Structure and luminescence of Eu3+-doped class I siloxane-poly(ethylene glycol) hybrids

Transparent, flexible, and luminescent EU3+-doped siloxane-poly(ethylene glycol) (PEG) nanocomposites have been obtained by the sol-gel process. The inorganic (siloxane) and organic PEG phases are usually linked by weak bonds (hydrogen bonds or van der Waals forces), and small-angle X-ray scattering (SAXS) measurements suggest that the structure of these materials consists of fractal siloxane aggregates embedded in the PEG matrix. For low Eu3+ contents, n = 300 and n = 80, the aggregates are small and isolated and their fractal dimensions are 2.1 and 1.7, respectively. These values are close to those expected for gelation mechanisms consisting of reaction-limited cluster-cluster aggregation (RLCCA) and diffusion-limited cluster-cluster aggregation (DLCCA). For high Eu3+ content, SAYS results are consistent with a two-level structure: a primary level of siloxane aggregates and a second level, much larger, formed by the coalescence of the primary ones. The observed increase in the glass transition temperature for increasing Eu3+ content is consistent with the structural model derived from SAXS measurements. Extended X-ray absorption fine structure (EXAFS) and luminescence spectroscopy measurements indicate that under the experimental conditions utilized here Eu3+ ions do not strongly interact with the polymeric phase.

Photopatternable di-ureasil-zirconium oxocluster organic-inorganic hybrids as cost effective integrated optical substrates

Organic-inorganic hybrids containing methacrylic acid (McOH, CH(2)= C(CH(3))COOH)) modified zirconium tetrapropoxide, Zr(OPr(n))(4), classed as di-ureasil-zirconium oxo-cluster hybrids, have been prepared and structurally characterized by X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies, Si and C nuclear magnetic resonance (NMR), and atomic force microscopy (AFM). XRD and SAXS results have pointed out the presence of Si- and Zr-based nanobuilding blocks (NBBs) dispersed into the organic phase. Inter-NBBs correlation distances have been estimated for the pure di-ureasil and a model compound obtained. by hydrolysis/condensation of Zr(OPr(n))(4):McOH (molar ratio 1: 1): d(Si) approximate to 26 +/- 1 angstrom and d(Zr) approximate to 16 +/- 1 angstrom, respectively. In the case of the di-ureasil-zirconium oxo-cluster hybrids, these distances depend on the Zr relative molar percentage (rel. mol. Zr %) (d(Si) ranges from 18 to 25 angstrom and d(Zr) from 14 to 23 angstrom, as the rel. mol. Zr % increases from 5 to 75), suggesting that the Si- and Zr-based clusters are interconstrained. Complementary data from FT-IR, FT-Raman, (29)Si and (13)C NMR, and AFM support to a structural model where McOH-modified Zr-based NBBs (Zr-OMc) are present over the whole range of composition. At low Zr-OMc contents (rel. mol. Zr % <30) the clusters are well-dispersed within the di-ureasil host, whereas segregation occurs at the 0.1 mu m scale at high Zr-OMc concentration (rel. mol. Zr % = 50). No Zr-O-Si heterocondensation has been discerned. Monomode waveguides, diffractions gratings, and Fabry-Perot cavities have been written through the exposure of the hybrid monoliths to UV light. FT-Raman has shown that the chemical process that takes place under illumination is the polymerization of the methacrylate groups of the Zr-OMc NBBs. The guidance region in patterned channels is a Gaussian section located below the exposed surface with typical dimensions of 320 mu m wide and 88 mu m deep. The effective refractive index is 1.5162 (maximum index contrast on the order of 1 x 10(-4)) and the reflection coeficient of the Fabry-Perot cavity (formed by a grating patterned into a 0.278 cm channel) is 0.042 with a free spectral range value of 35.6 GHz.

MS2SV: Tradução de modelos em Simulink para VHDL-AMS

This paper presents a methodology and a tool for projects involving analogue and digital signals. A sub-systems group was developed to translation a Matlab/Simulink model in the correspondent structural model described in VHDL-AMS. The developed translation tool, named of MS(2)SV, can reads a file containing a Simulink model translating it in the correspondent VHDL-AMS structural code. The tool also creates the directories structure and necessary files to simulate the model translated in System Vision environment. Three models of D/A converters available commercially that use R-2R ladder network were studied. This work considers some of challenges set by the electronic industry for the further development of simulation methodologies and tools in the field of mixed-signal technology. Although the objective of the studies has been the D/A converter, the developed methodology has potentiality to be extended to consider control systems and mechatronic systems.

First principles calculations on the origin of violet-blue and green light photoluminescence emission in SrZrO3 and SrTiO3 perovskites

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

Analysis of agonist and antagonist effects on thyroid hormone receptor conformation by hydrogen/deuterium exchange

Thyroid hormone receptors (TRs) are ligand-gated transcription factors with critical roles in development and metabolism. Although x-ray structures of TR ligand-binding domains (LBDs) with agonists are available, comparable structures without ligand (apo-TR) or with antagonists are not. It remains important to understand apo-LBD conformation and the way that it rearranges with ligands to develop better TR pharmaceuticals. In this study, we conducted hydrogen/deuterium exchange on TR LBDs with or without agonist (T 3) or antagonist (NH3). Both ligands reduce deuterium incorporation into LBD amide hydrogens, implying tighter overall folding of the domain. As predicted, mass spectroscopic analysis of individual proteolytic peptides after hydrogen/ deuterium exchange reveals that ligand increases the degree of solvent protection of regions close to the buried ligand-binding pocket. However, there is also extensive ligand protection of other regions, including the dimer surface at H10-H11, providing evidence for allosteric communication between the ligand-binding pocket and distant interaction surfaces. Surprisingly, Cterminal activation helix H12, which is known to alter position with ligand, remains relatively protected from solvent in all conditions suggesting that it is packed against the LBD irrespective of the presence or type of ligand. T 3, but not NH3, increases accessibility of the upper part of H3-H5 to solvent, and we propose that TR H12 interacts with this region in apo-TR and that this interaction is blocked by T 3 but not NH3.Wepresent data from site-directed mutagenesis experiments and molecular dynamics simulations that lend support to this structural model of apo-TR and its ligand-dependent conformational changes. (Molecular Endocrinology 25: 15-31, 2011). Copyright © 2011 by The Endocrine Society.

The Mode of Action of Recombinant Mycobacterium tuberculosis Shikimate Kinase: Kinetics and Thermodynamics Analyses

Tuberculosis remains as one of the main cause of mortality worldwide due to a single infectious agent, Mycobacterium tuberculosis. The aroK-encoded M. tuberculosis Shikimate Kinase (MtSK), shown to be essential for survival of bacilli, catalyzes the phosphoryl transfer from ATP to the carbon-3 hydroxyl group of shikimate (SKH), yielding shikimate-3-phosphate and ADP. Here we present purification to homogeneity, and oligomeric state determination of recombinant MtSK. Biochemical and biophysical data suggest that the chemical reaction catalyzed by monomeric MtSK follows a rapid-equilibrium random order of substrate binding, and ordered product release. Isothermal titration calorimetry (ITC) for binding of ligands to MtSK provided thermodynamic signatures of non-covalent interactions to each process. A comparison of steady-state kinetics parameters and equilibrium dissociation constant value determined by ITC showed that ATP binding does not increase the affinity of MtSK for SKH. We suggest that MtSK would more appropriately be described as an aroL-encoded type II shikimate kinase. Our manuscript also gives thermodynamic description of SKH binding to MtSK and data for the number of protons exchanged during this bimolecular interaction. The negative value for the change in constant pressure heat capacity (ΔCp) and molecular homology model building suggest a pronounced contribution of desolvation of non-polar groups upon binary complex formation. Thermodynamic parameters were deconvoluted into hydrophobic and vibrational contributions upon MtSK:SKH binary complex formation. Data for the number of protons exchanged during this bimolecular interaction are interpreted in light of a structural model to try to propose the likely amino acid side chains that are the proton donors to bulk solvent following MtSK:SKH complex formation. © 2013 Rosado et al.

Modelagem molecular da Chiquimato quinase de Mycobacterium leprae

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Caracterização molecular e bioquímica de uma esterase macho-específica em Zaprionus indianus

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo das propriedades ópticas, linear e não linear, e elétrica dos vidros da família Li2O-TeO2-WO3

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Geomorfologia do baixo curso do rio Ivinhema, MS: uma abordagem morfogenética e morfoestrutural

Pós-graduação em Geociências e Meio Ambiente - IGCE

Representação iterativa: um modelo para repositórios digitais

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Clonagem, expressão e caracterização de duas lipoxigenases de Shewanella woodyi

Pós-graduação em Microbiologia Agropecuária - FCAV

Tramas de subjetivação: analítica da fabricação do PARFOR-Pedagogia-Campus de Bragança/UFPA

O modelo de formação de professores brasileiro refere-se à democratização do país e as mudanças sociais alavancadas na década de 1980, tendo como marco legal a Constituição de 1988 e as reformas educacionais e curriculares que a sucederam. Este trabalho constitui-se em uma análise arqueogenealógica foucaultiana das práticas discursivas arquitetadas sobre o curso de Pedagogia do Plano Nacional de Formação de Professores da Educação Básica (PARFOR) do Campus Universitário de Bragança – Universidade Federal do Pará (UFPA). Partimos do estudo arqueológico das emergências históricas da formação de professores para localizarmos e darmos visibilidade a arena da formação docente como contingência contemporânea advinda de forças capilares que objetivam e, ao mesmo tempo, subjetivam o professor em formação. Sustentamo-nos na hipótese de que habitam, nesse jogo de saber-poder, tramas de subjetivação corporificadas no currículo sob em práticas de governamentalização. Tais tramas, por sua vez, culminam na produção de documentos dentre os quais alguns foram escolhidos para compor a análise crítica desse trabalho. Desse modo, objetivamos problematizar a formação enquanto fabricação do aluno PARFOR-Pedagogia, com ênfase no currículo elaborado pelo Campus de Bragança/UFPA visando percebê-lo em sua articulação com determinadas urgências de formação e regulação de professores. A pesquisa teve como fonte documentos que instalam a política de formação de professores no país, encarando-os como monumentos com efeitos na objetivação e subjetivação dos sujeitos, e formação de professores como prática histórica e dispositivo estratégico de governamentalidade. Organizando-se os documentos em subarquivos, a análise foi conduzida pela problematização – arqueológica e genealógica de Michel Foucault, articulada aos dispositivos de Gilles Deleuze e às práticas históricas de Paul Veyne. Fincado como ação afirmativa e conectado ao rol das políticas educacionais contemporâneas, o PARFOR apesar de ter impulsionado a formação em serviço, os sujeitos que dele fazem parte são objetivados ainda por prescrições curriculares destacadamente disciplinares e generalistas, descritas paradoxalmente no Projeto Pedagógico do Curso de Pedagogia e nos Planos de Curso como estratégia interdisciplinar de formação de professores. Concomitante a isso, os sujeitos são subjetivados por um devir minoritário em função do modelo estrutural que a política foi arquitetada, exercendo seu poder por práticas de resistência. De acordo com as práticas analisadas nesse estudo, o PARFOR-Pedagogia do Campus de Bragança/UFPA é fabricado por tramas históricas de subjetivação, as quais se sustentam tanto na govenamentalidade quanto em estratégias biopolíticas acionadas por dispositivos curriculares que forjam e ao mesmo tempo são forjados pelos jogos de saber-poder-resistência.

Vidros e vitrocerâmicas em sistemas oxifluoretos

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

Análise termoeconômica de uma mini-estação de tratamento de esgoto com auto-suficiência energética

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)