Functional model for catecholase-like activity: A mechanistic approach with manganese(III) complexes of salen type Schiff base ligands

Three new Mn(III) complexes [MnL1(OOCH)(OH2)] (1), [MnL2(OH2)(2)][Mn2L22(NO2)(3)] (2) and [Mn2L21(NO2)(2)] (3) (where H2L1 = H(2)Me(2)Salen = 2,7-bis(2-hydroxyphenyl)-2,6-diazaocta-2,6-diene and H2L2 = H(2)Salpn = 1,7-bis(2-hydroxyphenyl)-2,6-diazahepta-1,6-diene) have been synthesized. X-ray crystal structure analysis reveals that 1 is a mononuclear species whereas 2 contains a mononuclear cationic and a dinuclear nitrite bridged (mu-1 kappa O:2 kappa O') anionic unit. Complex 3 is a phenoxido bridged dimer containing terminally coordinated nitrite. Complexes 1-3 show excellent catecholase-like activity with 3,5-di-tert-butylcatechol (3,5-DTBC) as the substrate. Kinetic measurements suggest that the rate of catechol oxidation follows saturation kinetics with respect to the substrate and first order kinetics with respect to the catalyst. Formation of bis(mu-oxo)dimanganese(III,III) as an intermediate during the course of reaction is identified from ESI-MS spectra. The characteristic six line EPR spectra of complex 2 in the presence of 3,5-DTBC supports the formation of manganese(II)-semiquinonate as an intermediate species during the catalytic oxidation of 3,5-DTBC.

Synthesis, crystal structure, and catecholase activity of three trinuclear heterometallic NiII2-MnII complexes derived from a salen-type Schiff base ligand

Three new trinuclear heterometallic nickel(II)manganese(II) complexes, [(NiL)2Mn(NCS)2] (1), [(NiL)2Mn(NCO)2] (2), and [{NiL(EtOH)}2Mn(NO2)2]center dot 2EtOH (3), have been synthesized by using [NiL] as the so-called ligand complex [where H2L = N,N'-bis(salicylidene)-1,3-propanediamine] and have been structurally characterized. Crystal structure analyses revealed that complexes 1 and 2 are angular trinuclear species, in which two terminal four-coordinate square planar [NiL] moieties are coordinated to a central MnII through double phenoxido bridges. The MnII is in a six-coordinate distorted octahedral environment that is bonded additionally to two mutually cis nitrogen atoms of terminal thiocyanate (in 1) and cyanate (in 2). In complex 3, in addition to the double phenoxo bridge, the two terminal NiII ions are linked to the central MnII by means of a nitrite bridge (1?N:2?O) that, together with a coordinated ethanol molecule, gives rise to an octahedral environment around the NiII ions and consequently the structure becomes linear. Catecholase activity of these three complexes was examined by using 3,5-di-tert-butylcatechol (3,5-DTBC) as the substrate. All three complexes mimic catecholase activity and the rate of catechol oxidation follows saturation kinetics with respect to the substrate and first-order kinetics with respect to the catalyst. The EPR spectra of the complexes exhibit characteristic six line spectra, which indicate the presence of high-spin octahedral MnII species in solution state. The ESI-MS positive spectrum of 1 in the presence of 3,5-DTBC has been recorded to investigate possible complexsubstrate intermediates.

Modeling image motion in airborne Three-Line-Array (TLA) push-broom cameras

This paper presents an image motion model for airborne three-line-array (TLA) push-broom cameras. Both aircraft velocity and attitude instability are taken into account in modeling image motion. Effects of aircraft pitch, roll, and yaw on image motion are analyzed based on geometric relations in designated coordinate systems. The image motion is mathematically modeled by image motion velocity multiplied by exposure time. Quantitative analysis to image motion velocity is then conducted in simulation experiments. The results have shown that image motion caused by aircraft velocity is space invariant while image motion caused by aircraft attitude instability is more complicated. Pitch,roll and yaw all contribute to image motion to different extents. Pitch dominates the along-track image motion and both roll and yaw greatly contribute to the cross-track image motion. These results provide a valuable base for image motion compensation to ensure high accuracy imagery in aerial photogrammetry.

Modelling the line variations from the wind-wind shock emissions of WR 30a

The study of Wolf-Rayet stars plays an important role in evolutionary theories of massive stars. Among these objects, similar to 20 per cent are known to be in binary systems and can therefore be used for the mass determination of these stars. Most of these systems are not spatially resolved and spectral lines can be used to constrain the orbital parameters. However, part of the emission may originate in the interaction zone between the stellar winds, modifying the line profiles and thus challenging us to use different models to interpret them. In this work, we analysed the He II lambda 4686 angstrom + C IV lambda 4658 angstrom blended lines of WR 30a (WO4+O5) assuming that part of the emission originate in the wind-wind interaction zone. In fact, this line presents a quiescent base profile, attributed to the WO wind, and a superposed excess, which varies with the orbital phase along the 4.6-d period. Under these assumptions, we were able to fit the excess spectral line profile and central velocity for all phases, except for the longest wavelengths, where a spectral line with constant velocity seems to be present. The fit parameters provide the eccentricity and inclination of the binary orbit, from which it is possible to constrain the stellar masses.

Clinical and molecular delineation of the 17q21.31 microdeletion syndrome

Background: The chromosome 17q21.31 microdeletion syndrome is a novel genomic disorder that has originally been identified using high resolution genome analyses in patients with unexplained mental retardation. Aim: We report the molecular and/or clinical characterisation of 22 individuals with the 17q21.31 microdeletion syndrome. Results: We estimate the prevalence of the syndrome to be 1 in 16 000 and show that it is highly underdiagnosed. Extensive clinical examination reveals that developmental delay, hypotonia, facial dysmorphisms including a long face, a tubular or pear-shaped nose and a bulbous nasal tip, and a friendly/amiable behaviour are the most characteristic features. Other clinically important features include epilepsy, heart defects and kidney/urologic anomalies. Using high resolution oligonucleotide arrays we narrow the 17q21.31 critical region to a 424 kb genomic segment (chr17: 41046729-41470954, hg17) encompassing at least six genes, among which is the gene encoding microtubule associated protein tau (MAPT). Mutation screening of MAPT in 122 individuals with a phenotype suggestive of 17q21.31 deletion carriers, but who do not carry the recurrent deletion, failed to identify any disease associated variants. In five deletion carriers we identify a <500 bp rearrangement hotspot at the proximal breakpoint contained within an L2 LINE motif and show that in every case examined the parent originating the deletion carries a common 900 kb 17q21.31 inversion polymorphism, indicating that this inversion is a necessary factor for deletion to occur (p< 10(25)). Conclusion: Our data establish the 17q21.31 microdeletion syndrome as a clinically and molecularly well recognisable genomic disorder.

An orthotopic skull base model of malignant meningioma

Meningioma tumor growth involves the subarachnoid space that contains the cerebrospinal fluid. Modeling tumor growth in this microenvironment has been associated with widespread leptomeningeal dissemination, which is uncharacteristic of human meningiomas. Consequently, survival times and tumor properties are varied, limiting their utility in testing experimental therapies. We report the development and characterization of a reproducible orthotopic skull-base meningioma model in athymic mice using the IOMM-Lee cell line. Localized tumor growth was obtained by using optimal cell densities and matrigel as the implantation medium. Survival times were within a narrow range of 17-21 days. The xenografts grew locally compressing surrounding brain tissue. These tumors had histopathologic characteristics of anaplastic meningiomas including high cellularity, nuclear pleomorphism, cellular pattern loss, necrosis and conspicuous mitosis. Similar to human meningiomas, considerable invasion of the dura and skull and some invasion of adjacent brain along perivascular tracts were observed. The pattern of hypoxia was also similar to human malignant meningiomas. We use bioluminescent imaging to non-invasively monitor the growth of the xenografts and determine the survival benefit from temozolomide treatment. Thus, we describe a malignant meningioma model system that will be useful for investigating the biology of meningiomas and for preclinical assessment of therapeutic agents.

Accumulation of (5 ` S)-8,5 `-cyclo-2 `-deoxyadenosine in organs of Cockayne syndrome complementation group B gene knockout mice

Cockayne syndrome (CS) is a human genetic disorder characterized by sensitivity to UV radiation, neurodegeneration, premature aging among other phenotypes. CS complementation group B (CS-B) gene (csb) encodes the CSB protein (CSB) that is involved in base excision repair of a number of oxidatively induced lesions in genomic DNA in vivo. We hypothesized that CSB may also play a role in cellular repair of the DNA helix-distorting tandem lesion (5`S)-8,5`-cyclo-2`-deoxyadenosine (S-cdA). Among many DNA lesions. S-cdA is unique in that it represents a concomitant damage to both the sugar and base moieties of the same nucleoside. Because of the presence of the C8-C5` covalent bond, S-cdA is repaired by nucleotide excision repair unlike most of other oxidatively induced lesions in DNA, which are subject to base excision repair. To test our hypothesis, we isolated genomic DNA from brain, kidney and liver of wild type and csb knockout (csb(-/-)) mice. Animals were not exposed to any exogenous oxidative stress before the experiment. DNA samples were analysed by liquid chromatography/mass spectrometry with isotope-dilution. Statistically greater background levels of S-cdA were observed in all three organs of csb(-/-) mice than in those of wild type mice. These results suggest the in vivo accumulation of S-cdA in genomic DNA due to lack of its repair in csb(-/-) mice. Thus, this study provides, for the first time, the evidence that CSB plays a role in the repair of the DNA helix-distorting tandem lesion S-cdA. Accumulation of unrepaired S-cdA in vivo may contribute to the pathology associated with CS. Published by Elsevier B.V.

Spectroscopic investigation of the interactions between emeraldine base polyaniline and Eu(III) ions

The interactions of emeraldine base form of polyaniline (EB-PANI) and Eu(III) ions in 1-methyl-2-pyrrolidinone (NMP) solution and in films have been investigated by UV-vis-NIR, resonance Raman. luminescence and electron paramagnetic resonance (EPR) spectroscopies. These spectroscopic techniques allowed to characterize quinone and semiquinone segments in the polymeric chains. and the oxidation state of europium ions in Eu-PANI samples. For high values of Eu(III)/N molar ratio (24/1) the presence of a weak polaronic absorption band at 980 nm in UV-vis-NIR spectrum and the observation of bands at 1330 and 1378 (nu(center dot)(C-N+)) cm(-1) due to emeraldine salt in the Raman spectrum at 1064 nm indicate a low doping degree. Oxidation of EB-PANI to pernigraniline base (PB-PANI) occurs in diluted solutions. The experimental data showed that the solvent plays an important role on the nature of formed species. The narrow EPR signal at g = 2.006 (line width 8G) confirms the presence of PANI radical cations in Eu-PANI film. The absence of broad signal characteristic of Eu(II) in EPR spectrum suggested that europium ions are primarily at Eu(III) oxidation state. The luminescence spectra of Eu-PANI film presented emission bands at 405 and 418 nm assigned to PANI moieties and bands at 594,615 and 701 nm assigned to (5)D(0) -> (7)F(J) (J = 1, 2 and 4, respectively) transitions of Eu(III). EPR and photoluminescence data confirm that europium ions are mainly in Eu(III) oxidation state in Eu(III)/PANI films. (C) 2008 Elsevier B.V. All rights reserved.

Diagnóstico on-line do estilo cognitivo de aprendizagem do aluno em um ambiente adaptativo de ensino e aprendizagem na web: uma abordagem empírica baseada na sua trajetória de aprendizagem

Uma das questões críticas relacionadas com um Ambiente Adaptativo de Ensino e Aprendizagem baseado na Web diz respeito à eficácia da aprendizagem do aluno remoto. Assim como diversos trabalhos de pesquisa na literatura, nosso estudo preocupou-se com a modelagem do Estilo Cognitivo de Aprendizagem (ECA) do aluno visando, em um futuro próximo, a adaptação dos conteúdos pedagógicos a esta importante característica individual do aluno. Esta tese descreve a metodologia utilizada para investigar como modelar o ECA do aluno remoto, baseado na observação e análise de seu comportamento em um ambiente de ensino e aprendizagem na Web. Em nosso estudo, o ECA representa o estágio de desenvolvimento cognitivo do aluno, de acordo com a taxonomia de Bloom. Nós acreditamos que os principais benefícios de adaptar a instrução ao ECA do aluno estão relacionados com a possibilidade de oportunizar a ampliação de suas habilidades cognitivas, assim como oportunizar a aprendizagem em profundidade sobre os conteúdos em estudo. A metodologia quase-experimental usada para a modelagem do ECA do aluno compreendeu duas fases distintas: (i) geração das classes de ECA a partir da aplicação de um teste psicológico em uma amostra da população-alvo; e (ii) desenvolvimento do módulo de ensino experimental e o estudo das Trajetórias de Aprendizagem (TA) padrão das classes de ECA, a partir da observação de seus comportamentos durante a execução de uma sessão de estudo na Web. Como resultado deste estudo, identificamos os principais indicadores, que melhor discriminaram as classes de ECA consideradas. Os resultados foram obtidos a partir da observação e análise das TAs na Web. Todo o conhecimento obtido a partir desta investigação deverá nos permitir automatizar o diagnóstico do ECA do aluno remoto. Este conhecimento também será utilizado como base para o desenvolvimento dos conteúdos a serem oferecidos ao aluno pelo Ambiente Adaptativo de Ensino e Aprendizagem baseado na Web.

Sistema de divulgação dos serviços e produtos da Porto Santo Line na plataforma Android

A Porto Santo Line é a empresa responsável pela ligação marítima entre as ilhas Madeira e Porto Santo, oferecendo, para além do transporte, um conjunto de serviços e produtos que estão associado à sua actividade principal. A sua base de clientes inclui não só os residentes de ambas as ilhas, mas também muitos dos turistas que visitam o arquipélago. O posicionamento desta empresa no mercado é feito das formas tradicionais, onde se inclui uma rede de balcões e um site através do qual os clientes podem aceder aos produtos e serviços que constitui a oferta da Porto Santo Line. Num esforço de reforçar a sua presença no mercado e de intensificar a sua aposta na inovação, a empresa tem procurado encontrar novas formas e novos canais para chegar aos seus clientes. Este projecto visa dotar a Porto Santo Line de uma aplicação que estenda a sua presença no mercado, oferecendo aos seus clientes a possibilidade de aceder aos seus produtos e serviços através de equipamentos móveis. Este relatório documenta a realização deste projecto, dando principal enfase ao processo adoptado, assim como ao desenho do sistema e sua avaliação. Procurou-se igualmente evidenciar ao longo do relatório, as considerações mais relevantes na elaboração de um projecto com estas características.

Papel da proteína de reparo XPC na regulação das proteínas de reparo APE1, OGG1 e PARP-1 em células humanas e de camundongos

studies using UV as a source of DNA damage. However, even though unrepaired UV-induced DNA damages are related to mutagenesis, cell death and tumorigenesis, they do not explain phenotypes such as neurodegeneration and internal tumors observed in patients with syndromes like Xeroderma Pigmentosum (XP) and Cockayne Syndrome (CS) that are associated with NER deficiency. Recent evidences point to a role of NER in the repair of 8-oxodG, a typical substrate of Base Excision Repair (BER). Since deficiencies in BER result in genomic instability, neurodegenerative diseases and cancer, it was investigated in this research the impact of XPC deficiency on BER functions in human cells. It was analyzed both the expression and the cellular localization of APE1, OGG1 e PARP-1, the mainly BER enzymes, in different NER-deficient human fibroblasts. The endogenous levels of these enzymes are reduced in XPC deficient cells. Surprisingly, XP-C fibroblasts were more resistant to oxidative agents than the other NER deficient fibroblasts, despite presenting the highest of 8-oxodG. Furthermore, subtle changes in the nuclear and mitochondrial localization of APE1 were detected in XP-C fibroblasts. To confirm the impact of XPC deficiency in the regulation of APE1 and OGG1 expression and activity, we constructed a XPC-complemented cell line. Although the XPC complementation was only partial, we found that XPC-complemented cells presented increased levels of OGG1 than XPC-deficient cells. The extracts from XPC-complemented cells also presented an elevated OGG1 enzimatic activity. However, it was not observed changes in APE1 expression and activity in the XPCcomplemented cells. In addition, we found that full-length APE1 (37 kDa) and OGG1- α are in the mitochondria of XPC-deficient fibroblasts and XPC-complemented fibroblasts before and after induction of oxidative stress. On the other hand, the expression of APE1 and PARP-1 are not altered in brain and liver of XPC knockout mice. However, XPC deficiency changed the APE1 localization in hypoccampus and hypothalamus. We also observed a physical interaction between XPC and APE1 proteins in human cells. In conclusion, the data suggest that XPC protein has a role in the regulation of OGG1 expression and activity in human cells and is involved mainly in the regulation of APE1 localization in mice. Aditionally, the response of NER deficient cells under oxidative stress may not be only associated to the NER deficiency per se, but it may include the new functions of NER enzymes in regulation of expression and cell localization of BER proteins

Relationship of black layer and milk line development on maize seed maturity

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

Fontes de metionina em rações formuladas com base em aminoácidos totais ou digestíveis para frangas de reposição leves e semipesadas

Foram conduzidos dois experimentos com o objetivo de avaliar a utilização de duas fontes de metionina (em pó ou líquida) em rações formuladas com base em aminoácidos digestíveis ou totais para frangas de reposição leves e semipesadas, nas fases inicial (de 1 a 6 semanas de idade) e de crescimento (de 11 a 16 semanas de idade). em cada experimento, foram utilizadas 384 aves distribuídas em delineamento inteiramente ao acaso, em esquema fatorial 2 × 2 × 2, composto de duas linhagens (Hy-Line W36 e Hy-Line Brown), duas fontes de metionina (HMTBA - 88% e DL-Metionina - 99%) e dois critérios de formulação da dieta (aminoácidos totais e digestíveis), totalizando oito tratamentos, cada um com seis repetições de oito aves. Foram avaliados os consumos de ração, proteína bruta e energia metabolizável, o peso e ganho de peso corporal e a conversão alimentar das aves. Não houve interação entre os fatores para nenhuma das variáveis estudadas. As aves da linhagem Brown apresentaram maior consumo de ração, peso corporal e ganho de peso. As fontes de metionina e os critérios de formulação de ração não influenciaram as características de desempenho. As aves das linhagens W36 e Brown da linhagem Hy-Line apresentam diferentes perfis de desenvolvimento corporal. A metionina em pó (DL-metionina - 99%) ou a líquida (HMTBA - 88%), assim como os critérios de formulação de ração (aminoácidos totais ou digestíveis) proporcionam desempenho semelhante em aves de reposição.

Um algoritmo para estimação de estado em alimentadores de distribuição de energia elétrica com base no método da soma de potências

Most algorithms for state estimation based on the classical model are just adequate for use in transmission networks. Few algorithms were developed specifically for distribution systems, probably because of the little amount of data available in real time. Most overhead feeders possess just current and voltage measurements at the middle voltage bus-bar at the substation. In this way, classical algorithms are of difficult implementation, even considering off-line acquired data as pseudo-measurements. However, the necessity of automating the operation of distribution networks, mainly in regard to the selectivity of protection systems, as well to implement possibilities of load transfer maneuvers, is changing the network planning policy. In this way, some equipments incorporating telemetry and command modules have been installed in order to improve operational features, and so increasing the amount of measurement data available in real-time in the System Operation Center (SOC). This encourages the development of a state estimator model, involving real-time information and pseudo-measurements of loads, that are built from typical power factors and utilization factors (demand factors) of distribution transformers. This work reports about the development of a new state estimation method, specific for radial distribution systems. The main algorithm of the method is based on the power summation load flow. The estimation is carried out piecewise, section by section of the feeder, going from the substation to the terminal nodes. For each section, a measurement model is built, resulting in a nonlinear overdetermined equations set, whose solution is achieved by the Gaussian normal equation. The estimated variables of a section are used as pseudo-measurements for the next section. In general, a measurement set for a generic section consists of pseudo-measurements of power flows and nodal voltages obtained from the previous section or measurements in real-time, if they exist -, besides pseudomeasurements of injected powers for the power summations, whose functions are the load flow equations, assuming that the network can be represented by its single-phase equivalent. The great advantage of the algorithm is its simplicity and low computational effort. Moreover, the algorithm is very efficient, in regard to the accuracy of the estimated values. Besides the power summation state estimator, this work shows how other algorithms could be adapted to provide state estimation of middle voltage substations and networks, namely Schweppes method and an algorithm based on current proportionality, that is usually adopted for network planning tasks. Both estimators were implemented not only as alternatives for the proposed method, but also looking for getting results that give support for its validation. Once in most cases no power measurement is performed at beginning of the feeder and this is required for implementing the power summation estimations method, a new algorithm for estimating the network variables at the middle voltage bus-bar was also developed

Chave de identificação de espécies do estrato arbóreo da Mata Atlântica em Ubatuba (SP), com base em caracteres vegetativos

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