This work aimed to study the interaction of the drug pyrimethamine (PIR) and sulfadiazine (SDZ) with the biopolymer chitosan chemically modified with glutaraldehyde, after immobilization of copper (Quit-Cu). The release of these drugs in buffer pH 7.0 was also studied by heat-conduction calorimetry at 298 K. The matrices of chitosan modified with glutaraldehyde (QUIT-GLT) were used for immobilization of ions Cu (II), obtaining the material Quit-Cu. This material has 2.347 x 10-5 mol.g-1 of copper. It was obtained values of the interaction energies (Qint) and the amount of PIR and SDZ interacting with Quit-Cu matrix (Nint) at 298 K. Langmuir isotherm described the adsorption equilibrium behaviour in the entire concentration range studied. Negative values found for Gibbs free energy of the PIR and SDZ, ΔG = -16.7 ± 0.4 KJmol-1 and ΔG = - 15.7 ± 0.6 KJmol-1 respectively, confirm the feasibillity of procedures and their spontaneous nature. The release of the drugs from Quit-Cu was also estimated by calorimetry. The data obtained could be described by the model of Power Low. The n values obtained from the fits indicate an anomalous release of PIR and SDZ from Quit-Cu. PIR had a release rate higher than SDZ and a time of release lower than SDZ ( k = 11,31x10-2, 36 min to PIR and K=8,84x10-2, 60 min to SDZ). The results of PIR release were about 40 times greater than the inhibitory concentration dose of the PIR to toxoplasmosis DHFR (0.25 μM), suggesting that the material could be a good carrier to this drug. / Este trabalho teve como objetivo o estudo da interação dos fármacos pirimetamina (PIR) e sulfadiazina (SDZ) com o biopolímero quitosana modificado quimicamente com gluteraldeído e tendo cobre imobilizado (Quit-Cu), bem como o estudo de liberação desses fármacos em tampão pH 7,0 através da calorimetria isotérmica. As matrizes de quitosana modificadas com gluteraldeído (Qui-GLT) foram utilizadas para imobilização de íons Cu(II), obtendo o material Quit-Cu contendo 2,347 x 10-5 mols.g-1 de cobre. Utilizando a calorimetria isotérmica obtiveram-se valores das energias de interação (Qint) e da quantidade de fármaco que interage (Nint) com a matriz Quit-Cu, a 298 K. Os dados obtidos ajustaram-se ao modelo de Langmuir. Valores negativos encontrados para a energia livre de Gibbs da PIR e da SDZ, ΔG = −16,7 ± 0,4 KJmol−1 e ΔG = − 15,7 ± 0,6 KJmol−1 respectivamente, confirmam a viabilidade dos processos e a natureza espontânea dos mesmos. O processo de liberação dos fármacos da matriz Quit-Cu também foi avaliado por calorimetria e os dados obtidos ajustados ao modelo da lei das potências. Os valores de n obtidos dos ajustes indicam que tanto a PIR como a SDZ tem mecanismo de liberação anômalo. A PIR teve uma taxa de liberação maior da matriz Quit-Cu com um tempo menor (k = 11,31x10-2 em 36min) em relação à SDZ (k=8,84x10-2 em 60min). Os resultados de liberação da PIR foram cerca de 40 vezes maior que a concentração da dose inibitória da PIR para DHFR da toxoplasmose (0,25μM), existindo, portanto possibilidades de ser um bom carreador deste fármaco.

Os processos envolvidos em condução eletrônica de polímeros condutores são muito complicados devido à intricada morfologia estrutural de tais materiais. Realizamos medidas de condutividade alternada em filmes de polianilina em uma grande faixa de freqüência, variando o grau de dopagem dos filmes e temperatura. Ao mesmo tempo, desenvolvemos um modelo estatístico de rede de resistores para descrever a estrutura polimérica e para simular as componentes real e imaginária de sua resistividade alternada. Leva-se em conta a polidispersividade do material, assim como os mecanismos de transportes de carga intracadeia e intercadeia. Pela aplicação de uma técnica de matriz de transferência, o modelo reproduz medidas de resistividade alternada realizadas em filmes de polianilina em diferentes graus de dopagem e em diferentes temperaturas. Nossos resultados indicam que os mecanismos intercadeias governam o comportamento da resistividade em regiões de baixa freqüência enquanto que, para altas freqüências, mecanismos intracadeia são dominantes. Essa simulação foi desenvolvida para redes bi e tridimensional. Aplicamos, também, esse método para estudar sistemas isoenergéticos de estrutura desordenada (poliacetileno estirado), sistemas isoenergéticos de estrutura desordenada (poliacetileno não-estirado) e sistemas não-isoenergéticos de estrutura desordenada (polianilina). Finalmente, uma comparação entre esses três materiais, permitiu-se discutir, em detalhes, a distribuição de barreiras de energia potencial e a diferença dos níveis de energia que controlam o mecanismo de salto dos portadores eletrônicos. / The processes involved in electronic conduction of conducting polymers are very complicated due to the intricate morphological structure of such materials. We carried out alternating conductivity measurements in polyaniline films in a large frequency range, varying the doping degree of the films and temperature. At the same time, we developed a statistical model of resistor networks to describe a polymer structure and to simulate the real and imaginary components of their ac resistivities. This model takes into account the polydispersiveness of the material as well as intrachain and interchain charge transport mechanisms. By the application of a transfer-matrix technique, it reproduces ac resistivity measurements carried out with polyaniline films in different doping degrees and temperatures. Our results indicate the interchain mechanisms govern the resistivity behavior in the low frequency region while, for higher frequencies, intrachain mechanisms are dominated. These simulations were developed in bi and tridimensional lattice. We also applied this method to study ordered structure in isoenergetic systems (stretched polyacetylene), disordered structure in isoenergetic systems (normal polyacetylene), and disordered structure in non-isoenergetic systems (polyaniline). Finally, a comparison between these three materials, allowed us to discuss in detail the energy barriers distribution and the difference in energy levels, which control the hopping mechanisms of the electronic carriers.

Objetivos: Caracterizar o perfil audiológico dos indivíduos com malformações congênitas de orelha externa e/ou orelha média, na Divisão de Saúde Auditiva (DSA), do Hospital de Reabilitação de Anomalias Craniofaciais (HRAC), da Universidade de São Paulo (USP), campus Bauru e avaliar o benefício e a satisfação dos usuários de aparelhos de amplificação sonora individuais por condução óssea (AASI VO) retroauriculares. Modelo: Análise de prontuários, avaliação do benefício pelo teste de reconhecimento de sentenças com ruído competitivo e pelas medidas do ganho funcional e avaliação da satisfação pelo questionário internacional QI - AASI. Local: DSA, HRAC/USP, Bauru. Participantes: Foram analisados os prontuários de 170 indivíduos e, destes, selecionados 13, com malformações congênitas bilaterais de orelha externa e/ou orelha média, deficiência auditiva condutiva ou mista moderada ou severa e usuários de AASI VO retroauricular. Resultados: O perfil audiológico (n = 170) caracterizou-se pelo predomínio das malformações bilaterais (53%), das malformações no sexo masculino (61%), da deficiência auditiva condutiva moderada ou severa (80%) e da adaptação de AASI VO (56%). A orelha direita foi mais afetada (32%), quando consideradas apenas as malformações unilaterais. Na amostra selecionada (n = 13), o benefício foi comprovado pelo melhor desempenho obtido na avaliação proposta, na condição com AASI, quando comparada à condição sem AASI. A satisfação foi confirmada pelos escores elevados obtidos no QI-AASI. Conclusões: O uso do AASI VO retroauricular trouxe benefícios para o reconhecimento da fala no ruído e para a percepção do sinal acústico, além de satisfação aos indivíduos com malformações congênitas de orelha, portanto, esses dispositivos devem ser considerados como uma opção no tratamento dessa população. / Objectives: To characterize the audiological profile of the individuals with congenital malformations of the external and/or middle ear, in the Divisão de Saúde Auditiva (DSA) of the Hospital de Reabilitação de Anomalias Craniofaciais (HRAC) of Universidade de São Paulo (USP), in Bauru and to evaluate the benefits and satisfaction of patients fitted with bone conduction hearing aid (BCHA). Model: Analysis of files, evaluation of benefits by means of test of recognition of sentences with competitive noise and by the measures of the functional gain, and evaluation of satisfaction by International Outcome Inventory for Hearing Aids (IOI/HA). Participants: 170 patients? files were analyzed, from which 13 were selected with bilateral congenital malformations of the external and/or middle ear, moderate or severe conductive or mixed hearing loss, and patients fitted with BCHA. Results: The audiological profile (n=170) was characterized by the prevalence of bilateral malformations (53%), of malformations in males (61%), of the moderate or severe conductive hearing loss (80%) and of the fitting of BCHA (56%). The right ear was more affected (32%) when considered the unilateral malformations only. In the selected sample (n=13), the benefit was demonstrated by the best performance obtained in the proposed evaluation, in the condition with hearing aid, when compared to the condition without hearing aid. The satisfaction was confirmed by the high scores obtained in the IOI - HA. Conclusions: Fitting BCHA denoted improvement at speech perception in noise and sound detection. Individuals with congenital malformations of the ear were satisfied with this device, so that must be considered as an option to the treatment of this population.

Värmelära upplevs ofta som ett abstrakt område i gymnasiefysiken och elever tenderar att tolka känseln som en termometer. Värmelära kan därmed bli en tuff utmaning för många elever. Genom att introducera värmekameror i undervisningen ges elever möjligheten att se annars osynliga värmefenomen. Eftersom värmekameran inte ännu blivit etablerad i undervisningen finns det ett intresse att studera elevernas interaktion med värmekameran. Syftet med studien är att undersöka hur interaktionen ser ut och hur värmekameran kan hjälpa elever i begreppsbildandet av värmerelaterade fenomen. Denna studie har gjorts på ca 140 elever som går sitt första år på det naturvetenskapliga programmet på en gymnasieskola i Mellansverige. Eleverna fick utföra en laboration designad enligt prediction-observation-explanation-metoden. Laborationen innehöll tre stationer där de centrala begreppen var värmeledning, stöt och friktion. Eleverna använde en värmekamera som hjälpmedel för att förklara de olika fenomenen. Elevernas interaktioner vid laborationen dokumenterades med video- och ljudupptagning i syfte att ge grund för en kvalitativ analys. Analysen av materialet kom att handla om tre delar: hur eleverna resonerar kring värmeledning, respektive friktion och stöt, och hur värmekameran kan stimulera det kreativa tänkandet hos eleverna. Det visade sig att många elevgrupper kom långt i det makroskopiska och en bra bit i det mikroskopiska resonemanget kring värmeledning genom att tillämpa en modell av fria elektroner i metall de hade lärt sig från kemin. De flesta grupperna hade svårt att resonera kring energiomvandlingar vid stöt både på en makroskopisk och mikroskopisk nivå. Det kreativa undersökandet resulterade i en röra. Värmekameran lockar elevernas nyfikenhet, ger ”disciplinary affordance” och stimulerar dem till ”instant inquiry”. När eleverna gick utanför instruktionerna och bedrev egna undersökningar resulterade det i en röra då de prioriterade bort sina nykonstruerade hypoteser. / Thermodynamics is often perceived as an abstract field in secondary school physics. Thermodynamics can thus be a tough challenge for many students. By including thermal imaging cameras in teaching, students are given the opportunity to see otherwise invisible thermal phenomena. Since the infrared camera has not yet been established in teaching, there is an interest in studying the interaction between students and the thermal imaging camera. The purpose of this study is to investigate the interaction between student and the infrared camera and to see how the infrared camera can help students in the conceptual formation of heat-related phenomena. The study included about 140 students attending their first year on the science program at an upper secondary school in central Sweden. The students had to perform laboratory experiments designed according to the prediction-observation-explanation method. The laboratory experiments consisted of three stations where the key concepts were heat conduction, collision and friction. Students took help of an infrared camera to explain the various phenomena. The students' interactions at the lab were documented with video and audio recording in order to set the basis of a qualitative analysis. The analysis of the material consisted of three parts: how students reason concerning heat conduction, their reasoning concerning dissipative processes as friction and collision, and how the infrared camera can stimulate the students' creative thinking. Many student groups were successful in the macroscopic and quite successful in the microscopic reasoning regarding heat conduction by applying a model of free electrons in the metal which they had learned in chemistry class. Other studies have shown that students find it hard explaining heat conduction and that they tend to interpret the physical touch as a thermometer. The group that examined friction and collision found it difficult explaining the transformation from kinetic energy into thermal energy in collision at both the macroscopic and microscopic level. The creative investigation resulted in a mess. The infrared camera attracts students' curiosity, gives ”disciplinary affordance” and stimulates them to ”instant inquiry”. When the students went beyond their instructions and conducted own investigations it resulted in a mess when they prioritized away the recently created hypotheses.

Les modèles linéaires non entiers ont prouvé leur efficacité dans la modélisation de la diffusion thermique pour de faibles variations de température. Cependant, pour de grandes variations de température, les paramètres thermiques dépendent de la température. Par conséquent, la diffusion thermique est régie par un modèle non linéaire non entier. Dans cette thèse, une classe de modèles non linéaires non entiers, basée sur les séries de Volterra non entières, est proposée. Les paramètres non linéaires, tels que les s^n-pôles et l’ordre commensurable, sont estimés au même titre que les coefficients linéaires. Ensuite, le comportement thermique d’un échantillon de fer ARMCO est modélisé pour de grandes variations de température. / Linear fractional differentiation models have proven their efficacy in modeling thermaldiffusive phenomena for small temperature variations. However, for large temperature variations,the thermal parameters are no longer constant but vary along with the temperatureitself. Consequently, the thermal system could be modeled by non linear fractional differentialmodels. Volterra series are first extended to fractional derivatives. Volterra seriesare then used for modeling a non linear thermal system, constituted of an ARMCO iron sample,for large temperature variations.

The work and results presented in this dissertation concern two complimentary studies that are rooted in surface acoustic waves and transducer study. Surface acoustic wave devices are utilized in a variety of fields that span biomedical applications to radio wave transmitters and receivers. Of interest in this dissertation is the study of surface acoustic wave interaction with polydimethylsiloxane. This material, commonly known as PDMS, is widely used in the microfluidic field applications in order to create channels for fluid flow on the surface of a piezoelectric substrate. The size, and type of PDMS that is created and ultimately etched on the surface of the substrate, plays a significant role in its operation, chiefly in the insertion loss levels experienced. Here, through finite element analysis, via ANSYS® 15 Finite Element Modeling software, the insertion loss levels of varying PDMS sidewall channel dimensions, from two to eight millimeters is investigated. The simulation is modeled after previously published experimental data, and the results demonstrate a clear increase in insertion loss levels with an increase in channel sidewall dimensions. Analysis of the results further show that due to the viscoelastic nature of PDMS, there is a non -linear increase of insertion loss as the sidewall dimensions thicken. There is a calculated variation of 8.31 decibels between the insertion loss created in a microfluidic device with a PDMS channel sidewall thickness of eight millimeters verse a thickness of two millimeters. Finally, examination of the results show that insertion loss levels in a device are optimized when the PDMS sidewall channels are between two and four millimeters. The second portion of this dissertation concerns the calibration of an ultrasonic transducer. This work is inspired by the need to properly quantify the signal generated by an ultrasonic transducer, placed under a static loading condition, that will be used in measuring ultrasonic bone conducted frequency perception of human subjects. Ultrasonic perception, classified as perception beyond the typical hearing limit of approximately 20 kHz, is a subject of great interest in audiology. Among other reasons, ultrasonic signal perception in humans is of interest because the mechanism by which either the brain or the ear interprets these signals is not entirely understood. Previous studies have utilized ultrasonic transducers in order to study this ultrasonic perception; however, the calibration methods taken, were either incomplete or did not properly account for the operation conditions of the transducers. A novel transducer calibration method is detailed in this dissertation that resolves this issue and provides a reliable means by which the signal that is being created can be compared to the perception of human subjects.

L'agrégation des canaux sodium (Nav) aux nœuds de Ranvier est une étape importante pour la propagation électrique saltatoire rapide le long des axones myélinisés. L'assemblage des nœuds dépend d'interactions neurones-cellules gliales myélinisantes, les oligodendrocytes dans le système nerveux central (SNC) et les cellules de Schwann dans le système nerveux périphérique (SNP). Bien décrits dans le SNP, les mécanismes cellulaires et moléculaires restent à caractériser dans le SNC. Lors de ma thèse, je me suis focalisé sur les étapes précoces d'assemblage des nœuds dans le SNC. Ce travail montre que des agrégats de protéines nodales (ou pré-nœuds) sont formés le long des axones de neurones GABAergiques avant la myélinisation dans des cultures neurones-glies d'hippocampe et également au cours du développement chez les rongeurs. La formation de pré-nœuds dépend de protéines sécrétées par les oligodendrocytes et de la protéine axonale d'échafaudage, ankyrineG. En outre, la transition des isoformes de Nav le long des axones est régulée par la présence des cellules gliales. Enfin, les pré-nœuds permettent d'accélérer la vitesse de conduction de l'influx nerveux par un facteur 1,5, indépendamment de la myélinisation et du calibre axonal. Globalement, ces résultats renforcent notre connaissance des mécanismes d'assemblage des nœuds de Ranvier dans le SNC et suggèrent une fonction développementale de l'agrégation nodale avant le début de la myélinisation. Si la vitesse de conduction a été décrite comme liée aux propriétés isolantes de la gaine de myéline, les résultats de cette thèse apportent un concept novateur de régulation de la conduction axonale en l'absence de myéline. / The clustering of sodium channels (Nav) at the nodes of Ranvier is an important step in permitting rapid saltatory conduction along myelinated axons. Nodal assembly is neuron-glia dependent, mediated by myelinating oligodendrocytes of the central nervous system (CNS) and Schwann cells in the peripheral nervous system (PNS). While the mechanisms of nodal assembly are currently best characterized in the PNS, cellular and molecular mechanisms underlying their assembly in the CNS are only partially understood. In the core of my PhD dissertation, I focused on the early developmental steps of nodal protein clustering in the CNS and show that clusters of nodal proteins, called prenodes, are detected before myelination along GABAergic axons in hippocampal neuron-glia cultures and also in the developing rodent hippocampus. Prenodal clustering requires extrinsic oligodendroglial secreted proteinaceous factors, and also the intrinsic axonal cytoskeletal scaffolding protein ankyrinG. Furthermore, the transition of sodium channels isoforms is tightly regulated along GABAergic axons during development, but this transition is lost in the absence of the physical presence of glial cells. Lastly, prenodes increase axonal conduction by a factor of 1.5x, independently of myelination and axonal caliber. Taken together, these results further our understanding of CNS nodes of Ranvier assembly mechanisms and the developmental function of nodal clustering prior to myelin ensheathment. While conduction velocity along axons has long been thought to mostly rely on the insulating properties of myelin, these results may shed light on a new concept of axonal conduction in the absence of myelination.

When joining steel to aluminium there is a reaction between iron and aluminium which results in the formation of brittle intermetallic compounds (IMC). These compounds are usually the reason for the poor mechanical strength of the dissimilar metallic joints. The research on dissimilar metal joining is vast but is mainly focused on the automotive industry and therefore, the material in use is very thin, usually less than 1 mm. For materials with thicker sections the present solution is a transition joint made by explosion welding which permits joining of steel to aluminium and avoids the formation of IMCs. However, this solution brings additional costs and extra processing time to join the materials. The main goals of this project are to understand the mechanism of formation of the IMCs, control the formation of the IMCs, and understand their effects on the mechanical properties of the dissimilar Fe-Al joints during laser welding. Laser welding permits accurate and precise control of the welding thermal cycle and thereby the underpinning mechanism of IMC formation can be easily understood along with the factors which control the strength of the joints. The further goal of this project is to find an appropriate interlayer to restrict the Fe-Al reaction. The first stage of the work was focused on the formation and growth of the Fe-Al IMCs during laser welding. The understanding of how the processing conditions affect the IMC growth provides an opportunity to act and avoid its formation and thereby, to optimize the strength of the dissimilar metal joints. The results showed that even with a negligible amount of energy it was not possible to prevent the IMC formation which was composed of both Fe2Al5 and FeAl3 phases. The IMC growth increases exponentially with the applied specific point energy. However, for higher power densities the growth is more accentuated. The strength of the Fe-Al lap-joints was found to be not only dependent on the IMC layer thickness but also on the bonding area. In order to obtain sound joints it is necessary to achieve a balance between these two factors. The thermal model developed for the laser welding process in this joint configuration showed that for the same level of energy it is more efficient to use higher power densities than longer interaction iv times. Even though a thicker IMC layer is formed under this condition due to higher temperature there is also more melting of aluminium which creates a larger bonding area between the steel and the aluminium. The joint strength is thus improved ... [cont.].

No description available.

Actuellement, l’immense majorité des aimants supraconducteurs, notamment d’IRM, sont refroidis par un bain d’hélium liquide à pression atmosphérique. Néanmoins, ce type de refroidissement est onéreux et impose des contraintes sécuritaires importantes pour les grands volumes. Pour ces raisons, le refroidissement des aimants supraconducteurs est souhaitable sans l’hélium liquide. L’utilisation de cryogénérateur permet de refroidir par conduction solide jusqu’à 4 K et ainsi supprimer l’hélium liquide. Néanmoins, les faibles puissances disponibles combiner aux difficultés de mise en œuvre de ce type de refroidissement rendent difficile l’utilisation dans ces conditions du NbTi. En revanche à 10 K, la puissance des cryogénérateurs augmente d’un facteur 10, mais l’utilisation d’un supraconducteur à haute température critique est alors nécessaire. Notre choix s’est porté sur les conducteurs MgB2 R & W qui ont l’avantage d’être relativement économique à mettre en œuvre, mais qui ont, en revanche, le défaut d’être sensible à la déformation. Il est donc nécessaire d’être soigneux lors de leurs bobinages pour ne pas dégrader leurs performances supraconductrices. Dans le cadre de cette thèse, nous avons développé un insert froid refroidis par conduction solide permettant de mesurer le courant critique des conducteurs MgB2 R & W ainsi que des maquettes. Pour ce faire, un nouveau type de contact thermique à base de nitrure d’aluminium a été développé. En complément, nous avons conçu deux maquettes d’aimant MgB2 R & W : un solénoïde et une double galette. Cette dernière a été fabriquée (grâce à une nouvelle méthode de bobinage brevetée) et testée avec succès. / Currently, the majority of superconducting magnets, including MRI, are cooled by a bath of liquid helium at atmospheric pressure. Nevertheless, this type of cooling is expensive and imposes significant security constraints for large volumes. For these reasons, the cooling of superconducting magnets is desirable without liquid helium. Cryocooler provides dry cooling to 4 K without any liquid helium. However, the power available is low and dry cooling is difficult. In these conditions, it is complicate to use NbTi with dry cooling. But if we increase the operating temperature to 10 K, the power of cryocooler increases by a factor of ten. Nevertheless in this case, it is necessary to use of a high critical temperature superconductor. We choose to use MgB2 R & W conductors because it is relatively low cost but it has the handicap to be sensible at mechanical stress. It is therefore necessary to be careful during their winding to not degrade their superconducting performance. As part of this thesis, we have developed a dry test facility to measure the critical current of MgB2 R & W conductors as well as mock-ups. To do this, a new type of thermal contact based on aluminum nitride has been developed. In addition to this development, we designed two MgB2 R & W magnet mock-ups: a solenoid and a double pancake. The double pancake was manufactured (with a new patented winding method) and it has been successfully tested.