Crystal structure of garciniaphenone and evidences on the relationship between keto-enol tautomerism and configuration

Garciniaphenone (=rel-(1R,5R,7R)-3-benzoyl-4-hydroxy-8,8-dimethyl-1,7-bis(3-methylbut-2-en-1-yl)bicyclo[3.3.1]non-3-ene-2,9-dione; 1). a novel natural product, was isolated from a hexane extract of Garcinia brasiliensis fruits. The crystal structure of 1 as well as the selected geometrical and Configurational features were compared with those of known related polyprenylated benzophenones. Garciniaphenone is the first representative of polyprenylated benzophenones without a prenyl substituent at C(5). Notably, the absence of a 5-prenyl substituent has an impact on the molecular geometry. The tautomeric form of 1 in the solid state was readily established by a residual-electronic-density map generated by means of a difference Fourier analysis, and there is an entirely delocalized six-membered chelate ring encompassing the keto-enol moiety. The configuration at C(7) was used to rationalize the nature of the keto-enol tautomeric form within 1. The intermolecular array in the network is maintained by nonclassical intermolecular H-bonds.

Refraction corrected transmission ultrasound computed tomography for application in breast imaging

Purpose: We present an iterative framework for CT reconstruction from transmission ultrasound data which accurately and efficiently models the strong refraction effects that occur in our target application: Imaging the female breast. Methods: Our refractive ray tracing framework has its foundation in the fast marching method (FNMM) and it allows an accurate as well as efficient modeling of curved rays. We also describe a novel regularization scheme that yields further significant reconstruction quality improvements. A final contribution is the development of a realistic anthropomorphic digital breast phantom based on the NIH Visible Female data set. Results: Our system is able to resolve very fine details even in the presence of significant noise, and it reconstructs both sound speed and attenuation data. Excellent correspondence with a traditional, but significantly more computationally expensive wave equation solver is achieved. Conclusions: Apart from the accurate modeling of curved rays, decisive factors have also been our regularization scheme and the high-quality interpolation filter we have used. An added benefit of our framework is that it accelerates well on GPUs where we have shown that clinical 3D reconstruction speeds on the order of minutes are possible.

A non-parametric vessel detection method for complex vascular structures

Modern medical imaging techniques enable the acquisition of in vivo high resolution images of the vascular system. Most common methods for the detection of vessels in these images, such as multiscale Hessian-based operators and matched filters, rely on the assumption that at each voxel there is a single cylinder. Such an assumption is clearly violated at the multitude of branching points that are easily observed in all, but the Most focused vascular image studies. In this paper, we propose a novel method for detecting vessels in medical images that relaxes this single cylinder assumption. We directly exploit local neighborhood intensities and extract characteristics of the local intensity profile (in a spherical polar coordinate system) which we term as the polar neighborhood intensity profile. We present a new method to capture the common properties shared by polar neighborhood intensity profiles for all the types of vascular points belonging to the vascular system. The new method enables us to detect vessels even near complex extreme points, including branching points. Our method demonstrates improved performance over standard methods on both 2D synthetic images and 3D animal and clinical vascular images, particularly close to vessel branching regions. (C) 2008 Elsevier B.V. All rights reserved.

Structure effects of self-assembled Prussian blue confined in highly organized mesoporous TiO(2) on the electrocatalytic properties towards H(2)O(2) detection

Here we report the derivatization of mesoporous TiO(2) thin films for the preparation of H(2)O(2) amperometric sensors. The coordination of the bifunctional ligand 1,10 phenantroline, 5,6 dione on the surface Ti(IV) ions provides open coordination sites for Fe(II) cations which are the starting point for the growth of a layer of Prussian blue polymer. The porous structure of the mesoporous TiO(2) allows the growth, ion by ion of the coordination polymer. Up to four layer of Prussian blue can be deposit without losing the porous structure of the film, which results in an enhanced response of these materials as H(2)O(2) sensors. These porous confined PB modified electrodes are robust sensors that exhibit good reproducibility, environmental stability and high sensitivity towards H(2)O(2) detection. (C) 2010 Elsevier B.V. All rights reserved.

Simultaneous voltammetric determination of paracetamol and caffeine in pharmaceutical formulations using a boron-doped diamond electrode

A simple and highly selective electrochemical method was developed for the single or simultaneous determination of paracetamol (N-acetyl-p-aminophenol, acetaminophen) and caffeine (3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione) in aqueous media (acetate buffer, pH 4.5) on a boron-doped diamond (BDD) electrode using square wave voltammetry (SWV) or differential Pulse voltammetry (DPV). Using DPV with the cathodically pre-treated BDD electrode, a separation of about 550 mV between the peak oxidation potentials Of paracetamol and caffeine present in binary mixtures was obtained. The calibration curves for the simultaneous determination of paracetamol and caffeine showed an excellent linear response, ranging from 5.0 x 10(-7) mol L(-1) to 8.3 x 10(-7) mol L(-1) for both compounds. The detection limits for the simultaneous determination of paracetamol and caffeine were 4.9 x 10(-7) mol L-1 and 3.5 x 10(-8) mol L(-1), respectively. The proposed method Was Successfully applied in the simultaneous determination of paracetamol and caffeine in several pharmaceutical formulations (tablets), with results similar to those obtained using a high-performance liquid chromatography method (at 95% confidence level). (C) 2008 Elsevier BY. All rights reserved.

Síntese e caracterização físico-química de reticulados tridimensionais derivados de poli (isopreno) contendo grupos doadores e aceptores

Foram estudadas, neste trabalho, interacões por complexos de transferência de carga, através de medidas gravimétricas do grau de inchamento de géis de poli(isopreno) reticulado,contendo grupos aceptores de carga, em presença de grupos doadores de carga, de pequeno peso molecular, dissolvidos em tolueno. Para este fim, poli(isopreno) sintético proveniente da COPERBO - Companhia Pernambucana de Borracha Sintética, após purificação em clorofórmio, foi caracterizado por espectroscopia no infra-vermelho. O seu peso molecular médio foi determinado por viscosimetria em tolueno e o valor de Mv obtido foi 8,25 x 105. Através de epoxidação da dupla ligacão e hidrólise ácida do respectivo anel oxirano, foram introduzidos no poli(isopreno), previamente purificado, grupos aceptores de carga do tipo cloranil e ácido 3,5-dinitro-benzóico, e grupos doadores de carga do tipo carbazola. Obteve-se, desta forma, copolímeros aceptores do tipo poli (isopreno - co-cloranil) e poli(isopreno-co-(3,5-dinitro-benzoato)) e copolímero doador do tipo poli(isopreno- co-carbazola). A quantidade de cada espécie introduzida foi determinada por espectroscopia no ultra violeta. Poli(isopreno) e os copolímeros contendo grupos doadores ou aceptores foram reticulados em solução utilizando 4,4'-(4,4'-difenilmetileno)-bis- 1,2,4-triazolina-3,5-diona (BPMTD). Os filmes reticulados, após retirada a fase sol, e secos à vácuo, foram submetidos a inchamento em tolueno puro e em solução de tolueno contendo grupos aceptores ou doadores de carga, nas proporções 10:1, 1:1 e 1:10 (polímero: grupo doador ou polímero: grupo aceptor de carga), a 25, 30, 35 e 40ºC. Das medidas gravimétricas do grau de inchamento, foi verificado a formação de complexos por transferência de carga entre os copolímeros aceptores e carbazola. Foi verificado ainda que copolímeros contendo grupos aceptores do tipo cloranil possuem maior tendência a formar complexos por transferência de carga do que copolímeros aceptores contendo grupos 3,5-dinitro-benzoíla.

O processo decisório no município de Macaé

This research had as objective to identify as if it gives to the process of decisions in the City of Macaé. It was a case study, therefore to make possible this analysis, the used ways had been the research of field, bibliographical and documentary. The bibliographical survey was made in books, specialized periodicals, thesis, dissertations, monographs, sites and the pertinent legislation to the case, generating an analytical base of the subject considered for study. The research also was documentary, since internal document use of the City Hall of Macaé became. In the field, the public decision-making of Macaé, the previous management, had been interviewed, so that it was understood of that it forms if gives the process of taking of decisions in this city. Moreover, the interviewed ones had been encouraged to display its beliefs and feelings, to tell to experiences and personal characteristics. With this, one searched to better understand the universe lived for the respondents and, simultaneously, to compare the speeches and the reality. The data had suffered analysis of content based on the studies from Bardin (1979), Laville and Dione (1999) and Vergara (2005). The study it approaches the City of Macaé, and, in accordance with Yin (2001), studies of cases allow to work with an immense variety of evidences, as documents, devices, interviews and comments. The research bibliographical, documentary, of field, in the case study had been complementary and with its confrontation it searched to get a general vision of form to give to reply to the final question proposal. One concludes that the process of decisions politics and its implementation in the City of Macaé if gave by means of the awareness of the executive former-managers of the City Hall, in assuming roles of true entrepreneurs, the good relationship with the Common Council, in the search of chances and the combat to the problems and the establishment of public politics, focused in the access and the improvement of the quality of the public rendering of services, in the incentive the economic development and in the promotion of the citizenship for the population place.

Síndrome de burnout : um estudo junto aos educadores (professores e educadores assistentes) em escolas de educação infantil

O presente estudo investigou o nível de burnout, em cada uma de suas três dimensões, dos educadores (professores e educadores assistentes), que trabalham em escolas de Educação Infantil do Município de Porto Alegre, sendo duas da rede privada, duas da rede pública e uma escola comunitária. Também verificou os fatores reconhecidos como estressores no trabalho desses profissionais e a representação de estresse que fazem de seu trabalho. Os resultados evidenciaram níveis altos para a dimensão "Exaustão Emocional", baixo para "Despersonalização" e baixo para a dimensão "Reduzida Realização Profissional" independentemente do tipo de escola ou função exercida pelos sujeitos da amostra. Das variáveis demográficas, apenas o tempo disponível para o lazer apresentou associação significativa com a dimensão "Exaustão Emocional", indicando que os educadores que não dispunham de tempo para o lazer encontravam-se mais cansados emocionalmente. Com relação às variáveis ocupácionais, somente o número de alunos influenciou significativamente os níveis de burnout na dimensão "Exaustão Emocional" Os educadores avaliados consideram como baixo seu estresse no trabalho e relacionam o relacionamento com os familiares dos alunos como principal fator estressor. Os fatores estressores, organizados por ordem de importância , ao serem avaliados por tipo de escola , não apresentaram associação significativa entre as variáveis em estudo. Os fatores demanda mental e frustação causaram impacto na dimensão "Exaustão Emacional". Constatou-se, portanto, que as características do trabalho e a exigência das relações interpessoais são fatores desencadeantes da síndrome no grupo amostrado segundo os participantes da pesquisa.

A rastreabilidade de carnes segundo os atributos valorizados pelos consumidores : o caso da cadeia avícola do Rio Grande do Sul

Problemas de saúde pública causados pelo consumo de carnes envolvem diversos países e obrigam a cadeia agroalimentar a repensar o modo de produção e os sistemas de garantia de qualidade. Devido a este fato, esta pesquisa teve como objetivo estudar a rastreabilidade na cadeia avícola, tendo como foco o consumidor. Para isso foi realizado um survey, no qual foram realizadas entrevistas com 393 consumidores da cidade de Porto Alegre. Os questionários foram aplicados no período de abril a julho de 2004 em supermercados de pequeno, médio e grande porte, além do mercado público da cidade. Os atributos sanitários que o consumidor considera importantes para se rastrear na carne de frango são: Influenza Aviária (Gripe do Frango), Salmonela, Hormônios, Controle do Índice de Absorção de Água e Resíduos de Antimicrobianos. Além disso, os entrevistados consideram que as seguintes informações devam constar na embalagem da carne de frango: Data de Validade, o número do SIF, Certificado de Qualidade, Advertência quanto a Riscos de Toxinfecção Alimentar, Preço, Data de Abate e Origem/Procedência. São exploradas na pesquisa as correlações de diversas variáveis com o nível de escolaridade, renda e faixa etária. Com base nestes dados e utilizando a análise de filière, buscou-se propor maneiras de se atingir na rastreabilidade os pontos cruciais indicados pelos consumidores. Apesar da cadeia avícola ser bem organizada, foi evidenciada por esta pesquisa a necessidade de melhorar a circulação da informação na cadeia; para isso, sugere-se um sistema integrado de informação. Finalmente, foi proposto um modelo de rastreabilidade que contempla toda a cadeia avícola, incluindo todos os elos, desde o consumidor até o matrizeiro, indicando-se possíveis fatores que podem dificultar a construção do mesmo.

Uma análise empírica sobre o processo de recuperação econômica pela via judicial adotado pelas sociedades empresárias: a experiência no Tribunal de Justiça do Estado do Rio de Janeiro

Este estudo objetiva analisar os processos de recuperação judicial iniciados, desde a vigência da Lei de Recuperação de Empresas (fevereiro de 2005) até 31/06/2011 nas varas empresarias da comarca da capital do Tribunal de Justiça do Estado do Rio de Janeiro. Além da aferição do tempo médio de cada uma das etapas previstas na Lei de Recuperação de Empresas (deferimento do processamento da recuperação judicial, concessão da recuperação judicial e encerramento do processo após cumprimento de todas as obrigações previstas no plano que se vencerem até dois anos depois da concessão da recuperação judicial), busco também verificar se, de fato, alguma sociedade requerente conseguiu se recuperar. Para tanto, considerarei recuperada a sociedade que, após o encerramento do processo, estiver cumprindo plenamente o seu plano de recuperação, sem que tenha havido qualquer requerimento posterior de falência. Considerando que a Lei de Recuperação de Empresas já está no seu sétimo ano de vigência, bem como o fato de o legislador ter idealizado o processo para que dure no máximo 3 anos, entendo não haver óbices à adoção do conceito supra, tendo em vista que já haver tempo suficiente para o início e encerramento desse tipo de processo. Diante disso, o presente estudo observou que o tempo médio para cumprimento das etapas ultrapassa o limite do razoável, bem como que nenhuma sociedade conseguiu se recuperar até o desfecho da pesquisa, havendo casos, inclusive, de convolação da recuperação judicial em falência.

Effectiveness of different solid-phase microextraction fibres for differentiation of selected Madeira island fruits based on their volatile metabolite profile: identification of novel compounds

A headspace solid-phase microextraction (HS-SPME) procedure based on five commercialised fibres (85 μm polyacrylate – PA, 100 μm polydimethylsiloxane – PDMS, 65 μm polydimethylsiloxane/divinylbenzene – PDMS/DVB, 70 μm carbowax/divinylbenzene – CW/DVB and 85 μm carboxen/polydimethylsiloxane – CAR/PDMS) is presented for the characterization of the volatile metabolite profile of four selected Madeira island fruit species, lemon (Citrus limon), kiwi (Actinidia deliciosa), papaya (Carica papaya L.) and Chickasaw plum (Prunus angustifolia). The isolation of metabolites was followed by thermal desorption gas chromatography–quadrupole mass spectrometry (GC–qMS) methodology. The performance of the target fibres was evaluated and compared. The SPME fibre coated with CW/DVB afforded the highest extraction efficiency in kiwi and papaya pulps, while in lemon and plum the same was achieved with PMDS/DVB fibre. This procedure allowed for the identification of 80 compounds, 41 in kiwi, 24 in plums, 23 in papaya and 20 in lemon. Considering the best extraction conditions, the most abundant volatiles identified in kiwi were the intense aldehydes and ethyl esters such as (E)-2-hexenal and ethyl butyrate, while in Chicasaw plum predominate 2-hexenal, 2-methyl-4-pentenal, hexanal, (Z)-3-hexenol and cyclohexylene oxide. The major compounds identified in the papaya pulp were benzyl isothiocyanate, linalool oxide, furfural, hydroxypropanone, linalool and acetic acid. Finally, lemon was shown to be the most divergent of the four fruits, being its aroma profile composed almost exclusively by terpens, namely limonene, γ-terpinene, o-cymene and α-terpinolene. Thirty two volatiles were identified for the first time in the fruit or close related species analysed and 14 volatiles are reported as novel volatile metabolites in fruits. This includes 5 new compounds in kiwi (2-cyclohexene-1,4-dione, furyl hydroxymethyl ketone, 4-hydroxydihydro-2(3H)-furanone, 5-acetoxymethyl-2-furaldehyde and ethanedioic acid), 4 in plum (4-hydroxydihydro-2(3H)-furanone, 5-methyl-2-pyrazinylmethanol, cyclohexylene oxide and 1-methylcyclohexene), 4 in papaya (octaethyleneglycol, 1,2-cyclopentanedione, 3-methyl-1,2-cyclopentanedione and 2-furyl methyl ketone) and 2 in lemon (geranyl farnesate and safranal). It is noteworthy that among the 15 volatile metabolites identified in papaya, 3-methyl-1,2-cyclopentanedione was previously described as a novel PPARγ (peroxisome proliferator-activated receptor γ) agonist, having a potential to minimize inflammation.

A Humanização e a Formação Médica na Perspectiva dos Estudantes de Medicina da Universidade Federal do Rio Grande do Norte

The aim of this study is to understand the perception of medical students at the Federal University of Rio Grande do Norte (UFRN) about humanization in the context of their medical formation, using a qualitative approach. The focus group and participant observation techniques were used, involving a multidisciplinary team composed of professionals from the areas of anthropology and psychology, as well as professors from the medical course, who studied two groups of nine students in their final year. The data were analyzed using the categorical thematic content analysis technique, from which emerged three categories: student/patient relationship, teaching/learning and student/professor relationship. The first allows us to identify that student-patient contact is an essential experience for adopting a more humanized view of the disease process. The second category shows that unqualified professors in the pedagogic practices inherent to the teaching profession and the theory the practical dichotomy hinder the autonomous and holistic formation of knowledge. Similarly, the lack of practices outside the academic environment and the absence of multiprofessional stimulation interfere in the construction of an integral view of the individual. From the third category, the student/professor relationship, emerge two opposing subcategories (professor model and assymetric relationships), which reflect the importance of the professor`s ethical humanist position, as opposed to an authoritarian attitude, to form the professional attitude of the student. The results point important aspects of the medical formation that may open a discussion about humanization, in the context of new national curricular guidelines

Professores em contexto formativo: um estudo do processo de mudanças de concepções sobre o ensino da matemática

El objetivo en esta tesis consistió en estudiar el proceso de los cambios de los conceptos de profesores de la educación infantil y de los años iníciales de la educación básica referente a la enseñanza de la matemática. La investigación se desenvolvió en la escuela Presidente Kennedy, en la ciudad de Natal, en Rio Grande do Norte, teniendo como participante 05 (cinco) profesores del curso normal superior a través de la educación superior del instituto relacionado. El trabajo asocia el programa a él Programa de Pós-Graduação em Educação da Universidade Federal do Rio Grande do Norte, en la base de pesquisa Formação e Profissionalização Docente coordinada de los doctores Betânia Leite Ramalho e Isauro Beltran Núñez. El referencial teórico-metodológico en quien si apoya el trabajo se inserta en la señal conceptual usada por Giordan y de Vecchi (1996), de Carrillo y Contreras (1994), Ramalho; Núñez y Gauthier (2003), Ponte (1998), Guimarães (1988), Ernest (1989). En esta investigación, los conceptos de los profesores habían sido estudiados en el contexto educativo de la formación del nivel superior, usándola reflexiva crítico práctico como estrategia formativa. Estos conceptos se entienden como estructuras subyacentes al pensamiento del profesor. Dado la naturaleza del objeto del estudio, la información, para las intenciones de esta investigación, habían sido cosechados a través de los instrumentos siguientes: cuestionario, plan de la lección, entrevista diaria y del campo. El cuestionario fue constituido de preguntas abiertas y de las entrevistas de la mitad-structuralized. La organización de los datos permitió a La inferencia de los conceptos, usando la técnica de la triangulación de datos. La investigación divulgó que los conceptos de los profesores, a través del proceso formativo, se habían desarrollado de una plataforma para otra, yéndose puesto que los modelos didácticos tradicionales para otros modelos dirigidos a una tendencia didáctica de espontaneísta/investigativa. La reflexión crítica era considerada como elemento catalítico de los cambios de los conceptos de los profesores en la educación de las matemáticas, sin embargo déjenos verifican que estos cambios son difíciles de ocurrir para la naturaleza compleja de estos conceptos. Como facilitadores de los factores de estos cambios, encontramos y el investigativo el trabajo, la dinámica y la naturaleza de las actividades se convirtió en el colaborativo de proceso formativo, entre otros. Como obstáculos a los cambios, identificamos el contexto del trabajo de los profesores, de la cultura de los individualistas prácticos de sus profesores de los colegas, del concepto linear, estático y de los mecánicos de los procesos para enseñar, el conocimiento profesional construído durante la formación inicial, alineación con los modelos didácticos de sus viejos profesores, entre otros

As contribuições do proformação/pedagogia/UERN para a melhoria da prática pedagógica de professores

This dissertation aims at analyzing some relations established between teachers‟ formative proposal for docent knowledge and pedagogical practices in the Special Program of Professional Formation to Basic Education (Proformação in Portuguese) with the objective of investigating how teachers evaluate knowledge acquired during their course formation to identify its improvement in their pedagogical practice. This is a Pedagogical Program of the State University of Rio Grande do Norte chosen to be analyzed. The objective is to investigate how teachers, Proformação/Pedagogy course students evaluate privileged knowledge in that university formation and how the relation between this knowledge and their pedagogical practice are experienced in classroom as teachers, defining in which way knowledge constructed and reconstructed during the course contributes for an improvement of their pedagogical practices. We have interviewed fourteen Proformação/Pedagogy last-term teachers, emphasizing the analysis of their point of view as social actors related to docent university formation in service. The principles for this investigation comprehend a qualitative approach, in a case study modality, with an exploratory tendency, presented in the introductory section and along four chapters. The research is theoretically guided by Andoino (1998), Bardin (2009); Laville e Dione (1999); Bogdan and Biklen (1994), Hernandez Sampieri, Hernandez Collado and Baptista Lúcio (2006), among others. We justify this thematic choice, considering docent formation and its interface with an improvement for students‟ leaning, taking into account the strict relations between those elements. We have discussed on docent formative paradigms, based on a multireferential perspective, whose main authors that developed research in this area are: Gómez (1998), Sacristán e Gómez (1998), Tardif (2002), Altet (2001) Paquay e Wagner (2001), Garcia (1999), Baldi (2008), La Torre e Barrios (2002). We interviewed fourteen teachers, all of them in the last term of the Program. In the second chapter, we justify the choice of the subject, approaching docent formation and its relation with basic teaching. We understand that there is a strong relation between those aspects. In the third chapter, we discuss on some docent formative paradigms, among them, Gomes (1998), Sacristán and Gomez (1998), Tardig (2002), Altet (2001) Paquay and Wagner (2001), Garcia (1999), Baldi (2008), La Torre and Barrios (2002). We introduce the Pedagogical Program structure and specify which formative paradigms characterize it and identifying that one of the most prominent paradigm is a practical perspective with emphasis on reflexivity about the practice based on the premise that docent formation is be based on from learning to practice theory. We present an data analysis obtained from thematic categorization extracted subjects‟ discourses and, at the end, we discuss on evaluation of the teachers involved in the research related to the course contributions to provide an improvement for pedagogical practices developed by them inside their classrooms. We consider, thus, that teachers evaluate the Program as a guideline for (re)construction of diversified knowledge, which, in turn, provides the development of abilities to analyze classroom situations based on pedagogical theories and to develop investigative practice based on everyday experience. The results point out that some implications are relevant, among them: the thematic-choice, discussed previously, needs other kinds of investigations. The relation between theory and practice proposed in formation programs requires more systematic studies considering others aspects that characterize teaching process, and mainly, to provide investigative proposals of and about such practices