A educação fisica no curriculo basico para a escola publica do estado do Parana : Uma analise do discurso pedagogico dos professores ?

Universidade Estadual de Campinas . Faculdade de Educação Física

A study on the pretreatment of a sugarcane bagasse sample with dilute sulfuric acid

Experiments based on a 2(3) central composite full factorial design were carried out in 200-ml stainless-steel containers to study the pretreatment, with dilute sulfuric acid, of a sugarcane bagasse sample obtained from a local sugar-alcohol mill. The independent variables selected for study were temperature, varied from 112.5A degrees C to 157.5A degrees C, residence time, varied from 5.0 to 35.0 min, and sulfuric acid concentration, varied from 0.0% to 3.0% (w/v). Bagasse loading of 15% (w/w) was used in all experiments. Statistical analysis of the experimental results showed that all three independent variables significantly influenced the response variables, namely the bagasse solubilization, efficiency of xylose recovery in the hemicellulosic hydrolysate, efficiency of cellulose enzymatic saccharification, and percentages of cellulose, hemicellulose, and lignin in the pretreated solids. Temperature was the factor that influenced the response variables the most, followed by acid concentration and residence time, in that order. Although harsher pretreatment conditions promoted almost complete removal of the hemicellulosic fraction, the amount of xylose recovered in the hemicellulosic hydrolysate did not exceed 61.8% of the maximum theoretical value. Cellulose enzymatic saccharification was favored by more efficient removal of hemicellulose during the pretreatment. However, detoxification of the hemicellulosic hydrolysate was necessary for better bioconversion of the sugars to ethanol.

Regiospecific synthesis of 5-trichloromethyl-1H-pyrazole and 1H-pyrazole-5-carboxylic ester derivatives

Reaction of 1,1,1-trichloro-4-methoxy-3-penten-2-one (1) with hydrazines (2a-h) (NH2NHR, R = H, Me, t-Bu, Ph, 4-NO2-C6H4, C6F5, CO2Me, CONH2) under differing conditions regiospecifically affords different pyrazole derivatives, 3-methyl-5-trichloromethyl-5-hydroxy-4,5-dihydropyrazoles (3a, d-h), 3-methyl-5-trichloromethyl-1H-pyrazoles (4a,b,d-g) and 5-carboxyethyl-3-methyl-1H-pyrazoles (5a-e). The structural assignments were based on the analysis of their H-1/C-13 NMR and ESI-MS data.

Mesoionic pyridopyrimidinylium and pyridooxazinylium olates and non-mesoionic pyridopyrimidinones. Structures in the solid state, solution, and matrices

X-Ray crystal structures, C-13 NMR spectra and theoretical calculations (B3LYP/6-31G*) are reported for the mesoionic (zwitterionic) pyridopyrimidinylium- and pyridooxazinyliumolates 2a, 3a and 5a,b as well as the enol ether 11b and the enamine 11c. The 1-NH compounds like 1a, 2a and 3a exist in the mesoionic form in the crystal and in solution, but the OH tautomers such as 1b and 2b dominate in the gas phase as revealed by the Ar matrix IR spectra in conjunction with DFT calculations. All data indicate that the mesoionic compounds can be regarded as intramolecular pyridine-ketene zwitterions (cf. 16 --> 17) with a high degree of positive charge on the pyridinium nitrogen, a long pyridinium N-CO bond (ca. 1.44-1.49 Angstrom), and normal C=O double bonds (ca. 1.22 Angstrom). All mesoionic compounds exhibit a pronounced tilting of the olate C=O groups (the C=O groups formally derived from a ketene) towards the pyridinium nitrogen, giving NCO angles of 110-118 degrees. Calculations reveal a hydrogen bond with 6-CH, analogous to what is found in ketene-pyridine zwitterions and the C3O2-pyridine complex. The 2-OH tautomers of type 1b, 2b, and 11 also show a high degree of zwitterionic character as indicated by the canonical structures 11 12.

A Computational Study of Tetrafluoro-[2.2]Cyclophanes

A computational study of the isomers of tetrafluorinated [2.2]cyclophanes persubstituted in one ring, namely F-4-[2.2]paracyclophane (4), F-4-anti-[2.2]metacyclophane (5a), F-4-syn-[2.2]metacyclophane (5b), and F-4-[2.2]metaparacyclophane (6a and 6b), was carried out. The effects of fluorination on the geometries, relative energies, local and global aromaticity, and strain energies of the bridges and rings were investigated. An analysis of the electron density by B3PW91/6-31+G(d,p), B3LYP/6-31+G(d,p), and MP2/6-31+G(d,p) was carried out using the natural bond orbitals (NBO), natural steric analysis (NSA), and atoms in molecules (AIM) methods. The analysis of frontier molecular orbitals (MOs) was also employed. The results indicated that the molecular structure of [2.2]paracyclophane is the most affected by the fluorination. Isodesmic reactions showed that the fluorinated rings are more strained than the nonfluorinated ones. The NICS, HOMA, and PDI criteria evidenced that the fluorination affects the aromaticity of both the fluorinated and the nonfluorinated rings. The NBO and NSA analyses gave an indication that the fluorination increases not only the number of through-space interactions but also their magnitude. The AIM analysis suggested that the through-space interactions are restricted to the F-4-[2.2]metacyclophanes. In addition, the atomic properties, computed over the atomic basins, shave evidence that not only the substitution, but also the position of the bridges could affect the atomic charges. the first atomic moments, and the atomic volumes.

The use of electrospray ionization tandem mass spectrometry on the structural characterization of novel asymmetric metallo-organic supermolecules, based on pentafluorophenylporphyrins and ruthenium complexes

The novel asymmetric metallo-organic triads cis- and trans-[B(4-py)BPFPH(2){Ru(3)O(Ac)(6)(py)(2)}(Ru(bpy)(2)Cl}](PF(6))(2) (5a,b) for which cis- and trans-B(4-py)BPFPH(2)=5,10-bis(pentafluorophenyl)-15,20-bis(4-pyridyl)porphyrin and 5,15-bis(pentafluorophenyl)-10,20-bis(4-pyridyl)porphyrin, respectively; Ac = acetate; py = pyridine and bpy = 2,2`-bipyridine, as well as their corresponding monosubstituted dyads cis- and trans-[B(4-py)BPFPH(2){Ru(3)O(Ac)(6)(py)(2)}]PF(6) (4a,b) have been structurally characterized via electrospray ionization mass spectrometry (ESI-MS and ESI-MS/MS). The ESI-MS of dyads 4a,b display two characteristic Ru-multicomponent clusters of isotopologue ions corresponding to singly charged ions 4a,b(+) of m/z 1629 and doubly charged ions [4a,b+H](2+) of m/z 815 and the triads 5a,b are detected by ESI-MS as the intact doubly charged cluster of isotopologue ions of m/z 1039 [5a,b](2+). The ESI-MS/MS of 4a,b(+), [4a,b+H](2+) and [5a,b](2+) reveal characteristic dissociation pathways, which confirm the structural assignments providing additional information on the intrinsic binding strengths of the gaseous ions. Although the gas-phase behavior of each pair of isomers was rather similar, the less symmetric dyads 4a,b are distinguished via the (1)H NMR spectral profile of the pyrrolic signals. Exploratory photophysical assays have shown that both modifying motifs alter the porphyrinic core emission profile, opening the possibility to use these asymmetric systems as photophysical devices. (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis of naturally occurring diene and trienes by Te/Li exchange on (1Z,3Z)-butyltelluro-4-methoxy-1,3-butadiene

(1Z,3Z)-Butyltelluro-o-4-methoxy-1,3-butadiene 2 was obtained by the hydrotelluration of(Z)-1-methoxy-but-1-en-3-ynes 1. The butadienyllithium 3 obtained by the Te/Li exchange reaction in the (1Z,3Z)-1-butyltelluro-4-methoxy-1.3-butadiene 2 reacted with aldehydes to form the corresponding alcohols 4a-d with total retention of configuration. The alcohols formed undergo hydrolysis, resulting in the alpha,beta,gamma,delta-unsaturated aldehydes of (E,E) configuration, which are precursors of trienes obtained from natural sources. The products of this reaction were employed in the synthesis of methyl-(2E,4E)-decadienoate 7, which is a component of the flavor principles of ripe Bartlett pears. Performing the Wittig reaction of the methyl triphenylphosphorane with the deca-(2E,4E)-dienal 5a, we were able to synthesize the undeca-(1,3E,5E)-triene 6a. This compound is a sex-pheromone component of the marine brown algae Fucus serratus, Dictyopteris plagiograma, and Dictyopteris australis. Performing the Wittig reaction of methyl triphenylphosphorane with the octa-(2E,4E)-dienal 5c, the nona-(1,3E,5E)-triene 6b was synthesized. The compound obtained is a sex-pheromone component of the marine brown alga Sargassum horneri. The octa-( 1,3E,5E)-triene 6c was easily obtained from hepta-(2E,4E)-dienal 5d by the Wittig reaction with methyl triphenylphophorane. This compound is a sex-pheromone component of the marine brown alga Fucus serratus. (C) 2010 Elsevier Ltd. All rights reserved.

Polymorphisms in Alcohol Metabolizing Genes and the Risk of Head and Neck Cancer in a Brazilian Population

Aims: The incidence of head and neck cancer (HNC) in Brazil has increased substantially in recent years. This increase is likely to be strongly associated with alcohol and tobacco consumption, but genetic susceptibility also should be investigated in this population. The aim of this study was to evaluate the association of polymorphisms in genes of alcohol metabolism enzymes and the risk of HNC. Methods: A hospital-based case-control study was conducted in Sao Paulo, Brazil. We here investigated ADH1C Ile(350)Val, ADH1B Arg(48)His, ADH1B Arg(370)Cys and CYP2E1*5A PstI polymorphisms by PCR-RFLP Polymerase Chain Reaction - Restriction Fragment Length Polymorphism in 207 histopathologically confirmed HNC cases (184 males and 23 females) and 244 cancer-free controls (225 males and 19 females) admitted as in-patients in the same hospital. Results: Chronic alcohol intake increased approximately four times the risk of HNC. The mutant genotype ADH1B Arg(48)His was more frequent in controls (12.7%) than HNC patients (5.8%) conferring protection for the disease (odds ratio (OR) = 0.42; 95% confidence interval (CI ), 0.21-0.85). Similar results were observed for individuals with ADH1B*2 (OR = 0.41; 95% CI , 0.20-0.82) or ADH1B*2/ADH1C*1 (OR = 0.32; 95% CI , 0.13-0.79) mutated haplotypes. Multiple regression analyses showed that individuals with the mutant genotype ADH1B Arg(48)His who consume alcohol > 30 g/L/day have more than four times the risk for HNC (OR = 4.42; 95% CI, 1.21-16.11). Conclusions: The fast alcohol metabolizing genotypes may prevent HNC when the amount of alcohol intake is < 30.655 g/L/day.

High numbers of human skin cancers express MMP2 and several integrin genes

Background: Basal cell carcinomas (BCC), squamous cell carcinomas (SCC) and cutaneous malignant melanoma (MM) are solid skin cancers derived from different cell types, with different ability to metastasize. Several subtypes of integrins and matrix metalloproteinases (MMP) have been related to malignization and metastasis processes. This work aimed at a quantitative evaluation of skin cancers expressing eight integrins and MMP2 genes. Methods: Expression of integrins and MMP2 genes was evaluated on fresh tumor biopsies from BCC, SCC and MM, and respective controls, by the reverse transcriptase polychain reaction (RT-PCR) technique. Results: More than 90% tumors expressed alpha 6a, beta 1, beta 3 and beta 6 (non-melanoma), and alpha 5a, alpha 6a and MMP2 (MM). Up to 100% controls also expressed beta 1 and beta 3. The results were significant for alpha 6a in BCC (p = 0.026), alpha 6b in SCC (p = 0.035), alpha 2a in BCC (p = 0.003), beta 5 and beta 6 in BCC (p = 0.005). MMP2 was expressed in 100% MM (p = 0.0004). Conclusion: Integrin subunits alpha 2a and alpha 6a would be interesting targets for BCC anti-tumor therapy, as well as alpha 6b in case of SCC. The elevated number of BCC expressing alpha 2 and alpha 6, and of MM expressing alpha v and MMP2, corroborate literature data.

Differential Shh, Bmp and Wnt gene expressions during craniofacial development in mice

In this study, Bmp-4, Wnt-5a and Shh gene expressions were compared during early craniofacial development in mice by comparative non-isotopic in situ hybridization. Wild-type C57BL/6J mice were studied at various stages of embryonic development (from 8.5- to 13.5-day-old embryos - E8.5-13.5). During early odontogenesis, transcripts for Bmp-4, Shh and Wnt-5a were co-localised at the tooth initiation stage. At E8.5, Shh mRNA expression was restricted to diencephalon and pharyngeal endoderm. Before maxillae and mandible ossification, Bmp-4 and Wnt-5a signals were detected in the mesenchymal cells and around Meckel`s cartilage. During palatogenesis, Shh was expressed only in the epithelium and Wnt-5a only in the mesenchyme of the elevating palatal shelves. During tongue development, Shh expression was found in mesenchyme, probably contributing to tongue miogenesis, while Wnt-5a signal was in the epithelium, possibly during placode development and papillae formation. Taken together, these findings suggest that Bmp-4, Shh and Wnt-5a gene expressions may act together on the epithelial mesenchymal interactions occurring in several aspects of the early mouse craniofacial development, such as odontogenesis, neuronal development, maxillae and mandible ossification, palatogenesis and tongue formation. (C) 2009 Elsevier GmbH. All rights reserved.

Spray drift of pesticides arising from aerial application in cotton

This paper presents results from field studies carried out during the 1993-1998 Australian cotton (Gossypium hirsutum L.) seasons to monitor off-target droplet movement of endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin 3-oxide) insecticide applied to a commercial cotton crop. Averaged over a wide range of conditions, off-target deposition 500 m downwind of the field boundary was approximately 2% of the field-applied rate with oil-based applications and 1% with water-based applications. Mean airborne drift values recorded 100 m downwind of a single flight line were a third as much with water-based application compared with oil-based application. Calculations using a Gaussian diffusion model and the U.S. Spray Drift Task Force AgDRIFT model produced downwind drift profiles that compared favorably with experimental data. Both models and data indicate that by adopting large droplet placement (LDP) application methods and incorporating crop buffer distances, spray drift can be effectively managed.

Synthesis of fluorinated 2-phenyl-4-quinolones from pyrrole-2,3-diones

A series of substituted 2-phenyl-4-quinolones 8-11 have been synthesized in good yields via ash vacuum thermolysis (FVT) of 1-aryl-4-cyano-5-phenylpyrrole-2,3-diones 7a-e and 1-aryl-4-methoxycarbonyl-5-phenylpyrrole-2,3-diones 7f-j. The pyrrolediones 7 were prepared from amines 3 and benzoylacetonitriles 5a-e or methyl 3-arylamino-3-phenylprop-2-enoates 5f-j.

Interactions among endocrinology, seasonal reproductive cycles and the nesting biology of the female green sea turtle

We collected data on plasma levels of testosterone+5a-dihydrotestosterone (T+DHT) and corticosterone (CORT) from adult female green sea turtles (Chelonia mydas) from southern Queensland during distinct stages of their reproductive cycle. Those females capable of breeding in a given year had elevated plasma steroid levels (T+DHT 0.91 +/- 0.08; CORT 1.05 +/- 0.29 ng/ml), associated with follicular development, until courtship began in October. At the beginning of the nesting season in November plasma levels of 2 CORT were related to when the female first nested (r(2) = 0.06; F = 10.45; P = 0.01). However, they were not correlated with the number of clutches a female laid in that season (F = 3.65; P = 0.08). We repeatedly sampled 23 turtles over the nesting season and profiled changes in steroids immediately following oviposition of each clutch. Levels of T+DHT (range 0.41-0.58 ng/ml) and CORT (range 2.13-2.81 ng/ml) were similar through the early stages of the nesting season and inter-nesting period, and declined to near basal levels (T+DHT 0.37 +/- 0.03 and CORT 1.85 +/- ng/ml) following the last clutch for the season. Steroid hormone levels were also low (T+DHT 0.38 +/- 0.16; CORT 0.46 +/- 0.21 ng/ml) in four independent post-breeding (atretic) females; samples for these females were taken at a time when body condition was presumably at the lowest for the season. Subtle changes in the nesting environment, such as variation in nesting habitat or the time of night that nesting occurred, were associated with a small and slow CORT increase. We suggest CORT is increased in nesting females to assist in lipid transfer to prepare the ovarian follicles and/or the reproductive organs for ovulation.

Boletim eletr??nico de bibliografias especializadas: pol??tica de transfer??ncia condicionada de renda

As pol??ticas de Transfer??ncia Condicionada de Renda (TCR) s??o consideradas a mais nova gera????o de pol??ticas sociais. O fato tem chamado a aten????o de profissionais do setor p??blico e de acad??micos de diferentes ??reas. Nos ??ltimos anos, diversas experi??ncias, sobretudo na Am??rica Latina, t??m-se destacado pelo impacto positivo sobre os indicadores sociais da popula????o, entre elas: o Programa Bolsa Fam??lia, no Brasil; o Programa de Desarrollo Humano Oportunidades, no M??xico; e o Sistema Chile Solid??rio, no Chile. O Programa Bolsa Fam??lia, criado em 2003, constitui a maior pol??tica p??blica de TCR da Am??rica Latina, tanto em or??amento quanto em cobertura. Atualmente, atende cerca de 13.800.000 fam??lias, em todos os munic??pios do Pa??s. O Programa tem servido de modelo para a difus??o desse tipo de pol??tica no mundo. O tema envolve v??rias dimens??es da ??rea social, por se tratar de uma pol??tica essencialmente intersetorial. O Bolsa Fam??lia vem se destacando nos debates da administra????o p??blica, devido ?? sua forte capacidade de melhoria das condi????es das fam??lias benefici??rias. Diante disso, a 5a edi????o do Boletim Eletr??nico de Bibliografias Especializadas apresenta uma reuni??o de publica????es do acervo da Biblioteca Graciliano Ramos que abordam os seguintes temas: transfer??ncia condicionada de renda, programas sociais, desigualdade social, combate da pobreza e pol??ticas p??blicas. O objetivo ?? divulgar obras que auxiliem servidores p??blicos na reflex??o e compreens??o desses assuntos

New xanthenodione: synthesis and antioxidant activity evaluation

6th Spanish-Portuguese-Japanese Organic Chemistry Symposium, Lisboa, de 18 a 20 de Julho de 2012 (Poster Communication).