Indirect Measurement of Biologically Important Compounds by Means of X-Ray Microanalysis

 The main objective of our work was to investigate the possibility and usefulness of indirect methods in X-ray microanalysis for the quantification of biologically important compounds. Metallothionein-like proteins (MT-like proteins) from kidney and liver, rich in sulfur were chosen as an indicator of heavy metal presence in cells and their environment. Tissues from goldfish (Carassius auratus gibelio) were sampled after short and prolonged periods of exposure to Co⁺², CrO₄ ⁻², Pb⁺², Cu⁺² and control treatment and prepared for histochemical staining for peroxidated thiolate groups. Commonly used –S–S– bonds dye (Nitro Red) was replaced with iodine atoms and they were quantified at L line by means of X-ray microanalysis combined with SEM. After fish treatments with heavy metal solutions changes in MT-like proteins and in I atom contents were expected. There was statistically significant decrease in MT-like proteins level in kidney after lead treatment (Pb/C = 0.62). In liver a statistically significant increase in MT-like proteins concentration was observed after chromium, cobalt and lead ions treatment in comparison to control animals. The following ratios were noted: 3.04 for Cr/C, 2.18 for Co/C and 2.10 for Pb/C. Our finding indicates that the method of indirect measurement of MT-like proteins in fish and other animal tissues is possible. The concentration of iodine atoms is above their detection level by EDS and their changes are possible to identify. During histochemical procedures it is worth taking into account sample preparation methods which might disturb the quality and quantity of the analysed material.     

EPMA and X-Ray Diffraction of the Degraded Fuel Bundle from the Phebus FPT1 Test

 The degraded fuel rod bundle from the second Phebus test (FPT1) was examined at ITU, Karlsruhe. Metallographic and microprobe analysis of the degraded fuel pieces were carried out. The fuel samples from the upper bundle and cavity edge were porous and had remnants of thick oxidised cladding adhering to them. Electron microprobe analysis line scans across the cladding-fuel interface showed interdiffusion of U and Zr, with U diffusing down the grain boundaries of the oxidised cladding, while point analyses revealed noticeable amounts of Zr (1.5–4.2 wt%) in the UO₂ fuel. EPMA oxygen measurements revealed in the upper part of the bundle a superstoichiometry of x = 0.3–0.4 in UO _2 + x , indicating that fuel fragments in this position had undergone considerable oxidation. X-ray diffraction of the corium pool disclosed a deformed cubic fluorite lattice of UO₂. The lattice parameter of a = 5.2984 ? was considerably reduced compared with pure, stoichiometric UO₂ and was consistent with a lattice containing approximately 45 mol% ZrO₂ that had undergone little oxidation. The corium’s nominal composition of (U_0.5Zr_0.5) O₂ also corresponded to its observed single phase microstructure.     

Investigation of Co/Cu/NiFe-Multilayers by X-Ray Reflectometry and Diffraction

 Structural properties of sputtered multilayers with different Co-, Cu- and NiFe-sequences of about 2 nm individual layer thickness were investigated by means of synchrotron radiation techniques. Correlations between the layer combination and structural parameters such as layer thickness and rms interface roughness derived from specular scans were obtained, whereas the lateral characteristics of the interface morphology investigated by diffuse scattering were found to be similar for all multilayers. Wide angle diffraction measurements yielded lattice plane information, e.g. size-strain effects due to profile broadening and predominating <111> fibre textures.     

中草药板蓝根粉末的X射线衍射傅立叶指纹图谱分析

对来自不同地区的板蓝根粉末样品用X射线衍射傅立叶(Fourier)指纹图谱技术进行鉴定.由于不同产地的板蓝根样品的指纹图谱不同,因此,采用这一技术可对板蓝根样品作出区别和鉴定.试验结果表明该方法尚可应用于其他中药的鉴别.     

Short-Range Ordering in Liquid Bicyclohexyl by X-Ray Diffraction

Abstract

The paper reports results of the X-ray diffraction structural studies of liquid bicyclohexyl, C₆H₁₁—C₆H₁₁ at room temperature, using CuK _α radiation. Angular distribution of X-ray scattered intensity was measured, and the electron-density radial-distribution function was calculated. Computer techniques were used to minimize the effects of experimental errors, uncertainties in the scattering factors, and termination errors. Good agreement between the theoretical and experimental functions was obtained on assuming the statistically most probable model of this molecule. The structural data obtainable by X-ray analysis for liquid bicyclohexyl were discussed. The mean distances between the neighbouring molecules and the radii of coordination spheres were found. The maxima in the differential radial distribution function were at: r ₁ = 4.68, r ₂ = 5.57, r ₃ = 6.62, r ₄ = 8.05 Å. X-ray structural analysis was applied to determine the packing coefficient of bicyclohexyl molecules. A simple model of short-range arrangement of the molecules in liquid bicyclohexyl was proposed.     

Determination of Thiosemicarbazones by Means of the Induced Iodine-Azide Reaction

 The iodine-azide reaction induced by eight thiosemicarbazones was investigated. Inducing properties of thiosemicarbazones are different and depend on the parent carbonyl compound used for synthesis. The inductor coefficients of the examined thiosemicarbazones vary from 61 to 176. Optimum conditions for the determination of microamounts of thiosemicarbazones are given. The detection limit for the determination by the back-titration method depends on the inducing activity and is 0.9 μg for phenyl-thiosemicarbazones and 2 μg for diethyl-thiosemicarbazone in a 5-mL sample, and this corresponds to a concentration of 0.9 × 10⁻⁶ mol/L and , respectively. The automatic titration with the diluted iodine solution decreases the detection limit to about 50 ng in a 10-mL sample. Received October 28, 1998. Revision April 9, 1999.     

High-Spatial-Resolution Low-Energy Electron Beam X-Ray Microanalysis

 Performing X-ray microanalysis at beam energies lower than those conventionally used (< 10 keV) is known to significantly improve the spatial resolution for compositional analysis. However, the reduction in the beam energy which reduces the X-ray interaction diameter also introduces analytical difficulties and constraints which can diminish the overall analytical performance. This paper critically assesses the capabilities and limitations of performing low beam energy, high spatial resolution X-ray microanalysis. The actual improvement in the spatial resolution and the reduction in the X-ray yield are explored as the beam energy is reduced. The consequences for spectral interpretation, quantitative analysis and imaging due to the lower X-ray yield and the increased occurrence of X-ray line overlaps are discussed in the context of currently available instrumentation.     

Trace Analysis by Heavy Ion Induced X-Ray Emission

 Various K-, L- and M-shell X-ray production cross sections are measured for heavy ion impact on elements in the range Z ₂ = 13 to 83. The ion species range from Z ₁ = 10 to 36, and ion energies from 1 to 16 MeV are used. Enhanced cross sections are observed when the projectile K- or L- binding energy is similar to the energy of the target K-, L- or M-shell. This effect is used to improve the analysis sensitivity for selected elements. As an example trace analysis of Fe in glass with V, Mn, Co and Ni ions is investigated. Results are compared with proton induced X-ray emission analysis on the same samples. In these samples Fe-K_α X-ray production is similar for irradiation with 3 MeV protons and 14 MeV Ni ions. However the signal to background ratio is four times higher for the irradiation with Ni ions as compared to irradiation with protons. Advantages and drawbacks of heavy ion induced X-ray emission for quantitative analysis compared to proton induced X-ray emission analysis are discussed.     

Chromate-Free Zinc Conversion Coatings Characterised by Grazing Incidence X-Ray Diffractometry

 Alternative processes for chromate conversion coatings on zinc represent a research challenge for environmental reasons. A potential concept yielding a promising corrosion behaviour without the need for toxic chemical additives is the application of alternating currents (AC) together with the addition of inorganic nitrogen compounds in an electrochemical bath. A first grazing incidence X-ray diffractometry (GIXD) study of the composition and crystallinity of this novel conversion coating system is presented. GIXD has been employed because this technique has proved to be successful in the analysis of electrochemically formed conversion coatings down to 10 nm thickness. Various ion additives like and in NaOH solution were applied in the AC treatment. The nitrite anion, , yielded the best result. It increased the generation rate and crystallinity of the passive layers. The ratio of the crystalline ZnO to Zn(OH)₂ content could be influenced by the AC amplitude and the AC cycling time. GIXD decisively contributed to the improved understanding of this chromate-free zinc conversion process.     

Chemical Interactions by Low-Energy Electron-Induced X-Ray Emission Spectroscopy, LEXES

 The possibilities presented by low-energy electron-induced X-ray emission spectroscopy to study chemical interactions in solids are discussed. Examples of change observed for the emissions between core levels as a function of the chemical environment of the emitting atoms are given. By comparing the partial densities of the valence states associated to each type of atoms in the compound, it is shown that the strength of the metal-ligand interactions can be obtained. Information on the charge densities around each type of atoms can be deduced. Application to the study of the interactions at the atomic scale to solid–solid interfaces is presented.     

Hydration of dodecyltrimethyl-ammonium hydroxide micelles

 The hydration of dodecyltrimethylammonium hydroxide (DTAOH) micelles was determined by viscosity measurements, giving 39.2±7.0 water molecules per micellized dodecyltrimethylammonium ion. This result is lower than the hydration of DTAB micelles, which is about 65. This difference may be due to the effect of the electrorestrictive structure-making hydroxide ion on the hydration of the alkyltrimethylammonium head group, in comparison with the less hydrated structure-breaking bromide ion. Received: 29 January 1996 Accepted: 4 July 1996     

X-Ray Microanalysis of Thin Surface Films and Coatings

 The paper gives an overview of the present knowledge in the field of X-ray analysis of surface films and more generally stratified specimens. The aim of the paper is not to report the details and formulas of the available quantitative procedures, but to concentrate on the general ideas and orders of magnitude illustrating the capability and limits of the method, and on the optimal adaptation of the operating conditions to every particular problem. The various specific pitfalls which can be encountered are pointed out, in particular the fluorescence effects when using high-energy X-ray lines, or the anomalies due to chemical bonding, absorption uncertainties, and contamination effects when soft radiations are employed.     

Phase Recognition in AlN-Ti System by Energy Dispersive Spectroscopy and Electron Backscatter Diffraction

 The combination of energy dispersive spectroscopy (EDS) and electron backscatter diffraction (EBSD) techniques in scanning electron microscope was employed to characterize the reacted interface between Ti matrix and AlN particles. Due to the high localization of EDS and EBSD, representative measurements of chemical composition and reliable determination of the crystal structure were possible for each phase in the reaction zone with complex morphology. The TiN_1−x (cubic, NaCl type), Ti₃AlN (cubic, perovskite type) and Ti-rich Ti₃ Al (hexagonal, Ni₃Sn type) phases were identified in the reaction zone after annealing at 1100 °C. EDS+EBSD combination is an efficient tool for phase analysis at the interface in reactive multicomponent systems. Received August 21, 1999. Revision November 21, 1999.     

X-Ray Diffraction Study of Piperidine Octamolybdate

Piperidine octamolybdate [C₅H₅NH₂]₄[Mo₈O₂₆]·4H₂O (I) has been synthesized and characterized by X-ray diffraction analysis. Crystals I are monoclinic, space group P2₁/n, a=12.892(3), b=9.283(2), c=19.184(4) , =92.50(3)°, V=2293.7(9) ³, Z=2,_calc = 2.317 g/cm³.     

Energy Dispersive X-Ray Spectrometry by Microcalorimetry for the SEM

 Analytical X-ray spectrometry for electron beam instruments has advanced significantly with the development of the microcalorimeter energy dispersive X-ray spectrometer (μcal EDS). The μcal EDS operates by measuring the temperature rise when a single photon is absorbed in a metal target. A cryoelectronic circuit with electrothermal feedback and a superconducting transition edge sensor serves as the thermometer. Spectral resolution approaching 4.5 eV for high energy photons (6000 eV) and 2 eV for low energy photons below 2000 eV has been demonstrated in energy dispersive operation across a photon energy range from 250 eV to 8 keV. Spectra of a variety of materials demonstrate the power of the μcal EDS to solve practical problems while operating on a scanning electron microscope platform.     

Basics, Possibilities and Limitations of the Microscopic X-Ray Fluorescence Analysis

 Microscopic X-ray fluorescence (MXRF) analysis was used to investigate different samples: meteorites, Jasper, coated glas and, reference materials. The element distribution within sections of two different meteorites have been determined – one metal rich and one oxide rich. The metal rich showed a matrix of Fe with Ni-, Ti-, and Si-enriched regions. The oxide rich also showed a Fe rich matrix and regions with different concentrations of other elements. A reference sample with a flat and polished but systematically tilted surface was used to assure, that roughness of the sections of the meteorites has only negligible influence. Nondestructive investigations in Jasper with included Stromatolithes, which were fossilized more than 2 billion years ago, showed the Stromatolithes to have Fe as main element instead of Si in the Jasper matrix. The thickness of Yb-layers on glas was determined from the intensity of the Yb fluorescence peak. Calibration was done by using a sample without coating and a reference sample whose thickness of the layer was determined by XRD reflectometry. Futhermore it has been shown that materials can be analysed even if mounted in glas capillaries or covered by plastic foils. By using Mark capillaries the elements from S to U may be detected instead of Na to U while working in vacuum mode.     

A Study on the Hydration of Portland Limestone Cement by Means of TG

Subject of this paper is to investigate the hydration process of Portland limestone cement containing 10-35% limestone. Cements, produced by co-grinding of clinker, limestone and gypsum, were hydrated for periods 6 h to 28 d and were studied by means of TG and XRD. The Ca(OH)₂ content of the cements containing limestone is higher than in pure cements, specifically for 10% limestone content and ages more than 1 day. These results are in accordance with the strength development of the studied cements. In earlier ages the Ca(OH)₂ content is slightly lower in the limestone cements and independent of the limestone content. After 1 day curing, the increase of limestone addition causes a relative increase of the non evaporable water. The XRD patterns indicated the presence of carboaluminates in the hydrated limestone cements. This revised version was published online in July 2006 with corrections to the Cover Date.     

X-Ray Emission from Thin Films on a Substrate – Calculation and Experiments

 Monte Carlo simulation of electron transport in solids is widely used in electron microscopy, spectroscopy and microanalysis. The reliability of physical models incorporated in a Monte Carlo code is usually checked by comparing with experimental results. Elastic or inelastic collisions are usually considered as the basic interactions of electrons with atoms. In our Monte Carlo code the single scattering model is employed for simulation of X-ray emission from thin films of Au on the Si substrate. The electron beam energy was in the range 10–30 keV, the take-off-angle was 40°. The simulated values of X-ray production were calculated in our Monte Carlo code using several models of ionisation cross-sections. For the emitted intensities the depths of inelastic collision and X-ray absorption were taken into account, then the k-ratios were calculated. These data were compared with experimental values of k-ratios calculated from X-ray intensities of Au M and Au L characteristic lines. We followed mainly the dependence of the k-ratios of the film element on film thickness. The film thickness was in the range 0.05–1 μm. Reasonably good agreement was found for dependences of X-ray intensity on film thickness in the whole energy range and for both lines, especially for Powell’s model of the ionisation cross-section.     

Sensitive Determination of Adrenaline by Means of a Flow-Through Solid Phase UV Spectrophotometric Sensing Device

 A very sensitive flow-through optosensor with solid phase UV spectroscopic detection is proposed for the direct determination of adrenaline without prior derivatization. Sample is transported by the carrier stream (0.05 M NaCl/0.01 M NaOH) to the sensing microzone composed of Sephadex QAE A-25 resin placed in a flow-through cell, and its intrinsic absorbance is monitored at 287 nm. After development of the analytical signal adrenaline is easily and quickly desorbed from the solid support by a 0.7 M NaCl/0.01 M NaOH eluting solution stream. Adrenaline can be determined in the range 1–12 μg/ml, the detection limit being 0.17 μg/ml. The RSD (10 replicates) and sample throughput are 1.4% and 12 per hour, respectively. The procedure has been successfully applied to the determination of adrenaline in different medical formulations. Received May 26, 1999. Revision February 3, 2000     

面粉中滑石粉的X射线衍射分析

通过四氯化碳分离或高温灰化,X射线衍射分析测定面粉中掺入的滑石粉。其中灰化处理适宜温度为500~750℃。该方法简便、快速,灵敏度高,样品用量少,准确可靠,可推广为检测面粉质量的一种较理想的手段。