XPS study of residual oxide layers on p-GaAs surfaces

The total thickness and composition of a residual oxide layer after chemical etching of p-GaAs:Zn + In has been studied by X-ray photoelectron spectroscopy (XPS). The variation of the Ga to As oxides ratio along the depth has been determined. A concentration correlation of doping isovalent impurity and the dislocation density with the composition of residual oxides is looked for. The total thickness of the residual oxide layer on p- and semi-insulating GaAs is about 5–6 Å. It is found that the Ga₂O₃ quantity in the oxide bulk is greater than the same value of As₂O₃ in highly In-doped samples. In-doping in concentrations over 1.5 × 10¹⁹ cm⁻³ increases the Ga₂O₃ content and the density of the residual oxide. This influence is determined by reducing the dislocation density and changing the point defect environment. The presence of As-rich precipitates on the dislocations and in the matrix decreases the sputtering time and changes the composition of the residual oxide. The correlation between the type of high temperature dislocations revealed by Abrahams-Buiocchi (AB) etching and the oxide layer composition is shown. The results obtained could be used in the first stages of epitaxial growth, metallization and other technological processes of semiconductor device and ICs fabrication.     

IR-spectral investigation of the structure of glasses in the Fe2O3-V2O5 system

The structure of glasses in the Fe₂O₃-V₂O₅ system in the 0–50 mol% Fe₂O₃ range is studied by IR-spectroscopy. It is found that the introduction of Fe₂O₃ favours the transformation of the VO₅-groups into VO₄ ones. This effect may be shown with the aid of IR-spectra, owing to the fact that these glasses are characterized by two high-frequency bands at 1020 and 930 cm^–1. The first is determined by the vibrations of the short V=O nonbridging bonds in the VO₅-groups, while the second is assigned to the vibrations of the V—O-bonds in deformed VO₄-tetrahedra.

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IR-spektroskopische Strukturuntersuchung von Gläsern des Systems Fe₂O₃-V₂O₅

Zusammenfassung Die Struktur von Gläsern des Systems Fe₂O₃-V₂O₅ in dem Bereich von 0–50 Molprozent Fe₂O₃ wurde mit Hilfe der IR-Spektroskopie untersucht. Zusatz von Fe₂O₃ begünstigt die Umwandlung der VO₅- in VO₄-Gruppen. Das kann in den IR-Spektren durch zwei Banden bei 1020 und 930 cm^–1 festgestellt werden. Die erste wird durch Schwingungen der kurzen V=O-Nichtbrücken-bindungen in den VO₅-Gruppen verursacht, die zweite wird auf Schwingungen der V—O-Bindungen in dem deformierten VO₄-Tetraeder zurückgeführt.

     

Increasing the reliability of the identification by high-performance liquid chromatography by means of selective and/or sensitive detection

An approach for quantitative assessment of the reliability of identification at high-performance liquid chromatography is proposed. The quantitative assessment of identification is useful for determination of selectivity at validation of the analytical methods. Chromatograms and spectra of the analytes are presented as maps in which characteristics as retention times, detector's signals, maxima and minima and another characteristics of spectra are used for identification. A formula for quantitative determination of the contribution of these characteristics on the reliability of identification is given. Using the more selective diode array detector than the convenient UV detector increases the reliability by several orders. A similar result was obtained when the UV detector was replaced with the more sensitive and selective fluorescence detector. Despite of the small contribution of the separation to the reliability its influence is very important for distinguishing of isomers because their spectra are identical.     

A One‐Pot Synthesis of N‐Aryl‐2‐Oxazolidinones and Cyclic Urethanes by the Lewis Base Catalyzed Fixation of Carbon Dioxide into Anilines and Bromoalkanes

The multicomponent assembly of pharmaceutically relevant N‐aryl‐oxazolidinones through the direct insertion of carbon dioxide into readily available anilines and dibromoalkanes is described. The addition of catalytic amounts of an organosuperbase such as Barton's base enables this transformation to proceed with high yields and exquisite substrate functional‐group tolerance under ambient CO₂ pressure and mild temperature. This report also provides the first proof‐of‐principle for the single‐operation synthesis of elusive seven‐membered ring cyclic urethanes.     

Multiple-detector responses or multiple-retention times: what is more informative for gas chromatography peak identification?

Multiple-separation and -detection are two approaches applied at the identification of analytes in chromatography. Using them depends on the physico-chemical properties and elemental content of the analytes. When physico-chemical properties are similar multiple-separation gives better opportunities for the identification. In this case, the efficiency of the columns is very important. When analytes contain some characteristic groups as--NO2, halogen, or nitrogen atoms then multiple-detection will be more useful. The sensitivity and/or selectivity of the detectors increase reliability of identification significantly.     

Combined solid-phase extraction and 2D LC–MS for characterization of the neuropeptides in rat-brain tissue

A comprehensive two-dimensional capillary liquid chromatographic (2D LC) method has been established for determination of neuropeptides in rat brain tissue. Rats were exposed to different levels of stress before sacrificing and the aim of this study was to design a powerful separation and detection technique capable of characterizing differences between cerebral neuropeptide expression as a function of stress level. Rat brain samples were homogenized and subjected to clean-up by solid-phase extraction (SPE) on both a reversed-phase (C₁₈) and a weak cation-exchange (CBA) cartridge. The samples were divided in two fractions (A and B) depending on retention on the CBA column. Subsequently, 50 L of the sample were injected on to a strong cation exchanger (SCX) at a mobile phase pH of 3, which enabled preconcentration of positively charged compounds. The trapped compounds were eluted using step gradients of ammonium formate in water–ACN (90:10, v/v). Before enrichment in the second dimension, the eluate from the first dimension was diluted with water containing 0.1% TFA. The compounds eluting from the first dimension were trapped in the second dimension using a dual precolumn system consisting of two short capillary columns packed with Kromasil C₁₈, 10 m particles. Subsequently, the trapped compounds were backflushed on to a 10 cm long, 320 m I.D. analytical column packed with Kromasil C₁₈ 3.5 m particles, on which they were efficiently separated. Detection was performed using an ion-trap mass spectrometer (ITMS) in both the MS and the MS–MS mode. Comparison of base-peak chromatograms (BPC) from MS analysis of stressed and non-stressed rats clearly revealed several differences in neuropeptide expression. The MS–MS data obtained combined with Mascot software were employed for peptide identification.     

Determination and removal of impurities in 2-D LC-MS of peptides

Problems occurring during operation of a 2-D LC-MS system for separation and identification of neuropeptides, such as contamination of the used salts and column bleed, are described. When using polysulfoethyl aspartamide, which is widely used as a strong cation exchange stationary phase in the first dimension, interfering peaks were observed in the second-dimension reversed-phase chromatograms. The observed peaks, found to be caused by column bleeding, had abundance above the threshold value and influenced the quality of the analyses. The origin of the peaks was verified and appropriate measures are proposed. Additionally, peaks caused by polyethylene glycols (PEGs), covering approximately 5 min of feasible chromatographic time in every fraction, were observed. The commercial ammonium formate salts used to prepare the first-dimension mobile phase were found to contain PEG impurities, and in subsequent work the salt solutions were prepared from formic acid and ammonia to avoid any additional contaminations.     

Separation of strontium from calcium by the use of sodium hydroxide and its application for the determination of long-term background activity concentrations of <Superscript>90</Superscript>Sr in 100 km area around Kozloduy Nuclear Power Plant (Bulgaria)

The method for the determination of ⁹⁰Sr which employs sodium hydroxide for the separation of strontium from calcium was further improved introducing the use of elevated temperatures. The results from 11-year study of background activity concentrations of ⁹⁰Sr in different environmental objects in 100 km zone around Kozloduy Nuclear Power Plant (Bulgaria) are presented as an application of the analytical method. The measured mean values are as follows: air precipitation − 0.0015±0.0009 Bq(m^2.d), tap water − 0.0017±0.0012 Bq/L, soil − 1.90±1.26 Bq/kg, grass − 1.54±0.80 Bq/kg, milk − 0.023±0.012 Bq/L and for the Danube river: water − 0.0046±0.0026 Bq/L, bottom sediments − 0.64±0.60 Bq/kg, algae − 1.99±1.56 Bq/kg. The calculated transfer coefficients (soil-grass) are in the range of 0.33–0.84. Between 2 and 5 times reduction in actual background activities of ⁹⁰Sr is observed compared to 1972–1974.     

Obtaining ZnO/CIS heterostructures

ZnO/CuInSe₂ heterostructures were obtained by sequential evaporation of elements. Firstly, a layer of Zn was deposited on the glass substrate by the magnetron sputtering method in vacuum. Needle-shaped nanostructures of ZnO were grown from the prepared Zn films by thermal annealing in the air. Secondly, Se, In and Cu layers were sequentially deposited onto these structures. The obtained samples were then annealed at 400 °C to form the CuInSe₂ (CIS) compound. The morphology, composition and phase identification were obtained using the scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction analysis methods.