The emergence of multidrug resistance is a serious medical problem that has significantly affected the treatment of tumor cells and infectious diseases. This multidrug resistance phenotype is mediated by the action of a large family of membrane proteins that act as active transporters or energy driven efflux pumps in both of prokaryotic and eukaryotic cells. Most eukaryotic multidrug efflux pumps belong to the ATP binding cassette (ABC) family of transport proteins that include P-glycoprotein (P-gp1), Multidrug Resistance Associated Protein (MRP1), and Breast Cancer Resistance Protein (BCRP). In prokaryotic cells, Lactococcus lactis LmrA, a homolog of P-gp1, mediates drug resistance to antibiotics and cytotoxic drugs. The transport function of these proteins is facilitated by the hydrolysis of ATP. However, the mechanism by which these proteins bind to, and are able to transport structurally dissimilar drugs across the cell membrane remains poorly understood. In this thesis we have attempted to characterize the interactions of various ABC transporters (MRP1, BCRP, and LmrA) with structurally diverse drugs, using a well characterized photoreactive drug analogue of Rhodamine 123, [125I] iodoaryl azido-rhodamine 123 (IAARh123). In the case of MRP1 interaction with Rhodamine 123, it was of interest to determine the nature of MRP1 drug interactions. In that study, our results show that CHAPS (1-[(3-cholamidopropyl) dimethylamino]-1-propansulfate) and Brij35 inhibited the photolabeling of MRP1 with IAARh123, and this interaction occurred outside the lipid bilayer. These results were unexpected in light of previous results with another ABC transporter which also binds to Rhodamine 123. Consequently, we show that non-toxic concentrations of CHAPS and Brij35 potentiate the toxicity of two MRP1 substrates, vincristine and etoposide (VP16). In the second chapter, we have used IAARh123 to demonstrate for the first time that the BCRP mediates drug resi

P-glycoprotein (Pgp), which leads to multidrug resistance in tumour cells, is an ATP-dependent secretory drug efflux pump. In the intestine, as well as at specific other epithelial and endothelial sites, P-glycoprotein expression is localised to the apical membrane, consistent with secretory detoxifying and absorption limitation functions. The primary function of Pgp is to clear the membrane lipid bilayer of lipophilic drugs. Results from in vitro studies with human Caco-2 cells provide direct evidence for Pgp limiting drug absorption. Limitation has non-linear dependence of absorption on substrate (eg. vinblastine) concentration, increased absorption upon saturation of secretion and increased absorption upon inhibition of Pgp function, with modulators such as verapamil. The aim of this study was to investigate the effect of a known Pgp inhibitor (verapamil) and grapefruit juice components (naringenin, quercetin and bergamottin) on the transport of Rhodamine 123 across rat jejunum and to compare these results with those obtained in similar studies done in Caco-2 cells and in rat intestine (monodirectional). Verapamil, naringenin (442 µM, 662 µM and 884 µM), quercetin (73 µM, 183 µM and 292 µM) and bergamottin (12 µM, 30 µM and 48 µM) were evaluated as modulators of rhodamine 123 transport across rat jejunum using Sweetana-Grass diffusion cells. This study was done bidirectionally, with three cells measuring transport in the apical to basolateral direction (AP / BL) and three cells measuring transport in the basolateral to apical direction (BL / AP). The rate of transport was expressed as the apparent permeability coefficient (Papp) and the extent of active transport was expressed by calculating the ratio of BL/AP to AP/BL. The BL-AP/AP-BL ratio calculated for Rhodamine 123 with no modulators added was 2.31. The known modulator verapamil decreased the BL-AP/AP-BL ratio to 1.52. This was statistically significant and inhibition of active transport was clearly demonstrated. All modulators inhibited active transport. Only naringenin 884 µM, quercetin 183 µM and bergamottin 30 µM did not show a statistically significant decrease in the BL-AP/AP-BL ratio. All three components of grapefruit juice showed inhibition of active transport and should have an effect on the bioavailability of the substrates of Pgp and other active transporters. The results obtained in this study are similar to the results found in Caco-2 cells, which suggests that Sweetana-Grass diffusion method can be used for diffusion studies. / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2005.

Many orally administered drugs must overcome several barriers before reaching their target site. The first major obstacle to cross is the intestinal epithelium. Although lipophilic compounds may readily diffuse across the apical plasma membrane, their subsequent passage across the basolateral membrane and into blood is by no means guaranteed. Efflux proteins located at the apical membrane, which include P-glycoprotein (P-gp, MDR1) and Multidrug Resistance-associated Protein (MRP2), may drive compounds from inside the cell back into the intestinal lumen, preventing their absorption into the blood. Intestinal P-gp is localised to the villus tip enterocytes, i.e. the main site of absorption for orally administered compounds and in close proximity to the lumen. P-gp is therefore ideally positioned to limit the absorption of compounds by driving efflux back into the lumen. Drugs may also be modified by intracellular phase I and phase II metabolizing enzymes. This process may not only render the drug ineffective, but it may also produce metabolites that are themselves substrates for P-gp and/or MRP2. Drugs that reach the blood are then passed to the liver, where they are subjected to further metabolism and biliary excretion, often by a similar system of ATP binding cassette (ABC) transporters and enzymes to that present in the intestine. Thus a synergistic relationship exists between intestinal drug metabolizing enzymes and apical efflux transporters, a partnership that proves to be a critical determinant of oral bioavailability. Aim: The aim of this study was to investigate the effect of selected methoxy flavonoids (3-methoxyflavone, 5-methoxyflavone, 6-methoxyflavone and 7- methoxyflavone) on the mean ratio of Rhodamine123 (Rho 123) transport across rat intestine (jejunum) and to investigate structure activity relationships (SAR) of the selected flavonoids with reference to inhibition of P-gp. Methods: 3-Methoxyflavone, 5- methoxyflavone, 6-methoxyflavone and 7-methoxyflavone were evaluated at a concentration of 10μM and 20μM as modulators of Rho 123 transport across rat jejunum. The Sweetana-Grass diffusion cells were used to determine the transport of Rho 123. Each modulator was studied bidirectionally with two cells measuring transport in the apical to basolateral direction (AP/BL) and two cells measuring transport in the basolateral to apical direction (BUAP). The rate of transport was expressed as the apparent permeability coefficient (Papp)and the extent of active transport was expressed by calculating the ratio of BUAP to AP/BL. Each modulators Papp ratio was then compared with that of the control. Results: 3-Methoxyflavone decreased the Papp ratio from 3.34 (control) to 1.66 (10μM) and 1.33 (20μM) and showed statistical significant differences. 7-Methoxyflavone decreased the Papp ratio to 1.94 (10μM) and 1.55 (20μM) but only showed a statistical significant difference at 10μM. 5- Methoxyflavone decreased the Papp ratio to 2.41 (10μM) and 1.71 (20μM) and 6- methoxyflavone decreased the Papp to 3.03 (10μM) and 2.49 (20μM). Both 5- and 6- methoxyflavone showed no statistical significant differences from the control. The structure activity relationships with reference to P-gp inhibition clearly indicated that the C3 and C7 positioning of the methoxy-group on the A ring played a major role in the inhibition of Rho 123 transport. Conclusion: All the selected modulators showed inhibition of Rho 123 transport across the jejunum. This should affect the bioavailability of the substrates of P-gp and other active transporters. In summary, this study describe the inhibitory interaction of selected flavonoids with P-gp. Structure activity relationships were identified describing the inhibitory potency of the flavonoids based on methoxy groups positioning. The inhibitory potency results were 3-methoxyflavone > 7- methoxyflavone > 5-methoxyflavone> 6-methoxyflavone / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2005.

Background: Multidrug resistance (MDR) is resistance of cancer cells to multiple classes of chemotherapeutic drugs that can be structurally unrelated. MDR involves altered membrane transport that results in a lower cell concentration of cytotoxic drugs which plays an important role during cancer treatment. P-glycoprotein (Pgp) is localised at the apical surface of epithelial cell in the intestine and it functions as a biological barrier by extruding toxic substances and xenobiotics out of cells (Lin, 2003:54). The ATP-binding-cassette superfamily is a rapidly growing group of membrane transport proteins and are involved in diverse physiological processes which include antigen presentation, drug efflux from cancer cells, bacterial nutrient uptake and cystic fibrosis (Germann, 1996:928; Kerr, 2002:47). A number of drugs have been identified which are able to reverse the effects of Pgp, multidrug resistance protein (MRPI) and their associated proteins on multidrug resistance. The first MDR modulators discovered and studied during clinical trials were associated with definite pharmacological actions, but the doses required to overcome MDR were associated with the occurrence of unacceptable side effects. As a consequence, more attention has been given to the development of modulators with proper potency, selectivity and pharmacokinetic characteristics that it can be used at a lower dose. Several novel MDR reversing agents (also known as chemosensitisers) are currently undergoing clinical evaluation for the treatment of resistant tumours (Teodori et al., 2002:385). Aim: The aim of this study was to investigate the effect of selected flavonoids (morin, galangin, kaempferol and quercetin) at two different concentrations (10 μM and 20 μM) on the transport of a known Pgp substrate, Rhodamine 123 (Rho 123) across rat intestine (jejunum) and to investigate structure activity relationships (SAR) of the selected flavonoids with reference to the inhibition of Pgp. Methods: Morin, galangin, kaempferol and quercetin were evaluated as potential modulators of Rho 123 transport, each at a concentration of 10 μM and 20 μM across rat jejunum using Sweetana-Grass diffusion cells. This study was done bidirectionally, with two cells measuring transport in the apical to basolateral direction (AP-BL) and two cells measuring transport in the basolateral to apical direction (BL-AP). The rate of transport was expressed as the apparent permeability coefficient (Pap,) and the extent of active transport was expressed by calculating the ratio of BL-AP to AP-BL. Results: The BL-AP to AP-BL ratio calculated for Rho 123 with no modulators added was 3.29. Morin decreased the BL-AP to AP-BL ratio to 1.88 at a concentration of 10 μM and to 1.49 at a concentration of 20 μM. Galangin decreased the BL-AP to AP-BL ratio to 1.60 at a concentration of 20 μM. These two flavonoids showed statistically significant results and inhibition of active transport were clearly demonstrated. However, the other flavonoids inhibited active transport of Rho 123 but according to statistical analysis, the results were not significantly different. The two different concentrations (10 μM and 20 μM) indicated that galangin, kaempferol and quercetin showed practically significant differences according to the effect sizes. Morin, however, did not show any practically significant differences at the different concentrations. Regarding .the SAR, it was shown by Boumendjel and co-workers (2002:512) that the presence of a 5-hydroxyl group and a 3-hydroxyl group as well as the C2-C3 double bond are required for high potency binding to the nucleotide binding domain (NBD) of Pgp. All the flavonoids tested had the above-mentioned characteristics. Conclusion: All the selected flavonoids showed inhibition of active transport of Rho 123 and should have an effect on the bioavailability of the substrates of Pgp and other active transporters. This study described the inhibitory interaction of selected flavonoids on Pgp activity. Practical significant differences between the same modulator at different concentrations were also observed. Structure activity relationships were identified describing the inhibitory potency of the flavonoids based on hydroxyl group positioning / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2005.

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-07-11T13:13:10Z No. of bitstreams: 1 JOÃO FERNANDES DUARTE NETO - DISSERTAÇÃO (PPGCEMat) 2015.pdf: 2295774 bytes, checksum: d73166400ea15685ca449c373a12dc20 (MD5) / Made available in DSpace on 2018-07-11T13:13:10Z (GMT). No. of bitstreams: 1 JOÃO FERNANDES DUARTE NETO - DISSERTAÇÃO (PPGCEMat) 2015.pdf: 2295774 bytes, checksum: d73166400ea15685ca449c373a12dc20 (MD5) Previous issue date: 2015-02-24 / Este trabalho investigou o processo de adsorção, equilibrio e cinética de argilas esmectíticas da cidade de Boa Vista (Paraíba), usadas como adsorventes de corantes com comportamentos químicos distintos - rodamina B (RB), catiônico, e alaranjado de metila (AL), aniônico - em meio aquoso. Essas argilas foram escolhidas devido às suas propriedades características do argilomineral esmectítico, que possui sítios quimicamente ativos, provocado pela substituição isomórfica e interação das arestas, tornando-o atrativo sua aplicação para fins adsortivos. As argilas utilizadas são conhecidas como bentonita chocolate e bentonita chocobofe. Esses materiais foram utilizados na forma natural e após tratamento com carbonato de sódio, ácido clorídrico e organofilização (sal quaternário de amônio PRAEPAGEN). Todos os adsorventes foram caracterizados por fluorescência de raios X, difração de raios X, análises térmicas (TG, DTG e DTA) e determinação de tamanho de partícula. Os ensaios de adsorção dos corantes foram examinados por sistema de bateladas, alterando tempo de contato, quantidade de adsorvente, concentração dos corantes e pH inicial. Para a análise do comportamento de adsorção foi utilizado espectrofotometria UV-VIS. O modelo de isoterma de Freundlich foi o que melhor se ajustou aos dados experimentais das argilas naturais e modificadas. Porém nos processos adsortivos envolvendo as argilas organofilizadas, na interação com RB, tanto o modelo de Langmuir como o de Freundlich apresentaram um bom ajuste aos dados experimentais. Os dados cinéticos de adsorção foram ajustados ao modelo de pseudo-segunda ordem (R2>0,9). Os testes de capacidades de adsorção permitiram concluir que a maior eficiência em remover a RB ocorre quando as argilas são tratadas com ácido clorídrico. A maior eficiência na remoção do AL ocorre quando as argilas estudadas foram as organofilizadas. De modo geral, as argilas esmectíticas estudadas se mostraram adsorventes adequados para a remoção do corante RB, sendo, no entanto, necessário tratamentos específicos para maximizar ou melhorar a capacidade de adsorção dos corantes RB e AL. / This study investigated the process of adsorption, equilibrium and kinetics, of smectite clays from Boa Vista of Paraíba used as chemical adsorbents of dyes with different ionic behavior in aqueous media. Smectite clays known as chocolate and chocobofe and the dyes Rhodamine B (RB) (cationic) and Methyl Orange (AL), (anionic) were used in this study. The adsorbents were characterized by X-ray fluorescence, X-ray diffraction, thermal analysis (TG, DTA and DTG) and determination of particle size. Clays have been used in natural form and after treatment with sodium carbonate, acid and organophilization (quaternary ammonium salt – PRAEPAGEN). The dye adsorption was examined by a batch system, changing: contact time, amount of adsorbent, dye concentration and initial pH. UVVIS spectrophotometry was used for the analysis of the adsorption behavior. The clays were characterized as smectite clays and the efficiency of the treatments was confirmed by X-ray fluorescence and X-ray diffraction. The model of Freundlich isotherm presented the best fit to the experimental data of natural clays. However, in the adsorptive processes involving clays organophilizated both the Langmuir model and the Freundlich model showed good fitting to the experimental data. The kinetic adsorption data were fitted to the model of pseudo-second order (R2> 0.9). The adsorption capacities test showed that the highest efficiency in removing RB occurs when the clays are treated with hydrochloric acid. The highest efficiency of the removal of AL occurs when the clays are organophilizated. In general, the smectite clays were suitable adsorbent for the removal of the dye RB. However, special treatment is necessary to maximize or improve the adsorption ability of the dyes AL and RB.

Made available in DSpace on 2014-06-11T19:24:37Z (GMT). No. of bitstreams: 0 Previous issue date: 2004-03-30Bitstream added on 2014-06-13T19:52:05Z : No. of bitstreams: 1 souza_em_me_arafo.pdf: 1650623 bytes, checksum: 97003cfd54c5042d5a5a6e21f97e5ffc (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Banca: Idomeo Bonetti Filho / Banca: Marco Antônio Húngaro Duarte / A proposta deste trabalho foi comparar os níveis de infiltração apical determinados pelos corantes azul de metileno a 2% e Rodamina B a 2% em canais radiculares obturados com cimentos endodônticos de diferentes composições químicas. Foi também determinada a capacidade seladora apical dos cimentos Endofill, Sealer 26, AH Plus, Sealapex, EndoREZ e um cimento experimental à base de polímero de mamona (Polifil) em cada solução corante. Foram utilizados 176 dentes unirradiculares extraídos de humanos que foram instrumentados com limas do Sistema K3 de conicidade 0,04mm/mm e obturados pela técnica da condensação lateral modificada utilizando-se um cone principal de conicidade 0,04mm/mm e dois cones auxiliares. As raízes foram divididas em grupos de acordo com o cimento obturador utilizado e estes novamente divididos em subgrupos de 14 dentes cada de acordo com a solução corante a ser utilizada como traçador da infiltração. Oito dentes foram utilizados como controle sendo 4 controles positivo e 4 controles negativo. As raízes foram impermeabilizadas em toda superfície radicular externa com exceção do forame apical e submetidas à infiltração nas duas soluções corantes, em um ambiente de vácuo por 24 horas. Foram mensuradas as infiltrações apicais por meio do programa ImageTool for Windows versão 3.0 e os resultados submetidos à análise estatística pelos testes ANOVA, t-Student e Newman-Kells. Verificou-se que os níveis de infiltração determinados pelas soluções corantes dependem de qual cimento é avaliado. A solução de azul de metileno a 2% determinou nos cimentos Endofill, Sealer 26 e Sealapex menores níveis de infiltração que os determinados pela Rodamina B nos mesmos cimentos, sugerindo uma incapacidade da solução de azul de metileno a 2% em revelar a totalidade da falha da obturação realizada com estes cimentos... . / The purpose of this study was to compare the levels of apical leakage determined by the 2% methylene blue and 2% Rhodamine B dyes in root canals filled with endodontic sealers of different chemical compositions. It was also determined the apical sealing ability of the sealers Endofill, Sealer 26, AH Plus, Sealapex, EndoREZ and an experimental sealer based on castor oil polymer (Polifil) in each dyeing solution. It was used 176 single root teeth extracted from humans that were instrumented with K3 system files taper .04 and filled by the modified lateral condensation technique using a main cone taper .04 and two auxiliary cones. The roots were divided in groups according to the filling sealers that were used and these ones were divided again in subgroups of 14 teeth each one according to the dyeing solution used as infiltration tracer. Eight teeth were used as control group, four positive controls and 4 negative controls. The roots were impermeabilized on all external root surface, excepting for the apical foramen, and subjected to the infiltration into the two dye solutions in a vacuum environment for 24 hours. The apical leakage were measured by means of the software ImageTool® for Windows version 3.0 and the results were subjected to statistical analysis by the tests ANOVA, t-Student and Newman-Kells. It was noticed that the levels of leakage determined by the dye solutions depend on which sealer is evaluated. The 2%methylene blue solution in the sealers Endofill, Sealer 26 and Sealapex presented lower levels of leakage compared to the ones determined by 2% Rhodamine B in the same sealers, suggesting that 2% methylene blue dye is unable to determine the total extension of the leakage in those sealers. The other sealers did not present significant differences in the apical leakage levels determined by both dye solutions. In relation to the apical sealing... (Complete abstract, click electronic address below).

Orientador: Roberto Miranda Esberard / Banca: Idomeo Bonetti Filho / Banca: Marco Antônio Húngaro Duarte / Resumo: A proposta deste trabalho foi comparar os níveis de infiltração apical determinados pelos corantes azul de metileno a 2% e Rodamina B a 2% em canais radiculares obturados com cimentos endodônticos de diferentes composições químicas. Foi também determinada a capacidade seladora apical dos cimentos Endofill, Sealer 26, AH Plus, Sealapex, EndoREZ e um cimento experimental à base de polímero de mamona (Polifil) em cada solução corante. Foram utilizados 176 dentes unirradiculares extraídos de humanos que foram instrumentados com limas do Sistema K3 de conicidade 0,04mm/mm e obturados pela técnica da condensação lateral modificada utilizando-se um cone principal de conicidade 0,04mm/mm e dois cones auxiliares. As raízes foram divididas em grupos de acordo com o cimento obturador utilizado e estes novamente divididos em subgrupos de 14 dentes cada de acordo com a solução corante a ser utilizada como traçador da infiltração. Oito dentes foram utilizados como controle sendo 4 controles positivo e 4 controles negativo. As raízes foram impermeabilizadas em toda superfície radicular externa com exceção do forame apical e submetidas à infiltração nas duas soluções corantes, em um ambiente de vácuo por 24 horas. Foram mensuradas as infiltrações apicais por meio do programa ImageTool for Windows versão 3.0 e os resultados submetidos à análise estatística pelos testes ANOVA, t-Student e Newman-Kells. Verificou-se que os níveis de infiltração determinados pelas soluções corantes dependem de qual cimento é avaliado. A solução de azul de metileno a 2% determinou nos cimentos Endofill, Sealer 26 e Sealapex menores níveis de infiltração que os determinados pela Rodamina B nos mesmos cimentos, sugerindo uma incapacidade da solução de azul de metileno a 2% em revelar a totalidade da falha da obturação realizada com estes cimentos... (Resumo completo, clicar acesso eletrônico abaixo). / Abstract: The purpose of this study was to compare the levels of apical leakage determined by the 2% methylene blue and 2% Rhodamine B dyes in root canals filled with endodontic sealers of different chemical compositions. It was also determined the apical sealing ability of the sealers Endofill, Sealer 26, AH Plus, Sealapex, EndoREZ and an experimental sealer based on castor oil polymer (Polifil) in each dyeing solution. It was used 176 single root teeth extracted from humans that were instrumented with K3 system files taper .04 and filled by the modified lateral condensation technique using a main cone taper .04 and two auxiliary cones. The roots were divided in groups according to the filling sealers that were used and these ones were divided again in subgroups of 14 teeth each one according to the dyeing solution used as infiltration tracer. Eight teeth were used as control group, four positive controls and 4 negative controls. The roots were impermeabilized on all external root surface, excepting for the apical foramen, and subjected to the infiltration into the two dye solutions in a vacuum environment for 24 hours. The apical leakage were measured by means of the software ImageTool® for Windows version 3.0 and the results were subjected to statistical analysis by the tests ANOVA, t-Student and Newman-Kells. It was noticed that the levels of leakage determined by the dye solutions depend on which sealer is evaluated. The 2%methylene blue solution in the sealers Endofill, Sealer 26 and Sealapex presented lower levels of leakage compared to the ones determined by 2% Rhodamine B in the same sealers, suggesting that 2% methylene blue dye is unable to determine the total extension of the leakage in those sealers. The other sealers did not present significant differences in the apical leakage levels determined by both dye solutions. In relation to the apical sealing... (Complete abstract, click electronic address below). / Mestre

Este trabalho investigou a fotodegradação do corante Rodamina-B com o auxílio do catalisador semicondutor Dióxido de Titânio, utilizando como fonte de irradiação pulsos de 40 fs gerados por um sistema laser de Titânio - Safira. Os pulsos laser foram formatados espectralmente (modulação senoidal), gerando trens de pulsos cuja separação foi escolhida para ser ressonante com um modo Raman intenso do catalisador. A fotodegradação da Rodamina-B foi monitorada através de medidas de fluorescência excitada via absorção de dois fótons. Não observamos fotodegradação do corante mediante a irradiação com pulsos ultracurtos, mesmo na presença do catalisador, tanto para o pulso de menor duração alcançada quanto para os trens de pulsos com diferentes separações temporais. Contudo, observamos uma diminuição no espalhamento da luz de excitação devido às nanopartículas de Dióxido de Titânio. Este processo foi estudado com mais detalhes, tendo sido analisada a influência da formatação espectral senoidal no resultado da medida. A relação entre a irradiação com pulsos de femtossegundos e a quebra de aglomerados de nanopartículas foi intuída a partir dos resultados obtidos, sendo fortalecida por medidas de microscopia eletrônica de varredura de um filme das amostras. / This work investigated the photodegradation of Rhodamine-B assisted by Titanium Dioxide semiconductor catalyst, using as irradiation source a Ti:Sapphire laser system delivering 40 fs pulses. The laser pulses were spectrally shaped (sinusoidal modulation), generating pulse trains whose separation was chosen to be resonant with an intense catalysts Raman mode. The Rh-B photodegradation was monitored by two photon excited fluorescence measurements. We have not observed dye photodegradation by the ultrashort pulses irradiation, in the absence of the catalyst, neither with the shortest pulse obtained, nor with pulse trains. Nevertheless, we observed a decrease in the excitation light scattering due to the Titanium Dioxide nanoparticles. Such process was studied by analyzing the influence of sinusoidal spectral phase mask in the signal. The results indicate a relationship between femtosecond pulse irradiation and the breaking of nanoparticles clusters, which was also corroborated by scanning electron microscopy measurements.

Submitted by Irene Nascimento (irene.kessia@ufpe.br) on 2016-07-11T19:05:22Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE Renato Barbosa da Silva.pdf: 6315157 bytes, checksum: 2b3ac093113d303d28b902d531315c52 (MD5) / Made available in DSpace on 2016-07-11T19:05:22Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE Renato Barbosa da Silva.pdf: 6315157 bytes, checksum: 2b3ac093113d303d28b902d531315c52 (MD5) Previous issue date: 2015-08-27 / CAPES / Diferentes tipos de materiais foram abordados nesta tese visando sua possível aplicação na fotônica. Por isso, o texto foi dividido em duas partes. A Parte 1 trata da preparação de materiais para a aplicação em laser aleatório. O primeiro material sintetizado foram as nanocascas metálicas, cuja estrutura é formada por um caroço de sílica com uma casca metálica ao seu redor. Assim, foi descrito um procedimento experimental melhorado com o intuito de se obter nanocascas de ouro e de prata de maneira mais reprodutível no menor tempo possível. Neste experimento, foi demostrado que a taxa de agitação no final da síntese tem importante influência na formação ou não das nanocascas metálicas. O crescimento de nanocascas de ouro e prata ocorria para taxas de 190 rpm e 1500 rpm respectivamente. O segundo material consistiu de partículas sub-micrométricas de sílica com corante rodamina 640 encapsulado. O encapsulamento ocorreu pela simples adição de uma solução do corante durante a síntese das partículas de sílica. Assim, para uma concentração de corante de 10-2 M, foi descrito um experimento de laser aleatório bicromático. Ao contrário de outros trabalhos na literatura foi possível controlar a emissão do laser aleatório apenas mudando a intensidade de excitação. Durante estes experimentos também foi verificada a existência de frequency-pulling entre dímeros e monômeros nos experimentos. Finalmente na Parte 2 é discutida a síntese e caracterização de nanocristais de silício (ncSi). Os ncSi apresentam luminescência cujo comprimento de onda pode ser controlado variando o tamanho dos nanocristais. A síntese foi baseada no processamento termal em altas temperaturas do hidrossilicato HSiO1.5, derivado do triclorossilano (HSiCl3). Em seguida, os vidros são finamente macerados num almofariz e pistilo de ágata antes dos ncSi serem extraídos via extração ácida. Neste experimento o objetivo foi obter nanocristais de silício monodispersos sem a utilização de etapas pós-síntese como a ultracentrifugação. O objetivo foi alcançado adicionando cloreto de sódio (NaCl) durante a etapa maceração, com o intuito de diminuir o tamanho dos grãos e garantir uma extração uniforme dos mesmos / Different materials were reported in this thesis aiming their possible photonic applications. Therefore the content of this thesis was distributed in two parts. Part 1 is related to the synthesis of materials for applications in random laser. The first material synthesized were the metallic nanoshells, which structure is based in a silica core and a metallic shell around it. An improved experimental method was reported for synthesize gold and silver nanoshells in order to guarantee the reproducibility and decrease the time necessary for synthesis. It was shown that the stirring rate at the end of synthesis plays an important role on the growth of metallic nanoshells. The growth of gold nanoshells was performed using a stirring rate of 190 rpm, on the other hand, the growth of silver nanoshells was performed using a stirring rate of 1500 rpm. The second material consisted of sub-micrometer silica particles whith encapsulated rhodamine 640. The encapsulation was made by the simple addition of a dye solution to do during a Synthesis of silica particles. An bichromatic random laser was operated using a concentration of 10-2 M of laser dye. Unlike other works in the literature it was possible to control the emission of the random laser only changing the intensity of the excitation source. These experiments were also revealed the possibility of frequency-pulling between dimers and monomers of rhodamine through the shift of the laser emission. Finally, in Part 2 it is discussed the synthesis and characterization of silicon nanocrystals (ncSi). The ncSi present luminescence that can be tunable by changing the ncSi sizes The synthesis was based on the thermal processing at high temperatures of HSiO1.5 hydrosilicate derivative of trichlorosilane (HSiCl3). Then, the glasses are finely grounded in a agate mortar and pestle before been extracted via an acid etching. In this experiment the objective was to obtain monodisperse nanocrystals of silicon without the use of post-synthesis steps such as ultracentrifugation. The objective was reached added sodium chloride (NaCl) during the ground step in order to decrease the size of grain for to obtain a uniform etching.

A rodamina B e outros marcadores fluorescentes vêm sendo empregados na avaliação morfológica da interface de adesão com o auxílio de microscopia confocal de varredura a laser. Acrescentando-se rodamina B a sistemas adesivos, é possível observar as características de espessura da camada de adesivo, micromorfologia da camada híbrida, extensão e quantidade de tags, bem como diagnosticar defeitos ou alterações na interface de adesão. A literatura revela, entretanto, uma falta de precedentes sobre as quantidades de marcadores nos componentes resinosos. Além disso, ainda não se avaliou o efeito da concentração de rodamina B sobre a qualidade da análise da interface de adesão, bem como sobre o comportamento fotofísico dos marcadores nos sistemas adesivos. Este estudo foi realizado com o propósito de sistematizar um método de adição de rodamina B a sistemas adesivos, incluindo-se estratégias para a determinação de concentrações mínimas de rodamina nos componentes resinosos, porém, ainda viáveis para a realização da análise morfológica da interface de adesão através de microscopia confocal de varredura a laser. Para tal, os sistemas adesivos não simplificados e considerados padrão-ouro em suas categorias Adper™ Scotchbond™ Multi-Purpose (convencional de três passos) e Clearfil™ SE Bond (auto-condicionante de dois passos) foram modificados com rodamina B em cinco diferentes concentrações: C1 (0,5 mg/mL), C2 (0,10 mg/mL), C3 (0,02 mg/mL), C4 (0,004 mg/mL) e C5 (0,0008mg/mL) e o comportamento fluorescente da rodamina nos adesivos foi avaliado tanto no âmbito espectroscópico (espectroscopia de fotoluminescência), como no âmbito microscópico (microscopia confocal de varredura a laser). Para a modificação dos adesivos, utilizou-se uma técnica precisa de proporcionamento na qual o marcador fluorescente foi incorporado às resinas fluidas a partir de soluções de rodamina B em etanol. Os espectros de fluorescência mostraram diferenças nos máximos das bandas de emissão e de excitação, de acordo com as concentrações de rodamina B em cada material dispersante. A análise microscópica dos espécimes em dentina confirmou que é possível utilizar sistemas adesivos contendo rodamina B em concentrações muitas vezes menores do que as mencionadas na literatura. Ambos os sistemas avaliados puderam ser visualizados, microscopicamente, quando marcados com rodamina B nas três concentrações pré-selecionadas para a avaliação da interface de adesão: C2 (0,10 mg/mL), C3 (0,02 mg/mL) e C4 (0,004 mg/mL), sendo que C3 forneceu os melhores resultados em relação ao contraste e à saturação nas fotomicrografias. Concluiu-se que o comportamento fotofísico da rodamina B é influenciado tanto pela concentração, como pelo sistema adesivo no qual o marcador está dissolvido. A concentração de rodamina B também interfere na qualidade da análise morfológica da interface de adesão, sendo que o excesso do marcador pode dificultar a distinção de detalhes micromorfológicos. / Rhodamine B and other fluorescent markers have been used for the assessment of the bonding interface via confocal laser scanning microscopy. By adding rhodamine into adhesive systems, it is possible to study morphological characteristics of the hybrid layer, the extent and amount of resin tags and the adhesive layer thickness, as well as detecting potential defects or alterations at bonding interface. Meantime the literature reveals lack of standards among the quantities of fluorescent markers in resin-based polymers. The effects of rhodamine B concentration on the quality of the microscopic analysis, as well as on the photophysics of labeled adhesive systems were not assessed up to now. This study aimed to systematize methodologies for adding rhodamine B into adhesive systems, including suitable strategies for determining the minimum serviceable rhodamine concentrations to perform the morphological analysis of the bonding interface. Two non-simplified adhesive system considered gold standard categories Adper™ Scotchbond™ Multi-Purpose (3 steps conventional) and Clearfil™ SE Bond (2 steps self-etching) were modified with rhodamine B at five concentrations: C1 (0.5 mg/ml), C2 (0.10 mg/ml), C3 (0.02 mg/ml), C4 (0.004 mg/ml) and C5 (0.0008 mg/ml ) and the fluorescent behavior of the labeled resins was assessed both by photoluminescence spectroscopy and by confocal laser microscopy The preparation of the labeled resins was proceed by means of a precise proportioning technique in which the fluorescent marker was incorporated into the bonding agents from solutions of rhodamine B in ethanol. The fluorescence spectra showed differences in the intensity and wavelength fluorescence according to the rhodamine B concentration. Microscopic analysis of the dentin specimens confirmed adhesive systems can be modified with rhodamine B at far lower concentrations than those mentioned in the literature. Both evaluated systems were microscopically visualized while labeled with Rhodamine B at three pre-selected concentrations: C2 (0.10 mg/mL), C3 (0.02 mg/ml) and C4 (0.004 mg/ml), and C3 offered the best outcome with respect to contrast and saturation in photomicrographs. It was concluded that the photophysical behavior of rhodamine B depends on both the concentration and labeled adhesive system. The rhodamine B concentration also interferes with the quality of morphological analysis of the bonding interface, and the excess of the fluorescent marker may jeopardize the discrimination of morphological details.