Robert Feidenhans’l

Time-Resolved X-ray Scattering of an Electronically Excited State in Solution. Structure of the 3A2u State of Tetrakis-μ-pyrophosphitodiplatinate(II)

The structure of the (3)A(2u) excited state of tetrakis-mu-pyrophosphitodiplatinate(II) in aqueous solution is investigated by time-resolved X-ray scattering on a time scale from 100 ps to 1 micros after optical pumping. The primary structural parameter, the Pt-Pt distance, is found to be 2.74 A, which is 0.24 A shorter than the ground-state value. The contraction is in excellent agreement with earlier estimates based on spectroscopic data in solution and diffraction data in the crystalline state. As a second structural parameter, the distance between the P planes in the (3)A(2u) excited state was determined to be 2.93 A, i.e., the same as that in the ground state. This result implies that a slight lengthening of the Pt-P bond occurs following excitation.

Elliptical Structure of Phospholipid Bilayer Nanodiscs Encapsulated by Scaffold Proteins: Casting the Roles of the Lipids and the Protein

Phospholipid bilayers host and support the function of membrane proteins and may be stabilized in disc-like nanostructures, allowing for unprecedented solution studies of the assembly, structure, and function of membrane proteins (Bayburt et al. Nano Lett. 2002, 2, 853-856). Based on small-angle neutron scattering in combination with variable-temperature studies of synchrotron small-angle X-ray scattering on nanodiscs in solution, we show that the fundamental nanodisc unit, consisting of a lipid bilayer surrounded by amphiphilic scaffold proteins, possesses intrinsically an elliptical shape. The temperature dependence of the curvature of the nanodiscs prepared with two different phospholipid types (DLPC and POPC) shows that it is the scaffold protein that determines the overall elliptical shape and that the nanodiscs become more circular with increasing temperature. Our data also show that the hydrophobic bilayer thickness is, to a large extent, dictated by the scaffolding protein and adjusted to minimize the hydrophobic mismatch between protein and phospholipid. Our conclusions result from a new comprehensive and molecular-based model of the nanodisc structure and the use of this to analyze the experimental scattering profile from nanodiscs. The model paves the way for future detailed structural studies of functional membrane proteins encapsulated in nanodiscs.

In-situ x-ray characterization of wurtzite formation in GaAs nanowires

In-situ monitoring of the crystal structure formation during Ga-assisted GaAs nanowire growth on Si(111) substrates has been performed in a combined molecular beam epitaxy growth and x-ray characterization experiment. Under Ga rich conditions, we show that an increase in the V/III ratio increases the formation rate of the wurtzite structure. Moreover, the response time for changes in the structural phase formation to changes in the beam fluxes is observed to be much longer than predicted time scales of adatom kinetics and liquid diffusion. This suggests that the morphology of the growth interface plays the key role for the relative growth structure formation rates.

Direct Observation of Acoustic Oscillations in InAs Nanowires

Time-resolved X-ray diffraction and optical reflectivity are used to directly measure three different acoustic oscillations of InAs nanowires. The oscillations are excited by a femtosecond laser pulse and evolve at three different time scales. We measure the absolute scale of the initial radial expansion of the fundamental breathing eigenmode and determine the frequency by transient optical reflectivity. For the extensional eigenmode we measure the oscillations of the average radial and axial lattice constants and determine the amplitude of oscillations and the average extension. Finally we observe a bending motion of the nanowires. The frequencies of the eigenmodes are in good agreements with predictions made by continuum elasticity theory and we find no difference in the speed of sound between the wurtzite nanowires and cubic bulk crystals, but the measured strain is influenced by the interaction between different modes. The wurtzite crystal structure of the nanowires however has an anisotropic thermal expansion.

Imaging of Metastatic Lymph Nodes by X-ray Phase-Contrast Micro-Tomography

Invasive cancer causes a change in density in the affected tissue, which can be visualized by x-ray phase-contrast tomography. However, the diagnostic value of this method has so far not been investigated in detail. Therefore, the purpose of this study was, in a blinded manner, to investigate whether malignancy could be revealed by non-invasive x-ray phase-contrast tomography in lymph nodes from breast cancer patients. Seventeen formalin-fixed paraffin-embedded lymph nodes from 10 female patients (age range 37–83 years) diagnosed with invasive ductal carcinomas were analyzed by X-ray phase-contrast tomography. Ten lymph nodes had metastatic deposits and 7 were benign. The phase-contrast images were analyzed according to standards for conventional CT images looking for characteristics usually only visible by pathological examinations. Histopathology was used as reference. The result of this study was that the diagnostic sensitivity of the image analysis for detecting malignancy was 100% and the specificity was 87%. The positive predictive value was 91% for detecting malignancy and the negative predictive value was 100%. We conclude that x-ray phase-contrast imaging can accurately detect density variations to obtain information regarding lymph node involvement previously inaccessible with standard absorption x-ray imaging.

Structure of the Buried Metal-Molecule Interface in Organic Thin Film Devices

By use of specular X-ray reflectivity (XR) the structure of a metal-covered organic thin film device is measured with angstrom resolution. The model system is a Langmuir-Blodgett (LB) film, sandwiched between a silicon substrate and a top electrode consisting of 25 A titanium and 100 A aluminum. By comparison of XR data for the five-layer Pb2+ arachidate LB film before and after vapor deposition of the Ti/Al top electrode, a detailed account of the structural damage to the organic film at the buried metal-molecule interface is obtained. We find that the organized structure of the two topmost LB layers (approximately 5 nm) is completely destroyed due to the metal deposition.

Stages in molecular beam epitaxy growth of GaAs nanowires studied by x-ray diffraction

GaAs nanowires were grown by molecular beam epitaxy and studied by glancing-angle x-ray diffraction during five different stages of the growth process. An entire forest of randomly positioned epitaxial nanowires was sampled simultaneously and a large variation in the Au-Ga catalyst was found. Au, AuGa, AuGa(2) and the hexagonal beta phase were all identified in several orientations and in similar amounts. The nanowires are shown to consist of regular zinc blende crystal, its twin and the hexagonal wurtzite. The evolution of the various Au-Ga catalysts and the development in the twin to the wurtzite abundance ratio indicate that the Au catalyst is saturated upon initiation of growth leading to an increased amount of wurtzite structure in the wires. A specular x-ray scan identifies the various Au-Ga alloys, three Au lattice constants and a rough interface between nanowires and catalyst. Reciprocal space maps were obtained around Au Bragg points and show the development of the Au catalyst from a distribution largely oriented with respect to the lattice to a non-uniform distribution with several well-defined lattice constants.

Visualisation by high resolution synchrotron X-ray phase contrast micro-tomography of gas films on submerged superhydrophobic leaves

Floods can completely submerge terrestrial plants but some wetland species can sustain O2 and CO2 exchange with the environment via gas films forming on superhydrophobic leaf surfaces. We used high resolution synchrotron X-ray phase contrast micro-tomography in a novel approach to visualise gas films on submerged leaves of common cordgrass (Spartina anglica). 3D tomograms enabled a hitherto unmatched level of detail regarding the micro-topography of leaf gas films. Gas films formed only on the superhydrophobic adaxial leaf side (water droplet contact angle, Φ=162°) but not on the abaxial side (Φ=135°). The adaxial side of the leaves of common cordgrass is plicate with a longitudinal system of parallel grooves and ridges and the vast majority of the gas film volume was found in large ∼180μm deep elongated triangular volumes in the grooves and these volumes were connected to each neighbouring groove via a fine network of gas tubules (∼1.7μm diameter) across the ridges. In addition to the gas film retained on the leaf exterior, the X-ray phase contrast micro-tomography also successfully distinguished gas spaces internally in the leaf tissues, and the tissue porosity (gas volume per unit tissue volume) ranged from 6.3% to 20.3% in tip and base leaf segments, respectively. We conclude that X-ray phase contrast micro-tomography is a powerful tool to obtain quantitative data of exterior gas features on biological samples because of the significant difference in electron density between air, biological tissues and water.

Effect of phospholipid composition and phase on nanodisc films at the solid-liquid interface as studied by neutron reflectivity.

Nanodiscs are disc-like self-assembled structures formed by phospholipids and amphipatic proteins. The proteins wrap like a belt around the hydrophobic part of the lipids, basically producing nanometer-sized patches of lipid bilayers. The bilayer in the nanodisc constitutes a native-like model of the cell membrane and can act as a nanometer-sized container for functional single membrane proteins. In this study, we present a general nanodisc-based system, intended for structural and functional studies of membrane proteins. In this method, the nanodiscs are aligned at a solid surface, providing the ability to determine the average structure of the film along an axis perpendicular to the interface as measured by neutron reflectivity. The nanodisc film was optimized in terms of nanodisc coverage, reduced film roughness, and stability for time-consuming studies. This was achieved by a systematic variation of the lipid phase, charge, and length of lipid tails. Herein, we show that, although all studied nanodiscs align with their lipid bilayer parallel to the interface, gel-phase DMPC nanodiscs form the most suitable film for future membrane protein studies since they yield a dense irreversibly adsorbed film with low roughness and high stability over time. This may be explained by the appropriate matching between the thickness of the hydrophobic lipid core of gel phase DMPC and the height of the belt protein. Moreover, once formed the gel-phase DMPC nanodiscs film can be heated up to melt the lipid bilayer, thus providing a more biologically friendly environment for membrane proteins.

Ptychographic X-ray computed tomography of extended colloidal networks in food emulsions

As a main structural level in colloidal food materials, extended colloidal networks are important for texture and rheology. By obtaining the 3D microstructure of the network, macroscopic mechanical properties of the material can be inferred. However, this approach is hampered by the lack of suitable non-destructive 3D imaging techniques with submicron resolution. We present results of quantitative ptychographic X-ray computed tomography applied to a palm kernel oil based oil-in-water emulsion. The measurements were carried out at ambient pressure and temperature. The 3D structure of the extended colloidal network of fat globules was obtained with a resolution of around 300 nm. Through image analysis of the network structure, the fat globule size distribution was computed and compared to previous findings. In further support, the reconstructed electron density values were within 4% of reference values.