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.

Squeeze flow viscoelasticity of electrorheological fluids based on microcrystalline cellulose

Dynamic viscoelasticity of electrorheological fluids based on microcrystalline cellulose/castor oil suspensions was experimentally investigated in squeeze flow. The dependence of storage modulus G' and loss modulus G" parallel to external electric field on electric fields and strain amplitudes is presented. The experiments show that, when external electric field is higher than the critical field, the viscoelasticity of the ER fluids converts from linear to nonlinear, and the ER fluids transfer from solid-like state to fluid state with the growth of strain amplitude. The influences of strain amplitude and oscillatory frequency on the nonlinearity of viscoelasticity were also studied.

Confessionalism and conversion in the Reformation

Recent research on the Reformation has been concerned with the process by which lay people acquired a religious identity, whether it began merely as an act of political obedience or by a sudden ‘conversion’ to new doctrines. Confessional politics made it imperative for rulers to try to control the religious allegiances of their people, but the doctrine of conversion (as a spiritual change) made this theoretically impossible. Instead, a ‘culture of persuasion’ developed by which clerical and secular rulers sought to persuade their people to accept teachings authorized by the state. The possibility of religious dissent, of converting away from the state-sanctioned denomination, made conversion an issue whose importance was far greater than the actual number of converts. The study of confessionalism and conversion emphasises two theses fundamental to Reformation studies: that the era produced radical changes in the ways that people thought about their personal and communal identities, and that it made individuals’ religious choices the urgent concern of their governors.

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.

Allogeneic apoptotic thymocyte-stimulated dendritic cells expand functional regulatory T cells

P>Dendritic cells (DCs) play an important role in the clearance of apoptotic cells. The removal of apoptotic cells leads to peripheral tolerance, although their role is still not clear. We show that the uptake of apoptotic thymocytes by DCs converts these cells into tolerogenic DCs resistant to maturation by lipopolysaccharide, modulating the production of interleukin-12 and up-regulating the expression of transforming growth factor-beta(1) latency associated peptide. We also observed that DCs pulsed with apoptotic cells in the allogeneic context were more efficient in the expansion of regulatory T cells (Tregs), and that this expansion requires contact between DCs and the T cell. The Tregs sorted from in vitro culture suppressed the proliferation of splenocytes in vitro in a specific and non-specific manner. In the in vivo model, the transfer of CD4+ CD25- cells to Nude mice induced autoimmunity, with cell infiltrate found in the stomach, colon, liver and kidneys. The co-transfer of CD4+ CD25- and CD4+ CD25+ prevented the presence of cell infiltrates in several organs and increased the total cell count in lymph nodes. Our data indicate that apoptotic cells have an important role in peripheral tolerance via induction of tolerogenic DCs and CD4+ CD25+ Foxp3+ cells that present regulatory functions.

Template-based quadrilateral mesh generation from imaging data

This paper describes a novel template-based meshing approach for generating good quality quadrilateral meshes from 2D digital images. This approach builds upon an existing image-based mesh generation technique called Imeshp, which enables us to create a segmented triangle mesh from an image without the need for an image segmentation step. Our approach generates a quadrilateral mesh using an indirect scheme, which converts the segmented triangle mesh created by the initial steps of the Imesh technique into a quadrilateral one. The triangle-to-quadrilateral conversion makes use of template meshes of triangles. To ensure good element quality, the conversion step is followed by a smoothing step, which is based on a new optimization-based procedure. We show several examples of meshes generated by our approach, and present a thorough experimental evaluation of the quality of the meshes given as examples.

Sol-gel prepared AlPO(4) with incorporating Rhodamine 6G

Rhodamine 6G (RH6G) laser dye-doped AlPO(4) xerogel and glass were prepared via a simple sol-gel route by one-step process and two-step process, respectively. The aggregating behavior of dyes in xerogel and glass was studied by excitation and emission spectra. The results indicated the dye aggregates become significantly weak in AlPO(4) glass than in xerogel, which might be attributed to the enhanced interactions between dye and AlPO(4) network as well as the nano-scale separation of dye by the mesoporous structure of AlPO(4) glass. The (27)Al MAS NMR of AlPO(4) glass confirms the interaction of RH6G with AlPO(4) glass network. Incorporation of RH6G into AlPO(4) glass converts Al(4) to Al(6) units, resulting in the increase of Al(6) concentration with the doped RH6G concentration. (C) 2010 Elsevier B.V. All rights reserved.

Analytical Assessment of a Home Made Capillary Electrophoresis Equipment with Linear Charge Coupled Device for Visible Light Absorption Detection in the Determination of Food Dyes

The performance of modular home made capillary electrophoresis equipment with spectrophotometric detection, at a visible region by means of a miniaturized linear charge coupled device, was evaluated for the determination of four food dyes. This system presents a simple but efficient home made cell detection scheme. A computer program that converts the spectral data after each run into the electropherograms was developed to evaluate the analytical parameters. The dyes selected for analytical evaluation of the system were Brilliant Blue FCF, Fast Green FCF, Sunset Yellow FCF, and Amaranth. Separation was carried out in a 29cm length and 75 mu m I.D fused silica capillary, using 10mmolL-1 borate buffer at pH 9, with separation voltage of 7.5kV. The detection limits for the dyes were between 0.3 and 1.5mgL-1 and the method presented adequate linearity over the ranges studied, with correlation coefficients greater than 0.99. The method was applied for determination and quantification of these dyes in fruit juices and candies.

Acumulação de competências tecnológicas e os processos subjacentes de aprendizagem na indústria Mmtal - mecânica : o caso da empresa AGCO comércio e indústria LTDA em Santa Rosa - RS

This dissertation enfoca the relationship between technological competences accumulation and the learning underlying processes. This relationship is examined in the company AGCO Comércio and Indústria Ltda, during the period of 1970 to 2000. It is of a company metal-mechanics, agricultural machines manufacturer. In other words, the dissertation examines the processes technological learning implications for aA technological competences accumulation in the company in study. The dissertation enfoca the competences accumulation for three technological functions: processes and organization, products and equipments. The learning processes are examined to the light of four characteristic: variety, intensity, operation and interaction, from the structure existing analysis use in the literature. Based on study of individual case, this study found that the technological competences ways to accumulation in the studied company are associates to the several processes used to acquire technological knowledge and converts him in organizacional. Ademais, the simple incidence of these processes in the company didn't guarantee in the company a positive implication for the technological competences accumulation. The company accumulated level middleman-superior technological competence (level 6) to accomplish production and function products function processes and organization activities, and intermediary level (level 5) to accomplish function equipments activities. In haves to characteristic key, the learning processes introduce an oscillation differentiated along time: the variety oscillated of moderated the several; the intensity of intermittent the continuous; the operation of bad the good; and the interaction of weak the strong. Through the existing structure use in the literature, however applied to a previous studies different industry, this dissertation suggests that must there be an organized , continuous effort and integrated for the knowledge generation and sowing in every company in order to the technological training accumulation be accelerated in the company.

The rite of passage from regular to connoisseur consumer: the role of the taste transformation ritual in the specialty coffee context

Apesar de o campo da cultura de consumo ter abordado o papel do ritual no consumo, definindo e descrevendo este constructo e explicando suas dimensões, significados culturais, elementos, componentes e práticas, assim como revelando a diferenciação nas práticas dos consumidores, nenhuma pesquisa ainda identificou como os consumidores, por meio de práticas de ritual, estabelecem e manipulam suas próprias diferenciações em relação a outros consumidores durante o rito de passagem deles de uma categoria cultural de pessoa para outra. Tendo como base conceitos-chaves da teoria sobre ritual, minha pesquisa aborda o papel do ritual no consume de apreciação. Conduzindo um estudo etnográfico sobre consumo de apreciação de cafés especiais, eu realizei uma imersão no campo, visitando e observando consumidores em cafeterias independentes de destaque na América do Norte – Toronto, Montreal, Seattle e Nova York – de agosto de 2013 a julho de 2014. Eu também realizei uma imersão no contexto de cafés especiais no Brasil em Belo Horizonte e São Paulo, de agosto de 2014 a janeiro de 2015, para comparar e contrastar as culturas de consume de cafés especiais de Brasil, Estados Unidos e Canadá. Eu usei entrevistas longas, observação participante, netnografia, introspecção e análise histórica de artigos de jornais para coletar os dados, que foram interpretados utilizando a abordagem hermenêutica, comparando os consumidores em diferentes estágios durante o rito de passagem de apreciação. Para estender meu entendimento sobre o consumo de apreciação, eu também coletei dados sobre o contexto de consumo de vinho. Nesta tese, eu introduzo a ideia de ritual de transformação do gosto, teorizando sobre o processo do rito de passagem de apreciação, que converte consumidores regulares em consumidores apreciadores. Minha pesquisa revela que consumidores apreciadores são amadores em diferentes estágios do rito de passagem de apreciação. Eles se transformam pelo estabelecimento e reforço de oposições entre o consume de massa e de apreciação. O ritual de transformação do gosto envolve os seguintes elementos: (1) variação nas escolhas de produtos de alta qualidade, (2) o lugar para realizar a degustação, (3) o momento da degustação, (4) o ato de degustar, (5) investimento de tempo e dinheiro, (6) aumento do capital subcultural e social, (7) perseverança no rito de passagem. Os consumidores apreciadores participam da comunidade de consumo de apreciação. Essa comunidade heterogênea é composta por profissionais excelentes, apreciadores e consumidores regulares. As forças que direcionam a comunidade, de acordo com o que foi identificado no estudo, são a produção de capital social e subcultural, emulação do profissional e das práticas de ritual de consumo, tensões de performance entre os membros da comunidade, amizade comercial e jogo de status. Eu desenvolvo uma ampla consideração teórica que desenvolve e estende um número de conceitos em relação a ritual e consumo, gosto, comunidade heterogênea e consumidores apreciadores.

Leitora-criadora: a experiência situada na construção dramatúrgica

This study has the purpose of investigating the term reader-creator , on the textual aspects of the dramatical works A Morte nos Olhos , A Memória Ferida and Na Outra Margem (2010) by Antonia Pereira Bezerra. In this sense, we propose an analysis of these works based on author‟s life experience as creative matter for a autofictional narrative, highlighting the relations between the autobiographical elements (LEJEUNE, 2008; DOSSE, 2009) and fictional elements in the construction of dramatic narratives. The theoretical analysis pervades the studies fields of Reception Aesthetics (ISER, 1996), memory (RICOUER, 2007) and narrative (RICOEUR, 2010), evidencing the relation between the author and the pursuit of her memories and life experiences, the matter to elaboration of writing. Then we intend thinking a reader-creator of herself, that at the same time she seeks in her memories the biographic aspects to her narrative, she converts this reality with the insertion of fictional elements from the imagination (SARTRE, 2008)

Algorithm for probing the unitarity of topologically massive models

An uncomplicated and easy handling prescription that converts the task of checking the unitarity of massive, topologically massive, models into a straightforward algebraic exercise, is developed. The algorithm is used to test the unitarity of both topologically massive higher-derivative electromagnetism (TMHDE) and topologically massive higher-derivative gravity (TMHDG). The novel and amazing features of these effective field models are also discussed.

New class of spin projection operators for 3D models

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Temperature dependence and magnetocrystalline anisotropy studies of self-assembled L1(0)-Fe55Pt45 ferromagnetic nanocrystals

Temperature dependence and uniaxial magnetocrystalline anisotropy properties of the chemically synthesized 4 nm L1(0)-Fe55Pt45 nanoparticle assembly by a modified polyol route are reported. As-prepared nanoparticles are superparamagnetic presenting fcc structure, and annealing at 550 degrees C converts the assembly into ferromagnetic nanocrystals with large coercivity (H-C>1 T) in an L1(0) phase. Magnetic measurements showed an increasing in the ferromagnetically ordered fraction of the nanoparticles with the annealing temperature increases, and the remanence ratio, S=M-R/M-S congruent to 0.76, suggests an (111) textured film. A monotonic increase of the blocking temperature T-B, the uniaxial magnetocrystalline anisotropy constant K-U, and the coercivity H-C with increasing annealing temperature was observed. Magnetic parameters indicate an enhancement in the magnetic properties due to the improved Fe55Pt45 phase stabilizing, and the room-temperature stability parameter of 67, which indicates that the magnetization should be stable for more than ten years, makes this material suitable for ultrahigh-density magnetic recording application.(c) 2007 American Institute of Physics.

Arrays of gold microelectrodes made from split integrated circuit chips

A simple and inexpensive way to fabricate arrays of gold microelectrodes is proposed. Integrated circuit chips are sawed through their middle, normal to the longest axis, leading to destruction of the silicon circuit and rupture of the gold wires that interconnect it with the external terminals. Polishing the resulting rough surface converts the tips of the wires embedded in the chip halves into arrays of gold microdisks of about 25 mu m diameter. The number of active microelectrodes (MEs), of an array depends on the number of pins in the chip, n, being typically (n/2)-4. These MEs can be used individually or externally interconnected in any combination. X-ray images of the chips and micrographs of the resulting surface of the polished arrays have revealed variable distances between neighbor MEs, which are, however, larger than 10 times the radius of the disks. This feature of the MEs prevents diffusional cross-talk between electrodes. The use of these microdisk electrodes for analytical purposes exhibits sigmoidal voltammograms, and chronoamperometric experiments confirm the nonlinear i vs. t(1/2) plots, typical for processes where radial diffusion prevails. Satisfactory uniformity was observed for the response of each electrode of an array, indicating similarity of geometry and disk areas. The potentialities of these MEs were demonstrated by the determination of cadmium at ppb levels using square wave voltammetry with preconcentration. Due to the relative ease with which these MEs can be manufactured and their good performance in (chemical) analysis, wide applications in electrochemistry and electroanalysis is envisioned.