Highly textured Sr, Nb, co-doped BiFeO3 thin films grown on SrRuO3/Si substrates by rf-sputtering

In this study, (011)-highly oriented Sr, Nb co-doped BiFeO3 (BFO) thin films were successfully grown on SrRuO3/Si substrates by rf-magnetron sputtering. The presence of parasite magnetic phases was ruled out based on the high resolution x-ray diffraction data. BFO films exhibited a columnar-like grain growth with rms surface roughness values of 5.3 nm and average grain sizes of 65-70 nm for samples with different thicknesses. Remanent polarization values (2Pr) of 54 lC cm 2 at room temperature were found for the BFO films with a ferroelectric behavior characteristic of an asymmetric device structure. Analysis of the leakage mechanisms for this structure in negative bias suggests Schottky injection and a dominant Poole-Frenkel trap-limited conduction at room temperature. Oxygen vacancies and Fe3þ/Fe2þ trap centers are consistent with the surface chemical bonding states analysis from x-ray photoelectron spectroscopy data. The (011)-BFO/ SrRuO3/Si film structure exhibits a strong magnetic interaction at the interface between the multiferroic film and the substrate layer where an enhanced ferromagnetic response at 5 K was observed. Zero-field cooled (ZFC) and field cooled (FC) magnetization curves of this film system revealed a possible spin glass behavior at spin freezing temperatures below 30 K depending on the BFO film thickness.

The valence band alignment at ultrathin SiO2/Si interfaces

High resolution x-ray photoelectron spectroscopy has been used to determine the valence band alignment at ultrathin SiO2/Si interfaces. In the oxide thickness range 1.6-4.4 nm the constant band-offset values of 4.49 and 4.43 eV have been obtained for the dry SiO2/Si(100) and the wet SiO2/Si(100) interfaces, respectively. The valence band alignment of dry SiO2/Si(111) (4.36 eV) is slightly smaller than the case of the dry SiO2/Si(100) interface.

The Proteolytic Activation of (H3N2) Influenza A Virus Hemagglutinin Is Facilitated by Different Type II Transmembrane Serine Proteases.

UNLABELLED: Cleavage of influenza virus hemagglutinin (HA) by host cell proteases is necessary for viral activation and infectivity. In humans and mice, members of the type II transmembrane protease family (TTSP), e.g., TMPRSS2, TMPRSS4, and TMPRSS11d (HAT), have been shown to cleave influenza virus HA for viral activation and infectivityin vitro Recently, we reported that inactivation of a single HA-activating protease gene,Tmprss2, in knockout mice inhibits the spread of H1N1 influenza viruses. However, after infection ofTmprss2knockout mice with an H3N2 influenza virus, only a slight increase in survival was observed, and mice still lost body weight. In this study, we investigated an additional trypsin-like protease, TMPRSS4. Both TMPRSS2 and TMPRSS4 are expressed in the same cell types of the mouse lung. Deletion ofTmprss4alone in knockout mice does not protect them from body weight loss and death upon infection with H3N2 influenza virus. In contrast,Tmprss2(-/-)Tmprss4(-/-)double-knockout mice showed a remarkably reduced virus spread and lung pathology, in addition to reduced body weight loss and mortality. Thus, our results identified TMPRSS4 as a second host cell protease that, in addition to TMPRSS2, is able to activate the HA of H3N2 influenza virusin vivo IMPORTANCE: Influenza epidemics and recurring pandemics are responsible for significant global morbidity and mortality. Due to high variability of the virus genome, resistance to available antiviral drugs is frequently observed, and new targets for treatment of influenza are needed. Host cell factors essential for processing of the virus hemagglutinin represent very suitable drug targets because the virus is dependent on these host factors for replication. We reported previously thatTmprss2-deficient mice are protected against H1N1 virus infections, but only marginal protection against H3N2 virus infections was observed. Here we show that deletion of two host protease genes,Tmprss2andTmprss4, strongly reduced viral spread as well as lung pathology and resulted in increased survival after H3N2 virus infection. Thus, TMPRSS4 represents another host cell factor that is involved in cleavage activation of H3N2 influenza virusesin vivo.

Surface Studies of Thiolate Adsorbates on Some Metals

The results and discussions in this thesis are based on my studies about selfassembled thiol layers on gold, platinum, silver and copper surfaces. These kinds of layers are two-dimensional, one molecule thick and covalently organized at the surface. They are an easy way to modify surface properties. Self-assembly is today an intensive research field because of the promise it holds for producing new technology at nanoscale, the scale of atoms and molecules. These kinds of films have applications for example, in the fields of physics, biology, engineering, chemistry and computer science. Compared to the extensive literature concerning self-assembled monolayers (SAMs) on gold, little is known about the structure and properties of thiolbased SAMs on other metals. In this thesis I have focused on thiol layers on gold, platinum, silver and copper substrates. These studies can be regarded as a basic study of SAMs. Nevertheless, an understanding of the physical and chemical nature of SAMs allows the correlation between atomic structure and macroscopic properties. The results can be used as a starting point for many practical applications. X-ray photoelectron spectroscopy (XPS) and synchrotron radiation excited high resolution photoelectron spectroscopy (HR-XPS) together with time-offlight secondary ion mass spectrometry (ToF-SIMS) were applied to investigate thin organic films formed by the spontaneous adsorption of molecules on metal surfaces. Photoelectron spectroscopy was the main method used in these studies. In photoelectron spectroscopy, the sample is irradiated with photons and emitted photoelectrons are energy-analyzed. The obtained spectra give information about the atomic composition of the surface and about the chemical state of the detected elements. It is widely used in the study of thin layers and is a very powerful tool for this purpose. Some XPS results were complemented with ToF-SIMS measurements. It provides information on the chemical composition and molecular structure of the samples. Thiol (1-Dodecanethiol, CH3(CH2)11SH) solution was used to create SAMs on metal substrates. Uniform layers were formed on most of the studied metal surfaces. On platinum, surface aligned molecules were also detected in investigations by XPS and ToF-SIMS. The influence of radiation on the layer structure was studied, leading to the conclusion that parts of the hydrocarbon chains break off due to radiation and the rest of the layer is deformed. The results obtained showed differences depending on the substrate material. The influence of oxygen on layer formation was also studied. Thiol molecules were found to replace some of the oxygen from the metal surfaces.

Studies of Eu- and Yb-induced Reconstructions on the Si(100) Surface

This thesis presents experimental studies of rare earth (RE) metal induced structures on Si(100) surfaces. Two divalent RE metal adsorbates, Eu and Yb, are investigated on nominally flat Si(100) and on vicinal, stepped Si(100) substrates. Several experimental methods have been applied, including scanning tunneling microscopy/spectroscopy (STM/STS), low energy electron diffraction (LEED), synchrotron radiation photoelectron spectroscopy (SR-PES), Auger electron spectroscopy (AES), thermal desorption spectroscopy (TDS), and work function change measurements (Δφ). Two stages can be distinguished in the initial growth of the RE/Si interface: the formation of a two-dimensional (2D) adsorbed layer at submonolayer coverage and the growth of a three-dimensional (3D) silicide phase at higher coverage. The 2D phase is studied for both adsorbates in order to discover whether they produce common reconstructions or reconstructions common to the other RE metals. For studies of the 3D phase Yb is chosen due to its ability to crystallize in a hexagonal AlB2 type lattice, which is the structure of RE silicide nanowires, therefore allowing for the possibility of the growth of one-dimensional (1D) wires. It is found that despite their similar electronic configuration, Eu and Yb do not form similar 2D reconstructions on Si(100). Instead, a wealth of 2D structures is observed and atomic models are proposed for the 2×3-type reconstructions. In addition, adsorbate induced modifications on surface morphology and orientational symmetry are observed. The formation of the Yb silicide phase follows the Stranski-Krastanov growth mode. Nanowires with the hexagonal lattice are observed on the flat Si(100) substrate, and moreover, an unexpectedly large variety of growth directions are revealed. On the vicinal substrate the growth of the silicide phase as 3D islands and wires depends drastically on the growth conditions. The conditions under which wires with high aspect ratio and single orientation parallel to the step edges can be formed are demonstrated.

Spectroscopic characterization of phases formed by high-dose carbon ion implantation in silicon

High-dose carbon-ion-implanted Si samples have been analyzed by infrared spectroscopy, Raman scattering, and x-ray photoelectron spectroscopy (XPS) correlated with transmission electron microscopy. Samples were implanted at room temperature and 500°C with doses between 1017 and 1018 C+/cm2. Some of the samples were implanted at room temperature with the surface covered by a capping oxide layer. Implanting at room temperature leads to the formation of a surface carbon-rich amorphous layer, in addition to the buried implanted layer. The dependence of this layer on the capping oxide suggests this layer to be determined by carbon migration toward the surface, rather than surface contamination. Implanting at 500°C, no carbon-rich surface layer is observed and the SiC buried layer is formed by crystalline ßSiC precipitates aligned with the Si matrix. The concentration of SiC in this region as measured by XPS is higher than for the room-temperature implantation.

Calcium phosphate glasses: silanation process and effect on the bioactivity behavior of Glass-PMMA composites

This article presents the results of a study of the efficiency of silanation process of calcium phosphate glasses particles and its effect on the bioactivity behavior of glasspoly( methyl methacrylate) (PMMA) composites. Two different calcium phosphate glasses: 44.5CaO-44.5P2O5-11Na2O (BV11) and 44.5CaO-44.5P2O5-6Na2O-5TiO2 (G5) were synthesized and treated with silane coupling agent. The glasses obtained were characterized by Microprobe and BET while the efficiency of silanation process was determined using Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS) and Thermal Analysis (DTA and TG)techniques. The content of coupling agent chemically tightly bond to the silanated glasses ascended to 1.69 6 0.02 wt % for BV11sil glass and 0.93 6 0.01 wt % for G5sil glass. The in vitro bioactivity test carried out in Simulated Body Fluid (SBF) revealed certain bioactive performance with the use of both silanated glasses in a 30% (by weight) as filler of the PMMA composites because of a superficial deposition of an apatite-like layer with low content of CO3 22 and HPO4 22 in its structure after soaking for 30 days occurred. VC 2013 Wiley Periodicals,Inc. J Biomed Mater Res Part B: Appl Biomater 00B: 000-000, 2013.

Estudo do biomaterial Ti-6Al-4V empregando-se técnicas eletroquímicas e XPS

The Ti-6Al-4V alloy used as biomaterial has been used over the last years. The literature shows controversies concerning the kind and the chemical composition of the film naturally and elctrochemically formed on the surface of the titanium alloy. The presente work studies the film composition before and after the electrochemical polarization tests using the x Ray photoelectron spectroscopy (XPS) technique. The results showed that the film naturally formed on the metallic surface is constituted of a variety of oxides which do not cover the whole surface of the metallic alloy and therefore, metallic Ti, Al and V can be found on the uncovered areas. The tests of XPS made after the polarization up to 4V (SCE) showed that the electrochemically formed film is constituted only of TiO2 and that the peak current observed around 1,5 V (SCE) is due to the oxidation of any kind of titanium oxide or the growth of the film.

Estudo do efeito do cloreto em catalisadores de paládio usando a análise no infravermelho e de fotoelétrons excitados por raios x

Chloride poisoning is known as having an inhibitor effect in the activity of metal catalysis. In this work in situ infrared spectroscopy (FTIR) of adsorbed carbon monoxide and x-ray photoelectron spectroscopy (XPS) were used to investigate the effect of chloride presence in the electronic metal density in the d subshell of palladium dispersed on alumina. The chloride poisoning effect was interpreted as an electronic effect since a weak back-bonded Pd-CO was formed due to the decrease in the electronic density of the d subshell of palladium, which could be also detected by the higher Pd 3d5/2 binding energy in the chloride presence. A similar poisoning effect was also observed for chloride free Pd/Al2O3 reduced at 500 ºC, and it was interpreted based on the interaction of metal with the alumina surface. The use of molybdena/alumina binary system as support, yield a contrary effect due to the metal-support interaction.

Emprego de óxidos tipo perovskita nas oxidações do propano e CO

Simultaneous oxidation/co-precipitation of an equimolar mixture of La(III) and Co(II) nitrates and La(III) nitrate and Mn(II) chloride afforded a hydroxide gel, which was converted to LaCoO3 and LaMnO3 on calcination at 600 °C. After calcination, the obtained perovskites have been characterised by X-ray diffraction (XRD), X- ray photoelectron spectroscopy (XPS), thermogravimetric analysis (DTA - TGA) and BET specific surface determination. Specific surface areas of perovskites were 12 - 60 m²/g. XRD analysis showed that LaCoO3 and LaMnO3 are simple phase perovskite - type oxides. Traces of LaOCl, in addition to the perovskite were detected in the LaMnO3. The catalytic behavior was examined in the propane and CO oxidation. The LaCoO3 catalyst was more active to CO2 than the LaMnO3 catalyst.

Espectroscopia de fotoelétrons de limiares de átomos e moléculas

A threshold photoelectron spectrometer applied to the study of atomic and molecular threshold photoionization processes is described. The spectrometer has been used in conjunction with a toroidal grating monochromator at the National Synchrotron Radiation Laboratory (LNLS), Brazil. It can be tuned to accept threshold electrons (< 20 meV) and work with a power resolution of 716 (~18 meV at 12 eV) with a high signal/noise ratio. The performance of this apparatus and some characteristics of the TGM (Toroidal Grating Monochromator) beam line of LNLS are described and discussed by means of argon, O2 and N2 threshold photoelectron spectra.

Estudo da oxidação total do etanol usando óxidos tipo perovskita LaBO3 (B= Mn, Ni, Fe)

The present work investigated the effect of coprecipitation-oxidant synthesis on the specific surface area of perovskite-type oxides LaBO3 (B= Mn, Ni, Fe) for total oxidation of ethanol. The perovskite-type oxides were characterized by X-ray diffraction, nitrogen adsorption (BET method), thermogravimetric analysis (TGA-DTA), TPR and X-ray photoelectron spectroscopy (XPS). Through method involving the coprecipitation-oxidant was possible to obtain catalysts with different BET specific surface areas, of 33-51 m²/g. The results of the catalytic test confirmed that all oxides investigated in this work have specific catalytic activity for total oxidation of ethanol, though the temperatures for total conversion change for each transition metal.

Optical and microstructural properties of MgF2 UV coatings grown by ion beam sputtering process

The optical, mechanical, and microstructural properties of MgF2 single layers grown by ion beam sputtering have been investigated by spectrophotometric measurements, film stress characterization, x-ray photoelectron spectroscopy (XPS), x-ray diffraction, and transmission electron microscopy. The deposition conditions, using fluorine reactive gas or not, have been found to greatly influence the optical absorption and the stress of the films as well as their microstructure. The layers grown with fluorine compensation exhibit a regular columnar microstructure and an UV-optical absorption which can be very low, either as deposited or after thermal annealings at very low temperatures. On the contrary, layers grown without fluorine compensation exhibit a less regular microstructure and a high ultraviolet absorption which is particularly hard to cure. On the basis of calculations, it is shown that F centers are responsible for this absorption, whereas all the films were found to be stoichiometric, in the limit of the XPS sensitivity. On the basis of external data taken from literature, our experimental curves are analyzed, so we propose possible diffusion mechanisms which could explain the behaviors of the coatings.

Efeito do tratamento térmico na microestrutura, turbostraticidade e superfície de carbono vítreo reticulado analisado por XPS, espalhamento Raman e voltametria cíclica

The structural and surface properties of reticulated vitreous carbon (RVC) were discussed as a function of its heat treatment temperature (HTT), for samples produced in the range from 700 to 2000 ºC, using the furfuryl precursor resin. The samples were analyzed by x-ray photoelectron spectroscopy, first and second order Raman scattering as well as electrochemical response. Exploring the material turbostraticity concept, the interdependence between the RVC chemical surface variation and its defects were demonstrated. The influence of heteroatom presence was discussed in the material ordering for HTT lower than 1300 ºC while the graphitization process evolution was also pointed out for HTT higher than 1500 ºC.

Síntese e caracterização de nanopartículas de óxido de ferro suportadas em matriz carbonácea: remoção do corante orgânico azul de metileno em água

In this work were prepared composites of iron oxide and carbonaceous materials in two different weight proportions (Carbon/Fe 1/1 and 1/2). The physico-chemical properties of the composites were determined by temperature programmed reduction (TPR), adsorption/dessorption of N2, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and pulse titration H2. The XRD and XPS analysis showed a cubic iron oxide phase, identified as maghemite, formed over the carbon surface. The particle size of maghemite showed to be within 10-30 nm. Carbon/Fe 1/2 was the most active in MB removal kinetics and ESI-MS studies showed that MB removal by both composites leads to oxidized intermediates.