosa; and other extremotolerant and extremophilic microbes such as Aspergillus spp., Salinibacter ruber and Haloquadratum walsbyi. Some microbes, such as Escherichia coli, Mycobacterium smegmatis and Pseudoxylaria spp., exhibit characteristics of both weed and non-weed species. We propose that the concept of nonweeds represents a 'dustbin' group that includes species such as Synodropsis spp., Polypaecilum pisce, Metschnikowia orientalis, Salmonella spp., and Caulobacter crescentus. We show that microbial weeds are conceptually distinct from plant weeds, microbial copiotrophs, r-strategists, and other ecophysiological groups of microorganism. Microbial weed species are unlikely to emerge from stationary-phase or other types of closed communities; it is open habitats that select for weed phenotypes. Specific characteristics that are common to diverse types of open habitat are identified, and implications of weed biology and open-habitat ecology are discussed in the context of further studies needed in the fields of environmental and applied microbiology.

Preliminary clinical assessment of polyvinyl alcohol-tetrahydroxyborate hydrogels as potential topical formulations for local anesthesia of lacerations

The aim of this study was to assess a novel semisolid material as a potential topical drug delivery system for acute laceration. The objectives were to correlate physical characterization data using rheologic studies and to compare with clinical assessment of performance in an emergency department (ED).

The use of topical anaesthesia during repair of minor lacerations in Departments of Emergency Medicine:a literature review

There are currently a number of different methods available to obtain anaesthesia in minor dermatological procedures. Although intradermal infiltration of 1% lidocaine is the favoured method for anaesthesia induction in laceration repair, it can cause significant pain in itself. Topical anaesthesia has been investigated as an alternative to infiltration anaesthesia, with the majority of studies looking at preparations of either TAC (tetracaine, adrenaline and cocaine) or LAT (lidocaine, adrenaline and tetracaine).

Magma Evolution in the Primitive, Intra-oceanic Tonga Arc: Petrogenesis of Basaltic Andesites at Tofua Volcano

Tofua volcano is situated midway along the Tonga oceanic arc and has undergone two phases of ignimbrite-forming activity. The eruptive products are almost entirely basaltic andesites (52 center dot 5-57 wt % SiO2) with the exception of a volumetrically minor pre-caldera dacite. The suite displays a strong tholeiitic trend with K2O <1 wt %. Phenocryst assemblages typically comprise plagioclase + clinopyroxene +/- orthopyroxene with microlites of Ti-magnetite. Olivine (Fo(83-88)) is rare and believed to be dominantly antecrystic. An increase in the extent and frequency of reverse zoning in phenocrysts, sieve-textured plagioclase and the occurrence of antecrystic phases in post-caldera lavas record a shift to dynamic conditions, allowing the interaction of magma batches that were previously distinct. Pyroxene thermobarometry suggests crystallization at 950-1200 degrees C and 0 center dot 8-1 center dot 8 kbar. Volatile measurements of glassy melt inclusions indicate a maximum H2O content of 4 center dot 16 wt % H2O, and CO2-H2O saturation curves indicate that crystallization occurred at two levels, at depths of 4-5 center dot 5 km and 1 center dot 5-2 center dot 5 km. Major and trace element models suggest that the compositions of the majority of the samples represent a differentiation trend whereby the dacite was produced by 65% fractional crystallization of the most primitive basaltic andesite. Trace element models suggest that the sub-arc mantle source is the residuum of depleted Indian mid-ocean ridge basalt mantle (IDMM-1% melt), whereas radiogenic isotope data imply addition of 0 center dot 2% average Tongan sediment melt and a fluid component derived from the subducted altered Pacific oceanic crust. A horizontal array on the U-Th equiline diagram and Ra excesses of up to 500% suggest fluid addition to the mantle wedge within the last few thousand years. Time-integrated (Ra-226/Th-230) vs Sr/Th and Ba/Th fractionation models imply differentiation timescales of up to 4500 years for the dacitic magma compositions at Tofua.