Mössbauer studies on the series La1-xSrxFeO3

Mössbauer spectra have been recorded at 4.2 and 300 K on the series La_1–x Sr _x FeO₃, wherex varies from 0 to 1.0 in steps of 0.1. Neutron diffraction experiments have shown that the crystal structure is orthorhombic for 0x<0.3, rhombohedral for 0.4x0.7, and cubic for 0.8<x1.0. Mössbauer spectra at 4.2 K are composed of magnetic sextet components arising from different charge states of iron ions. In the orthorhombic and rhombohedral phases, the charge states Fe³⁺ and Fe⁵⁺ coexist. In the cubic phase, iron is present as Fe³⁺ and Fe⁴⁺ states. At 300 K, the samples are magnetically ordered in the range 0 x0.3 and the coexistence of Fe³⁺ and Fe⁵⁺ remains. For samples 0.4x1.0, the samples are paramagnetic. Fits to these spectra require two components, one corresponding to an Fe⁴⁺ state, the other being best described as an Fe³⁺ ion forx0.7 but forx>0.7 having a mean charge state which increases to 3.5 forx=1.0.     

Performance of an ultra-low elution-volume 96-well plate: drug discovery and development applications

Recently, sample preparation has been considered to be the major cause of bottlenecks during high-throughput analysis. With the assistance of robotic liquid handlers and the 96-well plate format, more samples can be prepared for subsequent liquid chromatography/tandem mass spectrometry (LC/MS/MS) analysis. Protein precipitation is still widely used despite potential loss of sensitivity or variable results due to ion suppression. The use of solid-phase extraction (SPE) clearly gives superior results but may not be as cost effective as protein precipitation due to the labor and material costs associated with the process. Here, a novel 96-well SPE plate is described that was designed to minimize the elution volume required for quantitative elution of analytes. The plate is packed with 2 mg of a high-capacity SPE sorbent that allows loading of up to 750 microL of plasma, while the novel design permits elution with as little as 25 microL. Therefore, the plate offers up to a 15-fold increase in sample concentration. The evaporation and reconstitution step that is typically required in SPE is avoided due to the concentrating ability of the plate. Examples of applications in drug discovery/development are shown and results are compared to protein precipitation. Excellent sensitivity and linearity are demonstrated.     

Determination of the atomic charge on sodium in sodium salts by numerical integration — a theoretical investigation

The electron density difference in a NaSCN crystal is set up from the ab initio densities of Na⁺ and SCN^? ions and compared to the experimental counterpart based on X-ray diffraction measurements. Numerical integration over the electron density difference is executed around the Na⁺ ion. The atomic charge (+0.20e) derived in this way is in good agreement with the analogous experimental charge (+0.27e) The low experimental value cannot therefore be taken as an indication for a predominantly non-ionic structure of NaSCN and similar sodium salts     

In-house validation for analytical methods and quality control for risk evaluation of chlordecone in food

Chlordecone was used until 1993 as a pesticide in the banana plantation of Martinique and Guadeloupe (French Antilles) against the root borer. This organochlorine pesticide was lipophilic, remnant, and toxic for human beings with both acute and chronic effects. Chlordecone was strongly absorbed and stored in soil and weakly decomposed in environment. Surveys conducted in 2001 revealed its presence in soil, rivers, and domestic food products. Local food (fruits and vegetables, cattle, poultry, and fish) was growing on soils, widely contaminated by chlordecone, used in the past as banana plantations. In 2003, French Administration asked for a risk evaluation for the Antilles population. The French Agency for Food Safety, proposed a Provisional Tolerable Daily Intake of 0.0005?mg?kg^?1?b.w.?day^?1, and an Acute Reference Dose of 0.01?mg?kg^?1?b.w.?day^?1, based on a toxicological risk assessment. The French National Reference Laboratory for pesticides has carried out two analytical methods, one for food of animal origin and another for food of fruit and vegetable origin. These methods were validated in the reference laboratory and dispatched to 13 laboratories for a proficiency test before the launch of two studies on Martinique and Guadeloupe food. About 900 samples from Martinique were sent to the network of laboratories for analysis of chlordecone. Performance parameters obtained through the proficiency test were briefly reported. The quality control test proposed in this study was discussed to shed light on the true variability achievable by intra-laboratory and inter-laboratory analysis. The limits of conventional quality-control procedures were discussed, and a process was proposed in order to get better confidence in analytical results.     

Enhanced π‐Backdonation from Gold(I): Isolation of Original Carbonyl and Carbene Complexes

The specific electronic properties of bent o‐carborane diphosphine gold(I) fragments were exploited to obtain the first classical carbonyl complex of gold [(DPCb)AuCO]⁺ (ν(CO)=2143 cm^?1) and the diphenylcarbene complex [(DPCb)Au(CPh₂)]⁺, which is stabilized by the gold fragment rather than the carbene substituents. These two complexes were characterized by spectroscopic and crystallographic means. The [(DPCb)Au]⁺ fragment plays a major role in their stability, as substantiated by DFT calculations. The bending induced by the diphosphine ligand substantially enhances π‐backdonation and thereby allows the isolation of carbonyl and carbene complexes featuring significant π‐bond character.     

Cover Picture

The cover picture shows how thrombosis occurs in the deep veins of the lower limbs. Stasis, which results from slow and turbulent blood flow, combined with hypercoagulation, caused, for example, by a surgical procedure, may result in thrombus formation. The synthetic sulfated pentasaccharide shown in part is a potent antithrombotic compound that exerts its effect by activation of the plasma protein antithrombin III. Conformationally locked monosaccharides have now been synthesized to demonstrate that L-iduronic acid, one part of the pentasaccharide, must adopt an unusual distorted conformation to activate antithrombin III. Such conformational effects might be relevant in explaining the unique biological properties of glycosaminoglycans that contain L-iduronic acid. In the background of the picture, a flight of vampire bats is attracted by the pentasaccharide. Vampire was the name given to South American blood-sucking bats (Latin name: desmodus rotundus) in 1761 by the French naturalist Georges Louis Leclerc Comte de Buffon (1707-1788). These bats are known to attack cattle and, very rarely, sleeping human beings. Although their saliva has been shown to contain an anticoagulant compound, they would also be happy to benefit from the pentasaccharide mentioned above, to suck the blood out of the vein more easily. More details about this compound which would be helpful to vampire bats are reported by Petitou, Sina? et al. on p. 1670 ff.