Complex study of nickel skeleton catalysts: V. Study of novel non-pyrophoric nickel skeleton catalysts by derivatograph

The structure and properties of non-pyrophoric skeleton catalysts prepared from NiSi, NiAlSi, NiMg and NiZn alloys have been studied—apart from other thermal methods—by means of the derivatograph.Our experimental results have contributed to the explanation of the non-pyrophoric behaviour of these catalysts. We demonstrated that the desorption of the hydrogen content in our catalysts is not accompanied by the oxidation of active nickel. This oxidation takes place only at higher temperatures, above 200°C, at a rate proportional to the amount of active nickel.Other constituents of the catalysts (adsorbed water, hydroxide content) were also determined from the experimental data. The outstandingly high Mg(OH)₂ content of the NiMg catalyst indicates that its structure is dissimilar: Mg(OH)₂ also acts as support for the catalyst.     

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.     

Isotope gas analysis of tritium-labelled organic compounds based on pyrolytical decomposition

Summary A procedure has been developed for the activity measurement of tritium-labelled organic compounds in the gas phase. The organic compounds are pyrolysed in hydrogen carrier gas at 1150° and the decomposition products are swept through a carbon packing in accordance with the principle of the oxygen determination developed byUnterzaucher andBürger. The radioactive gas mixture obtained from the sample is swept by the hydrogen carrier gas flowing continuously through the reactor into a proportional counter tube, after the addition of propanebutane counter gas. By closure of the counter tube at a suitable moment, the radioactive gas is quantitatively trapped in the counter tube. The activity is measured in the limited proportional region. No memory effect occurs. The preparation of the sample requires 12 minutes; the relative standard deviation of analysis is <0.5%.

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Zusammenfassung Ein Verfahren zur Aktivitätsbestimmung bei tritium-markierten organischen Verbindungen in der Gasphase wurde ausgearbeitet. Die organischen Substanzen werden in Wasserstoff als Trägergas bei 1150° pyrolysiert. Die Zersetzungsprodukte werden wie bei der Sauerstoffbestimmung nachUnterzaucher bzw.Bürger über eine Kohleschicht geleitet. Das radioaktive Gas-gemisch aus der Probe gelangt mit dem kontinuierlich strömenden Trägergas in ein Proportionalzählrohr, nachdem Propan-Butan-Zählgas zugesetzt wurde. Man schließt das Zählrohr im richtigen Augenblick, um das radioaktive Gas quantitativ zu erfassen. Die Aktivität wird im Proportionalbereich gemessen. Ein Memory-Effekt tritt nicht auf. Die Vorbereitung der Probe beansprucht 12 Minuten. Die relative Standardabweichung ist kleiner als 0,5%.

     

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.