Letter. On the activation of [CrCl3{R-SN(H)S-R}] catalysts for selective trimerization of ethene: a freeze-quench Cr K-edge XAFS study

Homogeneous chromium catalysts for the selective conversion of ethene to hex-1-ene are formed from Cr(III) reagents, amino-thioether ligands of the type HN(CH2CH2SR)2, and aluminum reagents. In this study the early activation steps are investigated by EPR, UV-visible and Cr K-edge XAFS spectroscopy; rapid stopped-flow mixing and a freeze-quench allows good quality EXAFS analysis of a species formed in ~ 1 second of reaction. This is shown to involve reduction to Cr(II) and deprotonation of a NH group of the auxiliary ligand. This 4-coordinate metal-center may act as precursor for the coordination of ethene and subsequent selective oligomerization

X-ray propagation through hollow channel: PolyCAD - a ray tracing code (1)

A new CAD program, PolyCAD, designed for X-ray photon tracing in polycapillary optics is described. To understand the PolyCAD code and its results, the theoretical basis of X-ray transmission by a single cylindrical channel (monocapillary) is discussed first. Then the simplest cases of cylindrically and conically shaped polycapillary optics are examined. PolyCAD allows any type of X-ray source to be used: an X-ray tube of finite beam dimensions or an astrophysical object can be simulated in combination with the polycapillary optics. The radiation distribution images formed on a screen located at various focal distances are discussed. The good agreement of some of the PolyCAD results with those reported in earlier papers validate the code. This is the first paper of a series dedicated to the development of an exhaustive CAD program, work is in progress to develop the code to include other polycapillary-optics shapes, such as semi-lenses and full-lenses.Comment: Submitted to Applied Optic

AGEs in human lens capsule promote the TGFβ2-mediated EMT of lens epithelial cells:Implications for age-associated fibrosis

Proteins in basement membrane (BM) are long-lived and accumulate chemical modifications during aging; advanced glycation end-product (AGE) formation is one such modification. The human lens capsule is a BM secreted by lens epithelial cells. In this study, we have investigated the effect of aging and cataracts on the AGE levels in the human lens capsule and determined their role in the epithelial-to-mesenchymal transition (EMT) of lens epithelial cells. EMT occurs during posterior capsule opacification (PCO), also known as secondary cataract formation. Wefound age-dependent increases in several AGEs and significantly higher levels in cataractous lens capsules than in normal lens capsules measured by LC-MS/MS. The TGFβ2-mediated upregulation of the mRNA levels (by qPCR) of EMT-associated proteins was significantly enhanced in cells cultured on AGE-modified BM and human lens capsule compared with those on unmodified proteins. Such responses were also observed for TGFβ1. In the human capsular bag model of PCO, the AGE content of the capsule proteins was correlated with the synthesis of TGFβ2-mediated a-smooth muscle actin (αSMA). Taken together, our data imply that AGEs in the lens capsule promote the TGFβ2-mediated fibrosis of lens epithelial cells during PCO and suggest that AGEs in BMs could have a broader role in aging and diabetes-associated fibrosis

Molybdenum sputtering film characterization for high gradient accelerating structures

Technological advancements are strongly required to fulfill the demands of new accelerator devices with the highest accelerating gradients and operation reliability for the future colliders. To this purpose an extensive R&D regarding molybdenum coatings on copper is in progress. In this contribution we describe chemical composition, deposition quality and resistivity properties of different molybdenum coatings obtained via sputtering. The deposited films are thick metallic disorder layers with different resistivity values above and below the molibdenum dioxide reference value. Chemical and electrical properties of these sputtered coatings have been characterized by Rutherford backscattering, XANES and photoemission spectroscopy. We will also present a three cells standing wave section coated by a molybdenum layer $\sim$ 500 nm thick designed to improve the performance of X-Band accelerating systems.Comment: manuscript has been submitted and accepted by Chinese Physics C (2012

Insights into the Structure of Dot@Rod and Dot@Octapod CdSe@CdS Heterostructures

CdSe@CdS dot@rods with diameter around 6 nm and length of either 20, 27, or 30 nm and dot@octapods with pod diameters of ?15 nm and lengths of ?50 nm were investigated by X-ray absorption spectroscopy. These heterostructures are prepared by seed-mediated routes, where the structure, composition, and morphology of the CdSe nanocrystals used as a seed play key roles in directing the growth of the second semiconducting domain. The local structural environment of all the elements in the CdSe@CdS heterostructures was investigated at the Cd, S, and Se K-edges by taking advantage of the selectivity of X-ray absorption spectroscopy, and was compared to pure reference compounds. We found that the structural features of dot@rods are independent of the size of the rods. These structures can be described as made of a CdSe dot and a CdS rod, both in the wurtzite phase with a high crystallinity of both the core and the rod. This result supports the effectiveness of high temperature colloidal synthesis in promoting the formation of core@shell nanocrystals with very low defectivity. On the other hand, data on the CdSe@CdS with octapod morphology suggest the occurrence of a core composed of a CdSe cubic sphalerite phase with eight pods made of CdS wurtzite phase. Our findings are compared to current models proposed for the design of functional heterostructures with controlled nanoarchitecture

Energy dispersive-EXAFS of Pd nucleation at a liquid/liquid interface

Energy dispersive extended X-ray absorption fine structure (EDE) has been applied to Pd nanoparticle nucleation at a liquid/liquid interface under control over the interfacial potential and thereby the driving force for nucleation. Preliminary analysis focusing on Pd K edge-step height determination shows that under supersaturated conditions the concentration of Pd near the interface fluctuate over a period of several hours, likely due to the continuous formation and dissolution of sub-critical nuclei. Open circuit potential measurements conducted ex-situ in a liquid/liquid electrochemical cell support this view, showing that the fluctuations in Pd concentration are also visible as variations in potential across the liquid/liquid interface. By decreasing the interfacial potential through inclusion of a common ion (tetraethylammonium, TEA+) the Pd nanoparticle growth rate could be slowed down, resulting in a smooth nucleation process. Eventually, when the TEA+ ions reached an equilibrium potential, Pd nucleation and particle growth were inhibited

Structure and effects of annealing in colloidal matrix-free Ge quantum dots

This research was supported by Queen Mary, University of London. We would like to thank Diamond synchrotron light source for the beamline (B18) and the corporation work. AK and OE acknowledge the Turkish Ministry of National Education. WL is grateful to the South East Physics Network (SEPnet). YZ was supported by Chinese Scholarship Council (CSC) for PhD study

Incorporation of Sb5+ into CeO2 : local structural distortion of the fluorite structure from a pentavalent substituent

Hydrothermal crystallisation of CeO2 from aqueous sodium hydroxide solution at 240oC using CeCl3·7H2O in the presence of hydrogen peroxide with addition of either SbCl3 or SbCl5 yields polycrystalline samples of antimony-containing ceria directly from solution. Powder X-ray diffraction shows a contraction of the cubic lattice parameter with increasing Sb content, and also a broadening of Bragg peaks, from which Scherrer analysis yields crystallite domain sizes of 5 - 20 nm. Scanning transmission electron microscopy provides consistent results with observation of highly crystalline particles of a few nm in diameter. X-ray absorption near edge structure spectroscopy at the Ce LIII and Sb K edges reveals the presence of Ce4+ and Sb5+ in the solids. To balance charge the presence of co-included Na is proposed, corroborated by elemental analysis. The general chemical formula of the materials can thus be written as (Ce1 xSbx)1 yNayO2-δ (where x < 0.4 and y ≥ x/3). Sb K-edge extended X-ray absorption fine structure spectroscopy of the substituted ceria samples shows that the local structure of Sb resembles that in NaSbO3, where six-coordinate metal sites are found, but with evidence of a longer interatomic correlation due to surrounding Ce/Sb atoms in the fluorite structure; this implies that the Sb is displaced from the ideal eight-coordinate site of the fluorite structure. This structural distortion gives materials that are unstable under reducing conditions, coupled by the ease of reduction to elemental antimony, which is extruded leading to phase separation

In situ XAFS Study of Palladium Electrodeposition at the Liquid/Liquid Interface

We report the use of XAFS (X-ray absorption fine structure) as an in situ method to follow the electrochemically driven deposition of palladium nanoparticles at a liquid/liquid interface. A novel glass/plastic hybrid electrochemical cell was used to enable control of the potential applied to the liquid/liquid interface. In situ measurements indicate that the nucleation of metallic nanoparticles can be triggered through chronoamperometry or cyclic voltammetry. In contrast to spontaneous nucleation at the liquid/liquid interface, whereby fluctuations in Pd oxidation state and concentration are observed, under a fixed interfacial potential the growth process occurs at a steady rate leading to a build-up of palladium at the interface. Raman spectroscopy of the deposit suggests that the organic electrolyte binds directly to the surface of the deposited nanoparticles. It was found that the introduction of citric acid results in the formation of spherical nanoparticles at the interface