Today’s society is currently performing an exit from fossilfuel energy sources. The change to sustainable alternativesrequires inexpensive and environmentally friendly energy storagedevices. However, most current devices contain expensive,rare or toxic materials. These materials must be replaced bylow-cost, abundant, nontoxic components.In this thesis, I suggest the production of paper-based electricdouble-layer capacitors (EDLCs) to meet the demand oflow-cost energy storage devices that provide high power density.To fulfill the requirements of sustainable and environmentallyfriendly devices, production of EDLCs that consist of paper,graphite and saltwater is proposed. Paper can be used as aseparator between the electrodes and as a substrate for theelectrodes. Graphite is suited for use as an active material in theelectrodes, and saltwater can be employed as an electrolyte.Westudied and developed different methods for the productionof nanographite and graphene from graphite. Composites containingthese materials and similar advanced carbon materialshave been tested as electrode materials in EDLCs. I suggest theuse of cellulose nanofibers (CNFs) or microfibrillated cellulose(MFC) as a binder in the electrodes. In addition to improvedmechanical stability, the nanocellulose improved the stabilityof graphite dispersions and the electrical performance of theelectrodes. The influence of the cellulose quality on the electricalproperties of the electrodes and EDLCs was investigated.The results showed that the finest nanocellulose quality is notthe best choice for EDLC electrodes; MFC is recommended forthis application instead. The results also demonstrated thatthe capacitance of EDLCs can be increased if the electrodemasses are adjusted according to the size of the electrolyte ions.Moreover, we investigated the issue of high contact resistancesat the interface between porous carbon electrodes and metalcurrent collectors. To reduce the contact resistance, graphitefoil can be used as a current collector instead of metal foils.Using the suggested low-cost materials, production methodsand conceptual improvements, it is possible to reduce the material costs by more than 90% in comparison with commercialunits. This confirms that paper-based EDLCs are apromising alternative to conventional EDLCs. Our findings andadditional research can be expected to substantially supportthe design and commercialization of sustainable EDLCs andother green energy technologies. / I dagens samhälle pågår en omställning från användning avfossila energikällor till förnybara alternativ. Denna förändringkräver miljövänliga och kostnadseffektiva elektriska energilagringsenheterför att möjliggöra en kontinuerlig energileverans.Dagens energilagringsenheter innehåller ofta dyra, sällsyntaeller giftiga material som behöver bytas ut för att nå hållbaralösningar.I denna avhandling föreslås att tillverka pappersbaseradesuperkondensatorer som möter kraven för kostnadseffektivaelektriska energilagrare med hög effekttäthet. För att nå kravenpå miljömässigt hållbara enheter föreslås användning avendast papper, grafit och saltvatten. Papper kan användas somseparator mellan elektroder likväl som substrat vid elektrodbestrykning.Grafit kan användas som aktivt elektrodmaterialoch saltvatten fungerar som elektrolyt. Olika metoder har härutvecklats för att producera nanografit och grafen från grafit.Dessa material har tillsammans med liknande, kommersiellt tillgängliga,avancerade kolmaterial testats i elektrodkompositerför superkondensatorer. Som bindemedel i dessa kompositerföreslås nanofibrillerad eller mikrofibrillerad cellulosa. Jaghar demonstrerat att nanocellulosa ökar dispersionsstabilitetensamt förbättrar den mekaniska stabiliteten och dom elektriskaegenskaperna i elektroderna. Hur cellulosans kvalitet påverkarelektroderna har undersökts och visar att den finaste kvaliteteninte är det bästa valet för superkondensatorer, istället rekommenderasmikrofibrillerad cellulosa. Utöver detta demonstrerasmöjligheten att öka superkondensatorernas kapacitans genomatt balansera elektrodernas massa med hänsyn till jonernasstorlek i elektrolyten. I avhandlingen diskuteras även svårigheternamed hög kontaktresistans i gränssnittet mellan porösakolstrukturer och metallfolie och hur detta kan undvikas omgrafitfolie används som kontakt.Genom att använda de material, produktionstekniker ochkonceptförbättringar som föreslås i avhandlingen är det möjligtatt reducera materialkostnaderna med mer än 90% i jämförelsemed kommersiella superkondensatorer. Detta bekräftar att pappersbaserade superkondensatorer är ett lovande alternativoch våra resultat tillsammans med vidare utveckling harstor potential att stödja övergången till miljömässigt hållbarasuperkondensatorer och annan grön energiteknik. / <p>Vid tidpunkten för disputationen var följande delarbeten opublicerade: delarbete 6 inskickat.</p><p>At the time of the doctoral defence the following papers were unpublished: paper 6 submitted.</p>

No description available.

Quando as atividades de um sistema mecatrônico são realizadas em ambientes com intenso campo elétrico e ou magnético, os dispositivos que irão executar as tarefas devem ser cuidadosamente projetados para que a presença de peças metálicas não se torne um risco. O campo elétrico pode gerar descargas elétricas e o campo magnético, exercer forças não previstas sobre peças metálicas. Assim o uso de alguns elementos, como motores elétricos, peças metálicas ou sensores eletrônicos se torna inviável. A motivação inicial para esse trabalho foi encontrar um atuador que possa ser construído sem o uso de elementos metálicos e com ele, construir um manipulador inerte a campos magnéticos e elétricos. Neste contexto, a transmissão de energia para os atuadores por meios hidráulicos ou pneumáticos se torna a opção mais indicada. Frequentemente, sistemas pneumáticos e hidráulicos apresentam atuadores com componentes metálicos, devido a resistência mecânica destes componentes. Em situações na qual os requisitos quanto a esforços são menores, elementos metálicos podem ser substituídos por materiais poliméricos de uso comum na Engenharia. Entre os atuadores hidráulicos e pneumáticos, um que já apresenta poucas partes metálicas é o músculo pneumático artificial (MPA). O MPA possui características tais como: baixo peso relacionado ao esforço gerado, escala de esforços similar a um cilindro pneumático de mesmo tamanho e construção simples. Assim, o MPA foi escolhido como atuador para o manipulador não-condutor desenvolvido neste trabalho. Adotando o MPA como elemento central, este trabalho tem por objetivo identificar as diretrizes para a aplicação do MPA na construção de um manipulador inerte a campos elétricos e magnéticos. Para isso, primeiramente foi desenvolvido um MPA livre de qualquer parte metálica. Visando sua aplicação, as características do músculo como: gama de esforços, tempo de resposta e histerese foram avaliadas através de testes. Algumas estratégias de controle do atuador foram testadas e comparadas, e com o atuador desenvolvido foi construído um manipulador inerte a campos magnéticos e elétricos. O manipulador construído tem como objetivo exercer movimentos distintos sobre a mão de um paciente, o mesmo deve acompanhar o paciente durante um exame de ressonância magnética. O atuador apresentou uma gama de esforços dentro do previsto, um tempo de resposta característico de atuadores pneumáticos e ao contrário do esperado, uma baixa histerese. Através de elementos mecânicos e com o uso de dois MPA, o manipulador foi capaz de exercer um trabalho sobre a mão de um voluntario fora do campo da RM, mostrando a viabilidade da aplicação. / When activities executed by a mechatronic system are performed in environments with strong magnetic and or electric field, the devices that will perform the tasks should be carefully designed so that the presence of metal parts does not become a risk. The electric field can generate electrical currents and the magnetic field may exert unexpected force in a metal part. Thus the use of some elements, such as electric motors, metallic parts or electronic sensors becomes unviable. The initial motivation for this work was to find an actuator that could be built without metallic elements and, using such actuator, build a manipulator inert to magnetic and electric fields. In this context, the use of hydraulic or pneumatic actuators becomes the most indicated option. Frequently, pneumatic and hydraulic systems have actuators with metal parts so as resist mechanical loads. In situations where the actuator is loaded by small loads, metal parts may be replaced by polymeric materials commonly used in Engineering. Among hydraulic and pneumatic actuators, one that already presents a few metal parts is the pneumatic artificial muscle (PAM). PAM has characteristics such as: low weight to effort ratio, simple construction as well as range of generated force and dimensions similar to a pneumatic cylinder. Thus, the PAM is chosen as the actuator for the non-conductive manipulator developed in this work. Adopting the PAM as a central element, this work aims identifying directives on using the PAM in the construction of a manipulator inert to electric and magnetic fields. For this, firstly it is developed a PAM free from any metal part. Next, the characteristics of the PAM such as range of efforts, response time and hysteresis curve are assessed through tests. Some strategies for the actuator control are tested and compared. Finally, using the developed actuator, a manipulator inert to magnetic and electric fields are constructed. The purpose of this manipulator is to induce motions to the fingers of a patient hand while the patient is examined in a MRI (magnetic resonance imaging) equipment. The actuator presented a range of efforts according to expectations, a response time compatible with pneumatic actuators and, contrary to expectations, low hysteresis.

Le dibenzoylméthane (DBM) a été étudié comme catalyseur pour la copolymérisation par ouverture de cycle du L-lactide (LA) et du ε-caprolactone (CL) amorcée par des alcools en masse à haute température. Des copolymères présentant des structures gradient à statistique ont été formés. L’étude cinétique a mis en évidence que le DBM est un faible activateur de bout de chaîne et de monomère, l’apparente accélération de la copolymérisation étant due à la formation in situ d’acides carboxyliques catalysant la réaction à leur tour. L’acide benzoïque (BA), un acide carboxylique faible, a ensuite été étudié pour les homopolymérisations par ouverture de cycle du LA et du CL amorcées par des alcools en masse à haute température. L’étude cinétique a mis en évidence un mécanisme bifonctionnel et une différence de réactivité des deux monomères en présence de BA validés par des calculs théoriques. Une gamme de copolymères statistiques présentant différentes compositions ont été synthétisés par copolymérisation par ouverture de cycle du LA et CL catalysé par BA et amorcé par différents alcools en masse à haute température. Finalement, plusieurs catalyseurs organiques ont été testés pour la copolymérisation du LA et CL. / Dibenzoylmethane has been investigated as organocatalyst for the bulk ring-opening copolymerization (ROcP) of L-Lactide (LA) and ε-caprolactone (CL) initiated by alcohols at high temperature. Copolymer presenting a gradient to statistical structure has been generated. Kinetic study has pointed out that DBM is a poor chain end and monomer activator, the apparent acceleration of the ROcP process may be due to the in situ generation of carboxylic acids which can catalyze the reaction as well. Benzoic acid, a weak carboxylic acid, has then been investigated for the efficient bulk ring-opening polymerization (ROP) of LA and CL initiated by various alcohols at high temperature. The kinetic study has pointed out that LA and CL have different reactivity in presence of benzoic acid which acts as a bifunctional activator. The experimental results were supported by computational calculations. An array of statistical copolymer of varying LA/CL compositions have been synthesized by ROcP of LA and CL catalyzed by BA in presence of various alcohol as initiators in bulk at high temperature. Finally, miscellaneous organocatalysts have been tested for the ROcP of LA and CL.

La chimie des composés à base d'iode hypervalent (i.e., iodanes) connaît un fort intérêt depuis le début des années 1990 comme en témoigne le panel de composés iodés disponibles commercialement et le nombre de transformations chimiques que ces réactifs peuvent promouvoir. Au cours de la dernière décennie,les recherches se sont essentiellement concentrées sur le développement d’iodanes chiraux et leurs applications en synthèse asymétrique. La plupart de ces iodanes sont utilisés pour la création hautement sélective de liaison carbone-hétéroatome (C–O, C–N, C–F…). La création asymétrique de liaison carbone-carbone (C–C) médiée par des iodanes chiraux a cependant été très peu étudiée jusqu'à présent. Dans ce contexte, notre groupe de recherche a décrit la synthèse de nouveaux iodanes-λ5chiraux biaryliques et de type Salen ainsi que leurs applications à la désaromatisation oxygénante asymétrique de 2-alkyl phénols avec des excès énantiomériques (ee) supérieurs à 90%. Ces travaux de thèse sont consacrés au développement de nouveaux iodanes-λ3 chiraux porteurs de ligands carbonés transférables pour la création asymétrique sans métal de liaison C–C. Sont plus particulièrement décrits la synthèse de bis(alcynyl-iodanes-λ3) biphényliques atropopurs et leur utilisation dans l’alcynylation énantiosélective de β-cétoesters (jusqu’à 68% ee) et, pour la première fois, de naphtols (jusqu’à 84% ee). / The chemistry of hypervalent organoiodine compounds (i.e., iodanes) has unarguably experienced an impressive development since the early 1990s, as evidenced by both the diversity of iodane reagents that are commercially available today and the number of chemical transformations that those reagents can promote.Over the last decade, the elaboration of new chiral iodanes and their applications in asymmetric synthesis have attracted special interests and research efforts. Most ofthem are involved in highly selective carbon-heteroatom bond-forming reactions (C–O, C–N, C–F…). However, C–C bond-forming reactions in a stereoselective fashion with chiral iodane are yet underexploited. In this context, our research group reported the synthesis of new biarylic and Salen-type chiral λ5‐iodanes and their successful application to the asymmetric hydroxylative phenol dearomatization of 2alkylphenols, with enantiomeric excesses (ee) above 90%. This thesis work is dedicated to the development of new chiral λ3‐iodanes bearing transferable carbon-basedligands for metal‐free asymmetric C–C bond construction. In particular, the synthesis of chiral biphenylic bis(alkynyl-λ3-iodanes) and their successful application to the enantioselective alkynylation of β‐ketoesters (up to 68% ee) and 2‐substituted naphthols (up to 84% ee) are described.

Quando as atividades de um sistema mecatrônico são realizadas em ambientes com intenso campo elétrico e ou magnético, os dispositivos que irão executar as tarefas devem ser cuidadosamente projetados para que a presença de peças metálicas não se torne um risco. O campo elétrico pode gerar descargas elétricas e o campo magnético, exercer forças não previstas sobre peças metálicas. Assim o uso de alguns elementos, como motores elétricos, peças metálicas ou sensores eletrônicos se torna inviável. A motivação inicial para esse trabalho foi encontrar um atuador que possa ser construído sem o uso de elementos metálicos e com ele, construir um manipulador inerte a campos magnéticos e elétricos. Neste contexto, a transmissão de energia para os atuadores por meios hidráulicos ou pneumáticos se torna a opção mais indicada. Frequentemente, sistemas pneumáticos e hidráulicos apresentam atuadores com componentes metálicos, devido a resistência mecânica destes componentes. Em situações na qual os requisitos quanto a esforços são menores, elementos metálicos podem ser substituídos por materiais poliméricos de uso comum na Engenharia. Entre os atuadores hidráulicos e pneumáticos, um que já apresenta poucas partes metálicas é o músculo pneumático artificial (MPA). O MPA possui características tais como: baixo peso relacionado ao esforço gerado, escala de esforços similar a um cilindro pneumático de mesmo tamanho e construção simples. Assim, o MPA foi escolhido como atuador para o manipulador não-condutor desenvolvido neste trabalho. Adotando o MPA como elemento central, este trabalho tem por objetivo identificar as diretrizes para a aplicação do MPA na construção de um manipulador inerte a campos elétricos e magnéticos. Para isso, primeiramente foi desenvolvido um MPA livre de qualquer parte metálica. Visando sua aplicação, as características do músculo como: gama de esforços, tempo de resposta e histerese foram avaliadas através de testes. Algumas estratégias de controle do atuador foram testadas e comparadas, e com o atuador desenvolvido foi construído um manipulador inerte a campos magnéticos e elétricos. O manipulador construído tem como objetivo exercer movimentos distintos sobre a mão de um paciente, o mesmo deve acompanhar o paciente durante um exame de ressonância magnética. O atuador apresentou uma gama de esforços dentro do previsto, um tempo de resposta característico de atuadores pneumáticos e ao contrário do esperado, uma baixa histerese. Através de elementos mecânicos e com o uso de dois MPA, o manipulador foi capaz de exercer um trabalho sobre a mão de um voluntario fora do campo da RM, mostrando a viabilidade da aplicação. / When activities executed by a mechatronic system are performed in environments with strong magnetic and or electric field, the devices that will perform the tasks should be carefully designed so that the presence of metal parts does not become a risk. The electric field can generate electrical currents and the magnetic field may exert unexpected force in a metal part. Thus the use of some elements, such as electric motors, metallic parts or electronic sensors becomes unviable. The initial motivation for this work was to find an actuator that could be built without metallic elements and, using such actuator, build a manipulator inert to magnetic and electric fields. In this context, the use of hydraulic or pneumatic actuators becomes the most indicated option. Frequently, pneumatic and hydraulic systems have actuators with metal parts so as resist mechanical loads. In situations where the actuator is loaded by small loads, metal parts may be replaced by polymeric materials commonly used in Engineering. Among hydraulic and pneumatic actuators, one that already presents a few metal parts is the pneumatic artificial muscle (PAM). PAM has characteristics such as: low weight to effort ratio, simple construction as well as range of generated force and dimensions similar to a pneumatic cylinder. Thus, the PAM is chosen as the actuator for the non-conductive manipulator developed in this work. Adopting the PAM as a central element, this work aims identifying directives on using the PAM in the construction of a manipulator inert to electric and magnetic fields. For this, firstly it is developed a PAM free from any metal part. Next, the characteristics of the PAM such as range of efforts, response time and hysteresis curve are assessed through tests. Some strategies for the actuator control are tested and compared. Finally, using the developed actuator, a manipulator inert to magnetic and electric fields are constructed. The purpose of this manipulator is to induce motions to the fingers of a patient hand while the patient is examined in a MRI (magnetic resonance imaging) equipment. The actuator presented a range of efforts according to expectations, a response time compatible with pneumatic actuators and, contrary to expectations, low hysteresis.

No description available.

The thesis entitled “Design and Development of Metal-Free Cross Dehydrogenative Coupling Reactions for the construction of C-S, C-O and C-C bonds” is divided into three Chapters. Chapter 1 is presented in five parts, which reveals the cross dehydrogenative coupling (CDC) strategies for the C–S bond forming reactions through C–H functionalization strategy using heterocyclic thiols and thiones. Chapter 2 presents tetrabutyl ammonium iodide (TBAI) catalyzed chemoselective α-aminoxylation of ketones with N-hydroxyimidates using TBHP as oxidant under cross dehydrogenative coupling (CDC) strategy. Chapter 3 describes a transition metal-free Minisci reaction for the acylation of isoquinolines, quinolines, and quinoxaline. Chapter 1 Iodine Promoted C-S Bond Forming Reactions using Dimethyl Sulfoxide as an Oxidant Chapter 1 reveals the utility of cross dehydrogenative coupling (CDC) reactions for the formation of C–S bonds by employing C–H functionalization strategies.1 The direct functionalization of C–H bonds to form C–C and C–X (N, O, S and P) bonds using metal-free reaction conditions is an interesting research topic in recent years.2 Use of dimethyl sulfoxide as an oxidant is emerging as one of the research topics of great interest and utility.3 Heterocyclic thiols and thiones are important precursors for synthesizing a variety of pharmaceuticals and biologically active compounds.4 Therefore it is useful to develop CDC reactions using heterocyclic thiols and thiones as precursors. In this chapter, we describe CDC reactions of heterocyclic thiols and thiones for the sulfenylation of ketones, aldehydes, α, β unsaturated methyl ketone derivatives, pyrazolones, enaminones and imidazoheterocycles using DMSO as an oxidant Chapter 1: Part 1 Iodine Promoted Regioselective α-Sulfenylation of Carbonyl Compounds using Dimethyl Sulfoxide as an Oxidant: In this chapter, a rare regioselective C–H sulfenylation of carbonyl compounds with heterocyclic thiones and thiols have been described using iodine and dimethyl sulfoxide as reagents. Thus, dimethyl sulfoxide (as an oxidant) and stoichiometric amount of iodine have been used for the sulfenylation of ketones using heterocyclic thiones. Whereas the sulfenylation of ketones with heterocyclic thiols required catalytic amount of iodine. This protocol offers a rare regioselective sulfenylation of (i) methyl ketones in the presence of more reactive α-CH2 or α-CH groups, and (ii) aldehydes under CDC method. A few representative examples are highlighted in Scheme 1.5 The application of this methodology has been demonstrated by synthesizing a few precursors for Julia-Kocienski olefination intermediates. Scheme 1. Iodine promoted rare regioselective α-sulfenylation of ketones and aldehydes Siddaraj , Y.; Prabhu, K. R. Org. Lett. 2016, 18, 6090 Chapter 1: Part 2 Regioselective Sulfenylation of α’-CH3 or α’-CH2 Groups of α, β Unsaturated Ketones using Dimethyl Sulfoxide as an Oxidant: In this chapter, an interesting regioselective sulfenylation of α’-CH3 or α’-CH2 groups of α, β unsaturated ketones using dimethyl sulfoxide as an oxidant and catalytic amount of aq. HI (20 mol %) as an additive has been described. This eco-friendly method uses readily available, inexpensive I2 or HI and DMSO. This methodology exhibits a high regioselectivity without forming Michael addition product in the presence of strong acid such as aq. HI or iodine, which is difficult to achieve under cross dehydrogenative coupling (CDC) conditions. Current methodology exhibits a broad substrate scope. A few examples are shown in Scheme 2.6 Scheme 2. HI and DMSO promoted α’-sulfenylation of α, β unsaturated ketones Siddaraju, Y.; Prabhu, K. R. (Manuscript submitted) Chapter 1: Part 3 Iodine Catalyzed Sulfenylation of Pyrazolones using Dimethyl Sulfoxide as an Oxidant: In this chapter, a sustainable and efficient strategy for the sulfenylation of pyrazolones has been described using metal-free conditions by employing DMSO as an oxidant and iodine as a catalyst. A variety of heterocyclic thiols, heterocyclic thiones and disulfides undergo C–H functionalization reaction with pyrazolone derivatives furnishing the corresponding sulfenylated products in short time. Most of the products are isolated in pure form without column purification. A few examples are presented in Scheme 3.7 Scheme 3. Iodine promoted sulfenylation of pyrazolones Siddaraju, Y.; Prabhu, K. R. Org. Biomol. Chem. 2017, 15, 5191 Chapter 1: Part 4 Iodine-Catalyzed Cross Dehydrogenative Coupling Reaction: Sulfenylation of Enaminones using Dimethyl Sulfoxide as an Oxidant: In this chapter, synthesis of poly functionalized aminothioalkenes has been described using substoichiometric amount of iodine and DMSO as an oxidant. This metal-free methodology enables a facile sulfenylation of enaminones with heterocyclic thiols and thiones. This methodology is one of the simple approaches for the sulfenylation of enaminones under cross dehydrogenative coupling method. A few examples are highlighted in Scheme 4.8 Scheme 4. Cross-dehydrogenative coupling approach for sulfenylation of enaminones Siddaraju, Y.; Prabhu, K. R. J. Org. Chem. 2017, 82, 3084 Chapter 1: Part 5 Iodine-Catalyzed Cross Dehydrogenative Coupling Reaction: A Regioselective Sulfenylation of Imidazoheterocycles using DMSO as an Oxidant: In this chapter, a simple synthetic approach for the regioselective sulfenylation of imidazoheterocycles using iodine as a catalyst and DMSO as an oxidant under cross dehydrogenative coupling (CDC) reaction conditions has been demonstrated. This protocol provides an efficient, mild and inexpensive method for coupling heterocyclic thiols and heterocyclic thiones with imidazoheterocycles. This is the first report on sulfenylation of imidazoheterocycles with heterocyclic thiols and heterocyclic thiones under metal-free conditions. A few examples are shown in Scheme 5.9 Scheme 5. Cross-dehydrogenative coupling approach for sulfenylation of imidazoheterocycles Siddaraju, Y.; Prabhu, K. R. J. Org. Chem. 2016, 81, 7838 Chapter 2 Chemoselective α-Aminoxylation of Aryl Ketones: Cross Dehydrogenative Coupling Reactions Catalyzed by Tetrabutyl Ammonium Iodide: In this chapter, chemoselective α-aminoxylation of ketones with N-hydroxyimidates catalyzed by tetrabutyl ammonium iodide (TBAI) has been presented. The coupling reaction of a variety of ketones with N-hydroxysuccinimide (NHSI), N-hydroxyphthalimide (NHPI), N-hydroxybenzotriazole (HOBt) or 1-hydroxy-7-azabenzotriazole (HOAt) using TBHP as oxidant has been investigated. This α-aminoxylation of ketones is chemoselective as aryl methyl ketones, aliphatic ketones as well as benzylic position are inactive under the reaction condition. A few examples are highlighted in Scheme 6.10 The application of this method has been demonstrated by transforming a few coupled products into synthetically useful vinyl phosphates. Scheme 6. Chemoselective α-aminoxylation of ketones with N-hydroxyimidates Siddaraju, Y.; Prabhu, K. R. Org. Biomol. Chem. 2015, 13, 11651 Chapter 3 A Transition Metal-Free Minisci Reaction: Acylation of Isoquinolines, Quinolines, and Quinoxaline: In this chapter, transition metal-free acylation of isoquinoline, quinoline and quinoxaline derivatives with aldehydes has been described by employing TBAB (tetrabutyl ammonium bromide, 30 mol %) and K2S2O8 as an oxidant under cross dehydrogenative coupling (CDC) reaction. This intermolecular acylation of electron-deficient heteroarenes provides an easy access and a novel acylation method of heterocyclic compounds. The application of this CDC strategy has been illustrated by synthesizing isoquinoline-derived natural products. A few representative examples are shown in Scheme 7.11 Scheme 7. CDC reactions of heteroarenes with aldehydes Siddaraju, Y.; Lamani, M.; Prabhu, K. R. J. Org. Chem. 2014, 79, 3856

Au cours de ce travail de nouvelles méthodes pour la formation de liaison C-N ont été développées. Dans la première partie de cette thèse une application de catalyse métal-ligand bifonctionnelle pour la réaction énantiosélective aza-Michael est démontrée. Dans la deuxième partie nous présentons le travail sur les cyclisations, en utilisant des alcaloïdes du quinquina facilement disponibles, comme catalyseurs des plus prometteurs, fournissant des β-amino-acides d’indoline avec jusqu'à 98% ee. Parmi eux, l’hydroquinidine ressort du lot comme étant le catalyseur donnant le meilleur excès énatiomérique. La troisième partie est liée à l'élaboration d'un nouveau processus intermoléculaires de diamination de styrènes, diènes et triènes, utilisant des bis-sulfonylimides comme source d'azote, en combinaison avec le diacétate de iodosobenzène, qui fournit une approche intéressante et efficace de diamines vicinales biologiquement et chimiquement important. La réaction peut être effectuée à température ambiante sans avoir besoin de protection par atmosphère inerte. / The concept of metal-ligand bifunctionality was successfully applied for an enantioselective aza-Michael reaction by employing well-defined ruthenium amido complexes. The catalyst was optimised and the corresponding chiral indoline β-amino acid derivatives were obtained with high enantioselectivities. Next, a straightforward enantioselective bifunctional organocatalytic approach was also developed. Employing hydroquinidine as catalyst the corresponding cyclic products were obtained in excellent enantioselectivities and quantitative yields. These compounds can be selectively deprotected and applied to peptide synthesis. Finally, we have developed unprecedented diamination reactions of styrenes, butadienes and hexatrienes employing easily accessible hypervalent iodine(III) reagents under robust reaction conditions. The first examples of the metal-free 1,2-diamination of butadienes were demonstrated and this oxidation methodology was further extended to the highly attractive 1,4 installation of two nitrogen atoms within a single step.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-07-13T15:19:13Z No. of bitstreams: 1 anacristinadarochaduquebeghini.pdf: 604681 bytes, checksum: 77222c9c607ebf796ce7a6f000f0c9c1 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-07-13T16:58:18Z (GMT) No. of bitstreams: 1 anacristinadarochaduquebeghini.pdf: 604681 bytes, checksum: 77222c9c607ebf796ce7a6f000f0c9c1 (MD5) / Made available in DSpace on 2016-07-13T16:58:18Z (GMT). No. of bitstreams: 1 anacristinadarochaduquebeghini.pdf: 604681 bytes, checksum: 77222c9c607ebf796ce7a6f000f0c9c1 (MD5) Previous issue date: 2011-05-02 / No presente estudo avaliou-se a radiopacidade de restaurações cerâmicas livres de metal de forma objetiva, subjetiva e por meio de MEV/EDS. Foram utilizadas as cerâmicas: Noritake EX-3 (Noritake), VM13 (Vita), IPS Empress II (Ivoclar Vivadent), IPS E.max ZirPress (Ivoclar Vivadent) e PM9 (Vita). Para a avaliação objetiva foram confeccionados cinco corpos de prova nas espessuras de 1, 2, 3 e 4 mm, que foram radiografados juntamente com uma escala de densidade e uma secção dental, utilizando-se sistema digital direto. As imagens radiográficas foram submetidas à leitura de densidade óptica. Para a avaliação subjetiva foram confeccionados phantoms, simulando a parte posterior das arcadas dentárias, no qual dois dentes de cada phantom foram submetidos a preparos inlay, restaurados com as cerâmicas estudadas, e radiografados pela técnica interproximal. Essas radiografias foram avaliadas por três grupos de examinadores: cirurgiões-dentistas, radiologistas e protesistas. Para a análise dos elementos químicos que dão características de radiopacidade aos materiais, foi realizada avaliação pelo MEV/EDS. Os resultados da avaliação objetiva indicaram diferenças significativas entre as radiopacidades das cerâmicas estudadas. Para 1 e 2 mm de espessuras todas as cerâmicas apresentaram radiopacidade superior a da dentina e inferior a do esmalte. A cerâmica Noritake EX3 apresentou maior radiopacidade em todas as espessuras. Não se puderam constatar, nas avaliações simulando condições clínicas, as diferenças de radiopacidades observadas na avaliação objetiva. O grupo dos cirurgiões-dentistas apresentou a menor acurácia diagnóstica quando comparados aos grupos de especialistas, sendo que os radiologistas apresentaram a maior acurácia diagnóstica para cerâmica (0,57). Independente do grupo de avaliadores, não foi possível a distinção radiográfica entre cerâmicas livre de metal e compósitos. O resultado da avaliação dos materiais pelo MEV/EDS indicou como possíveis elementos radiopacificadores: bário para as cerâmicas Noritake EX-3 (2,19%), VM13 (1,04%), PM9 (0,70%) e IPS Empress II (0,70%); e zinco (4,50%) e cério (1,45%) para a cerâmica IPS E.max ZirPress. / The aim of this study to evaluate the radiopacity of metal-free ceramic restorations in an objective, subjective and by SEM and EDS. Ceramics were used: Noritake EX-3 (Noritake), VM13 (Vita), IPS Empress II (Ivoclar Vivadent), IPS e.max ZirPress (Ivoclar Vivadent) and PM9 (Vita). For the objective evaluation were prepared five specimens with thickness of 1, 2, 3 and 4 mm, which were radiographed with a aluminum step and a dental section, using direct digital system. The radiographic images were submitted to the reading of optical density. For subjective evaluation were fabricated phantoms, simulating the back of the dental arches, in which two teeth of each phantom received an inlay preparation, were restored with the studied ceramics, and were x-rayed by the interproximal technique. These radiographs were evaluated by three groups of examiners, dentists, radiologists, and prosthetists. To analyze the chemical elements that provide radiopacity characteristics of the materials, evaluation was performed by SEM and EDS. The results of objective evaluation indicated significant differences between the radiopacity of the studied ceramics. For 1 and 2 mm in thickness and the ceramics were all higher radiopacity dentin and enamel below. Ceramics Noritake EX3 showed higher radiopacity in all thicknesses. There was evident on the evaluations simulating clinical conditions, the differences observed in the radiopacity of objective evaluation. The group of dentists had a lower diagnostic accuracy when compared to groups of specialists, and radiologists had the highest diagnostic accuracy for ceramics (0.57). Independent group of evaluators was not possible to distinguish between X-ray and metal-free ceramic composites. The result of evaluation of materials by SEM and EDS indicated as possible elements radiopacifiers barium to ceramic Noritake EX-3 (2.19%), VM13 (1.04%), PM9 (0.70%) and IPS Empress II (0.70%) and zinc (4.50%) and cerium (1.45%) for the ceramic IPS E.max ZirPress.