Surface chemistry of alanine on Cu{111}: Adsorption geometry and temperature dependence

Adsorption of l-alanine on the Cu{111} single crystal surface was investigated as a model system for interactions between small chiral modifier molecules and close-packed metal surfaces. Synchrotron-based X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy are used to determine the chemical state, bond coordination and out-of-plane orientation of the molecule on the surface. Alanine adsorbs in its anionic form at room temperature, whilst at low temperature the overlayer consists of anionic and zwitterionic molecules. NEXAFS spectra exhibit a strong angular dependence of the π ⁎ resonance associated with the carboxylate group, which allows determining the tilt angle of this group with respect to the surface plane (48° ± 2°) at room temperature. Low-energy electron diffraction (LEED) shows a p(2√13x2√13)R13° superstructure with only one domain, which breaks the mirror symmetry of the substrate and, thus, induces global chirality to the surface. Temperature-programmed XPS (TP-XPS) and temperature-programmed desorption (TPD) experiments indicate that the zwitterionic form converts into the anionic species (alaninate) at 293 K. The latter desorbs/decomposes between 435 K and 445 K.

Emulation of chiral hydrogenation catalysts by adsorbtion of small molecules onto Ni surfaces

Adsorption of small molecules on the Ni{111} and NiO{111} surfaces is investigated under UHV and elevated pressures (~10-1 mbar) of hydrogen and water. The molecules considered are chosen for their relevance to understanding the mechanism of enantioselective hydrogenation on Raney Nickel modified by chiral molecules. Adsorption of water onto, and its subsequent reaction with, oxygen-covered Ni{111} is dependent on the initial atomic oxygen coverage. An OH species (O1s binding energy 531.5eV), oriented perpendicular to the surface, forms at atomic oxygen coverages <0.25ML. The reaction does not consume all the adsorbed oxygen for coverages ≥0.12ML. The p(2×2) atomic oxygen uperstructure is unreactive, while an OH species is formed on the p(√3×√3) superstructure at binding energy 530.9eV. L-alanine is adsorbed on Ni{111} as a model chiral modifier molecule. At low coverages, alanine forms a presumed tridentate alaninate species for coverages ≥0.11ML at 250K. A minority, bidentate zwitterionic species forms at coverages >0.11ML, but was not observed at 300K. Saturation occurs at 0.25ML. At high alanine coverages (≥0.19ML) and H2 pressure (≥1×10-2 mbar), the tridentate L-alaninate converts to bidentate zwitterionic L-alanine at 300K. Thermal evolution of L-alanine on Ni{111} under varying hydrogen pressures is examined. Adsorption of L-alanine onto hydroxylated NiO{111} at 300K in UHV, mimicking a catalyst surface under aqueous conditions, yields the tridentate alaninate which is immune to the effects of elevated hydrogen pressure. Exposing the L-alanine/Ni{111} adsorption system to water (≤10-1 mbar) oxidises the surface and recreates the L-alanine/hydroxylated NiO{111} system. Pyruvic acid on Ni{111} is examined as a model for hydrogenation substrate adsorption. Behaviour is coverage dependent and several conformations are possible at low coverages (≤0.1ML). Annealing at coverages <0.2ML causes a condensation reaction, releasing water onto the surface. High coverages do not condense and a saturation coverage of ~0.35ML is found.

Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds

Asymmetric emission profiles of the stereoisomers of plant-derived volatile organic compounds vary with season, geography, plant type, and stress factors. After oxidation of these compounds in the atmosphere, the low-vapor pressure products ultimately contribute strongly to the particle-phase material of the atmosphere. In order to explore the possibility of stereochemical transfer to atmospheric aerosol particles during the oxidation of biogenic volatile organic compounds, second-order coherent vibrational spectra were recorded of the particle-phase organic material produced by the oxidation of different stereoisomeric mixes of alpha-pinene. The spectra show that the stereochemical configurations are not scrambled but instead are transferred from the gas-phase molecular precursors to the particle-phase molecules. The spectra also show that oligomers formed in the particle phase have a handed superstructure that depends strongly and nonlinearly on the initial stereochemical composition of the precursors. Because the stereochemical mix of the precursors for a material can influence the physical and chemical properties of that material, our findings suggest that chirality is also important for such properties of plant-derived aerosol particles. Citation: Ebben, C. J., S. R. Zorn, S.-B. Lee, P. Artaxo, S. T. Martin, and F. M. Geiger (2011), Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds, Geophys. Res. Lett., 38, L16807, doi: 10.1029/2011GL048599.

QoS-aware model driven architecture through the UML and CIM

The specification of Quality of Service (QoS) constraints over software design requires measures that ensure such requirements are met by the delivered product. Achieving this goal is non-trivial, as it involves, at least, identifying how QoS constraint specifications should be checked at the runtime. In this paper we present an implementation of a Model Driven Architecture (MDA) based framework for the runtime monitoring of QoS properties. We incorporate the UML2 superstructure and the UML profile for Quality of Service to provide abstract descriptions of component-and-connector systems. We then define transformations that refine the UML2 models to conform with the Distributed Management Taskforce (DMTF) Common Information Model (CIM) (Distributed Management Task Force Inc. 2006), a schema standard for management and instrumentation of hardware and software. Finally, we provide a mapping the CIM metamodel to a .NET-based metamodel for implementation of the monitoring infrastructure utilising various .NET features including the Windows Management Instrumentation (WMI) interface.

"Os bárbaros estão chegando": o processo de democratização do governo Richa no Paraná

O presente trabalho de pesquisa acadêmica abrange a análise da conjuntura política do processo de transição democrática no Brasil e no Paraná, ocorrida no final da década de 1970 e inícios dos anos 80. No capítulo introdutório examino os elementos teórico-metodológicos, que são as categorias de análise que utilizo no estudo da situação concreta brasileira, como contexto amplo, e da conjuntura das eleiçôes de 1982 e do governo de José Richa no Paraná. Era necessário examinar a concepçâo "ampliada" de Estado, o conceito de estrutura e de superestrutura do bloco histórico e a concepção da vertente da democracia liberal e da vertente da democracia popular, no enfoque da literatura do materialismo histórico-dialético, de autores clássicos e modernos. No segundo capítulo examino o projeto de transição democrática dos generais presidentes Geisel e Figueiredo: um plano dos militares e das elites brasileiras para salvar as elites no poder, na travessia pelo alto. O projeto não ia além da legitimação do regime e do modelo econômico pela passagem do governo militar aos civis, por um processo eleitoral duvidoso. No Paraná, objetivo principal da pesquisa, examino o projeto liberal do governo do PMDB de Richa, desde a organizaçâo partidária, a elaboraçâo das diretrizes de governo, a campanha eleitoral, a participaçâo de intelectuais de ponta na campanha, as alianças do PMDB com os setores populares da sociedade até a composição e a "direitização" do governo. "OS BÁRBAROS ESTÃO CHEGANDO", título principal da dissertação, era a denominação que a aristocracia (elite) curitibana atribuiu a José Richa, quando o mesmo ganhou as eleições ao governo do Paraná, pelo fato de ser do interior do Estado e não fazer parte do mundo civilizado da Curitiba cosmopolita. No terceiro capítulo examino a questão da democratização da escola pública do Estado pela instituição das eleições para diretor e vice-diretor da escola, pelos professores, servidores, alunos e pais de alunos. Digo que a democracia vai além do decreto governamental que estabelece as eleições. Digo ainda que o discurso na prática é outro, no caso do governo Richa e da educação. A questão básica da pesquisa é trabalhar a idéia de que a educação é um campo de disputas e confrontos de classes pela hegemonia do poder, em que a classe dominante luta para manter-se no poder como classe dirigente e as classes subalternas ora se mantém aliadas e como classes auxiliares à classe dominante, ora consentem e raras vezes rebelam-se contra a dominaçâo da classe dirigente.

Educação, Estado e cidadania: uma reflexão sobre a realidade atual do sistema educacional brasileiro

o objetivo central desse trabalho é desenvolver uma reflexão geral sobre a relação entre Estado, cidadania e educação e trazê-la para a realidade educacional bras ileira, com uma preocupaçao de atualidade. Parte-se de uma discussão dos conceitos formulados por Antonio Grams ci para o estudo'da superestrutura social, chegando-se aos conceitos de reforma intelectual e moral e de Estado "ético e educador", que permitem pensar o ensino público, obrigatório e gratuito, ministrado pela escola única e comum, como um "dever" do Estado burguês, democrata e re publicano - "elemento primordial" da extensão da cidada nia. Um estudo da ação pedagógica do Estado francês da Terceira República~ desenvolvido a partir de depoimentos de professores do ensino primário da época, evidencia as implicações ideológicas do ensino público quando é promo vido por um Estado "ético e educador", por meio de uma escola que é eficazmente "constitutiva de cidadania". A análise das especificidades e impasses da constituição (ou da não constituição) da cidadania na sociedade brasileira fundamenta uma reflexão sobre as condições atuais da educação pública no Brasil, em que se des tacam tematicamente duas questões: o significado social do ensino profissionalizante e a seletividade da escola elementar, analisada prioritariamente a partir dos fatores externos à escola que a determinam ou seja, as condi çoes de vida das classes subalternas, brevemente enfocados com base na interpretação de dados estatísticos relativos ã evasio escolar e ao poder aquisitivo do s~lirio mínimo. A conjuntura presente de transformaçio política e institucional da sociedade brasileira é avaliada como pr~ pícia ã retomada da luta pela instrução elementar pública e gratuita numa escola única e comum, pelo prolongamento da escolaridade, pela melhor qualidade do ensino, de tal modo que a escola possa finalmente dar a sua contribuição imprescindível à extensão da cidadania a todos os brasileiros.

Optimization analysis of dual-purpose systems

This paper aims to analyze dual-purpose systems focusing the total cost optimization; a superstructure is proposed to present cogeneration systems and desalination technologies alternatives for the synthesis process. The superstructure consists of excluding components, gas turbines or conventional steam generators with excluding alternatives of supplying fuel for each combustion system. Also, backpressure or condensing/extraction steam turbine for supplying process steam could be selected. Finally one desalination unit chosen between electrically-driven or steam-driven reverse osmosis. multi-effect and multistage flash should be included. The analysis herein performed is based on energy and mass conservation equations, as well as the technological limiting equation of equipment. The results for ten different commercial gas turbines revealed that electrically-driven reverse osmosis was always chosen together with both natural gas and gasified biomass gas turbines. (C) 2009 Elsevier B.V. All rights reserved.

Passivity Versus Unilateral Angular Misfit: Evaluation of Stress Distribution on Implant-Supported Single Crowns: Three-Dimensional Finite Element Analysis

The aim of this study was to evaluate the effect of unilateral angular misfit of 100 Km on stress distribution of implant-supported single crowns with ceramic veneering and gold framework by three-dimensional finite element analysis. Two three-dimensional models representing a maxillary section of premolar region were constructed: group 1 (control)-crown completely adapted to the implant and group 2-crown with unilateral angular misfit of 100 Km. A vertical force of 100 N was applied on 2 centric points of the crown. The von Mises stress was used as an analysis criterion. The stress values and distribution in the main maps (204.4 MPa for group 1 and 205.0 MPa for group 2) and in the other structures (aesthetic veneering, framework, retention screw, implant, and bone tissue) were similar for both groups. The highest stress values were observed between the first and second threads of the retention screw. Considering the bone tissue, the highest stress values were exhibited in the peri-implant cortical bone. The unilateral angular misfit of 100 Km did not influence the stress distribution on the implant-supported prosthesis under static loading.

Machined and plastic copings in three-element prostheses with different types of implant-abutment joints: a strain gauge comparative analysis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

External Hexagon and Internal Hexagon in Straight and Offset Implant Placement: Strain Gauge Analysis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Straight and Offset Implant Placement under Axial and Nonaxial Loads in Implant-Supported Prostheses: Strain Gauge Analysis

Purpose: The aim of this in vitro study was to quantify strain development during axial and nonaxial loading using strain gauge analysis for three-element implant-supported FPDs, varying the arrangement of implants: straight line (L) and offset (O). Materials and Methods: Three Morse taper implants arranged in a straight line and three implants arranged in an offset configuration were inserted into two polyurethane blocks. Microunit abutments were screwed onto the implants, applying a 20 Ncm torque. Plastic copings were screwed onto the abutments, which received standard wax patterns cast in Co-Cr alloy (n = 10). Four strain gauges were bonded onto the surface of each block tangential to the implants. The occlusal screws of the superstructure were tightened onto microunit abutments using 10 Ncm and then axial and nonaxial loading of 30 Kg was applied for 10 seconds on the center of each implant and at 1 and 2 mm from the implants, totaling nine load application points. The microdeformations determined at the nine points were recorded by four strain gauges, and the same procedure was performed for all of the frameworks. Three loadings were made per load application point. The magnitude of microstrain on each strain gauge was recorded in units of microstrain (mu). The data were analyzed statistically by two-way ANOVA and Tukey's test (p < 0.05). Results: The configuration factor was statistically significant (p= 0.0004), but the load factor (p= 0.2420) and the interaction between the two factors were not significant (p= 0.5494). Tukey's test revealed differences between axial offset (mu) (183.2 +/- 93.64) and axial straight line (285.3 +/- 61.04) and differences between nonaxial 1 mm offset (201.0 +/- 50.24) and nonaxial 1 mm straight line (315.8 +/- 59.28). Conclusion: There was evidence that offset placement is capable of reducing the strain around an implant. In addition, the type of loading, axial force or nonaxial, did not have an influence until 2 mm.

Luminescence of europium(III) and manganese(II) in barium and zinc orthosilicate

The aim of this work is to report on the luminescence properties of BaZnSiO4 activated by Eu3+ and Mn2+ ions. Doped and undoped powder samples were prepared by solid-state reaction starting from oxides and carbonates or Ba2SiO4:Eu3+ and Zn2SiO4:Mn2+ precursors. X-ray diffraction powder data, IR vibrational, and UV-vis luminescence spectroscopies were carried out. Results showed that doped and undoped samples from both types of precursors have the same structure and crystallize with a superstructure of hexagonal kalsilite. Vibrational spectroscopy has confirmed the formation of a silicate group, which outlines differences between products and silicate precursors. The observed luminescence assigned to Eu3+ and Mn2+ transitions covered most parts of the visible spectrum, an important requirement for phosphors in fluorescent low-pressure mercury vapor lamps.

Formation of colloidal particles of hydrous iron oxide by forced hydrolysis

The mechanism of formation and growth of hydrous iron oxide (FeOOH) during the initial stages of forced hydrolyses of ferric chloride aqueous solution was studied by small angle X-ray scattering (SAXS). The effect of the hydrolysis temperature (60°C, 70°C and 80°C) and of the addition of urea on the formation of colloidal particles under isothermal conditions were investigated. Based on the experimental scattering functions in the Guinier range, we suggest the presence of elongated colloidal particles. The particle diameter and length, and their variation with time, were determined by fitting the form factor of prolate ellipsoids to the experimental scattering functions. We have assumed that our solutions are in a dilute state and that all colloidal particles are approximately of the same size. The colloidal particles have geometrical shapes similar to those of the subcrystals that build up the superstructure of β-FeOOH crystals, indicating that the formation of this hydrous iron oxide is governed by an aggregation process. Otherwise, the addition of urea hinders the growth and yields smaller particles, with a reduction in size greater than 50%. © 2000 Elsevier Science B.V. All rights reserved.

O Estado no sistema sociometabólico do capital: uma relação de complementaridade na base material

Pós-graduação em Ciências Sociais - FFC

Comunicação e ciberativismo: boicotes : novas práticas para o exercício da cidadania

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)