Processos de scaffolding num contexto pedagógico mem em jardim-de-infância

Relatório da Prática Profissional Supervisionada Mestrado em Educação Pré-Escolar

Hydrogenating activity of Pt/zeolite catalysts focusing acid support and metal dispersion influence

Toluene hydrogenation was studied over catalysts based on Pt supported on large pore zeolites (HUSY and HBEA) with different metal/acid ratios. Acidity of zeolites was assessed by pyridine adsorption followed by FTIR showing only small changes before and after Pt introduction. Metal dispersion was determined by H2–O2 titration and verified by a linear correlation with the intensity of Pt0–CO band obtained by in situ FTIR. It was also observed that the electronic properties of Pt0 clusters were similar for the different catalysts. Catalytic tests showed rapid catalyst deactivation with an activity loss of 80–95% after 60 min of reaction. The turnover frequency of fresh catalysts depended both on metal dispersion and the support. For the same support, it changed by a 1.7-fold (HBEA) and 4.0-fold (HUSY) showing that toluene hydrogenation is structure-sensitive, i.e. hydrogenating activity is not a unique function of accessible metal. This was proposed to be due to the contribution to the overall activity of the hydrogenation of adsorbed toluene on acid sites via hydrogen spillover. Taking into account the role of zeolite acidity, the catalysts series were compared by the activity per total adsorbing sites which was observed to increase steadily with nPt/(nPt + nA). An increase of the accessible Pt atoms leads to an increase on the amount of spilled over hydrogen available in acid sites therefore increasing the overall activity. Pt/HBEA catalysts were found to be more active per total adsorbing site than Pt/HUSY which is proposed to be due to an augmentation in the efficiency of spilled over hydrogen diffusion related to the proximity between Pt clusters and acid sites. The intervention of Lewis acid sites in a greater extent than that measured by pyridine adsorption may also contribute to this higher activity of Pt/HBEA catalysts. These results reinforce the importance of model reactions as a closer perspective to the relevant catalyst properties in reaction conditions.

Silver coordination polymers with tri- and hexacyanoethyl-functionalized macrocyclic ligands

Tri-and hexa-cyanoethyl functionalized 17-(L-1) and 42-membered (L-2) macrocyclic compounds were obtained by [1 + 1] (for L-1) or [2 + 2] (for L-2) cyclocondensation of the corresponding dialdehyde and diethylenetriamine, followed by hydrogenation by KBH4 and subsequent cyano-functionalization with acrylonitrile. They react with silver nitrate, leading to the formation of [AgL1](NO3) (1) and of the metalorganic coordination polymers [Ag-2(NO3)(2)L-1](n) (2) and {[Ag2L2](NO3)(2)}(n) (3). The complexes were characterized by elemental analysis, H-1 NMR, C-13 NMR, IR spectroscopies, and ESI-MS; moreover, L-2, 1, 2 and 3 were also characterized by single crystal X-ray diffraction. The metal cation in 1 is pentacoordinated with a N3O2 coordination environment; in 2, the metal cations display N4O2 octahedral and N2O3 square-pyramid coordination and in 3 they are in square-planar N-4 sites. In 1, the ligand acts as a pentadentate chelator, and in the other two cases, the ligands behave as octadentate chelators in a 1 kappa N-3:kappa O-2,2 kappa N,3 kappa N,4 kappa N (in 2) or 1 kappa N-3,2 kappa N-3,3 kappa N,4 kappa N fashion (in 3). The cyanoethyl strands of the ligands are directly involved in the formation of the 2D frameworks of 2 and 3, which in the former polymer can be viewed as a net composed of hexametallic 36-membered macrocyclic rings and in the latter generates extra hexametallic 58-membered cyclic sets that form zig-zag layers. The thermal analytical and electrochemical properties of these silver complexes were also studied.

Preliminary study on the production of functionally graded materials by friction stir processing

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Mecânica

Projecto e concepção de um dispositivo experimental para medição e caracterização dos esforços aplicados no finca-pés de um caiaque de pista: Investigação, desenho e desenvolvimento

Após o enquadramento da canoagem, como modalidade Olímpica, verificou-se um aumento significativo de estudos e pesquisas acerca da biomecânica da modalidade, o que contribuiu para uma diminuição dos tempos na competição. Contudo poucos foram os que se focaram nas forças desenvolvidas e aplicadas ao caiaque através do finca-pés, criado assim oportunidade de desenvolvimento de dispositivos para a medição das mesmas. Assim, o objectivo primordial é desenvolver um sistema experimental capaz de quantificar as forças geradas em cada um dos lados do finca-pés (esquerdo e direito). Este, deverá não só ser passível de se utilizar em caiaque ergómetro como também num caiaque de pista, permitido avaliar as forças aplicadas durante o ciclo de pagaiada, tanto em compressão como em tracção. A sua concepção baseou-se num modelo de finca-pés já existente, tornando-o compatível com os caiaques de competição mais comercializados, e permitindo que no futuro se possa utilizar na água, bastando para isso apenas possuir um caiaque e embarcar o sistema de medição. Este sistema experimental foi testado em caiaque ergómetro por 7 (sete) sujeitos com níveis distintos: seis homens (um atleta olímpico medalhado e cinco de nível nacional) e uma mulher (de nível de selecção Portuguesa) que, entre outros, realizaram um plano definido por 60s a uma frequência de 75 pagaiadas por minuto, seguido de uma intensa mudança de ritmo e força (Sprint). Após análise dos dados obtidos em cada um dos diferentes sujeitos, conseguimos identificar algumas das suas características, tais como: esforço assimétrico dos membros inferiores; utilização de forma heterogénea da fita do finca-pés; diferença de forças máximas aplicadas entre atletas (Ex.: para um atleta olímpico as forças medidas (Min; Max): Pé Esquerdo (- 444; 1087) N e Pé Direito (- 476; 1068) N); etc. Os resultados não só são bastante promissores como também são motivantes e congruentes com estudos anteriores, nomeadamente Begon et al. 2008 e Sturm 2010 e 2012. Finalmente, consegue-se afirmar, com segurança, que foram alcançados os objectivos propostos com a concepção deste dispositivo de medição de forças. Este permite caracterizar os esforços desenvolvidos no finca-pés por cada membro inferior, com ou sem a fita de suporte, possibilitando aos treinadores e atletas uma visão, para muitos desconhecida, das forças transmitidas e das suas assimetrias. No final, este conhecimento permitirá aos atletas melhorar o seu desempenho desportivo bem como facilitar a gestão desportiva, com base nos principais princípios mecânicos inerentes ao movimento dos atletas desde desporto Olímpico.

Stackelberg leadership with demand uncertainty in a differentiated duopoly

On a symmetric differentiated Stackelberg duopoly model in which there is asymmetric demand information owned by leading and follower firms, we show that the leading firm does not necessarily have advantage over the following one. The reason for this is that the second mover can adjust its output level after observing the realized demand, while the first mover chooses its output level only with the knowledge of demand distribution.

Cyclopentadienyl-functionalised N-heterocyclic carbenes: synthesis, coordination to Mo, Ru, Rh

Dissertation presented to obtain the Ph.D degree in Chemistry

Purification, crystallization and preliminary X-ray diffraction analysis of adenosine triphosphate sulfurylase (ATPS) from the sulfate-reducing bacterium Desulfovibrio desulfuricans ATCC 27774

Acta Crystallogr Sect F Struct Biol Cryst Commun. 2008 Jul 1;64(Pt 7):593-5

Heterodimeric nitrate reductase (NapAB) from Cupriavidus necator H16: purification, crystallization and preliminary X-ray analysis

Acta Cryst. (2007). F63, 516–519

Stackelberg duopoly with demand uncertainty

We consider a symmetric Stackelberg model in which there is asymmetric demand information owned by first and second movers. We analyse the advantages of leadership and flexibility, and prove that when the leading firm faces demand uncertainty, but the follower does not, the first mover does not necessarily have advantage over the second mover. Moreover, we show that the advantage of one firm over the other depends upon the demand fluctuation and also upon the degree of substitutability of the products.

Price-setting dynamical duopoly with incomplete information

We consider a price competition in a duopoly with substitutable goods, linear and symmetric demand. There is a firm (F 1) that chooses first the price p 1 of its good; the other firm (F 2) observes p 1 and then chooses the price p 2 of its good. The conclusions of this price-setting dynamical duopoly are substantially altered by the presence of either differentiated goods or asymmetric information about rival’s production costs. In this paper, we consider asymmetric information about rival’s production costs. We do ex-ante and ex-post analyses of firms’ profits and market prices. We compare the ex-ante firms’ expected profits with the ex-post firms’ profits.

Uncertainty on a Bertrand duopoly with product differentiation

The conclusions of the Bertrand model of competition are substantially altered by the presence of either differentiated goods or asymmetric information about rival’s production costs. In this paper, we consider a Bertrand competition, with differentiated goods. Furthermore, we suppose that each firm has two different technologies, and uses one of them according to a certain probability distribution. The use of either one or the other technology affects the unitary production cost. We show that this game has exactly one Bayesian Nash equilibrium. We do ex-ante and ex-post analyses of firms’ profits and market prices. We prove that the expected profit of each firm increases with the variance of its production costs. We also show that the expected price of each good increases with both expected production costs, being the effect of the expected production costs of the rival dominated by the effect of the own expected production costs.

Análise da estrutura e da função da proteína morfogenética RodZ de Bacillus subtilis

Resumo: RodZ é um componente do sistema morfogenético das células bacterianas. É uma proteína transmembranar que localiza em bandas ao longo do eixo longitudinal da célula. Em Bacillus subtilis, RodZ consiste numa porção citoplasmática, RodZn, e em uma parte extra-citoplasmática, RodZc. RodZn contém um domínio em helixturn- helix (HTH), enquanto que RodZc pode ser dividido num domínio coiled-coil e num domínio terminal C, de função desconhecida. Um segmento transmembranar (TM) único separa RodZn de RodZc. A eliminação de rodZ causa alongamento do nucleóide e leva à produção de células polares nucleadas. Aqui, mostramos que RodZn é estruturado, estável e em hélice α. Descobrimos que as substituições Y32A e L33A na suposta hélice de reconhecimento (3) do motivo HTH, bem como as substituições Y49A e F53A, fora do motivo HTH (4), causam divisão assimétrica, mas apenas as últimas levam à deslocalização sub-celular de RodZ. Sugerimos que as hélices 3 e 4 são utilizadas para uma interacção proteína-proteína ou proteína- DNA essencial para divisão celular enquanto que 4 deve contactar um componente do citosqueleto, possivelmente MreB, uma vez que a correcta localização sub-celular de RodZ depende desta proteína. Em todos os mutantes as células polares são anucleadas, pelo que concluímos que o alongamento do nucleóide não é um prérequisito para divisão assimétrica. RodZc é largamente não estruturado mas com conteúdo de folha , sendo estabilizado pelo domínio coiled-coil. Mostramos uma relação homóloga entre RodZc e a bomba de transporte Na+/Ca2+ NCX1 e identificámos dois resíduos no domínio C, G265 e N275, essenciais para a manutenção da forma celular. Estes resíduos fazem parte de um motivo em gancho que pode actuar como um local de interacção com um ligando desconhecido. RodZn e RodZc são monoméricos em solução. Contudo, na membrana, RodZ interage consigo própria num sistema de dois híbridos (Split-Ubiquitin) em levedura, sugerindo que possa formar multímeros in vivo.-----------ABSTRACT: RodZ is a transmembrane component of the bacterial core morphogenic apparatus. RodZ localizes in bands long the longitudinal axis of the cell, and it is though to functionally link the cell wall to the actin cytoskeleton. In Bacillus subtilis, RodZ consists of a cytoplasmic moiety, RodZn, and an extracytoplasmic moiety, RodZc. RodZn contains a predicted helix-turn-helix domain, whereas RodZc is thought to contain a coiled-coil region and a terminal C domain of unknown function. A single transmembrane domain separates RodZn from RodZc. Deletion of rodZ causes elongation of the nucleoid and leads to the production of polar minicells containing DNA. Here, we have studied the structure and function of RodZn and RodZc. We show that RodZn is a stable, folded, -helical domain. We discovered that the Y32A and L33A substitutions within the presumptive recognition helix (3) of the HTH motif, as well as the Y49A and F53A substitutions outside of the HTH motif (in 4) cause asymmetric cell division. However, only the substitutions in 4 cause sub-celular delocalization of RodZ. We suggest that 3 and 4 are used for a protein-protein or protein-DNA interaction important for cell division, whereas 4 is likely to contact a cytoskeletal component, presumably MreB. The polar cells formed by all the mutants are anucleate. We conclude that nucleoid elongation is not a prerequisite for asymmetric division. RodZc appears to be a largely unstructured domain, with some -sheet content, and is stabilized by the coiled-coil region. We show a homology relationship between RodZc and the NCX1 Na+/Ca2+ transporter and we found two residues within the C domain, G265 and N275, that are important for cell shape determination. These residues are predicted to be essential determinants of a claw-like motif, which may act as a binding site for an unknown ligand. Both the isolated RodZn and RodZc proteins are monomeric in solution. However, because full-length RodZ interacts with itself in a split-ubiquitin yeast two-hybrid assay, we suggest that it may dimerize or form higher order multimers in vivo.

Symmetry-out asymmetry-in: the role of DMRT2

Dissertation presented to obtain the PhD degree in Biology

Crystal structure of the zinc-, cobalt-, and iron-containing adenylate kinase from Desulfovibrio gigas: a novel metal-containing adenylate kinase from Gram-negative bacteria

J Biol Inorg Chem (2011) 16:51–61 DOI 10.1007/s00775-010-0700-8