Resumo: O objetivo deste trabalho, dividido em três estudos, foi avaliar: (1) a influência da utilização de diferentes fontes de luz e métodos de fotoativação sobre o grau de conversão e a contração de polimerização de uma resina composta nanoparticulada; (2) a influência da utilização dos diferentes métodos de fotoativacao, disponibilizados por aparelhos LED de 2a geração, sobre a contração volumétrica das resinas compostas microhíbrida e nanopartículada e (3) as propriedades térmicas e o grau de conversão das resinas compostas microhíbrida e nanopartículada, submetidas aos diferentes métodos de fotoativação disponibilizados por aparelhos LED de 2a geracao. No primeiro estudo, o grau de conversão (GC) foi avaliado pelo metodo da espectroscopia infravermelha transformada de Fourier (FT-IR) e as forças de contração (C) mensuradas em máquina de ensaios universal (EMIC). Os dados obtidos para o GC e C foram analísados estatísticamente pelo teste da análise de variancia (ANOVA), sendo que para as forças de contração, a correção de Welch e o teste Tamhane também foram empregados. No segundo estudo, a contração volumétrica foi avaliada por um mecanismo de vídeo e imagem (AcuvolR/Bisco) e os dados obtidos foram análisados estatísticamente pelos testes ANOVA e Tukey. No terceiro estudo, o método da calorimetria exploratória diferencial foi empregado para avaliar a temperatura de transição vitrea (Tg) e de degradação dos materiais e o GC por FTIR. Os dados relativos ao GC foram análisados estatísticamente pelos testes ANOVA e Tukey. Os resultados demonstraram diferenças na contração de polimerização de acordo com o método de fotoativação empregado. No primeiro e segundo estudos, mesmo empregando diferentes metodologias, o método de fotoativação contínuo apresentou os maiores valores de contração. Por outro lado,o GC não... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The aim of this work, divided into three studies, was evaluate: (1) the influence of different light sources and photo-activation methods on degree of conversion and polymerization shrinkage of a nanocomposite resin; (2) the influence of different photo-activation methods, available by the 2nd generation LED light-curing units, on the volumetric shrinkage of microhybrid and nanocomposite resins and (3) thermal properties and degree of conversion of microhybrid and nanocomposite resins submitted to different photo-activation methods available by 2nd generation LED light-curing units. In the first study, degree of conversion (DC) was evaluated by Fourier transform infrared spectroscopy (FT-IR) and shrinkage forces (S) were measured in a universal testing machine (EMIC). The data obtained for DC and S were analyzed by Analysis of Variance test (ANOVA) and for S Welch's correction and Tamhane's tests were also employed. In the second study, volumetric shrinkage was evaluated by video-imaging device (AcuvolR/Bisco) and data were analyzed by ANOVA and Tukey's test. In the third study, differential scanning calorimetry was used in order to observe glass transition temperature (Tg) and degradation peak of the materials and DC was evaluated for FT-IR. The DC data were analyzed by ANOVA and Tukey's test. The results showed differences in the polymerization shrinkage according to photo-activation method employed. In the first and second studies, the continuous photo-activation methods presented the highest values for shrinkage even though different methodologies were used to assess. Moreover, DC was not influenced by the photo-activation method but was influenced by light sources. The lowest DC values were observed for halogen light-curing unit. In the second study beyond the influence of the photo-activation... (Complete abstract click electronic access below) / Orientador: Marcelo Ferrarezi de Andrade / Coorientador: Alessandra Nara de Souza Rastelli / Banca: Silmara Aparecida Milori Corona / Banca: Denise Pedrini / Banca: Osmir Batista de Oliveira Junior / Banca: José Roberto Cury Saad / Doutor

Orientadores: Cecília Amélia de Carvalho Zavaglia, Ana Beatriz Albino Almeida / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-18T02:56:18Z (GMT). No. of bitstreams: 1 Feliciano_DanielleFerreira_M.pdf: 2215803 bytes, checksum: 78c936869613a6b313b028d4e7b84078 (MD5) Previous issue date: 2011 / Resumo: Defeitos, doenças e acidentes que acometem a cartilagem articular para suportar às constantes solicitações mecânicas que estas regiões estão sujeitas, sendo indicada a utilização de estruturas viscoelástica resistente alto grau de atrito para preencher tais defeitos. Desta forma, foi selecionado o uso de hidrogéis para esta aplicação específica. Hidrogéis a base de poli(álcool vinilico) (PVAl) e polietileno glicol (PEG) apresentam propriedades mais adequadas, como biocompatibilidade, não estimulando reação imunológica ao organismo; baixa adesão de células sanguíneas, evitando coágulos; capacidade de absorção de água (intumecimento), proporcionando lubrificação do material e alto grau de transparência. O processo para obtenção desta blenda e formação de hidrogel foi realizado utilizando uma proporção de 1:9 (PEG:PVAl). O iniciador 2- hidroxi-4'-(2-hidroxietoxi)-2-metilpropiofenona foi adicionado à blenda, em 1% do volume total. È este iniciador, quando estimulado via temperatura, laser ou infravermelho, que irá desencadear as ligações intermacromoleculares de PEG-PVAl permitindo a formação de uma organização grafitizada da blenda dentro do hidrogel. Foi acompanhada a cinética de formação deste hidrogel através de reometria de placas, Espectroscopia de Infravermelho por Transformada de Fourier (FTIR) e Calorimetria Diferencial de Varredura (DSC). As amostras também foram devidamente caracterizadas quanto à condutividade térmica, densidade e absorção óptica. Observou-se que o iniciador ativou as ligações do grupo acetato do PVAl com as hidroxilas do PEG, resultando em formação de grupos ester. São estas ligações que caracterizam a formação do hidrogel grafitizado. Além disso, ocorreu a inversão do módulo viscoso em relação ao módulo de elasticidade, comprovando a reação de grafitização / Abstract: Defects, diseases and accidents that affect the articular cartilage can withstand constant mechanical stresses that they are subject, which indicated the use of viscoelastic structures resistant to high friction to fill these defects. In this way, the use was selected of hydrogels for this application it specifies. To base of I polished hydrogels polyvinyl alcohol (PVA) and polyethylene glycol (PEG) present more appropriate properties, biocompatibility, not stimulating reaction immunologically to the organism; low adhesion of blood cells, avoiding clots; capacity of absorption of water (swelling), providing lubrication of the material and high degree of transparency. The process for getting this blend and formation of hydrogel was carried out using a proportion of 1:9 (PEG:PVA). The initiator hidroxi 2-hidroxi-4 '-(2-hidroxietoxi)-2- metilpropiofenona was added to the blend, in 1 % of the total volume. This initiator, when stimulated he was seeing temperature, laser or infrared, what will be going to unleash the connections intermacromoleculares of PEG-PVA allowing the formation of an grafiting organization of the blend inside the hydrogel. There was accompanied the kinetic one of formation of this hydrogel through parallel plates rheometry, Fourier transform infrared spectroscopy (FTIR) and Differential scanning calorimetry (DSC). The samples also were characterized property as for the thermal condutivity, density and optical absorption. It noticed to itself that the initiator activated the connections of the group acetate of the PVA with the hydroxyl group of PEG, when ester is turning in formation of groups. It is these connections that characterize the formation of the hydrogel grafiting. Besides, it took place to inversion of the viscous module regarding the module of elasticity, proving the reaction of grafiting / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Orientadores: Giselle Maria Marchi Baron, Flavio Henrique Baggio de Aguiar, William Michael Johnston / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-15T10:15:56Z (GMT). No. of bitstreams: 1 Santos-Daroz_ClaudiaBatituccidos_D.pdf: 5048631 bytes, checksum: 73770753e4e1725beb03729a21bf12c9 (MD5) Previous issue date: 2009 / Resumo: O objetivo deste estudo foi avaliar o efeito da fonte de luz (FL) e tempo de fotoativação sobre a pigmentação, grau de conversão (GC), microdureza (KHN) e rugosidade de superfície (Ra) de diferentes tipos de resinas compostas. Espécimes (2,0 mm de altura e 5,0 mm de diâmetro) foram confeccionados a partir de diferentes tipos de resinas compostas (RC) [Nanoparticuladas: Filtek Supreme Plus A2D and Filtek Supreme XT A2E (3M ESPE); Microparticulada: Durafill A2 (Heraeus Kulzer); Microhíbridas: Filtek Z250 A2 (3M ESPE) e Venus A2 (Heraeus Kulzer)], utilizando-se dois tipos de fontes de luz, halógena (Optilux 501 - Demetron) e LED (Elipar FreeLight 2 - 3M ESPE) e com diferentes tempos de fotoativação (metade do tempo, dobro do tempo e tempo recomendado pelo fabricante). Após 24h, realizou-se acabamento e polimento. GC e cor inicial foram averiguados nas superfícies de topo (T) e base (B). Posteriormente, os espécimes foram armazenados em vinho tinto. Avaliação da alteração da cor (Sistema CIE L*a*b*) foi determinada após 1, 2, 7, 14, 20 e 30 dias no vinho. KHN e Ra foram determinados nas superfícies de topo e base antes e após armazenagem em vinho por 30 dias. Todos os fatores estudados foram estatisticamente significantes (ANOVA / Stepdown Bonferroni / Bonferroni Correction), havendo interações quádrupla (Resina X Luz X Superfície X Dias; p = 0,042) na avaliação da alteração de cor; e triplas, para GC (Luz X Resina X Tempo; p = 0,05; Luz X Resina X Superfície; p = 0,02), KHN (Luz X Resina X Superfície; p = 0,05; Luz X Resina X Vinho; p < 0,0001; Resina X Tempo X Superfície; p = 0,008) e Ra (Luz X Resina X Superfície; p = 0,045; Luz X Tempo X Vinho; p = 0,0008; Resina X Tempo X Superfície; p < 0,0001; Resina X Tempo X Vinho; p = 0,047; Resina X Vinho X Superfície; p = 0,022). A pigmentação da superfície de base foi significantemente maior que da superfície de topo para todos os tipos de RC e FL. A polimerização pelo dobro do tempo reduziu a pigmentação da base de dois tipos de RC. Observou-se diferença significante no GC entre T e B e a dureza do T foi maior que da B. Após armazenamento no vinho, houve diminuição da dureza do T. Não se observou diferença significante no Ra entre T e B; no entanto, após estocagem em vinho, o Ra da base da RC microparticulada foi significantemente aumentado, independentemente do tempo de fotoativação e FL utilizada. A fotopolimerização pelo dobro do tempo recomendado parece influenciar no grau de pigmentação da base de alguns materiais resinosos, porém, não foi capaz de manter a dureza da superfície de topo após armazenagem no vinho. Diferenças entre as FL depende do tipo de resina composta e tempo de fotoativação utilizado / Abstract: The objective of the present study was to evaluate the effect of LCU and light curing time on the discoloration, degree of conversion (DC), microhardness (KHN) and surface roughness (Ra) of different types of composite resins. Specimens (2.0 mm of height; 5.0 mm of diameter) were fabricated from different types of composite resins (CR) [Nanofilled: Filtek Supreme Plus A2D and Filtek Supreme XT A2E (3M ESPE); Microfilled: Durafill A2 (Heraeus Kulzer); Microhybrid: Filtek Z250 A2 (3M ESPE) and Venus A2 (Heraeus Kulzer)], using two types of LCUs; halogen (Optilux 501 - Demetron) and LED (Elipar FreeLight 2 - 3M ESPE) with different light curing times (half of-, double of- and the time recommended by the manufacturer). After 24h, specimens were finished and polished. DC and the initial color were evaluated at both the top (T) and bottom (B) surfaces. Further, the specimens were stored in red wine. The color change (CIE L*a*b* System) was established after 1, 2, 7, 14, 20 e 30 days in the wine. KHN and Ra were evaluated at both the top and the bottom surfaces before and after the storage in the wine for 30 days. All factors studied were a statistically significant factor (ANOVA / Stepdown Bonferroni / Bonferroni Correction), with quadruple interaction (Resin X Light X Surface X Days; p = 0.042) for the color change evaluation; and triple interaction for DC (Light X Resin X Time; p = 0.05; Light X Resin X Surface; p = 0.02), KHN (Light X Resin X Surface; p = 0.05; Light X Resin X Wine; p < 0.0001; Resin X Time X Surface; p = 0.008) and Ra (Light X Resin X Surface; p = 0.045; Light X Time X Wine; p = 0.0008; Resin X Time X Surface; p < 0.0001; Resin X Time X Wine; p = 0.047; Resin X Wine X Surface; p = 0.022). The discoloration of the bottom surface was significantly higher than the top surface for all types of CR and LCU. The light curing for double of the recommended time reduced the discoloration from the bottom surface of two types of CRs. Significant difference was observed between the DC of the T and B; and the hardness of T was higher than B. After the wine storage, the hardness of T was diminished. No significant difference in Ra between T and B was observed; however, after the storage in the wine, the Ra from the bottom surface of the microfilled composite was significantly higher, regardless the light curing time and LCU used. The lightcuring for double of the recommended time seems to influence on the degree of color change of the bottom surface of some composite materials, however, it was not capable to keep the hardness of the top surface after storage in the wine. The differences between the LCUs are dependent on the type of composite resin and light curing time used / Doutorado / Dentística / Doutor em Clínica Odontológica

Orientador: Regina Maria Puppin-Rontani / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-19T23:12:12Z (GMT). No. of bitstreams: 1 Inagaki_LucianaTiemi_M.pdf: 1637103 bytes, checksum: be2b43c0e245a141e813657feff8bca9 (MD5) Previous issue date: 2012 / Resumo: Esta dissertação foi dividida em dois capítulos: Capítulo 1 avaliou a atividade antimicrobiana de misturas não polimerizadas e polimerizadas por meio da mensuração da zona de inibição após difusão em ágar (Pour Plate); e determinou a Concentração Inibitória Mínima (CIM) e Concentração Mínima Bactericida (CMB) de misturas resinosas experimentais. Os ensaios microbiológicos foram realizados em triplicata, sendo o digluconato de clorexidina 0,12% utilizado como referência (antibacteriano padrão) e o infiltrante Icon® (DMG) utilizado como controle comercial. Cepas de Streptococus mutans UA159 e Lactobacillus acidophilus LYO50DCU-S foram utilizadas em todos os testes. Capítulo 2 determinou o grau de conversão e a dureza Knoop das misturas experimentais tendo como controle comercial o infiltrante Icon®. As misturas utilizadas nos ensaios experimentais foram: TEGDMA, TEGDMA/CHX 0,1%, TEGDMA/CHX 0,2%, TEGDMA/UDMA, TEGDMA/UDMA/CHX 0,1%, TEGDMA/UDMA/CHX 0,2%, TEGDMA/BisEMA, TEGDMA/BisEMA/CHX 0,1% e TEGDMA/BisEMA/CHX 0,2%. Os testes estatísticos utilizados nos ensaios de ambos os estudos foram ANOVA um critério seguido por teste de Tukey, e teste-t para comparação entre os grupos (p<0,05). O CIM e CMB mostraram que as misturas demonstraram ter atividade antibacteriana com baixas concentrações de CHX para as duas cepas bacterianas testadas. Antes da polimerização, a atividade antibacteriana da maioria das misturas foi maior que o Icon®. Para S. mutans, as misturas TEGDMA/BisEMA/CHX 0,1% e TEGDMA/BisEMA/CHX 0,2%, a concentração de CHX foi fator relevante para aumentar a zona de inibição. Após a polimerização, a mistura TEGDMA/UDMA/CHX 0,1% mostrou maior zona de inibição para S. mutans. Para o L. acidophilus, a atividade antibacteriana antes da polimerização foi maior para TEGDMA/CHX 0,2% e TEGDMA/UDMA/CHX 0,1%, independente da concentração de CHX. Após a polimerização, todas as misturas experimentais e Icon® não apresentaram atividade antibacteriana. Quando as zonas de inibição das misturas polimerizadas e não polimerizadas foram comparadas, a maioria das misturas não polimerizadas apresentaram maior efeito antibacteriano para as duas cepas. A adição de CHX não reduziu o DC das misturas; contudo, para as misturas a base de TEGDMA, o CHX influenciou positivamente e causou o aumento do DC. As misturas TEGDMA/UDMA, TEGDMA/UDMA/CHX 0,1% e TEGDMA/UDMA/CHX 0,2% apresentaram os maiores valores de DC e as misturas TEGDMA/BisEMA, TEGDMA/BisEMA/CHX 0,1% e TEGDMA/BisEMA/CHX 0,2% os menores valores de DC. Todas as misturas apresentaram valores de DC menores que o Icon®. Em relação à microdureza, TEGDMA/UDMA e TEGDMA/UDMA/CHX 0,2% apresentaram os maiores valores de dureza Knoop. A adição de CHX não afetou a dureza de superfície das misturas experimentais. Quando comparadas ao Icon®, todas as misturas apresentaram maior dureza Knoop. Assim, dentre as misturas avaliadas, a mistura TEGDMA/UDMA/CHX 0,1% apresentou os melhores resultados para o DC e para a atividade antibacteriana após polimerização / Abstract: This dissertation was divided into two chapters: Chapter 1 aimed to evaluate the antimicrobial activity of cured and uncured resin blends though measurement of inhibition zone using agar diffusion (Pour Plate), Minimal Inhibiting Concentration (MIC) and Minimum Bactericidal Concentration (MBC). For microbiological assays, that were performed in triplicate, the 0.12% chlorhexidine digluconate solution was used as reference standard antimicrobial and infiltrant Icon® (DMG) was used as commercial control group. Streptococcus mutans UA159 and Lactobacillus acidophilus LYO50DCU-S strains were selected for all assays. Chapter 2 aimed to determine DC and Knoop hardness of mixtures having Icon® as commercial control group. Mixtures were set as follow: TEGDMA, TEGDMA/0.1% CHX, TEGDMA/0.2% CHX, TEGDMA/UDMA, TEGDMA/UDMA/0.1% CHX, TEGDMA/UDMA/0.2% CHX, TEGDMA/BisEMA, TEGDMA/BisEMA/0.1% CHX and TEGDMA/BisEMA/0.2% CHX. Data obtained from all mixtures and Icon® were submitted to one-way ANOVA, followed by Tukey test, and in order to compare the groups t-test was used (p<0.05). The MIC and MBC tests showed that the mixtures demonstrated antibacterial activity in low concentrations of CHX against both of strains. Analyzing antibacterial activity against S. mutans before light curing process, the most of blends provided larger inhibition zones than Icon®, and for TEGDMA/BisEMA/0.1% CHX and TEGDMA/BisEMA/0.2% CHX the CHX concentration was significant factor to increase the inhibition zones. After light curing, the mixture TEGDMA/UDMA/0.1% CHX showed the highest inhibition zone against S. mutans. Analyzing antibacterial activity against L. acidophilus before light curing, the addition of CHX to the blends, regardless concentration, provided inhibition zones and TEGDMA/0.2% CHX and TEGDMA/UDMA/0.1% CHX showed the highest antibacterial effects. After light curing, no significant difference between all experimental blends, including Icon®, was observed. When the inhibition zones of uncured and cured blends were compared, the major of uncured blends demonstrate grater antimicrobial activity to both strains. The addition of CHX didn't reduce the DC of experimental infiltrants blends, but CHX had positive influence for TEGDMA neat monomer, increasing DC. TEGDMA/UDMA, TEGDMA/UDMA/0.1% CHX and TEGDMA/UDMA/0.2% CHX showed the highest DC than other mixtures, while TEGDMA/BisEMA, TEGDMA/BisEMA/0.1% CHX and TEGDMA/BisEMA/0.2% CHX the lowest DC. All mixtures showed significant lower values of DC than commercial infiltrant. Concerning hardness, TEGDMA/UDMA and TEGDMA/UDMA/0.2% CHX showed the highest Knoop hardness values. The addition of CHX didn't change surface hardness of mixtures. When Knoop hardness values of nine mixtures were compared with Icon®, all mixtures showed significant higher values than commercial infiltrant. Thus, among the experimental resin mixtures evaluated, TEGDMA/UDMA/0.1% CHX showed the best results to DC and to antimicrobial effect after polymerization / Mestrado / Odontopediatria / Mestre em Odontologia

This thesis focuses on the utilisation of mid-infrared techniques in technological atmospheric pressure, non-thermal plasma (NTP) diagnostics. Two mid-infrared techniques were demonstrated in this work namely laser absorption and Fourier transform infrared (FTIR) spectroscopy. The performance of external-cavity quantum cascade laser (EC-QCL), a relatively new laser type with broad tuning capability was also demonstrated as potential diagnostics tool for technological NTP applications. A dual plate dielectric barrier discharge (DBD) and a packed-bed NTP reactor were designed and fabricated to perform plasma process. Quantitative analysis of the laser absorption and FTIR spectroscopy techniques for gas detection were validated by using standard gas samples. Real-time CO monitoring by means of in-situ laser absorption spectroscopy measurements were performed for gas phase diagnostics in the decomposition of TEOS by means of plasma-enhanced chemical vapour deposition (PE-CVD) and in CO2 reforming of CH4 by means of NTP. In-line FTIR measurements simultaneously recorded the gas spectrum at the exhaust of the plasma reactors. Information from both measurements was found to provide useful information on the plasma processes and chemistry for the NTP applications. Finally, wavelength stability and linearity performance of a broad tuning range EC-QCL were evaluated by using the Allan variance technique. (LOD) at SNR = 1 was estimated to be ~ 2 ppm, achieved under atmospheric pressure, at the room temperature, and a path length of 41 cm for NO detection produced from the decomposition of dichloromethane (DCM) by means of NTP.

Introduction: Dupuytren's disease (DD) is an ill-defined fibroproliferative disorder affecting the palms of the hands of certain patient groups. Whether changes in DD fibroblasts are due to genetic alterations alone or related to metabolic dysregulation has not yet been investigated. Hypotheses: 1. DD is a disease of several networks rather than of a single gene. 2. DD may be investigated more effectively by employing systems biology. 3. Strict definition of cell passage number is important for the revelation of any DD phenotype. 4. Some of the differences between DD and healthy tissues reside in a difference in their respiratory metabolism. 5. Any such differences are akin the Warburg effect noted for tumour cells in the literature. Methods: We induced hypoxia in healthy and disease cells to test whether the difference in disease cell types and healthy is the same as the difference in control fibroblasts cultured in normoxia and hypoxia. We investigated both at the metabolic level (intracellular and extracellular) and at the transcript level. This study also employed Fourier transform infrared spectroscopy to permit profiling of cells: (1) DD cords and nodules against the unaffected transverse palmar fascia (internal control), (2) those (1) with carpal ligamentous fascia (external controls) (3) those in (1) against DD fat surrounding the nodule, and skin overlying the nodule. We then compared metabolic profiles of the above to determine the effect of serial passaging by assessment of reproducibility. Subsequently, a novel protocol was employed in carefully controlled culture conditions for the parallel extraction of the metabolome and transcriptome of DD-derived fibroblasts and control at normoxic and hypoxic conditions to investigate this hypothesis. Gas chromatography-mass spectrometry combined with microarrays was employed to identify metabolites and transcript characteristic for DD tissue phenotypes. The extracellular metabolome was also studied for a selected subset. The metabolic and transcriptional changes were then integrated employing a network approach. Results: Carefully controlled culture conditions combined with multivariate statistical analyses demonstrated metabolic differences in DD and unaffected transverse palmar fascia, in addition to the external control. Differences between profiles of the four DD tissue phenotypes were also demonstrated. In addition early passage (0-3) metabolic differences were observed where a clear separation pattern in clusters was observed. Subsequent passages (4-6) displayed asynchrony, losing distinction between diseased and non-diseased sample phenotypes. A substantial number of dysregulated metabolites involved in amino acid metabolism, carbohydrate metabolism and also metabolism of cofactors and vitamins including downregulated cysteine and aspartic acid have been identified from the integrative analyses. Metabolic and transcriptional differences were revealed between fibroblast cell samples (passage number 3) cultured in 1% and 21% oxygen. The hypothesis that the difference in disease and healthy cells maybe akin to the differences in healthy cells in normoxia and hypoxia was rejected as only a very small number of significant molecules from these studies coincided in perturbed fascia and disease samples. No lactic acid was observed and little difference in the pyruvate concentrations. Yet, upon perturbation several of these transcripts and metabolites involved in the afore-mentioned pathways were significantly dysregulated. Conclusion: Early, but not late, passage numbers of primary cells provide representative metabolic and transcript fingerprinting for investigating DD. A unique parallel analysis of transcript and metabolic profiles of DD fibroblasts and control, enabled a robust characterization of DD and correlation of parameters across the various levels of systemic description. The tools that should facilitate our understanding of these complex systems are immature, but the pleiotropy of the difference between healthy and DD tissue suggest the aetiology of a network-based disease.

Independent control of the surface and bulk properties is advantageous for many applications such as adhesives, release coatings, and antimicrobial films. Traditional methods for achieving independent control typically require multiple processing steps such as wet-on-wet or wet-on-dry coating methods. Independent control over the surface properties can achieved in a single step utilizing the temporal and spatial control inherent to photopolymerization. Specifically, a co-photopolymerization of monomers with different reactivities in the presence of a light gradient is capable of producing a polymer film with a surface chemistry that differs from the bulk chemistry. The light gradient, produced via the concentration of photoinitiator in the formulation, results in a reaction gradient through the film with the higher rates of reaction occurring in the high light intensity regions of the film. The preferentially reacting monomer adds at a greater rate in the high light intensity regions resulting in non-uniform consumption yielding a concentration gradient. Consequently, diffusion of the preferentially reacting monomer from the bulk to the surface of the film and a counter-diffusion of the other monomer from the surface to the bulk of the film occurs from the non-uniform monomer consumption thus producing a film with a concentration gradient through the depth of the film with the preferentially reacting monomer enriching the high light intensity regions. A variety of kinetic differences capable of producing a stratified film will be presented including inherent monomer reactivity, number of functional groups per monomer, oxygen inhibition, thiol-ene chemistry, and Norrish type two initiation. Additionally, parameters that control the degree of stratification, such as methods of varying polymerization rate and the light gradient, will be examined. Changes in surface properties (such as contact angle, surface hardness, adhesion) and bulk properties (such as mechanical properties measured by dynamic mechanical analysis and polymer swelling) are studied as a function of stratification. Finally, a mathematical model which describes and predicts the production of stratified films via photopolymerization is presented. Photopolymerization allows for a facile, single step method of generating stratified films with controllable surface chemistries.

The study aims to achieve an understanding of the artist’s materials and techniques used by Lucky Madlo Sibiya when he created his carved and painted wood panel artworks. A survey of the artist’s materials and techniques is of great importance, because he is represented in multiple institutional, corporate and private collections – including the University of Pretoria. His carved and painted wood panel artworks are also reaching an age (at least 20 years old, as 2019 is the twentieth anniversary of his death) when they would soon require conservation and restoration, if not stored and displayed according to sound conservation conditions and standards. For best-practice conservation and restoration, in-depth knowledge of the materiality of an artwork is needed. In order to reach an in-depth knowledge of the materiality of Sibiya’s carved and painted wood panel artworks, the survey intends to examine and document through the combination of various historical, visual and analytical techniques artworks with unrefuted provenance. The analytical techniques used are popular in heritage conservation, because they are non-invasive and non-destructive. They include provenance studies, visual examination, technical photography, X-ray Fluorescence and Fourier-transform Infrared Spectroscopy. In combination, the techniques should reveal the materials and techniques Sibiya employed. This knowledge will be used to safeguard and preserve this part of South African art heritage. / Mini Dissertation (MSocSci)--University of Pretoria, 2020. / Tangible Heritage Conservation / MSocSci (Tangible Heritage Conservation) / Unrestricted

Bismuth selenide belongs to a class of topological insulators---materials characterized by a intriguing electronic band structure, with a characteristic Dirac conical band on the surface. In this master thesis, the optical response of this material is explored in the infrared spectral range and in a broad range of magnetic fields. We mainly focus on the absorption of light due to free charge carriers having, when the magnetic field is applied, a form of cyclotron resonance. We find that the experimentally observed response is consistent with expectations for massive electrons in bulk rather than massless particles on the surface.

Cette thèse porte sur l’étude de la radio-sensibilité de Molécules AromatiquesHétérocycliques (MAH) à basse température exposées à une irradiation avec des ionslourds rapides. La présence de ces molécules dans les météorites carbonées sur Terre estune forte indication pour l’existence de cette catégorie de molécules dans l’espace.L’objectif de ce travail est de simuler l’effet des rayons cosmiques sur des MAH enphase solide et d’estimer leur résistance à l’irradiation. Les lignes de faisceaux deGANIL et de GSI permettent de simuler cet effet. L’évolution des MAH en phase solidea été monitorée par spectroscopie infrarouge à transformée de Fourier. Cela permet dequantifier la destruction des MAH, de déterminer leur section efficace de destruction etde détecter les molécules produites. Les sections efficaces de destruction de l’adénine etde la cytosine suivent une loi puissance en fonction du pouvoir d’arrêt électronique :σd~ Se1.2. Les nouvelles bandes d’absorption observées après l’irradiation des MAH sontprincipalement attribuées à des nitriles (R-C≡N), des isonitriles (R-N≡C) et (R-C≡C).L’évolution de la section efficace en fonction du pouvoir d’arrêt électronique a permisd’estimer la durée de vie de l’adénine dans l’espace : (14×106) années. Ces résultatspermettront de comprendre la stabilité et la chimie de ces molécules complexes dansl’espace. / The thesis concerns the study of the radio sensitivity of aromatic heterocyclic molecules(AHMs) at low temperature (12 K) exposed to swift heavy ion radiation. The presenceof aromatic heterocyclic molecules in carbonaceous meteorites on Earth is a strongindication that this class of molecules exists in outer space.The aim of this work was to study the effects of cosmic ray analogues on solid AHMsand to estimate their survival under radiation. The beam lines of GANIL and GSI allowto simulate the effects of cosmic rays in AHMs. The evolution of the solid AHMs underirradiation was monitored by Fourier transformed infrared absorption spectroscopy; thisallows to quantify the disappearance of AHMs, to determine their apparent destructioncross section and to detect their radioproducts. Furthermore, it was found that adenineand cytosine destruction cross sections (σd) follow a power law with the electronicenergy loss: σd~ Se1.2 .New IR absorption peaks arising from the AHMs degradationswere observed; these peaks can be attributed to nitriles (R-C≡N), isonitriles (R-N≡C),and (R-C≡C).The observed power law allowed the estimation of the lifetime of adeninein space exposed to galactic cosmic rays as (14×106) years. These findings may help tounderstand the stability and chemistry related to complex organic molecules in space.