453 research outputs found

    Proton transfer reactions of N-aryl triazolium salts: unusual ortho-substituent effects

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    Previous studies of the C(3)-hydrogen/deuterium exchange reactions of the triazolium ion conjugate acids of triazolyl N-heterocyclic carbenes revealed a change of mechanism under acidic conditions with N1-protonation to a dicationic salt. Interestingly, the data suggested an increase in pKaN1 in the presence of a N-pentafluorophenyl substituent relative to other N-aryl substituents with hydrogens or methyl substituents rather than fluorines at the ortho-positions. To probe the presence of an apparent donor effect of a N-pentafluorophenyl substituent, which differs from the more common electron withdrawing effect of this group, we have studied the analogous deuterium exchange reactions of four triazolium salts with heteroatoms or heteroatom substituents in the 2-position and/or 6-position of the N-aryl ring. These include triazolium salts with N-2,4,6-tribromophenyl 11, N-2,6-dichlorophenyl 12, N-2-pyridyl 13 and N-2-pyrimidinyl 14 substituents. The log kex – pD profiles for 11, 12 and 14 were found to show similar trends at lower pDs as for the previously studied N-pentafluorophenyl triazolium salt, hence supporting the presence an apparent donor effect on pKaN1. Surprisingly, the log kex – pD profile for N-pyridyl salt 13 uniquely showed acid catalysis at lower pDs. We propose herein that this data is best explained by invoking an intramolecular general base role for the N-(2-pyridyl) substituent in conjunction with N1-protonation on the triazolium ring. Finally, the second order rate constants for deuteroxide ion catalysed C(3)-H/D exchange (kDO, M−1 s−1), which could be obtained from data at pDs >1.5, were used to provide estimates of C(3)-carbon acid pKaC3 values for the four triazolium salts 11, 12, 13, 14

    Slow-light optical buffers: capabilities and fundamental limitations

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    Five-Year Wilkinson Microwave Anisotropy Probe (WMAP)Observations: Beam Maps and Window Functions

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    Cosmology and other scientific results from the WMAP mission require an accurate knowledge of the beam patterns in flight. While the degree of beam knowledge for the WMAP one-year and three-year results was unprecedented for a CMB experiment, we have significantly improved the beam determination as part of the five-year data release. Physical optics fits are done on both the A and the B sides for the first time. The cutoff scale of the fitted distortions on the primary mirror is reduced by a factor of approximately 2 from previous analyses. These changes enable an improvement in the hybridization of Jupiter data with beam models, which is optimized with respect to error in the main beam solid angle. An increase in main-beam solid angle of approximately 1% is found for the V2 and W1-W4 differencing assemblies. Although the five-year results are statistically consistent with previous ones, the errors in the five-year beam transfer functions are reduced by a factor of approximately 2 as compared to the three-year analysis. We present radiometry of the planet Jupiter as a test of the beam consistency and as a calibration standard; for an individual differencing assembly. errors in the measured disk temperature are approximately 0.5%

    SPIDER: Probing the Early Universe with a Suborbital Polarimeter

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    We evaluate the ability of SPIDER, a balloon-borne polarimeter, to detect a divergence-free polarization pattern ("B-modes") in the Cosmic Microwave Background (CMB). In the inflationary scenario, the amplitude of this signal is proportional to that of the primordial scalar perturbations through the tensor-to-scalar ratio r. We show that the expected level of systematic error in the SPIDER instrument is significantly below the amplitude of an interesting cosmological signal with r=0.03. We present a scanning strategy that enables us to minimize uncertainty in the reconstruction of the Stokes parameters used to characterize the CMB, while accessing a relatively wide range of angular scales. Evaluating the amplitude of the polarized Galactic emission in the SPIDER field, we conclude that the polarized emission from interstellar dust is as bright or brighter than the cosmological signal at all SPIDER frequencies (90 GHz, 150 GHz, and 280 GHz), a situation similar to that found in the "Southern Hole." We show that two ~20-day flights of the SPIDER instrument can constrain the amplitude of the B-mode signal to r<0.03 (99% CL) even when foreground contamination is taken into account. In the absence of foregrounds, the same limit can be reached after one 20-day flight.Comment: 29 pages, 8 figures, 4 tables; v2: matches published version, flight schedule updated, two typos fixed in Table 2, references and minor clarifications added, results unchange

    Five-Year Wilkinson Microwave Anisotropy Probe (WMAP) Observations: Likelihoods and Parameters from the WMAP Data

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    The Wilkinson Microwave Anisotropy Probe (WMAP), launched in 2001, has mapped out the Cosmic Microwave Background with unprecedented accuracy over the whole sky. Its observations have led to the establishment of a simple concordance cosmological model for the contents and evolution of the universe, consistent with virtually all other astronomical measurements. The WMAP first-year and three-year data have allowed us to place strong constraints on the parameters describing the ACDM model. a flat universe filled with baryons, cold dark matter, neutrinos. and a cosmological constant. with initial fluctuations described by nearly scale-invariant power law fluctuations, as well as placing limits on extensions to this simple model (Spergel et al. 2003. 2007). With all-sky measurements of the polarization anisotropy (Kogut et al. 2003; Page et al. 2007), two orders of magnitude smaller than the intensity fluctuations. WMAP has not only given us an additional picture of the universe as it transitioned from ionized to neutral at redshift z approx.1100. but also an observation of the later reionization of the universe by the first stars. In this paper we present cosmological constraints from WMAP alone. for both the ACDM model and a set of possible extensions. We also consider tlle consistency of WMAP constraints with other recent astronomical observations. This is one of seven five-year WMAP papers. Hinshaw et al. (2008) describe the data processing and basic results. Hill et al. (2008) present new beam models arid window functions, Gold et al. (2008) describe the emission from Galactic foregrounds, and Wright et al. (2008) the emission from extra-Galactic point sources. The angular power spectra are described in Nolta et al. (2008), and Komatsu et al. (2008) present and interpret cosmological constraints based on combining WMAP with other data. WMAP observations are used to produce full-sky maps of the CMB in five frequency bands centered at 23, 33, 41, 61, and 94 GHz (Hinshaw et al. 2008). With five years of data, we are now able to place better limits on the ACDM model. as well as to move beyond it to test the composition of the universe. details of reionization. sub-dominant components, characteristics of inflation, and primordial fluctuations. We have more than doubled the amount of polarized data used for cosmological analysis. allowing a better measure of the large-scale E-mode signal (Nolta et al. 2008). To this end we describe an alternative way to remove Galactic foregrounds from low resolution polarization maps in which Galactic emission is marginalized over, providing a cross-check of our results. With longer integration we also better probe the second and third acoustic peaks in the temperature angular power spectrum, and have many more year-to-year difference maps available for cross-checking systematic effects (Hinshaw et al. 2008)

    Groundwater resources in the Indo-Gangetic Basin : resilience to climate change and abstraction

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    Groundwater within the Indo‐Gangetic Basin (IGB) alluvial aquifer system forms one of the world’s most important and heavily exploited reservoirs of freshwater. In this study we have examined the groundwater system through the lens of its resilience to change – both from the impact of climate change and increases in abstraction. This has led to the development of a series of new maps for the IGB aquifer, building on existing datasets held in Pakistan, India, Nepal and Bangladesh, a review of approximately 500 reports and papers, and three targeted field studies on under‐researched topics within the region. The major findings of the study are described below. The IGB groundwater system 1. The IGB alluvial aquifer system comprises a large volume of heterogeneous unconsolidated sediment in a complex environmental setting. Annual rainfall varies from 2000mm in the Bengal basin, and the system is dissected by the major river systems of the Indus, Ganges and Brahmaputra. The groundwater system has been modified by the introduction of large scale canal irrigation schemes using water from the Indus and Ganges since the 19th and early 20th centuries. 2. High yielding tubewells can be sustained in most parts of the alluvial aquifer system; permeability is often in the range of 10 – 60 m/d and specific yield (the drainable porosity) varies from 5 – 20%, making it highly productive. 3. High salinity and elevated arsenic concentrations exist in parts of the basin limiting the usefulness of the groundwater resource. Saline water predominates in the Lower Indus, and near to the coast in the Bengal Delta, and is also a major concern in the Middle Ganges and Upper Ganges (covering much of the Punjab Region in Pakistan, southern Punjab, Haryana and parts of Uttar Pradesh in India). Arsenic severely impacts the development of shallow groundwater in the fluvial influenced deltaic area of the Bengal Basin. 4. Recharge to the IGB aquifer system is substantial and dynamic, controlled by monsoonal rainfall, leakage from canals, river infiltration and irrigation returns. Recharge from rainfall can occur even with low annual rainfall (350 mm) and appears to dominate where rainfall is higher (> 750 mm). Canal leakage is also highly significant and constitutes the largest proportion of groundwater recharge in the drier parts of the aquifer, partially mitigating the effects of abstraction on groundwater storage. 5. Deep groundwater (>150 m) in the Bengal basin has strategic value for water supply, health and economic development. Excessive abstraction poses a greater threat to the quality of this deep groundwater than climate change. Heavy pumping may induce the downward migration of arsenic in parts of Bangladesh, and of saline water in coastal regions, but field evidence and modelling both suggest that deep groundwater abstraction for public water supply in southern Bangladesh is in general secure against widespread ingress of arsenic and saline water for at least 100 years

    Production and Clinical Evaluation of Norwalk GI.1 Virus Lot 001-09NV in Norovirus Vaccine Development

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    Background: Human noroviruses (HuNoV) are the leading cause of gastroenteritis. No vaccine is currently available to prevent norovirus illness or infection. Safe, infectious challenge strains are needed to assess vaccine efficacy in the controlled human infection model (CHIM). Methods: A stock of HuNoV strain Norwalk virus ([NV] GI.1) was prepared. Healthy, genetically susceptible adults were inoculated with NV Lot 001-09NV and monitored for infection, gastroenteritis symptoms, and immune responses. Results: Lot 001-09NV induced gastroenteritis in 9 (56%) and infection in 11 (69%) of 16 genetically susceptible subjects. All infected subjects developed strong immune responses to GI.1 with a 30-fold (geometric mean titer) increase in blocking titers (BT50) and a 161-fold increase in GI.1-specific immunoglobulin (Ig)G titers when compared with baseline. GI.1-specific cellular responses in peripheral blood were observed 9 days postchallenge with an average of 3253 IgA and 1227 IgG antibody-secreting cells per million peripheral blood mononuclear cells. Conclusions: GI.1 Lot 001-09NV appears to be similar in virulence to previous passages of NV strain 8fIIa. The safety profile, attack rate, and duration of illness make GI.1 Lot 001-09NV a useful challenge strain for future vaccine studies aimed at establishing immune correlates

    Pilot scale microwave sorting of porphyry copper ores: Part 1: laboratory investigations

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    Microwave treatment followed by infrared thermal imaging (MW–IRT) has been proposed as a potential excitation-discrimination technique to facilitate sorting of porphyry copper ores. A continuous, high throughput (up to 100t/h), belt–based microwave cavity operating at up to 100kW has been designed to interface directly with commercially available sorters at industrially relevant scales. In this paper, the fragment-by-fragment thermal response of 16 porphyry copper ore samples following microwave treatment in the bespoke system is evaluated to elucidate key performance criteria and identify likely candidate ores for microwave sorting. Microwave treatment energy dose was found to be the driving force behind the ultimate average temperature fragments experience, with other process variables (e.g. belt speed, power, belt mass loading, thermal equilibration time) having little effect on sortability performance. While fragment mineralogical texture and ore textural heterogeneity were shown to influence the average temperature rise of the fragment surface presented to the thermal camera, in most cases this variability did not adversely affect sortability performance. An abundance of microwave-heating gangue minerals (e.g. iron sulphides, iron oxides and hydrated clays) was shown to be the dominant source of deviation from intrinsic sortability. However, low average moisture content and co-mineralisation of copper and iron sulphides (or bulk sulphide sorting) was found to mitigate the deviation and provide better sortability performance. An attractive separation could be proposed for many of the ores tested, either to remove a large proportion of barren fragments from ore-grade material or concentrate a large proportion of copper values from waste-grade material
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