Oxametallacycloalcanes : V. Synthese de sila-2, germa-2 et stanna-2 oxa-1 cyclopentanes par deshydrocondensation intramoleculaire d'hydrures silicies,germanies ou stanniques γ-hydroxyles

The γ-hydroxymetal hydrides

OH (M = Si, Ge, Sn) were synthesized by reduction of γ-acetoxychloro- or γ-hydroxychloro-silanes, -germanes and -stannanes. These derivatives with MH bonds lead, by cyclisation at room- or higher temperatures, with or without catalyst, depending on the nature of the metal, to various oxametallacyclopentanes. The cyclisation proceeds by intramolecular dehydrocondensation between MH and OH bonds. These dehydrocondensation reactions are analysed and discussed according to the polarity of the MH bonds. Intramolecular addition of the MH bond into the unsaturated carboncarbon bonds of the corresponding non-cyclic compounds is also an excellent way of preparing the same heterocycles.The IR and NMR analyses of all new compounds are given.     

Differentiation between dexamethasone and betamethasone in a mixture using multiple mass spectrometry

Direct gas chromatographic methods to analyse phenylurea pesticides are discouraged by the thermal instability of these compounds, that in conventional hot splitless inlet systems leads to extensive and irreproducible formation of isocyanates and amines. However a careful control of the operating conditions, like the inlet temperature, the pressure and the presence of suitable chemical additives (as acetic acid, low-molecular-mass amines, organic anhydrides) can either: (i) minimise the thermal decomposition enabling the direct GC-MS analysis of phenylureas, or (ii) lead to reproducible conversion to isocyanates. Experimental design was employed to study the effect of the experimental variables on the thermal transformation of phenylurea pesticides in splitless inlet system. Two strategies were alternatively optimised: (i) the minimisation of degradation reactions to increase the signal of phenylureas; (ii) the maximisation of the degradation to isocyanates that are in turn determined. The maximal yields in isocyanate were obtained with high inlet temperatures, low carrier flows in the injection phase and the presence of acetic anhydride. By contrast, the use of relatively low inlet temperatures, high carrier flows during the injection and the presence of an amine maximise the response of the parent compounds.     

Evaluation of hydrogen bonding complementarity between a secondary sulfonamide and an alpha-amino acid residue

[structure: see text] We report an initial step toward the development of sulfonamide-based complements for extended peptide strands. A molecule containing one secondary sulfonamide unit and one valine residue linked by a turn-forming segment was found by IR and NMR to exhibit a doubly hydrogen-bonded folding pattern in chloroform.     

Figures of merit of pneumatic and ultrasonic sample introduction systems in inductively coupled plasma–multichannel-based emission spectrometry in an ultra-clean environment

Conventional figures of merit such as limits of detection, signal to background ratio or repeatability, are used to determine the performance of pneumatic and ultrasonic sample introduction systems in an ultra-clean environment with an axially viewed inductively coupled plasma-atomic emission spectrometry and multichannel detection. We observed that the ultrasonic nebuliser offered a large improvement of signal intensity (10-133 greater) compared to a cyclone chamber coupled with a pneumatic Meinhard nebuliser. This improvement is associated with an average increase of signal to background ratio by a factor 86 and an average decrease of detection limits by a factor 6. The improvement factors generally depend on the element and for the same element on spectral lines. Typically, the observed values of detection limits in this work are lower than those published and obtained in non-ultra-clean conditions. The results emphasize that the environmental conditions of cleaning and analysis are essential to avoid and control cross contamination of the samples and hence to obtain low detection limits.     

Damping of Crank–Nicolson error oscillations

The Crank–Nicolson (CN) simulation method has an oscillatory response to sharp initial transients. The technique is convenient but the oscillations make it less popular. Several ways of damping the oscillations in two types of electrochemical computations are investigated. For a simple one-dimensional system with an initial singularity, subdivision of the first time interval into a number of equal subintervals (the Pearson method) works rather well, and so does division with exponentially increasing subintervals, where however an optimum expansion parameter must be found. This method can be computationally more expensive with some systems. The simple device of starting with one backward implicit (BI, or Laasonen) step does damp the oscillations, but not always sufficiently. For electrochemical microdisk simulations which are two-dimensional in space and using CN, the use of a first BI step is much more effective and is recommended. Division into subintervals is also effective, and again, both the Pearson method and exponentially increasing subintervals methods are effective here. Exponentially increasing subintervals are often considerably more expensive computationally. Expanding intervals over the whole simulation period, although capable of satisfactory results, for most systems will require more cpu time compared with subdivision of the first interval only.     

Dynamic mechanical and thermal behavior of thermotropic polyesters based on 4,4-alkane-1-ω-diylbis(4-hydroxybenzoic acid) and 4,4-(pentane-1,5-diyloxy)dibenzoic acid

Thermotropic polyesters based on 4,4^′-alkane-1-ω-diylbis(4-hydroxybenzoic acid) and 4,4^′-(pentane-1,5-diyloxy)dibenzoic acid were studied by dynamic mechanical spectroscopy, X-ray scattering, differential scanning calorimetry and polarizing microscopy. The effect of structure changes in the mesogenic group as well as in the flexible spacer, in particular the incorporation of Cl atoms into the mesogen, introduction of ether oxygen into spacer and the number of CH₂ groups in spacer was investigated. More complex mechanical and thermal behaviour was found on second heating scan than on first cooling of the isotropic melt; higher values of mechanical functions were observed in the isotropic state than in the nematic state of melts. While an even number of CH₂ groups and the presence of ether oxygen in spacer shifts the transition temperatures to higher values, the incorporation of Cl atoms into the mesogen leads to disappearance of ordered structure and the polymers behave as amorphous materials.     

Direct Determination of Uranium in the D2EHPA-TOPO Organic Phase Using EDXRF Spectrometry

The determination of uranium in liquid samples using energy dispersive X-ray fluorescence was investigated. The organic phase di-(2-ethyl hexyl) phosphoric acid and trioctyl phosphine oxide (D2EHPA-TOPO)/kerosene, which resulted from first and second cycles of uranium extraction from commercial phosphoric acid, was directly analyzed using ¹⁰⁹Cd as a primary excitation source. Copper was used as an internal standard, which led to a linear relation between relative intensity of uranium and its concentration. Three calibration curves, 0–100, 100–1000 and 1000–6500 g· ml^–1, according to uranium concentration in the studied samples, were constructed. The effect of different molarities of D2EHPA and TOPO was considered. The detection limit, precision and accuracy were 1.1 g · ml^–1, 3% and 1.4%, respectively. The obtained results were compared with other techniques such as -ray spectroscopy, UV spectrometry and volumetry.     

The crystal and molecular structure of 1,1,2,4,4,5-hexaphenyl-1,4-diphosphoniacyclohexadiene-2,5 dibromide

The crystal and molecular structure of 1,1,2,4,4,5-hexaphenyl-1,4-diphosphoniacyclohexadiene-2,5 dibromide has been determined by a single crystal, x-ray diffraction study using diffractometer data. The compound crystallizes in the space group P2₁/_c with unit cell constants a = 8.813(1), b = 36.736(4), c = 12.478(1) Å, and β = 120.91°(1). The structure was solved by the heavy atom method and refined by block-diagonal least-squares to a final R = 0.04 for the 2761 statistically significant reflections. The structure determination shows that the central phosphonium ring is a diene and not a delocalized structure as anticipated. The ring is in the boat conformation with the axial phenyl rings aligned essentially parallel to each other and 3.55 Å apart.     

Quantitative analysis of relative protein contents by Western blotting: comparison of three members of the dystrophin-glycoprotein complex in slow and fast rat skeletal muscle

We have developed a method for accurate quantitative analysis and statistical comparison of the relative contents of the dystrophin-glycoprotein complex (DGC) in skeletal muscle. This method was applied to compare DGC contents in slow (soleus) and in fast (extensor digitorum longus, EDL) rat skeletal muscles. The quantitative analysis combines a modified bicinchoninic acid (BCA) assay with Western blotting and enhanced chemiluminescence (ECL). This combination allows the use of high levels of detergents and reducing reagents essential for extracting DGC. In addition, the evaluation of the total amount of proteins in each sample makes it possible to have a reference and to accurately compare relative protein levels without using a specific standard. With a large gradient gel, we could concomitantly compare two groups (n = 9) and quantify all protein contents differing highly in their molecular masses (from 35 kDa to 427 kDa). Each experiment was triplicated and normalized; the two muscles were compared using the Mann-Whitney test (P<0.001) to establish their protein content. The DGC relative levels for the slow muscle soleus and the fast muscle EDL differed significantly: dystrophin, beta-dystroglycan, and gamma-sarcoglycan levels were 130%, 110% and 120% higher in the soleus, respectively. The differences observed in the expression level of cytoskeletal associated protein (dystrophin) and transmembranous anchorage components may correspond to a physiological response of the muscle fibers to duration, magnitude, and frequency of the imposed mechanical loading.     

New results on photoion pair formation from application of the velocity imaging photoionisation coincidence technique

The velocity imaging photoionisation coincidence (VIPCO) technique is shown to be a powerful tool for studies of ion pair formation. Sequential mechanisms are demonstrated for some three-body ion pair formation reactions. Observation of a new type of reaction producing one negatively and two positively charged ions plus an electron is reported.