In situ-XAS and catalytic study of acrolein hydrogenation over silver catalyst: Control of intramolecular selectivity by the pressure

The gas phase hydrogenation of acrolein over 7.5% Ag/SiO2 has been studied in a broad pressure range from 7.5 mbar to 20 bar. Higher pressures favour the formation of allyl alcohol (selectivities up to 42%), whereas at low pressures propionaldehyde is by far the main product. In situ-XAS has been performed at 7.5 mbar in order to gain insight into the interaction of acrolein with Ag(1 1 1). Hydrogenated propionaldehyde-like surface species could be detected which orientated parallel to the surface. The observed intermediate correlates perfectly with the online catalytic data

Grazing incidence x ray fluorescence analysis for non destructive determination of In and Ga depth profiles in Cu In,Ga Se2 absorber films

Development of highly efficient thin film solar cells involves band gap engineering by tuning their elemental composition with depth. Here we show that grazing incidence X ray fluorescence GIXRF analysis using monochromatic synchrotron radiation and well characterized instrumentation is suitable for a non destructive and reference free analysis of compositional depth profiles in thin films. Variation of the incidence angle provides quantitative access to the in depth distribution of the elements, which are retrieved from measured fluorescence intensities by modeling parameterized gradients and fitting calculated to measured fluorescence intensities. Our results show that double Ga gradients in Cu In1 x,Gax Se2 can be resolved by GIXR

Grazing angle X-ray fluorescence from periodic structures on silicon and silica surfaces

Various 3-dimensional nano-scaled periodic structures with different configurations and periods deposited on the surface of silicon and silica substrates were investigated by means of the grazing incidence and grazing emission X-ray fluorescence techniques. Apart from the characteristics which are typical for particle- and layer-like samples, the measured angular intensity profiles show additional periodicity-related features. The latter could be explained by a novel theoretical approach based on simple geometrical optics (GO) considerations. The new GO-based calculations were found to yield results in good agreement with experiment, also in cases where other theoretical approaches are not valid, e.g., periodic particle distributions with an increased surface coverage

Mathematical modelling of clostridial acetone-butanol-ethanol fermentation

Clostridial acetone-butanol-ethanol (ABE) fermentation features a remarkable shift in the cellular metabolic activity from acid formation, acidogenesis, to the production of industrial-relevant solvents, solventogensis. In recent decades, mathematical models have been employed to elucidate the complex interlinked regulation and conditions that determine these two distinct metabolic states and govern the transition between them. In this review, we discuss these models with a focus on the mechanisms controlling intra- and extracellular changes between acidogenesis and solventogenesis. In particular, we critically evaluate underlying model assumptions and predictions in the light of current experimental knowledge. Towards this end, we briefly introduce key ideas and assumptions applied in the discussed modelling approaches, but waive a comprehensive mathematical presentation. We distinguish between structural and dynamical models, which will be discussed in their chronological order to illustrate how new biological information facilitates the ‘evolution’ of mathematical models. Mathematical models and their analysis have significantly contributed to our knowledge of ABE fermentation and the underlying regulatory network which spans all levels of biological organization. However, the ties between the different levels of cellular regulation are not well understood. Furthermore, contradictory experimental and theoretical results challenge our current notion of ABE metabolic network structure. Thus, clostridial ABE fermentation still poses theoretical as well as experimental challenges which are best approached in close collaboration between modellers and experimentalists

Experimental determination of tantalum L shell fluorescence yields and Coster Kronig transition probabilities

Using radiometrically calibrated instrumentation of the Physikalisch Technische Bundesanstalt, the L shell fluorescence yields and Coster Kronig factors of tantalum including the uncertainty budget were experimentally determined based on transmission and X ray fluorescence experiments. The determined fluorescence yields amp; 969;L3 0.247 12 , amp; 969;L2 0.278 15 , amp; 969;L1 0.157 12 were independently validated through XRR GIXRF experiments. Both the Coster Kronig factors f23 0.123 84 , f13 0.328 152 , f12 0.14 11 as well as the fluorescence yields are in good agreement with the most established databases in the field of X ray fluorescenc

Characterization of High k Nanolayers by Grazing Incidence X ray Spectrometry

The accurate characterization of nanolayered systems is an essential topic for today’s developments in many fields of material research. Thin high-k layers and gate stacks are technologically required for the design of current and future electronic devices and can be deposited, e.g., by Atomic Layer Deposition (ALD). However, the metrological challenges to characterize such systems demand further development of analytical techniques. Reference-free Grazing Incidence X-ray Fluorescence (GIXRF) based on synchrotron radiation can significantly contribute to the characterization of such nanolayered systems. GIXRF takes advantage of the incident angle dependence of XRF, in particular below the substrate’s critical angle where changes in the X-ray Standing Wave field (XSW) intensity influence the angular intensity profile. The reliable modeling of the XSW in conjunction with the radiometrically calibrated instrumentation at the PTB allows for reference-free, fundamental parameter-based quantitative analysis. This approach is very well suited for the characterization of nanoscaled materials, especially when no reference samples with sufficient quality are available. The capabilities of this method are demonstrated by means of two systems for transistor gate stacks, i.e., Al2O3 high-k layers grown on Si or Si/SiO2 and Sc2O3 layers on InGaAs/InP substrates

Function of Hemoglobin Based Oxygen Carriers Determination of Methemoglobin Content by Spectral Extinction Measurements

Suspensions of hemoglobin microparticles HbMPs are promising tools as oxygen therapeutics. For the approval of clinical studies extensive characterization of these HbMPs with a size of about 750 nm is required regarding physical properties, function, pharmaco kinetics and toxicology. The standard absorbance measurements in blood gas analyzers require dissolution of red blood cells which does not work for HbMP. Therefore, we have developed a robust and rapid optical method for the quality and functionality control of HbMPs. It allows simultaneous determination of the portion of the two states of hemoglobin oxygenated hemoglobin oxyHb and deoxygenated hemoglobin deoxyHb as well as the content of methemoglobin metHb . Based on the measurement of collimated transmission spectra between 300 nm and 800 nm, the average extinction cross section of HbMPs is derived. A numerical method is applied to determine the composition of the HbMPs based on their wavelength dependent refractive index RI , which is a superposition of the three different states of Hb. Thus, light scattering properties, including extinction cross sections can be simulated for different compositions and sizes. By comparison to measured spectra, the relative concentrations of oxyHb, deoxyHb, metHb are accessible. For validation of the optically determined composition of the HbMPs, we used X ray fluorescence spectrometry for the ratio of Fe II oxyHb deoxyHb and Fe III metHb . High accuracy density measurements served to access heme free proteins, size was determined by dynamic light scattering and analytical centrifugation and the shape of the HbMPs was visualized by electron and atomic force microscop