Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-01-29T12:13:52Z No. of bitstreams: 1 giselebarbosa.pdf: 13872105 bytes, checksum: 80b53c78204148b2895105c24b335d8c (MD5) / Rejected by Adriana Oliveira (adriana.oliveira@ufjf.edu.br), reason: Adicionar instituição on 2016-02-01T15:45:14Z (GMT) / Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-02-01T16:10:54Z No. of bitstreams: 1 giselebarbosa.pdf: 13872105 bytes, checksum: 80b53c78204148b2895105c24b335d8c (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-02-01T20:10:28Z (GMT) No. of bitstreams: 1 giselebarbosa.pdf: 13872105 bytes, checksum: 80b53c78204148b2895105c24b335d8c (MD5) / Made available in DSpace on 2016-02-01T20:10:28Z (GMT). No. of bitstreams: 1 giselebarbosa.pdf: 13872105 bytes, checksum: 80b53c78204148b2895105c24b335d8c (MD5) Previous issue date: 2014-07-11 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Compostos adamantóides têm sido alvo de interesse desde a virada do século 20, devido a sua analogia com a estrutura do diamante. A estrutura única do adamantano é refletida em suas propriedades físicas e químicas altamente diferenciadas, que podem ter muitas aplicações, incluindo a concepção de medicamentos e carreação de fármacos. Estes estão presentes numa grande variedade de compostos bioativos, mostrando atividade contra alguns agentes infecciosos e em muitos distúrbios fisiológicos. Juntamente com as aminas e, principalmente, as poliaminas que são substâncias que ocorrem amplamente em materiais biológicos podendo estar envolvidas em muitos aspectos como crescimento, divisão e diferenciação celular, os compostos adamantóides são considerados um alvo potencial para a quimioterapia de várias doenças, principalmente as infecciosas. Nesse contexto, esse trabalho tem como proposta a preparação de novos derivados adamantóides diaminados e amino álcoois, que sejam potenciais agentes farmacológicos. Para obtenção dos compostos almejados, o 1- adamantano metanol teve o grupo hidroxila transformado em um melhor grupo abandonador e em seguida substituído por diferentes aminas e amino álcoois. E, para a síntese dos derivados da 2-adamantanona foi realizada a aminação redutiva da mesma com as diaminas e amino álcoois utilizados. Obteve-se 19 compostos, sendo 12 inéditos, os quais foram caracterizados por espectroscopia na região do Infravermelho e Ressonância magnética nuclear de 1H e 13C. Foram realizados diferentes ensaios biológicos e o composto 7 apresentou maior destaque nos testes realizados. / Adamantoids compounds have been the subject of interest since the turn of the 20th century due to its analogy with the diamond structure. The unique structure of adamantane is reflected in their highly differing physical and chemical properties, which can have many applications, including drug design and drug delivery, and is present in a variety of bioactive compounds showing activity against several infectious agents, and in many physiological disorders. Along with amines and especially polyamines which are substances that widely occur in biological material may be involved in many aspects such as growth, cell division and differentiation been considered a potential target for chemotherapy for several, especially infectious diseases. In this context, this paper aims at the preparation of new diamines and amino alcohols adamantoids derivatives, which are potential pharmacological agents. To obtain the desired compounds, 1-adamantane methanol has the hydroxyl group converted into a better leaving group, and then replaced by different amines and amino alcohols. For the synthesis of the 2- adamantanone derivatives it was employed reductive amination with diamines and amino alcohols followed by the reduction with NaBH3CN. It was prepared in this work 19 compounds, including 12 previously unpublished, which were characterized by infrared spectroscopy and 1H and 13C nuclear magnetic resonance. Preliminary biological evaluations were performed and compound 7 showed the best activity on the realized biological assays.

Este ensaio clínico randomizado, cego e controlado com placebo teve como objetivo principal avaliar a eficácia do diamino fluoreto de prata (DFP) a 30% no tratamento não operatório de lesões de cárie em superfícies proximais de molares decíduos e compará-la a eficácia do infiltrante resinoso e a do controle do biofilme interproximal pelo uso do fio dental. Além disso, também avaliou a custo-eficácia e o desconforto dos tratamentos e a satisfação dos participantes quanto ao tratamento recebido. Para isso, foram selecionadas 141 crianças entre 3 e 10 anos de idade, que apresentavam pelo menos uma superfície proximal com lesão de cárie clinicamente em esmalte. A alocação dos participantes foi aleatória, de acordo com o tratamento: DFP a 30%, infiltrante resinoso de cárie e orientação para o uso diário do fio dental (controle). Todos os participantes receberam o tratamento ativo para os quais foram alocados e também o placebo dos tratamentos realizados nos outros grupos. Os custos dos materiais utilizados nos tratamentos foram registrados. Ao final da consulta de tratamento, foi aplicada aos participantes a Escala Facial de Wong-Baker para avaliação do desconforto. Os responsáveis pelos participantes, que concluíram o seguimento da pesquisa, responderam a um questionário de satisfação sobre o tratamento recebido. As crianças foram examinadas após 1 mês para avaliação de higiene bucal e também de presença de biofilme nas superfícies tratadas. Após 6, 12 e 24 meses, foram realizados exames visual e tátil para verificar a progressão das lesões tratadas, além de exame radiográfico aos 12 e 24 meses. Para avaliar a eficácia dos tratamentos, consideraram-se como desfechos: (I) qualquer progressão clínica da lesão tratada e (II) progressão para cavidade em dentina. A progressão radiográfica foi utilizada como um desfecho secundário e para comparar com o padrão clínico de progressão das lesões. Análises de regressão foram realizadas para verificar se os grupos de tratamento influenciaram os desfechos testados após 12 e 24 meses de seguimento (análise por protocolo - Poisson multinível e análise de sobrevida). Valores pontuais de custo-eficácia dos tratamentos foram calculados e, para comparar a custo-eficácia da implementação do uso do DFP em relação às outras opções testadas foi utilizada a razão de custo-eficácia incremental. Análises de regressão de Poisson foram utilizadas para verificar a associação entre o desconforto e variáveis explicativas. A satisfação dos participantes e seus responsáveis foi explorada descritivamente. Um total de 316 superfícies proximais foram incluídas, sendo a maioria classificada como escore 2 do ICDAS (Sistema Internacional de Detecção e Avaliação de Cárie) associadas à ausência de imagem radiográfica (46,8%). As perdas de seguimento foram de 15% e 24% aos 12 e 24 meses, respectivamente. Não houve associação entre o grupo de tratamento e a progressão das lesões aos 12 e 24 meses, tanta pela análise por protocolo como pela análise de sobrevida. A taxa de progressão clínica das lesões para cavidade em dentina foi de 2,5% aos 12 meses e de 5,6% aos 24 meses. As lesões que não apresentavam imagem radiográfica inicial não progrediram para o 1/3 médio de dentina ou mais. A condição clínica inicial das lesões foi associada à progressão das lesões em todas as análises. Já o risco de cárie foi associado à progressão das lesões aos 24 meses e também na análise de sobrevida. O tratamento com infiltrante resinoso apresentou o custo mais elevado, fazendo com que o tratamento com DFP apresentasse melhor relação custo-eficácia do que este primeiro. Os participantes tratados com o DFP e os que receberam orientação para o uso do fio dental relataram menor desconforto do que os tratados com o infiltrante resinoso. Os responsáveis se mostraram satisfeitos com o tratamento recebido, independentemente do grupo ao qual foram alocados. Conclui-se que o tratamento com DFP é tão eficaz quanto o infiltrante resinoso e a orientação para o uso do fio dental no controle das lesões iniciais em proximal de molares decíduos. No entanto, causa menor desconforto e apresenta custo-eficácia superior ao infiltrante resinoso, devendo ser preferível para superfícies proximais de molares decíduos, em situações nas quais o tratamento dessas lesões possa ser necessário, como por exemplo, pacientes com experiência de cárie. / This randomized, blinded and placebo-controlled clinical trial aimed to evaluate the efficacy of 30% silver diamine fluoride (SDF) as a non-operative treatment of the approximal surfaces of primary molars and to compare it with the efficacy of resin infiltration and the mechanical control of the interproximal biofilm by flossing. We also evaluated the cost-efficacy and the discomfort of the treatments as well as the parent\'s satisfaction regarding treatments. One hundred forty-one, 3-to-10-year-old, children were included. They must present at least one caries lesion clinically into enamel sited on an approximal surface of primary molar. Participants were randomly allocated to the following groups according to active treatment to be received: 30% SDF, caries resin infiltration, flossing orientation (control). All participants received the active treatment, in which they were allocated and they also received the placebo treatment corresponding to the other groups. Costs of materials used in the treatment were registered. In the end of treatment session, the Wong-Baker faces scale was applied to evaluate participants\' reported discomfort. Children were examined after 1 month to evaluation of the oral hygiene and the presence of the biofilm on the treated surfaces. After 6, 12 and 24 months, visual and tactile examinations were performed to verify the lesions progression. Radiography was taken at 12- and 24-month follow-ups. To evaluate the efficacy of non-operative treatments, two outcomes were considered: (I) any clinical progression and (II) progression to cavity into dentine. The radiographic progression was used as a secondary outcome and to evaluate with clinical standard of lesions progression. Regression analyses were used to verify if the treatment influenced on these outcomes after 12 and 24 months (per-protocol analyses - multilevel Poisson and survival analysis). Cost-efficacy ratios were calculated for the treatments. To compare the cost-efficacy of implementing the use of DFP versus other options tested, the incremental cost-efficacy ratio was used. Poisson regression analyses were used to verify the association between discomfort and explanatory variables. The parents\' satisfaction about the treatments were explored descriptively. A total of 316 approximal surfaces were included. The majority of them were classified as ICDAS (International Caries Detection and Assessment System) score 2 associated with absence of radiographic image. The dropout in the study was 15% and 24% at 12-month and 24-month follow-up, respectively. There was no association between treatment groups and lesions progression at 12 and 24 months, both for the per-protocol analysis and by survival analysis. The rate of clinical lesions progression to cavity into dentine was 2.5% at 12 months and 5.6% at 24 months. Lesions without initial radiographic image did not progress into the middle of the dentine or more. Baseline clinical condition of caries lesions was associated with lesions progression in all analyses. The caries risk was also associated to caries progression in 24-month analyses and in the survival analyses. The treatment with resin infiltration was costlier. Consequently, the treatment with SDF was more cost-effective than resin infiltration. The participants allocated to SDF and control groups reported less discomfort than those who was allocated to the resin infitrant group. The parents were satisfied with the treatment received during the study, independently of the group to which their children had been allocated. It is possible to conclude that the SDF is as efficacious as the resin infiltration and flossing orientation to control initial lesions in the approximal surfaces of primary molars. However, SDF causes less discomfort and presents superior cost-efficacy relationship than resin infiltration and could be preferable to treat approximal caries in primary molars in those situations in which the treatment could be necessary, for example, depending on patients\' caries experience.

Este ensaio clínico randomizado, cego e controlado com placebo teve como objetivo principal avaliar a eficácia do diamino fluoreto de prata (DFP) a 30% no tratamento não operatório de lesões de cárie em superfícies proximais de molares decíduos e compará-la a eficácia do infiltrante resinoso e a do controle do biofilme interproximal pelo uso do fio dental. Além disso, também avaliou a custo-eficácia e o desconforto dos tratamentos e a satisfação dos participantes quanto ao tratamento recebido. Para isso, foram selecionadas 141 crianças entre 3 e 10 anos de idade, que apresentavam pelo menos uma superfície proximal com lesão de cárie clinicamente em esmalte. A alocação dos participantes foi aleatória, de acordo com o tratamento: DFP a 30%, infiltrante resinoso de cárie e orientação para o uso diário do fio dental (controle). Todos os participantes receberam o tratamento ativo para os quais foram alocados e também o placebo dos tratamentos realizados nos outros grupos. Os custos dos materiais utilizados nos tratamentos foram registrados. Ao final da consulta de tratamento, foi aplicada aos participantes a Escala Facial de Wong-Baker para avaliação do desconforto. Os responsáveis pelos participantes, que concluíram o seguimento da pesquisa, responderam a um questionário de satisfação sobre o tratamento recebido. As crianças foram examinadas após 1 mês para avaliação de higiene bucal e também de presença de biofilme nas superfícies tratadas. Após 6, 12 e 24 meses, foram realizados exames visual e tátil para verificar a progressão das lesões tratadas, além de exame radiográfico aos 12 e 24 meses. Para avaliar a eficácia dos tratamentos, consideraram-se como desfechos: (I) qualquer progressão clínica da lesão tratada e (II) progressão para cavidade em dentina. A progressão radiográfica foi utilizada como um desfecho secundário e para comparar com o padrão clínico de progressão das lesões. Análises de regressão foram realizadas para verificar se os grupos de tratamento influenciaram os desfechos testados após 12 e 24 meses de seguimento (análise por protocolo - Poisson multinível e análise de sobrevida). Valores pontuais de custo-eficácia dos tratamentos foram calculados e, para comparar a custo-eficácia da implementação do uso do DFP em relação às outras opções testadas foi utilizada a razão de custo-eficácia incremental. Análises de regressão de Poisson foram utilizadas para verificar a associação entre o desconforto e variáveis explicativas. A satisfação dos participantes e seus responsáveis foi explorada descritivamente. Um total de 316 superfícies proximais foram incluídas, sendo a maioria classificada como escore 2 do ICDAS (Sistema Internacional de Detecção e Avaliação de Cárie) associadas à ausência de imagem radiográfica (46,8%). As perdas de seguimento foram de 15% e 24% aos 12 e 24 meses, respectivamente. Não houve associação entre o grupo de tratamento e a progressão das lesões aos 12 e 24 meses, tanta pela análise por protocolo como pela análise de sobrevida. A taxa de progressão clínica das lesões para cavidade em dentina foi de 2,5% aos 12 meses e de 5,6% aos 24 meses. As lesões que não apresentavam imagem radiográfica inicial não progrediram para o 1/3 médio de dentina ou mais. A condição clínica inicial das lesões foi associada à progressão das lesões em todas as análises. Já o risco de cárie foi associado à progressão das lesões aos 24 meses e também na análise de sobrevida. O tratamento com infiltrante resinoso apresentou o custo mais elevado, fazendo com que o tratamento com DFP apresentasse melhor relação custo-eficácia do que este primeiro. Os participantes tratados com o DFP e os que receberam orientação para o uso do fio dental relataram menor desconforto do que os tratados com o infiltrante resinoso. Os responsáveis se mostraram satisfeitos com o tratamento recebido, independentemente do grupo ao qual foram alocados. Conclui-se que o tratamento com DFP é tão eficaz quanto o infiltrante resinoso e a orientação para o uso do fio dental no controle das lesões iniciais em proximal de molares decíduos. No entanto, causa menor desconforto e apresenta custo-eficácia superior ao infiltrante resinoso, devendo ser preferível para superfícies proximais de molares decíduos, em situações nas quais o tratamento dessas lesões possa ser necessário, como por exemplo, pacientes com experiência de cárie. / This randomized, blinded and placebo-controlled clinical trial aimed to evaluate the efficacy of 30% silver diamine fluoride (SDF) as a non-operative treatment of the approximal surfaces of primary molars and to compare it with the efficacy of resin infiltration and the mechanical control of the interproximal biofilm by flossing. We also evaluated the cost-efficacy and the discomfort of the treatments as well as the parent\'s satisfaction regarding treatments. One hundred forty-one, 3-to-10-year-old, children were included. They must present at least one caries lesion clinically into enamel sited on an approximal surface of primary molar. Participants were randomly allocated to the following groups according to active treatment to be received: 30% SDF, caries resin infiltration, flossing orientation (control). All participants received the active treatment, in which they were allocated and they also received the placebo treatment corresponding to the other groups. Costs of materials used in the treatment were registered. In the end of treatment session, the Wong-Baker faces scale was applied to evaluate participants\' reported discomfort. Children were examined after 1 month to evaluation of the oral hygiene and the presence of the biofilm on the treated surfaces. After 6, 12 and 24 months, visual and tactile examinations were performed to verify the lesions progression. Radiography was taken at 12- and 24-month follow-ups. To evaluate the efficacy of non-operative treatments, two outcomes were considered: (I) any clinical progression and (II) progression to cavity into dentine. The radiographic progression was used as a secondary outcome and to evaluate with clinical standard of lesions progression. Regression analyses were used to verify if the treatment influenced on these outcomes after 12 and 24 months (per-protocol analyses - multilevel Poisson and survival analysis). Cost-efficacy ratios were calculated for the treatments. To compare the cost-efficacy of implementing the use of DFP versus other options tested, the incremental cost-efficacy ratio was used. Poisson regression analyses were used to verify the association between discomfort and explanatory variables. The parents\' satisfaction about the treatments were explored descriptively. A total of 316 approximal surfaces were included. The majority of them were classified as ICDAS (International Caries Detection and Assessment System) score 2 associated with absence of radiographic image. The dropout in the study was 15% and 24% at 12-month and 24-month follow-up, respectively. There was no association between treatment groups and lesions progression at 12 and 24 months, both for the per-protocol analysis and by survival analysis. The rate of clinical lesions progression to cavity into dentine was 2.5% at 12 months and 5.6% at 24 months. Lesions without initial radiographic image did not progress into the middle of the dentine or more. Baseline clinical condition of caries lesions was associated with lesions progression in all analyses. The caries risk was also associated to caries progression in 24-month analyses and in the survival analyses. The treatment with resin infiltration was costlier. Consequently, the treatment with SDF was more cost-effective than resin infiltration. The participants allocated to SDF and control groups reported less discomfort than those who was allocated to the resin infitrant group. The parents were satisfied with the treatment received during the study, independently of the group to which their children had been allocated. It is possible to conclude that the SDF is as efficacious as the resin infiltration and flossing orientation to control initial lesions in the approximal surfaces of primary molars. However, SDF causes less discomfort and presents superior cost-efficacy relationship than resin infiltration and could be preferable to treat approximal caries in primary molars in those situations in which the treatment could be necessary, for example, depending on patients\' caries experience.

Cette thèse porte sur la synthèse de polyuréthanes thermoplastiques plus durables à partir de dérivés des huiles végétales. La première voie étudiée est basée sur la réaction, largement utilisée, entre un diol et un diisocyanate. Aussi, pour s’affranchir de l’utilisation des diisocyanates toxiques, une approche via la polyaddition entre un bis carbonate cyclique et une diamine a également été étudiée. Pour ce faire des précurseurs bi-fonctionnels : diols, bis carbonates cycliques à 5 et 6 chainons et diamines ont été préparés à partir de dérivés de l’huile de tournesol (oléate de méthyle) et de l’huile de ricin (undécénoate de méthyle et acide sébacique). Les propriétés thermo-mécaniques des polyuréthanes et poly(hydroxyuréthane)s thermoplastiques obtenus ont pu être ajustées par le choix adapté de la structure chimique des précurseurs (gras) utilisés. Les travaux réalisés démontrent un effet de la taille du cycle du carbonate sur la réactivité. En effet, les (bis) carbonates cycliques à 6 chainons se sont avérés plus réactifs que leurs homologues à 5 chainons. De plus, la synthèse de diamines via un intermédiaire dinitrile semble très prometteuse pour le « design » d’une plateforme de diamines issues d’acides gras et de poly(hydroxyuréthane)s entièrement bio-sourcés. / This thesis aims to synthesize more sustainable thermoplastic polyurethanes from vegetable oil derivatives. The first route that has been investigated is based on the well-known reaction between a diol and a diisocyanate. Then to avoid the use of diisocyanates, the route via the polyaddition of a bis cyclic carbonate and a diamine have been studied as well. For this purpose, bifunctional precursors such as diols, bis 5- and 6-membered cyclic carbonates and diamines have been prepared from sunflower oil derivative (methyl oleate) and castor oil derivatives (methyl undecenoate and sebacic acid) The thermo-mechanical properties of the PUs have been modulated by designing and selecting the chemical structure of the (fatty acid-based) monomers. The performed model reaction kinetics revealed the higher reactivity of the 6-membered cyclic carbonates compare to the 5-membered ones. Finally, the developed route to fatty acid-based diamines via dinitriles synthesis in mild conditions was really efficient and this route is really promising to develop a fatty acid based-diamines platform and fully bio-based poly(hydroxyurethane)s.

Purpose: The purpose of this study was to study the association between Silver Diamine Fluoride (SDF) and Oral Health-Related Quality of Life as assessed by “The Early Childhood Oral Health Impact Scale” questionnaire. Methods: Parents of healthy children (ASA I and II) ages 1-5 with early childhood caries with reversible pulpitis who had application of SDF filled out a questionnaire at baseline and again after one month. The questionnaire was designed to evaluate the child’s behavior, physical abilities, pain, temperament, and how well the child gets along with others. Results: Wilcoxon Signed Rank Test was used to determine if responses to various ECOHIS items and the total scores were different between the two time points. Conclusion: Children with dental caries who had application of SDF reported less dental pain, less eating problems, higher quality of sleep and overall higher quality of life at one-month follow up compared with the baseline.

Philosophiae Doctor - PhD / A novel monomer (N,N'-Bis-(1H-pyrrol-2-ylmethylene)-benzene-1,2-diamine-BPPD) was derived from the condensation reaction between o-phenylenediamine and a pyrrole derivative. The monomer was polymerized electrochemically to produce the new polymer material - polymerized(N,N'-Bis-(1H-pyrrol-2-ylmethylene)-benzene-1,2-diamine) PBPPD. This novel polymer material was deposited at the surface of a screen-printed carbon electrode, as a thin film, in the development of chemical sensors for the detection of polycyclic aromatic hydrocarbons (PAHs). The monomer material was characterized in terms of its optical (spectroscopy) and thermal properties. The polymer material was characterized in terms of its surface morphology and its redox electrochemistry. Fourier transform infrared spectroscopy (FTIR) was used to confirm the azomethine bond formation during the condensation reaction of an aldehyde and primary amine derivative. / 2020-08-31

No / Novel 1- and 1,4-substituted chloroethylaminoanthraquinones with DNA binding and alkylating properties along with their respective hydroxyethylaminoanthraquinone intermediates were synthesized. Selected chloroethylaminoanthraquinones were shown to cross-link DNA and alkylate guanines (at low nM concentration) with a preference for reaction sites containing 5'-PyG. A compound (Alchemix) with the bis-chloroethyl functionality confined to one side chain alkylated but did not cross-link DNA. All the 1,4-disubstituted chloroethylaminoanthraquinones were potently cytotoxic (nM IC50s) against cisplatin-resistant ovarian cancer cell lines.