Theory of nitride oxide adsorption on transition metal (111) surfaces: a first-principles investigation

In this work, we report a density functional theory study of nitric oxide (NO) adsorption on close-packed transition metal (TM) Rh(111), Ir(111), Pd(111) and Pt(111) surfaces in terms of adsorption sites, binding mechanism and charge transfer at a coverage of Theta(NO) = 0.25, 0.50, 0.75 monolayer (ML). Based on our study, an unified picture for the interaction between NO and TM(111) and site preference is established, and valuable insights are obtained. At low coverage (0.25 ML), we find that the interaction of NO/TM(111) is determined by an electron donation and back-donation process via the interplay between NO 5 sigma/2 pi* and TM d-bands. The extent of the donation and back-donation depends critically on the coordination number (adsorption sites) and TM d-band filling, and plays an essential role for NO adsorption on TM surfaces. DFT calculations shows that for TMs with high d-band filling such as Pd and Pt, hollow-site NO is energetically the most favorable, and top-site NO prefers to tilt away from the normal direction. While for TMs with low d-band filling (Rh and Ir), top-site NO perpendicular to the surfaces is energetically most favorable. Electronic structure analysis show that irrespective of the TM and adsorption site, there is a net charge transfer from the substrate to the adsorbate due to overwhelming back-donation from the TM substrate to the adsorbed NO molecules. The adsorption-induced change of the work function with respect to bare surfaces and dipole moment is however site dependent, and the work function increases for hollow-site NO, but decreases for top-site NO, because of differences in the charge redistribution. The interplay between the energetics, lateral interaction and charge transfer, which is element dependent, rationalizes the structural evolution of NO adsorption on TM(111) surfaces in the submonolayer regime.

The role of the steps in the cleavage of the C-C bond during ethanol oxidation on platinum electrodes

Ethanol oxidation has been studied on stepped platinum single crystal electrodes in acid media using electrochemical and Fourier transform infrared (FTIR) techniques. The electrodes used belong to two different series of stepped surfaces: those having (111) terraces with (100) monoatomic steps and those with (111) terraces with (110) monoatomic steps. The behaviors of the two series of stepped surfaces for the oxidation of ethanol are very different. On the one hand, the presence of (100) steps on the (111) terraces provides no significant enhancement of the activity of the surfaces. On the other hand, (110) steps have a double effect on the ethanol oxidation reaction. At potentials below 0.7 V, the step catalyzes the C-C bond cleavage and also the oxidation of the adsorbed CO species formed. At higher potentials, the step is not only able to break the C-C bond, but also to catalyze the oxidation of ethanol to acetic acid and acetaldehyde. The highest catalytic activity from voltammetry for ethanol oxidation was obtained with the Pt(554) electrode.

A new correlation between electronic parameters and glass forming ability of metallic alloys

A quantitative correlation between the glass forming ability and the electronic parameters of metallic alloys is presented. It is found that the critical cooling rate for glass formation (R(c)) correlates well with the average work function difference (Delta phi) and the average electron density difference (Delta n(ws)(1/3)) among the constituent elements of the investigated alloys. A correlation coefficient (R(2)) of 0.77 was found for 68 alloys in 30 metallic systems, which is better than the previous proposed correlation between the glass forming ability and the average Pauling electronegativity difference.

Low-frequency noise and static analysis of the impact of the TiN metal gate thicknesses on n- and p-channel MuGFETs

The impact of the titanium nitride (TIN) gate electrode thickness has been investigated in n and p channel SOI multiple gate field effect transistors (MuGFETs) through low frequency noise charge pumping and static measurements as well as capacitance-voltage curves The results suggest that a thicker TIN metal gate electrode gives rise to a higher EOT a lower mobility and a higher interface trap density The devices have also been studied for different back gate biases where the GIFBE onset occurs at lower front-gate voltage for thinner TIN metal gate thickness and at higher V(GF) In addition it is demonstrated that post deposition nitridation of the MOCVD HfSiO gate dielectric exhibits an unexpected trend with TIN gate electrode thickness where a continuous variation of EOT and an increase on the degradation of the interface quality are observed (C) 2010 Elsevier Ltd All rights reserved

Influence of the sidewall crystal orientation, HfSiO nitridation and TiN metal gate thickness on n-MuGFETs under analog operation

This work characterizes the analog performance of SOI n-MuGFETs with HfSiO gate dielectric and TiN metal gate with respect to the influence of the high-k post-nitridation. TiN thickness and device rotation. A thinner TiN metal gate is found favorable for improved analog characteristics showing an increase in intrinsic voltage gain. The devices where the high-k material is subjected to a nitridation step indicated a degradation of the Early voltage (V(EA)) values which resulted in a lower voltage gain. The 45 degrees rotated devices have a smaller V(EA) than the standard ones when a HfSiO dielectric is used. However, the higher transconductance of these devices, due to the increased mobility in the (1 0 0) sidewall orientation, compensates this V(EA) degradation of the voltage gain, keeping it nearly equal to the voltage gain values of the standard devices. (C) 2011 Elsevier Ltd. All rights reserved.

Exact nonequilibrium work generating function for a small classical system

We obtain the exact nonequilibrium work generating function (NEWGF) for a small system consisting of a massive Brownian particle connected to internal and external springs. The external work is provided to the system for a finite-time interval. The Jarzynski equality, obtained in this case directly from the NEWGF, is shown to be valid for the present model, in an exact way regardless of the rate of external work.

Comparison of the effects of carbon dioxide and helium pneumoperitoneum on renal function

Background and Purpose: Carbon dioxide pneumoperitoneum is associated with significant hypercarbia and acidosis. The aim of this study is to evaluate the effects of carbon dioxide and helium pneumoperitoneum on renal function. Materials and Methods: Thirty adult dogs were put randomly into one of three groups ( n = 10 animals each): group A - pneumoperitoneum not performed; group B - CO2 pneumoperitoneum; and group C - helium pneumoperitoneum. The groups were analyzed with consideration given to body weight, hematologic values, hemodynamic parameters ( heart rate, mean arterial pressure, central venous pressure, cardiac output, stroke volume, systemic vascular resistance, pulmonary vascular resistance, left cardiac work index, cardiac index, mean pulmonary artery pressure, and pulmonary capillary wedge pressure), and renal function ( plasma renin activity, urinary output, creatinine clearance, and sodium excretory fraction). Results: An accentuated decrease in urinary output was observed during pneumoperitoneum in groups B and C compared to the control group. In groups B and C, creatinine clearance declined significantly during pneumoperitoneum in comparison to group A, but after deflation a faster recovery of glomerular filtration was noticed for group C, and a significant increase in sodium excretory fraction was seen for group B. On the other hand, in comparison to the control group, group B had a significant increase in plasma renin activity, with late recovery of glomerular function. Conclusion: Helium ameliorates renal alterations when used for pneumoperitoneum, and it might be used for patients with compromised renal function who have to undergo laparoscopic surgery.

In situ delivery of bone marrow cells and mesenchymal stem cells improves cardiovascular function in hypertensive rats submitted to myocardial infarction

This work aimed to evaluate cardiac morphology/function and histological changes induced by bone marrow cells (BMCs) and cultured mesenchymal stem cells (MSCs) injected at the myocardium of spontaneously hypertensive rats (SHR) submitted to surgical coronary occlusion. Female syngeneic adult SHR, submitted (MI) or not (C) to coronary occlusion, were treated 24 h later with in situ injections of normal medium (NM), or with MSCs (MSC) or BMCs (BM) from male rats. The animals were evaluated after 1 and 30 days by echocardiography, histology of heart sections and PCR for the Y chromosome. Improved ejection fraction and reduced left ventricle infarcted area were observed in MSC rats as compared to the other experimental groups. Treated groups had significantly reduced lesion tissue score, increased capillary density and normal (not-atrophied) myocytes, as compared to NM and C groups. The survival rate was higher in C, NM and MSC groups as compared to MI and BM groups. In situ injection of both MSCs and BMCs resulted in improved cardiac morphology, in a more physiological model of myocardial infarction represented by surgical coronary occlusion of spontaneously hypertensive rats. Only treatment with MSCs, however, ameliorated left ventricle dysfunction, suggesting a positive role of these cells in heart remodeling in infarcted hypertensive subjects.

The Essential Nucleolar Yeast Protein Nop8p Controls the Exosome Function during 60S Ribosomal Subunit Maturation

The yeast nucleolar protein Nop8p has previously been shown to interact with Nip7p and to be required for 60S ribosomal subunit formation. Although depletion of Nop8p in yeast cells leads to premature degradation of rRNAs, the biochemical mechanism responsible for this phenotype is still not known. In this work, we show that the Nop8p amino-terminal region mediates interaction with the 5.8S rRNA, while its carboxyl-terminal portion interacts with Nip7p and can partially complement the growth defect of the conditional mutant strain Dnop8/GAL:NOP8. Interestingly, Nop8p mediates association of Nip7p to pre-ribosomal particles. Nop8p also interacts with the exosome subunit Rrp6p and inhibits the complex activity in vitro, suggesting that the decrease in 60S ribosomal subunit levels detected upon depletion of Nop8p may result from degradation of pre-rRNAs by the exosome. These results strongly indicate that Nop8p may control the exosome function during pre-rRNA processing.

On the solubility of proteins as a function of pH: Mathematical development and application

Thermodynamic relations between the solubility of a protein and the solution pH are presented in this work. The hypotheses behind the development are that the protein chemical potential in liquid phase can be described by Henry`s law and that the solid-liquid equilibrium is established only between neutral molecules. The mathematical development results in an analytical expression of the solubility curve, as a function of the ionization equilibrium constants, the pH and the solubility at the isoelectric point. It is shown that the same equation can be obtained either by directly calculating the fraction of neutral protein molecules or by integrating the curve of the protein average charge. The methodology was successfully applied to the description of the solubility of porcine insulin as a function of pH at three different temperatures and of bovine beta-lactoglobulin at four different ionic strengths. (C) 2011 Elsevier B.V. All rights reserved.

Nutrition in bean plants and anthracnose intensity in function of silicon and copper application.

Nutrition in bean plants and anthracnose intensity in function of silicon and copper application. The objective of this work was to evaluate the effect of calcium silicate and copper sulfate on anthracnose intensity and nutrition of bean plants. The experiment was conducted using an experimental design in randomized blocks following a 4 x 4 factorial arrangement , (four levels of calcium silicate and four levels of copper sulfate) and two additional treatments (plants without inoculation and plants sprinkled with Benomyl). Four evaluations of the incidence and severity of anthracnose were done, in addition to measuring, total leaf area. At the end of the evaluations, incidence: and data were integrated over time, obtaining the area under disease progress curve (AUDPC). Contents of N, P, K, Ca, Mg, B, Cu, Fe, Mn, Zn, Si and lignin were determined in the aerial Part. A linear decrease of the intensity AUDPC was observed with the increase of the doses of calcium silicate. The severity AUDPC was influenced by the doses of copper, obtaining a reduction of 35% on the higher dosage. The supply of silicon and copper altered the content of the K, mg, S, Zn, Ca and Si in the aerial part of the bean plants.

Evaluation of Postpolymerization as a Function of the Storage Time of Triethylene Glycol Dimethacrylate/2,2-Bis[4-(2-Hydroxy-3-Methacryloxy-Prop-1-Oxy)-Phenyl]-propane Bisphenyl-alpha-Glycidyl Ether Dimethacrylate Copolymers Used in Dental Resins by Differential Scanning Calorimetry and Dynamic Mechanical Analysis

The aim of this work was to evaluate the effect of the storage time on the thermal properties of triethylene glycol dimethacrylate/2,2-bis[4-(2-hydroxy-3-methacryloxy-prop-1-oxy)-phenyl]propane bisphenyl-alpha-glycidyl ether dimethacrylate (TB) copolymers used in formulations of dental resins after photopolymerization. The TB copolymers were prepared by photopolymerization with an Ultrablue IS light-emitting diode, stored in the dark for 160 days at 37 degrees C, and characterized with differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and Fourier transform infrared spectroscopy with attenuated total reflection. DSC curves indicated the presence of an exothermic peak, confirming that the reaction was not completed during the photopolymerization process. This exothermic peak became smaller as a function of the storage time and was shifted at higher temperatures. In DMA studies, a plot of the loss tangent versus the temperature initially showed the presence of two well-defined peaks. The presence of both peaks confirmed the presence of residual monomers that were not converted during the photopolymerization process. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 679-684, 2009

Self-perception and malocclusion and their relation to oral appearance and function

The aim of this study was to evaluate the relationship between malocclusion and self-perception of oral appearance/function, in 12/15-year-old Brazilian adolescents. The cluster sample consisted of 717 teenagers attending 24 urban public (n=611) and 5 rural public (n=107) schools in Maringá/PR. Malocclusion was measured using the Dental Aesthetic Index (DAI), in accordance with WHO recommendations. A parental questionnaire was applied to collect information on esthetic perception level and oral variables related to oral health. Univariate and multiple logistic regression analyses were performed. Multiple logistic regression confirmed that for 12-year-old, missing teeth (OR=2.865) and presence of openbite (open occlusal relationship) (OR=2.865) were risk indicators for speech capability. With regard to 15-year-old, presence of mandibular overjet (horizontal overlap) (OR=4.016) was a risk indicator for speech capability and molar relationship (OR=1.661) was a risk indicator for chewing capability. The impact of malocclusion on adolescents' life was confirmed in this study. Speech and chewing capability were associated with orthodontic deviations, which should be taken into consideration in oral health planning, to identify risk groups and improve community health services.

Mechanical properties and porosity of dental glass-ceramics hot-pressed at different temperatures

The objective of this work was to evaluate biaxial-flexural-strength (σf), Vickers hardness (HV), fracture toughness (K Ic), Young's modulus (E), Poisson's ratio (ν) and porosity (P) of two commercial glass-ceramics, Empress (E1) and Empress 2 (E2), as a function of the hot-pressing temperature. Ten disks were hot-pressed at 1065, 1070, 1075 and 1080 °C for E1; and at 910, 915, 920 and 925 °C for E2. The porosity was measured by an image analyzer software and s f was determined using the piston-on-three-balls method. K Ic and HV were determined by an indentation method. Elastic constants were determined by the pulse-echo method. For E1 samples treated at different temperatures, there were no statistical differences among the values of all evaluated properties. For E2 samples treated at different temperatures, there were no statistical differences among the values of σf, E, and ν, however HV and K Ic were significantly higher for 910 and 915 °C, respectively. Regarding P, the mean value obtained for E2 for 925 °C was significantly higher compared to other temperatures.

Isotermas de dessorção de filé de bonito (Sarda sarda) desidratado osmoticamente e defumado

O presente trabalho teve como objetivo a obtenção de isotermas de dessorção de filés de bonito (Sarda sarda), previamente salgados a vácuo e defumados com fumaça líquida. As isotermas foram obtidas a quatro temperaturas (5, 25, 40 e 60 ºC) em condições de dessorção, através do método gravimétrico estático, com soluções salinas saturadas. Os dados experimentais foram ajustados a quatro modelos da literatura (BET linearizado, GAB, Henderson e Oswin modificado). Os resultados mostraram que as isotermas tomaram forma sigmoidal de tipo II e que o modelo de Guggenheim-Anderson-deBoer (GAB) foi aceitável para modelar os dados experimentais. O calor isostérico de dessorção, um parâmetro necessário para simular e projetar adequadamente o secador, também foi calculado e pode ser representado através de um modelo matemático simples, em função da umidade de equilíbrio.