A high density of oxygen vacancies has been found in an experiment to determine the path of electrical conduction in Cr-doped SrTiO3 memory cells. The Cr acts as a seed for the localization of oxygen vacancies, leading to a statistically homogeneous distribution of charge carriers within the path. This warrants a controllable doping profile and improved device scaling down to the nanometer scale. The combination of laterally resolved micro-X-ray absorption spectroscopy and thermal imaging concludes that the resistance switching in Cr-doped SrTiO3 originates from an oxygen-vacancy drift to/from the electrode that was used as anode during the conditioning process. The experiments shows that this oxygen vacancy concept is crucial for the entire class of transition-metal-oxide-based bipolar resistance-change memory.

Role of Oxygen Vacancies in Cr‐Doped SrTiO3 for Resistance‐Change Memory

While Fe-N-C materials are a promising alternative to platinum for catalyzing oxygen reduction in acidic polymer fuel cells, limited understanding of their operando degradation restricts rational approaches towards improved durability. Here we show that Fe-N-C catalysts initially comprising two distinct FeNx sites (S1 and S2) degrade via the transformation of S1 into iron oxides while the structure and number of S2 were unmodified. Structure-activity correlations drawn from end-of-test 57Fe Mossbauer spectroscopy reveal that both sites initially contribute to the ORR activity but only S2 significantly contributes after 50 h of operation. From in situ 57Fe Mossbauer spectroscopy in inert gas coupled to calculations of the Mossbauer signature of FeNx moieties in different electronic states, we identify S1 to be a high-spin FeN4C12 moiety and S2 a low- or intermediate spin FeN4C10 moiety. These insights lay the ground for rational approaches towards Fe-N-C cathodes with improved durability in acidic fuel cells.

/pdf/identification-of-durable-and-non-durable-fenx-sites-in-fe-n-36zjtunkfs.pdf

Identification of Durable and Non-Durable FeNx Sites in Fe-N-C Materials for Proton Exchange Membrane Fuel Cells

TiO2 particles are commonly used as dietary supplements and may contain up to 36% of nano-sized particles (TiO2-NPs). Still impact and translocation of NPs through the gut epithelium is poorly documented. We show that, in vivo and ex vivo, agglomerates of TiO2-NPs cross both the regular ileum epithelium and the follicle-associated epithelium (FAE) and alter the paracellular permeability of the ileum and colon epithelia. In vitro, they accumulate in M-cells and mucus-secreting cells, much less in enterocytes. They do not cause overt cytotoxicity or apoptosis. They translocate through a model of FAE only, but induce tight junctions remodeling in the regular ileum epithelium, which is a sign of integrity alteration and suggests paracellular passage of NPs. Finally we prove that TiO2-NPs do not dissolve when sequestered up to 24 h in gut cells. Taken together these data prove that TiO2-NPs would possibly translocate through both the regular epithelium lining the ileum and through Peyer’s patches, would induce epithelium impairment, and would persist in gut cells where they would possibly induce chronic damage.

/pdf/titanium-dioxide-nanoparticle-impact-and-translocation-3il9tbqp1y.pdf

Titanium dioxide nanoparticle impact and translocation through ex vivo, in vivo and in vitro gut epithelia.

Spectroscopic approaches to plant and soil sciences have provided important information for several decades. However, many of these approaches suffered from a number of limitations and drawbacks especially in terms of spatial resolution and requirements for sample preparation. The advent of dedicated synchrotron facilities, that allow the exploitation of the particular qualities of synchrotron radiation as a research tool, has revolutionised the way we approach the investigation of nutrients and contaminants in environmental samples. Various synchrotron-based techniques are currently available that permit such investigations in situ and at the molecular level. The continuous development of these techniques is delivering substantial gains in terms of sensitivity and spatial resolution which allows analyses of diluted samples at the sub-micron scale. This paper aims at providing an introduction to synchrotron radiation and to the fundamentals of some widely used synchrotron-based techniques, in particular X-ray absorption, fluorescence and tomography. Furthermore, examples are provided regarding the applications of synchrotron-based techniques in the field of plant, soil and rhizosphere research. Finally, current limitations and future perspectives of synchrotron techniques are discussed.

Synchrotron-based techniques for plant and soil science: opportunities, challenges and future perspectives

Effect of phosphate, silicate, and Ca on Fe(III)-precipitates formed in aerated Fe(II)- and As(III)-containing water studied by X-ray absorption spectroscopy.

The beamline “LUCIA” (line for ultimate characterization by imaging and absorption) is a “tender” (0.8–8 keV) X-ray microprobe with capabilities for chemical speciation by micro-X-ray absorption spectroscopy (μ-XAS) and for elemental mapping by X-ray micro-fluorescence (μ-XRF). It allows the possibility to study heterogeneous samples at a micrometer scale and to combine these two element-specific and non-destructive techniques. A monochromatic beam of a few micrometer in size is incident on a sample which is mounted on a scanning x–y–z stage. μ-XRF shows the location of the elements, their relative abundances, and their association with other elements. One can take advantage of the monochromatic beam which allows separating out different elements by their absorption edges. After mapping the fluorescence, spots of interest can be analysed by XAS to determine the speciation (local chemistry, quantitative determination of the local geometric structure around the absorbing atom) of the elements and how they depend on the different components. Installed at first at the SLS of the Paul Scherrer Institute (Switzerland), the LUCIA beamline will be transferred to SOLEIL by the beginning of 2008. The energy range offered by the beamline corresponds to the best performances of SLS and SOLEIL in terms of brightness. It allows XAS experiments at the K edge of elements ranging from Na to Fe, L edges from Ni to Gd, and M edges of rare earths and actinides.

LUCIA, a microfocus soft XAS beamline

GALAXIES is an in-vacuum undulator hard X-ray micro-focused beamline dedicated to the study of the electronic structure of materials with high energy resolution using both photoelectron spectroscopy and inelastic X-ray scattering and under both non-resonant (NR-IXS) and resonant (RIXS) conditions. Due to the penetrating power of hard X-rays and the `photon-in/photon-out' technique, the sample environment is not a limitation. Materials under extreme conditions, for example in diamond anvil cells or catalysis chambers, thus constitute a major research direction. Here, the design and performance of the inelastic X-ray scattering end-station that operates in the energy range from ∼4 keV up to 12 keV is reported, and its capabilities are highlighted using a selection of data taken from recently performed experiments. The ability to scan `on the fly' the incident and scattered/emitted X-ray energies, and the sample position enables fast data collection and high experimental throughput. A diamond X-ray transmission phase retarder, which can be used to generate circularly polarized light, will also be discussed in the light of the recent RIXS–MCD approach.

/pdf/the-galaxies-inelastic-hard-x-ray-scattering-end-station-at-3hdy6x7q89.pdf

The GALAXIES inelastic hard X-ray scattering end-station at Synchrotron SOLEIL.

LURE‐SOLEIL (France) and the Swiss Light Source (SLS) are building together a new micro focused beamline for micro x‐ray absorption spectroscopy and micro imaging. This line is designed to deliver a photon flux of the order of 1012 ph/sec on a 1 × 1 μm spot within the energy domain of 0.8 to 7 keV. This beam line is being installed on the X07M straight section of SLS. The source is an APPLE II undulator with a period of 54 mm. The main advantage of this device lies in the delivery of any degree of polarization, linear or circular, over the whole energy range, without the need of a sample‐position change. The monochromator will be a fixed exit double crystal equipped with 5 sets of crystals, thanks to the very narrow photon beam from the undulator ( Beryl, KTP, YB66, InSb(111), Si(111) ). The optics includes a first horizontal focusing mirror (spherical), which produces an intermediate source for the horizontal mirror of a Kirkpatrick‐Baez (KB) system. The vertical mirror of the KB directly images the source. Finally, a low‐pass double mirror filter insures a proper harmonic rejection.

S. Bac

Papers

LUCIA, a microfocus soft XAS beamline

The GALAXIES inelastic hard X-ray scattering end-station at Synchrotron SOLEIL.

LUCIA — a new 1-7 keV μ-XAS Beamline

Data treatment at Synchrotron SOLEIL: automation, IA, on-demand computing, packaging