Monitoring Galvanic Replacement Through Three-Dimensional Morphological and Chemical Mapping

Galvanic replacement reactions on metal nanoparticles are often used for the preparation of hollow nanostructures with tunable porosity and chemical composition, leading to tailored optical and catalytic properties. However, the precise interplay between the three-dimensional (3D) morphology and chemical composition of nanostructures during Galvanic replacement is not always well understood as the 3D chemical imaging of nanoscale materials is still challenging. It is especially far from straightforward to obtain detailed information from the inside of hollow nanostructures using electron microscopy techniques such as SEM or TEM. We demonstrate here that a combination of state-of-the-art EDX mapping with electron tomography results in the unambiguous determination of both morphology transformation and elemental composition of nanostructures in 3D, during Galvanic replacement of Ag nanocubes. This work provides direct and unambiguous experimental evidence leading to new insights in the understanding of the galvanic replacement reaction. In addition, the powerful approach presented here can be applied to a wide range of nanoscale transformation processes, which will undoubtedly guide the development of novel nanostructures

Optimum spectral window for imaging of art with optical coherence tomography

Optical Coherence Tomography (OCT) has been shown to have potential for important applications in the field of art conservation and archaeology due to its ability to image subsurface microstructures non-invasively. However, its depth of penetration in painted objects is limited due to the strong scattering properties of artists’ paints. VIS-NIR (400 nm – 2400 nm) reflectance spectra of a wide variety of paints made with historic artists’ pigments have been measured. The best spectral window with which to use optical coherence tomography (OCT) for the imaging of subsurface structure of paintings was found to be around 2.2 μm. The same spectral window would also be most suitable for direct infrared imaging of preparatory sketches under the paint layers. The reflectance spectra from a large sample of chemically verified pigments provide information on the spectral transparency of historic artists’ pigments/paints as well as a reference set of spectra for pigment identification. The results of the paper suggest that broadband sources at ~2 microns are highly desirable for OCT applications in art and potentially material science in general

Ti-rich and Cu-poor grain-boundary layers of CaCu3_3Ti4_4O12_{12} detected by x-ray photoelectron spectroscopy

Cleaved and polished surfaces of CaCu$_3$Ti$_4$O$_{12}$ ceramics have been investigated by x-ray photoelectron spectroscopy (XPS) and energy dispersive x-ray spectroscopy (EDX), respectively. While EDX technique shows the identical CaCu$_3$Ti$_4$O$_{12}$ stoichiometry for the two surfaces, XPS indicates that the cleaved surface with grain-boundary layers is remarkably Ti-rich and Cu-poor. The core-level spectrum of Cu 2$p$ unambiguously shows the existence of monovalent copper only for the cleaved surface. Possible grain-boundary structure and its formation are discussed.Comment: 8 pages, 3 figure

Effects of Acid Treatment on the SEM-EDX Characteristics of Kaolin Clay

Raw kaolin was refluxed by sulphuric acid in variable concentrations of 2 M, 4 M, 6 M and 8 M. The morphology and elemental compositions of the acid-leached kaolin were analyse by Field Scanning Electron Microscopy (FESEM) and Energy Dispersive X-ray analysis (EDX) respectively. The disintegration and leaching of Al3+ ions of the clay are determined by FESEM studies. The acid treatment increases the silicon content and decreases aluminium content as revealed by EDX analysis. The leaching of Al3+ ions increases with gradual increase in concentration of the acid. Therefore, kaolin reflux with acid at lower strength (2 M and 4 M) are more dispersed and more industrially useful than that which is treated at higher acid strength

Trace element content and magnetic properties of commercial HOPG samples studied by ion beam microscopy and SQUID magnetometry

In this study, the impurity concentration and magnetic response of nine highly oriented pyrolytic graphite (HOPG) samples with different grades and from different providers were determined using ion beam microscopy and SQUID magnetometry. Apart from sideface contaminations in the as-received state, bulk contamination of the samples in most cases consists of disk-shaped micron-sized particles made of Ti and V with an additional Fe contamination around the grain perimeter. The saturation magnetization typically increases with Fe concentration, however, there is no simple correlation between Fe content and magnetic moment. The saturation magnetization of one, respectively six, out of nine samples clearly exceeds the maximum contribution from pure Fe or Fe3C. For most samples the temperature dependence of the remanence decreases linearly with T - a dependence found previously for defect-induced magnetism (DIM) in HOPG. We conclude that apart from magnetic impurities, additional contribution to the ferromagnetic magnetization exists in pristine HOPG in agreement with previous studies. A comparative study between the results of ion beam microscopy and the commonly used EDX analysis shows clearly that EDX is not a reliable method for quantitative trace elemental analysis in graphite, clarifying weaknesses and discrepancies in the element concentrations given in the recent literature.Comment: submitted to Carbo

Enzyme localization can drastically affect signal amplification in signal transduction pathways

Push-pull networks are ubiquitous in signal transduction pathways in both prokaryotic and eukaryotic cells. They allow cells to strongly amplify signals via the mechanism of zero-order ultrasensitivity. In a push-pull network, two antagonistic enzymes control the activity of a protein by covalent modification. These enzymes are often uniformly distributed in the cytoplasm. They can, however, also be colocalized in space, for instance, near the pole of the cell. Moreover, it is increasingly recognized that these enzymes can also be spatially separated, leading to gradients of the active form of the messenger protein. Here, we investigate the consequences of the spatial distributions of the enzymes for the amplification properties of push-pull networks. Our calculations reveal that enzyme localization by itself can have a dramatic effect on the gain. The gain is maximized when the two enzymes are either uniformly distributed or colocalized in one region in the cell. Depending on the diffusion constants, however, the sharpness of the response can be strongly reduced when the enzymes are spatially separated. We discuss how our predictions could be tested experimentally.Comment: PLoS Comp Biol, in press. 32 pages including 6 figures and supporting informatio

Influence of temperature and time on the Eu3+ reaction with synthetic Na-Mica-n (n = 2 and 4)

Bentonite is accepted as the best clay material for the engineered barrier of Deep Geological Repositories (DGRs). The performance of clay as the main component of the engineered barrier in the DGR has been intensively studied and the structure of the selected clay mineral play a crucial role. In this sense, a new family of synthetic swelling silicates, Na-Mica-n, with tuned layer charge (n) values between 2.0 and 4.0 per unit cell has recently been synthesized and a general synthetic method has been reported. These swelling high-charge micas could be highly valuable for the decontamination of harmful cations. The ability of these micas to immobilize Eu3+ under subcritical conditions has been probed. The adsorption was in both non-specific sites (cation exchange mechanism) and specific sites (chemical reaction or surface defects adsorption). Moreover, its adsorption capacity, under the same conditions is higher than in saponite and far superior to the bentonites.Junta de Andalucía P12-FQM-567European Union 29178

Mobile Knowledge, Karma Points, and Digital Peers: The Tacit Epistemology and Linguistic Representation of MOOCs

Media representations of massive open online courses (MOOCs) such as those offered by Coursera, edX and Udacity reflect tension and ambiguity in their bold promise of democratized education and global knowledge sharing. An approach to MOOCs that emphasizes the tacit epistemology of such representations suggests a richer account of the ambiguities of MOOCs, the unsettled linguistic and visual representations that reflect the strange lifeworld of global online courses and the pressing need for promising innovation that seeks to serve the restless global desire for knowledge. This perspective piece critically appraises the linguistic laboratory of thought such representation reveals and its destabilized rhetoric of technology and educational practice. The mobile knowledge of MOOCs, detached from context and educational purpose and indifferent to cultural boundary distortions, contains both the promise of democratized education and the shadow of post-colonial knowledge export