Nature of point defects on SiO2/Mo(112) thin films and their interaction with Au atoms

We have studied by means of periodic DFT calculations the structure and properties of point defects at the surface of ultrathin silica films epitaxially grown on Mo(112) and their interaction with adsorbed Au atoms. For comparison, the same defects have been generated on an unsupported silica film with the same structure. Four defects have been considered: nonbridging oxygen (NBO, [triple bond]Si-O(*)), Si dangling bond (E' center, [triple bond]Si(*)), oxygen vacancy (V(O), [triple bond]Si-Si[triple bond]), and peroxo group ([triple bond]Si-O-O-Si[triple bond]), but only the NBO and the V(O) centers are likely to form on the SiO(2)/Mo(112) films under normal experimental conditions. The [triple bond]Si-O(*) center captures one electron from Mo forming a silanolate group, [triple bond]Si-O(-), sign of a direct interaction with the metal substrate. Apart from the peroxo group, which is unreactive, the other defects bind strongly the Au atom forming stable surface complexes, but their behavior may differ from that of the same centers generated on an unsupported silica film. This is true in particular for the two most likely defects considered, the nonbridging oxygen, [triple bond]Si-O(*), and the oxygen vacancy, [triple bond]Si-Si[triple bond].     

Charge transfers at metal/oxide interfaces: a DFT study of formation of K delta+ and Au delta- species on MgO/Ag(100) ultra-thin films from deposition of neutral atoms

Ultra-thin oxide films grown on a metal substrate and of thickness smaller than 1 nm may exhibit unusual properties with respect to thicker films or single crystal oxide surfaces. In a previous study [G. Pacchioni, L. Giordano and M. Baistrocchi, Phys. Rev. Lett., 2005, 94, 226104] we have suggested that a Au atom adsorbed on a MgO/Mo(100) thin film becomes negatively charged by direct electron tunneling from the Mo metal and that this is related to the low MgO/Mo(100) work function. Here we show, based on periodic DFT supercell calculations, that charge transfer can occur also in the opposite direction by adsorption of electropositive K atoms on MgO/Ag(100) films. We predict the occurrence of a charge transfer also for Au on MgO/Ag(100) films despite the fact that here the work function is 1 eV larger than in MgO/Mo(100). The formation of a layer of adsorbed negative (Au delta-/MgO/Ag) or positive (K delta+/MgO/Ag) adsorbates results in an increase or decrease, respectively, of the MgO/Ag(100) work function as predicted by the classical Gurney model for ionic adsorbates on metal surfaces.     

Effective permittivity of materials containing graded ellipsoidal inclusions

We prove a generic theorem stating the equivalence between a graded dielectric ellipsoid (with gradation along a family of internal confocal ellipsoids) and an anisotropic homogeneous ellipsoid. We then describe a procedure to obtain the three principal permittivities of the effective ellipsoid for any given dielectric gradation profile. Finally, we apply a multiscale approach to homogenize dispersions of ellipsoidal graded particles.     

One-pot synthesis of orthogonally protected sugars through sequential base-promoted/acid-catalyzed steps: A solvent-free approach with self-generation of a catalytic species

A varied set of solvent-free, one-pot synthetic sequences were developed to carry out the orthogonal protection of saccharide polyols. These sequences are composed of an initial regioselective benzylation, silylation or iodination (under mildly basic conditions), followed by an acid catalyzed protection of two further hydroxyl sites via the generation of a cyclic acetal. These processes allow recycling of the ammonium or pyridinium side products generated in the former step as effective catalytic species for the latter step.     

Normalizing inclusive rare B decays

The inclusive semileptonic branching ratio is often employed to normalize other inclusive B   decays. Using recent determinations of the non-perturbative parameters of the Operator Product Expansion we compute the normalization factor for the branching ratio of B→Xsγ$B\to X_s\gamma$ and find a few percent enhancement with respect to previous determinations.     

High-Q factor single mode circular photonic crystal nano-resonator

In this work, the analysis, fabrication and optical characterization of a two-dimensional circular photonic crystal (2D-CPC) nano-resonator based on an air/GaAs/air slab waveguide are presented. Four InAs/InGaAs quantum dots (QDs) stacked layers emitting around 1300 nm at room temperature were embedded in a GaAs waveguide layer grown on an Al_0.7Ga_0.3As layer and GaAs substrate. The patterning of the structure and the membrane release were achieved by using electron beam lithography, ICP plasma etching and selective wet etching of the AlGaAs sacrificial layer. The micro-luminescence spectrum recorded from the fabricated nano-cavity shows a narrow optical transition at the resonance wavelength of about 1282 nm with a FWHM and Q-factor of 6.2 Å and more than 2000, respectively.     

A column‐switching HPLC‐MS/MS method for mucopolysaccharidosis type I analysis in a multiplex assay for the simultaneous newborn screening of six lysosomal storage disorders

Lysosomal storage disorders comprise a group of rare genetic diseases in which a deficit of specific hydrolases leads to the storage of undegraded substrates in lysosomes. Impaired enzyme activities can be assessed by MS/MS quantification of the reaction products obtained after incubation with specific substrates. In this study, a column‐switching HPLC‐MS/MS method for multiplex screening in dried blood spot of the lysosomal enzymes activities was developed. Mucopolysaccharidosis type I, Fabry, Gaucher, Krabbe, Niemann–Pick A/B and Pompe diseases were simultaneously assayed. Dried blood spots were incubated with substrates and internal standards; thereafter, supernatants were collected with minor manipulations. Samples were injected, trapped into an online perfusion column and, by a six‐port valve, switched online through the C₁₈ analytical column to perform separation of metabolites followed by MS/MS analysis. A total of 1136 de‐identified newborn screening samples were analyzed to determine references for enzymes activity values. As positive controls, we analyzed dried blood spots from three patients with Pompe, one with Fabry, one with Krabbe disease and two with MPS I, and in all cases the enzyme activities were below the cutoff values measured for newborns, except for an MPS I patient after successful hematopoietic stem cell transplantation. Copyright © 2014 John Wiley & Sons, Ltd.     

Adsorption of transition metal atoms on the NiO(100) surface and on NiO/Ag(100) thin films

We have studied the adsorption of Au, Pd, and Pt atoms on the NiO(100) surface and on NiO/Ag(100) thin films using plane wave DFT+U calculations. The scope of this work is to compare the adsorption properties of NiO, a reducible transition metal oxide, with those of MgO, a simple binary oxide with the same crystal structure and similar lattice parameter. At the same time, we are interested in the adsorption characteristics of NiO ultra-thin films (three atomic layers) deposited on Ag(100) single crystals. Also in this case the scope is to compare NiO/Ag(100) with the corresponding MgO/Ag(100) films which show unusual properties for the case of Au adsorption. The results show that the transition metal atoms bind in a similar way on NiO(100) and NiO/Ag(100) films, with Pt, Pd, and Au forming bonds of decreasing strength in this order. No charging effects occur for Au adsorbed on NiO/Ag(100) films, at variance with MgO/Ag(100). The reasons are analyzed in terms of work function of the metal/oxide interface. Possible ways to modify this property by growing alternate layers of MgO and NiO are discussed.     

Microchip micellar electrokinetic chromatography separation of alkaloids with UV-absorbance spectral detection

A microchip device is demonstrated for the electrophoretic separation and UV-absorbance spectral detection of four toxic alkaloids: colchicine, aconitine, strychnine, and nicotine. A fused-silica (quartz) microchip containing a simple cross geometry is utilized to perform the separations, and a miniature, fiber-optic CCD spectrometer is coupled to the microchip for detection. Sensitive UV-absorbance detection is achieved via the application of online preconcentration techniques in combination with the quartz microchip substrate which contains an etched bubble-cell for increased pathlength. The miniature CCD spectrometer is configured to detect light between 190 and 645 nm and LabView programming written in-house enables absorbance spectra as well as separations to be monitored from 210 to 400 nm. Consequently, the configuration of this microchip device facilitates qualitative and quantitative separations via simultaneous spatial and spectral resolution of solutes. UV-absorbance limits of quantification for colchicine, 20 microM (8 mg/L); strychnine, 50 microM (17 mg/L); aconitine, 50 microM (32 mg/L); and nicotine, 100 microM (16 mg/L) are demonstrated on the microchip. With the exception of aconitine, these concentrations are > or =20-times more sensitive than lethal dose monitoring requirements. Finally, this device is demonstrated to successfully detect each toxin in water, skim milk, and apple juice samples spiked at sublethal dose concentrations after a simple, SPE procedure.     

Synthesis, stoichiometry and thermal stability of Zn3N2 powders prepared by ammonolysis reactions

Zn₃N₂ powders were prepared by ammonolysis reactions at 600 °C and examined by thermogravimetric analysis, powder X-ray and neutron diffraction. The powders obtained in this way are unstable in an oxygen atmosphere above 450 °C. In an argon atmosphere, the powders are stable up to their decomposition point at around 700 °C. Structural models obtained from Rietveld refinements against the powder neutron diffraction data indicate that the Zn₃N₂ powders so-prepared have the anti-bixbyite structure and are almost certainly stoichiometric with no compelling evidence of nitrogen vacancies. Further, no evidence was found for aliovalent oxygen substitution at the nitrogen sites. The calculated bond valence sums imply that Zn₃N₂ cannot be described as a 100% ionic compound. The structural findings are supported by photoluminescence measurements that reveal a band gap of approximately 0.9 eV.