Correlative Multiscale 3D Imaging of a Hierarchical Nanoporous Gold Catalyst by Electron, Ion and X-ray Nanotomography.

Tomographic imaging of catalysts allows non-invasive investigation of structural features and chemical properties by combining large fields of view, high spatial resolution, and the ability to probe multiple length scales. Three complementary nanotomography techniques, (i) electron tomography, (ii) focused ion beam-scanning electron microscopy, and (iii) synchrotron ptychographic X-ray computed tomography, were applied to render the 3D structure of monolithic nanoporous gold doped with ceria, a catalytically active material with hierarchical porosity on the nm and µm scale. The resulting tomograms were used to directly measure volume fraction, surface area and pore size distribution, together with 3D pore network mapping. Each technique is critically assessed in terms of approximate spatial resolution, field of view, sample preparation and data processing requirements. Ptychographic X-ray computed tomography produced 3D electron density maps with isotropic spatial resolution of 23 nm, the highest so far demonstrated for a catalyst material, and is highlighted as an emerging method with excellent potential in the field of catalysis.

Nanostructured arrays of stacked graphene sheets.

Molecular oxygen etching of HOPG surfaces prepatterned by Ga(+) focused-ion-beam irradiation (FIB) has been used to generate large-area arrays of nanometer-sized graphite blocks. AFM and SEM imaging show that structures with lateral sizes down to ~100 nm and heights of between 30 and 55 nm can be routinely fabricated. The trenches separating the graphite blocks form in the early oxidation stages via preferential gasification (into CO and CO(2)) of the gridlike amorphized carbon regions written by FIB. In the later oxidative etching stages, gasification of the graphite nanoprism faces laterally terminating the graphite blocks becomes the major reaction channel. Correspondingly, graphite blocks are (further) reduced in lateral extent while the trenches in between are widened. Raman and photoionization spectroscopies indicate that the quality of the topmost nG sheet(s) covering the blocks also decreases with increasing etching time-as the size and lateral density of defect-mediated etch pits increases. nG block arrays are useful substrates with which to probe the size-dependent properties of nanographene, as they comprise large numbers of uniform sheets (ca. 4 × 10(10) cm(-2) for an array of 0.5 × 0.5 µm(2)) thus allowing for the application of area-integrating spectroscopic methods. We demonstrate this by examining the Raman features of nG block arrays which include a graphene-rim-region fingerprint mode. Individual nG sheets can be exfoliated from nG stacks by means of electron-irradiation-induced charging. We have explored a number of printing/manipulation strategies aimed at controllable electromechanical transfer of nG sheet arrays to silicon wafers.

Three-dimensional invisibility cloak at optical wavelengths.

We have designed and realized a three-dimensional invisibility-cloaking structure operating at optical wavelengths based on transformation optics. Our blueprint uses a woodpile photonic crystal with a tailored polymer filling fraction to hide a bump in a gold reflector. We fabricated structures and controls by direct laser writing and characterized them by simultaneous high-numerical-aperture, far-field optical microscopy and spectroscopy. A cloaking operation with a large bandwidth of unpolarized light from 1.4 to 2.7 micrometers in wavelength is demonstrated for viewing angles up to 60 degrees.

Cellular uptake of platinum nanoparticles in human colon carcinoma cells and their impact on cellular redox systems and DNA integrity.

Supercritical fluid reactive deposition was used for the deposition of highly dispersed platinum nanoparticles with controllable metal content and particle size distribution on beta-cyclodextrin. The average particle size and size distribution were steered by the precursor reduction conditions, resulting in particle preparations <20, <100, and >100 nm as characterized by transmission electron microscopy and scanning electron microscopy (SEM). These particle preparations of different size distributions were used to address the question as to whether metallic platinum particles are able to invade cells of the gastrointestinal tract as exemplified for the human colon carcinoma cell line HT29 and thus affect the cellular redox status and DNA integrity. Combined focused ion beam and SEM demonstrated that platinum nanoparticles were taken up into HT29 cells in their particulate form. The chemical composition of the particles within the cells was confirmed by energy-dispersive X-ray spectroscopy. The potential influence of platinum nanoparticles on cellular redoxsystems was determined in the DCF assay, on the translocation of Nrf-2 and by monitoring the intracellular glutathione (GSH) levels. The impact on DNA integrity was investigated by single cell gel electrophoresis (comet assay) including the formation of sites sensitive to formamidopyrimidine-DNA-glycosylase. Platinum nanoparticles were found to decrease the cellular GSH level and to impair DNA integrity with a maximal effect at 1 ng/cm(2). These effects were correlated with the particle size in an inverse manner and were enhanced with increasing incubation time but appeared not to be based on the formation of reactive oxygen species.