Monte Carlo Simulations of Electron Energy-Loss Spectra with the Addition of Fine Structure from Density Functional Theory Calculations.

A new approach is presented to introduce the fine structure of core-loss excitations into the electron energy-loss spectra of ionization edges by Monte Carlo simulations based on an optical oscillator model. The optical oscillator strength is refined using the calculated electron energy-loss near-edge structure by density functional theory calculations. This approach can predict the effects of multiple scattering and thickness on the fine structure of ionization edges. In addition, effects of the fitting range for background removal and the integration range under the ionization edge on signal-to-noise ratio are investigated.

Cerium oxide as a promoter for the electro-oxidation reaction of ethanol: in situ XAFS characterization of the Pt nanoparticles supported on CeO2 nanoparticles and nanorods.

In this study we probe the electrocatalytic activity of Pt nanoparticles supported on ceria nanoparticles (NPs) and nanorods (NRs) in the ethanol oxidation reaction (EOR) in alkaline media. The goal of this study was to relate morphology, support structure and composition to the EOR catalytic activity by using in situ X-ray absorption fine structure (XAFS) studies. Cyclic voltammetry experiments showed that both ceria supported catalysts (NP vs. NR) had similar peak current densities at fast scan rates, however at slow scan rates, the ceria NR catalyst showed superior catalytic activity. In situ XAFS studies in KOH showed that both ceria supported catalysts had more electron density in their d-band (with the ceria NR having more electron density overall) than ceria - free Pt/Vulcan standard. However, in an ethanol solution the ceria NR catalyst had the least electron density. We propose that this change is due to the increased charge transfer efficiency between the ceria nanorod support and platinum. In the KOH solution, the increased electron density makes the platinum less electrophilic and hinders Pt-OH bond formation. In the EtOH solution, platinum's increased nucleophilicity facilitates the bond formation between Pt and the electron deficient carbon in ethanol which in turn withdraws the electron density from platinum and increases the white line intensity as observed in the XAS measurements.

Surface energy engineering for tunable wettability through controlled synthesis of MoS2.

MoS2 is an important member of the transition metal dichalcogenides that is emerging as a potential 2D atomically thin layered material for low power electronic and optoelectronic applications. However, for MoS2 a critical fundamental question of significant importance is how the surface energy and hence the wettability is altered at the nanoscale in particular, the role of crystallinity and orientation. This work reports on the synthesis of large area MoS2 thin films on insulating substrates (SiO2/Si and Al2O3) with different surface morphology via vapor phase deposition by varying the growth temperatures. The samples were examined using transmission electron microscopy and Raman spectroscopy. From contact angle measurements, it is possible to correlate the wettability with crystallinity at the nanoscale. The specific surface energy for few layers MoS2 is estimated to be about 46.5 mJ/m(2). Moreover a layer thickness-dependent wettability study suggests that the lower the thickness is, the higher the contact angle will be. Our results shed light on the MoS2-water interaction that is important for the development of devices based on MoS2 coated surfaces for microfluidic applications.

Bottom-up solution synthesis of narrow nitrogen-doped graphene nanoribbons.

Large quantities of narrow graphene nanoribbons with edge-incorporated nitrogen atoms can be synthesized via Yamamoto coupling of molecular precursors containing nitrogen atoms followed by cyclodehydrogenation using Scholl reaction.

Curing of a bisphenol E based cyanate ester using magnetic nanoparticles as an internal heat source through induction heating.

We report on the control of cyclotrimerization forming a polycyanurate polymer using magnetic iron oxide nanoparticles in an alternating-current (ac) field as an internal heat source, starting from a commercially available monomer. Magnetic nanoparticles were dispersed in the monomer and catalytic system using sonication, and the mixture was subjected to an alternating magnetic field, causing the magnetic nanoparticles to dissipate the energy of the magnetic field in the form of heat. Internal heating of the particle/monomer/catalyst system was sufficient to start and sustain the polymerization reaction, producing a cyanate ester network with conversion that compared favorably to polymerization through heating in a conventional laboratory oven. The two heating methods gave similar differential scanning calorimetry temperature profiles, conversion rates, and glass transition temperatures when using the same temperature profile. The ability of magnetic nanoparticles in an ac field to drive the curing reaction should allow for other reactions forming high-temperature thermosetting polymers and for innovative ways to process such polymers.

EFhd2 is a novel amyloid protein associated with pathological tau in Alzheimer's disease.

EFhd2 is a conserved calcium-binding protein, abundant within the central nervous system. Previous studies identified EFhd2 associated with pathological forms of tau proteins in the tauopathy mouse model JNPL3, which expresses the human tau(P301L) mutant. This association was validated in human tauopathies, such as Alzheimer's disease (AD). However, the role that EFhd2 may play in tauopathies is still unknown. Here, we show that EFhd2 formed amyloid structures in vitro, a capability that is reduced by calcium ions. Electron microscopy (EM) analyses demonstrated that recombinant EFhd2 formed filamentous structures. EM analyses of sarkosyl-insoluble fractions derived from human AD brains also indicated that EFhd2 co-localizes with aggregated tau proteins and formed granular structures. Immunohistological analyses of brain slices demonstrated that EFhd2 co-localizes with pathological tau proteins in AD brains, confirming the co-aggregation of EFhd2 and pathological tau. Furthermore, EFhd2's coiled-coil domain mediated its self-oligomerization in vitro and its association with tau proteins in JNPL3 mouse brain extracts. The results demonstrate that EFhd2 is a novel amyloid protein associated with pathological tau proteins in AD brain and that calcium binding may regulate the formation of EFhd2's amyloid structures. Hence, EFhd2 may play an important role in the pathobiology of tau-mediated neurodegeneration.

Luminescent graphene quantum dots fabricated by pulsed laser synthesis.

Graphene has been the subject of intense research in recent years due to its unique electrical, optical and mechanical properties. Furthermore, it is expected that quantum dots of graphene would make their way into devices due to their structure and composition which unify graphene and quantum dots properties. Graphene quantum dots (GQDs) are planar nano flakes with a few atomic layers thick and with a higher surface-to-volume ratio than spherical carbon dots (CDs) of the same size. We have developed a pulsed laser synthesis (PLS) method for the synthesis of GQDs that are soluble in water, measure 2-6 nm across, and are about 1-3 layers thick. They show strong intrinsic fluorescence in the visible region. The source of fluorescence can be attributed to various factors, such as: quantum confinement, zigzag edge structure, and surface defects. Confocal microscopy images of bacteria exposed to GQDs show their suitability as biomarkers and nano-probes in high contrast bioimaging.

Single-step route to diamond-nanotube composite.

Candle wax was used as a precursor for the production of a diamond-nanotube composite in a single step. The composite films were fabricated by sulfur-assisted hot-filament chemical vapor deposition technique. The morphology of the composite films was analyzed by scanning electron microscopy and transmission electron microscopy. Raman spectra of the films show characteristic diamond band at 1,332 cm-1, D-band around 1,342 cm-1, and graphitic G-band around 1,582 cm-1. The electron energy-loss spectroscopy recorded at the carbon K-edge region shows signature features of diamond and carbon nanotube in the fabricated material. The ability to synthesize diamond-nanotube composites at relatively low temperatures by a single-step process opens up new possibilities for the fabrication of nanoelectronic devices.

Carbon-supported, selenium-modified ruthenium-molybdenum catalysts for oxygen reduction in acidic media.

The stability and oxygen reduction activity of two carbon-supported catalyst materials are reported. The catalysts, Se/Ru and Se/(Ru-Mo), were prepared by using a chemical reduction method. The catalyst nanoparticles were evenly dispersed onto globular amorphous carbon supports, and their average size was ca. 2.4 nm. Thermal treatment at 500 °C for 2 h in an inert argon atmosphere resulted in coarsening of the nanoparticles, and also in some decrease of their activity. A gradual reduction of activity was also observed for Se/Ru during potential-cycle experiments. However, the incorporation of small amounts of Mo into the Se/Ru catalysts considerably improved the stability of the catalyst against dissolution. The Mo-containing samples showed excellent oxygen reduction activities even after cycling the potential 1000 times between 0.7 and 0.9 V. Furthermore, they showed excellent fuel-cell behavior. The performance of the Se/Ru catalysts is greatly improved by the addition of small amounts of elemental Mo. Possible mechanisms responsible for the improvement of the activity are discussed.