Grâce à ses propriétés uniques, le groupement pentafluorosulfanyle (SF5) a récemment retenu beaucoup d'attention. Ce substituant encombrant, hautement lipophile et électro-attracteur est souvent considéré comme un "super groupement trifluorométhyl". Aujourd’hui, la chimie de groupement SF5 est un domaine de la chimie du fluor qui se développe rapidement, et les méthodologies de synthèse des nouveaux « building-blocks » pentafluorosulfanylés sont constamment développées. Néanmoins, les méthodes permettant l'introduction du groupement SF5 dans les hétérocycles restent encore assez limitées. L’objectif de cette thèse était de synthétiser des nouveaux « building-blocks » pentafluorosulfanylés, d’une part, et de développer des nouvelles approches synthétiques, conduisant à des hétérocycles azotés originaux, substitués par un groupement SF5, d’autre part. Dans la première partie de notre travail, nous avons développé une synthèse en 4 étapes, conduisant à de nouveaux esters et amides acryliques substitués par un groupement SF5, à partir des dérivés commerciaux de l’acetate allylique. En utilisant la même stratégie, quelques nouveaux allylsilanes pentafluorosulfanylés ont été synthétisés. Nous avons aussi développé une réaction d’allylation des aldéhydes, catalysée par indium, en utilisant le bromure SF5-allylique, conduisant aux alcools alpha- et gamma-homoallyliques correspondants.Dans la deuxième partie, deux stratégies différentes pour la synthèse de nouveaux hétérocycles SF5-substitués, ont été explorées. La première était la fluoration directe des thiols ou disulfures hétérocycliques, suivant la procédure de Umemoto. La deuxième approche était basée sur les réactions de cycloaddition de nos "building-blocks" pentafluorosulfanylés. Ainsi, nous avons développé avec succès la synthèse des premières pyrrolidines et isoxazolidines pentafluorosulfanylées. Enfin, des post-fonctionnalisations des SF5-pyrrolidines ont été effectuées, conduisant aux plusieurs "plateformes" pentafluorosulfanylées qui pourraient être facilement incorporées dans les molécules d’intérêt biologique. / Due to its unique properties, the pentafluorosulfanyl (SF5) group has recently reached much attention. This bulky, highly lipophilic and electron-withdrawing substituent is often called as a “super-trifluoromethyl group”. Currently, the SF5-chemistry is becoming a fast growing field of the fluorine chemistry and the new pentafluorosulfanylated building-blocks are under continuous development. Nevertheless, the methods for the introduction of the SF5-group into heterocycles remain still quite limited.The aim of this thesis was to synthesize new pentafluorosulfanylated building-blocks, on the one hand, and to develop new synthetic approaches leading to original pentafluorosulfanylated nitrogen-containing heterocyles, on the other hand.In the first part of our work, we have developed an efficient four-step synthesis of new SF5-acrylic esters and amides, starting from commercially available allyl acetate derivatives. Using the same strategy, several new pentafluorosulfanylated allylsilanes were synthesized. We have also developed an In-mediated allylation reaction of aldehydes, using the SF5-allyl bromide, leading to the corresponding pentafluorosulfanylated alpha- and gamma-homoallylic alcohols.In the second part, two different strategies for the synthesis of new SF5-substituted heterocycles were explored. The first one was the direct fluorination of heterocyclic thiols or disulfides, according to the Umemoto’s procedure. The second approach was based on the cycloaddition reactions of our pentafluorosulfanylated building-blocks. As a result, we have successfully developed the synthesis of the first SF5-substituted pyrrolidines and isoxazolidines. Finally, post-functionalizations of SF5-pyrrolidines were performed, leading to several pentafluorosulfanylated scaffolds which could be easily introduce into molecules of biological interest.

L’objectif de cette thèse est d’élargir la gamme des composés issus des aziridine-2-carboxylates, obtenues par leur utilisation comme matière première pour la synthèse d’azahétérocycles ciblés diversement substitués, via des réactions d’ouvertures nucléophiles et d’expansions de cycle. La synthèse d’hétérocycles azotés fluorés originaux sera abordée à partir d’aziridines-2-carboxylates trifluorométhylées ainsi que d’aminoalcools et aminoacides trifluorométhylés enantiopures. Les aziridines-2-carboxylates trifluorométhylées dont la synthèse à déjà été décrite dans la littérature conduiront à des hétérocycles fluorés variés selon des réactions d’ouverture et d’agrandissement de cycles faisant intervenir les méthodologies mise au point en série non fluorée par le partenaire Tunisien. Les aminoalcools et aminoacides trifluorométhylés conduiront également à des hétérocycles de type oxazolidinones. Les nouveaux hétérocycles synthétisés trouveront des applications en tant qu’unités pseudo-peptidiques utiles en chimie des peptides. / Our purpose in this thesis is to widen the range of compounds from aziridine-2-carboxylate, which obtained by its use as a feedstock for the synthesis of new hétérocycles through nucleophilic reactions openings and expansions cycle.The synthesis of fluorinated heterocycles will be approached from aziridine-2-carboxylate trifluorométhylées and amino alcohols and amino acids trifluoromethylated enantiopure.Fluorinated aziridines whose synthesis has already been described in the literature will lead to various fluorinated heterocycles according reactions and opening cycles of expansion methodologies involving setting the nonfluorinated series developed by the Tunisian partner.The new synthesized heterocycles find applications as chiral pseudo-peptide units useful in peptide chemistry.

Cet ouvrage porte sur la conception, la synthèse et la caractérisation de sphères supramoléculaires auto-assemblées. Si le groupe Dory a, par le passé, été en mesure d’effectuer la synthèse d’un type de sphères avec 4 unités monomères, le but de cette recherche a été de développer des monomères qui tendraient vers des sphères à 8 unités voire même 20. Suite à de nombreuses idées, nous avons orienté notre recherche davantage sur un type de monomère afin de pouvoir le synthétiser en quantité suffisamment importante pour pouvoir le caractériser. Une idée aussi novatrice a nécessité plusieurs mois de travail pour parvenir à un produit satisfaisant et suffisamment pur pour commencer la caractérisation.

Die vorliegende Arbeit beschäftigt sich mit der Synthese verschiedener bimodaler 1H/19F-Kontrastmittel und deren Relaxivitäts-Messungen. Außerdem werden die Synthese und die Bestimmung der physikalischen Parameter eines 19F-Markers für die Fluorbildgebung beschrieben. Der erste Teil beschreibt die Synthese bimodaler 1H-/19F-Kontrastmittel für die MR-Bildgebung, die sowohl für einen besseren Kontrast bei der herkömmlichen Protonenbildgebung sorgen als auch in der 19F-MRT Verwendung finden sollten. Die dazu verwendeten Ligandsysteme basieren auf dem offenkettigen DTPA bzw. auf dem ringförmigen DO3A. Der zweite Teil dieser Arbeit beschäftigt sich mit der Entwicklung eines 19F-Markers, der eine größtmögliche Anzahl an äquivalenten Fluoratomen besitzen und Verwendung in der 19F-MR-Bildgebung finden sollte. Aufgrund seiner Singleresonanz, der chemischen Verschiebung und seiner T1- und T2-Zeiten ist er besonders geeignet für den gemeinsamen Einsatz mit anderen Perfluorcarbonen / The present work deals with the synthesis of different bimodal 1H-/19F-contrast agents and the determination of their relaxivities. Furthermore, it describes the synthesis and characterization of a fluorine marker for 19F-MRI. The first part describes the synthesis of bimodal 1H-/19F-contrast agents for MR imaging, which provide both a better contrast for conventional proton imaging as well as a possible use in 19F-MRI. The ligand systems for these purposes are based on the open-chained DTPA and the cyclic DO3A, respectively. The second part of this work deals with the development of a 19F-marker, which has a maximized number of equivalent fluorine atoms. This marker is intended to be used in 19F-MR imaging. Because of the marker’s single resonance, its chemical shift, and its T1 and T2 times it is particularly suited for combined use with other perfluorocarbons.

Diss. Naturwiss. Bern. / Literaturverz.

Universiẗat, Diss., 2004--Köln.

Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro de Ciências da Saúde. / Made available in DSpace on 2012-10-17T12:45:42Z (GMT). No. of bitstreams: 0Bitstream added on 2014-09-25T19:21:23Z : No. of bitstreams: 1 170285.pdf: 2661540 bytes, checksum: 38717d7423cdc595ca804eda2f466630 (MD5) / Nesta pesquisa observou-se que a solução de fluoreto de diamino prata a 30% aplicada em esmalte decíduo incrementou a sua dureza, e esta esteve relacionada à presença da prata. A partir dos resultados, pode-se inferir que o mecanismo de ação preventivo da solução de FDP a 30% confirmado pelo aumento de dureza do esmalte deve-se à formação de compostos a base de prata observados pelo M.E.V. que mostrou formações poliédricas características da prata as quais foram confirmadas pelas análise químicas (E.D.E.).

Tese (doutorado) - Universidade Federal de Santa Catarina, Centro de Ciências da Saúde. Programa de Pós-Graduação em Odontologia. / Made available in DSpace on 2012-10-23T02:37:52Z (GMT). No. of bitstreams: 1 245550.pdf: 1934073 bytes, checksum: 44382b519349cd38232140aa3f939716 (MD5) / Esta tese é composta de dois artigos. No artigo 1, foi avaliado in situ o efeito de três protocolos de aplicação tópica de flúor (G1: Dentifrício Fluoretado - DF; G2: DF + 1 aplicação tópica de flúor - DF + 1ATF; G3: DF + 4 ATFs) na remineralização de lesões de cárie em dentina. Através de teste de microdureza, foi verificado que o grupo DF + 4ATFs promove maior recuperação mineral que os demais grupos. No artigo 2, foi verificado se a técnica de subtração digital radiográfica (SDR) é capaz de detectar modificações induzidas por desmineralização e remineralização in situ de blocos de dentina. Conclui-se que a SDR é uma ferramenta útil na mensuração de alterações minerais, com resultados semelhantes ao teste de microdureza.

Tese (doutorado) - Universidade Federal de Santa Catarina, Centro de Ciências Física e Matemáticas. Programa de Pós-Graduação em Química, Florianópolis, 2013 / Made available in DSpace on 2013-12-06T00:37:40Z (GMT). No. of bitstreams: 0 Previous issue date: 2013Bitstream added on 2014-09-24T20:27:43Z : No. of bitstreams: 1 319756.pdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Este trabalho tem como objetivo o desenvolvimento e a aplicação de métodos analíticos que permitem a determinação acurada, sensível e rotineira de flúor em amostras biológicas e industriais. Espectrometria de absorção molecular de alta resolução com fonte continua foi utilizado para a elaboração da técnica de determinação de flúor utilizando mono-fluoreto de cálcio, CaF, em comprimento de onda de 603,690 nm e de 606,440 nm, e também mono-fluoreto de gálio, GaF, no comprimento de onda 211,428 nm. Em amostras de creme dental, a determinação de flúor, via GaF, em forno de grafite, com temperatura de pirólise de 550 ºC e a temperatura de vaporização de 1550 ºC, a curva de calibração foi linear no intervalo entre 1 ? 50 µg/L, limite de detecção de 0,26 µg/L. Os valores para flúor encontrados em 10 amostras de creme dental foram condizentes com os valores informados pelos fabricantes. Cromatografia a gás acoplada à espectrometria de massas foi utilizada como uma técnica alternativa para a comparação dos dados obtidos, e os dois métodos não mostraram estatisticamente diferenças entre os resultados. Para a determinação de flúor em amostras de chá, via CaF, em forno de grafite, com temperatura de pirólise de 725 ºC e a temperatura de vaporização de 2100 ºC, a curva de calibração foi linear no intervalo entre 0,5 - 25 mg/L, com um coeficiente de correlação de R = 0,9994 e limite de detecção de 0,16 mg/L. Os valores para flúor encontrados em 10 amostras comerciais de chá variaram entre 42 mg/g e 87 mg/g; as infusões desses chás continham entre 21 mg/g e 56 mg/g F, o que significa um percentual de extração entre 48% e 74%. Para a determinação de flúor em amostras de saliva, via CaF, também utilizou-se a cromatografia a gás acoplada à espectrometria de massas como uma técnica comparativa, e mais uma vez os dois métodos mostraram-se eficazes. A concentração de flúor logo após a escovação é de cerca de 29 mg/L. Depois de 5 minutos, a concentração diminui cerca de 90% e, após 30 minutos, está abaixo do limite de quantificação. <br> / Abstract: This work is based on the development and application of an analytical method that enables an accurate, sensitive, routine determination of fluorine in biological and industrial samples. High-resolution continuum source graphite furnace molecular absorption spectrometry was used for the determination of fluorine using calcium mono-fluoride, CaF, at the wavelengths of 603.690 nm and 606.440 nm, and also gallium mono-fluoride, GaF, at a wavelength of 211.428 nm. In samples of toothpaste, determining fluorine via GaF with a pyrolysis temperature of 550 °C and an vaporization temperature of 1550 °C, the calibration curve was linear in the range between 1 - 50 µg/L and the limit of detection was 0.26 µg/L. The values for fluoride found in 10 samples of toothpaste were consistent with the values reported by the manufacturers. Gas chromatography coupled to mass spectrometry (GC-MS) was used as an alternative technique for comparing the data, and the two methods showed no statistical difference between the results. For the determination of fluorine in tea samples via CaF, with a pyrolysis temperature of 725 °C and a vaporization temperature of 2100 °C, the calibration curve was linear within the range of 0.5 - 25 mg/L, with a correlation coefficient of R = 0.9994 and a limit of detection of 0.16 mg/L. The fluorine values found for 10 samples of commercial tea ranged between 42 mg/g and 87 mg/g; infusions of these same tea samples contained between 21 mg/g and 56 mg/g F, which means a percentage of extraction between 48% and 74%. For the determination of fluorine in saliva samples, via CaF, GCMS was also used as a comparative technique, and the two methods proved effective. The fluoride concentration just after brushing is about 29 mg/L. After 5 minutes, the concentration decreases by about 90% and after 30 minutes it was below the limit of quantification.

Made available in DSpace on 2014-06-11T19:28:02Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-04-19Bitstream added on 2014-06-13T20:08:37Z : No. of bitstreams: 1 pinheiro_mc_me_arafo.pdf: 512491 bytes, checksum: 7c0cc39d1c41c985914ef27350be16db (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O tratamento da hipersensibilidade dentinária cervical ainda é tema de diversos estudos em odontologia, pois um resultado permanente e satisfatório para essa sintomatologia dolorosa ainda não foi encontrado. Uma possibilidade nova de tratamento pode ser a utilização de vidros bioativos, que podem formar hidroxicarbonatoapatita sobre a superfície dentinária e obliterar os túbulos dentinários, no entanto, as formulações disponíveis deste material apresentam inconvenientes que dificultam sua aplicação sobre a superfície dentinária. Este estudo buscou avaliar a dissolução das partículas de uma vitrocerâmica modificado, denominado Biosilicato®, sobre a superfície dentinária, em diferentes veículos de preparo e formas de aplicação. Foram obtidos espécimes de dentina para a aplicação do produto testado e divididos em grupos que variavam quanto à forma de aplicação do Biosilicato® (escova de Robinson ou microbrush) e veiculo utilizado para a aplicação do produto (água ou flúor). Após a aplicação do produto sobre os espécimes estes foram imersos em saliva artificial e deixados em repouso em diferentes tempos: 0 minuto; 15 minutos; 30 minutos; 1 hora; 2 horas; 12 horas e 24 horas e depois levados para secar antes de serem analisadas no microscópio eletrônico de varredura. Após a obtenção das fotomicrografias, estas foram examinadas por um examinador calibrado e cego que atribuiu a elas um escore que variou de 1 a 3, segundo um “Índice de Dissolução de Partículas”. A análise estatística não mostrou diferenças entre os meios utilizados para a dissolução do Biosilicato® e nem entre os métodos utilizados para sua aplicação. Não foram encontradas diferenças estatísticas entre os grupos em nenhum dos tempos analisados, no entanto uma diferença estatística foi encontrada... / Treatment of cervical dentin hypersensitivity is still the subject of several studies in dentistry, as a result of continuous and satisfactory to the painful symptoms that have not been found. A new possibility of treatment may be the use of bioactive glasses, which can form hidroxicarbonatoapatita on the dentin surface and obliterate the tubules, however, the formulations of this material available have drawbacks that hinder its application on the dentin surface. This study investigates the dissolution of particles of a modified ceramic, called Biosilicato ® on the dentin surface at different vehicle preparation and application methods. We obtained specimens of dentin to the application of the product tested and divided into groups that differed as to the application of Biosilicato ® (Robinson bristle brush or microbrush) and vehicle used for the application of the product (water or fluorine). After applying the product on these specimens were immersed in artificial saliva and left to stand at different times: 0 minutes, 15 minutes, 30 minutes, 1 hour, 2 hours, 12 hours and 24 hours and then taken to dry before be analyzed in a scanning electron microscope. After obtaining the photomicrographs, they were examined by one blinded and calibrated examiner who gave them a score ranging from 1 to 3, according to an Index of Dissolution of Particles. Statistical analysis showed no differences between the means used for the dissolution of Biosilicato ®, nor between the methods used for its implementation. There were no statistical differences between groups in any of the periods analyzed, but a statistical difference was found between the times of 1 hour and 24 hours for the group Robinson bristle brush with fluoride and between times of 15 minutes and 24 hours for microbrush group with fluorine.