Réactions d'addition-élmination à partir d'hétérocycles germaniés du type . III. Cas des diéthyl-2,2-germa-2-oxazolidines-1,3 (R = et; X = O; Y = NH,NMe)

Addition-elimination reactions from germanium heterocycles . III. 2,2-Diethyl-2-germa-1,-3-oxazolidines (R = Et; X = O; Y = NH, NMe) . The reactions of 2,2-diethyl-2-germa-1,3-oxazolidines with heterocumulenes (PhNCO, PhNCS, CS₂, CO₂, CH₂?C?O) and carbonyl compounds (aldehydes and ketones) are studied. Generally, monoinsertion derivatives are formed by addition of one molecule of the unsaturated compound accross the Ge? N bond. This bond is always the most reactive center of the molecule. In the case of the carbonyl compounds used, diinsertion may occur in a second step by a further addition across a Ge? O bond. Generally, this latter reaction is reversible. By thermal eliminat on of (Et₂GeO)_n or (Et₂GeS)₃ the monoaddition derivatives yield the corresponding oxazolidines and thiooxazolidines. The mechanisms of these reactions are discussed.     

Use of quasi-isoelectric buffers to limit protein adsorption in capillary zone electrophoresis

The use of quasi-isoelectric buffers consisting of narrow pH cuts of carrier ampholytes (NC) has been investigated to limit protein adsorption on capillary walls during capillary zone electrophoresis experiments. To quantify protein adsorption on the silica surface, a method derived from that of Towns and Regnier has been developed. alpha-Lactalbumin (14 kDa, pI 4.8) and alpha-chymotrypsinogen A (25 kDa, pI 9.2) have been used as model proteins. Acidic narrow pH cuts of carrier ampholytes (NC, pH 3.0) obtained from fractionation of Serva 4-9 carrier ampholytes were used as BGE in bare-silica capillaries, and allowed to decrease significantly protein adsorption, as compared to experiments performed with classical formate buffer. The use of NC as BGE appeared to be as efficient as the use of polydimethylacrylamide coating to prevent protein adsorption. This increase of protein recovery when using NC was attributed to the interaction of carrier ampholytes with the silica surface, leading to a shielding of the capillary wall.     

Ultra-fast chromatographic micro-assay for quantification of diphenidol in plasma: application in an oral multi-dose switchability trial

Pharmacokinetics of diphenidol (DPN) is limited due to the lack of analytical methodology. Here, a micro-assay for DPN quantification was developed, by coupling ultra-performance liquid chromatography with tandem mass spectrometry. The procedure involved plasma precipitation and injection of supernatant into UPLC with an Acquitytrade mark C18 column. Detection was in positive electrospray, following transitions of m/z 310.3 --> 292.3 and m/z 275.3 --> 230.2 for DPN and chlorphenamine (internal standard), respectively. The method was linear with a range of 4-400 ng/mL, and a 2 min run time. This method was applied in a switchability trial, where both formulations of DPN were bioequivalent.     

How important are temperature effects for cluster polarizabilities?

State-of-the-art first-principle all-electron density functional theory calculations on small sodium clusters are performed to study the temperature dependency of their polarizabilities. For this purpose Born-Oppenheimer molecular dynamics simulations with more than 100,000 time steps (>200 ps) are recorded employing gradient corrected functionals in combination with a double-zeta valence polarization basis set. For each cluster 18 trajectories between 50 and 900 K are collected. The cluster polarizabilities are then calculated along these trajectories employing a triple-zeta valence polarization basis set augmented with field-induced polarization functions. The analysis of these calculations shows that the temperature dependency of the sodium cluster polarizabilities varies strongly with cluster size. For several clusters characteristic changes in the polarizability per atom as a function of temperature are observed. It is shown that the inclusion of finite temperature effects resolves the long-standing mismatch between calculated and measured sodium cluster polarizabilities.     

A study of antimony complexed to soil-derived humic acids and inorganic antimony species along a Massachusetts highway

Antimony is a toxic metalloid and is often present in inorganic forms such as more toxic Sb(III) and less toxic Sb(V). Auto brake linings are major contributors to antimony emissions along heavily traveled highways. In this study the distribution of water extractable Sb(III) and Sb(V) species along a Massachusetts highway was investigated. Antimony complexed to roadside soil-derived humic acids was studied by ion chromatography (IC) and size exclusion chromatography (SEC) coupled to inductively coupled plasma-mass spectrometry (ICP-MS). Thirty surface soil and soil core samples along route 116 in western Massachusetts were collected. Two soil-derived humic acids were extracted from the roadside soils. Elevated levels of nitric acid-extractable Sb (range: 2.9-24.9 µg/kg) and Pb (range: 10.4-2420 mg/kg) were found in the soil along the road and correlated well with highway traffic patterns. Sb(V) was the dominant species present in both surface and soil core samples, and is mostly confined to the top 20-cm layer of soil. HA mediated Sb(III) to Sb(V) oxidation was relatively fast and demonstrated pseudo-first order kinetics, where pseudo rate constant k is 3.033 h^-1. Antimony bound to soil-derived humic acid molar mass fractions was identified.     

Real time inverse filter focusing through iterative time reversal

In order to achieve an optimal focusing through heterogeneous media we need to build the inverse filter of the propagation operator. Time reversal is an easy and robust way to achieve such an inverse filter in nondissipative media. However, as soon as losses appear in the medium, time reversal is not equivalent to the inverse filter anymore. Consequently, it does not produce the optimal focusing and beam degradations may appear. In such cases, we showed in previous works that the optimal focusing can be recovered by using the so-called spatiotemporal inverse filter technique. This process requires the presence of a complete set of receivers inside the medium. It allows one to reach the optimal focusing even in extreme situations such as ultrasonic focusing through human skull or audible sound focusing in strongly reverberant rooms. But, this technique is time consuming and implied fastidious numerical calculations. In this paper we propose a new way to process this inverse filter focusing technique in real time and without any calculation. The new process is based on iterative time reversal process. Contrary to the classical inverse filter technique, this iteration does not require any computation and achieves the inverse filter in an experimental way using wave propagation instead of computational power. The convergence from time reversal to inverse filter during the iterative process is theoretically explained. Finally, the feasibility of this iterative technique is experimentally demonstrated for ultrasound applications.     

Distortion-free single point imaging of multi-layered composite sandwich panel structures

The results of a magnetic resonance imaging (MRI) investigation concerning the effects of an aluminum honeycomb sandwich panel on the B1 and B0 fields and on subsequent image quality are presented. Although the sandwich panel structure, representative of an aircraft composite material, distorts B0 and attenuates B1, distortion-free imaging is possible using single point (constant time) imaging techniques. A new expression is derived for the error caused by gradient field distortion due to the heterogeneous magnetic susceptibility within a sample and this error is shown not to cause geometric distortion in the image. The origin of the B0 distortion in the sample under investigation was also examined. The graphite-epoxy 'skin' of the panel is the principal source of the B0 distortion. Successful imaging of these structures sets the stage for the development of methods for detecting moisture ingress and degradation within composite sandwich structures.     

Gas sensor array based on metal-decorated carbon nanotubes

Here we demonstrate design, fabrication, and testing of electronic sensor array based on single-walled carbon nanotubes (SWNTs). Multiple sensor elements consisting of isolated networks of SWNTs were integrated into Si chips by chemical vapor deposition (CVD) and photolithography processes. For chemical selectivity, SWNTs were decorated with metal nanoparticles. The differences in catalytic activity of 18 catalytic metals for detection of H(2), CH(4), CO, and H(2)S gases were observed. Furthermore, a sensor array was fabricated by site-selective electroplating of Pd, Pt, Rh, and Au metals on isolated SWNT networks located on a single chip. The resulting electronic sensor array, which was comprised of several functional SWNT network sensors, was exposed to a randomized series of toxic/combustible gases. Electronic responses of all sensor elements were recorded and the sensor array data was analyzed using pattern-recognition analysis tools. Applications of these small-size, low-power, electronic sensor arrays are in the detection and identification of toxic/combustible gases for personal safety and air pollution monitoring.