Chemoselective polymerizations from mixtures of epoxide, lactone, anhydride, and carbon dioxide

Controlling polymer composition starting from mixtures of monomers is an important, but rarely achieved, target. Here a single switchable catalyst for both ring-opening polymeri-zation (ROP) of lactones and ring-opening copolymerization (ROCOP) of epoxides, anhydrides and CO2 is investigated, using both experimental and theoretical methods. Different combinations of four model monomers: -caprolactone, cyclohexene oxide, phthalic anhydride and carbon dioxide are investigated using a single dizinc catalyst. The catalyst switches between the distinct polymerization cycles and shows high monomer selectivity resulting in block sequence control and predictable compositions (esters and car-bonates) in the polymer chain. The understanding gained of the orthogonal reactivity of monomers, specifically con-trolled by the nature of the metal-chain end group, opens the way to engineer polymer block sequences

Recommendations for raloxifene use in daily clinical practice in the Swiss setting

Background/aim: Raloxifene is the first selective estrogen receptor modulator that has been approved for the treatment and prevention of osteoporosis in postmenopausal women in Europe and in the US. Although raloxifene reduces the risk of invasive breast cancer in postmenopausal women with osteoporosis and in postmenopausal women at high risk for invasive breast cancer, it is approved in that indication in the US but not in the EU. The aim was to characterize the clinical profiles of postmenopausal women expected to benefit most from therapy with raloxifene based on published scientific evidence to date. Methods: Key individual patient characteristics relevant to the prescription of raloxifene in daily practice were defined by a board of Swiss experts in the fields of menopause and metabolic bone diseases and linked to published scientific evidence. Consensus was reached about translating these insights into daily practice. Results: Through estrogen agonistic effects on bone, raloxifene reduces biochemical markers of bone turnover to premenopausal levels, increases bone mineral density (BMD) at the lumbar spine, proximal femur, and total body, and reduces vertebral fracture risk in women with osteopenia or osteoporosis with and without prevalent vertebral fracture. Through estrogen antagonistic effects on breast tissue, raloxifene reduces the risk of invasive estrogen-receptor positive breast cancer in postmenopausal women with osteoporosis and in postmenopausal women at high risk for invasive breast cancer. Finally, raloxifene increases the incidence of hot flushes, the risk of venous thromboembolic events, and the risk of fatal stroke in postmenopausal women at increased risk for coronary heart disease. Postmenopausal women in whom the use of raloxifene is considered can be categorized in a 2×2 matrix reflecting their bone status (osteopenic or osteoporotic based on their BMD T-score by dual energy X-ray absorptiometry) and their breast cancer risk (low or high based on the modified Gail model). Women at high risk of breast cancer should be considered for treatment with raloxifene. Conclusion: Postmenopausal women between 50 and 70years of age without climacteric symptoms with either osteopenia or osteoporosis should be evaluated with regard to their breast cancer risk and considered for treatment with raloxifene within the framework of its contraindications and precaution

File Specification for the MERRA Aerosol Reanalysis (MERRAero): MODIS AOD Assimilation based on a MERRA Replay

This document describes the gridded output files produced by the Goddard Earth Observing System version 5 (GEOS-5) Goddard Aerosol Assimilation System (GAAS) from July 2002 through December 2014. The MERRA Aerosol Reanalysis (MERRAero) is produced with the hydrostatic version of the GEOS-5 Atmospheric Global Climate Model (AGCM). In addition to standard meteorological parameters (wind, temperature, moisture, surface pressure), this simulation includes 15 aerosol tracers (dust, sea-salt, sulfate, black and organic carbon), ozone, carbon monoxide and carbon dioxide. This model simulation is driven by prescribed sea-surface temperature and sea-ice, daily volcanic and biomass burning emissions, as well as high-resolution inventories of anthropogenic emission sources. Meteorology is replayed from the MERRA Reanalysis

Evaluation of GEOS-5 Sulfur Dioxide Simulations During the Frostburg, MD 2010 Field Campaign.

Sulfur dioxide (SO2) is a major atmospheric pollutant with a strong anthropogenic component mostly produced by the combustion of fossil fuel and other industrial activities. As a precursor of sulfate aerosols that affect climate, air quality, and human health, this gas needs to be monitored on a global scale. Global climate and chemistry models including aerosol processes along with their radiative effects are important tools for climate and air quality research. Validation of these models against in-situ and satellite measurements is essential to ascertain the credibility of these models and to guide model improvements. In this study the Goddard Chemistry, Aerosol, Radiation, and Transport (GOCART) module running on-line inside the Goddard Earth Observing System version 5 (GEOS-5) model is used to simulate aerosol and SO2 concentrations. Data taken in November 2010 over Frostburg, Maryland during an SO2 field campaign involving ground instrumentation and aircraft are used to evaluate GEOS-5 simulated SO2 concentrations. Preliminary data analysis indicated the model overestimated surface SO2 concentration, which motivated the examination of mixing processes in the model and the specification of SO2 anthropogenic emission rates. As a result of this analysis, a revision of anthropogenic emission inventories in GEOS-5 was implemented, and the vertical placement of SO2 sources was updated. Results show that these revisions improve the model agreement with observations locally and in regions outside the area of this field campaign. In particular, we use the ground-based measurements collected by the United States Environmental Protection Agency (US EPA) for the year 2010 to evaluate the revised model simulations over North America

Comparison of OMI ozone and UV irradiance data with ground-based measurements at two French sites

International audienceOzone Monitoring Instrument (OMI), launched in July 2004, is dedicated to the monitoring of the Earth's ozone, air quality and climate. OMI provides among other things the total column of ozone (TOC), the surface ultraviolet (UV) irradiance at several wavelengths, the erythemal dose rate and the erythemal daily dose. The main objective of this work is to validate OMI data with ground-based instruments in order to use OMI products (collection 2) for scientific studies. The Laboratoire d'Optique Atmosphérique (LOA) located in Villeneuve d'Ascq in the north of France performs solar UV measurements using a spectroradiometer and a broadband radiometer. The site of Briançon in the French Southern Alps is also equipped with a spectroradiometer operated by Interaction Rayonnement Solaire Atmosphère (IRSA). The instrument belongs to the Centre Européen Médical et Bioclimatologique de Recherche et d'Enseignement Supérieur. The comparison between the TOC retrieved with ground-based measurements and OMI TOC shows good agreement at both sites for all sky conditions. Comparisons of spectral UV on clear sky conditions are also satisfying whereas results of comparisons of the erythemal daily doses and erythemal dose rates for all sky conditions and for clear sky show that OMI overestimates significantly surface UV doses at both sites

The MERRA-2 Aerosol Reanalysis, 1980 Onward. Part I: System Description and Data Assimilation Evaluation

The Modern-Era Retrospective Analysis for Research and Applications, Version 2 (MERRA-2) updates NASA's previous satellite era (1980 - onward) reanalysis system to include additional observations and improvements to the Goddard Earth Observing System, Version 5 (GEOS-5) Earth system model. As a major step towards a full Integrated Earth Systems Analysis (IESA), in addition to meteorological observations, MERRA-2 now includes assimilation of aerosol optical depth (AOD) from various ground- and space-based remote sensing platforms. Here, in the first of a pair of studies, we document the MERRA-2 aerosol assimilation, including a description of the prognostic model (GEOS-5 coupled to the GOCART aerosol module), aerosol emissions, and the quality control of ingested observations. We provide initial validation and evaluation of the analyzed AOD fields using independent observations from ground, aircraft, and shipborne instruments. We demonstrate the positive impact of the AOD assimilation on simulated aerosols by comparing MERRA-2 aerosol fields to an identical control simulation that does not include AOD assimilation. Having shown the AOD evaluation, we take a first look at aerosol-climate interactions by examining the shortwave, clear-sky aerosol direct radiative effect. In our companion paper, we evaluate and validate available MERRA-2 aerosol properties not directly impacted by the AOD assimilation (e.g. aerosol vertical distribution and absorption). Importantly, while highlighting the skill of the MERRA-2 aerosol assimilation products, both studies point out caveats that must be considered when using this new reanalysis product for future studies of aerosols and their interactions with weather and climate

Benchmarking GOCART-2G in the Goddard Earth Observing System (GEOS)

The Goddard Chemistry Aerosol Radiation and Transport (GOCART) model, which controls the sources, sinks, and chemistry of aerosols within the Goddard Earth Observing System (GEOS), recently underwent a major refactoring and update, including a revision of the emissions datasets and the addition of brown carbon. A 4-year benchmark simulation utilizing the new version of the model code, termed GOCART Second Generation (GOCART-2G) and coupled to the Goddard Earth Observing System (GEOS) model, was evaluated using in situ and spaceborne measurements to develop a baseline and prioritize future development. A comparison of simulated aerosol optical depth between GOCART-2G and MODIS retrievals indicates the model captures the overall spatial pattern and seasonal cycle of aerosol optical depth but overestimates aerosol extinction over dusty regions and underestimates aerosol extinction over Northern Hemisphere boreal forests, requiring further investigation and tuning of emissions. This MODIS-based analysis is corroborated by comparisons to MISR and selected AERONET stations; however, discrepancies between the Aqua and Terra satellites indicate there is a diurnal component to biases in aerosol optical depth over southern Asia and northern Africa. Despite the underestimate of aerosol optical depth in biomass burning regions in GEOS, there is an overestimate in the surface mass of organic carbon in the United States, especially during the summer months. Over Europe, GOCART-2G is unable to match the summertime peak in aerosol optical depth, opposing the observed late fall and early spring peaks in surface mass concentration. A comparison of the vertical profile of attenuated backscatter to observations from CALIPSO indicates the GEOS model is capable of capturing the vertical profile of aerosol; however, the mid-troposphere plumes of dust in the North Atlantic and smoke in the southeastern Atlantic are perhaps too low in altitude. The results presented highlight priorities for future development with GOCART-2G, including improvements for dust, biomass burning aerosols, and anthropogenic aerosols.</p

Zirconium complexes of bipyrrolidine derived salan ligands for the isoselective polymerisation of rac-lactide

We report a series of Zr(iv) 2,2′-bipyrrolidine–salan derived complexes and their exploitation for the ROP of rac-lactide to afford highly isotactically enriched PLA.</p