Re-evaluating the Cu K pre-edge XAS transition in complexes with covalent metal–ligand interactions

Three [Me2NN]Cu(h2 -L2) complexes (Me2NN ¼ HC[C(Me)NAr]2; L2 ¼ PhNO (2), ArF 2N2 (3), PhCH]CH2 (4); Ar ¼ 2,6-Me2-C6H3; ArF ¼ 3,5-(CF3)2-C6H3) have been studied by Cu K-edge X-ray absorption spectroscopy, as well as single- and multi-reference computational methods (DFT, TD-DFT, CASSCF, MRCI, and OVB). The study was extended to a range of both known and theoretical compounds bearing 2p-element donors as a means of deriving a consistent view of how the pre-edge transition energy responds in systems with significant ground state covalency. The ground state electronic structures of many of the compounds under investigation were found to be strongly influenced by correlation effects, resulting in ground state descriptions with majority contributions from a configuration comprised of a Cu(II) metal center anti-ferromagentically coupled to radical anion O2, PhNO, and ArF 2N2 ligands. In contrast, the styrene complex 4, which displays a Cu K pre-edge transition despite its formal d10 electron configuration, exhibits what can best be described as a Cu(I):(styrene)0 ground state with strong pbackbonding. The Cu K pre-edge features for these complexes increase in energy from 1 to 4, a trend that was tracked to the percent Cu(II)-character in the ground state. The unexpected shift to higher preedge transition energies with decreasing charge on copper (QCu) contributed to an assignment of the pre-edge features for these species as arising from metal-to-ligand charge transfer instead of the traditional Cu1s / Cu3d designation

Hot gas ingestion characteristics and flow visualization of a vectored thrust STOVL concept

A 9.2 percent scale short takeoff and vertical landing (STOVL) hot gas ingestion model was designed and built by McDonnell Douglas Corporation (MCAIR) and tested in the NASA Lewis Research Center 9- by 15-Foot Low Speed Wind Tunnel (LSWT). Hot gas ingestion, the entrainment of heated engine exhaust into the inlet flow field, is a key development issue for advanced short takeoff and vertical landing aircraft. The Phase 1 test program, conducted by NASA Lewis and McDonnell Douglas Corporation, evaluated the hot ingestion phenomena and control techniques and Phase 2 test program which was conducted by NASA Lewis are both reported. The Phase 2 program was conducted at exhaust nozzles temperatures up to 1460 R and utilized a sheet laser system for flow visualization of the model flow field in and out of ground effects. Hot gas ingestion levels were measured for the several forward nozzle splay configurations and with flow control/lift improvement devices which reduced the hot gas ingestion. The model support system had four degrees of freedom, heated high pressure air for nozzle flow, and a suction system exhaust for inlet flow. The headwind (freestream) velocity for Phase 1 was varied from 8 to 90 kn, with primary data taken in the 8 to 23 kn headwind velocity range. Phase 2 headwind velocity varied from 10 to 23 kn. Results of both Phase 1 and 2 are presented. A description of the model, facility, a new model support system, and a sheet laser illumination system are also provided. Results are presented over a range of main landing gear height (model height) above the ground plane at a 10 kn headwind velocity. The results contain the compressor face pressure and temperature distortions, total pressure recovery, compressor face temperature rise, and the environmental effects of the hot gas. The environmental effects include the ground plane temperature and pressure distributions, model airframe heating, and the location of the ground flow separation. Results from the sheet laser flow visualization test are also shown

The silence of self-knowledge

Gareth Evans famously affirmed an explanatory connection between answering the question whether p and knowing whether one believes that p. This is commonly interpreted in terms of the idea that judging that p constitutes an adequate basis for the belief that one believes that p. This paper formulates and defends an alternative, more modest interpretation, which develops from the suggestion that one can know that one believes that p in judging that p

Estimating oceanic primary production using vertical irradiance and chlorophyll profiles from ocean gliders in the North Atlantic

An autonomous underwater vehicle (Seaglider) has been used to estimate marine primary production (PP) using a combination of irradiance and fluorescence vertical profiles. This method provides estimates for depth-resolved and temporally evolving PP on fine spatial scales in the absence of ship-based calibrations. We describe techniques to correct for known issues associated with long autonomous deployments such as sensor calibration drift and fluorescence quenching. Comparisons were made between the Seaglider, stable isotope (13C), and satellite estimates of PP. The Seaglider-based PP estimates were comparable to both satellite estimates and stable isotope measurements

Landscape Genetics Reveals Focal Transmission of a Human Macroparasite

Macroparasite infections (e.g., helminths) remain a major human health concern. However, assessing transmission dynamics is problematic because the direct observation of macroparasite dispersal among hosts is not possible. We used a novel landscape genetics approach to examine transmission of the human roundworm Ascaris lumbricoides in a small human population in Jiri, Nepal. Unexpectedly, we found significant genetic structuring of parasites, indicating the presence of multiple transmission foci within a small sampling area (∼14 km2). We analyzed several epidemiological variables, and found that transmission is spatially autocorrelated around households and that transmission foci are stable over time despite extensive human movement. These results would not have been obtainable via a traditional epidemiological study based on worm counts alone. Our data refute the assumption that a single host population corresponds to a single parasite transmission unit, an assumption implicit in many classic models of macroparasite transmission. Newer models have shown that the metapopulation-like pattern observed in our data can adversely affect targeted control strategies aimed at community-wide impacts. Furthermore, the observed metapopulation structure and local mating patterns generate an excess of homozygotes that can accelerate the spread of recessive traits such as drug resistance. Our study illustrates how molecular analyses complement traditional epidemiological information in providing a better understanding of parasite transmission. Similar landscape genetic approaches in other macroparasite systems will be warranted if an accurate depiction of the transmission process is to be used to inform effective control strategies

Performance of a BGO PET/CT with Higher Resolution PET Detectors

A new PET detector block has been designed to replace the standard detector of the Discovery ST PET/CT system. The new detector block is the same size as the original, but consists of an 8/spl times/6 (tangential× axial) matrix of crystals rather than the original 6/spl times/6. The new crystal dimensions are 4.7× 6.3× 30 mm/sup 3/ (tangential× axial× radial). Full PET/CT systems have been built with these detectors (Discovery STE). Most other aspects of the system are identical to the standard Discovery ST, with differences including the low energy threshold for 3D imaging (now 425 keV) and front-end electronics. Initial performance evaluation has been done, including NEMA NU2-2001 tests and imaging of the 3D Hoffman brain phantom and a neck phantom with small lesions. The system sensitivity was 1.90 counts/s/kBq in 2D, and 9.35 counts/s/kBq in 3D. Scatter fractions measured for 2D and 3D, respectively, were 18.6% and 34.5%. In 2D, the peak NEC of 89.9 kcps occurred at 47.0 kBq/cc. In 3D, the peak NEC of 74.3 kcps occurred at 8.5 kBq/cc. Spatial resolution (all expressed in mm FWHM) measured in 2D for 1 cm off-axis source 5.06 transaxial, 5.14 axial and for 10 cm source 5.45 radial, 5.86 tangential, and 6.23 axial. In 3D for 1 cm off-axis source 5.13 transaxial, 5.74 axial, and for 10 cm source 5.92 radial, 5.54 tangential, and 6.16 axial. Images of the brain and neck phantom demonstrate some improvement, compared to measurements on a standard Discovery ST

Nighttime removal of NOx in the summer marine boundary layer

The nitrate radical, NO3, and dinitrogen pentoxide, N2O5, are two important components of nitrogen oxides that occur predominantly at night in the lower troposphere. Because a large fraction of NO2 reacts to form NO3 and N2O5 during the course of a night, their fate is an important determining factor to the overall fate of NOx (=NO and NO2). As a comprehensive test of nocturnal nitrogen oxide chemistry, concentrations of O3, NO, NO2, NO3, N2O5, HNO3 and a host of other relevant compounds, aerosol abundance and composition, and meteorological conditions were measured in the marine boundary layer from the NOAA research vessel Ronald H. Brown off the East Coast of the United States as part of the New England Air Quality Study (NEAQS) during the summer of 2002. The results confirm the prominent role of NO3 and N2O5 in converting NOx to HNO3 at night with an efficiency on par with daytime photochemical conversion. The findings demonstrate the large role of nighttime chemistry in determining the NOx budget and consequent production of ozone. INDEX TERMS: 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry. Citation: Brown, S. S., et al. (2004), Nighttime removal of NOx in the summer marine boundary layer, Geophys. Res. Lett., 31, L07108, doi:10.1029/2004GL01941

Complementary role of cardiac CT in the assessment of aortic valve replacement dysfunction

Aortic valve replacement is the second most common cardiothoracic procedure in the UK. With an ageing population, there are an increasing number of patients with prosthetic valves that require follow-up. Imaging of prosthetic valves is challenging with conventional echocardiographic techniques making early detection of valve dysfunction or complications difficult. CT has recently emerged as a complementary approach offering excellent spatial resolution and the ability to identify a range of aortic valve replacement complications including structural valve dysfunction, thrombus development, pannus formation and prosthetic valve infective endocarditis. This review discusses each and how CT might be incorporated into a multimodal cardiovascular imaging pathway for the assessment of aortic valve replacements and in guiding clinical management

Pooling as a Strategy for the Timely Diagnosis of Soil-Transmitted Helminths in Stool: Value and Reproducibility

Background: The strategy of pooling stool specimens has been extensively used in the field of parasitology in order to facilitate the screening of large numbers of samples whilst minimizing the prohibitive cost of single sample analysis. The aim of this study was to develop a standardized reproducible pooling protocol for stool samples, validated between two different laboratories, without jeopardizing the sensitivity of the quantitative polymerase chain reaction (qPCR) assays employed for the detection of soil-transmitted helminths (STHs). Two distinct experimental phases were recruited. First, the sensitivity and specificity of the established protocol was assessed by real-time PCR for each one of the STHs. Secondly, agreement and reproducibility of the protocol between the two different laboratories were tested. The need for multiple stool sampling to avoid false negative results was also assessed. Finally, a cost exercise was conducted which included labour cost in low- and high-wage settings, consumable cost, prevalence of a single STH species, and a simple distribution pattern of the positive samples in pools to estimate time and money savings suggested by the strategy. Results: The sensitivity of the pooling method was variable among the STH species but consistent between the two laboratories. Estimates of specificity indicate a \u27pooling approach\u27 can yield a low frequency of \u27missed\u27 infections. There were no significant differences regarding the execution of the protocol and the subsequent STH detection between the two laboratories, which suggests in most cases the protocol is reproducible by adequately trained staff. Finally, given the high degree of agreement, there appears to be little or no need for multiple sampling of either individuals or pools. Conclusions: Our results suggest that the pooling protocol developed herein is a robust and efficient strategy for the detection of STHs in \u27pools-of-five\u27. There is notable complexity of the pool preparation to ensure even distribution of helminth DNA throughout. Therefore, at a given setting, cost of labour among other logistical and epidemiological factors, is the more concerning and determining factor when choosing pooling strategies, rather than losing sensitivity and/or specificity of the molecular assay or the method