PhD thesis - Faculty of Science / The main aim of this thesis has been to study the way in which Fe(III) and Co(II) incorporation into Si-MCM-41 synthesis gels affects the properties of the unmodified material. Another aim was to investigate the influence of these hetero-atoms on the dispersion and particle size distribution as well as the catalytic activity of supported Au nanoparticles in the CO oxidation reaction. Si-MCM-41 has been successfully synthesized in this work using mixtures containing CTAB as a structure-directing agent (SDA) and water-glass as a SiO2 source. Replacement of water-glass with pre-calcined Si-MCM-41 for SiO2 source in the secondary synthesis step has produced Si-MCM-41 with improved structural properties (XRD, HRTEM and Raman spectroscopy), including restructured and more crystalline pore walls (Raman spectroscopy). The conventional shortcomings of Si-MCM-41 as a support for catalyticallyactive (transition) metal components such as low hydrothermal stability, low PZC, lack of cation exchange capacity and no reducibility have been partially addressed by modification with Fe(III) and Co(II). The premodification was achieved both during framework synthesis and after synthesis by the incipient wetness impregnation (IWI) method. As opposed to the one-pot synthesis of metal-containing derivatives, the IWI method gave materials with high metal loadings and maximal retention of the properties of pristine Si-MCM-41. On the other hand, metal incorporation during synthesis to a loading of ~8.8 wt% using aqueous solutions of metal precursors showed some collapse of the mesostructure. Consequently methods were sought to incorporate this amount of metal (and up to double, i.e., 16 wt%) with maximal retention of the MCM-41 characteristics. These methods included (i) using Si-MCM-41 as a SiO2 source, (ii) dissolving the metal precursors in an acid solution before inclusion into the synthesis gel, and (iii) using freshly precipitated alkali slurries of the metal precursors. The first method produced a highly ordered 16wt% Fe-MCM-41 material with excellent reducibility (TPR showed three well-resolved peaks) and pore-wall structure (Raman spectroscopy). Like the aqueous route, the acid-mediated metal incorporation route did not produce ordered materials at metal contents of ~16 wt%. The base precipitate route produced highly ordered composite materials up to 16 wt% metal content, with characteristics similar to those of Si-MCM-41 (XRD, BET and HRTEM), although some metal phases were observed as a separate phase on the SiO2 surface. Thus, metal-containing MCM-41 materials could be obtained with conservation of MCM-41 mesoporosity. Raman spectroscopic studies have shown that the effect of transition metal incorporation in MCM-41-type materials is to strengthen the pore walls (shift of Si-O-Si peaks to higher frequencies), while TPR studies revealed that the essentially neutral framework of Si-MCM-41 could be rendered reducible by transition metal incorporation. Gold-containing mesoporous nanocomposites were prepared by both direct synthesis and post-synthetically. Catalysts prepared by direct hydrothermal synthesis were always accompanied by formation of large Au particles because of the need to calcine the materials at 500 oC in order to remove the occluded surfactant template. The presence of transition metal components in Me-MCM-41 (Me = Fe and Co) has been found to play a significant role in the particle size distribution and also the dispersion of Au nanoparticles when these materials were used as supports. In general, a base metal-containing support was found to produce smaller Au nanoparticles than the corresponding siliceous support. It has been proposed that the transition metal components serve as anchoring or nucleation sites for the Au nanoparticles, which are likely to sinter during calcination. The anchoring sites thus retard the surface mobility of Au at calcination temperatures above their TTammann. The use of the Au/Me-MCM-41 materials as catalysts in the CO oxidation reaction has led to the following observations: (i) catalyst on metal-containing supports showed better activity than those on Si-MCM-41, probably due to the induced reducibility in metal-MCM-41, (ii) catalysts prepared by direct synthesis showed inferior activity owing to large Au particles, (iii) increasing Au content improves the catalytic performance, (iv) increasing the Fe content of the support at constant Au improves the catalytic performance, and (v) changing the base metal component of the support from Fe to Co led to a significant improvement in catalytic activity. The similarity of the apparent activation energies (Ea) for the 5 wt% Au-containing 5 wt% Fe- and 5 wt% Co-MCM-41 suggested that the difference in catalytic activity is associated with the number of active sites possessed by each catalyst system. The observed order of catalytic activity of these 5 wt% Au-containing systems in terms of the support type is: Co-MCM-41 > Fe-MCM-41 > Si-MCM-41. This was further supported by the average Au particle size, which, in terms of the support, followed the order Co-MCM-41 < Fe-MCM-41 < Si-MCM-41. Thus, metal-support interactions between Au and MCM-41 have been enhanced by introducing Fe(III) and Co(II), which also induced framework charge, ion exchange capacity (IEC) and reducibility in the neutral siliceous support.

Este trabalho tem por objetivo a composição e caracterização de um dosímetro à base de DL-Alanina e Ferro-ll em forma de gel para aplicações em dosimetría para campos de doses da radiação gama do Co-60 experimentadas em procedimentos de radioterapia. O aminoácido DL-Alanina é dissolvido em solução ácida contendo o Fe-ll e adicionado o gel. Procedeu-se a uma série de ensaios variando reagente a reagente e realizando procedimentos para avaliar o comportamento em função do tempo do gel dosimétrico obtido. Os espectros de absorção antes e após a irradiação apresentam máximos em 457 nm e 588 nm, respectivamente. Esses dois picos correspondem aos comprimentos de onda de absorção das espécies Fe-ll e Fe-lll, respectivamente; estando ambas as espécies em equilíbrio. Com a irradiação, ocorre a formação de radicais que oxidam o Fe-ll em Fe-lll, alterando com isso o balanço entre as duas espécies - daí o aumento da concentração de Fe-lll - fazendo com que mude a tonalidade do gel, sendo, portanto, possível de ser determinada a dose absorvida. Nas análises dos espectros e respectivas curvas dose-resposta observou-se que o gel dosimétrico apresenta linearidade no intervalo de doses entre 0,5 e 40 Gy. A partir dos resultados obtidos de linearidade, estabilidade e menor dose detectável - 0,3 Gy - conclui-se que o presente Gel Dosimétrico à base de DL-Alanina e Fe-ll apresenta excelente potencial para a finalidade que é proposto, qual seja a determinação do campo de doses em radioterapia e futura aplicação como padrão na determinação desses campos, em 3D, utilizando-se a técnica de Imagem por Ressonância Magnética - IRM. / The aim of this work is to develop a DL-Alanine, Fe-ll based gel dosimeter to be applied in the dosimetry of the Co-60 gamma-radiation fields in the dose range of radiation therapy procedures. The aminoacid DL-Alanine is dissolved in an acid solution containing the Fe-ll and added to the gel. A series of essays was performed with different chemicals and different procedures were made to evaluate the behavior of the obtained dosimetric gel as function of the time. The absorption spectra, before and after the irradiation, present maximum in 457 nm and 588 nm, respectively. These two peaks correspond to absorption wavelengths of the chemical species Fe-ll and Fe-lll, respectively, both species being in equilibrium. With the irradiation, the formation of the radicals that oxide the Fe-ll into Fe-lll occurs, altering the chemical balance of both species - hence the increase of the Fe-lll - and causing the gel to change its tonality, in such a way that it is possible to determine the absorved dose. In the analysis of the spectra and respective dose-response curves it was observed that the dosimetric gel shows linearity in dose range of 0.5 to 40 Gy. From the obtained linearity results, stability and lower detectable dose - 0,3 Gy - it is possible to conclude that the present DL-Alanine, Fe-ll based dosimetric gel presents an excellent potential to the application to which it is proposed, namely, the determination of the dose fields in radiation therapy and its future application as a standard in the determination of these fields, in 3D, using the Magnetic Resonance Imaging.

Ce travail porte sur la formulation de nouveaux gels permettant de détecter visuellement par changement de couleur une contamination radioactive surfacique α ou γ. Un film mince de gel (< 1mm) est pulvérisé sur la paroi et est facilement récupéré après séchage. Des gels de gomme de xanthane transparents, viscoélastique et contenant des colorants radiosensibles ont été formulés. Des irradiations γ de colorants organiques et de complexe coloré Fer (II)- Xylénol orange dans des gels de silice et de xanthane ont été effectuées. Les mécanismes et les vitesses d'oxydation par radiolyse ont été précisés en fonction de la dose absorbée. Notamment, le xylénol orange et l'erioglaucine sont les deux colorants les plus radiosensibles. Le gel Fer (II)- Xylénol orange- Xanthane, noté FXX, a permis de révéler une tache contamination de 137Césium (émetteur γ d'activité0 = 20 KBq) au bout de 48 heures par oxydation du complexe coloré xylénol orange- Fe (II). Par ailleurs, ce même gel a permis de détecter une contamination surfacique de 239plutonium (émetteur α d'activité0 = 3720 Bq) au bout d'une journée.Pour la récupération après séchage, l'ajout de la silice dans le gel de xanthane a permis de mettre en évidence un résidu final qui délamine à faible concentration en silice ou qui fracture à une concentration élevée en silice. Enfin, l'ajout d'acide (> 2 M) a conduit à un séchage partiel du gel afin d'obtenir un film humide récupérable. / This work deals with the formulation of new gels to detect visually radioactive surface contamination α or γ by color changing. A thin gel film (<1mm) is sprayed onto the wall and is easily recovered after drying, Transparent, viscoelastic polymer xanthan gels and with radiosensitive dyes were selected.γ irradiation of organic dyes and colored complex Fe (II)- xylenol orange in silica and Xanthan gel were performed. Mechanisms and kinetics of oxidation by radiolysis were identified as a function of absorbed dose. The gel iron (II)-xylenol orange- Xanthane, noted FXX, revealed a spot of contamination by 137cesium (γ emitter of Activity0 = 20 KBq) after 48 hours by oxidation of the complex xylenol orange- ion (II). Moreover, the same gel detected a surface contamination by 239plutonium (transmitter Activity0 = 3720 Bq) after one day.For recovering after drying, the addition of silica to xanthan gel helped highlight a final dry residue delaminates at low concentration of silica or fracture at high silica concentration. However, the addition of acid (> 2 M) led to a partial drying of the gel giving a wet film recoverable.

Este trabalho tem por objetivo a composição e caracterização de um dosímetro à base de DL-Alanina e Ferro-ll em forma de gel para aplicações em dosimetría para campos de doses da radiação gama do Co-60 experimentadas em procedimentos de radioterapia. O aminoácido DL-Alanina é dissolvido em solução ácida contendo o Fe-ll e adicionado o gel. Procedeu-se a uma série de ensaios variando reagente a reagente e realizando procedimentos para avaliar o comportamento em função do tempo do gel dosimétrico obtido. Os espectros de absorção antes e após a irradiação apresentam máximos em 457 nm e 588 nm, respectivamente. Esses dois picos correspondem aos comprimentos de onda de absorção das espécies Fe-ll e Fe-lll, respectivamente; estando ambas as espécies em equilíbrio. Com a irradiação, ocorre a formação de radicais que oxidam o Fe-ll em Fe-lll, alterando com isso o balanço entre as duas espécies - daí o aumento da concentração de Fe-lll - fazendo com que mude a tonalidade do gel, sendo, portanto, possível de ser determinada a dose absorvida. Nas análises dos espectros e respectivas curvas dose-resposta observou-se que o gel dosimétrico apresenta linearidade no intervalo de doses entre 0,5 e 40 Gy. A partir dos resultados obtidos de linearidade, estabilidade e menor dose detectável - 0,3 Gy - conclui-se que o presente Gel Dosimétrico à base de DL-Alanina e Fe-ll apresenta excelente potencial para a finalidade que é proposto, qual seja a determinação do campo de doses em radioterapia e futura aplicação como padrão na determinação desses campos, em 3D, utilizando-se a técnica de Imagem por Ressonância Magnética - IRM. / The aim of this work is to develop a DL-Alanine, Fe-ll based gel dosimeter to be applied in the dosimetry of the Co-60 gamma-radiation fields in the dose range of radiation therapy procedures. The aminoacid DL-Alanine is dissolved in an acid solution containing the Fe-ll and added to the gel. A series of essays was performed with different chemicals and different procedures were made to evaluate the behavior of the obtained dosimetric gel as function of the time. The absorption spectra, before and after the irradiation, present maximum in 457 nm and 588 nm, respectively. These two peaks correspond to absorption wavelengths of the chemical species Fe-ll and Fe-lll, respectively, both species being in equilibrium. With the irradiation, the formation of the radicals that oxide the Fe-ll into Fe-lll occurs, altering the chemical balance of both species - hence the increase of the Fe-lll - and causing the gel to change its tonality, in such a way that it is possible to determine the absorved dose. In the analysis of the spectra and respective dose-response curves it was observed that the dosimetric gel shows linearity in dose range of 0.5 to 40 Gy. From the obtained linearity results, stability and lower detectable dose - 0,3 Gy - it is possible to conclude that the present DL-Alanine, Fe-ll based dosimetric gel presents an excellent potential to the application to which it is proposed, namely, the determination of the dose fields in radiation therapy and its future application as a standard in the determination of these fields, in 3D, using the Magnetic Resonance Imaging.

Orientador: Aristides Augusto Palhares Neto / Resumo: Introdução: A cicatriz desempenha um importante papel no resultado final de uma cirurgia. Muitos fatores são implicados no processo de cicatrização patológica, e diversos produtos e curativos foram desenvolvidos para prevenção de cicatriz hipertrófica e quelóide, porém poucos tem evidências que o suportem. Objetivos: Comparar o resultado da cicatriz cirúrgica após utilização da fita de silicone e da fita microporosa. Métodos: Realizamos um ensaio clínico controlado, cego e randomizado, onde um lado da incisão foi randomizado para receber a fita de silicone e o outro lado recebeu o tratamento controle (fita adesiva microporosa). Foram selecionadas pacientes submetidas a abdominoplastia ou mastoplastia de aumento com implantes de silicone no período de maio a outubro de 2016. A Escala de Cicatrização de Vancouver foi utilizada para avaliar as cicatrizes. Resultados: Foram selecionadas para o estudo 17 pacientes. A idade média das pacientes foi de 31,4 ± 6,7, sendo a mínima de 20 e a máxima de 45 anos. Vemos na comparação dos tipos de curativo que os valores de p foram próximos a 5%, sugerindo uma associação do uso da fita de silicone com melhores resultados estéticos e funcionais da cicatriz em relação à fita microporosa. Notamos também que os dois tipos de curativo tiveram uma redução significativa em seus escores do primeiro para o terceiro mês (traduzindo uma melhora no aspecto da cicatriz), porém a fita de silicone teve uma redução superior à fita microporosa (45,6% e 39,2%... (Resumo completo, clicar acesso eletrônico abaixo) / Mestre

Nous avons synthétisé des composites nanostructurés de nanotubes de carbone (CNT) par deux approches différentes. La première approche se base sur la dispersion dans une matrice d'intérêt d'un masterbatch de polymère fortement chargé en CNT optimisé pour d'une part aider à la dispersion des CNT et d'autre part pour induire une nanostructuration de la matrice. Un masterbatch de poly(styrene-b-butadiene-b-methyl methacrylate) et de CNT re-dispersé dans une matrice de polymère fluoré a permis d'obtenir des composites chargés et néanmoins ductiles. Nous avons aussi utilisé un masterbatch réactif à base de polyamide-6 (PA6). La morphologie co-continue réalisée après ajout de polyéthylène maléisé (PE*) permet d'obtenir des composites cumulant : rigidité, ductilité, résistance aux solvants et conductivité. Dans la deuxième partie de ce mémoire, nous avons démontré une interaction spécifique entre la phase PA6 et les CNT de composites à matrice PE*/PA6 nanostructurée. Le PA6 s'adsorbe sur les CNT ce qui conduit (au dessus d'un seuil de percolation) à des composites possédant comme microstructure un réseau de nanotubes consolidé à ses jonctions par du PA6. Ce réseau " brasé " permet d'obtenir des composites avec des propriétés uniques de tenue haute température. De manière surprenante, nous avons démontré qu'après extraction de la matrice PE* le réseau de nanotubes consolidé se comporte comme un gel. Ces gels originaux peuvent être gonflés par différents solvants de manière parfaitement réversible et possèdent des propriétés électriques dépendantes de leurs taux de gonflement.

Cette étude est consacrée à la dynamique ultralente et non - stationnaire d'un gel de vésicules multi lamellaires, dit oignons. Nous avons développé un expérience basée sur l'observation du système par microscopie optique et utilisé un ensemble de techniques d'analyse d'images, qui permettent de déterminer un champ de déplacement "coarse grained" au sein de l'échantillon. A partir des champs de déplacement obtenus lors d'expériences à température imposée, nous avons montré que le système présentaient des élongations et contractions d'ensemble, stationnaires et induites par des petites fluctuations de température expérimentalement inévitables, ainsi qu'une dynamique interne hétérogène spatialement et temporellement. <br />Nous avons démontré que la dynamique interne suit une loi de vieillissement exponentiel et que la température, et plus particulièrement ses fluctuations, semble jouer un rôle important en tant que "moteur" des réarrangements du système par le biais des sollicitations mécaniques imposées par les élongations/contractions. En nous intéressant à la fois à la structure temporelle et spatiale des déplacements, nous avons vu que deux types d'évènements ont lieu au sein du système. Tout d'abord des cisaillements, réversibles et orientés selon l'axe longitudinal du capillaire contenant l'échantillon, sont induits par les fluctuations de température de manière intermittente. Simultanément, d'autres évènements prennent place que nous avons pu montrer être irréversibles et correspondent à une évolution balistique du déplacement avec le temps. Pour les deux types d'évènements, nous avons montré que les réarrangements au sein du système sont corrélés sur de longues distances environ 1000 fois supérieures à la taille typique des vésicules.

Ce travail est consacré à l'étude des hétérogénéités dynamiques dans la relaxation lente de la matière molle vitreuse par des techniques originales de diffusion de la lumière multispeckle, développées au cours de cette thèse. La première technique, appelée « Corrélation Résolue dans le Temps » (TRC), permet de caractériser les hétérogénéités temporelles de la dynamique. Elle a été optimisée en considérant un système modèle, les mousses. Nous avons proposé diverses méthodes pour supprimer la contribution du bruit de la mesure, due au nombre limite de pixels de la camera CCD, dans des objets statistiques caractérisant les fluctuations de la dynamique (variance, fonction densité de probabilité et autocorrélation). La deuxième technique, appelée « Corrélation Résolue dans le Temps et dans l'Espace » (STRC), permet de caractériser les hétérogénéités spatiales de la dynamique. Grâce à la STRC, nous avons montré que la dynamique d'un gel concentré de vésicules lamellaires et celle d'un gel colloïdal fortement attractif sont, de façon surprenante, corrélées sur des distances très longues. Des mesures complémentaires sur le gel colloïdal, effectuées à plusieurs vecteurs de diffusion, ont mis en évidence la dépendance de la dynamique moyenne et de ses fluctuations temporelles avec la longueur sondée. Nous avons établi un modèle simple, basé sur une série de réarrangements corrélés spatialement et aléatoires dans le temps, qui est en accord avec les résultats expérimentaux.

Despite the plethora of information regarding cellular crowding and its importance on modulating protein function the effects of confinement on biological molecules are often overlooked when investigating their physiological function. Recently however, the encapsulation of biomolecules in solid state matrices (NafionTM, sol-gels, zirconium phosphate,etc.) has increased in importance as a method for examining protein conformation and dynamics in confined space as well as novel applications in biotechnology. Biotechnological applications include, but are not limited to, bioremediation, biosensors, biocatalysts, etc. In order to better utilize solid state materials as substrates for biological molecules an understanding of the effects of encapsulation on the detailed dynamics associated with physiological function is required as well as a complete characterization of the physical properties associated with the space in which the biological molecule is to be confined. The focus of this research is to probe the effects of confinement on the thermodynamics of ligand photo-release/rebinding to the prototypical heme protein, myoglobin, encapsulated within sol-gel glasses utilizing photoacoustic calorimetry (PAC) and photothermal beam deflection (PBD). Optical spectroscopies (including optical absorption and fluorescence) have also been employed to characterize the molecular environments of materials including Zr-phosphate and metal organic polyhedral (MOPs), thought to be good candidates for novel bio-hybrid materials. The assembly mechanisms associated with MOPs were also examined in order to develop a foundation through which new, bio-compatible MOPs can be designed. Overall the results presented here represent a technological breakthrough in the application of fast calorimetry to the study of proteins in confined space. This will allow for the first time the acquisition of detailed thermodynamic maps associated with the well-choreographed biomolecular dynamics in confined environments.

Telechelic associating polymer networks consist of polymer chains terminated by endgroups that have a different chemical composition than the polymer backbone. When dissolved in a solution, the endgroups cluster together to form aggregates. At low temperature, a strongly connected reversible network is formed and the system behaves like a gel. Telechelic networks are of interest since they are representative for biopolymer networks (e.g. F-actin) and are widely used in medical applications (e.g. hydrogels for tissue engineering, wound dressings) and consumer products (e.g. contact lenses, paint thickeners). In this thesis such systems are studied by means of a molecular dynamics/Monte Carlo simulation. At first, the system in rest is studied by means of graph theory. The changes in network topology upon cooling to the gel state, are characterized. Hereto an extensive study of the eigenvalue spectrum of the gel network is performed. As a result, an in-depth investigation of the eigenvalue spectra for spatial ER, scale-free, and small-world networks is carried out. Next, the gel under the application of a constant shear is studied, with a focus on shear banding and the changes in topology under shear. Finally, the relation between the gel transition and percolation is discussed.