Copper‐Catalyzed Asymmetric Conjugate Addition of Dimethylzinc to Acyl‐N‐methylimidazole Michael Acceptors: Scope,Limitations and Iterative Reactions

An efficient copper‐catalyzed enantioselective conjugate addition of dimethylzinc to unsaturated 2‐acyl‐N‐methylimidazoles has been achieved using a chiral bidentate hydroxyalkyl‐NHC ligand. The reactions proceed with excellent regioselectivity (1,4 vs. 1,6 and 1,8) in extended conjugated systems to afford the 1,4‐adducts in high enantioselectivities. This regioselectivity could be ascertained by DFT studies highlighting the crucial role of the imidazole ring. Thanks to the development of efficient protocols to regenerate the unsaturated 2‐acyl‐N‐methylimidazole moiety, an iterative process has been developed ultimately leading to 3,5,7 all‐syn or anti‐anti polydeoxypropionate stereodiads.

     

Stereoselective Monoamine Oxidase‐Catalyzed Oxidative Aza‐Friedel–Crafts Reactions of meso‐Pyrrolidines in Aqueous Buffer

We disclose the highly diastereoselective combination of monoamine oxidase‐catalyzed oxidation of meso‐pyrrolidines and aza‐Friedel–Crafts reactions in aqueous buffer to give valuable enantioenriched 2‐substituted pyrrolidines in a formal double C H activation process. A range of secondary as well as tertiary amines were shown to be suitable substrates for the biocatalytic oxidation and subsequent addition of a variety of C‐nucleophiles.

     

Binding Mode and Structure–Activity Relationships around Direct Inhibitors of the Nrf2–Keap1 Complex

An X‐ray crystal structure of Kelch‐like ECH‐associated protein (Keap1) co‐crystallised with (1S,2R)‐2‐[(1S)‐1‐[(1,3‐dioxo‐2,3‐dihydro‐1H‐isoindol‐2‐yl)methyl]‐1,2,3,4‐tetrahydroisoquinolin‐2‐carbonyl]cyclohexane‐1‐carboxylic acid (compound (S,R,S)‐ 1 a ) was obtained. This X‐ray crystal structure provides breakthrough experimental evidence for the true binding mode of the hit compound (S,R,S)‐ 1 a , as the ligand orientation was found to differ from that of the initial docking model, which was available at the start of the project. Crystallographic elucidation of this binding mode helped to focus and drive the drug design process more effectively and efficiently.     

Assessment of fly ash-aided phytostabilisation of highly contaminated soils after an 8-year field trial Part 2. Influence on plants

Aided phytostabilisation is a cost-efficient technique to manage metal-contaminated areas, particularly in the presence of extensive pollution. Plant establishment and survival in highly metal-contaminated soils are crucial for phytostabilisation success, as metal toxicity for plants is widely reported. A relevant phytostabilisation solution must limit metal transfer through the food chain. Therefore, this study aimed at evaluating the long-term efficiency of aided phytostabilisation on former agricultural soils highly contaminated by cadmium, lead, and zinc. The influence of afforestation and fly ash amendments on reducing metal phytoavailability was investigated as were their effects on plant development. Before being planted with a tree mix, the site was divided into three plots: a reference plot with no amendment, a plot amended with silico-aluminous fly ash and one with sulfo-calcic fly ash. Unlike Salix alba and Quercus robur, Alnus glutinosa, Acer pseudoplatanus and Robinia pseudoacacia grew well on the site and accumulated, overall, quite low concentrations of metals in their leaves and young twigs. This suggests that these three species have an excluder phenotype for Cd, Zn and Pb. After 8 years, metal availability to A. glutinosa, A. pseudoplatanus and R. pseudoacacia, and translocation to their above-ground parts, strongly decreased in fly ash-amended soils. Such decreases fit well together with the depletion of CaCl₂-extractable metals in amended soils. Although both fly ashes were effective to decrease Cd, Pb and Zn concentrations in above-ground parts of trees, the sulfo-calcic ash was more efficient.     

In vitro digestion and DGT techniques for estimating cadmium and lead bioavailability in contaminated soils: influence of gastric juice pH

A sensitivity analysis was conducted on an in vitro gastrointestinal digestion test (i) to investigate the influence of a low variation of gastric juice pH on the bioaccessibility of Cd and Pb in smelter-contaminated soils (F_B, using the unified bioaccessibility method UBM) and fractions of metals that may be transported across the intestinal epithelium (F_A, using the diffusive gradient in thin film technique), and (ii) to provide a better understanding of the significance of pH in health risk assessment through ingestion of soil by children. The risk of metal exposure to children (hazard quotient, HQ) was determined for conditions that represent a worst-case scenario (i.e., ingestion rate of 200 mg day^− 1) using three separate calculations of metal daily intake: estimated daily intake (EDI), bioaccessible EDI (EDI-F_B), and oral bioavailable EDI (EDI-F_A). The increasing pH from 1.2 to 1.7 resulted in: (i) no significant variation in Cd-F_B in the gastric phase but a decrease in the gastrointestinal phase; (ii) a decrease in soluble Pb in the gastric phase and a significant variation in Pb-F_B in the gastrointestinal phase; (iii) a significant decrease in Cd-F_A and no variation in Pb-F_A; (iv) no change in EDI-F_B and EDI-F_A HQs for Cd; (v) a significant decrease in EDI-F_B HQs and no significant variation in EDI-F_A HQ for Pb. In the analytical conditions, these results show that risk to children decreases when the bioavailability of Pb in soils is taken into account and that the studied pH values do not affect the EDI-F_A HQs. The present results provide evidence that the inclusion of bioavailability analysis during health risk assessment could provide a more realistic estimate of Cd and Pb exposure, and opens a wide field of practical research on this topic (e.g., in contaminated site management).     

Mercury and methylmercury concentrations in high altitude lakes and fish (Arctic charr) from the French Alps related to watershed characteristics

Total mercury (THg) and methylmercury (MeHg) concentrations were measured in the muscle of Arctic charr (Salvelinus alpinus) and in the water column of 4 lakes that are located in the French Alps. Watershed characteristics were determined (6 coverage classes) for each lake in order to evaluate the influence of watershed composition on mercury and methylmercury concentrations in fish muscle and in the water column. THg and MeHg concentrations in surface water were relatively low and similar among lakes and watershed characteristics play a major role in determining water column Hg and MeHg levels. THg muscle concentrations for fish with either a standardized length of 220 mm, a standardized age of 5 years or for individualuals did not exceed the 0.5 mg kg^− 1 fish consumption advisory limit established for Hg by the World Health Organization (WHO, 1990). These relatively low THg concentrations can be explained by watershed characteristics, which lead to short Hg residence time in the water column, and also by the short trophic chain that is characteristic of mountain lakes. Growth rate did not seem to influence THg concentrations in fish muscles of these lakes and we observed no relationship between fish Hg concentrations and altitude. This study shows that in the French Alps, high altitude lakes have relatively low THg and MeHg concentrations in both the water column and in Arctic charr populations. Therefore, Hg does not appear to present a danger for local populations and the fishermen of these lakes.     

Atmospheric mercury depletion event study in Ny-Alesund (Svalbard) in spring 2005. Deposition and transformation of Hg in surface snow during springtime

A field campaign was conducted in Ny-Alesund (78 degrees 54'N, 11 degrees 53'E), Svalbard (Norway) during April and May 2005. An Atmospheric Mercury (Hg) Depletion Event (AMDE) was observed from the morning of April 24 until the evening of April 27. Transport of already Hg and ozone (O3) depleted air masses could explain this observed depletion. Due to a snowfall event during the AMDE, surface snow Hg concentrations increased two fold. Hg deposition took place over a short period of time corresponding to 3-4 days. More than 80% of the deposited Hg was estimated to be reemitted back to the atmosphere in the days following the event. During the campaign, we observed night and day variations in surface snow Hg concentrations, which may be the result of gaseous elemental mercury (GEM) oxidation to divalent Hg at the snow/air interface by daylight surface snow chemistry. Finally, a decrease in the reactive Hg (HgR) fraction of total Hg (HgT) in the surface snow was observed during spring. We postulate that the transformation of HgR to a more stable form may occur in Arctic snow during spring.     

Ultrathin PECVD epitaxial Si solar cells on glass via low‐temperature transfer process

Fabrication of high‐quality ultrathin monocrystalline silicon layers and their transfer to low‐cost substrates are key steps for flexible electronics and photovoltaics. In this work, we demonstrate a low‐temperature and low‐cost process for ultrathin silicon solar cells. By using standard plasma‐enhanced chemical vapor deposition (PECVD), we grow high‐quality epitaxial silicon layers (epi‐PECVD) from SiH₄/H₂ gas mixtures at 175 °C. Using secondary ion mass spectrometry and transmission electron microscopy, we show that the porosity of the epi‐PECVD/crystalline silicon interface can be tuned by controlling the hydrogen accumulation there. Moreover, we demonstrate that 13–14% porosity is a threshold above which the interface becomes fragile and can easily be cleaved. Taking advantage of the H‐rich interface fragility, we demonstrate the transfer of large areas (∽10 cm²) ultrathin epi‐PECVD layers (0.5–5.5 µm) onto glass substrates by anodic bonding and moderate annealing (275–350 °C). The structural properties of transferred layers are assessed, and the first PECVD epitaxial silicon solar cells transferred on glass are characterized. Copyright © 2016 John Wiley & Sons, Ltd.     

XRD Analysis of the Role of Cesium in Sodium‐Based Geopolymer

The purpose of this work was to study the role of cesium in sodium‐based geopolymer and its thermal stability for nuclear waste management. A series of mixed sodium and cesium geopolymer samples (Na_1?x Cs _x )₂O·Al₂O₃·SiO₂·12H₂O (referred to as (Na_{1? x} Cs _x )‐GP, where x = 0, 0.08, 0.15, 0.42, 1) have been prepared. All geopolymer samples were heated at 1100°C for 24 h. Pollucite (CsAlSi₂O₆) and feldspathoid (CsAlSiO₄) were crystallized from Cs‐GP. Nepheline (NaAlSiO₄) and a small amount of crystallized silica were obtained from Na‐GP. The other geopolymers (Na_{1? x} Cs _x )‐GP (x = 0.08, 0.15, 0.42) led to pollucite and nepheline main phases. Amorphous silica phase was observed in all the geopolymer samples with various amounts. Phase quantification and scanning electron microscope revealed that higher Cs concentrations in Na‐GP tend to decrease the amorphous phase while improving pollucite and nepheline phase quantification. The amorphous geopolymers have also been studied by pair distribution function analysis. Tetrahedral chains formed by T–O bonding (with T = Si, Al) were shown to be more tighten around Cs⁺ than around Na⁺. It led to shorter Cs–T bond than Na–T bond matching the higher solvation property of Na⁺. Furthermore, thermal study analysis pointed out the fact that geopolymer samples (Na_{1? x} Cs _x )‐GP, can be considered as solid solutions.