General Catalytic Enantioselective Access to Monohalomethyl and Trifluoromethyl Cyclopropanes

International audienceAn efficient catalytic enantioselective access to chiral functionalized trifluoromethyl cyclopropanes from two classes of diazo compounds and α‐trifluoromethyl styrenes using Rh2((S)‐BTPCP)4 as a catalyst is described. This method provides an efficient and practical strategy for the synthesis of highly functionalized CF3‐cyclopropanes with excellent diastereoselectivities (up to 20:1) and enantioselectivities (up to 99 % ee). The depicted methodology represents, to date, the most efficient catalytic enantioselective method to access highly decorated chiral CF3‐cyclopropanes. Extension to chiral monohalomethyl cyclopropanes in high ee is also reported

²³⁴Th sorption and export models in the water column: a review

Over the past few decades, the radioisotope pair of 238U / 234Th has been widely and increasingly used to describe particle dynamics and particle export fluxes in a variety of aquatic systems. The present paper is one of five review articles dedicated to 234Th. It is focused on the models associated with 234Th whereas the companion papers (same issue) are focused on present and future methodologies and techniques (Rutgers van der Loeff et al.), C / 234Th ratios (Buesseler et al.), 234Th speciation (Santschi et al.) and present and future applications of 234Th [Waples, J.T., Benitez-Nelson, C.R., Savoye, N., Rutgers van der Loeff, M., Baskaran, M., Gustafsson, Ö., this issue. An Introduction to the application and future use of 234Th in aquatic systems. Marine Chemistry, FATE special issue]. In this paper, we review current 234Th scavenging models and discuss the relative importance of the non-steady state and physical terms associated with the most commonly used model to estimate 234Th flux. Based on this discussion we recommend that for future work the use of models should be accompanied by a discussion of the effect that model and data uncertainty have on the model results. We also suggest that future field work incorporate repeat occupations of sample sites on time scales of 1-4 weeks in order to evaluate steady state versus non-steady state estimates of 234Th export, especially during high flux events (> ca. 800 dpm m-2 d-1). Finally, knowledge of the physical oceanography of the study area is essential, particularly in ocean margins and in areas of established upwelling (e.g., Equatorial Pacific). These suggestions will greatly enhance the application of 234Th as a tracer of particle dynamics and flux in more complicated regimes

An assessment of particulate organic carbon to thorium-234 ratios in the ocean and their impact on the application of ²³⁴Th as a POC flux proxy

Thorium-234 is increasingly used as a tracer of ocean particle flux, primarily as a means to estimate particulate organic carbon export from the surface ocean. This requires determination of both the 234Th activity distribution (in order to calculate 234Th fluxes) and an estimate of the C / 234Th ratio on sinking particles, to empirically derive C fluxes. In reviewing C / 234Th variability, results obtained using a single sampling method show the most predictable behavior. For example, in most studies that employ in situ pumps to collect size fractionated particles, C / 234Th either increases or is relatively invariant with increasing particle size (size classes > 1 to 100s µm). Observations also suggest that C / 234Th decreases with depth and can vary significantly between regions (highest in blooms of large diatoms and highly productive coastal settings). Comparisons of C fluxes derived from 234Th show good agreement with independent estimates of C flux, including mass balances of C and nutrients over appropriate space and time scales (within factors of 2–3). We recommend sampling for C / 234Th from a standard depth of 100 m, or at least one depth below the mixed layer using either large volume size fractionated filtration to capture the rarer large particles, or a sediment trap or other device to collect sinking particles. We also recommend collection of multiple 234Th profiles and C / 234Th samples during the course of longer observation periods to better sample temporal variations in both 234Th flux and the characteristic of sinking particles. We are encouraged by new technologies which are optimized to more reliably sample truly settling particles, and expect the utility of this tracer to increase, not just for upper ocean C fluxes but for other elements and processes deeper in the water column

Cation dynamics in soils with different salinity levels growing irrigated rice

Salinity levels in soils of the Outer Coastal Plain of Rio Grande do Sul, Brazil, can be high, due to excess of Na in the irrigation water, evapotranspiration and soil development from marine sediments. The cultivation of irrigated rice could be an alternative, since ion uptake as well as leaching by the establishment of a water layer could mitigate the effects of soil salinity. This study aimed to evaluate the dynamics of basic cations in the solution of Albaqualf soils with different salinity levels growing irrigated rice. The plow layer contained exchangeable Na percentages (ESP) of 5.6, 9.0, 21.2 and 32.7 %. The plant stand, dry matter, Na, K and Ca + Mg uptake at full flowering and grain yield were evaluated. The levels of Na, K, Ca + Mg and electrical conductivity (EC) in the soil solution were also measured weekly during the rice cycle at four soil depths, in the water layer and irrigation water. The Na, K and Ca + Mg uptake by rice at full flowering was used to estimate ion depletion from the layer under root influence. Soil salinity induced a reduction in the rice stand, especially in the soil with ESP of 32.7 %, resulting in lower cation uptake and very low yield at that site. As observed in the water layer and irrigation water, the Na, K, Ca + Mg and EC levels in the soil solution decreased with time at depths of 5, 10 and 20 cm, regardless of the original soil salinity, showing that cation dynamics in the plow layer was determined by leaching and root uptake, rather than by the effect of evapoconcentration of basic cations in the soil surface layer

Thermodynamic optimisation of the systems PbO-SiO2, PbO-ZnO, ZnO-SiO2 and PbO-ZnO-SiO2

Liquidus-phase equilibrium data of the present authors for the PbO-ZnO-SiO system, combined with phase equilibrium and thermodynamic data from the literature, were optimized to obtain a selfconsistent set of parameters of thermodynamic models for all phases. The modified quasichemical model was used for the liquid slag phase. From these model parameters, the optimized ternary-phase diagram was back-calculated

Anabolic responses to resistance training in older men and women: A brief review

Resistance training has been shown to be the most effective exercise mode to induce anabolic adaptations in older men and women. Advances in imaging techniques and histochemistry have increased the ability to detect such changes, confirming the high level of adaptability that remains in aging skeletal muscle. This brief review presents a summary of the resistance-training studies that directly compare chronic anabolic responses to training in older (> 60 years) men and women. Sixteen studies are summarized, most of which indicate similar relative anabolic responses between older men and women after resistance training. Relatively small sample sizes in most of the interventions limited their ability to detect significant sex differences and should be considered when interpreting these studies. Future research should incorporate larger sample sizes with multiple measurement time points for anabolic responses