Molecular approaches to smart materials via interface recognition and conformationally switchable cavitands

In this thesis the molecular level design of functional materials and systems is reported. In the first part, tetraphosphonate cavitand (Tiiii) recognition properties towards amino acids are studied both in the solid state, through single crystal X-ray diffraction, and in solution, via NMR and ITC experiments. The complexation ability of these supramolecular receptors is then applied to the detection of biologically remarkable N-methylated amino acids and peptides using complex dynamic emulsions-based sensing platforms. In the second part, a general supramolecular approach for surface decoration with single-molecule magnets (SMMs) is presented. The self-assembly of SMMs is achieved through the formation of a multiple hydrogen bonds architecture (UPy-NaPy complexation). Finally we explore the possibility to impart auxetic behavior to polymeric material through the introduction of conformationally switchable monomers, namely tetraquinoxaline cavitands (QxCav). Their interconversion from a closed vase conformation to an extended kite form is studied first in solution, then in polymeric matrixes via pH and tensile stimuli by UV-Vis spectroscopy.

Mécanismes de transfert de proton d’une réaction acido-basique en phase aqueuse : une étude ab-initio

Les réactions de transfert de proton se retrouvent abondamment dans la nature et sont des processus cruciaux dans plusieurs réactions chimiques et biologiques, qui se produisent souvent en milieu aqueux. Les mécanismes régissant ces échanges de protons sont complexes et encore mal compris, suscitant un intérêt des chercheurs en vue d’une meilleure compréhension fondamentale du processus de transfert. Le présent manuscrit présente une étude mécanistique portant sur une réaction de transfert de proton entre un acide (phénol fonctionnalisé) et une base (ion carboxylate) en phase aqueuse. Les résultats obtenus sont basés sur un grand nombre de simulations de dynamique moléculaire ab-initio réalisées pour des systèmes de type « donneur-pont-accepteur », où le pont se trouve à être une unique molécule d’eau, permettant ainsi l’élaboration d’un modèle cinétique détaillé pour le système étudié. La voie de transfert principalement observée est un processus ultra-rapide (moins d’une picoseconde) passant par la formation d’une structure de type « Eigen » (H9O4+) pour la molécule d’eau pontante, menant directement à la formation des produits. Une seconde structure de la molécule d’eau pontante est également observée, soit une configuration de type « Zündel » (H5O2+) impliquant l’accepteur de proton (l’ion carboxylate) qui semble agir comme un cul-de-sac pour la réaction de transfert de proton.

Mécanismes de transfert de proton d’une réaction acido-basique en phase aqueuse : une étude ab-initio

Les réactions de transfert de proton se retrouvent abondamment dans la nature et sont des processus cruciaux dans plusieurs réactions chimiques et biologiques, qui se produisent souvent en milieu aqueux. Les mécanismes régissant ces échanges de protons sont complexes et encore mal compris, suscitant un intérêt des chercheurs en vue d’une meilleure compréhension fondamentale du processus de transfert. Le présent manuscrit présente une étude mécanistique portant sur une réaction de transfert de proton entre un acide (phénol fonctionnalisé) et une base (ion carboxylate) en phase aqueuse. Les résultats obtenus sont basés sur un grand nombre de simulations de dynamique moléculaire ab-initio réalisées pour des systèmes de type « donneur-pont-accepteur », où le pont se trouve à être une unique molécule d’eau, permettant ainsi l’élaboration d’un modèle cinétique détaillé pour le système étudié. La voie de transfert principalement observée est un processus ultra-rapide (moins d’une picoseconde) passant par la formation d’une structure de type « Eigen » (H9O4+) pour la molécule d’eau pontante, menant directement à la formation des produits. Une seconde structure de la molécule d’eau pontante est également observée, soit une configuration de type « Zündel » (H5O2+) impliquant l’accepteur de proton (l’ion carboxylate) qui semble agir comme un cul-de-sac pour la réaction de transfert de proton.

Beach face and berm morphodynamics fronting a coastal lagoon

This study documents two different modes of berm development: (I) vertical growth at spring tides or following significant beach cut due to substantial swash overtopping, and (2) horizontal progradation at neap tides through the formation of a proto-berm located lower and further seaward of the principal berm. Concurrent high-frequency measurements of bed elevation and the associated wave runup distribution reveal the details of each of these berm growth modes. In mode I sediment is eroded from the inner surf and lower swash zone where swash interactions are prevalent. The net transport of this sediment is landward only, resulting in accretion onto the upper beach face and over the berm crest. The final outcome is a steepening of the beach face gradient, a change in the profile shape towards concave and rapid vertical and horizontal growth of the berm. In mode 2 sediment is eroded from the lower two-thirds of the active swash zone during the rising tide and is transported both landward and seaward. On the falling tide sediment is eroded from the inner surf and transported landward to backfill the zone eroded on the rising tide. The net result is relatively slow steepening of the beach face, a change of the profile shape towards convex, and horizontal progradation through the formation of a neap berm. The primary factor determining which mode of berm growth occurs is the presence or absence of swash overtopping at the time of sediment accumulation on the beach face. This depends on the current phase of the spring-neap tide cycle, the wave runup height (and indirectly offshore wave conditions) and the height of the pre-existing berm. A conceptual model for berm morphodynamics is presented, based on sediment transport shape functions measured during the two modes of berm growth. (c) 2006 Elsevier B.V. All rights reserved.

A COMUNICAÇÃO INTERPESSOAL COMO REGULADORA DA PERCEPÇÃO DA QUALIDADE DOS SERVIÇOS DE SAÚDE

Quem utiliza, hoje, os serviços de uma organização especializada na área da saúde, encontra pela frente profissionais que desenvolvem atividades assistenciais, cujo exercício está a exigir bem mais do que apenas competência técnica. São médicos, enfermeiros, psicólogos, fisioterapeutas, nutricionistas, terapeutas ocupacionais, assistentes sociais, entre outros, que, além das ações e procedimentos relacionados às suas áreas específicas de conhecimento, têm de estabelecer sempre, com as pessoas que atende, relações de caráter interpessoal. Existe literatura suficiente indicando haver considerável alívio por parte dos pacientes (clientes) e melhoria das condições do trabalho assistencial quando o profissional de saúde está apto a conhecer mais de perto os motivos para muitos dos comportamentos dos seus pacientes. Nessa perspectiva, uma interação para melhor compreender suas necessidades, angústias, raivas e expectativas é de fundamental importância. É também conhecido o fato de que muitas das reclamações e insatisfações dos serviços prestados nessas instituições poderiam ser evitados ou atenuados quando os pacientes se sentem compreendidos e respeitados pelos profissionais envolvidos no seu atendimento. A falta de acolhimento das demandas da clientela e a observação, por parte desta, de que os aspectos emocionais na relação com quem o assiste está sendo negligenciada pode conduzir este paciente, enquanto cliente, à conclusão de que o serviço prestado é de má qualidade. Este estudo terá por objetivo conhecer, dentro do fenômeno da comunicação interpessoal, as modalidades de interações sociais constituídas através dela à formação das exigências, expectativas e percepções desses atores sociais, além do entendimento de como se dá a relação entre paciente e atendente. Para isso, estudaremos os principais conceitos de serviços, qualidade e os fundamentos teóricos do modelo conceitual formulado por PARASURAMAN, ZEITHAML & BERRY e seus posteriores refinamentos , que resultaram na escala Servqual, cuja concepção determina que a qualidade dos serviços de qualquer natureza detectada por uma clientela, resulta do hiato entre as expectativas iniciais e a performance percebida do serviço. A escala Servqual se constituirá assim, no principal instrumento teórico a ser utilizado neste trabalho. Entendendo a sociedade de hoje como uma rede sistêmica, estudaremos, por fim, as lacunas entre as expectativas e percepções de uma clientela específica dos serviços oferecidos por uma empresa hospitalar especializada na área de maternidade. É uma pesquisa na qual se procurará determinar em que dimensões da qualidade a comunicação interpessoal apresenta maior influência, funcionando como um mecanismo regulador da percepção dos serviços prestados sob uma ótica qualitativa.

A PESQUISA DA PRÓPRIA PRÁTICA PEDAGÓGICA: UMA AÇÃO POSSÍVEL?

O presente trabalho investigar como os professores das séries iniciais do ensino fundamental entendem o ato de pesquisar a própria prática; e cotejar as visões dos professores sobre pesquisa com o referencial teórico específico. Para dar concretude a esses objetivos utilizamos a abordagem qualitativa. Temos como público alvo desse estudo cinco professores de uma escola pública situada no Município de Salvador Bahia. Inicialmente, descrevemos brevemente o contexto histórico da pesquisa, seus fundamentos, bem como os do professor pesquisador, elencando definições de pesquisa, com falas e posicionamentos de teóricos que discutem o tema. Consta também de explanação sobre as categorias e subcategorias elegidas no decorrer das atividades de pesquisa realizadas em campo. Tais categorias emergem nas observações e entrevistas realizadas com gestores e professores da instituição pesquisada e por serem recorrentes nas falas desses sujeitos. Obtemos, a partir das categorias construídas no processo da pesquisa, como principais resultados: a compreensão dos sujeitos pesquisados sobre a pesquisa da própria prática é limitada e equivocada; o universo considerado é totalmente avesso ao processo de pesquisa da prática, pois os professores estão imersos num emaranhado de sérias problemáticas explicitadas em nossos registros de observação. Concluímos afirmando que, apesar dos professores pesquisados não realizarem a pesquisa da prática, a nosso ver, essa é uma ação possível e que se concretiza também através da formação contínua e em serviço.(AU)

Static energy analysis of MHC class I and class II peptide-binding affinity

Antigenic peptide is presented to a T-cell receptor (TCR) through the formation of a stable complex with a major histocompatibility complex (MHC) molecule. Various predictive algorithms have been developed to estimate a peptide's capacity to form a stable complex with a given MHC class II allele, a technique integral to the strategy of vaccine design. These have previously incorporated such computational techniques as quantitative matrices and neural networks. A novel predictive technique is described, which uses molecular modeling of predetermined crystal structures to estimate the stability of an MHC class II-peptide complex. The structures are remodeled, energy minimized, and annealed before the energetic interaction is calculated.

Structure of dysprosium and holmium phosphate glasses by the method of isomorphic substitution in neutron diffraction

The relative distribution of rare-earth ions R3+ (Dy3+ or Ho3+) in the phosphate glass RAl0.30P3.05O9.62 was measured by employing the method of isomorphic substitution in neutron diffraction and, by taking the role of Al into explicit account, a self-consistent model of the glass structure was developed. The glass network is found to be made from corner sharing PO4 tetrahedra in which there are, on average, 2.32(9) terminal oxygen atoms, OT, at 1.50(1) Å and 1.68(9) bridging oxygen atoms, OB, at 1.60(1) Å. The network modifying R3+ ions bind to an average of 6.7(1) OT and are distributed such that 7.9(7) R–R nearest neighbours reside at 5.62(6) Å. The Al3+ ion also has a network modifying role in which it helps to strengthen the glass through the formation of OT–Al–OT linkages. The connectivity of the R-centred coordination polyhedra in (M2O3)x(P2O5)1−x glasses, where M3+ denotes a network modifying cation (R3+ or Al3+), is quantified in terms of a parameter fs. Methods for reducing the clustering of rare-earth ions in these materials are then discussed, based on a reduction of fs via the replacement of R3+ by Al3+ at fixed total modifier content or via a change of x to increase the number of OT available per network modifying M3+ cation.

Bioactive organic/inorganic hybrids with improved mechanical performance

New sol-gel functionalized poly-ethylene glycol (PEGM)/SiO2-CaO hybrids were prepared with interpenetrating networks of silica and PEGM through the formation of Si-O-Si bonds. Bioactive and mechanical properties were investigated for a series of hybrids containing varying organic/inorganic ratios and PEG molecular weights. In contrast to the unmodified PEG/SiO2-CaO hybrids, which rapidly dissolved and crumbled, the epoxy modified hybrids exhibited good mechanical properties and bioactivity. The compressive strength and Young's modulus were greater for higher molecular weight PEGM hybrids (PEGM600 compared to PEGM300). Compressive strengths of 138 MPa and 81 MPa were found for the 50: 50 and 60: 40 organic/inorganic hybrid samples respectively, which are comparable with cortical bone. Young's modulus values of ∼800 MPa were obtained for the 50 : 50 and 60 : 40 organic/inorganic hybrids. Bioactivity tests were conducted by immersing the hybrids into simulated body fluid and observing the formation of apatite. Apatite formation was observed within 24 hours of immersion. PEGM600 hybrids showed enhanced apatite formation compared to PEGM300 hybrids. Increased apatite formation was observed with increasing organic/inorganic ratio. 70 : 30 and 60 : 40 hybrids exhibited the greatest apatite formation. All PEGM hybrids samples had good cell viability and proliferation. The 60 : 40 PEGM600 hybrids displayed the optimal combination of bioactivity and mechanical strength. The bioactivity of these hybrids, combined with the enhanced mechanical properties, demonstrate that these materials have significant potential for bone regeneration applications.

Functional carbon nanotubes for photonic applications

Carbon nanomaterials are an active frontier of research in current nanotechnology. Single wall Carbon Nanotube (SWNT) is a unique material which has already found several applications in photonics, electronics, sensors and drug delivery. This thesis presents a summary of the author’s research on functionalisation of SWNTs, a study of their optical properties, and potential for an application in laser physics. The first significant result is a breakthrough in controlling the size of SWNT bundles by varying the salt concentrations in N-methyl 2-pyrrolidone (NMP) through a salting out effect. The addition of Sodium iodide leads to self-assembly of CNTs into recognizable bundles. Furthermore, a stable dispersion can be made via addition polyvinylpyrrolidone (PVP) polymer to SWNTs-NMP dispersion, which indicates a promising direction for SWNT bundle engineering in organic solvents. The second set of experiments are concerned with enhancement of photoluminescence (PL), through the formation of novel macromolecular complexes of SWNTs with polymethine dyes with emission from enhanced nanotubes in the range of dye excitation. The effect appears to originate from exciton energy transfer within the solution. Thirdly, SWNT base-saturable absorbers (SA) were developed and applied to mode locking of fibre lasers. SWNT-based SAs were applied in both composite and liquid dispersion forms and achieved stable ultrashort generation at 1000nm, 1550nm, and 1800 nm for Ytterbium, Erbium and Thulium-doped fibre laser respectively. The work presented here demonstrates several innovative approaches for development of rapid functionalised SWNT-based dispersions and composites with potential for application in various photonic devices at low cost.

Metrópole digital: o jovem aprendiz na educação tecnológica

This thesis was elaborated in the scenario of Digital Metropolis Institute (IMD) – a supplementary unit at the Federal University of Rio Grande do Norte in the training of personnel with technical and higher level courses whose technical level training is associated with a process of digital inclusion, with the purpose of attracting young people to this area, with emphasis on Software and Hardware Development. It aims to investigate the cognitive change of young apprentice on technological education and his/her entrance into the labor market, through the formation and the social inclusion proposed by the Instituto Metrópole Digital; understanding the juvenile subjectivity production through the Instituto Metrópole Digital’s education by performance in the labor market; recognizing the Brazilian professional qualification public policies for youth and identifying the role of Tutoring in the learning process during the course of formation of the young apprentice of the technological education proposed by the Instituto Metrópole Digital.The clipping of the object of investigation was the process of cognitive change and constitution of subjectivity of the young apprentice in information technology (IT) in the IMD. It was searched support in theory Freireana as proposal that problematizes the policies and the process of formation and professional qualification, in the perspective of a citizen and liberating consciousness. By qualitative and ethnographic nature, descriptive-explanatory, it counts with the participation of young people, high school students from public and private schools, aged between 15 and 18 years. There are strong aspects: a cognitive change on the young apprentice of technological education onto overdrive high school as the student of the Instituto Metrópole Digital; it happened the social integration for those who remain in the course, both in the neighborhood where they reside and at school where he attended high school, the young man is recognized and becomes reference to other young, favoring him a life projection which when the activities of mentoring is learning motivator, it exerts a positive influence to the young on the continuity of studies, it provides intellectual and institutional affiliation and continuity in the investments to the academic life for a better insertion in the labor market, which refers to the modification of the life project-invest in academic training, in exchange for a technical job in the labor market. There are weak aspects: the absence of professor in the course, in his most important role, which involves awareness of his/her condition in action, in explicit position that the professional practice constitutes as this constitution requires reciprocity of its students and the context in which it operates; fragile formation of mentoring, absence of dialogues in the classroom that favors the formation of subject learning, mainly in guiding action, mediator of the young; There is a lack of methodological proposal to develop real projects on the labor market with problem solving and collaborative learning. It considers that without converting information into knowledge cannot discern clearly enough that there is no direct causal relationship between Professional and technological Education and the level of employability of the young worker certificate. It suggests to the evasion: a greater knowledge of the reality of the student of the Institute Metropolis Digital; better knowledge of youth and their expectations of life project; the Tutoring will be Teacher-tutor; investing in employability conditions effective the young into the labor market.

Characterization of New Carbosilane Liquid Crystalline Monomers and Dimers

‘De Vries-like’ smectic liquid crystals exhibit low layer contraction of approximately 1% on transitions from the SmA to the SmC phase. These materials have received considerable attention as potential solutions for problems affecting liquid crystal displays using surface-stabilized ferroelectric liquid crystals (SSFLC). In SSFLCs, layer contraction of 710% is normally observed during the SmA to SmC phase transition. A study by the Lemieux group has shown that liquid crystals with nanosegregating carbosilane segments exhibit enhanced ‘de Vries-like’ properties through the formation of smectic layers and by lengthening the nanosegregating carbosilane end-groups from monocarbosilane to tricarbosilane. This observed enhancement is assumed to be due to an increase in the cross-section of the free volume in the hydrocarbon sub-layer. To test this hypothesis, it is assumed that dimers with a tricarbosilane linking group have smaller cross-sections on time average. In his thesis, this hypothesis is tested through the characterization of new liquid crystalline monomers (QL39-n) and dimers (QL40-n) with 2-phenylpyrimidine cores and tricarbosilane end-groups and spacers, respectively. The thesis describes the synthesis of two homologous series of liquid crystals and their characterization using a variety of techniques, including polarized optical microscopy, differential scanning calorimetry and X-ray diffraction. The results show that the monomers QL39-n form a tilted SmC phase only, whereas the dimers QL40-n form an orthogonal SmA phase. These results are discussed in the context of our hypothesis.

Études d'ingénierie du ribozyme VS de Neurospora

Les ribozymes sont des ARN catalytiques fréquemment exploités pour le développement d’outils biochimiques et d’agents thérapeutiques. Ils sont particulièrement intéressants pour effectuer l’inactivation de gènes, en permettant la dégradation d’ARNm ou d’ARN viraux associés à des maladies. Les ribozymes les plus utilisés en ce moment pour le développement d’agents thérapeutiques sont les ribozymes hammerhead et hairpin, qui permettent la reconnaissance spécifique d’ARN simple brin par la formation de structures secondaires stables. In vivo, la majorité des ARN adoptent des structures secondaires et tertiaires complexes et les régions simples brins sont parfois difficiles d’accès. Il serait intéressant de pouvoir cibler des ARN repliés et un motif d’ARN intéressant à cibler est la tige-boucle d’ARN qui peut être importante dans le repliement global des ARN et pour accomplir des fonctions biologiques. Le ribozyme VS de Neurospora fait la reconnaissance de son substrat replié en tigeboucle de façon spécifique par une interaction kissing-loop, mais il n’a jamais été exploité pour faire la reconnaissance d’un ARN cible très différent de son substrat naturel. Le but des travaux présentés dans cette thèse est de déterminer si le ribozyme VS possède l’adaptabilité nécessaire pour l’ingénierie de ribozymes qui clivent des ARN cibles différents du substrat naturel. Dans le cadre de cette thèse, le ribozyme VS a été modifié pour l’adapter à différents substrats et des études de cinétiques ont été réalisées pour évaluer l’impact de ces modifications sur l’activité de clivage du ribozyme. Dans un premier temps, le ribozyme a été modifié pour faire la reconnaissance et le clivage de substrats possédant différentes longueurs de tiges Ib. Le ribozyme a été adapté avec succès à ces substrats de différentes longueurs de tige Ib, avec une activité qui est similaire à celle du ribozyme avec un substrat sans modification. Dans un deuxième temps, c’est l’interaction kissing-loop I/V du ribozyme qui a été substituée de façon rationnelle, dans le but de savoir si un ribozyme VS mutant peut reconnaitre et cliver un substrat ayant une boucle différente de celle de son substrat naturel. L’interaction kissing-loop I/V a été substituée pour les interactions kissing-loop TAR/TAR* de l’ARN du VIH-1 et L22/L88 de l’ARN 23S de Deinococcus radiodurans. La réaction de iii clivage des ribozymes comportant ces nouvelles interactions kissing-loop est toujours observée, mais avec une activité diminuée. Finalement, la sélection in vitro (SELEX) de ribozymes a été effectuée pour permettre un clivage plus efficace d’un substrat mutant avec une nouvelle boucle. Le SELEX a permis la sélection d’un ribozyme qui clive un substrat avec une boucle terminale mutée pour celle de l’ARN TAR du VIH-1 et cela avec une activité de clivage très efficace. L’ensemble de ces études démontre que le ribozyme VS peut être modifié de diverses façons pour la reconnaissance spécifique de différents substrats, tout en conservant une bonne activité de clivage. Ces résultats montrent le grand potentiel d’ingénierie du ribozyme VS et sont prometteurs pour la poursuite d’études d’ingénierie du ribozyme VS, en vue du clivage d’ARN cibles repliés en tige-boucle complètement différents du substrat naturel du ribozyme VS.

A estrutura de poder tradicional no stricto sensu: o caso do mestrado profissional em Administração Pública em Rede Nacional - PROFIAP

This study approaches bureaucratic organizational structures with the aim to understand the adherence procedure to virtual technologies in the stricto sensu educational administrative process. Thus, the author navigates through the formation of these organizations in Brazil with the intent to demonstrate the bureaucratic organizational culture and the consequent form of domination of those who detain power. In this epistemological construction, the author explores the culture s bureaucratic environment and the organizational power. In the analyses, it was observed the technological phenomenon in the ODL s administrative environment, which can explain the adherence procedure to structures and technological instruments for stricto sensu courses that, hypothetically, dilutes the traditional inherited organizational axiom. Therefore, it was utilized as object of study the Professional Master s degree in National Scale Public Administration PROFIAP, hence analyzing the documental content and the legislation related to institutionalization as well as the positioning of professors/coordinators and of the director of CAPES/MEC. Considering this axioms, it was concluded that the bureaucratic structures can admit ODL in the stricto sensu s environment. However, this can only be done as long as the adherence does not imply in a dilution of the traditional forms of power and institutional bureaucratic inherited dominance, as well as the alleged hegemony of the governmental structure in the educational administration adopted in person by the stricto sensu courses in Brazil

A estrutura de poder tradicional no stricto sensu: o caso do mestrado profissional em Administração Pública em Rede Nacional - PROFIAP

This study approaches bureaucratic organizational structures with the aim to understand the adherence procedure to virtual technologies in the stricto sensu educational administrative process. Thus, the author navigates through the formation of these organizations in Brazil with the intent to demonstrate the bureaucratic organizational culture and the consequent form of domination of those who detain power. In this epistemological construction, the author explores the culture s bureaucratic environment and the organizational power. In the analyses, it was observed the technological phenomenon in the ODL s administrative environment, which can explain the adherence procedure to structures and technological instruments for stricto sensu courses that, hypothetically, dilutes the traditional inherited organizational axiom. Therefore, it was utilized as object of study the Professional Master s degree in National Scale Public Administration PROFIAP, hence analyzing the documental content and the legislation related to institutionalization as well as the positioning of professors/coordinators and of the director of CAPES/MEC. Considering this axioms, it was concluded that the bureaucratic structures can admit ODL in the stricto sensu s environment. However, this can only be done as long as the adherence does not imply in a dilution of the traditional forms of power and institutional bureaucratic inherited dominance, as well as the alleged hegemony of the governmental structure in the educational administration adopted in person by the stricto sensu courses in Brazil