O objetivo deste estudo foi avaliar a alteração de cor de resinas acrílicas termopolimerizáveis (convencional e de microondas) após imersões em soluções químicas higienizadoras de próteses totais em diferentes períodos de tempo. Foram obtidos padrões em cera (15mm de diâmetro e 4mm de espessura), a partir de uma matriz de teflon, que foram incluídos em muflas convencionais e para microondas. Após a eliminação da cera, as resinas foram manipuladas, prensadas e polimerizadas segundo as instruções dos fabricantes. Foram confeccionados 200 corpos-de-prova, 100 de cada marca comercial das resinas Lucitone 550 (L) e Onda Cryl (OC), os quais foram imersos nas soluções: A)Água destilada-3 min.; B)Bony Plus -3 min.; C)Água destilada-5 min.; D)Corega Tabs-5 min.; E)Água destilada-20 min.; F)Hipoclorito de sódio a 0,5%-20 min.; G)Hipoclorito de sódio a 1%-20 min.; H)Água destilada-8 horas; I)Hipoclorito de sódio a 0,5%-8 horas; J)Hipoclorito de sódio a 1%-8 horas. A alteração de cor foi avaliada empregando-se um espectrocolorímetro (Color Guide 45/0 BYK-Gardner) antes e após a simulação de 180 dias de imersão. Os resultados foram comparados por meio da análise de variância (ANOVA) para dois fatores, seguida pelo teste de Student-Newman Keuls, com nível de significância de 0,05. Para correlacionar as diferenças de cor para o ambiente clínico, os dados foram calculados de acordo com as unidades da National Bureau of Standards (NBS). Os resultados mostraram que a resina Lucitone 550 (ΔE = 0,47±0,18) apresentou-se mais estável que a Onda-Cryl (ΔE = 0,53±0,31). Para ambas as resinas, as pastilhas, os hipocloritos por 20 minutos (0,5% e 1%) e por 08 horas (0,5%) não provocaram alterações maiores que seus respectivos controles (L-A: 0,27 ±0,10; L-B: 0,44±0,21; L-C: 0,48±0,21; L-D: 0,46±0,13; L-E: 0,29±0,07; L-F: 0,37±0,08; L-G: 0,47±0,10; L-H: 0,61±0,11; L-I: 0,55±0,10; OC-A: 0,22±0,08; OC-B: 0,43±0,32; OC-C: 0,65±0,35; OC-D: 0,41±0,11; OC-E: 0,31±0,11; OC-F: 0,29±0,07; OC-G: 0,37 ±0,11; OC-H: 0,78±0,10; OC-I: 0,79±0,08). As soluções de hipoclorito a 1% (L-J: 0,74±0,09; OC-J: 1,06 ±0,13) causaram maiores alterações que seus respectivos controles. As soluções empregadas por 08 horas (água e Hipocloritos a 0,5% e 1%) provocaram alterações classificadas como leves, segundo o sistema NBS. Os achados deste estudo revelaram que as pastilhas efervescentes, quando usadas de acordo com as instruções dos fabricantes, e o hipoclorito de sódio (0,5% e 1%) por 20 minutos apresentaram menores valores de alteração de cor nas resinas acrílicas após um período de uso simulado de 180 dias. Médias mais elevadas foram obtidas quando um regime de 8 horas foi simulado. / The aim of this study was to evaluate color alteration of heat-polymerized acrylic resins (conventional and microwave-polymerized), after immersion in chemicals solutions of denture cleansers for different periods of time. Wax patterns were obtained (15 mm in diameter and 4 mm thickness) from a teflon matrix and were invested in metallic or microwavable flasks. The wax had been eliminated and the resins were mixed, packed and polymerized according to the manufacturers instructions. Two hundred specimens were made, 100 specimens of each commercial resin Lucitone 550 (L) e Onda Cryl (OC), which were immersed in the solutions: A)Distilled water-3 min.; B)Bony Plus-3 min.; C)Distilled water-5 min.; D)Corega Tabs-5 min.; E) Distilled water -20 min.; F) 0,5% Sodium Hypochlorite-20 min.; G) 1% Sodium Hypochlorite-20 min.; H)Distilled water-8 hours; I)0,5% Sodium Hypochlorite-8 hours; J)1% Sodium Hypochlorite -8 hours. Color alteration was assessed by a spectrocolorimeter (Color Guide 45/0 (BYKGardner) before and after 180 days simulation. The results were analyzed statistically by a two-way analysis of variance (ANOVA), and Student Newman-Keuls test, with significance level of 0.05. To relate the color differences to a clinical environment, the data were quantified by National Bureau of Standards (NBS) units. The results showed that the resin Lucitone 550 (ΔE=0,47±0,18) was more stable than the resin Onda-Cryl (ΔE=0,53±0,31). For both resins, the tablets, the hypochlorite by 20 minutes (0,5% e 1%) and by 8 hours (0,5%) did not produce higher alterations than the respective controls (L-A: 0,27 ±0,10; L-B: 0,44±0,21; L-C: 0,48±0,21; L-D: 0,46±0,13; L-E: 0,29±0,07; L-F: 0,37±0,08; L-G: 0,47±0,10; L-H: 0,61±0,11; L-I: 0,55±0,10; OC-A: 0,22±0,08; OC-B: 0,43±0,32; OC-C: 0,65±0,35; OC-D: 0,41±0,11; OC-E: 0,31±0,11; OC-F: 0,29±0,07; OC-G: 0,37 ±0,11; OC-H: 0,78±0,10; OC-I: 0,79±0,08). The 1% hypochlorite solutions (L-J: 0,74±0,09; OC-J: 1,06 ±0,13) produced higher alterations than the respective controls. The solutions employed by 8 hours (water and 0,5% and 1% hipochlorite) produced alterations classified as slight, according to the NBS system. The findings of this study showed that the effervescent tablets, used according to the manufacturer´s instructions, and the sodium hypochlorite (0,5% and 1%) used by 20 minutes presented lower values of color alterations in acrylic resins after a period of 180 days simulation. Higher mean averages were obtained when a period of 8 hours was simulated.

Este estudo avaliou resinas acrílicas convencional (RAC) e de microondas (RAM), dentes artificiais (Vipi, Biolux e Trilux) e reembasadores resilientes (Elite Soft e Mucopren Soft) após imersão em 3 soluções: água; hipoclorito de sódio 1%; solução experimental de mamona 2%. A dureza Knoop e cor das resinas e, dureza ShoreA, rugosidade e cor dos reembasadores foram analisadas em espécimes circulares (15x3mm); rugosidade e resistência à flexão das resinas, em espécimes retangulares (10x65x3mm). A dureza e rugosidade dos dentes foram mensuradas na face palatina planificada e a cor, na face vestibular. Dez espécimes de cada material foram distribuídos, aleatoriamente, nos 3 grupos. Os ensaios foram realizados após obtenção dos espécimes e após 15 e 183 dias, simulando 3 anos de imersões diárias de 20 minutos e 18 meses de imersões diárias de 8 horas, respectivamente. Para os reembasadores, adicionou-se um período de 7 dias (18 meses de imersões diárias de 20 minutos). As variações (ΔT) dos dados foram submetidas aos Testes Anova e Tukey (P=0,05). Para ΔT15, a RAC sofreu maior variação de dureza quando imersa em água (P=0,00); a RAM, após imersão em mamona (P=0,00). A mamona causou a maior variação na rugosidade (P=0,015). Todas as soluções aumentaram a rugosidade. A variação de cor não foi significante (P=24,46). O hipoclorito reduziu a resistência à flexão (P=0,37). Após ΔT183, o hipoclorito e a mamona diminuíram a dureza da RAC (P=0,00). A RAM sofreu a maior variação de rugosidade (P=0,01). O hipoclorito aumentou a rugosidade dos espécimes, porém não houve diferença entre as soluções (P=2,84). A RAC apresentou maior variação de cor após imersão em mamona (P=0,214). O hipoclorito e a mamona promoveram menor resistência à flexão para RAM (P=0,89). Em ΔT15, o dente Vipi sofreu aumento da dureza e o Biolux, a maior variação (P=1,85). A mamona causou a maior variação e aumento da dureza (P=0,02). Para rugosidade, a mamona causou menor variação, mas com aumento (P=0,54). O dente Biolux apresentou a menor variação de cor (P=0,01). Após ΔT183, o Trilux sofreu a maior variação na dureza (P=0,00). A mamona promoveu a menor variação (P=1,03). O dente Biolux apresentou a maior variação e aumento de rugosidade (P=0,001). Não houve variação de cor (P=16,45). Após ΔT7, para dureza, Mucopren apresentou maior variação (P=0,05); não houve diferença entre as soluções (P=47,28). A imersão em água e hipoclorito aumentou a rugosidade do Mucopren. A solução de mamona causou a menor variação nesta propriedade (P=1,57). Para a cor, o Elite sofreu a maior variação quando imerso em hipoclorito; para o Mucopren, a mamona causou a maior variação (P=0,00). Em ΔT15, os materiais sofreram aumento da dureza. A maior variação ocorreu com Mucopren associado ao hipoclorito. (P=0,33). O Elite sofreu maior variação da rugosidade que o Mucopren. Entre as soluções, não houve diferença estatística (P=2,32). Os materiais sofreram maior variação de cor após imersão em hipoclorito (P= 0,00). Após ΔT183, a maior variação de dureza foi apresentada pelo Mucopren em todas as soluções. A mamona gerou a menor variação (P=2,64). Para a rugosidade, o Elite apresentou maior variação (P= 3,72). O hipoclorito e a mamona tiveram comportamentos semelhantes (P=0,024). O hipoclorito causou maior alteração de cor para o Elite e a mamona, para o Mucopren (P=0,001). A solução experimental promoveu variação das propriedades dos materiais avaliados, não apresentando superioridade em relação ao controle positivo, independente do período de imersão. / This study evaluated conventional (RAC) and microwave-polymerized (RAM) acrylic resins, artificial teeth (Vipi, Biolux and Trilux) and soft liners (Elite Soft and Mucopren Soft) after immersion in 3 solutions: water, sodium hypochlorite 1%; experimental solution of Riccinus communis (RC). The Knoop hardness and color alteration of resins, and shore A hardness, roughness and color alteration of soft liners were analyzed in circulars specimens (15x3mm), roughness and flexural strenght, in rectangular specimens (10x65x3mm). Hardness and roughness of artificial teeth were measured on the flat palatine face and color in the vestibular face. Ten specimens of each material were randomly distributed in three groups. The tests were conducted after specimens obtention and after 15 and 183 days, simulating 3 years of daily immersions in 20 minutes and 18 months of daily immersions of 8 hours, respectively. A period of 7 days (18 months of daily immersions, 20 minutes) was added for soft liners. Data variation (ΔT) were submitted to ANOVA and Tukey (P = 0.05). For ΔT15 RAC underwent more variation in hardness when immersed in water (P = 0.00) and the RAM, after immersion in RC solution (P = 0.00). The RC solution caused the largest variation in roughness (P=0.015). All solutions caused roughness increase. Color alteration was not significant (P=24.46). Sodium hypochlorite caused a decrease in flexural strenght (P=0.37). After ΔT183, sodium hypochlorite and RC solution caused a decrease in RAC hardness (P=0,00). The RAM suffered the largest roughness variation (P=0.01). The hypochlorite caused an increase in roughness, but there was not differences between the solutions (P=2.84). RAC presented the largest color alteration after immersion in RC (P=0.214). Sodium hypochlorite and RC caused the lowest values of flexural strenght for RAM (P=0.89). In ΔT15, Vipi underwent hardness increase and Biolux, the highest variation (P=1.85). RC caused the highest variation and hardness increase (P=0.02). For roughness, RC caused the lowest variation, with an increase (P=0.54). Biolux presented the lowest color alteration (P=0.01). After ΔT183, Trilux underwent the highest hardness variation (P=0.00). RC caused the lowest variation (P=1,03). Biolux presented the highest variation, with an increase in roughness (P=0.001). There was not color variation (P=16.45). After T7, for hardness, Mucopren presented the highest variation (P=0.05); there was not differences between the solutions (P=47.28). The immersion in water and hypochlorite increased the roughness of Mucopren. The RC solution caused the lowest variation on this property (P=1.57). About color, Elite underwent the highest variation after immersion in hypochlorite; for Mucopren, RC caused the highest variation (P=0.00). In ΔT15, the materials suffered hardness increase. The highest variation occured for Mucopren associated with hypochlorite (P=0.33). Elite underwent most roughness variation than Mucopren. There was not statistics differences between the solutions (P=2.32). Both materials suffered color alteration after immersion in hypochlorite (P=0.00). After ΔT183, the highest hardness alteration was presented for Mucopren in all solutions. The RC caused the lowest variation (P=2.64). For roughness, Elite presented the highest variation (P= 3.72). Sodium hyochlorite and Riccinus communis was statistically equal (P=0.024). Hypochlorite caused the the highest color alteration for Elite and Riccinus communis for Mucopren. (P=0,001). The experimental solution caused alterations on the properties of all tested materials, showing no superiority to the positive control, regardless of the immersion period.

This publication is the companion piece to “This Must Be the Place,” a 3D realization of my conceptual photography work exhibited in the Anderson Courtyard at VCU's 2019 School of the Arts MFA Show. I photograph scenes from nature and reproduce these images onto flattened plexiglass planes, arranging them in new, natural environments and photographing them again. The outcome is a scenic collage in which two unfamiliar locations become superimposed. It is my hope that as people experience the work they become a part of the texture of it.

Orientador: Marcelo Coelho Goiato / Coorientador: Daniela Micheline dos Santos / Banca: Aldiéris Alves Pesqueira / Banca: Marcelle Danelon / Resumo: Durante a reabilitação com próteses fixas, o uso de provisórios é importante para que se alcance o sucesso clínico e a longevidade da prótese definitiva, mantendo a saúde e protegendo os tecidos dentais e periodontais. O objetivo deste estudo foi avaliar a estabilidade de cor, microdureza, rugosidade e energia livre de superfície de resinas de restaurações provisórias, com e sem a aplicação de glaze fotopolimerizável, e avaliar a eficácia antibiofilme do digluconato de clorexidina a 0,12% sobre as mesmas. Para isso, foram confeccionadas amostras de resina de Bis-Acril (Protemp 4, 3M ESPE, São Paulo, Brasil) e de resina acrílica ativada quimicamente (RAAQ) (Dencor, Artigos Odontológicos Clássico LTDA, São Paulo, Brasil), de forma que, apenas metade dessas amostras foi submetida ao polimento químico com glaze fotopolimerizável. Essas amostras foram posicionadas em dispositivos palatinos contendo 4 nichos (1 RAAQ sem glaze, 1 RAAQ com glaze, 1 Bis-Acril sem glaze, 1 Bis-Acril com glaze), utilizados por voluntários (n=20). As fases experimentais foram: Os voluntários usaram o dispositivo contendo as amostras do grupo controle, durante sete dias, sendo realizada aplicação de sacarose 30% sobre as amostras. Posteriormente, usaram o dispositivo contendo novas amostras do grupo teste, durante mais sete dias, sendo realizado tratamento com digluconato de clorexidina a 0,12% e aplicação de sacarose 30%. A seguir, determinou-se a alteração de cor, microdureza, rugosidade e energia livre... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: During rehabilitation with ceramic fragments, it is important to use provisionalrestorations, which are essential to achieve clinical success and longevity of the definitive prosthesis, maintaining the health and protecting dental and periodontal tissues. The aimof this study was to evaluate colorstability, microhardness, roughness, and surface free energy of provisional prosthesissamples, with and without the application of light-curing glaze on the surface, and to evaluate the antibiofilm efficacy of 0.12% chlorhexidine digluconate in these samples.For this, resin samples of Bis-Acryl(Protemp, 3M ESPE, Sao Paulo, Brazil) and chemically-activated acrylic resin (CAAR)(Dencor, Artigos Odontológicos Clássico LTDA, Sao Paulo, Brazil)were made. Half of these samples were submitted to chemical polishing with light-curing glaze. These samples were placed in intraoral devices, whichcontained 4 niches(1 CAARwithout glaze, 1 CAARwith glaze, 1 Bis-Acrylwithout glaze, 1 Bis-Acrylwith glaze), used by volunteers (n=20). The experimental pases were: Thevolunteersinitially used the device containing the samples from the control group for seven days, in which 30% sucrose were applied. Then, theyused the device containing the samples from the test group for anotherseven days, in which 0.12% chlorhexidine digluconate and 30% sucrose wereapplied. Next, the tests of color change, microhardness, roughness and surface energy, initially and after theexperimentais phases, of all samples, and the bio... (Complete abstract click electronic access below) / Mestre

Du fait de leurs nombreux avantages, à savoir notamment leur faible coût, leurs meilleures possibilités de recyclage et de réparation, leur légèreté et leur bonne tenue en fatigue, les résines polymères thermoplastiques sont de plus en plus employées dans l’industrie des matériaux composites. Cependant, du fait de leur nature chimique, leur réponse mécanique dépend de la température, et ce, même dans un intervalle éloigné de leur température de transition vitreuse. Cette dépendance se répercute, dans une proportion moindre mais qui reste significative, sur la réponse mécanique des composites à matrice thermoplastique. Du fait des distributions locales des contraintes dans ces derniers et des micro- et méso- structures qui les composent, cette dépendance peut aussi se répercuter sur le scénario d’endommagement de ces derniers. Or, des structures telles que des pales d’éolienne sont amenées à fonctionner dans une plage de température allant de -20°C à 60°C. Il devient donc nécessaire d’étudier l’impact de la température sur le comportement mécanique et sur le scénario d’endommagement des composites à matrice thermoplastique, pour permettre notamment de mieux prévoir l’évolution de l’endommagement en fatigue des pales d’éolienne, dans leur intervalle de température de service. En effet, les pales d’éolienne sont généralement dimensionnées via une approche normative, qui requiert soit des campagnes expérimentales conséquentes pour obtenir le comportement en fatigue de tous les stratifiés constituant une structure telle qu’une pale d’éolienne soit la formulation d’hypothèses fortement conservatives, qui nuisent à l’optimisation de la conception des pales. Pour pallier à cela, un modèle d’endommagement permettant de décrire l’évolution de la résistance, de la rigidité et de la déformation résiduelle d’un pli unidirectionnel soumis à des chargements quasi-statiques ou de fatigue a été récemment développé. Les travaux présentés ici visent dans un premier temps à valider l’utilisation de ce modèle dans le cas d’un composite à matrice acrylique renforcé de fibres de verre, utilisé pour la fabrication de certaines pales d’éolienne. L’identification et la validation s’appuient à la fois sur des essais mécaniques en quasi-statique, en fatigue (traction/traction, traction/compression) sur plusieurs strates et sur des analyses physiques (micrographies sous charge, micro-tomographie à rayons X). Il s’agit ensuite d’analyser comment l’effet de la température sur le comportement mécanique et le scénario d’endommagement de ce composite se répercute sur les paramètres du modèle. / Thermoplastic polymer resins offer numerous benefits, such as their low cost, their better recycling and repair opportunities, their lightness and their long fatigue lifetime. This is why they are increasingly used in the composite material industry. However, due to their chemical nature, their mechanical response exhibits a temperature dependency even if the service temperature range is much lower than their glass transition temperature. This dependency has a knock-on effect, in a lower proportion but still significant, on the mechanical response of thermoplastic matrix composites. Due to the composite local stress distributions and their micro- and meso- structures, this dependency can also have a knock-on effect on their damage scenario. But structures such as wind turbine blades are brought to operate in a temperature range from -20 to 60°C. It is then necessary to study the temperature effect on the mechanical behavior and the damage scenario of thermoplastic matrix composites, to allow a better prediction of the fatigue damage evolution of wind turbine blades, in their temperature service range. Indeed, wind turbine blades are generally designed using a normative approach, which requires either consequent experimental campaigns in order to get the fatigue behavior of all the laminate composites in a structure such as a wind turbine blade, or the formulation of strongly conservative hypothesis, which affects the optimization of wind turbines blades design. To compensate this, a damage model allowing describing the strength, the stiffness and the residual strain of a unidirectional ply under quasi-static and fatigue loadings has been recently developed. The work presented here aim to validate the use of this model for a composite with an acrylic matrix reinforced with glass fibers, used for the manufacturing of some wind turbine blades in the first instance. The parameter identification and the validation rely simultaneously on mechanical tests under tensile and fatigue (tensile-tensile and tensile-compressive) loads on several layering and on physical analysis (microscope images under load, X-ray microtomography). Then, it is question to study how the temperature effect on the composite mechanical behavior and damage scenario affects the model parameters.

Doctor of Philosophy / The kinetics of electrosterically stabilized emulsion systems was studied. The aim of this was to understand the impact that steric and electrosteric stabilizers have on the kinetics of particle growth and particle formation in the area of emulsion polymerization. The well-established mechanisms that govern these processes for emulsions stabilized by conventional low molecular weight surfactants were used as a reference point for comparative purposes. Model latexes were synthesized that comprised of a poly(styrene) core stabilized by a corona of poly(acrylic acid). The advent of successful controlled radical polymerization techniques in heterogeneous media (via RAFT polymerization) allowed for latexes to be synthesized under molecular weight control. For the first time, the degree of polymerization of the stabilizing block on the particle surface was able to be controlled and verified experimentally using mass spectrometry techniques. Three latexes were made with different average degrees of polymerization of the stabilizing block; five, ten and twenty monomer units respectively. A methodology was developed to remove the RAFT functionality from the polymer chains present in the emulsion while retaining the desired particle morphology. Oxidation with tertbutylhydroperoxide (TBHP) was proven to be successful at eliminating the living character provided by the thiocarbonyl end-group. Extensive dialysis and cleaning of the latex was performed to ensure no residual TBHP or reaction by-products remained. Latexes with poly(styrene) cores were chosen for this work as poly(n-butyl acrylate) latexes were shown to be influenced by chain transfer to polymer, providing an additional kinetic complication. The three electrosterically stabilized emulsions were used as seed latexes in carefully designed kinetic experiments to measure the rate of polymerization as a function of time. Two independent techniques (chemically initiated dilatometry and γ-relaxation dilatometry) were used to measure the rate coefficients of radical entry (ρ) and exit (k) in these systems – the two parameters that essentially govern the rate of particle growth. The latexes were chosen such that they satisfied ‘zero-one’ conditions (i.e. that any given latex particle contains at most one growing radical at any given time) in order to simplify data analysis. Three different chemical initiators were used, each yielding a radical with a different electric charge. Results from γ-relaxation experiments demonstrated that the three electrosterically stabilized latexes gave very long relaxation times when removed from the radiation source, ultimately yielding very small k values. These values were up to a factor of 10 smaller than that predicted by the ‘transfer-diffusion’ model for exit for particles of that size. This reduction was attributed to a ‘restricted diffusion’ effect, where the exiting monomeric radical has to diffuse through a dense layer of polymer on the particle surface, where its mobility will be restricted. Modification of the Smoluchowski equation for diffusion-controlled adsorption/desorption to account for this postulate led to the development of a model that gave excellent semi-quantitative agreement with experiment. Chemically initiated dilatometric experiments (using three different types of initiator) gave the unusual result of very low reaction rates and low steady-state values of 'nbar', the average number of radicals per particle. Using the standard kinetic equations for styrene-based systems (where it is assumed that an exited monomeric radical undergoes re-entry), this led to the calculation of impossibly small values of the entry rate coefficient ρ (far below any background or ‘thermal’polymerization rate). However upon removing the assumption of re-entry and assuming that exited radicals undergo termination, the obtained values of ρ were in almost perfect agreement with the values predicted from the ‘control by aqueous phase growth’ entry mechanism. This unexpected result was attributed to chemical reaction with the poly(acrylic acid) stabilizers through chain transfer to polymer (via hydrogen-atom abstraction). This postulate was verified by separate experiments that demonstrated that poly(acrylic acid) could act as a reasonably efficient chain transfer agent for styrene polymerization. The addition of poly(acrylic acid) to the aqueous phase of a conventionally stabilized emulsion also led to the rate reduction seen previously. NMR experiments demonstrated the existence of poly(acrylic acid-graft-styrene), which could only be formed through termination of a poly(styrene) chain with a poly(acrylic acid) chain bearing a mid-chain radical (as the product of a chain transfer reaction). These additional terms of transfer and termination were included in the governing kinetic equations of emulsion systems (the Smith-Ewart equations) to develop a model to account for the behaviour of electrosterically stabilized latexes. The ultimate fate of an exiting radical was now shown to be a competition between fates; successful desorption into the aqueous phase, or chemical reaction (through transfer or termination) within the hairy layer. These additional terms were shown to significantly reduce the theoretical value of nbar, and were in excellent agreement with experiment. For small electrosterically stabilized particles with a densely packed ‘hairy layer,’ it was seen that transfer/termination is the dominant loss mechanism as opposed to desorption. The developed model showed that as the particle size was increased, the dominant loss mechanism once again became successful desorption into the aqueous phase. The model was shown to give excellent agreement with experimental data from ‘uncontrolled’ emulsion systems. To explain the highly unusual secondary nucleation behaviour seen in systems such as these, it was postulated that beta-scission of a poly(acrylic acid) chain bearing a mid-chain radical is an important mechanistic step in the nucleation mechanisms of these systems. Modelling (both steady-state and time-dependent) gave good agreement with experiment with a minimal number of adjustable parameters. Theory (and supporting experimental evidence) demonstrated that this nucleation mechanism is only significant at high particle numbers; under other conditions the well-known ‘homogeneous nucleation’ mechanism is once again dominant.

Poly(acrylic acid) (PAA) was grafted onto both termini of Pluronic F87 (PEO₆₇-PPO₃₉-PEO₆₇) via atom transfer radical polymerization to produce a novel muco-adhesive block copolymer PAA₈₀-b-F₈₇-b-PAA₈₀. It was observed that PAA₈₀-F₈₇-PAA₈₀ forms stable complexes with weakly basic anti-cancer drug, Doxorubicin. Thermodynamic changes due to the drug binding to the copolymer were assessed at different pH by isothermal titration calorimetry (ITC). The formation of the polymer/drug complexes was studied by turbidimetric titration and dynamic light scattering. Doxorubicin and PAA-b-F87-b-PAA block copolymer are found to interact strongly in aqueous solution via non-covalent interactions over a wide pH range. At pH>4.35, drug binding is due to electrostatic interactions. Hydrogen-bond also plays a role in the stabilization of the PAA₈₀-F₈₇-PAA₈₀/DOX complex. At pH 7.4 (α=0.8), the size and stability of polymer/drug complex depend strongly on the doxorubicin concentration. When CDOX <0.13mM, the PAA₈₀-F₈₇-PAA₈₀ copolymer forms stable inter-chain complexes with DOX (110 ~ 150 nm). When CDOX >0.13mM, as suggested by the light scattering result, the reorganization of the polymer/drug complex is believed to occur. With further addition of DOX (CDOX >0.34mM), sharp increase in the turbidity indicates the formation of large aggregates, followed by phase separation. The onset of a sharp enthalpy increase corresponds to the formation of a stoichiometric complex. / Singapore-MIT Alliance (SMA)

BACKGROUND: There is an increased need to replace materials derived from fossil sources by renewables. Sugar-cane derived carbohydrates are very abundant in Brazil and are the cheapest sugars available in the market, with more than 400 million tons of sugarcane processed in the year 2007. The objective of this work was to study the preparation of sugar acrylates from free sugars and free acrylic acid, thus avoiding the previous preparation of protected sugar derivatives, such as glycosides, or activated acrylates, such as vinyl acrylate. RESULTS: Lipase catalyzed esterification of three mono- and two disaccharides with acrylic acid, in the presence or absence of molecular sieves was investigated. The reactions were monitored by high-performance liquid chromatography (HPLC) and the products were analyzed by matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry. The main products are mono- and diacrylates, while higher esters are formed as minor products. The highest conversion to sugar acrylates was observed for the D-glucose and D-fructose, followed by D-xylose and D-maltose. Molecular sieves had no pronounced effect on the conversion CONCLUSIONS: A feasible method is described to produce and to characterize sugar acrylates, including those containing more than two acrylate groups. The process for production of these higher esters could potentially be optimized further to produce molecules for cross-linking in acrylate polymerization and other applications. The direct enzymatic esterification of free carbohydrates with acrylic acid is unprecedented.

SELF/PORTRAIT is an exploration of the creative process. Based in the genre of portraiture, this collection of work seeks to reveal the ways in which the artist's relationships and circumstances have factored into the creation of the resulting exhibition. This exploration involves the assessment of abandoned projects with the aim of gaining a greater understanding of their qualities that have served to motivate the creation of his art, and those that have hindered his artistic process. This thesis exhibition and support paper use an autobiographical approach to seek the elements of the artist's perception of art which have influenced the production of the work displayed, and how these are effected by the task of creating a Master's thesis exhibition. It explores the qualities of both Portraiture and Painting which have inspired and directed his endeavour. SELF/PORTRAIT seeks to display the artist's work as a process rather than a product.

Citrate-coated gadolinium trifluoride (Cit-GdF3) and poly(acrylic acid)-coated nanoparticles (PAA-GdF3 NPs) were synthesized, the former reproduced from literature (though using more refined conditions), the latter through a new, two-step, ligand exchange method. Diamagnetic nanoparticle analogs (Cit-YF3 NPs) were prepared to investigate citrate interactions with the nanoparticle surface using NMR. Citrate was found to bind in numerous conformations, with a total of between 29 – 46 % bound at 0 ºC. Exchange studies revealed short residence lifetimes of one and twelve seconds respectively for bound and free forms of citrate (0 ºC), perhaps explaining the colloidal instability of these nanoparticles. PAA-GdF3 NPs were synthesized by first producing their Cit-GdF3 counterparts, and then exchanging citrate for PAA. The impetus behind this latter synthesis was the relative enhancement in stability and relaxivity attainable by these nanoparticles. The displacement of citrate by PAA was verified using diffusion NMR studies.