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

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

Crystal design approaches for the synthesis of paracetamol co-crystals

Crystal engineering principles were used to design three new co-crystals of paracetamol. A variety of potential cocrystal formers were initially identified from a search of the Cambridge Structural Database for molecules with complementary hydrogen-bond forming functionalities. Subsequent screening by powder X-ray diffraction of the products of the reaction of this library of molecules with paracetamol led to the discovery of new binary crystalline phases of paracetamol with trans-1,4- diaminocyclohexane (1); trans-1,4-di(4-pyridyl)ethylene (2); and 1,2-bis(4-pyridyl)ethane (3). The co-crystals were characterized by IR spectroscopy, differential scanning calorimetry, and 1H NMR spectroscopy. Single crystal X-ray structure analysis reveals that in all three co-crystals the co-crystal formers (CCF) are hydrogen bonded to the paracetamol molecules through O−H···N interactions. In co-crystals (1) and (2) the CCFs are interleaved between the chains of paracetamol molecules, while in co-crystal (3) there is an additional N−H···N hydrogen bond between the two components. A hierarchy of hydrogen bond formation is observed in which the best donor in the system, the phenolic O−H group of paracetamol, is preferentially hydrogen bonded to the best acceptor, the basic nitrogen atom of the co-crystal former. The geometric aspects of the hydrogen bonds in co-crystals 1−3 are discussed in terms of their electrostatic and charge-transfer components.

Electron doping and phonon scattering in Ti1+xS2 thermoelectric compounds

Bulk polycrystalline samples in the series Ti1+xS2 (x = 0 to 0.05) were prepared using high temperature synthesis from the elements and spark plasma sintering. X-ray structure analysis shows that the lattice constant c expands as titanium intercalates between TiS2 slabs. For x=0, a Seebeck coefficient close to -300 μV/K is observed for the first time in TiS2 compounds. The decrease in electrical resistivity and Seebeck coefficient that occurs upon Ti intercalation (Ti off stoichiometry) supports the view that charge carrier transfer to the Ti 3d band takes place and the carrier concentration increases. At the same time, the thermal conductivity is reduced by phonon scattering due to structural disorder induced by Ti intercalation. Optimum ZT values of 0.14 and 0.48 at 300K and 700K, respectively, are obtained for x=0.025.

Characterization of the lipoxygenase (LOX) gene family in the Chinese white pear (Pyrus bretschneideri) and comparison with other members of the Rosaceae

Background Lipoxygenases (LOXs), a type of non-haem iron-containing dioxygenase, are ubiquitous enzymes in plants and participate in the formation of fruit aroma which is a very important aspect of fruit quality. Amongst the various aroma volatiles, saturated and unsaturated alcohols and aldehydes provide the characteristic aroma of the fruit. These compounds are formed from unsaturated fatty acids through oxidation, pyrolysis and reduction steps. This biosynthetic pathway involves at least four enzymes, including LOX, the enzyme responsible for lipid oxidation. Although some studies have been conducted on the LOX gene family in several species including Arabidopsis, soybean, cucumber and apple, there is no information from pear; and the evolutionary history of this gene family in the Rosaceae is still not resolved. Results In this study we identified 107 LOX homologous genes from five Rosaceous species (Pyrus bretschneideri, Malus × domestica, Fragaria vesca, Prunus mume and Prunus persica); 23 of these sequences were from pear. By using structure analysis, phylogenic analysis and collinearity analysis, we identified variation in gene structure and revealed the phylogenetic evolutionary relationship of this gene family. Expression of certain pear LOX genes during fruit development was verified by analysis of transcriptome data. Conclusions 23 LOX genes were identified in pear and these genes were found to have undergone a duplication 30–45 MYA; most of these 23 genes are functional. Specific gene duplication was found on chromosome4 in the pear genome. Useful information was provided for future research on the evolutionary history and transgenic research on LOX genes.

Expression and purification of human respiratory syncytial virus recombinant fusion protein

The Human Respiratory Syncytial Virus (HRSV) fusion protein (F) was expressed in Escherichia call BL21A using the pET28a vector at 37 degrees C. The protein was purified from the soluble fraction using affinity resin. The structural quality of the recombinant fusion protein and the estimation of its secondary structure were obtained by circular dichroism. Structural models of the fusion protein presented 46% of the helices in agreement with the spectra by circular dichroism analysis. There are only few studies that succeeded in expressing the HRSV fusion protein in bacteria. This is a report on human fusion protein expression in E. call and structure analysis, representing a step forward in the development of fusion protein F inhibitors and the production of antibodies. (c) 2008 Elsevier Inc. All rights reserved.

Cathepsin L-like genes of Trypanosoma vivax from Africa and South America - characterization, relationships and diagnostic implications

We characterized sequences from genes encoding cathepsin L-like (CatL-like) cysteine proteases from African and South American isolates of Trypanosoma vivax and T. vivax-like organisms, and evaluated their suitability as genetic markers for population structure analysis and diagnosis. Phylogenetic analysis of sequences corresponding to CatL-like catalytic domains revealed substantial polymorphism, and clades of sequences (TviCatL1-9) were separated by large genetic distances. TviCatL1-4 sequences were from cattle isolates from West Africa (Nigeria and Burkina Faso) and South America (Brazil and Venezuela), which belonged to the same T. vivax genotype. T. vivax-like genotypes from East Africa showed divergent sequences, including TviCatL5-7 for isolates from Mozambique and TviCatL8-9 for an isolate from Kenya. Phylogenetic analysis of CatL-like gene data supported the relationships among trypanosome species reflected in the phylogenies based on the analysis of small subunit (SSU) of ribosomal RNA gene sequence data. The discovery of different CatL-like sequences for each genotype, defined previously by ribosomal DNA data, indicate that these sequences provide useful targets for epidemiological and population genetic studies. Regions in CatL-like sequences shared by all T. vivax genotypes but not by other trypanosomes allowed the establishment of a specific and sensitive diagnostic PCR for epidemiological studies in South America and Africa. (C) 2008 Elsevier Ltd. All rights reserved.

Purification, and Biochemical and Biophysical Characterization of Cellobiohydrolase I from Trichoderma harzianum IOC 3844

Because of its elevated cellulolytic activity, the filamentous fungus Trichoderma harzianum has a considerable potential in biomass hydrolysis applications. Trichoderma harzianum cellobiohydrolase I (ThCBHI), an exoglucanase, is an important enzyme in the process of cellulose degradation. Here, we report an easy single-step ion-exchange chromatographic method for purification of ThCBHI and its initial biophysical and biochemical characterization. The ThCBHI produced by induction with microcrystalline cellulose under submerged fermentation was purified on DEAE-Sephadex A-50 media and its identity was confirmed by mass spectrometry. The ThCBHI biochemical characterization showed that the protein has a molecular mass of 66 kDa and pi of 5.23. As confirmed by small-angle X-ray scattering (SAXS), both full-length ThCBHI and its catalytic core domain (CCD) obtained by digestion with papain are monomeric in solution. Secondary structure analysis of ThCBHI by circular dichroism revealed alpha-helices and beta-strands contents in the 28% and 38% range, respectively. The intrinsic fluorescence emission maximum of 337 nm was accounted for as different degrees of exposure of ThCBHI tryptophan residues to water. Moreover, ThCBHI displayed maximum activity at pH 5.0 and temperature of 50 degrees C with specific activities against Avicel and p-nitrophenyl-beta-D-cellobioside of 1.25 U/mg and 1.53 U/mg, respectively.

Spectroscopic investigation of conjugated polymers derived from nitroanilines

For the first time, the resonance Raman spectroscopy was used to characterize polymers derived from meta- and para-nitroanilines. In order to improve the polymer structure analysis, other techniques were also used such as FTIR, UV-vis, XRD, XPS, EPR and N K-XANES. The insertion of strong electron-withdrawing groups (NO2) in polyaniline (PANI)-like backbone causes drastic changes in the lower energy charge transfer states, related to the polymer effective conjugation length. The resonance Raman data show that the NO2 moiety has a minor contribution on the CT state in poly(meta-nitroaniline), PMN, while in the poly(para-nitroaniline), PPN, the quinoid structure induced by para-substitution increases the charge density of NO2 groups, causing a more localized chromophore. The characterization of the imine nitrogen and of the protonated segments was done by XPS, N K-XANES and EPR spectroscopies and the lower polymerization degree of PPN, in comparison to PMN, is confirmed by XRD and TG data. (C) 2007 Elsevier B.V. All rights reserved.

Crystal and molecular structures of three 2-sulphur-substituted cyclohexanones studied by X-ray crystallography and by ab initio molecular orbital calculations

The conformational features of three 2-sulphur-substituted cyclohexanone derivatives, which differ in the number of sulphur-bound oxygen atoms, i.e. zero (I), one (II) and two (III), were investigated by single crystal X-ray crystallography and geometry optimized structures determined using Hartree-Fock method. In each of (I)-(III) an intramolecular S center dot center dot center dot O(carbonyl) interaction is found with the magnitude correlated with the oxidation state of the sulphur atom, i.e. 2.838(3) angstrom in (I) to 2.924(2) angstrom in (II) to 3.0973(18) angstrom in (III). There is an inverse relationship between the strength of this interaction and the magnitude of the carbonyl bond. The supramolecular aggregation patterns are primarily determined by C-H center dot center dot center dot O contacts and are similarly influenced by the number of oxygen atoms in the molecular structures. Thus, a supramolecular chain is found in the crystal structure of (I). With an additional oxygen atom available to participate in C-H center dot center dot center dot O interactions, as in (II), a two-dimensional array is found. Finally, a three-dimensional network is found for (III). Despite there being differences in conformations between the experimental structures and those calculated in the gas-phase, the S center dot center dot center dot O interactions persist. The presence of intermolecular C-H center dot center dot center dot O interactions involving the cyclohexanone-carbonyl group in the solid-state, disrupts the stabilising intramolecular C-H center dot center dot center dot O interaction in the energetically-favoured conformation. (I): C(12)H(13)NO(3)S, triclinic space group P (1) over bar with a = 5.392(3) angstrom b = 10.731(6) angstrom, c = 11.075(6) angstrom, alpha = 113.424(4)degrees, beta = 94.167(9)degrees, gamma = 98.444(6)degrees, V = 575.5(6) angstrom(3), Z = 2, R(1) = 0.052; (II): C(12)H(13)NO(4)S, monoclinic P2(1)/n, a = 7.3506(15) angstrom, b = 6.7814(14) angstrom, c = 23.479(5) angstrom, beta = 92.94(3)degrees, V = 1168.8(4) angstrom(3), Z = 4, R(1) = 0.046; (III): C(12)H(13)NO(5)S, monoclinic P2(1)/c, a = 5.5491(11) angstrom, b = 24.146(3) angstrom, c = 11.124(3) angstrom, beta = 114.590(10)degrees, V = 1355.3(5) angstrom(3), Z = 4, R(1) = 0.051.

Construção de vínculos de confiança empresarial

O trabalho apresentado neste relatório tem por objetivo pesquisar a constituição e o desenvolvimento da confiança entre os empresários participantes do programa Cooperar para Competir, o qual compõe o conjunto de treinamentos oferecidos para o Arranjo Produtivo Local de Birigui pelo SEBRAE-SP em parceria com instituições locais como o Sindicato da Indústrias do Calçado e Vestuário de Birigui, o SESI de Birigui, entre outros. Em termos de metodologia, foi escolhido o método qualitativo para desenvolver uma pesquisa exploratória de estudo de caso (o Cooperar para Competir) e foram utilizadas duas técnicas de pesquisa – a entrevista aberta ou não-dirigida e a técnica de história oral. Para o seu desenvolvimento, foram estabelecidas três grandes áreas de investigação que, juntas, ofereceriam uma visão abrangente do tema analisado: a) a primeira grande área é responsável pelo estudo do contexto e da estrutura econômica do APL em geral, bem como de seus agentes presentes naquela região e suas particularidades. Nesta primeira parte são apresentadas discussões sobre clusters, sua importância e representatividade no Brasil e no mundo, bem como uma análise do cluster calçadista de Birigui de acordo com o Modelo Diamante proposto por Porter (1999); b) a segunda área abrange tanto a estrutura formal do Cooperar para Competir em cada uma das turmas quanto o processo dinâmico do curso, seus momentos críticos e as estratégias pedagógicas adotadas a cada momento em vista dos desafios. Esta parte contextualiza o programa, apresenta sua estrutura e reflete a construção das bases de cooperação em sala de aula por uma perspectiva axiológica; c) a terceira área, por fim, é caracterizada pela pesquisa de campo, quando foram investigadas as vivências, experiências e impactos dos e nos participantes do ponto de vista subjetivo e como eles entenderam os efeitos em suas vidas profissional e pessoal. As entrevistas abertas foram realizadas com dois grupos de participantes, o Grupo Graduado e o Grupo Novo, a fim entender o desenvolvimento de ambos os grupos, os resultados alcançados pelo primeiro e o efeito da suspensão do programa no segundo. Todo o processo seguido durante a pesquisa permitiu que se chegasse a inúmeras conclusões, como o porquê do sucesso do programa Cooperar para Competir – o sucesso, neste caso, reside no desenho pedagógico que atende a dimensão axiológica, ou seja, não apenas se falou de cooperação, mas se produziu cooperação ao integrar competências, interesses e valores. O programa serviu, então, como um espaço filosófico e laboratorial. Assim, o conteúdo e a sequência seguidos também tem sua importância relativizada frente as relações e a construção de algo que transcende o caráter utilitarista ou funcionalista das disciplinas. As entrevistas individuais e em grupo mostraram que se reconhecerem como iguais foi um fator gerador de confiança entre os participantes, a qual também é expressa quando estes se abrem para compreenderem o modo como os outros atribuem significados para a relação de desconfiança e confiança e passam a estabelecer um sistema de significação comum. Além disso, a consciência de sua realidade e o reconhecimento de sua responsabilidade junto a si mesmo, à sua empresa, ao projeto desenvolvido no Cooperar para Competir e à comunidade de Birigui marcam, também, a mudança do esquema mental de sapateiro para empresário.

Processo de planejamento estratégico em universidade pública: o caso da Universidade Federal do Pará

The goal of this research is to check if the strategic planning developed between 2001 and 2009 into the State University of Para (Universidade Federal do Pará - UFPA) was consolidated into its Academic Centers as a management practice. To this end, we identified the planning formalization degree of the Academic Centers, the conceived tools for the planning, the conception and the methodological process used in the tools elaboration, as also its implementation. The research used a qualitative approach: it is descriptive and it uses the case study technique. The data were gathered from primary and secondary sources, through bibliography, documents, and field researches through semi-structure interviews. The analysis and data interpretation were done by each investigated Academic Center from the analytics categories guided by the specifics goals. We used theoretic fundamental based principles and the university as a study empiric reference based on its structure analysis, organizational processes and institutional strategic plan. We inspected how the strategic planning process was developed throughout the fixed period and how the investigated Academic Centers are from the collected documents and interviews. The theoretical foundation was built from three axis: the Brazilian undergraduate and posgraduate education system; the university itself including its singularity and complexity as an organization; and the planning as a strategic management process. The main results show us that the UFPA has updated regulatory milestones, presenting organizational structure, laws, instructions, manuals and deployed management model that give the strategic planning development conditions beyond its administration, i. e., into its Academic Centers. The centers also present those established milestones and develop the basic planning processes of the institution. Those processes are conceived based on the institutional strategic planning and the managers mainly use the procedural orientation defined by the university management, from where the conceptual foundation is originated and propagated. According to the literature and to the research done in this work, we can conclude that the Academic Centers from the UFPA developed the strategic planning practice. This planning is organized and founded and guided the plans and decisions which avoided the disordered management and, according to the managers, allowed the advances and performance improvement. We can conclude that the UFPA built an important foundation with respect to the management professionalization. On the other hand, we can not conclude that the management practice is consolidated since there are weaknesses into the structuring of the technical teams and there is not any management tool for the implementation of the elaborated plans

Dimensões didática, afetiva e formativa de docência que tecem as representações sociais entre licenciandos da UFPI

This study intends to analyze the social representation of teaching for students of first years of undergraduate courses in Education, Letters and Biology. The field of this research was the Federal University of Piaui - Campus of Picos in 2009. To reach the objective proposed above, was used the theory of social representations to the seizure of the elements which constitute such representations according to Moscovici and colleagues, considering the contribution of Abric with his Theory of Central Nucleus and Wagner with the Theory of Sociogenesis. Data were collected in two phases: first, through the Technique of Free Association of Words (TFAW) of which 100 subjects evoked representations of their teaching through the inductor terms 'to teach', 'student' and 'teacher'. For those data we used the EVOC software that promoted to detect the elements of the core and to conclude that the social representation of teaching is one of the work performed by a master / teacher who transmits, directed to an apprentice who learns, confined to the school involving the student with all his virtues to be smart, interested and dedicated, and teacher to be friend, wise bearer of knowledge and also intelligent. Then, using the Multiple Classification Procedure (MCP) only 10 subjects made ratings of 25 more evoked words in the first phase, for the analysis of data from the MPC with the use of the SPSS software we used Multidimensional Statistical Analysis (MSA) for the Free Classification we found three dimensions of Social Representation of Teaching: The Didactic, that focuses on teacher and student being superimposed, meaning the inseparability of these elements, the Affective, which presents the elements inherent in teachers with love as the strong point of this dimension, and the Formative, that is as ambiguous as ambivalent because it sees the teacher as a professional directed to help students get an education; for Directed Classification with Similarity Structure Analysis (SSA), we learn that teaching is a profession that materializes in the classroom, which is extremely true because the action happens in this teaching space, supposing a caring, loving, cheerful, capable, apt, patient, partner, responsible, dedicated, committed educator, who has wisdom and knows how to teach and help students through dialogue to there study and learning. All of it s necessary to occur the result of teaching, which is education in a disciplinary manner. The results point to a very traditional social representation of what is the role of teachers, the role of students and the role of the relationship itself between teaching and learning through the act of teaching. With this statement, we can confirm that the structure of Social Representation of Teaching for the investigated subjects reflects the sociogenetic conditions that engendered them, and that these conditions permeate their structural organization, in particular time-context in which social representation was captured

Mecanismos sócio-genéticos da representação social de trabalho docente por grupos de licenciandos de física e de química da Universidade Federal do Rio Grande do Norte

This research aims to understand the social representations Teaching Work in groups of undergraduate students of Physics and Chemistry of the Federal University of Rio Grande do Norte. For this, the proposal was based on the three theoretical and methodological consensus Carvalho (2012) in the explanation of socio-genetic mechanisms constituents of dynamic consensus that has functionality to your organization. It Was used to achieve this goal, the theoretical-epistemological Serge Moscovici (1978, 2003), Jodelet (2011), Wagner (1998,( 2011) and Carvalho (2012). The corpus analyzed results from a qualitative and quantitative research, developed in three stages. The first two (2) questionnaires to fifty (50) of each undergraduate course, a questionnaire and another profile for collection of free associations concerning motes inductors "Give Lesson," "Student" and "Teacher". The second step in the procedure Multiple Classifications, Roazzi (1995), aimed for another thirty (30) undergraduate students for each course, as well as Document Analysis of Educational Projects Curriculum courses in Physics and Chemistry. The data analysis of the first stage focused on descriptive statistics and frequency and average order of the words associated with motes inductors. The results from the Multiple Classification Procedure submitted to multidimensional analysis (MSA multidimensional scalogram analysis) and SSA (Similarity Structure Analysis), were interpreted by the theoretical and methodological proposal of the three consensus, supported by analysis of the rhetorical nature of justifications classifications and categorizations of words, boosted in times of application of Procedure Multiple Classification. The data revealed that the groups surveyed were the same Social Representation with specific dynamic consensual. Thinking Teaching Work for these groups it is considered in three dimensions: the BE-DO-HAVE of teaching. In the group of Physics consensus was clear semantic, which expressed a dynamic in which the interpretations of "Teaching Work" peacefully coexist on perceptions of two concepts: An identity around the "BE" "Teacher" or "BE" "Educator" and the other, how they think about professional development. The type of group consensus Chemistry pointed to a consensual logic hierarchical order in which the gradual between the elements of BE-DO-HAVE attested conflicts and disagreements about the perceptual object "Teaching Work", around what value most, whether they are the attributes of personal or professional-technical dimension of teaching, in the course of professional development. The thesis to explain the mechanisms of socio-genetic Representation Social Teaching Work by theoretical and methodological proposal was confirmed

Expression and purification of human respiratory syncytial virus recombinant fusion protein

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

Dichloro(cyclohexilidene-1-methylene)(phenyl)Te(IV). Looking for the theoretical treatment

C(13)H(16)Cl(2)Te,M(r)=370.76,P2(1)/a, a = 8.1833(8), b = 8.4163(8), c = 20.787(2) A, beta = 99.52(1)degrees, Z = 4, R(1) = 0,0275. The primary coordination around the Te(IV) atom is consistent with a pseudo-trigonal bipyramidal bond configuration with two Cl atoms occupying axial positions while the C atoms and the lone pair of electrons occupy the equatorial positions. The Te(IV) atom is involved in an intermolecular secondary interaction resulting in the self assembly of zigzag-chains supramolecular array. In order to determine the theoretical basis set for the Te atom which leads to the best agreement with the experimental data, a large series of geometry optimizations were performed on dichloro dimethyl Te(IV), as a model compound, and the results compared with the mean distances and angles obtained from 45 X-ray structures. The Ahlrichs basis set plus the Hay & Wadt ECP was selected and used for a series of calculations performed on the title compound.