Local structure and near-infrared emission features of neodymium-based amine functionalized organic/inorganic hybrids

Nd3+-based organic/inorganic hybrids have potential application in the field of integrated optics. Attractive sol-gel derived di-urea and di-urethane cross-linked poly (oxyethylene) (POE)/siloxane hybrids (di-ureasils and di-urethanesils, respectively) doped with neodymium triflate (Nd(CF3SO3)(3)) were examined by Fourier transform mid-infrared (FT-IR), Raman (FT-Raman), Si-29 magic-angle spinning (MAS) nuclear magnetic resonance (NMR) and photoluminescence spectroscopies, and small-angle X-ray scattering (SAXS). The goals of this work were to determine which cation coordinating site of the host matrix (ether oxygen atoms or carbonyl oxygen atoms) is active in each of the materials analyzed, its influence on the nanostructure of the samples and its relation with the photoluminescence properties. The main conclusion derived from this study is that the hydrogen-bonded associations formed throughout the materials play a major role in the hybrids nanostructure and photoluminescence properties.

Hormonal therapy in the senescence: Prostatic microenvironment structure and adhesion molecules

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

Structure of thrombin complexed with selective non-electrophilic inhibitors having cyclohexyl moieties at P1

The crystal structures of five new non-electrophilic β-strand-templated thrombin active-site inhibitors have been determined bound to the enzyme. Four co-crystallize with hirugen and inhibitor isomorphously to produce thrombin-hirugen crystals (monoclinic, space group C2), while one co-crystallizes in the hexagonal system, space group P65. A 1,4-substituted cyclohexyl moiety is conserved at the P1 position of all the inhibitors, along with a fused hetero-bicyclic five- and six-membered ring that occupies the P2 site. Amino, amidino and aminoimidazole groups are attached to the cyclohexyl ring for recognition at the S1 specificity site, while benzylsulfonyl and diphenyl groups enhance the binding at the S3 subsite. The cyclohexyl groups at the P1 positions of three of the inhibitors appear to be in the energetically favored chair conformation, while the imidazole-substituted cyclohexyl rings are in a boat conformation. Somewhat unexpectedly, the two cyclohexyl-aminoimidazole groups bind differently in the specificity site; the unique binding of one is heretofore unreported. The other inhibitors generally mimic arginyl binding at S1. This group of inhibitors combines the nonelectrophilicity and selectivity of DAPA-like compounds and the more optimal binding features of the S1-S3 sites of thrombin for peptidic molecules, which results in highly potent (binding constants 12 nM-16 pM, one being 1.1 μM) and selective (ranging from 140 to 20 000 times more selective compared with trypsin) inhibitors of thrombin. The binding modes of these novel inhibitors are correlated with their binding constants, as is their selectivity, in order to provide further insight for the design of therapeutic antithrombotic agents that inhibit thrombin directly at the active site.

Length-weight relationships, condition and population structure of the genus Atlantoraja (Elasmobranchii, Rajidae, Arhynchobatinae) in Southeastern Brazilian waters, SW Atlantic Ocean

During the present study, 107 specimens of Atlantoraja castelnaui, 188 of A. platana, and 770 of A. cyclophora, were obtained by commercial vessels operating in Southeastern Brazil from March 2005 to April 2006. Males of A. castelnaui ranged from 17.9-111.0 cm and females from 17.4-116.0 cm total length. Males of A. platana ranged from 13.1-70.0 cm and females from 12.5-76.0 cm total length. Males of A. cyclophora ranged from 13.3-58.5 cm and females from 11.5-68.0 cm total length. Length-weight curves were sexually dimorphic in the three species. The analysis of the angular coefficient (b) demonstrated that growth (in weight) in relation to length was allometric (b>3) in males of A. castelnaui and A. platana, while isometric (b = 3) in females of these species. Conversely, growth of A. cyclphora was isometric in males, while in females it was allometric (b>3). The condition factor varied significantly throughout the year only in females of A. castelnaui.

Local electronic structure, optical bandgap and photoluminescence (PL) properties of Ba(Zr0.75Ti0.25)O3 powders

Ba(Zr0.75Ti0.25)O3 (BZT-75/25) powders were synthesized by the polymeric precursor method. Samples were structurally characterized by X-ray diffraction (XRD), Rietveld refinement, X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) techniques. Their electronic structures were evaluated by first-principle quantum mechanical calculations based on density functional theory at the B3LYP level. Their optical properties were investigated by ultraviolet-visible (UV-Vis) spectroscopy and photoluminescence (PL) measurements at room temperature. XRD patterns and Rietveld refinement data indicate that the samples have a cubic structure. XANES spectra confirm the presence of pyramidal [TiO5] clusters and octahedral [TiO6] clusters in the disordered BZT-75/25 powders. EXAFS spectra indicate distortion of Ti-O and Ti-O-Ti bonds the first and second coordination shells, respectively. UV-Vis absorption spectra confirm the presence of different optical bandgap values and the band structure indicates an indirect bandgap for this material. The density of states demonstrates that intermediate energy levels occur between the valence band (VB) and the conduction band (CB). These electronic levels are due to the predominance of 4d orbitals of Zr atoms in relation to 3d orbitals of Ti atoms in the CB, while the VB is dominated by 2p orbitals related to O atoms. There was good correlation between the experimental and theoretical optical bandgap values. When excited at 482 nm at room temperature, BZT-75/25 powder treated at 500 C for 2 h exhibited broad and intense PL emission with a maximum at 578 nm in the yellow region. © 2013 Elsevier Ltd. All rights reserved.

Seasonal variation in the copepod community structure from a tropical Amazon estuary, Northern Brazil

O presente estudo teve como objetivo principal avaliar a variação sazonal na estrutura da comunidade dos copépodos durante os meses de julho, setembro e novembro de 2003 (período seco) e janeiro, março e maio de 2004 (período chuvoso) no estuário do Curuçá, Norte do Brasil. As amostras foram coletadas nas marés de quadratura com auxílio de uma rede de plâncton com 200µm de abertura de malha, rebocada por meio de uma pequena embarcação a motor. As medidas de condutividade da água foram realizadas in situ utilizando-se um condutivímetro eletrônico e a salinidade foi posteriormente obtida através da transformação dos valores de condutividade. Os valores de salinidade variaram sazonalmente de 7, 2 ± 0, 1a 39, 2 ± 1, 8 (média ± desvio padrão), tendo sido principalmente influenciados pelas diferenças nas taxas de precipitação entre os períodos de amostragem estudados. Foram identificados no total 30 táxons, com Acartia tonsa constituindo a espécie mais representativa durante todo o período de estudo,seguida por Acartia lilljeborgii, Subeucalanus pileatus e Paracalanus quasimodo. Durante este trabalho, os valores de densidade, índices ecológicos e dominância das espécies de copépodos apresentaram um padrão sazonal claro, mostrando que a área estudada pode ser considerada sazonalmente heterogênea em relação a estes parâmetros investigados.

Trabalho docente universitário: participação dos professores na materialização da contrarreforma da educação superior na UFPA

O objetivo central deste estudo é analisar como o trabalho docente, desenvolvido por professores da Universidade Federal do Pará, materializa a contrarreforma da educação superior que tem como uma de suas centralidades a privatização/mercantilização da universidade pública. Considera que a investigação sobre o trabalho docente universitário, alterado em função do processo de contrarreforma da educação superior, pressupõe a compreensão da totalidade social, com seus condicionantes estruturais e conjunturais, ou seja, inserido no modo de produção capitalista. Dessa forma, analisa o trabalho docente, considerando sua natureza e especificidade, enquanto fração da classe-que-vive-do-trabalho, no contexto da crise estrutural do capital e do consequente processo de reestruturação produtiva, com a constituição do regime de acumulação flexível. Destaca o processo de contrarreforma da educação superior brasileira, orientada por organismos internacionais, principalmente o Banco Mundial, e efetivada a partir da atual LDB. Apresenta como hipótese de Tese que é, principalmente, por meio do trabalho docente que a contrarreforma da educação superior se efetiva, sendo que nesse processo, os professores identificam as mudanças em seu trabalho como consequência da privatização/mercantilização da universidade pública, porém, hegemonicamente não percebem que essas modificações estão articuladas na estrutura societal capitalista, legitimando, assim, a mesma. Dessa forma, com base em suportes teórico-metodológicos do materialismo histórico-dialético, analisa a concepção de universidade dos trabalhadores (a partir de indicadores, tais como: democracia, autonomia, prestação de serviços, relação universidade e mercado), para compreender os fundamentos político-ideológicos do trabalho desenvolvido por professores universitários. Foram utilizados dados estatísticos, documentos e entrevistas com docentes da Universidade Federal do Pará, analisados com base nos postulados bakhtinianos, da Análise do Discurso. Em suma, a pesquisa desenvolvida confirmou a hipótese de Tese anunciada, com o acréscimo da seguinte conclusão: o trabalho docente universitário insere-se no contexto da luta de classes e, assim sendo, essa resistência também implica na reafirmação de uma universidade pública e gratuita, diretamente vinculada aos interesses da classe-que-vive-do-trabalho.

Processamento e propriedades magnéticas de manganitas multiferróicas = Mise en forme et propriétés magnétiques de manganites multiferróïques

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Maternal obesity disturbs the postnatal development of gonocytes in the rat without impairment of testis structure at prepubertal age

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The community-level effect of light on germination timing in relation to seed mass: a source of regeneration niche differentiation

Within a community, species may germinate at different times so as to mitigate competition and to take advantage of different aspects of the seasonal environment (temporal niche differentiation). We illustrated a hypothesis of the combined effects of abiotic and biotic competitive factors on germination timing and the subsequent upscale effects on community assembly. We estimated the germination timing (GT) for 476 angiosperm species of the eastern Tibetan Plateau grasslands under two light treatments in the field: high (i.e. natural) light and low light. We also measured the shift in germination timing (SGT) across treatments for all species. Furthermore, we used phylogenetic comparative methods to test if GT and SGT were associated with seed mass, an important factor in competitive interactions. We found a significant positive correlation between GT and seed mass in both light treatments. Additionally, small seeds (early germinating seeds) tended to germinate later and large seeds (late germinating seeds) tended to germinate earlier under low light vs high light conditions. Low light availability can reduce temporal niche differentiation by increasing the overlap in germination time between small and large seeds. In turn, reduced temporal niche differentiation may increase competition in the process of community assembly.

Changes in the phytoplankton structure downstream a large reservoir: effects of tributaries on the assemblages attributes

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

Supramolecular organization-electrical properties relation in nanometric organic films

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

Titanium K-edge XAS study on local structure of Pb1-xCaxTiO3 ferroelectric ceramics

In order to characterize the local structure of Pb1-xCaxTiO3 (PCT) samples, Ti K-edge XANES measurements were performed and showed that Ca incorporation to PbTiO3 structure leads to a decreasing of local distortion of Ti atoms in relation to oxygen atoms at the TiO6 octahedra. Moreover, according to EXAFS measurements, the local structure around Ti atoms exhibits tetragonal symmetry with P4mm space group for samples with x <= 0.475, whereas orthorhombic symmetry with Pbnm space group was observed for x equals to 0.50 and 0.55.

Structure-activity relationship of mastoparan analogs: effects of the number and positioning of Lys residues on secondary structure, interaction with membrane-mimetic systems and biological activity

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