Showing papers by "Christian Sternemann published in 2014"

X-ray reflectivity measurements of liquid/solid interfaces under high hydrostatic pressure conditions.

Abstract: A high-pressure cell for in situ X-ray reflectivity measurements of liquid/solid interfaces at hydrostatic pressures up to 500 MPa (5 kbar), a pressure regime that is particularly important for the study of protein unfolding, is presented. The original set-up of this hydrostatic high-pressure cell is discussed and its unique properties are demonstrated by the investigation of pressure-induced adsorption of the protein lysozyme onto hydrophobic silicon wafers. The presented results emphasize the enormous potential of X-ray reflectivity studies under high hydrostatic pressure conditions for the in situ investigation of adsorption phenomena in biological systems.

Temperature-driven adsorption and desorption of proteins at solid-liquid interfaces.

Abstract: The heat-induced desorption and adsorption of the proteins lysozyme, ribonuclease A, bovine serum albumin, and fibronectin at protein layers was investigated in two different environments: pure buffer and protein solution. Using two different environments allows us to distinguish between thermodynamic and kinetic mechanisms in the adsorption process. We observed a desorption in buffer and an adsorption in protein solution, depending upon protein properties, such as size, stability, and charge. We conclude that the desorption in buffer is mainly influenced by the mobility of the proteins at the interface, while the adsorption in protein solution is driven by conformational changes and, thereby, a gain in entropy. These results are relevant for controlling biofilm formation at solid-liquid interfaces.

Pressure-Induced Changes on The Electronic Structure and Electron Topology in the Direct FCC → SH Transformation of Silicon

Abstract: X-ray diffraction experiments at 80 K show that when silicon is compressed under hydrostatic conditions the intermediate high-pressure phases are bypassed leading to a direct transformation to the simple hexagonal structure at 17 GPa. A maximum entropy analysis of the diffraction patterns reveals dramatic alterations in the valence electron distribution from tetrahedral covalent bonding to localization in the interstitial sites and along the one-dimensional silicon atom chain running along adjacent hexagonal layers. Changes in the orbital character of the unoccupied states are confirmed using X-ray Raman scattering spectroscopy and theoretical Bethe-Salpeter equation calculations. This is the first direct observation indicating that the silicon valence electrons in 3s and 3p orbitals are transferred to the 3d orbitals at high density which proves that electrons of compressed elemental solids migrate from their native bonding configuration to interstitial regions.

Pressure induced spin transition revealed by iron M2,3-edge spectroscopy

Abstract: We present a method to characterize pressure induced magnetic high to low spin transition in iron sulphide using x-ray Raman scattering spectroscopy at the iron M2,3-edge. The advantage of this method is that the observed spectral changes between pressures of 1.7 GPa and 10.1 GPa can be used with the help of atomic multiplet calculations to determine the crystal field splitting parameters associated with the spin transition. We discuss the potential of this M2,3-edge spectroscopy to investigate the irons electronic spin state in-situ at the conditions of the inner Earth, i.e., at high temperature and high pressure, providing exciting opportunities for geophysical and materials science applications.

Supramolecular x-ray signature of susceptibility amplification in hydrogen-bonded liquids.

Abstract: Mixing two nonconducting hydrogen-bonded liquids, each exhibiting a low dielectric relaxation strength, can result in a highly electrically absorbing fluid. This susceptibility amplification effect is demonstrated for mixtures of monohydroxy alcohols. Whereas in the pure liquids a tendency to form ringlike low-dipole moment clusters prevails, in the mixtures such supramolecular structures are disfavored leading to an up to tenfold enhancement of the dielectric loss. The compositional evolution of density and mean cluster-cluster separation is traced using x-ray scattering and indicates deviations from ideal mixing with decreased C-C but simultaneously increased O-O correlation lengths. Thus, the variation in the supramolecular absorption strength could be tracked using a static scattering technique. These observations are in harmony with volume exclusion and ring open effects that predict an optimized susceptibility amplification for mixtures in which the two components occupy equal volume fractions as experimentally observed.

Iron speciation in minerals and glasses probed by \hbox{M}_{2/3}-edge X-ray Raman scattering spectroscopy

Abstract: We present a spectroscopic study of the iron $$\hbox{M}_{2/3}$$ -edge for several minerals and compounds to reveal information about the oxidation state and the local coordination of iron. We describe a novel approach to probe the iron $$\hbox{M}_{2/3}$$ -edge bulk sensitively using X-ray Raman scattering. Significant changes in the onset and shape of the Fe $$\hbox{M}_{2/3}$$ -edge were observed on ferrous and ferric model compounds with Fe in octahedral and tetrahedral coordination. Simulation of the spectra is possible using an atomic multiplet code, which potentially allows determination of, e.g., crystal-field parameters in a quantitative manner. A protocol is discussed for determination of the Fe oxidation state in compounds by linear combination of spectra of ferric and ferrous end members. The presented results demonstrate the capabilities of Fe $$\hbox{M}_{2/3}$$ -edge spectroscopy by X-ray Raman scattering to extract information on the ratio of trivalent to total iron $$\hbox{Fe}^{3+}/\sum \hbox{Fe}$$ and local coordination. As X-ray Raman scattering is performed with hard X-rays, this approach is suitable for in situ experiments at high pressure and temperature. It thus may provide indispensable information on oxidation state, electronic structure and local structure of materials that are important for physical and chemical processes of the deep Earth.

The Ba 4d-4f giant dipole resonance in complex Ba/Si compounds

Abstract: The shape of the Ba 4d?4f giant dipole resonance is studied for Ba atoms embedded inside complex Si networks covering structures consisting of Si nanocages and nanotubes, i.e. the clathrate Ba8Si46, the complex compound BaSi6, and the semiconducting BaSi2. Here, non-resonant x-ray Raman scattering is used to investigate confinement effects on the shape of the giant resonance in the vicinity of the Ba NIV, V-edge. The distinct momentum transfer dependence of the spectra is analyzed and discussed. The measurements are compared to calculations of the giant resonance within time-dependent local density approximation in the dipole limit. No modulation of the giant resonance?s shape for Ba atoms confined in different local environments was observed, in contrast to the calculations. The absence of such shape modulation for complex Ba/Si compounds is discussed providing important implications for further studies of giant resonance phenomena utilizing both theory and experiment.

Polaron-induced lattice distortion of (In,Ga)As quantum dots by optically excited carriers

Abstract: We report on a high resolution x-ray diffraction study unveiling the effect of carriers optically injected into (In,Ga)As quantum dots on the surrounding GaAs crystal matrix. We find a tetragonal lattice expansion with enhanced elongation along the [001] crystal axis that is superimposed on an isotropic lattice extension. The isotropic contribution arises from excitation induced lattice heating as confirmed by temperature dependent reference studies. The tetragonal expansion on the femtometer scale is attributed to polaron formation by carriers trapped in the quantum dots.