Investigation of polycapillary half lenses for quantitative confocal micro-X-ray fluorescence analysis.

The use of polycapillary optics in confocal micro-X-ray fluorescence analysis (CMXRF) enables the destruction-free 3D investigation of the elemental composition of samples. The energy-dependent transmission properties, concerning intensity and spatial beam propagation of three polycapillary half lenses, which are vital for the quantitative interpretation of such CMXRF measurements, are investigated in a monochromatic confocal laboratory setup at the Atominstitut of TU Wien, and a synchrotron setup on the BAMline beamline at the BESSY II Synchrotron, Helmholtz-Zentrum-Berlin. The empirically established results, concerning the intensity of the transmitted beam, are compared with theoretical values calculated with the polycap software package and a newly presented analytical model for the transmission function. The resulting form of the newly modelled energy-dependent transmission function is shown to be in good agreement with Monte Carlo simulated results for the complete energy regime, as well as the empirically established results for the energy regime between 6 keV and 20 keV. An analysis of possible fabrication errors was conducted via pinhole scans showing only minor fabrication errors in two of the investigated polycapillary optics. The energy-dependent focal spot size of the primary polycapillary was investigated in the laboratory via the channel-wise evaluation of knife-edge scans. Experimental results are compared with data given by the manufacturer as well as geometric estimations for the minimal focal spot size. Again, the resulting measurement points show a trend in agreement with geometrically estimated results and manufacturer data.

X-ray Fluorescence Techniques for Element Abundance Analysis in Wine.

The elemental composition has been extensively used to characterize wine and to find correlations with environmental and winemaking factors. Although X-ray fluorescence (XRF) techniques offer many advantages, they have been rarely used for wine analysis. Here, we show the comparison of wine elemental composition results obtained by total reflection X-ray fluorescence (TXRF) and energy dispersive X-ray fluorescence (EDXRF) for elements K, Ca, Mn, Fe, Cu, Zn, Br, Rb, and Sr. The results obtained by TXRF and EDXRF have been additionally verified by inductively coupled plasma-mass spectrometry. The important analytical features of XRF techniques in wine science have been described, the preservation of volatile elements (e.g., Br) being one of their main advantages. In addition, we have shown that XRF techniques offer an optimal analytical approach for building large data sets containing highly reliable and reproducible results of elemental abundances in wines, corresponding soils, and grape juice. Such data sets are especially important for the geographic authentication of wine. This has been shown for 37 Austrian and Croatian wines collected together with respective soils from selected wine regions. The element abundances in soil reflect in a large portion in grape juice and finished wine suggesting that the contribution of the soil, that is, the plant uptake capacity expressed as c i(wine)/c i(soil) concentration factors, can be a highly discriminating factor for wine fingerprinting. This indeed has been proved in the present study in comparison to discrimination based only on wine element abundances. We have identified Fe, Zn, Br, Rb, and Sr as the best discriminator elements for the geographical authentication of wine. The study opens a new perspective in extending the application of XRF techniques as a cost-effective analytical tool for creating large databases of soil, grape juice, and wine element abundances for the evaluation of soil characteristics and other environmental parameters on wine composition.

Dynamics of Pd Dopant Atoms inside Au Nanoclusters during Catalytic CO Oxidation.

Doping gold nanoclusters with palladium has been reported to increase their catalytic activity and stability. PdAu24 nanoclusters, with the Pd dopant atom located at the center of the Au cluster core, were supported on titania and applied in catalytic CO oxidation, showing significantly higher activity than supported monometallic Au25 nanoclusters. After pretreatment, operando DRIFTS spectroscopy detected CO adsorbed on Pd during CO oxidation, indicating migration of the Pd dopant atom from the Au cluster core to the cluster surface. Increasing the number of Pd dopant atoms in the Au structure led to incorporation of Pd mostly in the S-(M-S) n protecting staples, as evidenced by in situ XAFS. A combination of oxidative and reductive thermal pretreatment resulted in the formation of isolated Pd surface sites within the Au surface. The combined analysis of in situ XAFS, operando DRIFTS, and ex situ XPS thus revealed the structural evolution of bimetallic PdAu nanoclusters, yielding a Pd single-site catalyst of 2.7 nm average particle size with improved CO oxidation activity.

Microanalytical method development for Fe, Cu and Zn determination in colorectal cancer cells.

Microanalytical methods suitable for the determination of Fe, Cu in HT-29 (human colon adenocarcinoma) cells treated with different iron compounds (Fe(II) sulfate, Fe(III) chloride, Fe(III) citrate and Fe(III) transferrin) and cultured in medium supplemented or not with 10% (v/v) fetal calf serum (FCS) by total reflection X-ray fluorescence spectrometry (TXRF) and simultaneous graphite furnace atomic absorption spectrometry (GF-AAS) were developed. The developed TXRF method was also suitable for Zn determination in the samples. The main advantage of the proposed methods is the execution of all sample preparation steps following incubation and prior to the elemental analysis in the same Eppendorf tubes. Sample preparation was performed at microscale (115 µL sample volume) with 65% nitric acid and 30% hydrogen peroxide. According to scanning electron microscopic measurements, the organic matrix of the cell samples could be eliminated to the extent that accurate results were obtained for Cu and Fe by analyzing the same samples by TXRF and GF-AAS. Concerning the iron uptake, HT-29 cells incubated in FCS-free medium contained Fe in cca. 5-50 times higher amounts compared to cells cultured in FCS supplemented medium. Pronounced differences in the iron uptake compared to the iron supply (inorganic vs. organic chelated as well as iron(II) vs. iron(III)) were observed in the case of cell lines incubated in FCS-free medium.