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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
371

Design, Preparation and Characterization of Novel Pseudorotaxanes, Semirotaxanes, Rotaxanes, Non-Covalent Supramolecular Polymers and Polycatenanes

Niu, Zhenbin 17 October 2011 (has links)
Design and preparation of novel host/guest systems, such as pseudorotaxanes, semirotaxanes, rotaxanes and catenanes, with high association constants, enhanced yields and the abilities to respond to external stimuli are of great importance and significance due to their topological novelty and potential application. The convergence of supramolecular chemistry with polymer science provides an important way to extend the scope of polymer and material sciences by incorporating designed host/guest systems into polymers, and the resulting non-covalently linked supramolecular polymers are expected to have unusual properties due to their unique architectures compared with traditional polymers. After discovery of bis(meta-phenylene)-32-crown-10 (BMP32C10) derivative/paraquat complexes, for about a quarter century only “taco”-shaped complexes were observed by X-ray crystallography. Here, by the self-assembly of a BMP32C10 bearing two electron-donating groups (carbazoles) with electron-accepting paraquat derivatives, the first [2]pseudorotaxane and the first pseudocryptand-type poly[2]pseudorotaxane based on BMP32C10 were isolated as crystalline solids as shown by X-ray analyses. The first dual component pseudocryptand-type [2]pseudorotaxanes were designed and prepared via the self-assembly of synthetically easily accessible BMP32C10 pyridyl, quinolyl and naphthyridyl derivatives with paraquat. The formation of the pseudocryptand structures in the complexes remarkably improved the association constants by forming the third pseudo-bridge via H-bonding with the guest and π-stacking of the heterocyclic units. A pseudocryptand-type [2]pseudorotaxane was formed via the self-assembly of a dipyridyl BMP32C10 derivative and a paraquat derivative. Due to the basicity of the pyridyl group, which forms the third pseudo-bridge of the pseudocryptand, this pseudorotaxane represents the first system with acid-base adjustable association constants, i. e., finite both under acidic and neutral conditions. The first pseudocryptand-type supramolecular [3]pseudorotaxane was designed and prepared via the self-assembly of a bispicolinate BMP32C10 derivative and a bisparaquat. The complexation behavior was cooperative. In addition, the complex comprised of the BMP32C10 derivative and a cyclic bisparaquat demonstrated strong binding; interestingly, a poly[2]pseudocatenane structure was formed in the solid state for the first time. Two novel BMP32C10 cryptands, bearing covalent and metal complex linkages, were designed and prepared. By employing the self-assembly of these biscryptands, which can be viewed as AA monomers, and a bisparaquat, which can be viewed as a BB monomer, the first AA/BB-type linear supramolecular polymers with relatively high molecular weights were successfully prepared. Via the self-assembly of two BMP32C10-based cryptands, bearing covalent and metal complex (ferrocene) linkages, with dimethyl paraquat, novel [3]pseudorotaxanes were formed statistically and anticooperatively, respectively. From a hydroxyl-functionalized secondary ammonium salt a [2]semirotaxane and a [2]rotaxane were prepared successfully with dibenzo-24-crown-8 (DB24C8). X-ray analysis of a single crystal of the [2]semirotaxane confirmed its semirotaxane nature. In addition, the formation of the [2]semirotaxane can be reversibly controlled by adding KPF6 and 18C6 sequentially. This system affords a way to prepare novel supramolecular polymers. Dibenzo-30-crown-10 (DB30C10) derivatives and pyridine-based DB30C10 cryptands were prepared by employing the templating method established by our group. A [2]pseudorotaxane was prepared based on DB30C10 diol and paraquat diol. The [3]pseudorotaxane formed via the self-assembly between DB30C10 cryptand and bisparaquat diol occurred in a cooperative manner. In addition, a bromo-functionalized DB30C10 cryptand was successfully designed and prepared. An alkyne-functionalized DB30C10 cryptand was designed and is under preparation; its precursors have been prepared successfully. In the future, based on these functionalized cryptands and paraquat salts, AA and AB type monomers will be prepared. Via the self-assembly between these monomers, non-covalent supramolecular polymers with high molecular weight will be afforded. A novel DB30C10 cryptand bearing an organometallic bridge, ferrocene, was prepared via 1-(3'-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI) coupling of the crown ether diol with ferrocene dicarboxylic acid. The cryptand is dimerized in the solid state via π, π-stacking and hydrogen bonds. The ferrocene-based cryptand formed novel [2]pseudorotaxanes with paraquat and diquat PF₆ salts with association constants (Kₐ) of 1.7 ± 0.1 x 10³ and 4.2 ± 0.3 x 10⁴ M⁻¹ in acetone-d₆, respectively. In order to prepare linear polycatenanes, the preparation of which represent a real synthetic challenge, a series phenanthroline derivatives were designed and prepared. A “U” shaped monomer was successfully prepared in relative high yield with good solubility. In the future, real linear polycatenanes will be prepared. In addition, a novel diphenanthroline-based BMP32C10 derivative was prepared in high yield and the complexation behavior between it and dimethyl paraquat was studied. / Ph. D.
372

Einfluss der Jungpflanzenqualität auf die Etablierung von Spargelanlagen

Aldenhoff, Ludger 24 January 2005 (has links)
Spargelanlagen werden fast ausschließlich durch Pflanzung einjähriger Kronen im Frühjahr etabliert. Die spätere Ertragsleistung wird neben verschiedenen Maßnahmen in der Kulturführung auch maßgeblich vom Wachstum der Pflanzen im ersten Standjahr beeinflusst. In der vorliegenden Arbeit wurde der Einfluss unterschiedlicher Merkmale und Maßnahmen bei Spargeljungpflanzen anhand von Feld- und Gefäßversuchen auf das Wachstum im ersten Standjahr untersucht. Als wichtigstes Kriterium zur Beurteilung der Qualität von Spargeljungpflanzen hat sich eine hohe Pflanzmasse im Frühjahr herausgestellt. Jeweils im Vergleich zu 100-g-Pflanzen im Frühjahr war bei 50g der Verlust an Zuwachs jedoch größer, als der Zugewinn bei 150g. Aus diesem Grund ist nicht nur die durchschnittliche Pflanzmasse für eine gute Etablierung von Interesse, sondern auch der Anteil kleinerer Pflanzen. Ein Verlust an Wurzelmasse brachte bis auf die Auswirkungen der geringeren Pflanzmasse keine zusätzlichen Effekte auf die Etablierung. Auch der Gehalt löslicher Reservekohlenhydrate im Frühjahr erwies sich von eher untergeordneter Rolle. Bezüglich unterschiedlicher Behandlungen vor der Pflanzung konnten keine ausgeprägten Effekte der Temperatur bei einer kurzfristigen Lagerung und eines unterschiedlichen Pflanztermins bzw. der Lagerdauer nachgewiesen werden. Zwar zeigte sich bei einer Lagerung von über zwei Monaten eine Reduktion der Laub- und Kronenmasse im Herbst, jedoch ist die Ursache hierfür eher in der Verkürzung der Vegetationszeit zu suchen. Als ein wichtiges Qualitätsmerkmal sind in Fungizidlösungen getauchte Pflanzen (Beizung) zu nennen. Zwar ergaben sich je nach Pflanzbedingungen nicht in jedem Fall fördernde Effekte, in der Summe der Versuchsauswertungen über mehrere Jahre und Mittel war aber eine deutliche Steigerung des Wachstums durch Tauchbehandlungen nachzuweisen. Da auch die alleinige Tauchung der Jungpflanzen in Wasser zu einer Vitalitätssteigerung führte, sollte die Beizung möglichst direkt vor der Pflanzung durchgeführt werden. Als Fazit der vorliegenden Untersuchungen ist bezüglich der Jungpflanzenqualität bei Spargel vornehmlich auf gleichmäßig hohe Pflanzmassen sowie einer kurz vor der Pflanzung erfolgten Beizung Wert zu legen. / Asparagus plantings are usually established by planting one year old crowns in the spring. The later yield potential is influenced by culture practical measurements and the growth of the plants in the first year. This work deals with the influence of different characters and measurements of young asparagus plants on the growth in the first year by trials in the field and pots. The most important criterion of the evaluation of the quality of asparagus plants had been the weight of the plants in spring. Comparing with 100-g-plants in the spring the lack of growing of plants with 50g was higher than the better growing with 150g. So it is not only interesting to have a high average plant weight for a good establishment of an asparagus planting but although the part of smaller plants. A lack of root weight showed not more effects than only the lack of plant weight. Although the content of soluble concentration of carbohydrates in the spring showed no to be important. Due to different treatments before planting there were no strange effects of the temperature during a short storage and a different time of planting or period of storage. There was a reduction of fern- and crown weight in autumn after storage before planting over a period of two months, but the reason seems to be the reduction of the vegetation period. An important criterion of quality is a preplant fungicide dip for asparagus crowns. Although because of different conditions after planting there was not every time a better establishment of the plants, but in consideration of all trials in different years and fungicides there was a significant increase of the growth because of dipping treatments. Because the dipping of the crowns only in water before planting showed effects of a better vitality the fungicide dips should be done directly before planting. The result of this work concerning the quality of asparagus crowns is a constant high crown weight and a fungicide dip just before planting.
373

Pour une histoire et une esthétique de l'écran fragmenté au cinéma

Mathieu, Philippe 11 1900 (has links)
Bien que son existence soit presque aussi vieille que le cinéma, l‘écran fragmenté (que les académiciens et autres professionnels du cinéma de langue anglaise désignent communément sous l‘appellation « split screen ») n‘a jamais fait l‘objet d‘analyses véritablement approfondies. Quand il est mentionné dans les livres d‘histoire, l‘écran fragmenté est rapidement esquivé. Pourtant, ses apparitions sont nombreuses. Ce mémoire de maîtrise cherche à corriger nombre d‘idées préétablies en exposant l‘histoire de cette manifestation visuelle, en commençant des débuts (le « cinéma des premiers temps ») jusqu‘à l‘arrivée du « cinéma numérique » du nouveau millénaire. / Despite the fact its existence is almost as old as cinema itself, the fragmented screen (commonly known as « split screen » in the academic and professional world of the seventh art) has never been the object of serious and exhaustive analysis. When mentioned in history books, the fragmented screen is quickly eluded. And yet its appearances are numerous. This Master thesis aims at rectifying a number of pre-established ideas by exposing the history behind this visual manifestation, from early cinema to the arrival of digital films.
374

Pour une histoire et une esthétique de l'écran fragmenté au cinéma

Mathieu, Philippe 11 1900 (has links)
Bien que son existence soit presque aussi vieille que le cinéma, l‘écran fragmenté (que les académiciens et autres professionnels du cinéma de langue anglaise désignent communément sous l‘appellation « split screen ») n‘a jamais fait l‘objet d‘analyses véritablement approfondies. Quand il est mentionné dans les livres d‘histoire, l‘écran fragmenté est rapidement esquivé. Pourtant, ses apparitions sont nombreuses. Ce mémoire de maîtrise cherche à corriger nombre d‘idées préétablies en exposant l‘histoire de cette manifestation visuelle, en commençant des débuts (le « cinéma des premiers temps ») jusqu‘à l‘arrivée du « cinéma numérique » du nouveau millénaire. / Despite the fact its existence is almost as old as cinema itself, the fragmented screen (commonly known as « split screen » in the academic and professional world of the seventh art) has never been the object of serious and exhaustive analysis. When mentioned in history books, the fragmented screen is quickly eluded. And yet its appearances are numerous. This Master thesis aims at rectifying a number of pre-established ideas by exposing the history behind this visual manifestation, from early cinema to the arrival of digital films.
375

Propriétés supramoléculaires des cations diimidazolium disubstitués : des complexes d’inclusion en solution aux interactions à l’état cristallin et cristal liquide

Noujeim, Nadim 08 1900 (has links)
Les sels d’imidazolium ont un rôle important dans certaines protéines et acides nucléiques et ont été utilisés à de nombreuses reprises dans des assemblages supramoléculaires en raison de leurs propriétés uniques. Les sels de diimidazolium dérivés sont toutefois moins connus. Ils ont pour l’instant uniquement été utilisés comme des précurseurs de carbènes N-hétérocycliques. Ils sont donc à la base de plusieurs catalyseurs utilisés pour des réactions de couplage croisés mais leurs propriétés sont toutefois méconnues dans le cadre de la chimie supramoléculaire. Cette classe de composés a nottament attiré notre attention en raison de la facilité de modification de leurs propriétés physico-chimiques par modification de leur structure chimique. L’objectif général des travaux présentés dans cette thèse est l’étude des propriétés supramoléculaires des sels de diimidazolium disubstitués en solution (aqueuse ou organique), ainsi qu’en phase solide ou cristal-liquide. L’influence de l’espaceur entre les deux noyaux imidazolium ainsi que l’influence des substituants latéraux et des contre-ions a été étudiée. Dans un premier temps, les propriétés de complexation des sels de diimidazolium à des macrocycles sont étudiées. Les sels bromure sont étudiés en solution aqueuse avec plusieurs cyclodextrines et le cucurbit[7]uril, et les sels hexafluorophosphate sont étudiés en solution organique pour leur complexation avec l’éther couronne DB24C8 et un calix[4]arène. Cette nouvelle classe de composés a montré de très bonnes propriétés de complexation à ces différents macrocycles en solution et a également permis de contrôler différents assemblages supramoléculaires à l’interface air-eau. Dans un deuxième temps, l’étude des sels de phénylènediimidazolium a permis de modifier les propriétés de complexation en solution pour obtenir la formation de complexes multiples avec le cucurbit[7]util en solution aqueuse. Cette même famille de composés a également permis la formation de cristaux liquides ioniques lorsque les substituants sont des chaînes alkyles plus longues. La résolution de plusieurs structures cristallines de différents sels de diimidazolium a finalement permis de comprendre la nature des interactions intermoléculaires à l’état cristallin. La recherche présentée dans cette thèse a donc permis une étude détaillée des propriétés supramoléculaires des sels de diimidazolium dans tous les états de la matière qui leur sont accessibles. / Imidazolium salts play an important role in different proteins and nucleic acids and have been used many times in supramolecular assemblies due to their unique properties. Diimidazolium salts derived from imidazolium salts are less known. To date, they have only been used as precursors for N-heterocyclic carbenes, which are used to catalyze various cross-coupling reactions. Their properties are not well known in supramolecular chemistry. This class of compounds attracted our attention because of the ease of tuning their properties by modifying their chemical structure. The main goal of the research presented in this thesis was to study the supramolecular properties of disubstituted diimidazolium salts in solution (aqueous or organic solution), in the solid state and in the liquid-crystalline state. The role of the spacer between the two imidazolium moieties, of the sidechains and of the counterions was studied. Firstly, the complexation between diimidazolium salts and various macrocycles was studied. Bromide salts were studied in aqueous solution with cyclodextrins and cucurbit[7]uril, while hexafluorophosphate salts were studied in organic solution with a DB24C8 crown ether and a calix[4]arene. This novel class of compounds showed very promising complexation properties with these macrocycles in solution and also allowed us to control the formation of various supramolecular assemblies at the air-water interface. Secondly, phenylenediimidazolium salts were studied and allowed the modification of the complexation properties in aqueous solution. Multiple complexes can be formed simultaneously with cucurbit[7]uril in aqueous solution. The same class of compounds also has the ability to yield ionic liquid crystals when the alkyl sidechains are long. The resolution of the crystalline structures of some synthesized diimidazolium salts allowed us to understand the nature of the intermolecular interactions in the solid state. The research presented in this thesis is a complete study of the supramolecular properties of diimidazolium salts in every accessible state of matter.
376

Vybrané otázky ekonomického myšlení dětí na 1. stupni základní školy / Questions of Economics Understanding of Primary School Students

Bartakovičová, Sylva January 2014 (has links)
BARTAKOVIČOVÁ, Sylva. Questions of Economics Understanding of Primary School Students. Prague, 2014. Diploma thesis. UK, PedF. The aim of this thesis is to analyze the economic thinking of third grade students in primary school. On the basis of identified deficiencies, a set of ideas leading to more effective teaching is proposed. The theoretical section includes an examination of the state of economic thinking in primary school pupils in the Czech Republic and abroad. This explains the present form of financial education in the Czech Republic, and examines children's understanding, particularly in relation to constructivism. The practical section describes the preparation and implementation of qualitative research in the form of semi-structured individual interviews with pupils in their 3rd year, and 1st grade of primary school. In the conclusion, a set of ideas aimed to develop the financial thought processes of younger school students, supplement their knowledge, and strengthen their overall economic thinking, is proposed.
377

Začlenění Lucemburska mezi země Koruny české / Incorporation of Luxembourg among the Lands of the Bohemian Crown

Stehlík, Martin January 2013 (has links)
The object of this diploma thesis is the incorporation of Luxembourg among the Lands of the Bohemian Crown. This theme was chosen primarily for the reason that it have not been compiled and analyzed by historiography so far. Available literature usually takes the incorporation of Luxembourg in the Bohemian Crown automatically as a fact without further reasoning. As a result of this approach there is considerable amount of inaccuracies and mistakes in literature. Primary inaccuracy is in a date or in a time period determining the incorporation of Luxembourg in the Bohemian Crown, when literature often indicate the reign of King Charles IV or even the reign of King John of Luxembourg. The purpose of this diploma thesis is not only analyzing the process of incorporation, but also disproves continuing inaccuracies. For this reason the diploma thesis draws and analyzes essential facts primarily from original sources and confront them with available literature. First chapter briefly introduces the institution of the Bohemian Crown for her distinguish from the Kingdom of Bohemia. Further it analyzes the terms "crown" and "incorporation". At last it describes a beginning of the Bohemian Crown and analyzes fundamental documents of this institution. Following second chapter describes the personal union...
378

Conception de nouveaux inhibiteurs d'enzymes et de chélatants de métaux à base d'iminosucres / Iminosugars-based macrocycles to deliver new sweet azacrowns

Bordes, Alexandra 02 December 2016 (has links)
Les iminosucres, analogues de sucres dans lesquels l'oxygène endocyclique a été remplacé par un atome d'azote, constitue une classe importante de mimes de sucres. Aujourd'hui, leurs applications se limitent au domaine biologique car ces composés ont montré un potentiel thérapeutique prometteur. Il serait intéressant d'élargir le domaine d'application de ces iminosucres, et la combinaison de ces structures présentant un azote endocyclique pourrait conduire à de nouveaux macrocycles inédits présentant des propriétés de chélation innovantes. Pour cela, l'introduction d'une chaîne alkyle en position pseudoanomérique donne accès à une nouvelle classe de composés, les iminosucres C-glycosides dont la fonctionnalisation en positions C-5 et C-1 est nécessaire.La première partie de ce travail se focalise sur le développement d'une voie de synthèse rapide et efficace d'iminosucres C-glycosides à six et sept chaînons au moyen d'une réaction tandem de Staudinger aza-Wittig. Pour accéder à ces composés de choix, notre stratégie se base sur des réactions de fonctionnalisation diastéréosélectives et stéréocontrollées. La seconde partie de cette thèse a été consacrée à la synthèse d'iminosucres aza-couronnes, dont les structures constituent un nouveau type de récepteurs moléculaires. L'étude des propriétés de chélation de ces nouveaux macrocycles des cations métalliques a montré des premiers résultats prometteurs et encourageants grâce à des analyses par RMN et par fluorimétrie. / Iminosugars, sugar analogs in which the endocyclic oxygen has been replaced by nitrogen, constitute a major class of sugar mimetics. Their application has been limited to the biological field so far as these compounds have shown promising therapeutic properties[1]. Interestingly, their structural analogy with sugars combined with the presence of an endocyclic nitrogen atom could deliver innovative macrocycles that could display chelation properties as well as catalytic potential when bound to metals and associated as duplex or higher multiplicity scaffolds. For this purpose, efficient introduction of an alkyl chain at the pseudoanomeric position of the iminosugar to yield an iminosugar C-glycoside[2] displaying two arms at C-5 and C-1 position is necessary. The first part of this work focused on the development of an efficient and convergent synthesis of seven and six membered iminosugars C-glycosides using a highly diastereoselective tandem Staudinger-Aza-Wittig reaction is presented. To access to these new compounds, our strategy is based on a highly diastereoselective and stereocontrolled functionalization. The second part of this work is based on the use of these structures to build up unprecedented iminosugar-aza-crowns, a new type of molecular receptors, using the strategy way developed in the first part. These news sweet aza-crowns displaying with various linkages showed promising results through their preliminary chelation properties by NMR and fluorimetric techniques.
379

Activation non-métallique de la polymérisation anionique par ouverture de cycle des cyclopropane-1,1-dicarboxylates : application à la synthèse de transporteurs transmembranaires

Illy, Nicolas 10 December 2009 (has links)
La base phosphazène ButP4 associée au thiophénol ou au bis (2-mercaptoéthyl) éther a été utilisée avec succès pour amorcer quantitativement la polymérisation anionique par ouverture de cycle des monomères cyclopropane-1,1-dicarboxylates de dialkyle. Pour des températures comprises entre 30 et 60°C dans le THF ou entre 30 et 100°C dans le toluéne, le mécanisme observé est celui d'une polymérisation anionique vivante qui conduit à des polymères présentant des indices de polymolécularité faibles et dont les Mn expérimentaux (mesurés par SEC et RMN 1H) sont en accord avec les valeurs théoriques. D'autres systèmes déamorçage comme le carbazole ou des composés possédant un proton acide associés à ButP4 conduisent également à des polymères bien définis. Une étude cinétique montre que l'ordre interne en monomère est égal à 1 sur l'ensemble de la gamme de conversion. Le système déamorçage thiophénol / ButP4 dans le THF présente une réactivité bien supérieure à celle du thiophénolate de sodium dans le DMSO qui est le système classique d'amorçage pour ce type de polymérisation. Différents agents de terminaison, comme l'acide chlorhydrique, le bromure d'allyle ou le bromure de propargyle, ont été utilisés pour terminer les réactions et ont conduit à l'obtention de polyméres hétérotéléchéliques. D'autres dérivés de cyclopropanes présentant des substituants variés ont également été examinés. Ces résultats ouvrent de très intéressantes perspectives dans la préparation d'architectures complexes comme des copolyméres à blocs, greffés ou en étoile. Les premières expériences de copolymérisation ont d'ailleurs été couronnées de succès. Afin d'obtenir de nouveaux canaux ioniques artificiels, différents monomères cyclopropane-1,1- dicarboxylates porteurs d'éthers-couronne ont été synthétisés. La polymérisation anionique par ouverture de cycle de ceux-ci a été étudiée en utilisant soit le thiophénolate de sodium soit le système thiophénol / ButP4 comme amorceur. Ces travaux ont également permis l'obtention d'un nouveau type de poly(éther-ester) qui s'est révélé intéressant comme perméabilisant membranaire. Les interactions des oligo(éther-ester)s avec des membranes modèles planes, des vésicules unilamellaires et des cellules ont été étudiées en collaboration avec des physiciens et des biologistes. Des résultats prometteurs en termes de transport d'ions ont été obtenus et sont présentés dans ce mémoire / The tetrameric phosphazene base ButP4 in association with thiophenol or bis(2-mercaptoethyl) ether has been successfully used in order to initiate the anionic ring-opening polymerization of di-n-alkyl cyclopropane-1,1-dicarboxylates. Well-defined monofunctional or difunctional polymers with a very narrow molecular weight distribution were obtained through a living process at temperatures between 30 and 60°C in THF or between 30 and 100°C in toluene. An excellent agreement is observed between theoretical and experimental Mn values (measured by SEC and by NMR). Other initiating systems such as carbazole or compounds with an acidic proton in association with ButP4 lead also to welldefined polymers. A kinetic study shows a first order with respect to the monomer concentration over the entire conversion range. The initiating system thiophenol / ButP4 in THF shows a much higher reactivity compared to the alkali metal thiophenolate which is the classical one. The living ends were reacted with different terminating agents such as hydrochloric acid, allyl and propargyl bromide thus leading to telechelic polymers. Other cyclopropane derivatives with various substituents have been also examined. These results open very exciting perspectives for the preparation of new architectures such as block and graft copolymers, star polymers. The first copolymer attempts were very successful. With the aim of designing new ion channel biomimics, cyclopropane-1,1-dicarboxylate monomers with crown-ethers substituents were synthesized. The anionic ring-opening polymerization of these monomers has been investigated using either sodium thiophenolate or thiophenol activated by ButP4. Moreover a new alternating poly(ether-ester) was obtained which is an interesting membrane permeabilizer. Its interaction with unilamellar vesicles, planar phospholipidic membranes and cells was studied in collaboration with biophysicists and biologists. Very promising results have been obtained
380

Estudo dos fatores interferentes na adaptação marginal de próteses confeccionadas em titânio comercialmente puro e ligas alternativas / Study of determining factors for the marginal fit of prosthesis made of commercially pure titanium and alternative alloys

Soriani, Natércia Carreira 08 April 2011 (has links)
O desajuste de copings obtidos por fundição por cera perdida está sujeita à vários fatores tais como: contração de fundição do metal, expansão do revestimento, uso de espaçadores, entre outros. O objetivo do estudo foi avaliar o desajuste marginal pré e pós cimentação de copings obtidos com três ligas de metais básicos - Ni-Cr-Be (VB), Ni-Cr (V2) e Co-Cr (KE) fundidos a partir de dois revestimentos - Termocast (TE) e Microfine (MI) e Titânio comercialmente puro (TR) fundido com dois revestimentos - Rematitan Plus (RP) e Rematitan Ultra (RU), nas condições E0, sem espaçador, E1, com uma camada de espaçador e E2, com duas camadas de espaçador. A partir de uma matriz metálica, foram obtidos 240 copings, sendo 10 para cada combinação metal-revestimento-espaçador. Foi utilizado Microscópio Óptico para determinação do desajuste nas condições pré e pós cimentação, efetuada com cimento de fosfato de zinco. Foi realizado teste de tração pós cimentação para determinação da carga de remoção dos copings da combinação KE-MI. Foram realizados ensaios dilatométricos para a definição dos coeficientes de expansão térmico linear dos metais e dos revestimentos, determinação da expansão de presa dos revestimentos, além de ensaio para determinação da variação dimensional das fundições e análises de microscopia eletrônica de varredura (MEV). Os dados de desajuste marginal foram analisados estatisticamente pelos testes Anova e Student-Newman-Keulsa que revelaram significância estatística (0,05) para os fatores isolados. Para os metais, os valores de desajuste (&mu;m) foram V2 (85) = VB (89) < KE (119) < TR (171) e para os revestimentos, MI (68) < TE (128) < RP (153) < RU (188). Para o espaçador os desajustes foram E2 (76) < E1 (125) < E0 (147). Os menores valores de desajuste pós cimentação foram obtidos pelas combinações: VB-MI-E2 (44), V2-MI-E2 (47), VB-MI-E1 (52), VB-MI-E0 (55), TR-RU-E2 (67), V2-MI-E1(70), V2-TE-E2 (77), V2-MI-E0 (86), VB-TE-E2 (103), todas as demais combinações tiveram valores acima de 120 &mu;m, adotado como referência clinicamente aceitável. Houve diferença significante para as cargas de remoção entre as condições E2 (49 Kgf) < E1 (74 Kgf) < E0 (102 Kgf). Os valores de expansão de presa foram: TE (1,05%), MI (0,88%), RP (0,19%) e RU (0,02%). Para o ensaio dilatométrico, os valores de contração dos metais foram: KE (0,270%), V2 (0,262%), VB (0,256%) e TR (0,160%). Para os revestimentos, houve diferença significante, entre MI (0,74%) e RU (-1,63%). A análise da variação dimensional revelou diferença significante para os metais: V2 (0,08%) &ge; VB (-0,12%) &ge; KE (-0,21%) &ge; R (-0,85%) e para os revestimentos: MI (0,09%) > TE (-0,26%) = RP (-0,50%) > RU (-1,19%). Os revestimentos MI e RU apresentaram micro estrutura mais refinada, contendo cristais mais homogêneos e menos porosidade que os revestimentos RP e TE. Com base nos dados analisados, é válido afirmar que, embora a utilização de revestimentos com boas propriedades dilatométricas facilite a confecção de copings com ajuste marginal adequado, a utilização de espaçadores pode ser indispensável para obtenção de resultados clínicos satisfatórios. / The marginal fit of copings made by lost-wax casting are subject to different variation factors, such as contraction of molten metal, investment thermal expansion, die spacer use and others. This study aimed to evaluate the marginal adaptation of copings before and after cementation, obtained with three basic alloys - Ni-Cr-Be (VB), Ni-Cr (V2) and Co-Cr (KE), melted with two investments - Termocast (TE) and Microfine (MI) - and commercially pure titanium (TR) melted with Rematitan Plus (RP) and Rematitan Ultra (RU), in the conditions: E0 (without die spacer), E1 (one die spacer layer) and E2 (two die spacer layers). From a metal matrix, 240 copings were obtained, 10 for each combination metal-investment-spacer. An optical microscope was used to determine the misfit before and after the cementation with zinc phosphate cement. A tensile strength test was carried out after the cementation in order to determine the remotion load. Dilatometric tests were used to calculate the linear thermal expansion coefficients of metals and investments, to determine the setting expansion of the investments and to determine the dimensional variation as well. After the tests, the data were analyzed statistically. The analysis of variance for the marginal adaptation showed statistical significance (0.05) for all variation factors. For the metals, the misfit, in &mu;m, was: V2 (85) = VB (89) < KE (119) < TR (171); and for investments, MI (68) < TE (128) < RP (153) < RU (188). The misfit for factor die spacer was: E2 (76) < E1 (125) < E0 (147). Having accepted the value of 120 &mu;m as a reference limit of clinically acceptable results, the lowest misfit values for different combinations after cementation were: VB-MI-E2 (44), V2-MI-E2 (47), VB-MI-E1 (52), VB-MI-E0 (55), RU-TR-E2 (67 &mu;m), V2-MI-E1 (70), E2-V2-TE (77), V2-MI-E0 (86), VB-TE-E2 (103). All the other combinations had values above 120 &mu;m. There was a significant difference for tensile strength under the conditions E2 (49 Kgf), E1 (74 Kgf) and E0 (102 kgf). The setting expansion values were: TE (1.05%), MI (0.88%), RP (0.19%) and RU (0.02%). According to the dilatometer test, the values of contraction for the metals were: KE (0.27%), V2 (0.262%), VB (0.256%) and TR (0.16%), and for the investments: MI (0.74%) and RU (-1.63%). The analysis of variance revealed significant differences for metals dimensional variation: V2 (0.08%) &ge; VB (-0.12%) &ge; KE (-0.21%) &ge; TR (-0.85%) and investments: MI (0.09%) > TE (-0.26%) = RP (-0.50%) > RU (-1.19%). In conclusion, the use of investments with good dilatometric properties improves the marginal fit of the copings, but the die spacer use may be essential for obtaining satisfactory clinical results.

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