Les protéines MCM (minichromosome maintenance) forment un complexe hétérohexamérique composé des protéines MCM2 à MCM7 qui possède une activité hélicase nécessaire lors de la réplication de l’ADN. Ce complexe est la cible des protéines ATM et ATR, kinases responsables de l’initiation de la réponse cellulaires aux dommages à l’ADN, pour permettre l’arrêt de la réplication lors de la détection de cassure double brin. De plus, les MCM permettent le remodelage de la chromatine par leur activité hélicase mais aussi par leur association avec une chaperone d’histone la protéine ASF1. Toutefois, la majorité des complexes MCM ne co-localisent pas avec les origines de réplication. De plus, la quantité des protéines MCM dans la cellule est nettement supérieure à la quantité requise lors de la réplication. Ces deux faits laissent présager que ce complexe hélicase pourrait jouer un second rôle. Des études effectuées au laboratoire ont démontré une augmentation de la fixation à la chromatine des protéines MCM suite au traitement avec l’étoposide, un inhibiteur de la topoisomérase II qui cause des cassures double brin. L’étude des interactions de la protéine MCM2 par spectrométrie de masse ainsi que par immunobuvardage ont démontré une augmentation de l’interaction entre la protéine MCM2 et ASF1 suite aux dommages. Ceci suggère que les protéines MCM pourraient être impliquées dans les mécanismes de réparation de l’ADN. La nature de l’interaction entre la protéine MCM2 et ASF1 a été déterminée in vitro par des immunobuvardages de type Far western et des Dot blot avec des mutants de la protéine MCM2. Des cellules U2OS-Flp-in ont été utilisées pour générer des lignées stables exprimants les protéines MCM2 à MCM7 avec une étiquette GFP ou fusionnées avec une biotine-ligase (BirA). Les cellules ont été cultivées dans du milieu SILAC et des immunoprécipitations ont été effectuées sur des cellules contrôles (R0K0), des cellules qui expriment MCM-GFP ou BirA (R6K4) non-traitées et des cellules qui expriment MCM-GFP ou BirA traitées à l’étoposide (R10K8). Les immunoprécipitations ont été analysés au spectromètre de masse pour déterminer la modulation des interactions avant et après dommages à l’ADN. Les études d’interactions in vitro ont permis d’identifier que l’interaction entre la protéine MCM2 et ASF1 se situe entre les acides aminés 81-162 sur la protéine MCM2. L’approche de spectrométrie de masse a permis d’identifier plusieurs protéines liant le complexe MCM qui sont impliquées non seulement dans la réplication de l’ADN mais aussi dans le remodelage de la chromatine. De plus, certains de ces nouveaux partenaires augmentent leur interaction avec le complexe suite à l’induction de dommages. Ces résultats suggèrent que les protéines MCM jouent un rôle dans la réorganisation de la chromatine dans les mécanismes de réparation de l’ADN.

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Complete and accurate DNA replication is essential to maintain the genetic integrity in all organisms. In eukaryotes, the minichromosome maintenance (MCM) complex forms the catalytic core of the CMG helicase that unwinds DNA at the replication fork. We have previously identified a conserved MCM complex binding protein (MCM-BP) through a proteomic screen in human cells. In chapter two of this thesis, I show that MCM-BP makes an important contribution to nuclear morphology in human cells by affecting centrosome duplication. I also show that MCM-BP depletion results in G2 checkpoint signaling and the induction of replication stress. A recent study in Xenopus egg extracts has suggested that MCM-BP functions to unload the MCM complex from chromatin during S-phase. However, the mechanism of this process remains enigmatic. In chapter three of this thesis, I show that MCM-BP directly binds the de-ubiquitylating enzyme, USP7 and that this interaction is mediated by S158 on MCM-BP and the USP7 TRAF domain. Furthermore, I indicate a novel role for USP7 in DNA replication that involves unloading of the MCM complex during S-phase. Finally, my data suggest that MCM-BP tethers an interaction between the USP7 and the MCM complex to facilitate MCM complex unloading at the end of S-phase.

Made available in DSpace on 2014-06-12T18:02:35Z (GMT). No. of bitstreams: 2 arquivo164_1.pdf: 3053526 bytes, checksum: 2e5eafdf454df7889e3e5ba1c87ceb2a (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2011 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / A corrosão por ácidos naftênicos a altas temperaturas nas unidades de refino é um dos maiores problemas nas refinarias de todo o mundo, uma vez que, podem causar envenenamento de catalisadores e paradas operacionais de alto custo. Os ácidos naftênicos correspondem a uma mistura complexa de ácidos carboxílicos presentes no petróleo, responsáveis diretamente pela sua acidez e corrosividade. Tais compostos também estão presentes nas frações destiladas do petróleo, causando diversos problemas na qualidade final do produto. Dentre estas frações do petróleo pode-se destacar o querosene de aviação (QAV) que é produzido através do fracionamento por destilação à pressão atmosférica. Os óleos nacionais estão cada vez mais ácidos, estimulando a busca por novos e eficientes métodos de mitigação. Métodos propostos por estudos científicos e industriais para minimizar a corrosão provocada por ácidos naftênicos vêm apresentando custos elevados e problemas de operação. O processo de adsorção tem a vantagem da possibilidade de recuperação dos ácidos orgânicos, que são precursores de surfactantes e aditivos para lubrificantes, não havendo formação de resíduos poluentes e contribuindo com o meio ambiente. As peneiras moleculares mesoporosas (MCM-41) vêm despertando grande interesse na comunidade científica em função da perspectiva da sua aplicação em processos de adsorção e catálise. A fim de reduzir o alto custo dos processos de separação por adsorção, principalmente devido ao elevado valor de alguns adsorventes, a utilização de resíduos agroindustriais como adsorventes vem se destacando como método alternativo. O objetivo deste trabalho foi a remoção da acidez naftênica de uma mistura modelo de QAV (ácido dodecanóico em ndodecano) com uso do adsorvente Sr-MCM-41 e de adsorvente preparado a partir de resíduo agroindustrial. No presente trabalho foi sintetizada a peneira molecular mesoporosa Sr-MCM- 41, na qual a incorporação do estrôncio resultou no aumento da basicidade do material e consequentemente da sua afinidade pelos ácidos. O adsorvente Sr-MCM-41 foi caracterizado por análise termogravimétrica (TG) e termogravimétrica diferencial (DTG), difração de raios- X (DRX), medida de área superficial por adsorção de N2 (BET), espectrometria de emissão óptica com plasma indutivamente acoplado (ICP-OES) e espectroscopia na região do infravermelho com transformada de Fourier (FT-IR). Os resultados da caracterização deste material indicaram que a incorporação do estrôncio não comprometeu a estrutura mesoporosa e que os materiais sintetizados apresentaram um bom grau de organização. Foi utilizada a técnica de planejamento fatorial para otimização do processo adsortivo visando a determinação das melhores condições de operação. Em seguida foram realizados estudos de cinética e equilíbrio de adsorção com o adsorvente Sr-MCM-41, obtendo-se como capacidade máxima adsortiva 2,0 gácido.g-1 adsorvente, a partir do estudo de equilíbrio de adsorção. Os dados de equilíbrio foram ajustados a isoterma de BET tipo IV. A cinética de adsorção foi modelada considerando-se um modelo de força motriz linear. Também foi preparado o carvão ativado a partir da casca da laranja, o qual foi caracterizado através da medida de área superficial por adsorção de N2 (BET) apresentando isoterma do tipo I, característica de materiais microporosos e foram realizados testes para avaliação de sua capacidade adsortiva que foi em torno de 0,40 gácido.g-1 adsorvente. O estudo de adsorção utilizando a Sr-MCM-41 apresentou significativa eficiência, uma vez que o adsorvente apresentou uma alta capacidade adsortiva. Para o adsorvente carvão ativado preparado a partir da casca da laranja constatou-se a potencialidade de sua aplicação por ser um resíduo agroindustrial, porém, verificou-se a necessidade de um estudo mais detalhado

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-19T16:09:58Z No. of bitstreams: 1 VITÓRIA DE ANDRADE FREIRE - DISSERTAÇÃO PPGEQ 2016..pdf: 2687690 bytes, checksum: 093bc81d91144a15964f2333d08a5c8f (MD5) / Made available in DSpace on 2018-03-19T16:09:58Z (GMT). No. of bitstreams: 1 VITÓRIA DE ANDRADE FREIRE - DISSERTAÇÃO PPGEQ 2016..pdf: 2687690 bytes, checksum: 093bc81d91144a15964f2333d08a5c8f (MD5) Previous issue date: 2016-04-29 / Capes / A pesquisa no desenvolvimento de estruturas do tipo micro-mesoporosas tem por intuito a obtenção de materiais porosos com características superiores, uma vez que busca unir a ácidez elevada da zeólita MCM-22, com o sistema de mesoporos, da peneira molecular MCM-41, consequentemente melhorar a difusão de moléculas volumosas. Nesta pesquisa foram sintetizadas as seguintes estruturas porosas: Inicialmente foi obtido o percussor lamelar MCM22-(P) com razão molar SiO2\Al2O3 = 30 e ativada para obter sua forma zeólítica MCM-22 a 550 0C por 5 horas. Em seguida, foi realizada a síntese do material micro-mesoporoso do tipo MCM-22/MCM-41, tratando 2 g da zeólita MCM-22, com uma solução de 25 mL de brometo de cetiltrimetilamônio (CTABr) a 10 % em massa, onde o material permaneceu em estufa a 1100C por 7 dias. Com o intuito de obter um novo material com melhor organização estrutural, utilizou-se a MCM-22 nas seguintes proporções (5%, 10% e 15%), permanecendo em estufa a 300C por 24 horas, sendo ativado em corrente de ar por 5500C por 5 horas. Os resultados das caracterizações de difratometria de raios-X, evidenciaram a formação do precursor MCM-22 (P) e sua forma zeólítica MCM22, com os picos da topologia MWW. A curvas obtidas por meio da análise termogravimétrica (TG/DrTG), demostraram as perdas de massa da água e demais adsorvatos. As micrografias (MEV), apresentou formato toroidal com depreciamento na região central para a MCM-22. Por meio dos resultados de adsorção física de N2, verifica-se que as zeólitas MCM-22, com isotermas do tipo I e loop de histerese do tipo H4. A partir dos difratogramas de raios - X para os materiais micro-mesoporosos foi possível observar a formação das estruturas porosas, com a identificação dos picos de reflexão pertinentes a fase microporosa da MCM-22 e da peneira molecular MCM-41, coexistindo em uma única fase estrutural. As imagens obtidas por MEV, detectam a formação de aglomerados de partículas da fase mesoporosa sendo constituída em torno da fase microporosa. A análise textural mostraram uma diminuição do volume de microporos e um aumento do volume de mesoporos, com isotermas do tipo IV e histereses 2. Demonstrando assim que as caracterizações foram eficazes na elucidação das estruturas porosas. Foi possível obter os materiais micromesoporosos para ambas as metodologias adotadas, sendo o teor de 5% de zeólita MCM-22 a melhor condição de síntese para obtenção desse novo material. / The research on the development of micro-mesoporous structures has the purpose of obtaining porous materials with superior characteristics, once it seeks to join the high acidity of MCM-22 zeolite with the mesoporous system of MCM41 molecular sieve, consequently improving the diffusion of bulky molecules. In this research, the following porous structures were synthesized: Initially, the MCM-22-(P) lamellar precursor was obtained with molar ratio of SiO2\Al2O3 = 30 and was activated to obtain its MCM-22 zeolite form at 550 °C for 5 hours. Then, MCM-22/MCM-41 micro-mesoporous material was synthesized by treating 2 g of MCM-22 zeolite with a solution of 25 mL of 10% wt cetyltrimethylammonium bromide (CTABr), where the material remained in an incubator at 110 °C for 7 days. In order to obtain a new material with better structural organization, the MCM-22 was used in the following proportions (5%, 10% and 15%), remaining in an incubator at 30 °C for 24 hours, being activated in air stream at 550 °C for 5 hours. The results of the X-ray diffraction characterization demonstrated the MCM-22 (P) precursor formation and its MCM-22 zeolite form, with MWW topology peaks. The curves obtained by means of the thermogravimetric analysis (TG/DrTG), showed the losses of water mass and other adsorbates. The micrographs (SEM) presented toroidal format with depreciation in the central region for MCM-22. By means of the results of physical adsorption of N2, it was verified for MCM-22 zeolites: type I isotherms and hysteresis loops of type-IV. From the X-ray diffractograms for the micro-mesoporous materials, it was possible to observe the formation of the porous structures, with the identification of the reflection peaks pertinent to the microporous phase of MCM-22 and the MCM-41 molecular sieve, coexisting in a single structural phase. The SEM images detected the formation of particle agglomerates of the mesoporous phase being constituted around the microporous phase. The textural analysis showed a decrease in the volume of micropores and an increase in the volume of mesopores, with type IV isotherms and hysteresis loops of type-II. Thus demonstrating that the characterizations were effective in elucidating the porous structures. It was possible to obtain the micro-mesoporous materials for both methodologies, being the 5% content of MCM-22 zeolite the best synthesis condition to obtain this new material.

Made available in DSpace on 2014-12-17T15:42:29Z (GMT). No. of bitstreams: 1 MirnaFF_TESE.pdf: 7322446 bytes, checksum: 0ef1d9562cc97f24609fa13f5580a92e (MD5) Previous issue date: 2013-04-29 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Statistics of environmental protection agencies show that the soil has been contaminated with problems often resulting from leaks, spills and accidents during exploration, refining, transportation and storage oil operations and its derivatives. These, gasoline noteworthy, verified by releasing, to get in touch with the groundwater, the compounds BTEX (benzene, toluene, ethylbenzene and xylenes), substances which are central nervous system depressants and causing leukemia. Among the processes used in remediation of soil and groundwater contaminated with organic pollutants, we highlight those that use hydrogen peroxide because they are characterized by the rapid generation of chemical species of high oxidation power, especially the hydroxyl radical ( OH), superoxide (O2 -) and peridroxil (HO2 ), among other reactive species that are capable of transforming or decomposing organic chemicals. The pH has a strong effect on the chemistry of hydrogen peroxide because the formation of different radicals directly depends on the pH of the medium. In this work, the materials MCM-41 and Co-MCM-41 were synthesized and used in the reaction of BTEX removal in aqueous media using H2O2. These materials were synthesized by the hydrothermal method and the techniques used to characterize were: XRD, TG/DTG, adsorption/desorption N2, TEM and X-Ray Fluorescence. The catalytic tests were for 5 h of reaction were carried out in reactors of 20 mL, which was accompanied by the decomposition of hydrogen peroxide by molecular absorption spectrophotometry in the UV-Vis, in addition to removal of organic compounds BTEX was performed as gas chromatography with detection photoionization and flame ionization and by static headspace sampler. The characterizations proved that the materials were successfully synthesized. The catalytic tests showed satisfactory results, and the reactions containing BTEX + Co-MCM-41 + H2O2 at pH = 12.0 had the highest percentages of removal for the compounds studied / Dados estat?sticos das ag?ncias de prote??o ambiental demonstram que o solo tem sido contaminado frequentemente com problemas decorrentes de vazamentos, derrames e acidentes durante a explora??o, refino, transporte e opera??es de armazenamento do petr?leo e seus derivados. Destes, a gasolina merece destaque, verificado pela libera??o, ao entrar em contanto com a ?gua subterr?nea, dos compostos BTEX (benzeno, tolueno, etilbenzeno e xilenos), que s?o subst?ncias depressoras do sistema nervoso central e causadoras de leucemia. Dentre os processos utilizados em remedia??o de solos e ?guas contaminadas por poluentes org?nicos, destacam-se os que utilizam o per?xido de hidrog?nio por serem caracterizados pela r?pida gera??o de esp?cies qu?micas de alto poder de oxida??o, principalmente o radical hidroxil ( OH), super?xido (O2 -) e peridroxil (HO2 ), dentre outras esp?cies reativas que s?o capazes de transformar ou decompor produtos qu?micos org?nicos. O pH tem um forte efeito na qu?mica do per?xido de hidrog?nio, pois a forma??o dos diferentes radicais depende diretamente do pH do meio. Neste trabalho, os materiais MCM-41 e Co-MCM-41 foram sintetizados e utilizados na rea??o de remo??o dos BTEX em meio aquoso utilizando H2O2. Estes materiais foram sintetizados atrav?s do m?todo hidrot?rmico e as t?cnicas utilizadas na caracteriza??o foram: DRX, TG/DTG, adsor??o/dessor??o de N2, MET e Fluoresc?ncia de Raios-X. Os testes catal?ticos ocorreram durante 5 horas de rea??o e foram realizados em reatores de 20 mL, onde foi acompanhada a decomposi??o do per?xido de hidrog?nio por espectrofotometria de absor??o molecular na regi?o do UV-Vis, al?m da remo??o dos compostos org?nicos BTEX que foi realizada por cromatografia em fase gasosa com detec??o por fotoioniza??o e ioniza??o de chama e amostrador por headspace est?tico. As caracteriza??es comprovaram que os materiais foram sintetizados com sucesso. Os testes catal?ticos apresentaram resultados satisfat?rios, sendo que as rea??es contendo BTEX + Co- MCM-41 + H2O2 em pH = 12,0 apresentaram os maiores percentuais de remo??o para os compostos estudados

Aquest treball descriu el desenvolupament d'un sistema Smart Sensor per a acceleròmetres piezoresistius emprant la tecnologia de mòduls multixip de tipus D (MCM-D). En el camp dels Smarts Sensors existeixen dues aproximacions bàsiques: l'aproximació monolítica que integra el sensor i els circuits en el mateix xip, i la versió multixip, que integra de forma híbrida tant el sensor com els circuits, fabricats per separat. Les dues tecnologies emprades en aquest treball han estat, la dels acceleròmetres piezoresistius en oblies BESOI i la dels mòduls multixip, silici sobre silici, mitjançant la tècnica de muntatge flip-chip. Aquesta tècnica proporciona a l'encapsulat de sensors nivell d'integració més elevat, a la vegada que redueix els problemes termo-mecànics pel fet d'emprar un substrat de silici.En aquest estudi s'ha treballat en el desenvolupament d'aquest Smart Sensor per tal, principalment, d'aconseguir un encapsulat robust i lliure d'estrès. En aquest sentit, s'ha dut a terme el disseny d'una cavitat hermètica per a la protecció de les parts mòbils de l'acceleròmetre. L'hermeticitat s'obté mitjançant la pasta de soldadura que s'aplica en el mateix moment en que es fan les connexions elèctriques o solder bumps. Aquest fet ha requerit d'una modificació en la tecnologia de pads del sensor. Per altra banda, s'han dut a terme una sèrie de simulacions per elements finits per tal d'avaluar en les etapes de disseny l'estrès que podia aportar l'encapsulat a aquests dispositius sensibles a esforços mecànics. Els resultats de les simulacions demostren que si bé es dóna un cert grau d'estrès, aquest no arriba a perjudicar el comportament del sensor.Les caracteritzacions tant elèctriques com mecàniques realitzades a l'encapsulat multixip, demostren que aquest encapsulat no modifica els paràmetres elèctrics més importants, com ara la sensibilitat o la tensió d'offset. La caracterització dinàmica demostra, però, que l'encapsulat multixip afegeix un més elevat grau d'esmorteïment modificant així la resposta del sensor. Aquesta variació es tradueix en una disminució de la freqüència de ressonància i del guany del sensor a aquesta freqüència. Aquest fet, en aplicacions DC, és una característica apreciada doncs evita una eventual ruptura del sensor. / This work describes the development of a Smart Sensor system for piezoresistive accelerometers using Multi Chip Module type D (MCM-D) technology. There are two main approaches in the Smart Sensors field: The monolithic integration of the process circuitry with the sensor itself in the same chip, and the multichip approach, where both parts are independently fabricated and connected using hybrid integration. Two technologies have been used in the present work: CNM's piezoresistive accelerometers technology based on BESOI wafers and silicon-on-silicon multichip module technology, based on the flip-chip interconnection. This technique provides higher levels of integration for the packaging of sensors. In addition, the inclusion of a silicon substrate reduces thermo-mechanical problems.The development of the Smart Sensor has been mainly oriented to obtain a robust and unstressed package. In this sense, mobile parts of the accelerometer have been protected with an specifically designed hermetic cavity. This cavity is built using solder paste, and is defined simultaneously with the electrical connections or solder bumps. This point required modifications of the sensor's pad technology. Furthermore, finite element simulations have been performed in order to evaluate the package induced stresses on the sensor, which is extremely sensitive to mechanical efforts. The simulation results showed that even if small stress appear, they don't adversely affect the behaviour of the sensor. Electrical and mechanical characterisation of the multichip Smart Sensor, showed that the packaging process doesn't modify the main electrical parameters, such as sensitivity and off-set voltage. Vibration tests showed that multichip package increases mechanical damping, modifying the dynamic response of the sensor. In this sense, the resonance frequency and the gain of the sensor at this frequency decrease. This behaviour is useful for DC applications, preventing the failure of the sensor.

The purpose of this thesis was to conduct preliminary research into the feasibility of using MCM-41 as a catalyst support material in the treatment of organochloride contaminated water. Specifically, the stability of MCM-41 in water and its efficiency as a Pd metal catalyst support in the degradation of trichloroethylene (TCE) was examined. MCM-41 is a mesoporous siliceous material that was developed by scientists with the Mobile Corporation in 1992. Since its development, MCM-41 has been the subject of a great deal of research into its potential application in catalytic sciences. The material possesses two especially notable characteristics. First, the diameter of its pores can be adjusted between 2 and 10 nm depending on the reagents and procedure used in its synthesis. Second, MCM-41 has an exceptionally high surface area, often in excess of 1 000 m2/g in well-formed samples. Other researchers have succeeded in grafting a variety of different catalytic materials to the surfaces and pores of MCM-41 and reported dehalogenation reactions proceeding in the presence of hydrogen. Thus, MCM-41 shows promise in treating a variety of chlorinated volatile organic compounds (cVOCs), such as chlorinated benzenes, trichloroethylene (TCE), perchloroethylene (PCE) and some polychlorinated biphenyls (PCBs). Preliminary stages of this research were devoted to synthesising a well-formed sample of MCM-41. The method of Mansour et al. (2002) was found to be a reliable and repeatable procedure, producing samples with characteristic hexagonal crystallinity and high surface areas. Crystallinity of all materials was characterized by small angle X-ray powder diffraction (XRD). Samples of MCM-41 prepared for this research exhibited a minimum of three distinct peaks in their XRD traces. These peaks are labelled 100, 110, and 200 according to a hexagonal unit cell. The 100 peak indicates that the sample is mesoporous. The 100, 110, and 200 peaks together indicate a hexagonal arrangement of the mesopores. An additional peak, labelled 210, was also observed in materials prepared for this research, reflecting a high degree of crystallinity. The position of the 100 peak was used to calculate the unit cell parameter - “a” - of the samples according to Bragg’s Law. The value of the unit cell parameter corresponds to the centre to centre distance of the material’s pores and thus the relative diameter of the pores themselves. The unit cell parameter of samples prepared for this research ranged from 4.6 nm to 5.3 nm with an average value of 4.8 nm. Surface areas of prepared samples were determined by BET nitrogen adsorption analysis and ranged from 1 052 to 1 571 m2/g with an average value of 1 304 m2/g. Field emission scanning electron microscope (SEM) images of a representative sample of MCM-41 revealed a particle morphology referred to as ‘wormy MCM-41’ by other researchers. A sample of aluminum-substituted MCM-41 (Al-MCM-41) was also synthesized. The crystallinity of Al-MCM-41 was characterized by small angle XRD. The XRD trace of the material showed only one distinct peak centred at 2.1 degrees 2θ. The 110 and 200 peaks seen in MCM-41 were replaced by a shoulder on the right hand side of the 100 peak. The shape of this trace is typical of Al-MCM-41 prepared by other researchers and is indicative of the lower structural quality of the material, i.e. a less-ordered atomic arrangement in Al-MCM-41 compared to that of regular MCM-41. The unit cell parameter of the Al-MCM-41 sample was 4.9 nm. The surface area of the sample was determined through BET nitrogen adsorption analysis and found to be 1 304 m2/g. Attempts were made to synthesize an MCM-41 sample with enlarged pores. Difficulties were encountered in the procedure, specifically with regards to maintaining high pressures during the crystallization stage. Higher temperatures used during these procedures caused failure of the O-ring used in sealing the autoclave, allowing water to be lost from the reaction gel. Samples generated in these attempts were amorphous in character and were subsequently discarded. A solubility study involving MCM-41 was undertaken to determine the stability of the material in water at ambient temperature and pressure. The experiment included several different solid/water ratios for the dissolution experiments: 1/200, 1/100, 1/75, 1/25. Results indicated that MCM-41 is metastable at ambient temperatures and more soluble than amorphous silica in water. The maximum silica concentration observed during the experiment was used to calculate a minimum Gibbs free energy of formation for MCM-41 of - 819.5 kJ/mol. The higher free energy value compared to quartz (- 856.288 kJ/mol) is indicative of the metastability of the material in water. Supersaturation with respect to amorphous silica was observed in samples prepared with relatively high concentrations of MCM-41. A subsequent decrease in dissolved silica concentration with time in these samples represented precipitation of amorphous silica, driving the concentration downward towards saturation with respect to this phase (120 ppm). The equilibrium concentration of 120 ppm recorded in these samples represented 4.8 mg out of 200, 400, 500, and 1 600 mg of initial MCM-41 dissolving into solution in the solid/liquid ratios of 1/200, 1/100, 175, and 1/25, respectively. Supersaturation with respect to amorphous silica did not occur in experiments with very low solid/water ratios. It also did not occur in higher solid/water experiments from which the SiO2 saturated supernatant was decanted and replaced with fresh deionized water after two weeks of reaction. The difference in dissolution behaviour is believed to result from deposition of a protective layer of amorphous silica from solution onto the MCM-41 surfaces, which reduces their dissolution rate. Thus, supersaturation with respect to amorphous silica is only manifested at early time and only when relatively large amounts of fresh MCM-41 are added to water. The solubility experiment was repeated using samples of Al-MCM-41 to determine the effect of Al substitution on the stability of the MCM-41. Dissolution curves for the Al-MCM-41 samples revealed behaviour that was analogous to that of the silica-based MCM-41 at similar solid/water ratios. Substitution of Al into the structure of MCM-41 appeared to have no positive or negative effects on the stability of the material in water. Solid MCM-41 material was recovered on days 28 and 79 of the solubility experiment and dried under vacuum. Solid material was also recovered from the Al-MCM-41 solubility experiment on day 79. These recovered samples were characterized by XRD and BET nitrogen adsorption analysis. An increase in background noise in the XRD plot of MCM-41 from the fresh to the 79 d sample indicated an increased proportion of an amorphous phase in the sample. The XRD plot of the 79 d sample of Al-MCM-41 also showed increased background noise corresponding to an increased proportion of an amorphous phase. The increased amorphous phase would have resulted from the continuous dissolution of the crystalline MCM-41 and reprecipitation as amorphous silica in the samples. BET surface area analysis of recovered MCM-41 compared to the freshly prepared material showed no significant change in surface area after 28 and 79 days in water. Analysis of the 79 d Al-MCM-41 indicated a 10% decrease in surface area relative to the as-prepared material. A set of SEM images were taken of the day 28 and 79 MCM-41 samples and compared to a sample of freshly prepared material. No substantial change in morphology was observed in the day 28 sample when compared to the fresh material. Some change was noted in the day 79 sample particle morphology, with worm-like structures appearing to be better developed than in the as-synthesized material. A series of palladized MCM-41 (Pd/MCM-41) samples with varying mass percent loadings of Pd was prepared to investigate the dehalogenation efficiency of Pd/MCM-41 in contact with TCE. TCE degradation was investigated in batch experiments. MCM-41 samples were prepared with calculated Pd loadings of 0.1, 1, and 5 mass %. The actual palladium content of the materials was determined using an EDAX-equipped SEM. The success of the loading technique was better at lower mass loadings of Pd, i.e. there was a greater deviation of actual Pd content from targeted or calculated contents at higher loadings of Pd. It was found that a procedure designed to yield 1% by mass Pd/MCM-41 produced an average loading of 0.95% Pd by mass. A procedure designed to produce a 5% Pd/MCM-41 sample resulted in an average loading of 2.6 mass %. These deviations were attributed to error inherent in the EDAX analysis and reduced effectiveness of the loading technique at higher Pd concentrations. All batch experiment reaction bottles were prepared with solid/liquid ratios of 1/800. The various Pd/MCM-41 samples induced rapid dehalogenation reactions, with the maximum extent of TCE degradation occurring before the first sample was taken at 7 to 12 min and within 35 min in the case of 0.1% Pd/MCM-41. The 0.1% Pd/MCM-41 sample degraded 70% of total TCE in solution with an estimated degradation half-life of 14 min. The 1% Pd/MCM-41 sample degraded 92% of total TCE in solution with an estimated half life of between 3 and 6 min. The 5% Pd/MCM-41 sample degraded only 22% of total TCE in solution; degradation half-life could not be determined. The seemingly paradoxical result of lower degradation efficiency at higher Pd loadings is proposed to result from absorption of hydrogen from solution by Pd, which is unreactive relative to the dissolved hydrogen in solution. Production of reaction intermediates and daughter products was also lower in the 1% by mass Pd/MCM-41 experiment compared to the 0.1 and 5% by mass Pd/MCM-41. Analysis of degradation products results from the experiments indicated that TCE degrades to ethane in the presence of Pd/MCM-41 with relatively low concentrations of chlorinated daughter products resulting from a random desorption process. A batch experiment using pure silica MCM-41 was also conducted to determine if there was adsorption of TCE to the support material itself. A lack of change in TCE concentration between the control sample and the MCM-41 sample during the experiment indicated no significant adsorption of TCE onto MCM-41. The conclusion of this research is that although MCM-41 is relatively unstable in water, its high TCE degradation efficiency shows promise for its application in developing water treatment technologies. However, more research needs to be conducted to fully determine the potential use of MCM-41 in water treatment and to investigate ways to improve its long-term stability in water.

Solid state ¹H MAS NMR spectroscopy was used to investigate the temperature and hydration dependance of water and hydroxyl proton spectra of hydrated mesoporous MCM-41. The NMR spectra show a complex peak structure, with hydroxyl proton resonances seen in dry MCM-41 disappearing as water is introduced into the pores, and new peaks appearing representing water and hydrated silanol groups. Until now the assignment of these peaks was unclear and the consensus was that magnetization exchange played an important role in the coalescence of the various peaks which appear in the spectra. It was found recently that magnetization exchange is not necessary to produce the spectral featured observed [Niknam, M., M.Sc. Thesis, University of Waterloo (2010)]. In the present study a simplified model, based on chemical shift averaging by the making and breaking of hydrogen bonds as water undergoes rotational motion and translational self-diffusion on the pore surface, has been developed to explain the NMR spectral results. The model is able to reproduce the experimental ¹H MAS NMR spectra for all hydrations and temperatures studied. For the first time, definitive spectral assignments for all hydroxyl and water protons in the sample has been achieved. Spectral features arising due to temperature change have been explained by using the known result that the proton chemical shift of a hydrogen atom involved in hydrogen bonding varies linearly with temperature. Furthermore, it is reported for the first time, that with increasing hydration, water molecules begin to favour forming two hydrogen bonds to the surface. This may represent the first step in the pore filling process.

Solid state ¹H MAS NMR spectroscopy was used to investigate the temperature and hydration dependance of water and hydroxyl proton spectra of hydrated mesoporous MCM-41. The NMR spectra show a complex peak structure, with hydroxyl proton resonances seen in dry MCM-41 disappearing as water is introduced into the pores, and new peaks appearing representing water and hydrated silanol groups. Until now the assignment of these peaks was unclear and the consensus was that magnetization exchange played an important role in the coalescence of the various peaks which appear in the spectra. It was found recently that magnetization exchange is not necessary to produce the spectral featured observed [Niknam, M., M.Sc. Thesis, University of Waterloo (2010)]. In the present study a simplified model, based on chemical shift averaging by the making and breaking of hydrogen bonds as water undergoes rotational motion and translational self-diffusion on the pore surface, has been developed to explain the NMR spectral results. The model is able to reproduce the experimental ¹H MAS NMR spectra for all hydrations and temperatures studied. For the first time, definitive spectral assignments for all hydroxyl and water protons in the sample has been achieved. Spectral features arising due to temperature change have been explained by using the known result that the proton chemical shift of a hydrogen atom involved in hydrogen bonding varies linearly with temperature. Furthermore, it is reported for the first time, that with increasing hydration, water molecules begin to favour forming two hydrogen bonds to the surface. This may represent the first step in the pore filling process.