Três novas supermoléculas, aqui designadas por ZnTCP4+, MnTCP5+ e CoTCP5+, foram obtidas pela coordenação de quatro acetatos trinucleares assimétricos de rutênio, [Ru3O(CH3CO2)6(py)2(CH3OH)]+, aos resíduos piridínicos de meso-tetra(4-piridil)porfirinato de ZnII, MnIII e CoIII, respectivamente (ZnTPyP, MnTPyP e CoTPyP). A caracterização destas supermoléculas foi efetuada por espectroscopia de ressonância magnética nuclear e espectroscopia eletrônica. O comportamento eletroquímico foi investigado por voltametria cíclica e espectroeletroquímica. Os efeitos dos acetatos trinucleares periféricos sobre a reatividade do núcleo porfirínico foram analisados: (i) para ZnTCP4+, além da supressão da luminescência, verificou-se que as constantes de coordenação axial determinadas em diclorometano para piridina e imidazol, quando comparadas às respectivas constantes de ZnTPyP e de meso-tetra(fenil)porfirinato de zinco, indicaram um aumento significativo da acidez de Lewis do íon Zn2+; (ii) MnTCP5+ revelou-se um catalisador mais seletivo que MnTPyP na oxidação de ciclohexano em fase homogênea, utilizando-se iodosilbenzeno como doador de oxigênio; (iii) os eletrodos modificados por filmes de CoTCP5+ apresentaram uma eficiente atividade catalítica na redução tetra-eletrônica de dioxigênio a água, comportamento que contrasta com o descrito na literatura para filmes de CoTPyP. A redução tetra-eletrônica de dioxigênio catalisada pelos filmes de CoTCP5+ foi confirmada por voltametria cíclica, voltametria de eletrodo disco rotatório e voltametria de eletrodo de anel e disco rotatórios. / Three novel supermolecules designated as ZnTCP4+, MnTCP5+, and CoTCP5+ were obtained by coordination of four assymetric trinuclear ruthenium acetate species, [Ru3O(CH3CO2)6(py)2(CH3OH)]+ to pyridine residues of ZnII -, MnIII -, and CoIIITPyP, respectively (TPyP = meso-tetra(4-pyridil)porphyrinate). These new compounds were characterized by nuclear magnetic resonance spectroscopy and electronic spectroscopy. The electrochemical behavior was investigated by cyclic voltammetry, and spectroelectrochemistry. The influence of the peripheral trinuclear acetate on the porphyrin core reactivity was assayed: (i) for ZnTCP4+, besides the luminescence quenching, the calculated equilibrium constants for axial coordination of pyridine and imidazole in dichloromethane demonstrated a significant increase in the Zn2+ Lewis acidity in comparison with the respective constants from ZnTPyP and zinc meso-tetra(phenyl)porphyrinate; (ii) MnTCP5+ exhibited improved selectivity as catalyst for ciclohexane oxidation (homogeneous phase) in comparison with MnTPyP using iodosylbenzene as oxygen donor; (iii) modified electrodes by CoTCP5+ films showed an outstanding catalytic activity in the tetraelectronic reduction of dioxygen to water, in contrast with CoTPyP films described in the literature; the dioxygen tetraelectronic reduction was confirmed by cyclic voltammetry, rotating disk electrode voltammetry, and rotating ring and disk electrode voltammetry.

In real-world conversational groups, interactants adjust their body position and orientation relative to one another in order to see and hear clearly. We use an agent-based modelling approach to compare alternative models for simulating the spatial patterns of conversational groups. The models are based on simple rules that control the movement, positioning, and orientation behaviour of individual agents, which in turn leads to the emergence of agent clusters. We identify which model alternative produces agent clusters with characteristics typical of real-world conversational groups. The centroid-based approach, where agents readjust their position and orientation with respect to the group centroid point, is a commonly used method to simulate conversational groups, but has not been empirically validated. This thesis replicates, evaluates, and validates the centroid-based model in a systematic way. Another model, where agents perform positional-orientational readjustments to see as many neighbours as possible within a 180 field of view, called the field-of-view approach is proposed, implemented, evaluated, and validated. Analysis of the spatial patterns of conversational groups has hitherto mostly relied on visual verification. We, novelly, use a combination of qualitative and quantitative methods to analyse the spatial patterns of conversational groups. Evaluations show that the field of- view model and centroid-based model produce agent clusters with significantly different social, spatial, and temporal characteristics. Validation is performed using a dataset which captures the spatial behaviour of 21 participants for the entire duration of a party. This validation shows that the characteristics of agent clusters resulting from the field-of-view model most closely reflects the characteristics of real-world conversational groups. We also show that a local neighbourhood influence works better than an extended neighbourhood influence to simulate conversational groups. The influence of objects in the environment on the spatial patterns of agent clusters are also discussed.

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Made available in DSpace on 2019-03-29T23:17:40Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-06-30 / This paper focuses on the role which public policies have in the development of Local Productive Arrangements in the Northeast of Brazil. One way for the government to bolster LPAs is by creating policies which provide support and help develop such business clusters. Such policies to foster LPAs in Brazil are becoming consistent and one can already see satisfactory results. This paper analyzes, through a case study, an example of policies which have been implemented in an LPA in the Northeast of Brazil. The following question has guided this study: What are the existing public policies in the selected LPA in the state of Ceará? In order to answer the core question, this paper used a qualitative approach in the form of a case study. The main objective of this paper was to analyze the impact of public policies implemented at the sheep and goat farming LPA of Quixadá, in Ceará. Research has shown that the public policies implemented at this sheep and goat farming LPA had significant impact. According to local farmers, they have been experiencing an improvement in flock management, which in turn has resulted in increased production of dairy products; this represents significant benefits to LPA members. We also noticed the strengthening of the activity itself by means of government support, resulting in increased development for the region. / Este trabalho enfoca o papel das políticas públicas para o desenvolvimento de Arranjos Produtivos Locais na região Nordeste. Uma das formas do governo alavancar os APL s é a criação de políticas que apóiem e ajudem no desenvolvimento destas aglomerações de empresas. Estas políticas de incentivos aos APL s no Brasil tem se tornado consistentes e já se pode visualizar resultados satisfatórios. Neste trabalho é analisado, através de um estudo de caso, um exemplo de políticas implementadas em um APL na região Nordeste. A seguinte questão norteou este estudo: Quais as políticas públicas existentes no APL selecionado no estado do Ceará? Para responder a questão central, este trabalho utilizou uma abordagem qualitativa por meio de estudo de caso. O objetivo geral do trabalho foi analisar o impacto da política pública implementada no APL de ovinocaprinocultura,no município de Quixadá, no Ceará. Com a pesquisa constatou-se que as políticas públicas implementadas no APL de ovinocaprinocultura estudado tiveram um significativo impacto. Segundo os produtores da região, eles têm experimentado melhoria nos processos de manejo do rebanho, ensejando uma melhor produção dos produtos derivados da atividade produtiva, representando ganhos significativos para os participantes do APL. Foi observado também o fortalecimento da atividade por meio do apoio do poder público, que tem repercutido um maior desenvolvimento para a região.

Orientador: Jaqueline Costa Teixeira Caramori / Resumo: Introdução: A evolução clínica da doença renal crônica está associada a altas taxas de morbidade. As complicações decorrem da progressão da doença renal, levando ao declínio cognitivo, anemia, distúrbios minerais e ósseos, fraturas, riscos nutricionais e aumento da mortalidade cardiovascular e por outras causas. Dentre as alterações nutricionais está a sarcopenia, definida como diminuição global e progressiva da força e massa muscular, com efeitos na função muscular, diminuição da mobilidade e da atividade física. Em diálise, maior atenção merece ser dada para esses fatores, visando prevenir mais complicações. A complexidade da doença renal avançada sugere que sejam buscadas ferramentas que possam avaliar a maior gravidade dos pacientes. Neste contexto, torna-se importante, identificar grupos de pacientes com características semelhantes e considerando o risco de desfechos. Objetivo: Interpretar por análise de agrupamento de parâmetros clínicos e nutricionais, uma população de pacientes prevalentes em hemodiálise, considerando a evolução clínica e com ênfase no diagnóstico de sarcopenia. Metodologia: Estudo de coorte, retrospectivo, descritivo e observacional. Foram identificadas características clínicas, laboratoriais e nutricionais, seguido da investigação de sarcopenia e análise de agrupamento com acompanhamento de desfechos clínicos dos pacientes em hemodiálise. Para diagnóstico de sarcopenia foi realizada avaliação da composição corporal usando bioimpedância unifrequencia... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Background: Clinical evolution of chronic kidney disease is associated with high morbidity rates. Complications arise from the progression of renal disease, leading to cognitive decline, anemia, mineral and bone disorders, fractures, nutritional risk and increased cardiovascular and all causes mortality. Among the nutritional changes, sarcopenia, which is defined as a global and progressive reduction of muscle strength and mass, with effects on function muscle, decreases mobility and physical activity. In dialysis, these factors should receive greater attention, in order to prevent further complications. The complexity of advanced kidney disease suggests that tools that assess the severity of patients should be sought. In this context, it is important to identify groups of patients with similar characteristics considering the risk of outcomes. Objective: To analyze clinical and nutritional parameters using cluster analysis of a population of patients on maintenance hemodialysis, considering the clinical evolution with emphasis in sarcopenia diagnosis. Methods: This is a cohort, retrospective, descriptive and observational study. Clinical, laboratory and nutritional characteristics were identified, followed by sarcopenia investigation and cluster analysis, with follow-up of clinical outcomes of patients in maintenance hemodialysis. For sarcopenia diagnosis, body composition evaluation was performed using unifrequencial bioimpedance and handgrip strength. To compare the samples... (Complete abstract click electronic access below) / Mestre

Dusty star-forming galaxies (DSFGs) are highly luminous (LFIR ≳ 10¹² L⊙), very distant (z ≳2.5) and ≳ 10x rarer then 'normal', NIR-selected (BzK), star-forming galaxies. Capable of producing a Mstars ≳ 10¹¹-M⊙ galaxy after a tburst ~ 100-Myr burst of late-stage, merger-induced star formation, DSFGs naturally provide extreme laboratories with which to study the formation and evolution of massive structures within the Universe. Thus far, however, theoretical models have struggled to reconcile the observed abundance and redshift distribution of these massive, dust-enshrouded galaxies that occupy the high-end tail of the galaxy stellar mass function. Therefore, it is of paramount importance, from an observational point of view, to both increase the number of known distant (z ≳ 4) DSFGs and to thoroughly explore their extreme environments in order to provide further constraints on such models. Thus, in Chapter 2 of this thesis, I report on efforts to substantially increase the number of distant DSFGs using the uniquely wide H-ATLAS imaging survey. I analysed a sample of 109, so-called 'ultra-red galaxies' selected via their red Herschel-SPIRE flux densities (σ500 > 3.5 and S500 < 100mJy) and flux-density ratios (S500/S250 > 1.5 and S500/S350 > 0.85). Ground-Based continuum imaging at ~ 850 μm with the JCMT and APEX telescopes allowed me to locate the dust peaks of these S500 ≳ 30-mJy ultra-red galaxies and derive a median photometric redshift of zphot = 3.66 (3.30-4.27, IQR) for them (assuming that they can satisfactorily be represented by a Tdust ~ 30-K template SED). Using 25 spectroscopically confirmed DSFGs with SPIRE flux densities matching this ultra-red criteria, I determined that these FIR photometric redshift estimates have a minimum intrinsic scatter of σ = 0.14(1 + zspec) and systematically under-estimate the spectroscopic redshifts below zspec ≲ 5. With over a third of these ultra-red galaxies lying above z > 4, I derived a space density of at least p ≈ 6 x 10⁻⁷Mpc⁻³ for this sample (assuming a tburst = 100-Myr burst of star formation), which is only a factor of 7x less numerous than that of the most massive (Mstars ≳ 10¹¹M⊙), compact, quiescent galaxies selected in the NIR at z ~ 3. Finally, although the space density of z > 4 ultra-red galaxies aligns very well with that of massive (MBH ≳ 10⁸M⊙) AGN at z > 6, none have yet to be uncovered within this sample to date. In the following chapter, I present wide images obtained with LABOCA of a sub-sample of 22, representative ultra-red galaxies to see if these galaxies are signposting over-dense regions in the early Universe, as might be expected if they were to evolve into the most massive, compact, quiescent galaxies at z ~ 0. This LABOCA ultra-red galaxy survey covers an area of ≈ 0.8 deg² down to an average r.m.s. of 3.9mJy beam⁻¹, with the five deepest images going ≈ 2x deeper still. I catalogue 86 galaxies detected above > 3.5σ870 surrounding these 22 ultra-red galaxies, which implies a δ ≈ 100 ± 30% over-density of S870 > 8.5-mJy (LFIR ≈ (7-30) x 10¹² L⊙) DSFGs when compared against LESS. Thus, I am 99.93% confident that these ultra-red galaxies are pinpointing over-dense regions in the Universe, and ≈ 95% confident that these regions are over-dense by a factor of at least ≥ 1.5x. Using the same template SEDs as in the previous chapter, I derived a consistent median photometric redshift of z = 3.2 ± 0.2 with an IQR of z = 2.8-3.6 for these ultra-red galaxies. I constrained the surrounding galaxies likely responsible for this over-density to within |∆z| ≤ 0.65 of their respective ultra-red galaxies. However, on average, I was only able to associate one surrounding galaxy to within |∆z| ≤ 0.5 of its respective ultra-red galaxy. These 'associated' galaxies are radially distributed within (physical) distances of 1.6 ± 0.5Mpc from their ultra-red galaxies, have median SFRs of vI≈ (1.0±0.2)x10³M⊙ yr⁻¹ (assuming a Salpeter stellar IMF) and median gas reservoirs of Mgas ~ 1.7 x 10¹¹M⊙. These candidate proto-clusters have average total SFRs of at least Ψ ≈ (2.3 ± 0.5) x 10³M⊙ yr⁻¹ and a space density of ~ 9 x 10⁻⁷Mpc⁻³, consistent with the idea that their constituents may occupy the centres of rich galaxy clusters seen today. Finally, in Chapter 4 of this thesis, I extracted Herschel-SPIRE photometry at the 850-μm positions of DSFGs detected within in the S2CLS and S2COSMOS imaging surveys. I then analysed the multi-wavelength environmental properties around a robust sample of 64 ultra-red galaxies selected via their 'ultra-red probability'. Similar to the findings in Chapter 3, I found that these ultra-red galaxies are preferentially located in over-dense regions extending over scales of ~ 5' (or ~ 2Mpc at z ~ 3). Furthermore, I found that these candidate, high-redshift proto-clusters have FIR total dust masses and total SFRs of Mdust ~ 10⁹M⊙ and Ψ ~ 10³M⊙ yr⁻¹, respectively. Ground-Based, optical/NIR imaging around a subset of 42 ultra-red galaxies shows a factor of ~ 5x increase in both the stellar mass and the (MB -MI )-colour of associated LBGs as the radial distance decreases from . 500 kpc - consistent with the emergence of a galaxy red sequence at z ~ 3. Furthermore, these data show a 1-σ increase in the fraction of 'green-valley' galaxies within scales of ~ 5' compared to the field - supporting the concept that red-sequence galaxies are appearing at a faster rate around ultra-red galaxies compared to the field. There is a sizeable contribution of Mstars ~ 10¹²M⊙ from these high-redshift LBGs within the environments of ultra-red galaxies. On average, I was able to associate ≈ 28 LBGs to a given ultra-red galaxy (~ 30x the number of associated DSFGs). Although these systems have average optical/NIR/FIR properties that are consistent with their evolution into present-day galaxy clusters with DM halos of mass Mhalo ~ 10¹⁴-10¹⁵M⊙, I am still likely missing a sizeable contribution from unassociated LBGs and DSFGs due to the large photometric redshift uncertainties for the ultra-red galaxies. Therefore, the results presented in this thesis should be regarded as firm lower limits on these environmental properties around ultra-red galaxies, which can now only be improved upon when spectroscopic data increases the accuracy of the photometric redshift estimates presented here.

Made available in DSpace on 2014-06-12T17:41:17Z (GMT). No. of bitstreams: 2 arquivo7304_1.pdf: 664683 bytes, checksum: b9018a542188e640d732d0ca41465dc7 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2007 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Arranjos Produtivos Locais são exemplos de um fenômeno de aglomeração de fatores econômicos via concentração geográfica de empresas, instituições e recursos humanos. Correspondem a casos particulares de uma tendência maior de efeitos aglomerativos, denominada de clusterização. O principal objetivo deste trabalho é indicar ações e políticas públicas que possam contribuir para o desenvolvimento de regiões que experimentam os efeitos das economias de aglomeração. Após estudar a Cadeia Têxtil / Confecção, em nível regional e internacional, foi possível conhecer o atual paradigma de competitividade, localização, produção e comercialização do setor, no Brasil e no mundo. Para estudar o Pólo de Confecções na Região Agreste de Pernambuco, foram observados diversos aspectos relacionados à governança, organização empresarial, e comercialização. A partir das informações obtidas, foram propostas ações e políticas públicas que poderiam fazer parte de uma agenda de atividades com o objetivo de desenvolver diversos Arranjos Produtivos Locais, a exemplo do Pólo de Confecções da Região Agreste de Pernambuco

Três novas supermoléculas, aqui designadas por ZnTCP4+, MnTCP5+ e CoTCP5+, foram obtidas pela coordenação de quatro acetatos trinucleares assimétricos de rutênio, [Ru3O(CH3CO2)6(py)2(CH3OH)]+, aos resíduos piridínicos de meso-tetra(4-piridil)porfirinato de ZnII, MnIII e CoIII, respectivamente (ZnTPyP, MnTPyP e CoTPyP). A caracterização destas supermoléculas foi efetuada por espectroscopia de ressonância magnética nuclear e espectroscopia eletrônica. O comportamento eletroquímico foi investigado por voltametria cíclica e espectroeletroquímica. Os efeitos dos acetatos trinucleares periféricos sobre a reatividade do núcleo porfirínico foram analisados: (i) para ZnTCP4+, além da supressão da luminescência, verificou-se que as constantes de coordenação axial determinadas em diclorometano para piridina e imidazol, quando comparadas às respectivas constantes de ZnTPyP e de meso-tetra(fenil)porfirinato de zinco, indicaram um aumento significativo da acidez de Lewis do íon Zn2+; (ii) MnTCP5+ revelou-se um catalisador mais seletivo que MnTPyP na oxidação de ciclohexano em fase homogênea, utilizando-se iodosilbenzeno como doador de oxigênio; (iii) os eletrodos modificados por filmes de CoTCP5+ apresentaram uma eficiente atividade catalítica na redução tetra-eletrônica de dioxigênio a água, comportamento que contrasta com o descrito na literatura para filmes de CoTPyP. A redução tetra-eletrônica de dioxigênio catalisada pelos filmes de CoTCP5+ foi confirmada por voltametria cíclica, voltametria de eletrodo disco rotatório e voltametria de eletrodo de anel e disco rotatórios. / Three novel supermolecules designated as ZnTCP4+, MnTCP5+, and CoTCP5+ were obtained by coordination of four assymetric trinuclear ruthenium acetate species, [Ru3O(CH3CO2)6(py)2(CH3OH)]+ to pyridine residues of ZnII -, MnIII -, and CoIIITPyP, respectively (TPyP = meso-tetra(4-pyridil)porphyrinate). These new compounds were characterized by nuclear magnetic resonance spectroscopy and electronic spectroscopy. The electrochemical behavior was investigated by cyclic voltammetry, and spectroelectrochemistry. The influence of the peripheral trinuclear acetate on the porphyrin core reactivity was assayed: (i) for ZnTCP4+, besides the luminescence quenching, the calculated equilibrium constants for axial coordination of pyridine and imidazole in dichloromethane demonstrated a significant increase in the Zn2+ Lewis acidity in comparison with the respective constants from ZnTPyP and zinc meso-tetra(phenyl)porphyrinate; (ii) MnTCP5+ exhibited improved selectivity as catalyst for ciclohexane oxidation (homogeneous phase) in comparison with MnTPyP using iodosylbenzene as oxygen donor; (iii) modified electrodes by CoTCP5+ films showed an outstanding catalytic activity in the tetraelectronic reduction of dioxygen to water, in contrast with CoTPyP films described in the literature; the dioxygen tetraelectronic reduction was confirmed by cyclic voltammetry, rotating disk electrode voltammetry, and rotating ring and disk electrode voltammetry.

Tese (Doutorado em Engenharia de Produção) - Escola Politécnica da Universidade de São Paulo, São Paulo, 2006

Within bioinformatics, phylogenetics is the study of the evolutionary relationships between different species and organisms. The genetic revolution has caused an explosion in the amount of raw genomic information that is available to scientists for study. While there has been an explosion in available data, analysis methods have lagged behind. A key task in phylogenetics is identifying homology clusters. Current methods rely on using heuristics based on pairwise sequence comparison to identify homology clusters. We propose the Orthology Group Cleaner (the OGCleaner) as a method to evaluate cluster level verification of putative homology clusters in order to create higher quality phylogenetic tree reconstruction.