Use of an open-tubular trapping column as phase-switching interface in on-line coupled reversed-phase liquid chromatography—capillary gas chromatography

The applicability of open-tubular traps for phase switching in coupled RPLC—GC was studied. The phase-switching process involves sorption of the analytes of interest from a methanol—water mobile phase into the stationary phase of an open-tubular column, removal of the aqueous phase by purging the trap with nitrogen and desorption of the analytes with hexane. Water elimination carried out in this manner appears to be highly efficient. In the sorption step the sampling flow-rate and the capacity factors of the analytes in the trap are critical parameters. Using a 2 m × 0.32 mm I.D. trap with a swollen 5-μm stationary phase at flow-rates not exceeding 100 μl/min, polycyclic aromatic hydrocarbons are trapped quantitatively from 300 μl of aqueous phases containing up to 65% (v/v) of methanol. For desorption 70–125 μl of hexane are needed. These volumes are easy to handle in solvent elimination carried out using a PTV injector prior to transfer of the analytes to a GC column.     

Determination of triazine herbicides in surface and drinking waters by off-line combination of liquid chromatography and gas chromatography-mass spectrometry

Summary Mass spectra of 12 triazines were obtained by electron impact (EI), positive-ion chemical ionization (PCI) and negative-ion chemical ionization (NCI) using methane and isobutane as reagent gases. EI mass spectrometry is more sensitive than PCI and NCI, although the chemical ionization modes increase selectivity markedly. A pre-column packed with polymer stationary phase was employed to preconcentrate surface and drinking water samples. After desorption of the analytes with ethyl acetate, an aliquot was injected directly into the GC-MS system. Atrazine and simizine were found in these samples at 10–80 ppt levels. The limits of detection for both herbicides were below 10 ppt in drinking water.     

Ion formation of N-Methyl carbamate pesticides in thermospray mass spectrometry: The effects of additives to the liquid chromatographic eluent and of the vaporizer temperature

The effects of three additives—ammonium acetate, ammonium formate, and nicotinic acid—to the liquid chromatographic (LC) eluent and of the vaporizer temperature on the ion formation of N-methyl carbamate pesticides in thermospray (TSP) mass spectrometry was investigated by using filament- or discharge-assisted ionization. Nineteen carbamates and 12 of their known environmental degradation products were used as model compounds. The additives cause a strong reduction in the abundance of the characteristic fragment ions [M + H ? CH₃NCO]⁺ and [M ? H ? CH₃NCO]^? for some of the carbamates. The addition of nicotinic acid reduces the quasimolecular ion intensity and, in most cases, produces nicotinic acid adduct ions. The addition of ammonium acetate or ammonium formate increases the intensity of the quasimolecular ion and in most cases produces a base peak for the ammonium adduct ion. The combination of a suppression of fragmentation and an enhancement of quasimolecular ion formation produces an overall gain in sensitivity. As to more specific effects, the addition of the ammonium salts reduces the intensity of M^?? with the chlorinated carbamate barban and suppresses the formation of “odd” adduct ions in the TSP mass spectra of most other carbamates. Monitoring the intensity of the fragment and the quasimolecular ion signal as a function of the probe stem temperature, and the related probe tip temperature, proved to be an easy method to study the thermal degradation of the carbamates. This monitoring procedure showed that methiocarb and its sulfone already suffer from thermal degradation at a stem temperature of 90°C and that these compounds will therefore present problems in quantitation with LC/TSP mass spectrometry.     

Photoemission study of UFe2 and UPt3 using synchrotron radiation

The U 5f density of states in UPt₃ and UFe₂ has been determined experimentally using synchrotron radiation. Cross section variations were exploited to separate the valence band contributions. By means of difference spectra, the variations in the U 5f density at the Fermi level have been measured.     

Comparison of thick film capillaries with packed columns from the point of view of loadability in combination with high resolving power

The present paper compares the potential of high pressure packed column gas chromatography, with a particle size in the range of 30–80 μm and conventional packed column GC. with that of thick film capillaries for obtaining the maximum loadability at a given performance in efficiency and speed of separation. An alternative treatment, discussing the maximum efficiency of the three column types at normalized loadability and speed of separation is given. Known and established relationships describing plate height, loadability, and linear velocity are used to arrive at the said comparisons. The conclusion of the paper indicates a reconsideration of packed column GC for particular types of analyses where large amounts or high concentrations are required in the detection step.     

Gasanalyse

Ohne Zusammenfassung     

High resolution electron energy loss spectroscopic study of the interaction of oxygen with magnesium single crystal surfaces.

From the beginning of the interaction of oxygen with the clean Mg(0001) and Mg(1$\text{1}$00) surfaces, two vibrational bands were measured by HREELS. The first one at 480 cm^?1 is attributed to atomic oxygen adsorbed at the surface. The second band at 620 cm^?1 is related to the stretching vibration of incorporated oxygen precursor to oxide formation. No specific difference was observed in the position and evolution of the two bands for both surfaces, but the electronic intensity reflected in the specular peak exhibited a totally different behaviour. The widths of the vibrational bands suggest a strong coupling with the continuum of electron-hole pairs of the metal.     

On-line diode array UV-visible spectrometry in screening for drugs and drug metabolites by high-performance liquid chromatography

The direct coupling of a multi-channel diode array UV-visible spectrophotometer to a powerful reversed-phase HPLC separation system is considered, especially for use in qualitative analysis, e.g., screening/identification of drugs and drug metabolites. The approach is illustrated by the screening for metabolites of butoprozine and ticlopidine directly in human and rat bile.     

J-complexes of retinol formed within the nanoparticles prepared from microemulsions

Retinol nanoparticles have been obtained by direct precipitation of retinol in the inner water cores of AOT/heptane/water microemulsions. The retinol dissolved in chloroform was injected into the microemulsion. The diameter of the so-obtained nanoparticles was measured using transmission electron microscope pictures where the revelation was made thanks to adsorbed iodine on the nanoparticles. The size is ca 6.0 nm, and it is not dependent either on the size of the water droplets or the concentration of the retinol molecules. This phenomenon is explained by the thermodynamic stabilization of the nanoparticles at a certain size. UV-visible spectra of the nanoparticles show a new band the maximum of which has a bathochromic shift with respect to the absorption band of the retinol monomers. If the bathochromic shift is plotted as a function of the line width, a linear correlation is obtained, the line width is decreasing with increasing shift. This behavior is interpreted as being due to an excitonic transition of a J-complex. Quantum chemical calculations have been carried out to confirm the presence of J-complexes. Taking into account the various possible geometries, the results confirm the presence of J-complexes composed of three head-to-tail molecules on the average.