Theoremes de Viabilite Pour les Inclusions Differentielles du Second Ordre

This paper gives conditions ensuring the existence for an initial value (x ₀,v ₀) of a solution to the second order differential inclusionx″(t) ∈F[x(t),x′(t)],x(0)=x ₀,x′(0)=v ₀ such thatx(t) ∈K for allt whereK is a nonempty given subset ofR ⁿ .      

Total and partial photoionization cross-sections of O2 from 100 to 800 Å

The branching ratios and absolute values of the total and partial photoionization cross-sections for producing O₂⁺ in its various electronic states are given as a function of wavelength in the range 100–800 Å. Cross-sections for dissociative ionization are given based on the premise that some of the bound ionic states predissociate. Photoelectron spectroscopy and absorption techniques utilizing a double ionization chamber were used to obtain the data.     

Hydrodistillation-headspace solvent microextraction, a new method for analysis of the essential oil components of Lavandula angustifolia Mill

A new method involving concurrent headspace solvent microextraction combined with continuous hydrodistillation (HD-HSME) for the extraction and pre-concentration of the essential oil of Lavandula angustifolia Mill. into a microdrop is developed. A microdrop of n-hexadecane containing n-heptadecane (as internal standard) extruded from the needle tip of a gas chromatographic syringe was inserted into the headspace above the plant sample. After extraction for an optimized time, the microdrop was retracted into the syringe and injected directly into a GC injection port. The effects of the type of extracting solvent, sample mass, microdrop volume and extraction time on HD-HSME efficiency were investigated and optimized. Using this method, thirty-six compounds were extracted and identified. Linalool (32.8%), linalyl acetate (17.6%), lavandulyl acetate (15.9%), alpha-terpineol (6.7%) and geranyl acetate (5.0%) were found to be the major constituents. To the best of our knowledge this is the first report on the use of continuous headspace solvent microextraction coupled with hydrodistillation for investigation of essential oil components.     

Modelling of migration behaviour of inorganic anions in ion-exchange capillary electrochromatography

A theoretical model to explain the observed mobility of inorganic anions in capillary electrochromatography (CEC) using ion-exchange (IE) stationary phases has been derived. The model divides contributions to the observed mobility of an analyte ion into capillary electrophoretic (CE) and IE components. The CE component includes the influence of varying the ionic strength of the background electrolyte on the electrophoretic mobility of the analyte, while the IE component accounts for the variation in retention of the analyte ion caused by changing the composition of the background electrolyte. The model was verified using a mixture of UV-absorbing inorganic ions in electrolytes of differing eluotropic strength in both packed and open-tubular CEC systems, with excellent agreement (r2 > 0.98) for both systems. Values of constants in the model equation determined by nonlinear regression were used to estimate the relative strengths of the interactions of different analytes with the stationary phase and these were found to agree well with elution orders observed in conventional IE chromatography.     

Capillary electrophoresis using high ionic strength background electrolytes containing zwitterionic and non-ionic surfactants and its application to direct determination of bromide and nitrate in seawater

In capillary electrophoresis, it is commonly considered that even a moderately high ionic concentration in the background electrolyte (BGE) leads to high currents, resulting in Joule heating and serious peak distortion. As a new approach to overcome this problem, zwitterionic (Zwittergent-3-14) and/or non-ionic (Tween 20) surfactants have been added to BGEs containing high salt concentrations (e.g. 0.3 M NaCl) and have been shown to result in acceptable separation currents (<200 microA). In turn, these BGEs could be applied to the separation of samples containing high salt concentrations (such as undiluted seawater) without the occurrence of any significant peak broadening due to electrodispersion of the sample. For example, a BGE comprising 10 mM Zwittergent-3-14, 50 mM Tween 20, 0.3 M NaCl and 5 mM phosphate (ph 7) could be used for the determination of UV-absorbing anions in seawater, giving good peak shapes and detection limits of 0.8 microM and 0.6 microM for nitrate and bromide, respectively. The beneficial effects of the non-ionic surfactant on the separation were attributed largely to suppression of the electro-osmotic flow. On the other hand, the zwitterionic surfactant was found to be capable of the incorporation of some anions in accordance with the behaviour of these same surfactants in electrostatic ion chromatography. This incorporation resulted in a decreased conductivity of the BGE and also a change in the separation selectivity of the system.     

Action des composes dicarbonyles-1,2 sur des composes du phosphore dicoordonne a liaison pn et sur leurs oligomeres.

Triazaphospholes react with 1,2-diketones to give spirocyclic phosphorus compounds by a 1.1 addition at phosphorus atom; with o-quinones one obtains spirobicyclic hexacoordinated phosphorus compounds. The reaction of 1,2-diketones with λ³-phosphazene oligomers appears different, to some extent, and can be used as a test for the existence of a monomer-oligomer equilibrium.     

A superior method for the reduction of secondary phosphine oxides

[reaction: see text] Diisobutylaluminum hydride (DIBAL-H) and triisobutylaluminum have been found to be outstanding reductants for secondary phosphine oxides (SPOs). All classes of SPOs can be readily reduced, including diaryl, arylalkyl, and dialkyl members. Many SPOs can now be reduced at cryogenic temperatures, and conditions for preservation of reducible functional groups have been found. Even the most electron-rich and sterically hindered phosphine oxides can be reduced in a few hours at 50-70 degrees C. This new reduction has distinct advantages over existing technologies.     

Indirect spectrophotometric detection of inorganic anions in ion-exchange capillary electrochromatography

The application of indirect spectrophotometric detection was investigated for a capillary electrochromatographic system in which an anion-exchange stationary phase (in the form of aminated latex particles) was coated onto the wall of a fused-silica capillary. The study has focused on the choice of the type and concentration of the absorbing coion (probe) added to the background electrolyte and the role of this species in manipulating the ion-exchange contributions to the separation with a view to controlling the selectivity of the separation. Common inorganic anions were used as analytes and nitrate, p-toluenesulfonate, nicotinate, and chromate were investigated as probes. It was found that most of these probes produced only a limited range of separation selectivities when their concentration was varied over the practically accessible range. p-Toluenesulfonate provided the greatest variation in selectivity, but peak distortion due to electromigration dispersion was evident for the faster ions. When variation of the separation selectivity - from predominantly electrophoretic in nature to predominantly ion-exchange in nature - was desired, this was best achieved by varying the type of probe rather than its concentration. For example, the nitrate probe provided predominantly electrophoretic separations with good peak shapes and high efficiencies. A comprehensive list of probes, ranked in order of ion-exchange selectivity coefficients determined by ion chromatography, was compiled and this proved to be a useful tool to assist in the selection of a probe for a desired separation selectivity. The limits of detection for the analytes and probes studied ranged from 20-55 micromol for the chromate system to 230-600 micromol for the nicotinate system, with nitrate and p-toluenesulfonate giving intermediate values.     

Analysis of inorganic anions by electrostatic ion chromatography using zwitterionic/cationic mixed micelles as the stationary phase

The inability to separate fluoride, phosphate and sulfate by electrostatic ion chromatography (EIC) was overcome by using an ODS silica column coated with mixed zwitterionic-cationic surfactants as the stationary phase. The best results were obtained using the zwitterionic surfactant, 3-(N,N-dimethylmyristylammonium)-propanesulfonate (C19H41NO3S), and the cationic surfactant, myristyltrimethylammonium, CH3(CH2)13N+(CH3)3, in a 10:1 molar ratio in the column coating solution. With a dilute solution of sodium tetraborate as the eluent the model analyte anions were completely separated in the following elution order: F, HPO42-, SO42-, Cl-, NO2-, Br-, NO3-. The very early elution of phosphate and sulfate is most unusual and is unique to this system. Detection limits better than 1.1 x 10(-4) mM and linear calibration plots up to 7.0 mM were obtained with a suppressed conductivity system.     

Determination of inorganic ions using microfluidic devices

The separation and detection of inorganic ions on microfluidic devices has received little attention since the 'lab-on-a-chip' concept has revolutionised the field of electrokinetically driven analysis. This review presents a summary and discussion of the published literature on inorganic analysis using microfluidic devices and includes sections on electromigration separation methods, namely isotachophoresis (ITP), capillary electrophoresis (CE), and hyphenated ITP-CE, together with a brief account of flow injection analysis. The review concludes with the authors' perspective on future directions for inorganic analysis on microfluidic devices.