Siderophores as anchors in artificial metalloenzymes

Fundacao de Amparo a Pesquisa do Estado de Sao PauloConselho Nacional de Desenvolvimento Cientifico e TecnologicoCAPESInst Chem UNESP, Araraquara, SP, Brazil|Univ Fed Sao Paulo, EPM, Dept Pharmacol, Sao Paulo, SP, BrazilInst Chem USP, Sao Carlos, SP, BrazilUniv Fed Sao Paulo, EPM, Dept Pharmacol, Sao Paulo, SP, BrazilFAPESP: 2016/177115CNPqCAPESWeb of Scienc

O sistema PBL, problem-based learning, no ensino de medicina no Brasil : análise bibliográfica sobre a sua execução

Introdução: Entre as estratégias de ensino e aprendizagem utilizadas nas práticas pedagógicas, a Problem Based Learning (PBL) (Aprendizagem Baseada em Problemas) é utilizada desde 1960, em especial nos cursos de Medicina. Mesmo sendo uma estratégia valiosa, um dos seus obstáculos é a pouca prática dos alunos em atividades autodirigidas, pesquisa e construção coletiva do conhecimento. Objetivo: Rastrear elementos constitutivos da PBL através de dados colhidos em artigos pesquisados em sítios de divulgação científica; Avaliar, nos estudos selecionados, os aspectos positivos e negativos que estejam relacionados com a metodologia do Sistema PBL aplicada ao ensino médico no Brasil. Metodologia: Estudo bibliográfico de 13 textos utilizando um modelo de desconstrução, denominada Análise Textual Discursiva (ATD) que consiste em: transformação dos artigos em pedaços menores; análise textual; identificação de padrões convergentes e divergentes em relação a PBL; organização e síntese dos dados, culminando com a elaboração de estratégia adaptativa da PBL para o curso de Medicina. Resultados: Foram encontradas 116 citações que convergiam para referências positivos acerca da metodologia PBL e 40 citações que divergiam acerca dos pontos positivos. Os aspectos positivos como o desenvolvimento de atitudes e habilidades; desenvolvimento de competências anteriores ao curso; efeitos positivos depois de terminada a graduação, como autonomia de estudo e a articulação entre currículo e realidade profissional, representam pontos a serem reforçados na aula. Em contraponto, foi observado que dentre os negativos a não compreensão do papel do professor como tutor; necessidade de conteúdo formal tradicional pelos alunos e a expectativa que o professor retire as suas dúvidas são pontos a serem evitados. Conclusões: A metodologia PBL deverá servir como metodologia ativa para aproveitar ao máximo as habilidades que os alunos já apresentam, potencializando o aprendizado na educação médica em sala de aula. Palavras-Chave: PBL; curso de medicina; metodologia ativa; educação médica.ABSTRACT Introduction: Among the teaching and learning strategies used in teaching practices, the Problem Based Learning (PBL) (Problem Based Learning) has been used since 1960, especially in medical courses. Although a valuable strategy, one of its obstacles is the lack of practice of students in self-directed activities, research and collective construction of knowledge. Objective: Tracking constitutive elements of PBL through data collected on items surveyed in science communication sites and arrange them in order to develop a student's adaptation strategy to this methodological way. Evaluate the selected studies, the positive and negative aspects that are related to the methodology of PBL system applied to medical education in Brazil. Methodology: bibliographic study of 13 texts using a deconstruction model, called Discursive Textual Analysis (DTA) consisting of: transforming items into smaller pieces; textual analysis; identifying convergent and divergent patterns in relation to PBL; organization and synthesis of data, culminating with in the development of adaptive strategy of PBL to Medical Course. Results: It has been found 116 quotes that converged into positive notes about the PBL methodology and 40 quotes that differed about the positive ones. These quotations are placed in lines of analysis, based on a model of adaptation of the PBL student body. The positive aspects represent points to be reinforced in the classroom and the negative ones to be avoided. Conclusions: The PBL methodology should serve as active methodology to make the most of the skills that students already have, enhancing learning in medical education in the classroom Keywords: PBL; medical schools; active methodology; medical education

Mixed-Ligand Complexes of Technetium and Rhenium with Tridentate Benzamidines and Bidentate Benzoylthioureas

Mixed-ligand complexes of technetium(V) or rhenium(V) containing tridentate N-[(dialkylamino)(thiocarbonyl)]benzamidine (H(2)L(1)) and bidentate N,N-dialkyl-N`-benzoylthiourea (HL(2)) ligands were formed in high yields when (NBu(4))[MOCl(4)] (M = Tc or Re) or [ReOCl(3)(PPh(3))(2)] was treated with mixtures of the proligands. Other approaches for the synthesis of the products are reactions of [MOCl(L(1))] complexes with HL(2) or compounds of the-composition [ReOCl(2)(PPh(3))(L(2))] with H(2)L(1). The resulting air-stable [MO(L(1))(L(2))] complexes possess potential for the development of metal-based radiopharmaceuticals. [TcO(L(1))(L(2))] complexes are readily reduced by PPh3 with formation of [Tc(L(1))(L(2))(PPh(3))]. The resulting Tc(III) complexes undergo two almost-reversible oxidation steps corresponding to one-electron transfer processes. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)Government of Vietnamgovernment of VietnamDAAD (Germany)DAAD (Germany)CAPES (Brazil)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES

Oxotechnetium(V) Complexes with a Novel Class of Tridentate Thiosemicarbazide Ligands

A novel tridentate thiosemicarbazide-type ligand class with an SNS donor set, H(2)L(1), was prepared by reactions of N-[N`,N`-dialkylamino(thiocarbonyl)]benzimidoyl chlorides with thiosemicarbazides. H(2)L(1) ligands readily react with (NBu(4))[TcOCl(4)] in MeOH under the formation of red oxotechnetium(V) complexes of composition [TcOCl(L(1))]. The monomeric, five-coordinate compounds are air-stable and bind (L(1))(2-) tridentate in the equatorial coordination sphere. The compounds represent the first examples of oxotechnetium(V) complexes with NS chelate-bonded thiosemicarbazones.DAADDAADCNPqConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)government of Vietnamgovernment of Vietna

Cationic and neutral phenylmercury(II) complexes with heterocyclic thione ligands. X-ray structures of [HgPh(dmpymtH)][BF(4)] center dot H(2)O and [{HgPh}(2)(mu-dtu)]

The neutral complex [HgPh(dmpymt)] 1 (dmpymtH = 4,6-dimethylpyrimidine-2(1H)-thione) reacts with HBF(4) to give the cationic complex [HgPh(dmpymtH)][BF(4)] 2. The X-ray molecular structure of the later revealed a [2+1] coordination sphere about the mercury(II) atom (C-Hg-S and Hg center dot center dot center dot N). In the dinuclear complex [(HgPh)(2)(mu-dtu)] 3 [dtuH(2) = 2,4(1H,3H)-pyrimidinedithione or dithiouracil] the coordination spheres are also [2+1] although dissimilar regarding the Hg center dot center dot center dot N secondary bonds. NMR spectroscopy ((1)H, (13)C and (199)Hg) studies were undertaken in solution and the results discussed in the light of the X-ray structures. (C) 2008 Elsevier B. V. All rights reserved.FINEP CT-INFRA[970/01]Financiadora de Estudos e Projetos (FINEP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)CNP

Synthesis and characterization of heptacoordinated tin(IV) complexes. X-ray crystal structure of [nBu2Sn(dappt)]·(Me 2CO)0.5 [H2dappt = 2,6-diacetylpyridine bis(4-phenylthiosemicarbazone)]

The reactions of the 2,6-diacetylpyridine bis(4-phenylthiosemicarbazone) ligand, H2dappt, with R4-mSnXm (m = 2, 3; R = Me, nBu, Ph and X = Cl) led to the formation of four new heptacoordinated organotin(IV) complexes, which were characterized by microanalyses and by IR and Mössbauer spectroscopies. The n-butyl derivative [nBu2Sn(dappt)]·(Me 2CO)0.5 was also analyzed by a single crystal X-ray diffraction study. It crystallized in the monoclinic system with a space group C2/c, with a = 36.164(14), b = 9.7050(15), c = 26.194(11) Å, beta = 132.00(2)º, Z = 8. The structure determination revealed a neutral complex of Sn(IV) in a distorted pentagonal bipyramidal (PBP) geometry, with the equatorial plane defined by the SNNNS donor system of the ligand and with the two n-butyl groups in the axial positions. Also, a correlation between Mössbauer and X-ray data based on the point-charge model is discussed

An extended π-system and enhanced electronic delocalization on symmetric [Ru3O(CH3COO)6(L)3]n complexes combined with azanaphthalene ligands

FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOWe report on the investigation of a new series of symmetric trinuclear ruthenium complexes combined with azanaphthalene ligands: [Ru3O(CH3COO)6(L)3]PF6where L = (1) quinazoline (qui), (2) 5-nitroisoquinoline (5-nitroiq), (3) 5-bromoisoquinoline (5-briq),462479267938FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO2015/20302-72013/22127-2305415/2015-

Synthesis, Spectroscopic Studies and X-ray Crystal Structures of New Pyrazoline and Pyrazole Derivatives

The synthesis and characterization of some pyrazoline compounds of 1,3-diketones with hydrazine derivatives, namely, 1-(S-benzyldithiocarbazate)-3-methyl-5-phenyl-5-hydroxypyrazoline (1); 1-(2-thiophenecarboxylic)-3-methyl-5-phenyl-5-hydroxypyrazoline (2); 1-(2-thiophenecarboxylic)-3,5-dimethyl-5-hydroxypyrazoline (3); 1-(S-benzyldithiocarbazato)-3-methyl-5-phenylpyrazole (4); 1-(2-thiophenecarboxylic)-3-methyl-5-phenylpyrazole (5) and 1-(S-benzyldithiocarbazate)-3,5-dimethylpyrazole (6) are reported. Studies by IR, ((1)H, (13)C)-NMR spectroscopies and single crystal X-ray diffraction revealed that compounds (1)(,) (2) and (3) are formed as pyrazoline, whereas (4) and (5) are formed as pyrazole derivatives only under acidic conditions. Compound (1) crystallizes in orthorhombic P2(1)2(1)2(1), a = 6.38960(10) angstrom, b = 12.9176(3) angstrom, c = 21.2552(5) angstrom, (2) crystallizes in monoclinic, P2(1)/n, a = 11.3617(2) angstrom, b = 8.4988(2) angstrom, c = 92.8900(10)angstrom and beta = 92.8900(5)degrees, (3) crystallizes in monoclinic, C2/c, a = 15.9500(5) angstrom, b = 9.3766(3) angstrom, c = 16.6910(5)angstrom and beta = 113.825(2)degrees, (4) crystallizes in monoclinic, P2(1)/c, a = 15.228(4) angstrom, b = 5.5714(13) angstrom, c = 19.956(5)angstrom and beta = 91.575(7)degrees and (6) crystallizes in orthorhombic, P2(1)2(1)2(1), a = 5.3920(2) angstrom, b = 11.2074(5) angstrom, c = 21.885(1)angstrom . The (3) derivative represents the first pyrazoline compound prepared from 2,4-pentanedione and characterized crystallographically.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)CNPqFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)FAPESPFinanciadora de Estudos e Projetos (FINEP)FINEP[CT-INFRA 0970/01]Conselho Nacional de Desenvolvimento Cientifico e Tecnologico-CNPq[307412/2008-3]Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Crystal structure of di-μ-methanolato-bis{[N′-(1-benzoylprop-1-en-2-yl)thiophene-2-carbohydrazidato-κ3O,N′,O′]oxidovanadium(V)}

The neutral binuclear molecule of the title complex, [V2(C15H12N2O2S)2(CH3O)2O2], exhibits inversion symmetry and consists of two oxidovanadium(V) (VO)3+ fragments, each coordinated by a dianionic and O,N′,O′-chelating N′-(1-benzoylprop-1-en-2-yl)thiophene-2-carbohydrazidate ligand. The V5+ cations are bridged by two asymmetrically bonding methanolate ligands [V—O = 1.8155 (12) and 2.3950 (13) Å] originating from the deprotonation of the methanol solvent. The coordination sphere of the VV atom is distorted octahedral, with the equatorial plane defined by the three donor atoms of the thiophene-2-carbohydrazidate ligand and the O atom of a methanolate unit. The axial positions are occupied by the oxide group and the remaining methanolate ligand. The axially bound methanolate ligand shows a longer V—O bond length due to the trans influence caused by the tightly bonded oxide group. The packing of the complex molecules is dominated by dispersion forces