Thermal degradation behaviour of some polydithiooxamide metal complexes

The thermal decomposition behavior of the Fe(II), Co(II), Ni(II) and Zn(II) complexes of polydithiooxamide has been investigated by thermogravimetric analysis (TGA) at a heating rate of 20°C min-1 under nitrogen. The Coats-Redfern integral method is used to evaluate the kinetic parameters for the successive steps in the decomposition sequence observed in the TGA curves. The processes of thermal decomposition taking place in the four complexes are studied comparatively as the TGA curves indicate the difference in the thermal decomposition behavior of these complexes. The thermal stabilities of these complexes are discussed in terms of repulsion among electron pairs in the valence shell of the central ion and electronegativity effects.

Analysis of the structural and electronic properties of 1-(5-Hydroxymethyl - 4 -[ 5 - (5-oxo-5-piperidin-1-yl-penta-1,3dienyl)-benzo[1,3]dioxol-2-yl] -tetrahydro-furan-2-yl)-5-methyl-1H-pyrimidine-2,4dione molecule

The structural and electronic properties of 1-(5-Hydroxymethyl - 4 -[ 5 - (5-oxo-5-piperidin- 1 -yl-penta- 1,3 -dienyl)-benzo [1,3] dioxol- 2 -yl]-tetrahydro -furan-2 -yl)-5-methy l-1Hpyrimidine-2,4dione (AHE) molecule have been investigated theoretically by performing density functional theory (DFT), and semi empirical molecular orbital calculations. The geometry of the molecule is optimized at the level of Austin Model 1 (AM1), and the electronic properties and relative energies of the molecules have been calculated by density functional theory in the ground state. The resultant dipole moment of the AHE molecule is about 2.6 and 2.3 Debyes by AM1 and DFT methods respectively, This property of AHE makes it an active molecule with its environment, that is AHE molecule may interacts with its environment strongly in solution.

Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

Dinâmica da vegetação natural no nordeste do estado de São Paulo, entre 1988 e 2003

As imagens de sensoriamento remoto orbital juntamente com as ferramentas em Sistemas de Informações Geográficas têm possibilitado diversos estudos sobre as alterações na cobertura das terras. O objetivo deste trabalho foi detalhar os resultados do mapeamento de uso e cobertura das terras e alterações em uma região no Nordeste do Estado de São Paulo entre 1988 e 2003, especificamente em relação à vegetação natural. A avaliação da dinâmica das áreas de remanescentes de vegetação natural das terras revelou retração de 0,14% em relação à área total dos municípios (51.649,5 km2). Mas houve avanço da vegetação ripária de 0,22% em relação à área total. Dos 125 municípios da região em estudo e possuidores de remanescentes de vegetação natural, 60,8% mantiveram praticamente a mesma porcentagem de cobertura vegetal natural (florestas estacionais, secundárias, cerrado e vegetação ripária) em 2003 com relação a 1988. Considerando somente as áreas com floresta estacional, secundária e cerrado, o número de municípios cresce para 79,2% do total. Os municípios que mantiveram os maiores percentuais de cobertura vegetal natural de Floresta Estacional, Floresta Secundária e Cerrado no período foram: Águas da Prata, com 39,9% de sua área municipal total, Rifaina (31,7%), São Sebastião da Grama (24,9%) e Pedregulho (24,0%). A ocupação das terras de 1988 a 2003 caracterizou-se pela dinâmica de substituição entre atividades que competem por área no setor rural, comum nas regiões administrativas tecnicamente mais avançadas do Estado de São Paulo.

Identificação e mapeamento de áreas de milho na região sul do Brasil utilizando imagens MODIS

O presente trabalho teve como proposta avaliar a identificação e o mapeamento das áreas de milho da região noroeste do Estado do Rio Grande do Sul a partir de dados multitemporais do sensor MODIS (Moderate Resolution Imaging Spectroradiometer) a bordo do satélite Earth Observing System - EOS-AM (Terra). O algoritmo de classificação supervisionada Spectral Angle Mapper (SAM) foi aplicado com sucesso em uma série multitemporal de imagens EVI pré-processadas. Verificou-se que as áreas classificadas como milho na imagem coincidiam plenamente com áreas mais extensas ou contínuas (> 90 ha) de milho. Áreas de menor extensão ou localizadas em encostas de morros, ao lado de vegetação arbórea, não foram detectadas pelo classificador devido à baixa resolução espacial das imagens. A maior utilidade prática da identificação e da classificação digital das áreas de milho obtidas das imagens MODIS está na sua aplicação para isolar ou complementar o mapeamento das áreas agrícolas visando ao seu monitoramento a partir de diferentes índices de vegetação, derivados de imagens de alta resolução temporal e baixa resolução espacial.

Estimativa de parâmetros biofísicos de plantios de café a partir de imagens orbitais de alta resolução espacial

O uso de recursos de sensoriamento remoto orbital constitui um grande avanço no levantamento de dados sobre a cafeicultura, sobretudo por seu caráter temporal e baixo custo. Sendo assim, o objetivo do trabalho foi avaliar a utilização da imagem do satélite QUICKBIRD na determinação de parâmetros biofísicos importantes para a cultura cafeeira. Foram utilizados 25 talhões com plantios de café localizados entre os municípios de Ribeirão Corrente, Franca e Cristais Paulista (SP). Os parâmetros biofísicos utilizados foram os espaçamentos entre linhas e plantas, altura, IAF, diâmetro da copa, porcentagem de cobertura vegetal, rugosidade, variedade e biomassa. Foram utilizados valores de refletância real das bandas espectrais do satélite QUICKBIRD e os índices de vegetação NDVI, GVI, SAVI e RVI. A partir desses dados, foram feitas análises de regressão linear e não linear para a geração dos modelos de estimativa. A utilização de modelos de regressão baseados em equações não lineares mostrou-se mais adequado para determinar os parâmetros IAF e a porcentagem de biomassa, importantes como indicativos da produtividade da cultura cafeeira.

Use of data mining and spectral profiles to differentiate condition after harvest of coffee plants

This study aimed at identifying different conditions of coffee plants after harvesting period, using data mining and spectral behavior profiles from Hyperion/EO1 sensor. The Hyperion image, with spatial resolution of 30 m, was acquired in August 28th, 2008, at the end of the coffee harvest season in the studied area. For pre-processing imaging, atmospheric and signal/noise effect corrections were carried out using Flaash and MNF (Minimum Noise Fraction Transform) algorithms, respectively. Spectral behavior profiles (38) of different coffee varieties were generated from 150 Hyperion bands. The spectral behavior profiles were analyzed by Expectation-Maximization (EM) algorithm considering 2; 3; 4 and 5 clusters. T-test with 5% of significance was used to verify the similarity among the wavelength cluster means. The results demonstrated that it is possible to separate five different clusters, which were comprised by different coffee crop conditions making possible to improve future intervention actions.

Analysis of land use and occupancy in permanent preservation areas according to the hydrography of Ribeirão Água Fria - Bofete, SP - Brazil

The use conflicts are determined by the inadequate occupations of the soil, as it is the case of soil occupation inside of permanent preservation areas. This study aimed to determine the classes of the soil use and if there are conflicts inside of permanent preservation areas along the drainage network of the Água Fria Stream watershed, located in Bofete city - São Paulo, Brazil. It locates geographically between the coordinates: 48°09'30" to 48°18'30" longitude WGr., 22°58'30" to 23°04'30" latitude S, with an area of 15242.84 ha. The map of soil use was elaborated through the interpretation directly in the computer screen of satellite digital image. In the orbital data, the study area is inserted in the quadrant A, of image TM/Landsat - 5, orbit 220, point 76, passage 9/8th/2007. The Geographical Information System used was CartaLinx. The conflict areas of the watershed were obtained from the crossing between the maps of soil use and of PPAs. The results allowed the conclusion that more than half of the area (51.09%) is occupied by pastures, reflex of sandy soils and low fertility. It was also verified that although almost half of the watershed is covered with some type of vegetation (48.78% of natural forest /reforestation), it has approximately a third of permanent preservation areas used inappropriately by pastures (88.15%), reforestation (10.42%) and exposed soil (1.43%), totaling 343.07ha of conflicting areas, in a total of 993.26 ha of PPAs.

Seasonality of net radiation in two sub-basins of Paracatu by the use of modis sensor products

The net radiation (Rn) represents the main source of energy for physical and chemical processes that occur in the surface-atmosphere interface, and it is used for air and soil heating, water transfer, in the form of vapor from the surface to the atmosphere, and for the metabolism of plants, especially photosynthesis. If there is no record of net radiation in certain areas, the use of information is important to help determine it. Among them we can highlight those provided by remote sensing. In this context, this work aims to estimate the net radiation, with the use of products of MODIS sensor, in the sub-basins of Entre Ribeiros creek and Preto River, located between the Brazilian states of Goiás and Minas Gerais. The SEBAL (Surface Energy Balance Algorithm for Land) was used to obtain the Rn in four different days in the period of July to October, 2007. The Rn results obtained were consistent with others cited in the literature and are important because the orbital information can help determine the Rn in areas where there are not automatic weather stations to record the net radiation.

Sinusite recorrente de causa incomum

The authors present a case of chronic recurrent sinusitis of rare etiology in a man submitted previously to a facial peeling. The computed tomography and the sinusal endoscopy revealed periorbital fat in the maxilary sinus. There was a history of old orbital floor fracture.

Hitsauksen mekanisoinnin ja automatisoinnin oppimisympäristön kehittäminen

Hitsaavan teollisuuden kilpailukyvyn tehostamiseksi yksi keino on hitsauksen mekanisoinnin ja automatisoinnin osuuden lisääminen hitsaustuotannossa. Työn on tehty Etelä-Karjalan aikuisopiston toimeksiannosta hitsauksen mekanisoinnin ja automatisoinnin oppimisympäristön kehittämiseksi paikallisten hitsaavien yritysten koulutustarpeiden mukaisesti. Työ toteutettiin sekä kirjallisuustutkimuksena että haastattelututkimuksena Etelä-Karjalan alueen hitsaavan teollisuuden yrityksissä. Kirjallisuusosiossa on läpikäyty hitsauksen mekanisointia, kappaleenkäsittelyä, orbitaalihitsausta sekä robottihitsausta. Kirjallisen käsittelyn pohjana oli kansainvälisen mekanisoidun-, orbitaali- ja robottihitsauksen henkilöstön operaattorikoulutusohjelma. Operaattorikoulutusohjelmassa koulutuslinjat jaetaan mekanisoituun hitsaukseen, orbitaalihitsaukseen ja robottihitsaukseen. Käytännön osiossa on analysoitu kohdeyrityksille tehdyt haastattelut, määritelty kohdeyritysten hitsauksen automaatiotasot sekä hitsaustyössä käytössä oleva laitekanta. Tutkimuksen tuloksia tullaan käyttämään hyödyksi kehitettäessä Etelä-Karjalan aikuisopiston (AKTIVA) oppimisympäristöä etelä-karjalaisten hitsaavien yritysten tarpeiden mukaisesti.

Avaliação da abordagem palpebral subtarsal no tratamento cirúrgico das fraturas zigomático-orbitais

OBJETIVO: avaliar as complicações, vantagens e desvantagens da abordagem subtarsal quando utilizada para exposição da borda infra-orbital e do assoalho da órbita em fraturas zigomático-orbitais. MÉTODOS: Estudo retrospectivo de 41 incisões subtarsais empregadas em 39 pacientes com fraturas do complexo zigomático e/ou do assoalho da órbita do tipo blow-out, no período de janeiro de 2002 a dezembro de 2006. RESULTADOS: As complicações observadas foram conjuntivite, epífora e cicatriz aparente em seis (14,6%), cinco (12,2%) e dois (4,9%) dos casos, respectivamente. Não houve presença de ectrópio, entrópio ou esclera aparente nos pacientes reavaliados. CONCLUSÃO: As principais vantagens dessa abordagem são os resultados estéticos e funcionais associados aos benefícios trans-operatórios.

Outbreaks of rhinofacial and rhinopharyngeal zygomycosis in sheep in Paraíba, northeastern Brazil

Two outbreaks of zigomycosis with rhinofacial and two other with rhinopharyngeal lesions involving fungi with filamentous coaenocytic hyphae characteristic of entomoph-thoramycetous fungi are reported in the state of Paraíba, northeastern Brazil. One outbreak of rhinofacial zygomycosis occurred during the rainy season affecting 5 sheep. Another outbreak of the clinical form affected one out of 40 sheep during the dry season. Common clinical signs of the rhinofacial infection were bilateral serosanguineous nasal discharge with swelling of nostrils, upper lip, and the skin of the face. At necropsy the nasal mucosa showed dark brownish ulcerated areas which extended from the mucocutaneous region to 10cm inside the nasal vestibule. The mucosa of the hard palate was also ulcerated. The cutting surface of nostrils and palate showed a brownish or red spongeous tissue of friable consistency. One outbreak of rhinopharyngitis took place on an irrigated coconut farm; 7 out of 60 adult sheep were affected. Another outbreak affected a sheep in a flock of 80 during the dry season. Clinical signs as noisy respiration and dyspnoea due to mechanical blockage of the nasal cavities, swelling of the nostrils, and serosanguineous nasal discharge were observed. Six out of 8 sheep in this group showed exophthalmia, keratitis and unilateral corneal ulceration of the eye. The sheep either died of their infection or were euthanized after a clinical course of 7-30 days. At necropsy there was a dense yellow exudate in the nasopharyngeal area affecting the ethmoidal region, turbinate bones, paranasal sinuses, hard and soft palates, orbital cavity, pharynges, regional muscles and lymph nodes. Histopathologically both forms of the disease showed multifocal granulomas with an eosinophilic necrotic reaction (Splendore-Hoeppli phenomenon) containing ribbon-type coenocytic hyphae with 7-30mum in diameter similar to hyphae of zygomycetous fungi, possibly Conidiobolus spp. Outbreaks of both forms of mycotic rhinitis are common in northeastern Brazil and in other regions of the country.

Lagrangian multipliers for coast-arcs of optimum space trajectories

Some properties of generalized canonical systems - special dynamical systems described by a Hamiltonian function linear in the adjoint variables - are applied in determining the solution of the two-dimensional coast-arc problem in an inverse-square gravity field. A complete closed-form solution for Lagrangian multipliers - adjoint variables - is obtained by means of such properties for elliptic, circular, parabolic and hyperbolic motions. Classic orbital elements are taken as constants of integration of this solution in the case of elliptic, parabolic and hyperbolic motions. For circular motion, a set of nonsingular orbital elements is introduced as constants of integration in order to eliminate the singularity of the solution.

Manifestation of the pairing symmetry in the vortex core structure in iron-based superconductors

The superconducting gap is a basic character of a superconductor. While the cuprates and conventional phonon-mediated superconductors are characterized by distinct d- and s-wave pairing symmetries with nodal and nodeless gap distributions respectively, the superconducting gap distributions in iron-based superconductors are rather diversified. While nodeless gap distributions have been directly observed in Ba1–xKxFe2As2, BaFe2–xCoxAs2, LiFeAs, KxFe2–ySe2, and FeTe1–xSex, the signatures of a nodal superconducting gap have been reported in LaOFeP, LiFeP, FeSe, KFe2As2, BaFe2–xRuxAs2, and BaFe2(As1–xPx)2. Due to the multiplicity of the Fermi surface in these compounds s± and d pairing states can be both nodeless and nodal. A nontrivial orbital structure of the order parameter, in particular the presence of the gap nodes, leads to effects in which the disorder is much richer in dx2–y2-wave superconductors than in conventional materials. In contrast to the s-wave case, the Anderson theorem does not work, and nonmagnetic impurities exhibit a strong pair-breaking influence. In addition, a finite concentration of disorder produces a nonzero density of quasiparticle states at zero energy, which results in a considerable modification of the thermodynamic and transport properties at low temperatures. The influence of order parameter symmetry on the vortex core structure in iron-based pnictide and chalcogenide superconductors has been investigated in the framework of quasiclassical Eilenberger equations. The main results of the thesis are as follows. The vortex core characteristics, such as, cutoff parameter, ξh, and core size, ξ2, determined as the distance at which density of the vortex supercurrent reaches its maximum, are calculated in wide temperature, impurity scattering rate, and magnetic field ranges. The cutoff parameter, ξh(B; T; Г), determines the form factor of the flux-line lattice, which can be obtained in _SR, NMR, and SANS experiments. A comparison among the applied pairing symmetries is done. In contrast to s-wave systems, in dx2–y2-wave superconductors, ξh/ξc2 always increases with the scattering rate Г. Field dependence of the cutoff parameter affects strongly on the second moment of the magnetic field distributions, resulting in a significant difference with nonlocal London theory. It is found that normalized ξ2/ξc2(B/Bc2) dependence is increasing with pair-breaking impurity scattering (interband scattering for s±-wave and intraband impurity scattering for d-wave superconductors). Here, ξc2 is the Ginzburg-Landau coherence length determined from the upper critical field Bc2 = Φ0/2πξ2 c2, where Φ0 is a flux quantum. Two types of ξ2/ξc2 magnetic field dependences are obtained for s± superconductors. It has a minimum at low temperatures and small impurity scattering transforming in monotonously decreasing function at strong scattering and high temperatures. The second kind of this dependence has been also found for d-wave superconductors at intermediate and high temperatures. In contrast, impurity scattering results in decreasing of ξ2/ξc2(B/Bc2) dependence in s++ superconductors. A reasonable agreement between calculated ξh/ξc2 values and those obtained experimentally in nonstoichiometric BaFe2–xCoxAs2 (μSR) and stoichiometric LiFeAs (SANS) was found. The values of ξh/ξc2 are much less than one in case of the first compound and much more than one for the other compound. This is explained by different influence of two factors: the value of impurity scattering rate and pairing symmetry.