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Attempts to prepare low-valent molybdenum complexes that feature a pentadentate 2,6-bis(imino)pyridine (or pyridine diimine, PDI) chelate allowed for the isolation of two different products. Refluxing Mo(CO)6 with the pyridine-substituted PDI ligand, PyEtPDI, resulted in carbonyl ligand substitution and formation of the respective bis(ligand) compound (PyEtPDI)2Mo (1). This complex was investigated by single-crystal X-ray diffraction, and density functional theory calculations indicated that 1 possesses a Mo(0) center that back-bonds into the π*-orbitals of the unreduced PDI ligands. Heating an equimolar solution of Mo(CO)[subscript 6] and the phosphine-substituted PDI ligand, Ph2PPrPDI, to 120 °C allowed for the preparation of (Ph2PPrPDI)Mo(CO) (2), which is supported by a κ5-N,N,N,P,P-Ph2PPrPDI chelate. Notably, 1 and 2 have been found to catalyze the hydrosilylation of benzaldehyde at 90 °C, and the optimization of 2-catalyzed aldehyde hydrosilylation at this temperature afforded turnover frequencies of up to 330 h–1. Considering additional experimental observations, the potential mechanism of 2-mediated carbonyl hydrosilylation is discussed.
A brief review of manganese-catalyzed hydrosilylation is presented along with a personal account of how the design for the highly active catalyst, (Ph2PPrPDI)Mn, was conceived. The reductive transformations achieved using this catalyst are described and put into further context by comparing the observed activities with those attained for leading late first-row transition-metal catalysts.
Most current approaches for quantification of RNA species in their natural spatial contexts in single cells are limited by a small number of parallel analyses. Here we report a strategy to dramatically increase the multiplexing capacity for RNA analysis in single cells in situ. In this method, transcripts are detected by fluorescence in situ hybridization (FISH). After imaging and data storage, the fluorescence signal is efficiently removed by photobleaching. This enables the reinitiation of FISH to detect other RNA species in the same cell. Through reiterative cycles of hybridization, imaging and photobleaching, the identities, positions and copy numbers of a large number of varied RNA species can be quantified in individual cells in situ. Using this approach, we analyzed seven different transcripts in single HeLa cells with five reiterative RNA FISH cycles. This approach has the potential to detect over 100 varied RNA species in single cells in situ, which will have wide applications in studies of systems biology, molecular diagnosis and targeted therapies.
The notable increase in biofuel usage by the road transportation sector in Brazil during recent years has significantly altered the vehicular fuel composition. Consequently, many uncertainties are currently found in particulate matter vehicular emission profiles. In an effort to better characterise the emitted particulate matter, measurements of aerosol physical and chemical properties were undertaken inside two tunnels located in the São Paulo Metropolitan Area (SPMA). The tunnels show very distinct fleet profiles: in the Jânio Quadros (JQ) tunnel, the vast majority of the circulating fleet are light duty vehicles (LDVs), fuelled on average with the same amount of ethanol as gasoline. In the Rodoanel (RA) tunnel, the particulate emission is dominated by heavy duty vehicles (HDVs) fuelled with diesel (5% biodiesel). In the JQ tunnel, PM2.5 concentration was on average 52 μg m-3, with the largest contribution of organic mass (OM, 42%), followed by elemental carbon (EC, 17%) and crustal elements (13%). Sulphate accounted for 7% of PM2.5 and the sum of other trace elements was 10%. In the RA tunnel, PM2.5 was on average 233 μg m-3, mostly composed of EC (52%) and OM (39%). Sulphate, crustal and the trace elements showed a minor contribution with 5%, 1%, and 1%, respectively. The average OC : EC ratio in the JQ tunnel was 1.59 ± 0.09, indicating an important contribution of EC despite the high ethanol fraction in the fuel composition. In the RA tunnel, the OC : EC ratio was 0.49 ± 0.12, consistent with previous measurements of diesel-fuelled HDVs. Besides bulk carbonaceous aerosol measurement, polycyclic aromatic hydrocarbons (PAHs) were quantified. The sum of the PAHs concentration was 56 ± 5 ng m-3 and 45 ± 9 ng m-3 in the RA and JQ tunnel, respectively. In the JQ tunnel, benzo(a)pyrene (BaP) ranged from 0.9 to 6.7 ng m-3 (0.02–0.1‰ of PM2.5)] whereas in the RA tunnel BaP ranged from 0.9 to 4.9 ng m-3 (0.004–0. 02‰ of PM2.5), indicating an important relative contribution of LDVs emission to atmospheric BaP.
Wetlands are the world's largest natural source of methane, a powerful greenhouse gas. The strong sensitivity of methane emissions to environmental factors such as soil temperature and moisture has led to concerns about potential positive feedbacks to climate change. This risk is particularly relevant at high latitudes, which have experienced pronounced warming and where thawing permafrost could potentially liberate large amounts of labile carbon over the next 100 years. However, global models disagree as to the magnitude and spatial distribution of emissions, due to uncertainties in wetland area and emissions per unit area and a scarcity of in situ observations. Recent intensive field campaigns across the West Siberian Lowland (WSL) make this an ideal region over which to assess the performance of large-scale process-based wetland models in a high-latitude environment. Here we present the results of a follow-up to the Wetland and Wetland CH4 Intercomparison of Models Project (WETCHIMP), focused on the West Siberian Lowland (WETCHIMP-WSL). We assessed 21 models and 5 inversions over this domain in terms of total CH4 emissions, simulated wetland areas, and CH4 fluxes per unit wetland area and compared these results to an intensive in situ CH4 flux data set, several wetland maps, and two satellite surface water products. We found that (a) despite the large scatter of individual estimates, 12-year mean estimates of annual total emissions over the WSL from forward models (5.34 ± 0.54 Tg CH4 yr-1), inversions (6.06 ± 1.22 Tg CH4 yr-1), and in situ observations (3.91 ± 1.29 Tg CH4 yr-1) largely agreed; (b) forward models using surface water products alone to estimate wetland areas suffered from severe biases in CH4 emissions; (c) the interannual time series of models that lacked either soil thermal physics appropriate to the high latitudes or realistic emissions from unsaturated peatlands tended to be dominated by a single environmental driver (inundation or air temperature), unlike those of inversions and more sophisticated forward models; (d) differences in biogeochemical schemes across models had relatively smaller influence over performance; and (e) multiyear or multidecade observational records are crucial for evaluating models' responses to long-term climate change.
Climate factors including soil temperature and moisture, incident solar radiation, and atmospheric carbon dioxide concentration are important environmental controls on methane (CH4) emissions from northern wetlands. We investigated the spatiotemporal distributions of the influence of these factors on northern high-latitude wetland CH4 emissions using an enhanced version of the Variable Infiltration Capacity (VIC) land surface model. We simulated CH4 emissions from wetlands across the pan-Arctic domain over the period 1948–2006, yielding annual average emissions of 36.1 ± 6.7 Tg CH4 yr-1 for the period 1997–2006. We characterized historical sensitivities of CH4 emissions to air temperature, precipitation, incident long- and shortwave radiation, and atmospheric [CO2] as a function of average summer air temperature and precipitation. Emissions from relatively warm and dry wetlands in the southern (permafrost-free) portion of the domain were positively correlated with precipitation and negatively correlated with air temperature, while emissions from wetter and colder wetlands further north (permafrost) were positively correlated with air temperature. Over the entire period 1948–2006, our reconstructed CH4 emissions increased by 20 %, the majority of which can be attributed to an increasing trend in summer air temperature. We estimated future emissions in response to 21st century warming as predicted by CMIP5 (Coupled Model Intercomparison Project Phase 5) model projections to result in end-of-century CH4 emissions 38–53 % higher than our reconstructed 1997–2006 emissions, accompanied by the northward migration of warmer and drier than optimal conditions for CH4 emissions, implying a reduced role for temperature in driving future increases in emissions.
About 2.5 × 106 snapshots on microcrystals of photoactive yellow protein (PYP) from a recent serial femtosecond crystallographic (SFX) experiment were reanalyzed to maximum resolution. The resolution is pushed to 1.46 Å, and a PYP structural model is refined at that resolution. The result is compared to other PYP models determined at atomic resolution around 1 Å and better at the synchrotron. By comparing subtleties such as individual isotropic temperature factors and hydrogen bond lengths, we were able to assess the quality of the SFX data at that resolution. We also show that the determination of anisotropic temperature factor ellipsoids starts to become feasible with the SFX data at resolutions better than 1.5 Å.
Background: Urbanization can strongly impact the physiology, behavior, and fitness of animals. Conditions in cities may also promote the transmission and success of animal parasites and pathogens. However, to date, no studies have examined variation in the prevalence or severity of several distinct pathogens/parasites along a gradient of urbanization in animals or if these infections increase physiological stress in urban populations.
Methodology/Principal Findings: Here, we measured the prevalence and severity of infection with intestinal coccidians (Isospora sp.) and the canarypox virus (Avipoxvirus) along an urban-to-rural gradient in wild male house finches (Haemorhous mexicanus). In addition, we quantified an important stress indicator in animals (oxidative stress) and several axes of urbanization, including human population density and land-use patterns within a 1 km radius of each trapping site. Prevalence of poxvirus infection and severity of coccidial infection were significantly associated with the degree of urbanization, with an increase of infection in more urban areas. The degrees of infection by the two parasites were not correlated along the urban-rural gradient. Finally, levels of oxidative damage in plasma were not associated with infection or with urbanization metrics.
Conclusion/Significance: These results indicate that the physical presence of humans in cities and the associated altered urban landscape characteristics are associated with increased infections with both a virus and a gastrointestinal parasite in this common songbird resident of North American cities. Though we failed to find elevations in urban- or parasite/pathogen-mediated oxidative stress, humans may facilitate infections in these birds via bird feeders (i.e. horizontal disease transmission due to unsanitary surfaces and/or elevations in host population densities) and/or via elevations in other forms of physiological stress (e.g. corticosterone, nutritional).
