Uranium determination in seawater by total reflection X-ray fluorescence spectrometry

A study regarding uranium determination in seawater by total reflection X-ray fluorescence (TXRF) spectrometry is reported. Uranium, present in seawater in concentration of about 3.3 ng/mL, was selectively extracted in diethyl ether and determined by TXRF after its preconcentration by evaporation and subsequent dissolution in a small volume of 1.5% suprapure HNO₃. Yttrium was used as an internal standard. Before using diethyl ether for selective extraction of uranium from seawater, its extraction behavior for different elements was studied using a multielement standard solution having elemental concentrations in 5 ng/mL levels. It was observed that the extraction efficiency of diethyl ether for uranium was about 100% whereas for other elements it was negligible. The detection limit of TXRF method for uranium in seawater samples after pre-concentration step approaches to 67 pg/mL. The concentrations of uranium in seawater samples determined by TXRF are in good agreement with the values reported in the literature. The method shows a precision within 5% (1σ). The study reveals that TXRF can be used as a fast analytical technique for the determination of uranium in seawater.     

Mass spectrometry/gas chromatography-mass spectrometry approach for rapid screening/quantitative determination of perchloroethylene in air

A new mass spectrometry/gas chromatography-mass spectrometry (MS/GC-MS) approach has been developed for the screening and quantitative determination of perchloroethylene (PERC) in workplace and outdoor air samples, which could be extended to the screening and analysis of other analytes and samples. This approach may be rapidly modified in order to be used directly as an MS detector for screening purposes or alternatively as a common GC-MS, for confirmation. The screening alternative by MS is approximately 20 times faster than the quantitative-confirmatory determination by GC-MS. Detection limits of both alternatives are sufficiently low to screen and determine PERC in the above-mentioned matrixes. The advantage of this approach over others previously described is that, in the present case, the sample passes through the chromatographic column only when the confirmatory GC-MS is used. For the MS screening method, the chromatographic column is bypassed by using an appropriate selection valve. In this way, the column lifetime is extended and screening time is considerably shortened.     

Structure determination of triplet diphenylcarbenes by in situ X-ray crystallographic analysis

Crystalline-state photoreactions of the following diphenyldiazomethanes were investigated by in situ X-ray crystallography, spectroscopy, and theoretical calculations: bis(2,4,6-trichlorophenyl)diazomethane (1-N2), bis(2,4,6-tribromophenyl)diazomethane (2-N2), bis(2,6-dibromo-4-methylphenyl)diazomethane (3-N2), bis(2,6-dibromo-4-tert-butylphenyl)diazomethane (4-N2), (2,4,6-tribromophenyl)-(2,6-dimethyl-4-tert-butylphenyl)diazomethane (5-N2), bis(4-bromophenyl)diazomethane(6-N2), and diazofluorene (7-N2). Crystal structures of photoinduced triplet diphenylcarbenes (DPCs) of 1, 2, and 4 were determined. We found remarkable differences between their structural information obtained in the crystalline state and that previously obtained spectroscopically in a glass matrix. Although the triplet DPCs of 1, 2, and 4 have significantly different stabilities in solution, only subtle differences in their structural parameters, except for their C(:)-Ar bond lengths, are observed. It is noteworthy that the average bond length of C(:)-Ar for 4 (1.374 A) is considerably shorter than those for (3)1 and (3)2 (1.430 and 1.428 A, respectively), provided that the two C(:)-Ar bonds being compared were chemically equivalent. The most likely explanations for the small and large differences in bond lengths in 1, 2, and 4 may be derived from the packing effect. The packing patterns of 1 and 2 are identical, but that of 4 is totally different from those of 1 and 2. Moreover, these results are interpreted as indicating that triplet DPCs undergo relaxation upon softening of the environments. Theoretical calculations indicate that the potential energy surface of triplet DPCs in terms of the carbene angle is extremely flat and changes in the angles have little effect on the energies. Triplet DPCs with a sterically congested carbene center are trapped in a structure dictated by the precursor structure in a rigid matrix, even if this is not the thermodynamically most stable geometry, but undergo geometrical relaxation upon softening the matrix to relieve steric compression. ESR studies indicate that the interplanar angles are more flexible than the bond angles.     

X-ray studies on layer structure and bistability in ferroelectric liquid crystals

X-ray diffraction measurements of thin chiral smectic C (S_c*) liquid crystals between solid plates coated with rubbed polymer film were performed under an electric field. A variety of local layer structures which depend upon the boundary conditions could be observed, including bookshelf and chevron, and some distorted structures. Moreover, the method of layer deformation could be seen in a stepwise induced field, and seven deformation types could be detected. The relation between a bistability effect and the type of layer deformation was clarified and four deformation types were found favourable to bistability. A vertical layer structure at the boundary, like the bookshelf structure, was necessary to produce bistability. A high pretilt film seemed to have a smectic layer reform a tilted structure even under an induced field and it was difficult to produce bistability with the high pretilt one.     

Nondestructive analysis of single crystals of selenide spinels by X-ray spectrometry techniques

The paper presents possibilities and difficulties in nondestructive analysis of small multielement single crystals performed by means of X-ray spectrometry techniques: micro-X-ray fluorescence spectrometry (μ-XRF), energy-dispersive electron probe microanalysis (ED-EPMA), and X-ray photoelectron spectroscopy (XPS). The capability of the X-ray spectroscopy techniques in elemental analysis is demonstrated with the single crystals of selenide spinels of the general formula M _x N _y Cr _z Se₄ (M⁺² and N⁺³ are, for example, Zn⁺², V⁺³, Ga⁺³, Cd⁺², In⁺³, and Sb⁺³). The results of the nondestructive analyses (μ-XRF, ED-EPMA, and XPS) are compared with those obtained by inductively coupled plasma optical emission spectrometry (ICP-OES) and wavelength-dispersive X-ray spectrometry (WDXRF) following sample digestion. The present study shows satisfactory agreement between the results of μ-XRF analysis performed using the standardless fundamental parameter method and the results obtained with the WDXRF and ICP-OES analyses. If the measured single crystal is precisely positioned, the difference between μ-XRF and wet analysis (WDXRF and ICP-OES) does not exceed 5% rel. The reliable results of ED-EPMA can be obtained only if the measured area is sufficiently large, i.e., of 200 × 300 μm. Even if this condition is fulfilled, the relative difference between the ED-EPMA and the wet analysis may reach 10% rel. In case of the XPS analysis, the accuracy of results depends on the proper preparation of the sample surface. It should be free of contamination that can be obtained by scraping in situ in ultrahigh vacuum. The ion etching, commonly used for cleaning the surface, leads to preferential sputtering; therefore, the reliable results cannot be obtained.     

Mass spectrometry for direct determination of proteins in cells: applications in biotechnology and microbiology

A number of different procedures have been developed in recent years that utilize mass spectrometry for the direct determination of proteins in complex mixtures of biological origin. Specific examples of these include the use of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) or directly combined liquid chromatography-electrospray ionization mass spectrometry (LC/ESI-MS) for rapid profiling of protein expression in bacterial and eucaryotic cells and cell-free extracts. Approaches to sample cleanup, contaminant removal, and initial separation of analytes on-line for the direct determination of proteins in cells using MALDI- and ESI-MS are discussed. Advantages of these techniques over traditional biochemical methods are highlighted, and a critical review of their utility and potential as standard tools in the biomolecular and microbiological research laboratory is presented.     

Mass spectrometry for direct determination of proteins in cells: applications in biotechnology and microbiology

A number of different procedures have been developed in recent years that utilize mass spectrometry for the direct determination of proteins in complex mixtures of biological origin. Specific examples of these include the use of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) or directly combined liquid chromatography-electrospray ionization mass spectrometry (LC/ESI-MS) for rapid profiling of protein expression in bacterial and eucaryotic cells and cell-free extracts. Approaches to sample cleanup, contaminant removal, and initial separation of analytes on-line for the direct determination of proteins in cells using MALDI- and ESI-MS are discussed. Advantages of these techniques over traditional biochemical methods are highlighted, and a critical review of their utility and potential as standard tools in the biomolecular and microbiological research laboratory is presented.     

Mass spectrometry determination of the isotopic composition of uranium hexafluoride

An absolute method for the determination of isotopic composition of substances in multiple collector mass spectrometers was proposed. The detailed analysi of terms used in the method for the determination of the isotopic composition of uranium hexafluoride was given. Parabolic nature of occurring constant measurement error, obtained in theory, was proved by test data for ²³⁵U within a wide range of its concentrations. In order to use the method of measurements in practice, the registration of constant error, through linear discriminatory relations Δc _i (c _i ), preliminary determined using uranium hexafluoride with standard isotopic composition, was proposed. The advantages of the developed method in comparison with the traditional analysis procedures, applied at present, were considered.     

熔融X射线荧光光谱法测定高炉返粉组份

建立了X射线荧光光谱法测定高炉返粉中化学成分的方法,采用高温熔融法将试样制成玻璃状体,消除了基体干扰;通过对熔样条件、干扰元素、仪器参数、工作曲线拟合方式等方面进行实验研究,确定了最佳分析条件,实现了高炉返粉中主要成分SiO2等8种成分的同时测定,方法具有准确度高、同时测定多元素、分析速度快等特点。