Near-Field Electron Energy Loss Spectroscopy in Porous Silicon

First results of an Electron Energy Loss Spectroscopy in the Near Field (NFEELS) mode of n⁺ porous silicon are described here. Sequences of EELS spectra in the low loss energy range (0–30 eV) were recorded, using a scanning transmission electron microscope, as the e-beam was scanned across a nano-hole surrounded by Si platelets. This technique is shown to be very sensitive to spectral and spatial changes in the electromagnetic field distribution outside the surface of nanoparticles, governed by their local nature and shape.     

Capping Groups Induced Size and Shape Evolution of Magnetite Particles Under Hydrothermal Condition and their Magnetic Properties

Three simple capping molecules (urea, 3-aminopropanol, and polyethylene glycol) with different functional groups (−NH₂ for urea, −NH₂ and −OH for 3-aminopropanol, and −O− for polyethylene glycol) have been designed to prepare magnetite (Fe₃O₄) particles with various shapes. The crystal structure, morphologies, and magnetic properties of the products have been characterized by X-ray diffraction, electron microscopy, and vibrating sample magnetometer. The results indicate that the capping functional groups play a major role in determining the size, shape, and thus magnetic properties of the magnetite nanocrystals. The morphology evolution of the magnetite under the hydrothermal condition is discussed in detail, particularly for the interaction between the various capping groups and surface structure and chemistry of the nanocrystals.     

Thermal stability of morpholine additive in the steam-water cycle of CANDU-PHW nuclear power plants

The thermal decomposition of morpholine, an additive used in the steam-water cycles of nuclear power plants, was studied using a laboratory high-pressure reactor. The measured decomposition rate constants are 2.67, 8.73 and 21.25 × 10^?7 s^?1 at 260, 280 and 300°C respectively. The kinetics were found to be first-order and the activation energy was 131.9 kJ/mol. Ammonia, ethanolamine, 2-(2-aminoethoxy) ethanol, methylamine, ethylamine, ethylene glycol, and acetic and glycolic acids were identified as the major breakdown products. The decomposition route proposed was validated in the field by tracking these breakdown products in water samples taken at Gentilly 2 power plant.     

Sintering of Industrial Mullites in the Presence of Magnesia as a Sintering Aid

The sinterability of two industrial mullite powders, in the presence of MgO as a sintering aid, was investigated. A glassy phase, which was generated during preparation, was present in both powders; this glassy phase had a strong influence on sintering, depending on its content, composition, and spatial distribution. MgO promoted sintering in the presence of a liquid phase, both in the as-received materials and in samples washed with HF, in which most of the pre-existing glassy phase was eliminated. Investigations using transmission electron microscopy, coupled with energy-dispersive spectroscopy, as well as dilatometric measurements and X-ray diffraction data, on washed and unwashed materials and on quenched and slow-cooled samples allowed a better understanding of the influence of MgO and the glassy phase on the sintering behavior and the formation of new phases. Most of the phases, in fact, can be explained by using the MgO–Al₂O₃–SiO₂ phase diagram, even in such complex systems.     

Comparison of Urinary Scents of Two Related Mouse Species, <Emphasis Type="Italic">Mus spicilegus</Emphasis> and <Emphasis Type="Italic">Mus domesticus</Emphasis>

Whereas the house mouse (Mus domesticus) has been studied extensively in terms of physiology/behavior and pheromonal attributes, the evolutionarily related mound-building mouse (Mus spicilegus) has received attention only recently due to its divergent behavioral traits related to olfaction. To date, no chemical studies on urinary volatile compounds have been performed on M. spicilegus. The rationale for our investigations was to determine if there are differences in urinary volatiles of intact and castrated M. spicilegus males and to explore further whether this species could utilize the same or structurally similar pheromones as the male house mouse, M. domesticus. The use of capillary gas chromatography/mass spectrometry (GC-MS) together with sorptive stir bar extraction sampling enabled quantitative comparisons between the intact and castrated M. spicilegus urinary profiles. Additionally, through GC-MS and atomic emission (sulfur-selective) detection, we identified qualitative molecular differences between intact M. spicilegus and M. domesticus. A series of volatile and odoriferous lactones and the presence of coumarin were the unique features of M. spicilegus, as was the notable absence of 2-sec-butyl-4,5-dihydrothiazole (a prominent M. domesticus male pheromone) and other sulfur-containing compounds. Castration of M. spicilegus males eliminated several substances, including δ-hexalactone and γ-octalactone, and substantially decreased additional compounds, suggesting their possible role in chemical communication. Some other M. domesticus pheromone components were also found in M. spicilegus urine. These comparative chemical analyses support the notion of metabolic similarities as well as the uniqueness of some volatiles for M. spicilegus, which may have a distinct physiological function in reproduction and behavior.     

Efficient Telomerization of Butadiene with Starch in Water: The Role of the Surfactant

The synthesis of hydrophobic starch was performed via palladium-catalyzed telomerization of butadiene with native starch. This reaction is efficiently performed in water in the presence of neutral or cationic surfactant with high HLB. After optimization of the reaction conditions, TOF up to 446 was achieved.     

Recognition of chiral carboxylic anions by artificial receptors

Many carboxylic molecules, ranging from drugs to flavors and fragrances, contain chiral centers. As a consequence, research has been carried out in order to design and synthesize artificial receptors for carboxylic anions. Many problems have to be solved for binding anions. The results obtained in the binding of carboxylic anions by guanidine, secondary ammonium and metal-center have been selected. The last part of this review focuses on chiral recognition of carboxylic anions by organic and metal-based chiral receptors.     

myo-Inositol trispyrophosphate: a novel allosteric effector of hemoglobin with high permeation selectivity across the red blood cell plasma membrane

myo‐Inositol trispyrophosphate (ITPP), a novel membrane‐permeant allosteric effector of hemoglobin (Hb), enhances the regulated oxygen release capacity of red blood cells, thus counteracting the effects of hypoxia in diseases such as cancer and cardiovascular ailments. ITPP‐induced shifting of the oxygen–hemoglobin equilibrium curve in red blood cells (RBCs) was inhibited by DIDS and NAP‐taurine, indicating that band 3 protein, an anion transporter mainly localized on the RBC membrane, allows ITPP entry into RBCs. The maximum intracellular concentration of ITPP, determined by ion chromatography, was 5.5×10^?3 M , whereas a drop in concentration to the limit of detection was observed in NAP‐taurine‐treated RBCs. The dissociation constant of ITPP binding to RBC ghosts was found to be 1.72×10^?5 M . All data obtained indicate that ITPP uptake is mediated by band 3 protein and is thus highly tissue‐selective towards RBCs, a feature of major importance for its potential therapeutic use.     

Stress corrosion cracking susceptibility of P285NH and API 5L X65 steel grades in the high-level radioactive waste repository cell concept

Since 2014, the concept developed for the disposal of high-level radioactive waste in the French deep geological repository project Cigéo includes a cement-based grout material. This cement-based grout material will be injected between the casing and the claystone to neutralize the potential acidity resulting from the claystone oxidation induced by the drilling process of the disposal cell. In these conditions of pH (around 10.5) and temperature (90°C, maximum expected during the disposal), the metallic materials could be sensitive to stress corrosion cracking (SCC). In this project, different environments (aerated or deaerated, at room temperature or at 90°C) and synthetic solutions are considered to reproduce the different periods expected during the long life repository. The project is based on electrochemical measurements (polarization curves to define the SCC critical domain of potentials), slow strain rate tensile tests, and long-term immersion for crack initiation and propagation tests.     

Spark plasma sintering of double-walled carbon nanotubes

Bulk samples of double-walled carbon nanotubes are prepared for the first time. The best spark plasma sintering conditions are (1100 °C, 100 MPa). Raman spectroscopy and scanning electron microscopy show that the nanotubes are undamaged. The density is equal to 1.29 g cm⁻³ and the pores are all below 6 nm in diameter. The electrical conductivity is equal to 1650 S cm⁻¹. The transverse fracture strength is equal to 47 MPa.