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Submitted by Guilherme Lemeszenski (guilherme@nead.unesp.br) on 2013-08-22T18:48:33Z No. of bitstreams: 1 S0100-40422004000300016.pdf: 381839 bytes, checksum: c2621b29331946b6c28b12fb50ab7b00 (MD5) Made available in DSpace on 2013-08-22T18:48:33Z (GMT). No. of bitstreams: 1 S0100-40422004000300016.pdf: 381839 bytes, checksum: c2621b29331946b6c28b12fb50ab7b00 (MD5) Previous issue date: 2004-06-01 Made available in DSpace on 2013-09-30T19:38:29Z (GMT). No. of bitstreams: 2 S0100-40422004000300016.pdf: 381839 bytes, checksum: c2621b29331946b6c28b12fb50ab7b00 (MD5) S0100-40422004000300016.pdf.txt: 23095 bytes, checksum: 294c30efdd227218ece28d420c1a8725 (MD5) Previous issue date: 2004-06-01 Submitted by Vitor Silverio Rodrigues (vitorsrodrigues@reitoria.unesp.br) on 2014-05-20T15:10:19Z No. of bitstreams: 2 S0100-40422004000300016.pdf: 381839 bytes, checksum: c2621b29331946b6c28b12fb50ab7b00 (MD5) S0100-40422004000300016.pdf.txt: 23095 bytes, checksum: 294c30efdd227218ece28d420c1a8725 (MD5) Made available in DSpace on 2014-05-20T15:10:19Z (GMT). No. of bitstreams: 2 S0100-40422004000300016.pdf: 381839 bytes, checksum: c2621b29331946b6c28b12fb50ab7b00 (MD5) S0100-40422004000300016.pdf.txt: 23095 bytes, checksum: 294c30efdd227218ece28d420c1a8725 (MD5) Previous issue date: 2004-06-01 Drug therapy involving bone tissue diseases is difficult, calling for the design of specific drugs. The present paper is a brief review of a new site-directed system termed ODDS (osteotropic drug delivery system), based on a latenciation process, using bisphosphonates as bone carriers. This is an important tool for the rational prodrug design for obtaining selective drugs. Universidade Estadual Paulista Júlio de Mesquita Filho Faculdadade de Ciências Farmacêuticas Departamento de Fármacos e Medicamentos Universidade Federal de São Carlos (UFSCar) Instituto de Química Departamento de Química Universidade de São Paulo Faculdade de Ciências Farmacêuticas Departamento de Farmácia Universidade Estadual Paulista Júlio de Mesquita Filho Faculdadade de Ciências Farmacêuticas Departamento de Fármacos e Medicamentos

In this work a series of {[RuCl2(dppb)](μ-4,4′-N-N)}4 complexes were synthesized and characterized by elemental analysis, cyclic voltammetry and differential pulse voltammetry and UV–Vis and 31P{1H} NMR spectroscopies; [(μ-4,4′-N-N=pyrazine (pz), 4,4′-bipyridine=(4,4′-bipy), 1,2-bis-trans-(4-pyridyl)ethane = (pyeta) and 1,2-bis-trans-(4-pyridyl)ethylene=(pyetil) as bridging alterdentate ligands (alterdentate ligands are molecules (or ions), with two equivalent ligating atoms or ligating sites that do not simultaneously bind to a metallic center [Zelewsky von A. in Stereochemistry of Coordination Compounds, Inorganic Chemistry, A Textbook Series; John Wiley & Sons, Inc.: New York, 1995: p. 45] [1]) and 1,4-bis(diphenylphosphino)butane=dppb]. Electrochemical experiments (cyclic voltammetry and differential pulse voltammetry) suggest that for longer ligands the interaction between two ruthenium atoms is weak and for short ligands like pyrazine the corresponding interaction is strong. The analysis of the X-ra...

Here we describe a new chemical route for obtaining highly dispersed nanometric Ni particles embedded in different matrices based on Al2O3, MgO, and TiO2 and in the heterogeneous matrices CeO2-doped Al2O3 and MgO-doped Al2O3. The synthesis method is based on a modification of the polymeric precursor method. The Ni nanoparticles (particles in the range of 1-40 nm) were obtained in a single process, without the use of an external reducing agent (hydrogen atmosphere).

The porphyrin 5,10,15,20-tetrakis[4-(1,4,7,10,13-pentaoxacyclopentadecane-2-aminomethyl)2,3,5,6-tetrafluorophenyl]porphyrin,T15C5P, was synthesized by the reaction of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin with the crown ether 2-aminomethyl-(15-crown-5). The crowned porphyrin showed a distinct spectroscopic behavior in the presence of sodium and potassium ions. Dimerization studies based on absorption measurements clearly indicate that T15C5P aggregates in the presence of potassium ions in chloroform/methanol medium (1.0 × 10−5 mol.L −1 or 1.0 × 10−4 mol.L −1), with a dimerization constant ( K D ) of 2.14 × 10−5 and 2.23 × 10−5, respectively. The same formalism applied to the T15C5P in the presence of sodium ions indicated absence of the aggregation process. The ionic radius of Na + is suitable to fit well into the cavity of 15-crown-5 moieties, leading to intramolecular complexes only. Potassium ion is too large to lie in the hole of the crown ether entities and is probably located between two porphyrin molecules, promoting 2:1 aggregated complexes through it's sandwiching, as is observed for phthalocyanines.

The bioassay-guided fractionation of stems from Kielmeyera variabilis, traditionally used in Brazilian folk medicine, yielded assiguxanthone-B (1), kielcorin (4), 2,5-dihydroxybenzoic acid (3), and a mixture of xanthones containing assiguxanthone-B (1) and 1,3,5,6-tetrahydroxy-2-prenylxanthone (2) (1:1 w/w). The xanthone mixture inhibited Staphylococcus aureus and Bacillus subtilis at a concentration of 6.25 µg/ml. When tested alone, the minimal inhibitory concentration of assiguxanthone-B was 25 µg/ml against B. subtilis. Kielcorin and 2,5-dihydroxybenzoic acid were inactive against both strains. None of the fractions was active against Escherichia coli or Pseudomonas aeruginosa. Viable cells of S. aureus were reduced by a 1-3 log CFU/ml within 12 h after exposure of one to eight times the MIC of the xanthone mixture. It is not known whether the tetrahydroxy-2-prenylxanthone or other components of the xanthone mixture are responsible for the main antibacterial activity or whether additive or synergistic action is involved

Methanol extract obtained from Kielmeyera variabilis stems showed significant molluscicidal activity against Biomphalaria glabrata. The phytochemical studies of the plants stem to the isolation of three xanthones (assiguxanthone-B, kielcorin and 1,3,5,6-tetrahtydroxy-2-prenylxanthone) and a organic acid (2,5-dihydroxy benzoic acid). The structures of these compounds were identified by IR, MS, ¹H and 13C NMR spectral analysis and comparison with literature data.

From woods of Picrasma crenata, a new stereoisomer dihydronorneoquassin was obtained together with others well knowns dihydronorneoquassin, parain, alpha-neoquassin, beta-neoquassin and quassin. The structures were determined by spectroscopic data and chemical evidence.

The efficiency of microwave-assisted acid digestion of plants using different concentrations of nitric acid (2.0, 3.0, 5.0, 7.0 and 14 mol l−1) with hydrogen peroxide (30% v/v) was evaluated by measuring the residual carbon content (RCC) using inductively coupled plasma optical emission spectrometry (ICP-OES) with axial viewing. Certified reference materials were used for evaluating the accuracy attained when 2 mol l−1 HNO3 was employed for digestion. Under all experimental conditions RCC values were always lower than 13% w/v, and even the highest concentration did not cause any interference with element recovery. It seems that the high pressure reached for closed-vessel operation improved the oxidative action of nitric acid due to consequent temperature increase, even when this reagent was not used at high concentrations. According to acid–base titration data, residual acid in the digestates varied from 1.2 to 4.0 mol l−1, depending on the acid concentration initially added. It can be concluded that for plant materials, microwave-assisted acid digestion can be carried out under mild conditions, which implies that digestates do not need extensive dilution before introduction by pneumatic nebulization to ICP-OES. An additional advantage is the lower amount of residue generated when working with less concentrated acid solutions.

Nickel nanoparticles supported on amorphous silica ceramic matrix were synthesized by the polymeric precursor method. The nanostructure was characterized by NMR, BET, XRD, SEM, TEM, and flame atomic absorption spectrometry techniques. It was observed a dependence of the crystallite size on the thermal annealing, under a N2 atmosphere. The materials presented a high catalytic activity and selectivity upon the beta-pinene hydrogenation reaction. The magnetic hystereses were also correlated with the morphology of the processed material.

The fac-[RuCl3(NO)(dppb)] complex I has been prepared from solution of the correspondent mer isomer in refluxing methanol (dppb=1,4-bis(diphenylphosphino)butane). The mer-[RuCl3(NO)(diop)] (II) has been obtained from the mer-[RuCl3(diop)(H2O)] by bubbling NO for 1 h in dichloromethane (diop=2S,3S-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane). The complexes have been characterized by microanalysis, cyclic voltammetry (CV), IR and 31P{1H} NMR spectroscopies. The crystal and molecular structures of these two compounds have been determined from X-ray studies. The mer-[RuCl3(NO)(dppb)] isomer III was characterized in solution by NMR spectra (31P{1H}, 1H{31P}, 31P1H HETCORR, COSY 1H1H, HMQC 1H13C and HMBC 1H13C).

This work presents the synthesis and characterization of SiO2:metal (Ni, Co, Ag, and Fe) nanocomposites processed by the polymerizable complex method. The polymeric precursor solutions obtained were characterized by means of FT-Raman and 13C NMR spectroscopy. The results show the formation of a hybrid polymer with carbon and silicon in the macromolecule chain and the transition metal cation arrested within this polymeric chain. The nanocomposites are formed during the controlled polymeric precursor pyrolysis. The reduction of the metal cation is promoted by the CO/CO2 atmosphere resulting from the pyrolysis of the organic material. Microstructural characterization, performed by TEM and X-ray diffraction (XRD), showed that the nanocomposites are formed by metal nanoparticles embedded in a amorphous matrix formed by SiO2 and carbon. In the SiO2:Fe system, Fe3C was also detected by XRD.

Fractionation of the crude methanol extract of the ascidian Cystodytes dellechiajei collected in Brazil yielded two novel alkaloids, sebastianine A (1) and sebastianine B (2). The structures of both 1 and 2 were established by analysis of spectroscopic data, indicating an unprecedented ring system for both compounds, comprising a pyridoacridine system fused with a pyrrole unit in sebastianine A (1) and a pyridoacridine system fused with a pyrrolidine system condensed with alpha-hydroxyisovaleric acid in sebastianine B (2). Both alkaloids displayed a cytotoxic profile against a panel of HCT-116 colon carcinoma cells indicative of a p53 dependent mechanism.

A new ruthenium nitric oxide complex with the bidentate phosphine, 1,2-bis(diethylphosphino)ethane (depe), has been synthesized and characterized by UV–Vis, infrared, EPR, NMR, electrochemical techniques and X-ray structure determination. The electronic spectrum showed a typical band of dπ→pπ* charge-transfer (CT) transition, assigned to Ru(II)NO transition, and the vibrational spectrum exhibited a peak of nitrosyl ligand at ( ν NO =1851 cm −1 ). A model structure for this complex has been proposed based on 1 H, 1 H{ 31 P}, 31 P{ 1 H}, 13 C{ 1 H}, COSY 1 H 1 H{ 31 P}, J -Resolved, HSQC, HMBC, HSQC 1 H 13 C{ 31 P} and 1 H 13 C HSQC/ 1 H 1 H TOCSY spectral data, and confirmed by X-ray diffraction. The nitrosonium character for the NO ligand become evident through both electron paramagnetic resonance and X-ray data (angle RuNO=177.4(3)°). The reversible monoeletronic process at E 1/2 =0.040 V versus SHE was assigned to the ligand NO + /NO redox couple. Under treatment with Cd(Hg) solutions containing the [Ru(NO)(depe) 2 Cl](PF 6 ) 2 yields a signal in the EPR spectrum ( g ⊥ =1.99 and g // =1.88) which fitted quite well with the simulated spectra of coordinated NO species.

From the aerial parts of Cissus sicyoides , a new coumarin glycoside 5,6,7,8-tetrahydroxycoumarin-5 g -xylopyranoside was obtained together with known coumarin sabandin, two flavonoids kaempferol 3-rhamnoside and quercetin 3-rhamnoside and two steroids, sitosterol and 3 g - O - g - d -glucopyranosylsitosterol. The structure of compounds was elucidated by spectral analyses.

In Comparative Education the others must play a leading role. Aspiring to a social-dynamic approach, we believe that this education must comply with the premise of comprehensive learning, which translates into the declared purpose of achieving new knowledge of complex social realities. Comprehensive learning does not tolerate any sort of authoritarianism. Rather, it requires intellectual commitment to assessing the legitimacy of the knowledge produced and raising new questions or using other research methods or techniques. Comprehensive learning integrates and articulates knowledge, it is designed with the process, while searching for meaning in all sorts of information. The others here are not only part of the reality under study, who obviously cannot be ignored. They are also the peers and other people, from different disciplinary, cultural and ideological fields, who tackle the issue, and are the rather active and influential counterparts in the production, regulation and monitoring of the soundness of learning. Keywords: Comparative Education, social-dynamic approach, plurality and interdisciplinarity.

There are numerous organic pollutants that lead to several types of ecosystem damage and threaten human health. Wastewater treatment plants are responsible for the removal of natural and anthropogenic pollutants from the sewage, and because of this function, they play an important role in the protection of human health and the environment. Nuclear magnetic resonance (NMR) has proven to be a valuable analytical tool as a result of its versatility in characterizing both overall chemical composition as well as individual species in a wide range of mixtures. In addition, NMR can provide physical information (rigidity, dynamics, etc.) as well as permit in depth quantification. Hyphenation with other techniques such as liquid chromatography, solid phase extraction and mass spectrometry creates unprecedented capabilities for the identification of novel and unknown chemical species. Thus, NMR is widely used in the study of different components of wastewater, such as complex organic matter (fulvic and humic acids), sludge and wastewater. This review article summarizes the NMR spectroscopy methods applied in studies of organic pollutants from wastewater to provide an exhaustive review of the literature as well as a guide for readers interested in this topic.

A nossa análise fixou-se sobre o período de afirmação do dispositivo curricular liceal e a consolidação do programa da modernidade em Portugal, entre as décadas de trinta e cinquenta do século passado. Contudo, o Estado Novo ao demarcar-se de preocupações como o prolongamento da escolaridade e as teses da escola única recolocou na ordem do dia o problema da identidade do ensino do liceu. O debate incidiu, particularmente, sobre três eixos, os objetivos do ensino liceal, a organização curricular e a democratização. Centramo-nos na reflexão sobre os objetivos definidos para o ensino liceal e na sua organização curricular. Nesta perscrutamos a controvérsia em torno do regime de classe e do regime de disciplinas. Damos conta da discussão e das sucessivas tomadas de decisão a propósito da duração e estruturação dos ciclos de estudos. Articulado com os objetivos propostos para o ensino liceal, adquiriu alguma relevância a problemática das disciplinas que deveriam integrar, ou não, o plano de estudos bem como a justificação das opções adotadas. Convocamos, para este nosso estudo, como fontes, muito especialmente, a legislação que sustentou as alterações nos planos curricular e disciplinar, os diários da Assembleia Nacional e os pareceres da Câmara Corporativa aí insertos, bem como textos publicados na imprensa de educação e ensino, ainda que cônscios dos efeitos perversos da censura prévia. Our analysis focused on the establishment of the curricula of lyceums and the consolidation of the programme for modernity in Portugal, from the nineteen thirties to the fifties. The New State, however, a conservative and nationalist regime, while losing touch with concerns like extending schooling and the theses of a single secondary education, put back on the agenda the issue of the identity of education performed in lyceums. The discussion was focused, particularly, on three pillars: the goals of education in lyceums, the curricular organization and democratization. Our study was centred on the objectives established for lyceums and the organization of its curricula. Herein, we address the controversy about the class regime and the subject regime. We carried out the discussion and the decisions taken on the duration and structure of the study cycles. Connected to the objectives proposed for lyceums, the topic of the subjects which should or should not be included in the studies plan and the grounds on which such choices were made gained additional importance. As sources for our study we selected in particular the legislation which supported the changes to the curricula and subject plan, the diaries of the National Assembly and the opinions of the Corporativist Chamber addressed in this case, as well as publications by the media specialized in education and teaching, without losing sight of the perverse effects of the censorship.

The application of the title catalysts is presented in the Michael—addition of several functionalized nucleophiles to β—nitrostyrenes under mild conditions.

In the present investigation, two specimens of the nudipleuran mollusc Pleurobranchus areolatus have shown to accumulate oxidized rodriguesin A derivatives. Rodriguesic acid presents a carboxylic acid replacing the terminal methyl group of the alkyl chain of rodriguesin A. A hydroxamate group was also present on the diketopiperazine moiety of a rodriguesic acid derivative. The structures of both rodriguesic acid and of rodriguesic acid hydroxamate have been established by analysis of spectroscopic data, including their absolute configuration. Two methyl esters of the rodriguesic acids have been isolated as major compounds, but were considered to be isolation artifacts.

Desde 2005 que se assiste à assunção da Carta Educativaenquanto instrumento legitimador do planeamento estratégico e do reordenamento prospetivo das redes educativas municipais, cujos efeitos mais visíveis são traduzidos pelo encerramento de largas centenas de escolas do ensino primário (1º Ciclo do ensino básico) e pela construção de centenas de Centros Escolares. O presente artigo, com base numa investigação em curso, em catorze municípios da região central, está focado na identificação e análise das principais tendências de reordenamento da rede educativa do 1º Ciclo preconizadas nas respetivas Cartas Educativase cuja interpretação tem em conta a forma como todo o processo foi encarado, em termos de planeamento. A passagem de um planeamento de caraterísticas centralizadoras a um planeamento estratégico ofereceu ao reordenamento da rede escolar novas lógicas que se traduziram por diferentes respostas por parte dos municípios portugueses. Since 2005 the municipal School-chart has established itself as a tool for the legitimization of strategic planning and for the prospective reorganization of school networks at the municipal level, its most visible effects being the closing of many hundreds of primary schools (also known as 1st cycle, i.e., first through fourth grades) and the building of hundreds of School Centers. Based on current research carried out in fourteen municipalities of Portugal's central region, the present article aims to identify and analyze major trends in the reorganization of the network of primary schools as laid out in their School-charts, with special attention being paid to how the entire process was dealt with in the context of planning. The shift from a centralizing type of planning to strategic planning allowed for the emergence of fresh rationales in the reorganization of the school network, which in turn resulted in a variety of responses on the part of the municipalities. Desde el año 2005 se viene observado la ascensión de la Carta Educativa como instrumento legitimador de la planificación estratégica y de la reordenación prospectiva de las redes educativas municipales, cuyos efectos más visibles se traducen en el cierre de centenas de escuelas de la enseñanza primaria (1º Ciclo de enseñanza básica) y también en la construcción de centenas de Centros Escolares. El presente artículo, basado en una investigación en marcha, realizada en catorce municipios de la región central brasileña, se focaliza en la identificación y análisis de las principales tendencias de reordenación de la red educativa del 1º Ciclo preconizadas en las respectivas Cartas Educativas y cuya interpretación toma en cuenta la forma como todo el proceso se elaboró, en términos de planificación. El pasaje de una planificación de características centralizadoras a una planificación estratégica ofreció nuevas lógicas a la reordenación de la red escolar que se traducen en distintas respuestas por parte de los municipios portugueses.

* Doutor em Ciencias da Educacao. Professor Associado e Sub-Diretor da Faculdade de Psicologia e Ciencias da Educacao da Universidade de Coimbra. E-mail : antonio@fpce.uc.pt ** Doutor em Ciencias da Educacao, especializacao em Formacao de Professores. Professor Auxiliar no Departamento de Educacao e Ensino a Distância da Universidade Aberta, Portugal. E-mail : jmoreira@uab.pt Resumo No presente estudo procurou-se indagar a forma como os professores de Educacao Fisica em Portugal organizam as suas aulas. Procurou-se, ainda, perceber a relacao existente entre as suas praticas pedagogicas, as suas vivencias, as suas posturas e a influencia das suas escolas de formacao. Recorrendo a uma metodologia de cariz qualitativo o estudo centrou-se num grupo de quinze professores com formacoes iniciais realizadas nas instituicoes portuguesas mais marcantes. Concluiu-se que estes professores defendem uma aula bastante estruturada, baseada numa rigorosa planificacao, nao descurando a questao das motivacoes dos alunos. Concluiu-se, tambem, que a existencia de praticas pedagogicas (e posturas) diferenciadas, possivelmente devem-se as diferentes formacoes, ao contexto historico especifico e as diferentes vivencias, personalidades e motivacoes de cada professor. Estas diferencas sugerem, pois, a existencia de uma relacao entre as praticas pedagogicas e um habitus que se traduz nas vivencias adquiridas em diferentes ambientes culturais, politicos e educativos. Palavras-chave: Educacao Fisica. Professores. Praticas pedagogicas. Formacao inicial. Abstract The aim of this study is to analyse how Physical Education teachers in Portugal organise their lessons. Moreover, we sought to understand the existing relationship between those practices, their experiences, attitudes and the influence of training schools. Based on a qualitative methodology, the study focused on a group of fifteen teachers with varied degrees in Physical Education, who graduated from some of the most distinguished schools in Portugal. We concluded that these teachers defend the use of well structured classes, based on strict planning, not neglecting students’ motivations. Moreover, that the existence of different pedagogical practices (and attitudes) is possibile due to different training, to the specific historical context and different experiences, personalities and motivations of each teacher. These differences suggest, therefore, there is a relationship between pedagogical practices and a habitus, which means experiences acquired in different cultural, political and educational environments. Keywords : Pedagogical. Practices. Physical Education. Teachers. Apoio: Fundacao para a Ciencia e a Tecnologia

No presente estudo procurou-se analisar as representações que os professores das diferentes escolas de Educação Física em Portugal possuem acerca da relação existente entre a sua formação inicial e o exercício da profissão docente, nomeadamente a nível da sua adequabilidade, das limitações dessa formação e das expetativas criadas. Recorrendo a uma metodologia de cariz qualitativo o estudo centrou-se num grupo de quinze professores com formações iniciais realizadas nas instituições portuguesas mais marcantes do século XX: o Instituto Nacional de Educação Física, as Escolas Superiores de Educação Física, os Institutos Superiores de Educação de Lisboa e do Porto e as Faculdades de Ciências do Desporto e Educação Física. Concluiu-se que estes professores, independentemente da sua escola, consideram que a sua formação inicial, apesar de algumas limitações em áreas muito específicas, os preparou adequadamente para o exercício da sua atividade enquanto professores de Educação Física, tendo correspondido, na sua generalidade, às suas expectativas.

Aliphatic and aromatic sulfides, ketosulfides, sulfinyl acids and esters, and olefinic sulfides were oxidized to sulfoxides using oxodiperoxo complexes of molybdenum coated on silica gel (150 A pore size) in very high yields. Complete chemoselectivity was observed for the oxidation of all functional sulfides. Sulfones were, however, the main products of the reaction when the complexes were not coated on silica gel. The influence of silica gel as the support of these reactions was also investigated and it was demonstrated that it alters the reactivity of the complex but it is not responsible for the excellent chemoselectivity of the complexes. The complex [MoO(O2)2(pyrazole) (H2O)] proved to be more reactive than [MoO(O2)2(Opyr) (H2O)].

The sporting practices in the city of Porto in the year 1900 A book published in the 1940’s criticised the people of Porto because they considered themselves as sports people when all they did was watch their own team’s games and argue about football. Its author alleged that, in Porto in 1900, people took part in swimming, “jogo do pau”, fencing, equestrian events, gymnastics, rowing, cycling, bullfighting and weightlifting, and that young people were neither disinterested in physical activity nor in competitive sport. In order to establish the quality of the abovementioned opinion, we intend, with this article, to highlight the range of sports activities in Porto, at the beginning of the last century. We also intend to reveal the social importance of these activities in the country‘ s second largest city, based on the impact they had on two newspapers published at that time.

Investigation of the leaves of Raulinoa echinata Cowan (Rutaceae) has led to the isolation of several furofuran (2,6-diaryl-3,7-dioxabicyclo[3.3.0]-octane) lignan derivatives, namely (+)-sesamin, (+)-eudesmin, (+)-methylpiperitol (= kobusin), (+)-piperitol-γ,γ-dimethylallylether and the corresponding epi compounds: (+)-asarinin, (+)-epieudesmin, (+)-methylxanthoxylol, (+)-methylpluviatilol, (+)-xanthoxylol-γ,γ-dimethylallylether and (+)-pluviatilol-γ,γ-dimethylallylether. This is the first report of the chromatographic separation of the epimers (+)-methylxanthoxylol/(+)-methylpluviatilol and (+)-xanthoxylol-γ,γ-dimethylallylether/(+)-pluviatilol-γ,γ-dimethylallylether and of their NMR nOe difference studies. Copyright © 2001 John Wiley & Sons, Ltd.

Manganese(III) 5-(pentafluorophenyl)-10,15,20-tri(2,6-dichlorophenyl)porphyrin, Mn(PFTDCPP), and manganese(II) 2,3,7,8,12,13,17,18-octachloro-5-(pentafluorophenyl)-10,15-20-tri(2,6-dichlorophenyl)porphyrin, Mn(PFTDCCl 8 PP), have been synthesised and used as catalysts in hydrocarbon oxidations by iodosylbenzene and hydrogen peroxide both in solution and covalently bound to aminopropylated silica. The former shows higher efficiency in the epoxidation of alkenes by iodosylbenzene, whereas the perchlorinated manganese porphyrin is more efficient in the hydroxylation of alkanes by this oxidant. The supported manganese(III) porphyrin show the same activity as its homogeneous analogue. With hydrogen peroxide as oxygen donor, Mn(PFTDCPP) is a stable and effective catalyst in the presence of imidazole. The perchlorinated analogue is a poor catalyst with this oxidant. The eight additional chlorine atoms on the porphyrin ring stabilise Mn(II) and unfavour the formation of the active species, Mn V O.

The synthesis of a hybrid network consisting of alternating porphyrin as optical active agent and siloxane units (porphyrinosilica) can be achieved by sol–gel process. Due to several applications of these hybrids, we search for new methods to prepare them. A porphyrinosilica with a urea linker was synthesized through the reaction of NH2 groups present in the phenyl rings of mesotetrakis p-aminophenyl porphyrin (TAMPPH2) with 3-isocyanatopropyltriethoxysilane (IPTES) followed by condensation with tetraethoxysilane (TEOS). The polymerization reactions were carried out in ethanol or dimethylformamide using acidic or basic catalysis. The formation of urea bonds was confirmed by infrared spectroscopy. The absorption and luminescence spectra confirmed the presence of porphyrin in the network and were also established by thermal analysis. Nuclear magnetic resonance 29Si data for the porphyrinosilica addressed the degree of condensation and the extent of network formation.

Arenosclerins A (2), B (3), and C (4), as well as haliclonacyclamine E (1), are new tetracyclic alkylpiperidine alkaloids isolated from a new species of marine sponge belonging to the order Haplosclerida, Arenosclera brasiliensis, a species endemic to the southeastern Brazilian coast. The alkaloids were isolated as their hydrochloride salts and identified by analysis of spectroscopic data. Data obtained from (1)H-(1)H COSY, HMBC, and HSQC-TOCSY NMR experiments allowed complete assignment of the (1)H and (13)C resonances, and analysis of the NOESY and ROESY spectra showed that the only differences between 2, 3, and 4 were the relative stereochemistries of the bispiperidine ring system. Arenosclerins A-C are the first haliclonacyclamine/halicyclamine-related alkaloids with a hydroxy group in the bridging alkyl chain.

Mandevilla velutina , a native plant to Brazil, is a source for bioactive triterpenoids which selectively and in a competitive way inhibited bradykinin (BK)-induced contractions of isolated rat uterus and guinea-pig ileum. These compounds were also found in cell cultures with an anti-BK action about two orders of magnitude larger than those from tuber extracts. Biomass from cell cultures was used to determine the basic composition of the cell wall, pursuing in further studies whether that parameter might be used to distinguish between cell lines and between cells of different ages. Hemicellulosic fractions showed a predominant neutral sugar composition, with d -Glc, l -Rha and d -Xyl as the major components. The deoxy-sugar l -Fuc was also found as a minor constituent. 13 C NMR spectrum of the hemicellulose A (5 M KOH) revealed β and α conformations for d -Glc and l -Rha, respectively; the discrete signal for the carboxyl from the uronyl moiety (downfield), and the absence of (1-2) and (1-3) linkages. Spectroscopy also suggested a β (1-6) linking for a polyglucose backbone or block. A more detailed structural analysis for the presence of l -Fuc is in progress.

Submitted by Guilherme Lemeszenski (guilherme@nead.unesp.br) on 2013-08-22T18:58:49Z No. of bitstreams: 1 S0103-50532000000500005.pdf: 190509 bytes, checksum: 2bc1d49b5678f0ebc0ec0adbb660b532 (MD5) Made available in DSpace on 2013-08-22T18:58:49Z (GMT). No. of bitstreams: 1 S0103-50532000000500005.pdf: 190509 bytes, checksum: 2bc1d49b5678f0ebc0ec0adbb660b532 (MD5) Previous issue date: 2000-10-01 Made available in DSpace on 2013-09-30T19:54:53Z (GMT). No. of bitstreams: 2 S0103-50532000000500005.pdf: 190509 bytes, checksum: 2bc1d49b5678f0ebc0ec0adbb660b532 (MD5) S0103-50532000000500005.pdf.txt: 39972 bytes, checksum: c8b1dabcdf29b072b2563b56979a599f (MD5) Previous issue date: 2000-10-01 Submitted by Vitor Silverio Rodrigues (vitorsrodrigues@reitoria.unesp.br) on 2014-05-20T14:18:56Z No. of bitstreams: 2 S0103-50532000000500005.pdf: 190509 bytes, checksum: 2bc1d49b5678f0ebc0ec0adbb660b532 (MD5) S0103-50532000000500005.pdf.txt: 39972 bytes, checksum: c8b1dabcdf29b072b2563b56979a599f (MD5) Made available in DSpace on 2014-05-20T14:18:56Z (GMT). No. of bitstreams: 2 S0103-50532000000500005.pdf: 190509 bytes, checksum: 2bc1d49b5678f0ebc0ec0adbb660b532 (MD5) S0103-50532000000500005.pdf.txt: 39972 bytes, checksum: c8b1dabcdf29b072b2563b56979a599f (MD5) Previous issue date: 2000-10-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) As porfirinas aniônicas 5,10,15-tris(4-carboxifenil), 20-mono(2-nitrofenil) porfirina (1), 5,10(ou 15)-bis(4-carboxifenil), 15(or 10),20-bis(2-nitrofenil)porfirina (2) and 5-mono(4-carboxifenil), 10,15,20-tris(2-nitrofenil)porfirina (3), foram sintetizadas diretamente através da reação de pirrol com os benzaldeídos substituídos em meio de ácido propiônico/nitrobenzeno. A relação molar dos benzaldeídos foi controlada para otimizar a síntese e purificação das porfirinas desejadas. Esta nova série de porfirinas foi caracterizada por cromatografia em camada delgada, espectrometria de massas (FAB MS), RMN ¹H, UV/Vis, IV e eletroquímica. As porfirinas 5,10,15,20-tetrakis(4-carboxifenil)porfirina (4) e 5,10,15,20-tetrakis(2-nitrofenil)porfirina (5) também foram estudadas para comparação, tornando a série completa. A redução eletroquímica das porfirinas base livre e correspondentes ferro(III) porfirinas foi investigada em eletrodos de carbono e mercúrio. Os potenciais de redução mostraram a dependência esperada do número de grupos nitro, fortemente retirador de elétrons, presentes no anel porfirínico, fornecendo evidências adicionais para a caracterização dos compostos sintetizados. The anionic 5,10,15-tris(4-carboxyphenyl), 20-mono(2-nitrophenyl) porphyrin (1), 5,10(or 15)-bis(4-carboxyphenyl), 15(or 10),20-bis(2-nitrophenyl)porphyrin (2) and 5-mono(4-carboxyphenyl), 10,15,20-tris(2-nitrophenyl)porphyrin (3) were sinthesized directly by reaction of pyrrole with substituted benzaldehydes in nitrobenzene/propionic acid media. The benzaldehydes molar ratio was controlled to optimize the synthesis and purification of the desired porphyrins. This new series of porphyrins was characterised by TLC, mass spectrometry (FAB MS), ¹H NMR, UV/Vis, IR and electrochemistry. 5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrin (4) and 5,10,15,20-Tetrakis(2-nitrophenyl)porphyrin (5) were also characterised for comparative purposes, completing the series The electrochemical reduction was investigated for the free base and corresponding iron(III) porphyrins on glassy carbon and mercury electrodes. The reduction potentials showed the expected dependence on the number of electron-withdrawing nitro groups present on the porphyrin ring providing additional evidences for the characterisation of the synthesised compounds. Universidade de São Paulo Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto Departamento de Química Universidade Federal de São Carlos (UFSCar) Departamento de Química Universidade Estadual Paulista Instituto de Química Universidade Estadual Paulista Instituto de Química

The synthesis, characterization and catalytic activity of the cationic iron porphyrins Fe[M(4-N-MePy)TDCPP]Cl2 and Fe[M(4-N-MePy)TFPP]Cl2 in the epoxidation of (Z)-cyclooctene by PhIO in homogeneous solution and supported on silica gel (SG), imidazole propyl gel (IPG) or SG modified with 2-(4-sulfonatophenyl)ethyl groups (SiSO3) have been accomplished. When supported on IPG, both cationic FeP bind to the support via Fe–imidazole coordination. Fe[M(4-N-MePy)TDCPP]IPG contains a mixture of low-spin bis-coordinated FeIIIP and high-spin mono-coordinated FeIIIP species, whereas Fe[M(4-N-MePy)TFPP]IPG only contains high-spin mono-coordinated FeIIIP. These FePIPG catalysts also contain FeIIP species, whose presence was confirmed by EPR spectroscopy using NO as a paramagnetic probe. Both cationic FePs coordinate to SG through Fe–O ligation and they are present as high-spin FeIIIP species. The cationic FePs supported on SiSO3− are also high-spin FeIIIP species and they bind to the support via electrostatic interaction between the 4-N-methylpyridyl groups and the SO3− groups present on the matrix. In homogeneous solution, both Fe[M(4-N-MePy)TDCPP]Cl2 and Fe[M(4-N-MePy)TFPP]Cl2 have similar catalytic activity to Fe(TDCPP)Cl and Fe(TFPP)Cl, leading to cis-epoxycyclooctane yields of 92%. When supported on inorganic matrices, both FePs lead to epoxide yields comparable to their homogeneous analogues and their anchoring enables catalyst recovery and re-use. Recycling of Fe[M(4-N-MePy)TDCPP]SiSO3− shows that this FeP maintains its activity in a second reaction.

Quantum mechanics calculations at the ab initio HF/3-21G∗ level were carried out with Nuclear Magnetic Resonance (NMR) measurements to characterize citric acid and lithium interactions. The results indicate the formation of a tridentate organometallic compound with one lithium and one citric acid molecule and a tridentate and bidentate compound of two lithium atoms and one citric acid molecule. The results are in agreement with the experimental and theoretical data.

Porphyrin was incorporated in a silicate network, via a covalent bond, by grafting a functional group with 3-aminopropyltriethoxysilane, using a sol–gel process. We have carried out the synthesis and measured the absorption spectra, nuclear magnetic resonance spectra, infrared (IR) spectra, luminescence spectra and lifetime of these hybrid silicates, porphyrinosilicas. These samples contained the following free-base porphyrins: meso-tetrakis- p -chlorobenzoylporphyrin, meso-tetrakis-2,6-dichloro-3-chlorosulfonylphenylporphyrin. The obtained porphyrinosilicas have similar absorption and luminescence spectra to the free base porphyrins in solution. IR spectra confirm the formation of monomeric species. Lifetime measurement for porphyrinosilica reveals that 32% ± 2% of porphyrin is covalently bonded to the silica network.

The objective of this study was to evaluate the larvicidal activity of diterpenoids obtained from the oil-resin of Copaifera reticulata against Aedes aegypti larvae, the principal vector of dengue and urban yellow fever. Four diterpenes were obtained from oil-resin extraction with organic solvents and subsequent chromatographic and spectroscopic procedures allowed to isolation and identification of these compounds as 3-b-acetoxylabdan-8(17)-13-dien-15-oic acid (1), alepterolic acid (2), 3-b-hidroxylabdan-8(17)-en-15-oic acid (3), and ent-agatic acid (4). Each compound was previously dissolved in dimethylsulphoxide, and distilled water was added to obtain the desired concentrations. Twenty larvae of third instars were placed into plastic beckers, containing the solution test (25 mL), in a five repetitions scheme, and their mortality, indicated by torpor and darkening of the cephalic capsule, was recorded after 48h. Probit analyses were used to determine lethal concentrations (LC50 and LC90) and their respective 95% confidence intervals. This study showed that only diterpenoids 1 and 2 exhibited larvicidal properties with LC50 of 0.8 ppm and 87.3 ppm, respectively, revealing the former as the most toxic compound against third instars of Ae. aegypti. Therefore, this compound seems to be an interesting source for new metabolite to be exploited.

The stem bark of Trichilia estipulata afforded three novel meliacin butenolides, 7 α -23-dihydroxy-3-oxo-24,25,26,27-tetranorapotirucall-1,14,20(22)-trien-21,23-olide, 7-deacetyl-23-hydroxyneotrichilenonelide and 7-deacetyl-21-hydroxyneotrichilenonelide, which were identified on the basis of spectroscopic analyses. Scopoletin, isofraxidin, 7-oxo-24 β -, 7-oxo-24 α -sitosterols and 3 β - O - β - d -glucopyranosylsitosterol were also isolated. The known compounds, velozonol, carnaubadiol, velozona, carnauba-21-ol-3-one, isofouqueriol, isofouquerinone, sitostenone and sitosterol were isolated from the leaves.

Fourteen complexes in the series [RuCl2(CO)(L)(PPh3)2] (where L = N-heterocycles) have been prepared and characterized by IR and NMR spectroscopies, and cyclic voltammetry. A good correlation is found between observed and calculated electrochemical potentials; E 1 2 vs pKa or (Gp, σm for a series of similar ligands. It is now reported that the carbonyl stretching frequency, νCO, and the 13C and 31P NMR signals do not correlate well with any of the physico-chemical parameters used ( E 1 2 , Taft's and Hammett's parameters). This behaviour is probably due to the characteristics of the Ru(II) species, which does not transmit the steric and electron donor/acceptor properties of the ligands to the carbonyl group, or because the measurements are not able to detect the effect induced by the changes in the ligand L. Indeed, good correlations are obtained when the measurements directly involve the metal centre, as is the case in the E 1 2 measurements. Crystals of [RuCl2(CO)(4-pic)(PPh3)] are monoclinic, space group P21/n, a = 12.019(2), b = 13.825(3) and c = 22.253(3) . The structure was solved by the Patterson method and was refined by full-matrix least-squares procedure to R = 0.054 and Rw = 0.055, for 2114 reflections with I > 3σ(I). For L = 2-acetylpyridine and 2-methylimidazole, complexes with formulae [RuCl2(CO)(L)(PPh3)] · L and [RuC12(CO)(L)2 (PPh3)], respectively, were obtained.

The methanol extract of the stem bark of Trichilia estipulata afforded four aryltetralin lignan glycosides which were identified on the basis of spectroscopic analysis of their acetates as (−)-isolariciresinol-3α-O-β-D-xylopyranoside and the new lignans (+)-4′-0-methyl-9′-deoxiisolariciresinol-3α-O-β-D-glucopyranoside, (−)-lyoniresinol-3α-L-rhamnopyranoside.

The main purpose of this work is to describe the use of the technique Site-Specific Natural Isotopic Fractionation of hydrogen (SNIF-NMR), using ²H and ¹H NMR spectroscopy, to investigate the biosynthetic origin of acetic acid in commercial samples of Brazilian vinegar. This method is based on the deuterium to hydrogen ratio at a specific position (methyl group) of acetic acid obtained by fermentation, through different biosynthetic mechanisms, which result in different isotopic ratios. We measured the isotopic ratio of vinegars obtained through C3, C4, and CAM biosynthetic mechanisms, blends of C3 and C4 (agrins) and synthetic acetic acid.

Since natural substances like pseudoxanthins exert a positive effect on the cellulogenic ability of Acetobacter xylinum when producing cellulosic pellicles suitable for skin burn therapy, new defined and complex modulators were sought. Ca2+ and Mg2+ (4 mM) were strongly stimulatory. Na+ had no effect and K+ was inhibitory. Ammonium dihydrogen phosphate (0.12 g/L) ensured the same nitrogen supply as the same concentration of yeast extract as measured by cellomembrane dry wt./yield albeit higher yeast extract supplies produced thicker membranes. Corn steep liquor (CSL) was also progressively beneficial from 0.125 to 0.5 mL/L, and this yield could be further improved by the combination of CSL with a tea infusion (source of caffeine). Uridine (precursor for UDP-Glc, sugar donor in cellulose biosynthesis), guanine, guanosine, and its butirylated derivatives (precursors for the positive modulator of cellulose synthetase, di-cGMP) resulted in only moderate stimulation. Sodium phytate and betaine were also slightly stimulatory. The fibrilar product from a new Acetobacter isolate (Ax-M) was characterized as cellulose by comparison with the solid-state(13)C-NMR of algal cellulose. Its X-ray diffractogram was a confirmatory analysis. After incorporation of tamarind xyloglucan to previously air-dried cellulosic pellicles, diffractometry displayed only slight differences. Mercerized (5M NaOH) fresh cellulosic biofilms underwent drastic size reduction (3.5-fold), turning compact nut still flexible if maintained wet.

The chemical reactions carried out by microorganisms have been used as a tool in modern chemistry. This paper reports the production of mycophenolic acid and a new phthalide by the endophytic fungus Penicillium crustosum obtained from coffee seeds. The fungus was cultivated in a liquid medium for a period of seven days and after that the culture medium was divided into four treatments: A, B, C and D, to which different organic substances were added. Treatment A was maintained as the control to evaluate the occurrence of biotransformation. Organic acids were added to the culture media of treatments B (ferulic and quinic acids) and C [cinnamic and 3,4-(methylenedioxy) cinnamic acids], and caffeine was added in the treatment D. All these organic compounds were dissolved in DMSO, and the fermentation was maintained for more 13 days, totalizing 20 days. Mycophenolic acid was isolated from the culture with no added acids (treatment A). Mycophenolic acid and a new phthalide, 5-hydroxy-7-methoxy-4-methylphthalide were isolated from treatments B and C, and mycophenolic acid and caffeine (added to the culture medium) were isolated from treatment D. The structures were determined by NMR techniques and confirmed by MS and MS/MS techniques. As reações químicas realizadas por microorganismos têm sido utilizadas como uma ferramenta na química moderna. Este artigo relata a produção de ácido micofenólico e uma nova ftalida pelo fungo endofítico Penicillium crustosum obtido a partir de grãos de café. O fungo foi cultivado em meio líquido durante um período de sete dias, e depois disso, o meio de cultura foi dividido em quatro lotes: A, B, C e D, nos quais diferentes substâncias orgânicas foram adicionadas. O lote A foi mantido como controle para avaliar a ocorrência de biotransformação. Os ácidos orgânicos foram adicionados ao meio de cultura dos lotes B (ácidos ferúlico e quínico) e C [ácido cinâmico e 3,4-(metilenodioxi) cinâmico], e cafeína foi adicionada ao lote D. Todos estes compostos orgânicos foram dissolvidos em DMSO, e a fermentação foi mantida por mais 13 dias, totalizando 20 dias. O ácido micofenólico foi isolado a partir da cultura sem adição de ácidos (lote A). O ácido micofenólico e uma nova ftalida, 5-hidroxi-7-metoxi-4-metilftalida, foram isolados a partir dos lotes B e C, e ácido micofenólico e cafeína (adicionada ao meio de cultura) foram isolados a partir do lote D. As estruturas foram determinadas pela técnica de RMN e confirmadas pelas técnicas de MS e MS/MS.

Este trabalho pretende interpretar o processo de construção do grupo profissional dos enfermeiros portugueses, entre os anos de 1940 e 1980 do século XX. Partimos da discussão conceptual sobre o papel formativo e credencialista das instituições escolares de enfermagem, em articulação com o Estado, para compreender a construção identitária deste grupo, caraterizando os sujeitos que frequentaram a Escola de Enfermagem de Castelo Branco/Dr. Lopes Dias (Portugal), no arco temporal previsto. A metodologia assumida na construção deste artigo é a análise sócio-histórica, numa perspetiva diacrónica. A História da Educação e a Sociologia das Profissões constituem os principais domínios científicos em que o trabalho assenta.

The defensive secretion of the frontal gland from termite soldiers is a mixture of monoterpenes, sesquiterpenes and diterpenes, the latter being the most representative. Analyses of the dichloromethane extract from soldiers of the Brazilian termite, Nasutitermes macrocephalus (Silvestri, 1903) (Isoptera, Nasutitermitinae), described for the first time, allowed to identify the presence of two monoterpenes (alpha-pinene and limonene) and two sesquiterpenes (beta-trans-caryophyllene and gamma-selinene) [corrected] by GC-EIMS, and the isolation of one rippertane and six trinervitane diterpenes by RP-HPLC. The chemical structures of the purified compounds were elucidated by interpretation of their spectroscopic data (1D and 2D NMR, EIMS, HRESIMS, and specific optical rotation) and the complete unequivocal assignment of the 3a-hydroxy-trinervita-1(15),8(19)-dien-2-one (6) was included in this paper, to complement the lack of information in the literature. Antibacterial, antifungal and cytotoxicity against cancer cell lines activities were evaluated. In particular, the compounds 2alpha,3beta-dihydroxytrinervita-l(15),8(19)-diene (2) and 3alpha-hydroxy-15-rippertene (7) exhibited the better activities against the clinically isolated Gram-positive bacterium methicillin-resistant Staphylococcus aureus BMB 9393, both with a MIC value of 31.2 microg mL(-1). This is the first description of a rippertane diterpene (7) as an antibacterial agent.

A model betalainic dye was semisynthesized from betanin, the magenta pigment of the red beet, and was effective for live-cell imaging of Plasmodium-infected red blood cells. This water-soluble fluorescent probe is photostable, excitable in the visible region and cell membrane-permeable, and its photophysical properties are not notably pH-sensitive. Fluorescence imaging microscopy of erythrocytes infected with Plasmodium falciparum, a causative agent of malaria in humans, showed that only the parasite was stained. Z-stacking analysis suggested that the probe accumulates proximal to the nucleus of the parasite. Indicaxanthin, one of the natural fluorescent betalains found in the petals of certain flowers, did not stain the parasite or the red blood cell.

A nossa análise incide sobre o modelo de formação de professores das Escolas Normais Superiores, particularmente sobre a escola anexa à Universidade de Coimbra. Instituições inspiradas na École Normale Supérieur de Paris, marcadas pela pedagogia do movimento da Escola Nova e portadoras de um caráter inovador, peça-chave num projeto educativo mais vasto, encetado pelos republicanos após outubro de 1910, fundado na crença de regenerar a Pátria por via da instrução, fabricando um cidadão novo e construindo a Nação republicana, constituíram a primeira tentativa de formar professores para todos os graus de ensino, com exceção do ensino primário geral. Numa perspetiva teórica e ideal, a legislação traduziu um momento significativo na nossa História da Educação (Gomes, 1990); no entanto, o contexto e as condições - nomeadamente as materiais - impediram-na que se viesse a transformar na escola modelo que se almejava. Our analysis focuses on the model of teacher training from Escolas Normais Superiores, particularly concerning the school belonging to the University of Coimbra. Inspired by the École Normale Supérieure in Paris, those institutions were marked by the pedagogy of the New School Movement, carrying innovative proposals. A key part of a wider educational project initiated by Republicans after October 1910, founded on the belief of regenerating homeland by education, the creation of a new citizen and the building of the Republican nation, these institutions constituted the first attempt to train teachers on all levels of education, except the general primary education. On an ideal and theoretical perspective, the legislation meant a significant milestone in our history of education (Gomes, 1990). However, the context and conditions, including materials, prevented the school from becoming the desired model. Notre analyse met l'accent sur le modèle de formation des Écoles Normales Supérieures de formation des enseignants, particulièrement sur l’école rattaché à l’Université de Coimbra. Institutions inspirées par l'Ecole Normale Supérieure de Paris, marquées par la pédagogie du mouvement d’École Nouvelle et avec un caractère novateur, un élément-clé dans un grand projet éducatif, commencé par les républicains après Octobre 1910, fondé sur la croyance de la régénération de la patrie au moyen de l’instruction, fabrication d’un nouveau citoyen et l’édification de la nation républicaine, a constitué la première tentative pour former les enseignants pour tous les niveaux de l’éducation, à l’exception de l’enseignement primaire général. Dans une perspective théorique et idéale, la Loi traduit un moment important de notre histoire de l’éducation (Gomes, 1990); malgré tout, le contexte et les conditions notamment matérielles l’empêchait de devenir l’école modèle désiré.

The purpose of this study was to report evidence obtained in Communities of Inquiry (CoI) as framed by the work of Garrison, Anderson and Archer (2000) that was carried out in different groups, and identify the emergent learning skills of its students. The study comprised 510 undergraduate students enrolled in blended online courses offered through Moodle platform during one semester. It considered students from different Portuguese schools, of University and Polytechnic in Health, Education and Psychology Courses. Moreira and Almeida (2011) have suggested that CoI framework is a valid, reliable, and efficient measure of its dimensions within the Portuguese population. Assuming the CoI survey as a useful evaluation tool for providing feedback about the effectiveness of online courses in the construction of effective learning communities, we’ve studied the skills students recognize they acquire in virtual environments of learning, using the adapted Self-Learning Competence Scale (Lima-Santos, Rurato, & Faria, 2000). We’ve con- cluded that in both institutions, University and Polytechnic, relevant learning experiences have been fos- tered, towards the emergence of communities of inquiry, in which the students perceived that they have developed self-learning competences. Fundação para a Ciência e a Tecnologia

The reserve polymeric inulin from dahlia tuber (>12% or >60% yield, wet or dry basis, respectively) follows as an attractive source for both free fructose or difructofuranose anhydride (DFA III). Although DFA biological activity is not completely understood, there is interest in characterizing other DFA III-producers besides Arthrobacter ureafaciens. The inulinolytic bacterial isolate named YLW, owing to the yellow hue in agar slants, is such a producer. Its biochemical characterization showed the presence of galactosylated and mannosylated glycolipids associated with the bacterial cells. Immobilization of fungal inulinase I and bacterial inulinase II, the respective enzymatic catalysts for the production of fructose and DFA III by inulin hydrolysis, was attempted using controlled-pore silica (CPS). The effects of pH, temperature, and incubation time was analyzed and compared for both enzymes in the free and immobilized forms.

The informal (and/or illegal) e-commerce of pharmaceutical formulations causes problems that governmental health agencies find hard to control, one of which concerns formulas sold as natural products. The purpose of this work was to explore the advantages and limitations of DOSY and HPLC-UV-SPE-NMR. These techniques were used to identify the components of a formula illegally marketed in Brazil as an herbal medicine possessing anti-inflammatory and analgesic properties. DOSY was able to detect the major components present at higher concentrations. Complete characterization was achieved using HPLC-UV-SPE-NMR, and 1D and 2D NMR analyses enabled the identification of known synthetic drugs. These were ranitidine and a mixture of orphenadrine citrate, piroxicam, and dexamethasone, which are co-formulated in a remedy called Rheumazim that is used to relieve severe pain, but it is prohibited in Brazil because of a lack of sufficient pharmacokinetic and pharmacodynamic information.