On the electronic nature of silicon and germanium based oxynitrides and their related mechanical,optical and vibrational properties as obtained from DFT and DFPT

Electronic structure, bonding and optical properties of the orthorhombic oxynitrides Si₂N₂O and Ge₂N₂O are studied using the density function theory as implemented in pseudo-potential plane wave and full-potential (linearized) augmented plane wave plus local orbitals methods. Generalized gradient approximation is employed in order to determine the band gap energy. Indeed, the Si₂N₂O exhibits a large direct gap whereas Ge₂N₂O have an indirect one. Bonding is analyzed via the charge densities and Mulliken population, where the role of oxygen is investigated. The analysis of the elastic constants show the mechanical stability of both oxynitrides. Their bulk and shear modulus are slightly smaller than those reported on nitrides semiconductors due to the oxygen presence. The optical properties, namely the dielectric function, optical reflectivity, refractive index and electron energy loss, are reported for radiation up to 30 eV. The phonon dispersion relation, zone-center optical mode frequency, density of phonon states are calculated using the density functional perturbed theory. Thermodynamic properties of Si₂N₂O and Ge₂N₂O, such as heat capacity and Debye temperature, are given for reference. Our study suggests that Si₂N₂O and Ge₂N₂O could be a promising potential materials for applications in the microelectronics and optoelectronics areas of research.     

Triple junction transport and the impact of grain boundary width in nanocrystalline Cu

Triple junctions (TJ), singular topological defects of the grain boundary (GB) structure, get a dominant role for grain growth and atomic transport in nanocrystalline matter. Here, we present detailed measurements by atom probe tomography, even of the temperature dependence of TJ transport of Ni in nanocrystalline Cu in the chemical regime of interdiffusion. An unexpected variation of the effective width of merging GBs with temperature is detected. It is demonstrated that proper measurement of TJ transport requires taking into account this remarkable effect. TJ diffusion is found to be a factor of about 200 faster than GB diffusion. Its activation energy amounts to only two-thirds of that of the GB.     

Repeated oral dose toxicity of iron oxide nanoparticles: biochemical and histopathological alterations in different tissues of rats

Iron oxide (Fe2O3) nanoparticles are widely used in different fields of nanotechnology. However, studies on its toxicological effects in humans and the environment are scarce. Therefore in this investigation 28 days repeated dose oral toxicity studies were conducted on Fe2O3-30 nanoparticles and its counterpart Fe2O3-Bulk with special reference to target biochemical enzymes and histopathological changes in different tissues of female albino Wistar rats. The alterations observed after Fe2O3-30 treatment in various tissues of exposed rats were dose dependent. Low dose was less effective than medium and high doses with low dose demonstrating "no observed adverse effect" (NOAEL). Further, high dose treated rats showed toxic sign and symptoms but no mortality. Due to the repeated doses of Fe2O3-30 nanoparticles, significant inhibition was observed in total, Na(+)-K+, Mg2+ and Ca(2+)-ATPases in brain of exposed rats. Similarly, significant inhibition was recorded in RBC and brain acetylcholinesterase indicating that both synaptic transmission and nerve conduction were affected by this compound. Fe2O3-30 significantly increased aspartate amino transferase, alanine amino transferase and lactate dehydrogenase in serum and liver, whereas, these enzymes were significantly decreased in kidney indicating tissue necrosis and possible leakage of these enzymes into the blood stream. Increased levels of these enzymes in liver as well as in serum might be an adaptive mechanism due to the stress of iron nanoparticles. High dose treated rats of Fe2O3-30 showed dilated central vein, perivascular round cell collections in liver along with focal areas of necrosis, whereas kidney showed focal tubular damage and red pulp congestion, whereas prominent white pulp indices were observed in spleen. However, histopathological analysis of heart and brain tissues failed to show any adverse changes in their architecture exposed to repeated doses of Fe2O3-30 when compared with controls. Fe2O3-Bulk did not induce any adverse effects in either biochemical parameters or histopathology in the treated rats and the changes observed were near to controls and mostly insignificant, indicating that the counter part of nanoparticles i.e., bulk material is less potent than the nanoparticles in causing toxicity in the exposed animals. These results suggested that as particle size decreases, this iron nanoparticle showed increased toxicity, even though the same material is relatively inert in bulk form. The changes observed in these target enzyme activities could be useful as biomarkers of exposure to nanoparticles.     

Stand-off detection of solid targets with diffuse reflection spectroscopy using a high-power mid-infrared supercontinuum source

We measure the diffuse reflection spectrum of solid samples such as explosives (TNT, RDX, PETN), fertilizers (ammonium nitrate, urea), and paints (automotive and military grade) at a stand-off distance of 5 m using a mid-infrared supercontinuum light source with 3.9 W average output power. The output spectrum extends from 750-4300 nm, and it is generated by nonlinear spectral broadening in a 9 m long fluoride fiber pumped by high peak power pulses from a dual-stage erbium-ytterbium fiber amplifier operating at 1543 nm. The samples are distinguished using unique spectral signatures that are attributed to the molecular vibrations of the constituents. Signal-to-noise ratio (SNR) calculations demonstrate the feasibility of increasing the stand-off distance from 5 to ~150 m, with a corresponding drop in SNR from 28 to 10 dB.     

Quantitative determination of higher harmonic content in the soft x-ray spectra of toroidal grating monochromator using a reflection multilayer

Use of a grating monochromator causes a problem of higher harmonic contaminations in a synchrotron beamline operating in the soft x ray/vacuum ultraviolet region. Generally gratings are used to experimentally determine the higher harmonic contaminations. In this method, the relative contribution of contaminant wavelengths is measured with respect to the first harmonic wavelength (desired wavelength). The quantitative fit of grating spectra is rather complex, and therefore qualitative analysis is carried out. Analysis of multilayer reflectivity data has become rather simple with recent advances in the theoretical modeling. Therefore we propose to use a multilayer mirror and analyze its reflectivity data for quantitative determination of harmonic contamination in a soft x ray beamline. In the present study we used a Mo/Si multilayer of d=97 ? to quantify the spectral purity of 600 lines/mm toroidal grating at the reflectivity beamline of Indus-1 450 MeV synchrotron source. The measured reflectivity spectra at each wavelength is analyzed and the actual contribution of higher harmonics in the incident beam is obtained. Details of methodology and results are discussed.     

Pathogen‐Mimicking MnO Nanoparticles for Selective Activation of the TLR9 Pathway and Imaging of Cancer Cells

Here, design of the first pathogen‐mimicking metal oxide nanoparticles with the ability to enter cancer cells and to selectively target and activate the TLR9 pathway, and with optical and MR imaging capabilities, is reported. The immobilization of ssDNA (CpG ODN 2006) on MnO nanoparticles is performed via the phosphoramidite route using a multifunctional polymer. The multifunctional polymer used for the nanoparticle surface modification not only affords a protective organic biocompatible shell but also provides an efficient and convenient means for loading immunostimulatory oligonucleotides. Since fluorescent molecules are amenable to photodetection, a chromophore (Rhodamine) is introduced into the polymer chain to trace the nanoparticles in Caki‐1 (human kidney cancer) cells. The ssDNA coupled nanoparticles are used to target Toll‐like receptors 9 (TLR9) receptors inside the cells and to activate the classical TLR cascade. The presence of TLR9 is demonstrated independently in the Caki‐1 cell line by western blotting and immunostaining techniques. The magnetic properties of the MnO core make functionalized MnO nanoparticles potential diagnostic agents for magnetic resonance imaging (MRI) thereby enabling multimodal detection by a combination of MR and optical imaging methods. The trimodal nanoparticles allow the imaging of cellular trafficking by different means and simultaneously are an effective drug carrier system.     

Folate content in foods commonly consumed in Egypt

The folate content in some Egyptian foods was determined using RP-HPLC-FL. Trienzyme treatment was used for legumes, dienzyme treatment for cereals and starchy vegetables, and monoenzyme treatment for vegetables and fruits. The highest folate content (633 μg/100 g) was found in dried Jew’s mellow due to low water content, followed by legumes (e.g. 150 μg/100 g for chick peas) and leafy vegetables (100 μg/100 g). For other foods, folate content ranged from 10–90 μg/100 g. In all foods, the predominant folate form was 5-CH₃–H₄folate, except for dried Jew’s mellow, which contained more than 80% 10-HCO–PteGlu. Using folate data from our own analyses and food tables and food consumption data, the dietary folate intake per capita in Egypt was estimated. However, representative and validated food composition data for folate in Egyptian foods are needed for estimating and evaluating the adequacy of the population’s folate intake.     

Preliminary data on the presence of mycotoxins (ochratoxin A, citrinin and aflatoxin B1) in black table olives "Greek style" of Moroccan origin

Many mould strains, in particular Aspergillus and/or Penicillium, are able to develop on olive and produce ochratoxin A (OTA) and/or citrinin (CIT) and/or aflatoxin B (AFB) after harvest, during drying and storage of olives. The development of fungi on olives is responsible for the reduction of nutritional quality of olive because they can disturb the synthesis of the fatty acids. OTA, CIT and AFB are particularly dangerous for health, inducing cancer of urinary tracts or liver carcinoma. In this study, ten olive samples bought at retailer and at supermarket in Morocco were analyzed for their OTA, CIT and AFB contents. These three mycotoxins were extracted simultaneously by a method based on solvent partition validated in-house, then separated by HPLC coupled to a fluorescence detector. All olive samples contain OTA ranging from LOQ to 1.02 microg/kg. Respectively, 50 and 25% from retailer and supermarket samples were contaminated by more than 0.65 microg/kg. In addition, 80% of olive samples contained CIT above LOD, and 100% of olive tested contained AFB above 0.5 microg/kg. As simultaneous presence of these toxins increases toxic risks, it is thus essential to have a good control of the conservation of olives after harvest.     

Analysis of secondary organic aerosol compounds from the photooxidation of d-limonene in the presence of NOx and their detection in ambient PM2.5

Chemical analysis of secondary organic aerosol (SOA) from the photooxidation of a d-limonene/NOx/air mixture was carried out. SOA, generated in a smog chamber, was collected on Zefluor filters. To determine the structural characteristics of the compounds, the filter samples were solvent extracted and derivatized using analytical techniques that characterize functional groups contained in the compound: BF3-methanol derivatization was used for carboxylic groups, BSTFA for acidic and nonacidic hydroxyl groups, and PFBHA for ketone and aldehyde groups. The resulting derivative compounds were analyzed by GC-MS in the methane Cl and El modes. GC-MS analysis showed the occurrence of 103 oxygenated organic compounds in the filter extracts, 28 of which were identified. The major components include five tracer compounds previously identified from the photooxidation of alpha-pinene/NOx or beta-pinene/NOx systems, C4-C6 linear dicarboxylic acids, ketolimononaldehyde, limonic acid, and ketolimonic acid. Time profiles, yields, and proposed reaction schemes are provided for selected compounds. The laboratory SOA yield was 0.51 at a SOA concentration of 1470 microg m(-3). To determine the contributions of SOA products from d-limonene to ambient PM2.5, an analysis was performed for eight ambient PM2.5 samples collected in the southeastern United States in summer 2003. GC-MS analysis showed the occurrence of 21 d-limonene SOA compounds, indicating the impact of d-limonene on the regional aerosol burden. Based on our analysis, two compounds (nos. 55 and 69), not observed from the photooxidation of alpha-pinene or beta-pinene, are candidate tracers for d-limonene in atmospheric particulate matter.