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Dobbs, William Douce Laurent. "Imidazoliums supramoléculaires aux propriétés ajustables." Strasbourg : Université de Strasbourg, 2009. http://eprints-scd-ulp.u-strasbg.fr:8080/00001026.
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Dobbs, William. "Imidazoliums supramoléculaires aux propriétés ajustables." Université Louis Pasteur (Strasbourg) (1971-2008), 2008. https://publication-theses.unistra.fr/restreint/theses_doctorat/2008/DOBBS_William_2008.pdf.
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Réalisé par l’intermédiaire du noyau imidazolium, la combinaison du domaine des liquides ioniques avec celui des cristaux liquides nous a permis de créer un ensemble de nouveaux matériaux associant judicieusement plusieurs fonctions. Ces dernières découlent respectivement des propriétés spécifiques des constituants, des liquides ioniques, des cristaux liquides et du résultat de leur association au sein d’un unique composé. L’étude de cette intéressante association nous a permis : d’élaborer une architecture cationique habile vis à vis de son environnement, qui permet l’émergence des propriétés mésomorphes ; de réaliser la synthèse de nanoparticules d’or et d’argent sous le contrôle d’une architecture ordonnée ; de collaborer avec Polyplus Transfection et d’étudier les propriétés biologiques de composés amphiphiles liquides cristallins ; d’incorporer des complexes volumineux luminescents aux sein d’édifices mésomorphesThe merger of ionic liquid and liquid crystal fields, obtained by using the imidazolium ring as common element, has allowed us to tailor a new set of materials which associate several specific functionalities. These functionalities are consequences of the original properties of the component, ionic liquids, liquid crystals and their association in a single compound. The study of this interesting association led us to: elaborate environment-flexible cationic architectures from which mesomorphic properties emerge; synthesize gold and silver nanoparticles templated by an ordered architecture; collaborate with Polyplus Transfection to study the biological properties of amphiphilic liquid crystalline compounds; incorporate voluminous luminescent complexes in mesomorphous structures
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Chardin, Charline. "Design et synthèse de nouveaux sels organiques pour le développement de polyélectrolytes." Thesis, Normandie, 2018. http://www.theses.fr/2018NORMC278/document.
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Depuis le début du 21ème siècle, les liquides ioniques (LIs) représentent une importante source d'innovation dans la recherche académique et industrielle en chimie puisqu'ils peuvent être synthétisés, modulés puis utilisés dans de nombreuses applications. De par leurs avantages, les LIs font l'objet d'un véritable engouement dans le domaine des matériaux polymères. Ainsi, ce travail décrit la synthèse de sels organiques originaux pour le développement de polyélectrolytes inédits. Pour cela, nous avons développé de nouvelles voies d'accès à des imidazoliums fonctionnalisés par des fonctions époxydes par l’utilisation d'une méthodologie d'oxydation efficace, flexible et transposable sur une échelle de plusieurs grammes. L'analyse thermique de ces sels a dévoilé une excellente stabilité thermique jusqu'à 400 °C et une température de transition vitreuse basse généralement comprise entre -60 °C et -26 °C. A la suite de ces résultats, la stratégie a été élargie aux anions afin de proposer des fonctions époxydes associées à des sulfonimides inédits. Au cours de cette deuxième phase, l'insertion de fonctions époxydes sur l'anion sulfonimide a été réalisée avec succès permettant un accès à différents prépolymères comme un cation/anion triépoxyde. Dans une deuxième partie, nous avons réalisé une étude mécanistique en utilisant un sel monoépoxyde en présence de différentes amines pour identifier les principaux sites actifs lors de la polymérisation. Grace à ces informations, nous avons confirmé la stabilité de l’imidazolium et la très bonne réactivité de l’époxyde vis-à-vis de diverses amines conduisant à une meilleure compréhension de l'architecture globale du réseau. A partir de ces travaux, un réseau époxy inédit a été mis en œuvre en collaboration avec le laboratoire d'ingénierie des matériaux polymères (IMP) de l'INSA de Lyon. Pour cela, un sel diépoxyde a été sélectionné puis copolymérisé avec un durcisseur diamine (Jeffamine D230) afin de concevoir des réseaux époxy/amine flexibles présentant des propriétés très intéressantes par rapport aux réseaux époxy classiquesSince the beginning of the 21th century, Ionic liquids (ILs) have been an important source of innovation in chemical academic and industrial research because they can be synthesized, modulated and used then in many applications. Because of their advantages, ILs are of great interest in the field of polymer materials. Thus, this work describes the synthesis of original organic salts to develop innovative polyelectrolytes. For this, we have developed new routes to access to imidazolium salts functionalized by reactive epoxide functions thanks to the development of an effective and flexible oxidative methodology, feasible on a large scale. The thermal analysis of this salts revealed a very good thermal stability up to 400°C and a low glass transition temperature between -60 °C and -26 °C generally. Following these results, the study was extended to anions to provide epoxides associated with novel sulfonimides. During this second phase, the insertion of epoxide functions on the sulfonimide anion was successfully carried out allowing access to different prepolymers such as a triepoxide cation/anion. In a second part, we carried out a mechanistic study using a monoepoxide salt in the presence of different amines to identify the main active sites during the polymerization. According to this information, we have confirmed the stability of the imidazolium and the very good reactivity of the epoxide with various amines leading to a better understanding of the overall architecture of the network. From this work, a novel epoxy network was prepared in collaboration with the polymer materials engineering laboratory (IMP) of INSA of Lyon. For this, a diepoxide salt was selected and copolymerized in the presence of a diamine hardener (Jeffamine D230) in order to design flexible epoxy/amine networks having very interesting properties in comparison with conventional epoxy networks
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Ward, G. J. "Imidazolines in peptide chemistry." Thesis, University of Nottingham, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.381082.
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Lambert, Romain. "Nouveaux copolymères et nanostructures dérivés de liquides ioniques à base d'imidazoliums : applications en catalyse et comme additifs conducteurs ioniques." Thesis, Bordeaux, 2016. http://www.theses.fr/2016BORD0306/document.
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Des poly(liquides ioniques) (PILs) arrangés sous la forme de copolymères statistiques,de nanoparticules à chaine unique ou bien sous la forme de copolymères à blocs autoassemblés ont été employés comme précurseurs de carbènes N-hétérocycliques (NHC)s à des fins de catalyses organiques ou organométalliques. L’introduction d’anions acétate dans des unités PIL dérivés d’imidazolium permet la génération in situ de NHCs actifs en catalyse. Les nanoparticules composées d’une chaine unique polymère repliée sur elle-même (SCNP) ont été spécialement conçues selon deux stratégies impliquant, d’une part, une réaction d’autoquaternisation entre groupements fonctionnels antagonistes portés par la chaine et, d’autre part, une réaction de complexation organométallique à l’aide d’un sel de palladium. Dans lesdeux cas, les chaines polymères ont été obtenues par polymérisation contrôlée (méthode RAFT). Les copolymères à blocs amphiphiles comportant un bloc PIL fonctionnalisé par du palladium ont été synthétisés par polymérisation RAFT et auto-assemblés dans l’eau sous forme de micelles.Un effet de confinement des sites catalytiques a clairement été démontré à travers des réactions de catalyse pour les couplages de Suzuki et de Heck dans l’eau, avec un gain cinétique très net par rapport à des homologues non micellisés, en plus d’une grande facilité de recyclage de ces supports micellaires.Enfin, des copolymères à blocs à base de PIL-benzimidazolium à contre anion bis(trifluoromethane)-sulfonylimide de lithium ont été développés comme agents dopants conducteurs ioniques de matrices structurantes PS-b-PEO. Des mélanges configurés en films minces avec une quantité minimale d’agent dopant ont conduit dans certaines conditions à des valeurs optimales de conductivité ionique grâce à une nano structuration des films à longue distancePoly(ionic liquid)s (PILs) in the form of random copolymers, single chain nanoparticles(SCNPs), or self assembled block copolymers have been used as N-heterocyclic carbenes(NHCs) precursors for the purpose of organic and organometallic catalysis. Introducing acetate derivative counter anion in imidazolium based PIL units enable in situ generation of catalyticallyactive NHC. SCNPs have been specially designed along two strategies including, firstly, a self quaternization reaction involving two antagonists groups supported on to the polymer chain and,secondly, an organometallic complexation featuring palladium salt. Both polymeric precursors were obtained using RAFT as controlled polymerization method. Amphiphilic block copolymers composed of a PIL block functionalized by palladium have been synthesized by RAFT and self-assembled in water, leading to micellar structures. Confinement effect has been demonstrated through Suzuki and Heck coupling in water showing kinetic gain compared to molecular homologue in addition to an easier recycling method.Finally, PIL-benzimidazolium based block copolymers with lithium bis(trifluoromethane)-sulfonylimide anion have been developed as ionic conductor doping agent for PS-PEO matrix. Thin films blends with minimum doping agent amount led to optimum ionic conductivity owing tolong range order
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Nichols, John Richard. "Synthetic methods involving 2-imidazolines." Thesis, University of Nottingham, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.236028.
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Dimopoulos, Paschalis A. "2-imidazolines in annulation studies." Thesis, Open University, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.310229.
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Soula, Catherine. "Imidazolines fonctionnalisées : structures et réactivité." Université Joseph Fourier (Grenoble), 1989. http://www.theses.fr/1989GRE18002.
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Kadel, Rajesh. "Surface structure study of imidazolium based ionic liquid." Manhattan, Kan. : Kansas State University, 2008. http://hdl.handle.net/2097/1004.
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Archer, Raymond Humphrey Davis Mark E. Davis Mark E. "Molecular sieve synthesis using imidazolium structure directing agents /." Diss., Pasadena, Calif. : California Institute of Technology, 2009. http://resolver.caltech.edu/CaltechETD:etd-06022009-100039.
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Gisbert, Patricia. "Functionalized imidazolium salts as components in catalytic systems." Doctoral thesis, Universidad de Alicante, 2019. http://hdl.handle.net/10045/98987.
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CAPÍTULO I. Sales de Hierro e Imidazolio Sustituidas con Grupo Acilo para el Acoplamiento Oxidativo-Tionación de Aminas. En el capítulo I, se ha llevado a cabo el acoplamiento oxidativo de aminas mediado por un catalizador de hierro, para la preparación de tioamidas, de forma eficiente y selectiva en una reacción multicomponente. En la misma, se han utilizado dos aminas diferentes, fosfato de sodio y azufre elemental, bajo calentamiento por microondas. Durante el estudio se ha observado la importancia del catalizador, formado por tetracloroferratos de imidazolio, en el acoplamiento oxidativo y posterior formación del enlace C-S. Esta metodología ha permitido la utilización tanto de bencilaminas primarias y alquilaminas, con diversas propiedades electrónicas, como de derivados de piperidina, demostrando la importancia de esta ruta sintética en la preparación de importantes intermedios sintéticos de productos naturales. CAPÍTULO II. Sistemas Catalíticos Formados por Paladio y Sales de Imidazolio Sustituidas con Grupos Acilo. En el capítulo II, se han sintetizado diferentes sales de imidazolio mono- y di-funcionalizadas con un grupo amido como precursores de sistemas catalíticos en combinación con acetato de paladio(II), usándolos en la reacción de acoplamiento de Heck-Matsuda. A partir del estudio comparativo, se puede concluir que la presencia de un único grupo amido en el precursor del sistema catalítico, formado con una relación 1:1 metal/ligando, es más beneficioso durante el proceso, tal y como se observa en los análisis por espectroscopía UV/Vis. CAPÍTULO III. Cloruro de 1,3-Bis(carboximetil)imidazolio como Catalizador sin Metales para la Síntesis de Quinolinas y Acridinas. En el capítulo III, se ha utilizado el cloruro de 1,3-bis(carboximetil)imidazolio, como catalizador heterogéneo para la preparación, libre de metales y sin uso de disolventes, de quinolinas y acridinas. Esta metodología, sencilla y eficaz para la síntesis de heterociclos con nitrógeno, ha permitido el empleo de diversas cetonas y 2-aminoarilcetonas como precursores, siendo posible la reacción en escala de multigramo. Asimismo, se ha demostrado la aplicabilidad del proceso llevando a cabo la transformación de algunos compuestos a las correspondientes quinolilchalconas mediante una reacción tándem. Además, se ha llevado a cabo el estudio de reciclabilidad del catalizador (hasta 8 ciclos) en la reacción modelo sin observar pérdida de su actividad, remarcando su robustez. Por último, se ha comprobado la sostenibilidad del proceso calculando el factor-E para la formación de quinolinas y la reacción tándem. CAPÍTULO IV. Formación de Enlaces C-C y C-S Catalizada por Cloruro de 1,3-Bis(carboximetil)imidazolio: Síntesis de Tiofenos. En el capítulo IV, se ha empleado el cloruro de 1,3-bis(carboximetil)imidazolio como catalizador para la síntesis de 2,4-diariltiofenos, a través de una autocondensación sulfurativa de la acetofenona. En este proceso, se han estudiado diferentes acetofenonas y cicloalcanonas como precursores, demostrando la simplicidad y eficiencia del proceso para la formación de tiofenos. Además, se ha podido llevar esta reacción a escala de multigramo, siendo, desde el punto de vista de la sostenibilidad, una ruta sintética atractiva.
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Kelley, John J. "The Synthesis and Characterization of Imidazolium Lithium Phthalocyanines." Wright State University / OhioLINK, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=wright1221535816.
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Winston, Scott. "Functionlised N-heterocyclic carbenes and amido imino mixed donors as supporting ligands in organometallic catalysis." Thesis, University of Southampton, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.274654.
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Anna, Gabriela da Silva Sant. "Efeito de 2-aril(heteroaril)-4,5-diidro-1h-imidazóis sobre a atividade da enzima monoamina oxidase in vitro." Universidade Federal de Santa Maria, 2008. http://repositorio.ufsm.br/handle/1/11095.
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Coordenação de Aperfeiçoamento de Pessoal de Nível SuperiorMonoamine oxidase (MAO) is a flavin adenine dinucleotide (FAD)-containing enzyme attached to the mitochondrial outer membrane of neurons, glia, and other cells. Its roles include regulation of the levels of biogenic and xenobiotic amines in the brain and peripheral tissues by catalyzing their oxidative deamination. On the basis of their substrate and inhibitor specificities, two isoforms of MAO have been described (A and B). Due to their role in the metabolism of catecholamines neurotransmitters, MAO-A and MAO-B have long been of pharmacological interest. Accordingly, and reversible and irreversible inhibitors of MAO-A and MAO-B have been used in the clinics to treat neurological disorders including depression and Parkinson´s disease. Since the demonstration that I2- imidazoline sites are associated with mitochondrial membranes 15 years ago, several studies have provided evidence that these sites represent regions on MAOs. In line with this view, it has been demonstrated that imidazoline derivatives inhibit MAO activity. This effect has been attributed to a high affinity I2 binding site on MAO-B (I2B) and to a similar lower affinity site on MAO-A (I2A). This study investigated the effect of 4,5-dihydro-1H-imidazole-2-substituted compounds on MAO activity in vitro by spectrophotometric and fluorimetric methods using kynuramine as substrate. Among the compounds that inhibited MAO-A (3c-e, 3j), compound 3d was 73-fold more selective towards MAO-A than MAO-B. Among the compounds that selectively inhibited MAO-B (3g-I, 3k, 3o), imidazoline 3g was shown to be potent with Ki value of 5,3 μM. Some of compounds that selectively bind to I2-sites, such as 3l (benazoline), 3n (2-BFI), and 3p (BU224) showed good inhibitory activity especially against MAO-B. Imidazolines inhibited MAO-A and MAO-B activities in liver with less selectively than in rat brain. The compounds 3d and 3g reversibly inhibited MAO, and kinetics studies showed that compound 3d and 3g inhibited MAO in a mixed manner (decreased Vmax and increased Km values). These results confirm that imidazolines inhibit MAO activity and suggest a relationship between I2 binding site and modulation of central MAO
A monoamina oxidase (MAO) é uma enzima que contém o dinucleotídeo adenina-flavina (FAD) e que está presente na membrana externa da mitocôndria de células neuronais, glia e outras células. Seu papel inclui a regulação dos níveis de aminas biogênicas e xenobióticas no cérebro e em tecidos periféricos pela desaminação oxidativa. Com base na especificidade a substrato e inibidores, são descritas duas isoformas da MAO (A e B). Devido aos seus papéis no metabolismo das catecolaminas neurotransmissoras, a MAO-A e a MAO-B são consideradas farmacologicamente interessantes, e inibidores reversíveis e irreversíveis destas isoformas são usados clinicamente para tratar doenças neurológicas incluindo depressão e doença de Parkinson. Nos últimos 15 anos, desde a demonstração que sítios I2 estão associados com frações da membrana mitocondrial, muitos estudos provem evidências de que estes sítios representam regiões da MAO. Além disso, alguns estudos têm demonstrado que derivados imidazolínicos são capazes de inibir a atividade da MAO. Este efeito tem sido atribuído a sítios I2 de alta afinidade na MAO-B (I2B) e a um sítio similar de baixa afinidade na MAO-A (I2A). Assim, este estudo teve como objetivo investigar o efeito in vitro de compostos 4,5-diidro-1H-imidazol-2-substituídos sobre a atividade da enzima monoamina oxidase através de métodos espectrofotométricos e fluorimétricos usando quinuramina como substrato. Entre os compostos estudados que inibiram preferencialmente a MAO-A (3c-e, 3j) apenas o composto 3d foi seletivo, apresentando um Ki para a MAO-A de aproximadamente 73 vezes menor do que seu Ki para MAO-B. Entre os compostos obtidos que seletivamente inibiram MAO-B (3g-l, 3K, 3o), apenas a imidazolina 3g mostrou ser potente, com valores de Ki de 5,3 μM. Alguns compostos que exercem ligação potente e seletiva à sítios I2, como o 3l (benazolina), 3n (2-BFI) e 3p (BU224) mostraram boa atividade inibitória especialmente contra MAO-B. Em fígado de ratos, as imidazolinas inibiram com menos seletividade a MAO-A e MAO-B quando comparado com cérebro de ratos. Os compostos 3d e 3g inibiram a MAO de maneira reversível e apresentaram inibição de natureza mista (diminuindo o valor de Vmáx e aumentando o valor de Km) sobre a enzima MAO. Estes resultados confirmam que drogas imidazolinas podem inibir a atividade da MAO e sugerem uma relação entre sítios I2 e a modulação da atividade da enzima.
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Roberts, Huw John. "Synthesis of novel aryl and alkyl phosphine-imidazolium salts." Thesis, Cardiff University, 2007. http://orca.cf.ac.uk/54669/.
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Several chelating phosphine-imidazolium salts have been synthesised and their activity tested in the hydrosilylation of styrene with triethylsilane and the Heck coupling of aryl bromides and chlorides with butyl acrylates. A number of synthetic routes have been established to synthesise aryl substituted phosphine-imidazolium salts. New synthetic routes have been established to synthesise borane-protected alkyl substituted phosphine-imidazolium salts. These methodologies have increased the scope to synthesise new alkyl substituted phosphine-imidazolium salts. Several group 9 and 10 complexes of these new aryl substituted phosphine-NHC ligands have been synthesised and characterised. The NHC's were generated in situ and reacted with suitable metal precursors. Platinum (0) complexes of these ligands were tested in the hydrosilylation of styrene with triethylsilane. Pd(0) complexes of these ligands were tested in the Heck coupling of aryl bromides and chlorides with butyl acrylate.
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HernaÌndez, GuzmaÌn Maira. "Reactions of some rhodium complexes in imidazolium ionic liquids." Thesis, University of Sheffield, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.398386.
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Milhaud, Didier. "Excitotoxicité et calcitoxicité : neuroprotection par les imidazolines." Montpellier 1, 2002. http://www.theses.fr/2002MON1T007.
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Les imidazolines sont connues pour leur effet neuroprotecteur dans des modeles d'ischemie cerebrale globale et focale chez le rat sans que leur mecanisme d'action ne soit etabli. Nous avons repris cette etude sur des modeles plus simples, les neurones du cervelet, du striatum et de l'hippocampe en culture primaire. Nous avons trouve un effet neuroprotecteur des imidazolines contre la mort neuronale declenchee par hypoxie-reoxygenation ou application de nmda dans ces neurones, l'antazoline etant la plus puissante. En "patch clamp", les imidazolines inhibent de facon voltage-dependante, non-competitive et rapidement reversible les courants nmda, l'antazoline etant la plus active. [. . . ] en somme, les imidazolines agissent sur plusieurs proteines, en particulier proteines-canaux, possedant des sites de type pcp d'affinite variable. Les imidazolines sont donc des bloqueurs non competitifs et de faible affinite des recepteurs nmda, mais aussi des canaux calciques voltage-dependants impliques dans la neurosecretion. Les imadazolines representent donc des molecules au potentiel therapeutique prometteur.
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Lapouge, Pahlawan Sophie. "Synthèse et réactivité de nouveaux synthons imidazoliques." Aix-Marseille 3, 1997. http://www.theses.fr/1997AIX30124.
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Ce travail est consacre d'une part, a l'etude de deux reactions nouvelles decouvertes au laboratoire de chimie moleculaire organique : - synthese du 1,2-dimethyl-4-(1,1,2-trimethyl-2-nitropropyl) imidazole a partir du 1,2-dimethyl-5-nitroimidazole (dimetridazole, emtryl) et du 2-nitropropane en exces en milieu basique faisant intervenir une reaction de cine-substitution suivie d'une reaction de transfert monoelectronique (s#r#n1). - hydrolyse du 1,2-dimethyl-4-(1,1,2-trimethyl-2-nitropropyl)imidazole au reflux de l'eau en alcool tertiaire correspondant, et d'autre part, a la valorisation chimique de ces nouveaux synthons imidazoliques. Ces reactions ont ete generalisees a d'autres 5-nitroimidazoles, diversement substitues en position 1,2 et 5 dont le metronidazole, flagyl, antiparasitaire et antimicrobien utilise en therapeutique humaine, afin de determiner l'influence des substituants sur ces deux reactions et d'en trouver les limites. Les nouveaux derives imidazoliques prepares ont ete utilises dans diverses reactions pour valoriser ces molecules possedant le squelette de l'histamine par la synthese de nouveaux composes utiles en chimie pharmaceutique.
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Siraj, Ibrahim T. "Novel imidazolium salts, N-Heterocyclic carbenes and their coordination polymers." Thesis, University of Strathclyde, 2012. http://oleg.lib.strath.ac.uk:80/R/?func=dbin-jump-full&object_id=25459.
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N-heterocyclic carbenes (NHCs) have been developed in the last two decades as an important material in homogenous catalysis. Also MOFs have recently been receiving a great deal of attention due to their potential applications e.g. gas storage, adsorption and catalysis. This study involved the synthesis of new imidazolium salt functionalised with nitriles, carboxylates and pyridyl and their conversion into NHC complexes and porous coordination polymers. A series of nitrile substituted imidazolium salts were synthesised. 1,1-bis(4-cyanophenyl)-3,3-methylenediimidazolium and 1-bromomethyl-3-(4-cyanophenyl)imidazolium salts were synthesised by N-arylation and N-alkylation of 4-cyanophenyl imidazole. The bisimidazolium salt was used to synthesise a dimeric silver(I) NHC complex. Reaction of this silver complex with [Ru(p-cy)Cl₂]₂ results in transmetallation and the formation of the NHC complex [Ru(L)Cl]BF₄. A platinum diNHC complex, [Pt(L)Br₂], was synthesized by in situ deprotonation of the bisimidazolium salt precursor, using NaOAc and [Pt(COD)Cl₂]. All were characterised crystallographically. Picolyl substituted imidazolium salts were synthesised, 1,3-bis(4-picolyl)imidazolium, 1,3-bis(2-picolyl)imidazolium and 1-(4-cyanophenyl)-3-(4-picolyl)imidazolium salt were synthesised using solvothermal synthesis and were characterised spectroscopically, by elemental analysis and X-ray crystallographic analysis. 1,3-bis(2-picolyl)imidazolium chloride was prepared according to literature method while the 1-methyl-3-(4-picolyl)imidazolium salt was synthesised from the methyl imidazole and 4-picolyl chloride. All the picolyl substituted imidazolium salts were converted to Ag(I) NHC complexes of the type [Ag(NHC₂]⁺. The bis 4-picolyl imidazolium was used to synthesise two isostructural highly porous coordination polymers of Ag(I) and Cu(I). New carboxylate imidazolium salts, 3,3'-methylenebis(1-(4-carboxyphenyl)-1H-imidazol-3-ium), 1,3-bis(4-carboxyphenyl)-1H-imidazol-3-ium, 1,3-bis(3-carboxyphenyl)-1H-imidazol-3-ium, 3-(4-carboxyphenyl)-1-methyl-1H-imidazol-3-ium and 1-benzyl-3-(4-carboxyphenyl)-1H-imidazol-3-ium salts were prepared from hydrolysis of the corresponding nitrile imidazolium salts in HX (X = Br, Cl). The 1-benzyl-3-(4-carboxyphenyl)-1H-imidazol-3-ium imidazolium salt formed a rhodium diNHC complex [Rh(L)₂Br(CO)] by reacting the ligand with rhodium acetate in a solvothermal process. The 1,3-bis(4-carboxyphenyl)imidazolium salt reacted with LnCl₃.XH₂O in DMF under a solvothermal process to give two isostructural MOFs of La(III) and Ce(III).
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Matzke, Marianne. "Behaviour and toxicity of imidazolium based ionic liquids in soils." kostenfrei, 2008. http://d-nb.info/989990311/34.
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Richards, Stephen Paul. "Imidazolium salts as convenient precursors to novel metal-carbene complexes." Thesis, University of Bath, 2004. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.413916.
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Stromyer, Michael L. "Synthesis, Characterization, and Evaluation of Biological Activity of Imidazolium Salts." University of Akron / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=akron1561652352514381.
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Roche, Annie. "L'apport des nouveaux dérivés imidazoliques dans les mycoses." Bordeaux 2, 1995. http://www.theses.fr/1995BOR2P083.
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Farger, Pierre. "Synthèse inothermale de réseaux hybrides multiferroïques." Thesis, Strasbourg, 2016. http://www.theses.fr/2016STRAE029/document.
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Ce manuscrit présente la synthèse de nouveaux réseaux hybrides organiques/inorganiques à base de différents ligands imidazoliums. Trois ligands imidazoliums possédant chacun des caractéristiques spécifiques ont été synthétisés et utilisés avec l’objectif de parvenir à la formation de réseaux hybrides multiferroïques c’est-à-dire des réseaux qui possède à la fois un ordre magnétique et un ordre électrique. La modification du ligand a ainsi permis d’obtenir des composés répondant aux critères (de symétrie en particulier) à remplir pour la présence d’un ordre électrique. Pour construire le réseau inorganique magnétique nous avons travaillé sur la synthèse de composés à base de métaux de transition de la première série ou de lanthanides. L’ensemble des composés obtenus a été caractérisé par un ensemble de techniques (diffraction des rayons X, spectroscopie FTIR et UV-Vis, analyses thermiques et élémentaires). Les propriétés magnétiques, de luminescence et de ferroélectricité des composés ont aussi été étudiéesThis thesis presents the syntheses of new hybrid coordination networks based on imidazolium ligands. Three kinds of ligands possessing their own features were synthesized and used with the main objective to obtain multiferroic hybrid networks meaning networks which display a magnetic order and a ferroelectric order. The modification of the ligand allowed to obtain compounds filling criteria (on the symmetry) for a ferroelectric order. The magnetic inorganic network was built due to the synthesis of compounds based on first row metals or lanthanides. All compounds were characterized by several techniques (X-rays diffraction, spectroscopic measurements, thermal and elemental analyses). Magnetic, luminescence and ferroelectric properties were also studied
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Fournier, Antoine. "Développement de procédés écoresponsables pour la synthèse de solvants et d'organocatalyseurs biosourcés." Thesis, Bourgogne Franche-Comté, 2018. http://www.theses.fr/2018UBFCK046/document.
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Les oxazolidinones sont des composés prometteurs pour des applications industrielles, mais aucune méthode ne convient à ce jour pour les produire à large échelle, à cause de l'utilisation de réactifs et de catalyseurs métalliques nocifs pour la santé et l'environnement. Une nouvelle méthode de synthèse de ces composés a donc été élaborée en utilisant des aminoalcools et du carbonate de diéthyle. Cette réaction est catalysée par un hydrogénocarbonate d'imidazolium biosourcé qui est produit par voie électrochimique afin de réduire son impact sur l'environnement.Cette méthode de synthèse d'oxazolidinones a ensuite été appliquée à la synthèse d'une oxazolidinone biosourcée. Pour cela, la synthèse d'un aminoalcool a été réalisée, et sa structure a été établie à partir de réactifs pouvant être issus de ressources renouvelables. La voie de synthèse a fait l'objet de modifications pour permettre la production de l'aminoalcool à plus grande échelle dans des conditions plus sûres.La seconde thématique de ces travaux porte sur les liquides ioniques, des sels liquides très peu volatils, couramment utilisés comme solvants. Ces composés sont généralement chers, ainsi, plutôt que de les éliminer à la fin de leur utilisation, il est plus intéressant de les recycler. Mais leur faible volatilité empêche leur recyclage par distillation, contrairement aux solvants organiques usuels. Il a ainsi été développé une première méthode électrochimique, économe en énergie, qui permet le recyclage de liquides ioniques biosourcés par la formation d'un hydrogénocarbonate d'imidazolium intermédiaire. Cette méthode a été comparée à d'autres procédés de recyclage grâce à une étude préliminaire du cycle de vie.Mots clés : oxazolidinone, aminoalcool, imidazolium, liquide ionique, biosourcé, recyclage, électrochimie, développement durable, écoconception, cycle de vieOxazolidinones are promising compounds for industrial applications, but nowadays there is not convenient method to produce them on large scale, because of the use of reactants and metallic catalysts harmful for health and environment. A new synthesis method of these compounds was thus elaborated using aminoalcohols and diethyl carbonate. This reaction is catalysed by a biobased imidazolium hydrogen carbonate which is produced by an electrochemical pathway in order to reduce its impact on the environment.This oxazolidinones synthesis method was then applied to the synthesis of a biobased oxazolidinone. To achieve this, an aminoalcohol synthesis was realised, and its structure was established from reactants that can come from renewable resources. The synthesis pathway was the object of modifications to permit the production of the aminoalcohol on a larger scale in safer conditions.The second thematic of these works is based on ionic liquids, very low volatile liquid salts, commonly used as solvents. These compounds are usually expensive, so, rather than to eliminate them at the end of their use, it is more interesting to recycle them. But their low volatility prevents their recycling by distillation, unlike common organic solvents. So, a first electrochemical method was developed, low energy consuming, permitting the recycling of biobased ionic liquids by the formation of an imidazolium hydrogen carbonate as intermediate. This method was compared with other recycling processes through a preliminary life cycle study.Keywords: oxazolidinone, aminoalcohol, imidazolium, ionic liquid, biobased, recycling, electrochemistry, sustainable development, eco-design, life cycle
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Southerland, Marie R. "SYNTHESIS AND BIOLOGICAL EVALUATION OF IMIDAZOLIUM SALTS AS ANTI-CANCER AGENTS." University of Akron / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=akron1524075623735265.
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Spence, Graeme T. "Imidazolium- and triazolium-based interlocked structures for anion recognition and sensing." Thesis, University of Oxford, 2012. http://ora.ox.ac.uk/objects/uuid:3de31ccf-db32-402c-b2b4-fca475500080.
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This thesis describes the synthesis and investigation of novel anion templated interlocked structures which incorporate the positively charged imidazolium and triazolium binding motifs for applications in anion recognition and sensing. Chapter One introduces the fields of anion supramolecular chemistry and mechanically interlocked structures, focusing on topics of particular relevance to this thesis, including anion recognition, anion sensing and the templated synthesis of interlocked architectures. Chapter Two details the incorporation of the imidazolium motif into the axle components of anion templated rotaxane hosts to achieve selective anion recognition by virtue of their interlocked binding cavities. The effects of exploiting imidazolium motifs with contrasting hydrogen bond donor arrangements and reducing the macrocycle size on the anion recognition properties of such systems were investigated using 1H NMR spectroscopy. Chapter Three reports the work undertaken to utilise fluorescent reporter groups as stoppers in the synthesis of anion sensing rotaxanes. Imidazolium- and triazolium based systems containing either luminescent ruthenium(II) bipyridyl complexes or the organic fluorophore anthracene were prepared and their anion sensing behaviours explored using fluorescence spectroscopy. Synthetic efforts to construct suitable photo-active rotaxanes are detailed. Chapter Four describes investigations of the novel naphthalimide triazolium motif both for use in interlocked molecular motion systems, and for fluorescence sensing applications. The preparation of a naphthalimide triazolium rotaxane, capable of selective, anion-induced, uni-directional shuttling which was investigated extensively using 1H NMR spectroscopy and optically signalled by perturbations in the UV/Vis spectrum, is detailed. Preliminary research studies into the potential to exploit this motif for surface based fluorescence sensing devices are also included. Chapter Five presents research into the utilisation of acyclic receptors displaying considerable binding induced conformational changes for fluorescence anion sensing. The recognition properties of a series of imidazolium-based receptors were studied, whilst the ability of a pyrene appended analogue to signal anion complexation via changes in excimer emission is reported. The control of interpenetrated assembly formation using anion-induced conformational changes within the threading component of a pseudorotaxane is also discussed. Chapter Six provides the experimental procedures and characterisation details for the compounds synthesised in this thesis. Chapter Seven is a summary of conclusions from Chapters Two, Three, Four and Five. Supplementary information relating to titration protocols, crystallographic data and surface studies is provided in the Appendices.
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Morvan, Didier. "Synthèses de sels d'imidazolium fonctionnalisés précurseurs de carbènes N-hétérocycliques et applications en chimie organométallique." Brest, 2007. http://www.theses.fr/2007BRES2020.
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Les sels d’imidazolium possèdent des propriétés chimiques singulières qui permettent des utilisations diverses notamment comme précurseurs de carbène N-hétérocycliques (NHC). Les NHC sont largement utilisés comme ligand en chimie organométallique puisqu’ils sont connus pour être d’excellent ligand σ-donneur et avoir la particularité d’être fonctionnalisables sur les atomes d’azote. Le premier chapitre constitue un rappel des propriétés des sels d’imidazolium et des NHC correspondant. Ces composés sont ensuite utilisés comme ligands dans diverses applications organométalliques. Le travail principal de cette thèse a été de synthétiser des modèles biomimétiques des hydrogénase à fer seul incorporant des ligands NHC. Ces modèles peuvent nous permettre de mieux comprendre le fonctionnement des hydrogénases qui catalysent la réduction des protons en dihydrogène. Une autre partie de ce travail a constitué à synthétiser des ligands imidazolium-phosphonate potentiellement hemilabiles et à les complexer sur du rhodiumImidazolium salts have singular chemical properties and are widely used in organic or organometallic chemistry. This organic salt which has been employed as an excellent Nheterocyclic carbene (NHC) precursor. N-Heterocyclic carbene ligands are widely used in organometallic chemistry for its well-known σ-donor properties and interestingly the incorporation of functionality is possible on the nitrogen atoms. In the first part of my PhD thesis, we developed, following a methodologic approach, the synthesis of functionalised imidazolium salts. New methods or simplified methods have been identified to produce imidazolium salts with a wide range of fonctions. The second aspect of this PhD thesis, has concern the exploration of the coordination properties of the new functionalised imidazolium salt, to design models of hydrogenase (hydrogenases are metalloenzymes that catalyze the reduction of protons to dihydrogen at very high rates) and to study the hemilability of these new ligands on rhodium complexes
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Andrews, Karen Leanne 1973. "Characterisation of novel imidazolines with KATP channel antagonist activity." Monash University, Dept. of Pharmacology, 2001. http://arrow.monash.edu.au/hdl/1959.1/9020.
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Miel, Hugues. "Synthèse de nouvelles guanidines et imidazolines à visée thérapeutique." Caen, 1998. http://www.theses.fr/1998CAEN4074.
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Zhang, Chengda. "SYNTHESES OF PEG/ALKYL-BASED IMIDAZOLIUM/PYRIDINIUM IONIC LIQUIDS AND APPLICATIONS ON H2S ABSORPTION& SYNTHESES OF POLYSULFONE BASED FUNCTIONALIZED IMIDAZOLIUM IONIC POLYMERS AND APPLICATIONS ON GAS SEPARATION." OpenSIUC, 2015. https://opensiuc.lib.siu.edu/theses/1797.
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The synthesis method for PEG/alkyl-based imidazolium/pyridinium ionic liquids was studied. Four steps were used to fabricate the membranes: polymerization, chloromethylation, linkage of the polymers with the pendent groups and membrane cast. Permeabilities and CO2/N2 selectivity of two membranes were examined and each showed remarkable CO2/N2 selectivity. CO2 permeability of the [PSM-MIM][Cl] membrane is better than that of the [PSM-MEIM][Cl] membrane, which is due to the steric hindrance of the methoxyethyl group. The syntheses of PEG/alkyl-based imidazolium/pyridinium ionic liquids (IL) were studied. PEG-based ILs were demonstrated to have better H2S solubilities than the alkyl-based ILs. H2S solubilities of the imidazolium ILs and pyridinium ILs were compared. The anion effects on H2S solubilities have been investigated, while the temperature effects on H2S solubilities will need to be studied in the near future.
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Schunkert, Daniel [Verfasser]. "Synthese und Charakterisierung neuer Imidazolium-Geminitenside mit Siloxan- oder Carbosilanseitenketten / Daniel Schunkert." München : Verlag Dr. Hut, 2019. http://d-nb.info/1196414866/34.
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DeBord, Michael. "Synthesis, characterization, and anti-cancer structure-activity relationship studies of imidazolium salts." University of Akron / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=akron1489414733025495.
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Tomlinson, Sean R. "The solubility and secondary structure of zein in imidazolium-based ionic liquids." Diss., Kansas State University, 2013. http://hdl.handle.net/2097/15511.
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Doctor of PhilosophyDepartment of Chemical Engineering
Jennifer L. Anthony
Ionic liquids are low melting salts composed of an organic cation and an inorganic or organic anion. Ionic liquids are of interest for their wide range of applications and unique properties, such as the negligible vapor pressure of some types of ionic liquids, and the ability to modify ionic liquid properties by selection of the cation or anion. It has been hypothesized that over one million binary ionic liquids (meaning a single cation/anion pair) are possible. Due to the vast number of potential combinations, it should be possible to design ionic liquids specifically for an application of interest. One potential application is their use as protein solvents. However there is little understanding of how ionic liquids affect proteins. This research examined the solubility and secondary structure of the hydrophobic corn protein zein in seven ionic liquids and three conventional solvents as a function of temperature and solvent properties. Zein’s solubility in the solvents was measured gravimetrically from 30 to 60 degrees Celsius. Solubility was then related to solvent properties to gain an understanding of what solvent properties are important, and how to design an ionic liquid to dissolve zein. It was found that a good solvent for zein has a small molecular volume, a low polarity, and is a weak hydrogen bond acceptor. Infrared spectroscopy with curve fitting was used to examine the secondary structure of zein as a function of both solvent and temperature from 25 to 95 degrees Celsius. It was found that most of the ionic liquids change zein’s secondary structure, but those secondary structure changes were not affected by temperature. Aprotic ionic liquids increase the amount of β-turn secondary structure through non-polar interactions between the mixed aromatic-alkyl imidazolium cations and the non-polar portions of the zein. Strong hydrogen bond accepting molecules were found to increase the amount of β-turn secondary structure. It is hypothesized from this research that suitable solvents for zein will have a small molar volume, low polarity, and be poor hydrogen bond acceptors. This combination of properties will enhance zein’s solubility and limit secondary structure changes that can harm protein properties.
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França, Luis Aracelly. "Síntese, comprovação estrutural e avaliação da atividade anti-T cruzi de derivados imidazacrídinicos e imidazolidínicos." Universidade Federal de Pernambuco, 2008. https://repositorio.ufpe.br/handle/123456789/3351.
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Previous issue date: 2008Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
A doença de Chagas é uma infecção causada pelo Trypanosoma cruzi, o qual é transmitido ao homem através da picada de insetos pertencentes à espécie Triatoma infestans. Em sua fase aguda, a doença provoca febre e miocardite. No entanto, alguns pacientes podem desenvolver a forma crônica, quando então surgem as principais conseqüências cardíacas e gastrointestinais. Muitos estudos foram feitos na busca de novos fármacos e alguns deles descrevem o potencial efeito anti-T. cruzi de derivados imidazolidínicos e acridínicos, ambos conhecidos pelo suas variadas ações biológicas. Neste trabalho, descreve-se a síntese e características físico-químicas de novos derivados imidazolidínicos e imidazacridínicos. Todos os compostos sintetizados tiveram suas estruturas químicas comprovadas por espectroscopia de Infravermelho (IV), Ressonância Magnética Nuclear de Hidrogênio (RMN1H), espectrometria de Massas (MS) e cristalografia. Adicionalmente, investigou-se a citotoxicidade de todos os compostos utilizando-se células esplênicas de camundongos. O estudo da atividade anti-parasitária dos derivados imidazacridínicos e do composto 5-(9H-fluoren-2-il-metileno)-2-(4-nitrobenzilsulfonil)- 3,5-diidro-imidazol-4ona (LPSF/NN-237) foi realizado através da técnica de ensaio MTT. O cálculo da IC50, para esses mesmos compostos, foi determinado por meio de uma regressão linear simples utilizando o software Prisma 4 Graphpad. Os resultados demonstraram que o composto 5-(acridin-9-il-metileno)- 3-benzil-4-tioxo-imidazolidin-2-ona (LPSF/AC-128) obteve os melhores resultados de atoxidade e atividade anti-parasitária para T.cruzi, sendo um potencial candidato a novos fármacos no combate à doença de Chagas
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Hesler, Valerie Jane. "N-Heterocyclic carbene-metal complexes derived from imidazolium-linked cyclophane and biimidazolium salts." University of Western Australia. School of Biomedical, Biomolecular and Chemical Sciences, 2008. http://theses.library.uwa.edu.au/adt-WU2009.0088.
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This thesis presents an investigation into the synthesis of metal complexes of (Nheterocyclic carbene)-based cyclophanes. There were three main areas of focus: synthesis and complexation of bis(4,5-dihydroimidazolium) salts; the synthesis and complexation of phenol-functionalised imidazolium cyclophanes; and the synthesis and complexation of (N-heterocyclic carbene)-based cyclophanes by C-C bond activation of biimidazolium salts with electron-rich metals. The synthesis of xylyl-linked bis(4,5-dihydroimidazolium) salts was investigated. Attempts to prepare these compounds by the cyclisation of a tetraamine (linear or macrocyclic) were unsuccessful due difficulties in preparing the tetraamines. The target compounds could be prepared by adapting the methods developed for the synthesis of bis(imidazolium) salts however problems associated with purification and stability of the products prevented complexation studies. A series of phenol-, phenoxide- and anisole-functionalised imidazolium cyclophanes were prepared. Their structural properties were investigated using dynamic nmr studies and X-ray crystallography. Complexation of the functionalised cyclophanes was investigated. The phenol cyclophane I formed a dinuclear complex with mercury(II). This complex is the first example of a complex derived from a phenol-functionalised imidazolium cyclophane. However the anisole cyclophane II and the unsymmetrical phenol/ortho cyclophane III were unable to form complexes possibly due to steric hindrance and instability of the cyclophane respectively. Preliminary complexation studies of the bis(imidazolium)phenol V suggested that complexation with palladium(II) and mercury(II) were possible but more work is required to determine the optimum reaction conditions. A series of biimidazolium salts VI (both new and known) were prepared. Previously reported biimidazolium salts have very low solubility in common solvents therefore the incorporation of long alkyl chains to the bridging group was investigated as a means to improve the solubility. The structure of the salts was explored using a range of techniques including dynamic nmr spectroscopy, cyclic voltammetry, UV/Visible spectroscopy, X-ray crystallography and mass spectrometry. Some of the biimidazolium salts were able to rotate about the C2-C2' bond and the free energy of activation for this process was estimated using dynamic nmr studies. C-C bond activation of the biimidazolium salts with palladium(0) was used to form a series of palladium(II) complexes (VII) of (NHC)-based cyclophanes. These reactions are the first examples of the synthesis of bis(NHC) complexes by C-C bond activation. The reactivity of the biimidazolium salts with palladium(0) was compared to their solution structure and it was found that only the biimidazolium that were able to rotate about the C2-C2' bond could react with palladium(0).
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Wong, Wallace W. H. "Transition metal dithocarbamate and imidazolium-based receptors for a variety of guest models." Thesis, University of Oxford, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.409269.
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Yanthavakilla, Santha. "Synthesis and capillary eleltrophoretic studies of 3-methyl-1-(1-phenethyl)-imidazolium tetrafluoroborate." Cincinnati, Ohio : University of Cincinnati, 2004. http://rave.ohiolink.edu/etdc/view?acc%5Fnum=ucin1085759230.
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Jiao, Dezhi. "Alkyl and aryl imidazolium salts in aqueous supramolecular systems with cucurbit[n]uril." Thesis, University of Cambridge, 2012. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.610692.
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Kidd, Bryce Edwin. "Cation and Anion Transport in a Dicationic Imidazolium-Based Plastic Crystal Ion Conductor." Thesis, Virginia Tech, 2013. http://hdl.handle.net/10919/23300.
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Here we investigate the organic ionic plastic crystal (OIPC) 1,2-bis[N-(N\'-hexylimidazolium-d2(4,5))]C2H4 2PF6- in one of its solid plastic crystal phases by means of multi-nuclear solid-state (SS) NMR and pulsed-field-gradient (PFG) NMR. We quantify distinct cation and anion diffusion coefficients as well as the diffusion activation energies (Ea) in this dicationic imidazolium-based OIPC. Our studies suggest a change in transport mechanism for the cation upon varying thermal and magnetic treatment (9.4 T), evidenced by changes in cation and anion Ea. Moreover, variable temperature 2H SSNMR lineshapes further support a change in local molecular environment upon slow cooling in B0. Additionally, we quantify the percentage of mobile anions as a function of temperature from variable temperature 19F SSNMR, where two distinct spectral features are present. We also comment on the pre-exponential factor (D0), giving insight into the number of degrees of freedom for both cation and anion as a function of thermal treatment. In conjunction with previously reported conductivity values for this class of OIPCs and the Stokes-Einstein relation, we propose that ion conduction is dominated by anion diffusion between crystallites (i.e., grain boundaries). Using our experimentally determine diffusion coefficient and previously reported PF6- hydrodynamic radius (rH), viscous (" = 4.1 Pa " s) ionic liquid (IL) is present with a cation rH of 0.34 nm. NMR measurements are very powerful in elucidating fundamental OIPC properties and allow a deeper understanding of ion transport within such materials.Master of Science
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YATHAVAKILLA, SANTHA V. "SYNTHESIS AND CAPILLARY ELECTROPHORETIC STUDIES OF 3-METHYL-1-(1-PENETHYL)-IMIDAZOLIUM TETRAFLUOROBORATE." University of Cincinnati / OhioLINK, 2004. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1085759230.
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Naghmouchi, Haithem. "4-t-butylCalix [4] arènes fonctionnalisé avec des groupes d'imidazolium captifs : de nouveaux ligands pour la chimie organométallique et la complexation des anions." Thesis, Strasbourg, 2015. http://www.theses.fr/2015STRAF069.
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La synthèse de nouveaux calixarènes fonctionnalisés par des groupes d’imidazolium occupe un grand intérêt qui se justifie par la facilité de fonctionnalisation des atomes d’azote de l’imidazole d’une part et d’autre part, par les propriétés de reconnaissance anionique liée à la charge positive délocalisée.Au cours de la première étape, nous avons effectué la fonctionnalisation des calixarènes au niveau de la partie basse en gardant le t-butyle au niveau de la partie haute. Dans un second temps, nous avons réalisé une substitution des atomes de brome par des dérivés d’imidazoles tel que 1-méthylimidazole, 2,4,6-triméthlimidazole, 2,6-diisopropylimidazole, l’imidazole et le benzimidazole afin de créer des ligands imidazolium, par la suite une réaction des sels d’imidazolium avec le nickelocène a conduit à la formation des complexes du NiCp. Dans une dernière étape, nous avons déterminé les propriétés complexantes des dérivés d’imidazolium vis-à-vis des anions organiques et inorganiquesThe synthesis of new calixarenes functionalized with groups imidazolium occupies a large interest, which is justified by the ease of functionalization of the nitrogen atoms of the imidazole on the one hand and on the other hand, by the anionic recognition properties related the delocalized positive charge.During the first step, we conducted the functionalisation of calixarenes at the lower part bearing the t-butyl at the top. Secondly, we made a substitution of bromine atoms by imidazole derivatives such as 1-methylimidazole, 2,4,6-triméthlimidazole, 2.6-diisopropylimidazole, imidazole and benzimidazole to create imidazolium ligands, subsequently a reaction imidazolium salts with nickelocene led to the formation of complexes NiCp.In a last step, we determined the complexing properties of imidazolium derivatives vis-à-vis organic and inorganic anions
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Suisse, Jean-Moïse. "Electrosynthèse de nanoparticules métalliques en milieu liquide ionique supramoléculaire." Strasbourg, 2009. http://www.theses.fr/2009STRA6071.
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La première partie de cette thèse décrit comment l'introduction de groupements alkoxyphényles en position 1 et 3 d'une unité imidazolium induit des propriétés supramoléculaires à ce matériau liquide ionique. L'étude s'intéresse à l’évolution des propriétés mésomorphes en fonction des modifications structurales apportées (longueur de la chaîne aliphatique) en s'appuyant sur une caractérisation complète des phases cristal liquides (microscopie optique à lumière polarisée, calorimétrie différentielle, diffraction de rayons X). Nous nous sommes également intéressés à l'activité catalytique du complexe de palladium II obtenu à partir de la forme déprotonnée de l'un de nos ligands imidazolium. De surcroît, nous avons mesuré la mobilité des porteurs de charge au sein de la mésophase. La partie mésogène des dérivés cationiques a été ajustée pour créer de nouveaux cristaux liquides ioniques fonctionnels, en vue de l'électrosynthèse de nanopaticules métalliques (par introduction de cyanométallates). La deuxième partie de cette thèse s'intéresse donc à l'électrocristallisation de nanoparticules d'or et d'argent en milieu liquide ionique auto-organisé. Les études montrent notamment qu'il est possible d'utiliser l'architecture supramoléculaire d'une mésophase pour influencer la morphologie des dépôts obtenus par électroréduction. Cette thèse présente enfin une nouvelle voie pour la synthèse de nanoparticules métalliques offrant un meilleur contrôle sur le processus de réduction que les méthodes chimiques traditionnellesThe first section of this thesis describes the synthesis of a new family of ionic liquid crystalline compounds based on imidazolium cations. The study focuses mainly on the mesomorphic behavior of these materials as a function of the molecule backbone (alkyl tail length). All compounds were fully characterized by polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction studies. We report also the synthesis, lamellar crystal structure and catalytic activity of the palladium (II) complex of the (deprotonated) carbene form of one of these salts. In addition, we measured the charged carrier mobilities in the mesophase. The molecular design of our ionic liquid crystalline materials has then been modified to incorporate cyanometallate to endow the products with electrochemical properties. The second section of this thesis is devoted to the development of a new route for the preparation of metallic nanoparticles by electrocrystallization. This approach allow direct and accurate control of the reduction process, of the size of the nanoparticles and of their density of nucleation on the substrate. Of particular significance is the demonstration herein that the supramolecular structure of the liquid-crystal phase can be used to influence the morphology of metal nanoparticles deposited by electrochemical reduction
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ROSA, Getúlio de Souza. "Planejamento e Síntese de Híbridos PIrazol-Imidazolinas com potencial atividade Antiprotozoária." reponame:Repositório Institucional da UNIFEI, 2017. http://repositorio.unifei.edu.br/xmlui/handle/123456789/891.
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As doenças causadas por protozoários afetam, segundo a OMS, 1 bilhão de pessoas em 149 países, com uma taxa de mortalidade superior a 500 mil casos anuais. Muitas dessas doenças são consideradas negligenciadas devido ao baixo investimento na criação de estratégias efetivas de controle e erradicação. Dentre as doenças negligenciadas destacam-se as leishmanioses que, segundo a OMS, apresentam uma incidência de 1,3 milhão de novos casos por ano e são endêmicas em 98 países. O tratamento é complicado, prolongado, alguns medicamentos têm alto custo e apresentam um grande número de efeitos colaterais. A doença de Chagas é outra doença negligenciada, sendo endêmica em 21 países latino-americanos. Estima-se que entre 8 e 10 milhões de pessoas estejam infectadas e 28 milhões com risco de infecção crônica. Os únicos medicamentos disponíveis para tratamento são o benzonidazol e o nifurtimox que apresentam muitos efeitos colaterais em aproximadamente 40% dos pacientes. Nosso grupo de pesquisa tem planejado, sintetizado e avaliado diversos derivados heterocíclicos quanto à atividade antileishmania, principalmente sistemas híbridos pirazóis/imidazolinas, dois sistemas de grande importância na química medicinal e na quimioterapia de doenças protozoárias. Dessa forma, a partir dos bons resultados já obtidos pelo grupo e com as evidências de que o mecanismo de ação seja semelhante tanto para inibição de crescimento de Leishmania sp quanto T. cruzi, o objetivo principal desse trabalho é sintetizar os derivados inéditos do sistema 1-aril-5-bromo-4-(4,5-di-hidro-1H-imidazol-2-il)-1H-pirazóis 1(a-h) e 5-amino-1-aril-4-(4,5-di-hidro-1H-imidazol-2-il)-1H-pirazóis 2(a-h), para avaliá-los quanto às atividades antileishmania e antitripanossoma, respectivamente. Os intermediários-chave 5-amino-1-aril-1H-pirazol-4-carbonitrilas 4(a-h) foram obtidos com rendimentos na faixa de 78 a 96% e os derivados 1-aril-5-bromo-1H-pirazol-carbonitrilas 3(a-e) foram obtidos, assim como os subprodutos 1-aril-1H-pirazol-4-carbonitrilas 6(a-e). Na última etapa, os produtos planejados 1-aril-5-bromo-4-(4,5-di-hidro-1H-imidazol-2-il)-1H-pirazóis 1(a,d) não foram obtidos a partir dos intermediários 3(a,d), mas, sim, os derivados 1-aril-4-(4,5-di-hidro-1H-imidazol-2-il)-1H-pirazóis 7(a,d), além dos produtos substituídos na posição 5 do pirazol 8(a,d), cujas estruturas não foram elucidadas. Utilizando uma metodologia alternativa, o derivado 1a foi obtido com rendimento bruto de 15%, abrindo uma nova técnica para obter os demais produtos 1(b-h). Os derivados 2(a-h) foram sintetizados com rendimentos entre 16 e 84%, sendo que, 2(a,c,e,g) foram avaliados quanto à citotoxicidade em células VERO e mostraram altos valores de CC₅₀, todos acima de 500 μM, exceto o derivado 2c, cujo valor foi de 338,86 μM.
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Del, Vecchio Franklin A. "An investigation into the asymmetric synthesis of imidazolinones via reaction of chiral a-amino acid esters with nitriles /." Online version of thesis, 1991. http://hdl.handle.net/1850/11069.
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Phipps, Dale E. "Imidazolium and Calix[4]arene based Anion Receptors for the Selective Recognition of Fluoride." Thesis, University of Oxford, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.514979.
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Vidal, Marc. "Développement de nouveaux sels Binol-imidazoliums : de la catalyse asymétrique aux applications biologiques." Thèse, 2013. http://hdl.handle.net/1866/10519.
Full textAbstract:
Le 1,1'-bi-2-naphtol ou Binol, présentant une chiralité axiale, est un ligand très utilisé en catalyse asymétrique. Au cours des vingt dernières années, le Binol a servi de synthon à l’élaboration de très nombreux ligands permettant la catalyse asymétrique de tous types de réactions, allant de l’hydrogénation, à l’alkylation, en passant par diverses réactions péricycliques. Le grand intérêt pour ce ligand vient de sa versatilité et des nombreuses possibilités de fonctionnalisation qu’il offre, permettant d’altérer ses propriétés catalytiques à volonté, aussi bien en modifiant son caractère électronique, qu’en introduisant des facteurs stériques autour du site catalytique.
Parallèlement aux développements de la catalyse par des dérivés de Binol, le domaine des liquides ioniques a connu un intérêt croissant ces dernières années. Les liquides ioniques, sels dont le point de fusion est inférieur à 100°C, cumulent de nombreuses qualités convoitées : faible pression de vapeur, stabilité thermique et chimique et fort pouvoir de solvatation. Dû à ces propriétés, les liquides ioniques ont principalement été étudiés dans l’optique de développer une gamme de solvants recyclables. Alors que les propriétés des liquides ioniques sont facilement modulables en fonction de l’anion et du cation choisi, le concept de liquide ionique à tâche spécifique va plus loin et propose d’introduire directement, sur le cation ou l’anion, un groupement conférant une propriété particulière.
En suivant cette approche, plusieurs ligands ioniques ont été rapportés, par simple couplage d’un cation organique à un ligand déjà connu. Étonnamment, le Binol a fait l’objet de très peu de travaux pour l’élaboration de ligands ioniques. Dans cette thèse, nous proposons l’étude d’une famille de composés de type Binol-imidazolium dont les unités Binol et imidazolium sont séparées par un espaceur méthylène. Différents homologues ont été synthétisés en variant le nombre d’unités imidazolium et leur position sur le noyau Binol, la longueur de la chaîne alkyle portée par les unités imidazolium et la nature du contre-anion. Après une étude des propriétés thermiques de ces composés, l’utilisation des Binol-imidazoliums en tant que ligands dans une réaction asymétrique d’éthylation d’aldéhydes aromatique a été étudiée en milieu liquide ionique. La réaction a été conduite en solvant liquide ionique dans le but de recycler aussi bien le ligand Binol-imidazolium que le solvant, en fin de réaction. Cette étude nous a permis de démontrer que la sélectivité de ces ligands ioniques dépend grandement de leur structure. En effet, seuls les Binols fonctionnalisés en positions 6 et 6’ permettent une sélectivité de la réaction d’éthylation.
Alors que les dérivés de Binol fonctionnalisés en positions 3 et 3’ ne permettent pas une catalyse énantiosélective, il a déjà été rapporté que ces composés avaient la capacité de complexer des anions. D’autre part, il a déjà été rapporté par notre groupe, que les composés comportant des unités imidazolium pouvaient permettre le transport d’anions à travers des bicouches lipidiques en fonction de leur amphiphilie. Ceci nous a amenés à la deuxième partie de cette thèse qui porte sur les propriétés ionophores des Binols fonctionnalisés en positions 3 et 3’ par des unités imidazoliums. Dans un premier temps, nous nous sommes intéressés à l’étude de la relation structure-activité et au mécanisme de transport de ces composés.
Le transport d’anions étant un processus clé dans la biologie cellulaire, l’activité biologique des composés présentant une activité ionophore dans des systèmes modèles (liposomes) a été étudiée par la suite. L’activité antibactérienne des nos composés a été testée sur quatre souches de bactéries. Il s’est avéré que les composés Binol-imidazolium sont actifs uniquement sur les bactéries Gram positives. Finalement, la cytotoxicité des composés présentant une activité antibactérienne a été étudiée sur des cellules humaines.1,1'-Bi-2-naphthol or Binol, having an axial chirality, is a widely used ligand in asymmetric catalysis. Over the last twenty years, Binol was used as a synthon for the synthesis of numerous ligands for the asymmetric catalysis of various reactions including hydrogenation, alkylation and various pericyclic reactions. The interest in this ligand comes from its versatility and possibilities to modify its electronic character and to introduce steric bulk around the catalytic site. Paralleling interest in the study of Binol derivatives as ligands for asymmetric catalysis has been a growth in research on ionic liquids. Ionic liquids are salts with melting points below 100°C. They combine many interesting properties, such as low vapor pressure, thermal and chemical stability and high solvation power. Due to these properties, ionic liquids have been investigated to develop a range of recyclable solvents. Recently, the concept of task-specific ionic liquids has emerged in which the properties of the ionic liquids are tuned by selecting different cations and anions, to accomplish specific applications. Following this approach, several ionic ligands have been made by coupling known ligands to an ionic liquid cation. Rarely, Binol has been used for this purpose. In this thesis, we study a family of Binol-imidazolium type compounds, in which Binol and imidazolium units are linked by a methylene spacer. Several analogs were synthesized by varying the number of imidazolium units and their position on the Binol moiety, the alkyl chain length on the imidazolium units and the counter-anion. After a study of the thermal properties, the use of Binol-imidazoliums as ligands was described in the asymmetric ethylation of aromatic aldehydes. The reaction was conducted in ionic liquid solvent and both Binol-imidazolium ligand and the solvent were recycled at the end of the reaction. This study demonstrates that the selectivity of these ligands greatly depends on their structure. Indeed, only Binol analogs functionalized at the 6 and 6’ positions were selectivite. Although Binol derivatives functionalized at the 3 and 3' positions did not serve as enantioselective catalysts, they were able to complex anions. Furthermore, it has already been reported by our group, that imidazolium compounds can transport anions across lipid bilayers depending on their amphiphilicity. In the second part of this thesis, we cover the ionophoric properties of Binol derivatives functionalized at the 3 and 3' positions by imidazolium moieties. First, a study will be presented of their structure-property relationships in the transport through liposomes. Thereafter, the transport mechanism will be discussed. Finally, the biological activity of our compounds with ionophore activity was studied, because the anion transport is a key process in cell biology. Their antibacterial activity was tested on four strains of bacteria. Binol-imidazolium compounds exhibited activity on Gram positive bacteria. Their cytotoxicity was also studied on human cells.
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Lin, Meng-Che, and 林孟哲. "Diffirent imidazolium Salts Protected Palladium Nanoparticles." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/84539321611183865731.
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Hu, Chung-Hao, and 胡忠豪. "Coordination Chemistry of Imidazolium-Carboxylate Ligand." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/68459662189977954968.
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碩士國立臺灣大學
化學研究所
102
Since the publication of the first N-heterocyclic carbene (NHC) by Ardruengo’s group in 1991, NHCs have been widely used in several fields. Due to their electron donating ability and good stability, NHC containing organometallic catalysts generally possess superb catalytic performances. Recently, poly-dentate NHC ligands have drawn much attention for their potential application in organometallic supramolecules. To contribute to the poly-NHC field, we have synthesized a bifuctional ligand, which contains a carboxylate moiety and an imidazolium unit to serve as the metal coordination site and the carbene precursor, respectively. When the bifuctional ligand coordinates to the oxophilic metal centers, multikis imidazolium salts, which could function as bridging ligands for framework materials, are expected. To this end, we successfully synthesized a Co(II) linked bis-imidazolium salt and a Zn(II) connected tetrakis-imidazolium salt. Furthermore, a Cu(II) linked tetra-imidazolinethione complex, and a Cu(II) based tetradentate ligand, which was oxidized to form an imidazolidinone coordinated extended structure, were also synthesized.
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Lin, Chiao-Yang, and 林樵揚. "1.Synthesis and Application of Chiral Imidazolium Salts2.Synthesis and Studies the Mesomorphic Behavior of Imidazolium Salts." Thesis, 2006. http://ndltd.ncl.edu.tw/handle/76537475142966621394.
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碩士國立東華大學
化學系
93
There are two parts of the thesis. The first part involves the synthesis of ionic liquids with imidazolium cation moiety. Ionic liquid exhibit very unique physical properties, such as low melting point, non-vapor pressure, being thermo stable and used as a recyclable organic solvent (so called “Green Solvent”). In addition, N-heterocyclic carbene generated on imidazolium cation C-2 position, is regarded as a good nucleophile, which can chalet with metals and be used for synthesis as a catalyst. N-heterocyclic carbene cannot only accelerate the reaction but also control regio-selectivity under mild condition and it can be recovered easily. The experiment was started with (S)-(─)-methyl lactate as the starting material and ended up the chiral imidazolium salts which were applied to introducing chirality by N-heterocyclic carbene nucleophilicity. The second part of this thesis describes the synthesis of 1-alkoxyl-3-methyl imidazolium salts. The physical properties of 1-alkyoxyl-3-methyl-imidazolium salts with two different counter anions were discussed. Differences between 1-alkoxyl- and 1-alkyl-, 3-methyl imidazolium salts were also described.