Дисертації з теми "Diazonia"
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Labro, Marine. "Synthèse de nouvelles prodrogues photoactivables ciblant les G-quadruplexes : étude de la photoréaction et design moléculaire pour améliorer la biocompatibilité et l'efficacité d'une nouvelle thérapie anti-cancer." Electronic Thesis or Diss., Lyon, École normale supérieure, 2024. http://www.theses.fr/2024ENSL0020.
Повний текст джерелаCancer is a major public health problem: in 2020, it caused the death of approximately 10 million people worldwide, equivalent to one in six deaths. Recent research efforts against cancer have led to the emergence of targeted and innovative therapies. These advancements aim to minimize collateral damage to healthy cells and reduce side effects in treated patients, while ensuring maximum treatment efficacy for tumor eradication. In this thesis, we study a new original photochemical reaction allowing the development of a new photoactivatable anti-cancer prodrug. From a helical molecule of bis-quinoline type, an intramolecular double SNAr* photoreaction leads to the formation of an extended diazonia, a G-quadruplexes ligand which is fluorescent and capable of generating cytotoxic singlet oxygen. Thus, this photochemical reaction facilitates the development of a novel anti-cancer treatment at the intersection of photodynamic therapy and photo-uncaging. Furthermore, light serves as a non-harmful external stimulus within a certain range of wavelengths (particularly infrared), allowing controlled spatiotemporal drug release, rendering the prodrug's mode of action highly targeted and promising. In this thesis, we apprehended the mechanism of the photoreaction by studying the effect of different physico-chemical experimental parameters. Also, we rationalized the influence of the nature of the leaving group on the efficiency of the double SNAr* on the quantum yield of the photoreaction. Then, we improved the design of the prodrug for its biological application in order to 1) ensure treatment biocompatibility by triggering the photoreaction in the biological transparency window, 2) enhance prodrug cellular internalization, and 3) develop a combined therapy by associating multiple anticancer agents and implementing targeting strategies
Costenaro, Edson Roberto. "Utilização de enecarbamatos endociclicos na sintese de azanucleosideos." [s.n.], 2005. http://repositorio.unicamp.br/jspui/handle/REPOSIP/249883.
Повний текст джерелаTese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica
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Resumo: Nos últimos anos existe um grande interesse na obtenção de nucleosídeos e derivados estruturalmente relacionados em virtude do amplo espectro de atividades biológicas apresentadas por essa classe de compostos. Diversos tipos de análogos apresentando as mais diversas alterações estruturais têm sido relatados, entre os quais os azanucleosídeos, onde o átomo de oxigênio da porção glicosídica é substituído por um átomo de nitrogênio. Na primeira parte deste trabalho vários enecarbamatos endocíclicos quirais de cinco membros, enantiomericamente puros (CG-quiral), foram obtidos em uma seqüência de sete etapas a partir do ácido L-glutâmico e utilizados na síntese de azanucleosídeos. Na segunda parte deste trabalho utilizou-se a adição eletrofílica de brometo de fenilselenenila à enecarbamatos endocíclicos como etapa chave na obtenção de uma série de N-azanucleosídeos inéditos (estruturalmente relacionados às drogas atualmente utilizadas no coquetel anti-HIV). Na última parte deste trabalho, durante um estudo que avaliou os fatores que determinam a diastereosseletividade facial na arilação de Heck de enecarbamatos endocíclicos com sais de diazônio, foi desenvolvida a síntese total e estereosseletiva do C-azanucleosídeo de Schramm (uma pirrolidina sintética com potente atividade tripanocida). Este estudo ilustra a versatilidade de enecarbamatos endocíclicos como intermediários sintéticos na construção de moléculas mais complexas
Abstract: There was a great interest in the preparation of nucleosides and derivatives in the last years due to the large spectrum of biological activities of these substances. Several analoges with structural modifications have been reported in the literature, such as azanucleosides, where the oxigen atom of the glicosidic portion is replaced by a nitrogen. In the first part of this work, several five membered ring endocyclic enecarbamates, that are enantiomerically pure (chiral-GC), were obtained in seven steps sequence from L-glutamic acid and used in the synthesis of azanucleosides. In the second part of this work, the eletrophilic addition of phenylselenenyl bromide to endocyclic enecarbamates was used as the key step in synthesis of a unpublished series of N-azanucleosides (structurally related to the drugs presents in the anti-HIV cocktail). In the last step of this work, during a study to determinate the factors that command the facial diastereoselectivity on the Heck arylation of endocyclic enecarbamates with diazonium salts, a total and stereoselective synthesis of Schramm C-azanucleoside (a synthetic pyrrolidine with potent tripanocidal activity) was performed. These studies have show the versatility of endocyclic enecarbamates as synthetic intermediates to the building of more complex molecules
Doutorado
Quimica Organica
Doutor em Ciências
Valiulytė, Giedrė. "Azodažiklių sintezė iš aromatinių aminų diazonio druskų." Master's thesis, Lithuanian Academic Libraries Network (LABT), 2014. http://vddb.library.lt/obj/LT-eLABa-0001:E.02~2014~D_20140630_134139-62079.
Повний текст джерелаAim of the work: synthesis of azo dyes from aromatic amines diazonium salts by two methods, determination of their pKa values, spectral features and applicability as indicators of produced azo dyes. Main objectives: to obtain azo dyes from methylanilines and 4-nitroaniline by hydrolysis of their diazonium salts or by binding with 1-naphtol and 2-naphtol, to calculate yields of obtained compounds, to determine their pKa values, spectral features and their possible application as indicators. Methods: Two methods of azo dyes synthesis are used to perform the assay. Percentage yields of synthesized compounds, obtained by both methods, are calculated. Purity of compounds is evaluated by HPLC. pKa values and range of pH where the colour changes of received compounds are evaluated by potentiometric titration. Aqueous solutions of azo dyes are assessed by measuring absorption peaks and optical densities with a spectrophotometer. Results: it is necessary to synthesise aromatic amines diazonium salts with conc. HCl and to perform hydrolysis in 104-110 oC temperature when hydrolysate consist of 44 ml water and 20 ml conc. H2SO4 in order to obtain azo dyes by experimental method. Yields of traditional method are good-very good (average yield is 76,95 proc.), yields of experimental method are moderate (average yield is 41,44 proc.). pKa values of naphtolic azo dyes which are obtained by traditional method are 8,8-11,0 and phenolic azo dyes – 7,5-8,0. Spectrophotometric studies showed that... [to full text]
Ahmed, Nihad Kamal Ibrahim. "A novel electrochemical platform based on screen printed carbon electrodes (SPCEs) for molecular diagnostics." Doctoral thesis, Universitat Rovira i Virgili, 2020. http://hdl.handle.net/10803/669466.
Повний текст джерелаEl objetivo de este trabajo es desarrollar dispositivos de diagnóstico molecular electroquímico de bajo coste basados en microsistemas de electrodos serigrafiados. Esta tesis se centra en métodos que incrementen la reproducibilidad y la fiabilidad de ensayos moleculares utilizando este tipo de electrodos. Para desarrollar el concepto se usó como modelo a detectar Karlodinium armiger, un alga tóxica. Se escogió el método isotérmico de amplificación: Recombinase Polymerase Amplification (RPA) ya que puede ser incorporado fácilmente en dispositivos portátiles de análisis. El principal problema de los electrodos serigrafiados reside en las interacciones no específicas que ocurren con los poros y la superficie irregular de los electrodos, cosa que puede afectar a la fiabilidad de los resultados. Para solucionar este problema, proponemos dos métodos: en el primer método una sal carboxilada de diazonio se electrodeposita i posteriormente se modifica covalentemente con una sonda de ADN carboxilada, formando una capa de reconocimiento en la superficie del SPCE. Con esta metodología se consiguió la hibridación i detección de muestras de ADN amplificadas por RPA en estado sólido i líquido, obteniendo límites de detección de 0,1fM i 0,3fM respectivamente. Aun así, este método requiere de reacciones química en solución y la activación electroquímica de los electrodos durante la fabricación, hecho que incrementa la complejidad y el coste de producción. Una mejor alternativa para la fabricación de electrodos a gran escala consiste en la modificación de estos por deposición.
The objective is to develop an electrochemical platform based on screen printed microsystems that enable low cost, point of use molecular diagnostics. This thesis focuses on methods to increase the reliability and reproducibility of screen printed electrode-based molecular assays. As proof of concept Karlodinium armiger, a toxic microalgae used as target. Recombinase Polymerase Amplification (RPA), an isothermal amplification method, was chosen because it can be easily incorporated in portable, point-of-use devices. Non-specific interactions with the porous and irregular surface of the SPCEs affect the reliability of the results. We demonstrate two methods can solve these problems: the first approach electro-grafted carboxylated diazonium was linked covalently to the aminated DNA probes (recognition layer) on the SPCE surface. DNA hybridization and detection were achieved in both solid and liquid phase RPA achieving detection limits (LODs) of 0.1 fM and 0.3 fM respectively. This approach requires wet chemistry and electrochemical activation of the electrodes during manufacturing, complicating production and increasing its cost. Surface modification by drop casting is more appropriate for large scale production. Basically, the surface of SPCEs was modified with poly (L-Lysine) polymer crosslinked with polyethylene glycol diglycidyl ether (PEGDE) that attached the aminated DNA probes. Polyethylene glycol (PEG) used to block the non-specific adsorption of horseradish (HRP) labels that were used for detection
Akwi, Faith Mary. "Scalable chemistry involving diazonium salts." Thesis, Nelson Mandela Metropolitan University, 2016. http://hdl.handle.net/10948/6909.
Повний текст джерелаSchotten, Christiane. "Investigating multistep continuous flow processes using diazonium salts." Thesis, Cardiff University, 2018. http://orca.cf.ac.uk/113812/.
Повний текст джерелаAddo, Isaac D. "Diazonium 4-(trifluorovinyloxy) Perfluorobutanesulfonyl Benzenesulfonimide Zwitterionic Monomer Synthesis." Digital Commons @ East Tennessee State University, 2016. https://dc.etsu.edu/etd/3137.
Повний текст джерелаMesnage, Alice. "Diazonium salts induced anchoring process : mechanism, application(s)." Palaiseau, Ecole polytechnique, 2011. https://pastel.hal.science/docs/00/62/90/41/PDF/Manuscrit_Alice_Mesnage.pdf).
Повний текст джерелаAu cours de ce travail, trois procédés de fonctionnalisation de surface à partir de sels de diazonium ont été étudiés, à savoir : un procédé spontané, un procédé activé chimiquement et le procédé appelé Graftfast (activation chimique en présence de monomères vinyliques). Ces procédés, dits de chimie verte, fonctionnent à température ambiante, pression atmosphérique, en milieu aqueux et sans apport extérieur d'énergie. Ils conduisent à la formation de films organiques (notamment de polymères dans le cas du procédé Graftfast) stables, greffés de manière covalente et d'épaisseur contrôlée (procédés activés chimiquement). Contrairement aux méthodes d'électrogreffage de sels de diazonium, ces procédés peuvent s'appliquer à tout type de substrats allant des isolants aux conducteurs en passant par les nanomatériaux. Le substrat ainsi modifié peut présenter de nouvelles propriétés (par exemple d'hydrophilie, de protection contre la corrosion,. . . ) ce qui est d'un intérêt majeur dans certaines problématiques industrielles. L'objectif majeur de ce travail a été de comprendre les mécanismes réactionnels de ces trois procédés et plus particulièrement du procédé Graftfast en étudiant la composition chimique des films, leur structure mais aussi la composition des solutions réactionnelles. Comme pour une polymérisation radicalaire en chaîne conventionnelle, le mécanisme réactionnel du procédé Graftfast (cas le plus complexe) procède en trois étapes : amorçage, propagation, terminaison. La polymérisation est amorcée par les radicaux aryles en solution, issus de la réduction chimique des sels d'aryldiazonium (mécanisme en sphère interne ou en sphère externe selon le réducteur chimique). Parallèlement, les radicaux aryles peuvent se greffer à la surface du substrat et former une sous couche d'accroche de polyphenylene jouant un rôle essentiel dans la construction des films. La propagation s'achève lorsque les chaînes polymères en croissance réagissent par des réactions de transfert sur les noyaux aromatiques déjà greffés sur le substrat (étape de terminaison). Les films obtenus sont alors de structure mixte : groupements aryles, polymères. Ce procédé a notamment été testé dans le but d'améliorer la dispersion des nano-objets dans l'eau, dans le cadre d'une étude préliminaire sur les crèmes solaires à base de nanoparticules de dioxyde de titane
Jones, Jason Robert. "Mechanism, catalysis and control in aromatic diazonium ion chemistry." Thesis, University of York, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.306605.
Повний текст джерелаSalmi, Zakaria. "Surface, Sels de diazonium et Polymères : Synergie et Applications." Paris 7, 2013. http://www.theses.fr/2013PA077270.
Повний текст джерелаThe work of this Phd consist in the study of surface chemistry of diazonium sait on different surfaces (ITO, carbon nanotubes, clays, and diamond) and to graft on those surfaces a polymer by the "grafting onto" or the "grafting from" method. The first method involves grafting a coupling agent on the surface and makes react a polymer terminated with end functionality. Namely we used the diazonium chemistry to graft an alkyne functionality on carbon nanotubes then make react a polymer with an antagonist end functionality (azide). The second method is based on the grafting of an initiator then the growth of a polymer chain from this surface. In particular we graft a photopolymerisation initiator on clays, ITO and diamond surfaces. Then we polymerized respectively polyglycidyl methacrylate, a molecular imprinted polymer and a polyhyroxyethyl methacrylate
Ben, Sghaier Asma. "Hybrides polymer materials organic/inorganic nanoparticule." Thesis, Paris Est, 2018. http://www.theses.fr/2018PESC1163.
Повний текст джерелаDiazonium interface chemistry has progressed over the last few years and practically involved in all areas of materials science and engineering. The rationale for employing diazonium salts is that they attach to surfaces with remarkable bond energies, particularly on sp² carbon materials, making them an ideal coupling agent for polymers to surfaces In this context, novel CNT-polytriazole (CNT-PTAz) and CNT-dye nanohybrids were designed and thoroughly characterized. First, CNT-PTAz nanohybrid was prepared by click polymerization: multiwalled carbon nanotubes (CNTs) were modified with azidophenyl groups (CNT-N3) from 4-azidobenzenediazonium precursor and served as nanoscale platform for the surface confined polyaddition. The CNT-PTAz nanohybrid was characterized by TGA, XPS, IR, and Raman. The robust CNT-PTAz is robust and has potential in developing heavy metal adsorbents, nanosupport for catalysts or for gas storage. In the second major part, we grafted CNT with diazotized Neutral red (NR), Azure A (AA) and Congo Red (CR) dyes by simple, spontaneous reaction of the diazonium salts and CNTs in water, at RT. A thorough investigation of the nanohybrids showed that the adhesion is strong (CNT-dye C-C bond energy higher than 150 kJ/mol), and the layer is uniform. These nanohybrids further served to reinforce ethylene-vinyl acetate (EVA) an elastomeric matrix. The reinforced matrix is flexible and serves as optothermal actuators where the grafted dye catches the light to induce mechanical changes in the matrix monitored by dynamic mechanical analysis. CNT/dye-reinforced EVA is a promising flexible composite for developing new types of visual-aid tablet for visually impaired people. The versatile CNT-dye nanohybrids are also unique chemiresistive gas sensors for the molecular recognition of acetone vapours. In a final application, CNT-CR nanohybrid was investigated as an electrocatalyst for the Direct Oxidation of Methanol. Interesting results were obtained with these nanohybrids but significant improvements (3-fold) of the electrocatalytic properties were achieved with CNT-CR decorated with gold nanoparticles. The newly designed electrocatalytic system could be regarded for different promising applications most likely as for sensors, biosensors, heterogeneous catalysts for fuel cells and for nanotechnology To summarize, newly designed CNT-based nanohybrids have unique performances ascribed to the versatility of the diazonium interface chemistry in efficiently attaching functional molecular and macromolecular layers. The novel nanohybrids serve as building blocks for designing high performance nanocomposite materials relevant to challenging timely social economic issues, namely environment, biomedicine and energy
Merrington, James. "Towards the combinatorial synthesis of azo dyes." Thesis, University of Southampton, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.274573.
Повний текст джерелаMesnage, Alice. "Procédé d'ancrage induit par des sels de diazonium : mécanisme, application(s)." Phd thesis, Ecole Polytechnique X, 2011. http://pastel.archives-ouvertes.fr/pastel-00629041.
Повний текст джерелаRycroft, A. D. "Chemistry of diazonium tetraflouroborates : Studies on the enantioselective synthesis of lycorine." Thesis, Teesside University, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.384639.
Повний текст джерелаKist, Madelyn M. "Light-induced surface site manipulation of gold nanoparticles using diazonium salt." Kent State University / OhioLINK, 2021. http://rave.ohiolink.edu/etdc/view?acc_num=kent1626960076521484.
Повний текст джерелаPatto, Daniela da Cunha Souza. "Estudo da reação de arilação de Heck de enecarbamatos, enamidas e enoleteres endociclicos utilizando sais de diazonio." [s.n.], 2003. http://repositorio.unicamp.br/jspui/handle/REPOSIP/249869.
Повний текст джерелаTese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica
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Doutorado
Lenne, Quentin. "Interfaces et nano-objets fonctionnels et biomimétiques pour l'électrocatalyse." Thesis, Rennes 1, 2021. http://www.theses.fr/2021REN1S143.
Повний текст джерелаThe work presented in this manuscript is focused on the surface functionalization of metallic nanoparticles with a covalently-bound monolayers of calix[4]arenes. The catalytic activity of these modified systems was then studied for the activation of small fuel molecules such as oxygen, methanol, and carbon dioxide
Lee, Lita. "Modification of Glassy Carbon Electrodes with Diazonium Cation Terminated Films: "Sticky Surfaces"." Thesis, University of Canterbury. Chemistry, 2011. http://hdl.handle.net/10092/6202.
Повний текст джерелаCunha, Silvio do Desterro. "Reações de alquifenilciclopropenonas com diazois : reatividade e estudo de orbitais moleculares." [s.n.], 1993. http://repositorio.unicamp.br/jspui/handle/REPOSIP/250511.
Повний текст джерелаDissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica
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Mestrado
Tatunashvili, Elene. "Innovations in radical chemistry." Thesis, The University of Sydney, 2021. https://hdl.handle.net/2123/27376.
Повний текст джерелаHeynert, Sven. "Der Einfluss von Amilorid und Diazoxid auf die Innenohrfunktion der Taube (Columba livia)." [S.l.] : [s.n.], 2001. http://deposit.ddb.de/cgi-bin/dokserv?idn=963793780.
Повний текст джерелаAhmad, Husan. "Synthesis of Diazonium Perfluoroalkyl(Aryl) Sufonimide (PFSI) Zwitterions for Solid Acid Alkylation Catalysts." Digital Commons @ East Tennessee State University, 2015. https://dc.etsu.edu/honors/314.
Повний текст джерелаAlharbi, Helal, and Hua Mei. "SYNTHESIS OF DIAZONIUM N-(PERFLUOROALKYL) BENZENESULFONIMIDE ZWITTERIONIC POLYMERS FOR PROTON EXCHANGE MEMBRANE FUEL CELLS." Digital Commons @ East Tennessee State University, 2018. https://dc.etsu.edu/asrf/2018/schedule/197.
Повний текст джерелаAlharbi, Helal. "Synthesis of Diazonium N-(Perfluoroalkyl) Benzenesulfonimide Polymers for Proton Exchange Membrane Fuel Cells (PEMFCs)." Digital Commons @ East Tennessee State University, 2019. https://dc.etsu.edu/etd/3601.
Повний текст джерелаMenanteau, Thibaud. "Contrôle de la fonctionnalisation par réduction des sels de diazonium via le piégeage radicalaire." Thesis, Angers, 2016. http://www.theses.fr/2016ANGE0059/document.
Повний текст джерелаThe surface functionalization by diazonium salt reduction is a powerful grafting method. However, despite that this approach allows the preparation of robust materials, it leads to thick and unorganized organic films. In this context, we have developped a method allowing the grafting control in order to obtain films having controlled thickness. Based on the use of radical scavengers, this method gives access to monolayer formations on carbon substrates. The control strategy was then exploited to selectively block the radical grafting mechanism and allows to assess the role of non-radical mechanisms in the process. This study provided a better understanding of the layer growth, highlighting the impact of precursor substituent.This knowledge has been used to elaborate a multifunctional platform monolayer. The establishment of sutructure/properties relathionships revealed better performances for electronic transfert and electrocatalysis. Finally, the control method was transposed to the spontaneous grafting and gives similar results than those obtained for the electrochemical one. This approach was validated by the performance optimization of supercapacitor made of carbon powder
Taylor, Alec Brian. "New investigations into Sandmeyer chemistry." Thesis, University of York, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.323495.
Повний текст джерелаJanin, Marion. "Apports du microscope électrochimique à balayage pour la formation et l'étude de contacts atomiques et de jonctions moléculaires." Paris 7, 2011. http://www.theses.fr/2011PA077240.
Повний текст джерелаThis work is about the use of SECM for electrochemistry on the nanometer scale, in order to fabricate and study stable systems with controllable properties on the molecular or atomic scale. We first showed the possibility to modify microelectrodes by the reduction of phenyl diazonium salts. These proved to be fitting for SECM usage. We then used the SECM to study electroactive films of PANI, PEDOT and gold nanoparticles deposited on an insulating substrate. In a second chapter, we fabricated conducting polymer junctions via SECM. According to conductance values in nS range, stable nanojunctions which can be switched electrochemically have been obtained. Such behavior has been attributed to the formation of metal/polymer/oligomer/metal junctions, where few oligomers strands control the transport properties. In addition, the nanojunctions have been performed using modified electrode interface, obtained by grafting of diazonium salts. Moreover, the effect of reducing the substrate size from millimeter to micrometer scale in the formation of nanojunctions has been investigated. Lastly, we fabricated copper atomic contacts by a self-terminated electrochemical method, in water and in surfactant media. At low concentration, the anionic surfactant shows a very strong and selective adsorption on the atomic contact, inducing a drop in the conductance of the contact to a value below the conductance quantum. Those experiments have been successfully adapted on the SECM, first on a two-electrode setup, then on a four-electrode setup which would enable to make stable atomic contacts that can be switched electrochemically
Le, Callonnec Francois. "Nouveaux développements dans la chimie des sels de diazonium en catalyse organométallique : catalyse hétérogène en milieux aqueux." Thesis, Bordeaux, 2014. http://www.theses.fr/2014BORD0044/document.
Повний текст джерелаDiazonium salts are reactive and versatile when used as electrophiles. Unfortunately, their reputation as instable compounds strongly limited their use in chemical synthesis. This work lead to the discovery of new procedure for a safer and more environmentally friendly use of diazonium salts in organometallic coupling reactions. We studied palladium catalised carbon-carbon coupling reactions and copper catalyzed C-H arylatons. A major part of this work is also focalized in the development of new heterogeneous catalysts. New catalysts for the Meerwein reaction were also discovered. Finally, the last part of this research work focused on new active heterogeneous supports as nanoreactors for organometallic reactions
Alayyaf, Abdulmajeed A. "Synthesis of Two Monomers for Proton Exchange Membrane Fuel Cells (PEMFCs)." Digital Commons @ East Tennessee State University, 2016. https://dc.etsu.edu/etd/3015.
Повний текст джерелаMarchal, Laureline. "Développement d'une nouvelle technologie Li-ion fonctionnant en solution aqueuse." Phd thesis, Université de Grenoble, 2011. http://tel.archives-ouvertes.fr/tel-00728179.
Повний текст джерелаHartig, Prosper. "Engineering of Si(111) surfaces by electrochemical deposition of organic layers from diazonium salt solutions." [S.l. : s.n.], 2002. http://deposit.ddb.de/cgi-bin/dokserv?idn=965241157.
Повний текст джерелаLee, Lita. "Preparation of monolayer tethers via reduction of aryldiazonium salts." Thesis, University of Canterbury. Chemistry, 2015. http://hdl.handle.net/10092/10500.
Повний текст джерелаHammond, Roger C. "Kinetic studies directed towards the improvement of Sandmeyer reactions." Thesis, University of York, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.296294.
Повний текст джерелаDiallo, Saer. "Spectrofluorimetrie des derives nitroses (nitrites et n-nitrosamines apres denitrosation alcaline) par diazotation de la coumarine 120* puis hydrolyse en 4-methylombelliferone : interet de son ionisation a l'etat excite) (doctorat : sciences pharmaceutiques)." Paris 11, 1999. http://www.theses.fr/1999PA114841.
Повний текст джерелаLe, Comte Annaïg. "Greffage de molécules électroactives sur carbone pour les électrodes de supercondensateur hybride." Nantes, 2014. http://archive.bu.univ-nantes.fr/pollux/show.action?id=9b2ba2c3-308e-4eb5-8c4f-2392935c81f9.
Повний текст джерелаNowadays, everybody is conscious of the need to develop new sustainable and environmentally friendly energy sources. These sources mostly intermittent (solar, wind) must be associated with storage systems. The two main electrochemical energy storage devices are batteries and supercapacitors. Batteries store energy through Faradaic reactions and therefore display high specific energy. The charge storage mechanism in supercapacitors is based on capacitive processes that ensure high specific power and life time up to 106 cycles. Hybrid systems combine battery-type electrode which increases the stored capacity, with a supercapacitor electrode which maintains fast charge/discharge kinetics. In this thesis we have developed strategies to increase the energy density stored in these systems. The chosen approach was the covalent grafting of electroactive molecules onto the surface of a porous carbon to add a faradaic contribution to the total capacity of the supercapacitor electrode. The chemistry of diazonium salts was used for the modification of carbon powders. The choice of the molecule has been especially investigated. The formation of a covalent bond between the molecule and the substrate has been highlighted by characterization techniques. Finally, the assembly and the cycling of complete devices have proven that the grafting induces an increase of the energy density without impacting on the power density
Lebon, Florian. "Nano-composants à base de films minces organiques électrogreffés : Fabrication, caractérisation, étude du transport électronique et intégration." Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLS286/document.
Повний текст джерелаThe main objective of this PhD thesis is to show the potential for organic electronics of molecular thin films covalently bounded and formed by electrochemical grafting. These 5 to 100 nm thick layers aim to propose an alternative to organic thin films of thickness above 100 nm and to self-assembled monolayers of thickness between 1 and 5 nm.This work first establishes the optimal electrografting conditions of three diazonium salts : a derivative from the tris-bipyridine iron (II), a diazonium salt with a long fluorinated chain and another with a thiol function). In particular, a fine tuning of the thickness of the resulting layers is demonstrated on micrometric patterned electrodes.Double layer electrografting is then studied. It consists in using an electrode electrografted with electroactive molecules, here the tris-bipyridine iron (II) derivative, as a working electrode for the electrografting of a second diazonium salt. This technique allows the formation of organic double-layers of thickness controlled by the first layer and presenting terminal functions controlled by the choice of the second compound (here, thiol functions or fluorinated chains).The potential of these layers is then evaluated in vertical metal-molecules-metal junctions using various top electrodes : electrodes printed from an aqueous gold nanoparticle ink through a method developed in this thesis, and electrodes made by metal evaporation in vacuum. To conclude, field-effect transistors based on MoS2 using these electrografted thin layers as gate-dielectric are fabricated and studied. Their performances (electronic mobility of 46 cm2.(V.s)-1, ION/IOFF ratio of 9.107,etc.) confirm the quality of these organic electrografted insulators. The method is thus efficient and versatile for the preparation of robust organic layers with adjustable surface properties and thickness
Podvorica, Fetah. "Greffage de groupes aryles sur la surface des metaux par reduction electrochimique de sels de diazonium." Paris 7, 2000. http://www.theses.fr/2000PA077186.
Повний текст джерелаKamaleddine, Hanine. "Fonctionnalisation de Nanotubes pour la fabrication de batteries Lithium/Soufre et Lithium/Organique." Thesis, université Paris-Saclay, 2021. http://www.theses.fr/2021UPASF008.
Повний текст джерелаLithium/organic batteries are receiving a lot of attention for energy storage. The interest of these batteries lies in their organic electrode materials, prepared from abundant, inexpensive and easily recyclable precursors. However, organic materials have two major disadvantages: their dissolution in organic electrolytes and their low electronic conductivity.The work carried out during this thesis aims at developing organic active materials for the positive electrodes of lithium batteries. In order to overcome the problematics of active material dissolution and poor electronic conductivity, the strategy is to graft covalently the electroactive molecules onto carbon nanotubes, via the chemical reduction of diazonium salts.The first part of this thesis is devoted to the grafting of anthraquinone active material onto different carbon electrodes, and their chemical and electrochemical characterizations. A detailed study of the chemical grafting procedure is carried out to better understand the grafting process and its limitations.In the second part of this thesis, other electroactive molecules (phenanthrenequinone, naphthoquinone, benzoquinone and a molecule containing disulfide bonds) are synthesized and grafted onto nanotubes. The results show that the rate of grafting onto nanotubes is low regardless of the nature of the grafted electroactive molecule
Chrouda, Amani. "Élaboration de nouveaux matériaux d’électrodes modifiées pour application biocapteurs." Thesis, Lyon 1, 2015. http://www.theses.fr/2015LYO10074.
Повний текст джерелаThe objective of the research work was to the development of modified electrode materials for biosensor application. The work was devided into three parts: electrografting of diazonium salt for immunosensor application, electroadressing of antibodies and electrodeposition of PEG spacer for aptasensor application. In the first part of this work, the modification of gold surfaces with nitrobenzene diazonium cation was investigated in order to develop an immunosensors for the detection of Staphylococcus aureus. A detection limit of 10 CFU/mL has been obtained. The second part was focused on the electrically addressable deposition of diazonium functionalized antibodies on boron-doped diamond (BDD) microcells for the detection of OTA. A detection limit of 0.007ng/mL has been obtained and the immunosensor was tested on real samples. Finally, we developed an amperometric aptasensor based on electrochemical grafting of a PEG-COOH spacer on a BDD microcell for the detection of OTA biotoxin. A detection limit of 0.01 ng/L has been obtained and application to a real sample (rice) has been demonstrated. The amperometric and impedimetric techniques used in this work lead to promising results in terms of sensitivity, specificity and reproductibility
Zhang, Lin. "Co-immobilisation du complexe (2,2'-bipyridyl) (pentaméthylcyclopentadiényl)-rhodium et de déshydrogénases NAD-dépendantes pour l’électrosynthèse enzymatique énantiosélective." Thesis, Université de Lorraine, 2016. http://www.theses.fr/2016LORR0283/document.
Повний текст джерелаIn this work we developed methods for the co-immobilization of NAD-dependent dehydrogenases and the (2,2'-bipyridyl) (pentamethylcyclopentadienyl)-rhodium complex ([Cp*Rh(bpy)Cl]+) on porous carbon electrodes for application in the electroenzymatic synthesis of chiral alcohols and sugars. The goal was to avoid the degradation of the enzymatic activity coming from the interaction of functional groups from the enzyme surface (eg.-SH, -NH2) with [Cp*Rh(bpy)Cl]+ and to promote the recyclability of the catalyst. Diazonium electrografting was used to introduce alkene and azide groups on a carbon surface (flat glassy carbon, porous carbon felt or carbon nanotubes layers). Thiol-ene click chemistry was applied to bind a D-sorbitol dehydrogenase with cysteine tags (either 1 or 2 cysteine moieties at the N terminus of the polypeptide chain) onto carbon electrodes. Azide-alkyne Huisgen cyclo-addition reaction was used to bind an alkyne-modified [Cp*Rh(bpy)Cl]+. Then co-immobilization of the redox enzymes (D-sorbitol and galactitol dehydrogenase) with the complex [Cp*Rh(bpy)Cl]+ was tested by encapsulation of the proteins in a silica gel layer, inside a rhodium-functionalized porous carbon felt. The immobilized [Cp*Rh(bpy)Cl]+ was stable over weeks for NADH regeneration, but this electrode architecture led to the inhibition of the enzymatic activity, possibly because of the local environment (increase of pH and product accumulation in the porous electrode). The combination of ‘thiol-ene’ and Huisgen cyclo-addition was then investigated for sequential immobilization of [Cp*Rh(bpy)Cl]+ and cysteine-tagged D-sorbitol dehydrogenase on an azide-alkene bi-functionalized electrode. Finally, considering the different lifetime of enzymes and [Cp*Rh(bpy)Cl]+ catalyst, and the need for a better separation of these elements from the bioelectrochemical system, the best configuration was achieved by associating a porous silica layer with the immobilized enzyme with a bucky paper of carbon nanotubes functionalized with [Cp*Rh(bpy)Cl]+. The reusability of this functionalized electrode was proved and the designed bioelectrode was successfully applied to a bioelectrochemical conversion of D-fructose to D-sorbitol
Tijunelyte, Inga. "Development of SERS nanosensor for detection of water pollution." Thesis, Sorbonne Paris Cité, 2016. http://www.theses.fr/2016USPCD007/document.
Повний текст джерелаEnvironmental water pollution by organic compounds is in continues worldwide concern. Low molecular mass aromatic molecules consisting in benzene rings have received considerable attention due to a documented significant toxicity and carcinogenicity. Within the objectives of the European Water Framework Directives (2000/60/EC, 2006/118/EC and 2006/11/EC) aiming in water quality improvement, the development of analytical tools allowing in-situ accurate and sensitive detection is of primary importance and would be a meaningful innovation. With this regard, the main scope of this study was to design sensitive, reproducible, specific and reusable nanosensor for the detection of organic pollutants in environmental waters using Surface Enhanced Raman Spectroscopy (SERS).During this study the main attention was paid to the selection of suitable receptors and strategies for SERS nanosensor surface functionalisation in order to preconcentrate targeted pollutants. The application of antibodies and antigen binding fragments (F(ab)2) for surface decoration was found to be promising approach for highly selective nanosensor design. Another strategy exploited during this study was related with an application of cyclodextrins (CDs). Using Raman and SERS spectroscopies the size selective encapsulation of analytes was demonstrated. Finally, taking advantage of molecular identification in the complex environments offered by SERS technique, nanosensors providing non-specific molecular pre-concentration was considered. For this purpose several diazonium salts (DSs) were studied and applied to the surface functionalisation to create highly hydrophobic coating layer. The performance of such nanosensor was evaluated by detection of aromatic pollutants
Xia, Zhonghua. "Gold(I) Catalysis Under Visible Light." Thesis, Sorbonne université, 2018. http://www.theses.fr/2018SORUS606.
Повний текст джерелаThis thesis has focused on the study of a dual catalytic process involving gold catalysis and photocatalysis. We aimed to synthesize benzofuran derivatives from o-alkynylphenols and aryl diazonium salts or iodoalkynes in the presence of a catalytic mixture of a gold(I) complex and a photocatalyst under visible light irradiation. Firstly, we present a novel dual photoredox/gold catalysis process by arylative cyclization of o-alkynylphenols with aryldiazonium salts. This reaction occurs smoothly at room temperature in the absence of base and/or additives and offers an efficient approach to heterocyclic scaffolds. The reaction is proposed to proceed through a photoredox-promoted generation of a vinylgold(III) intermediate, formed by addition of the aryl radical to the gold catalyst and modulation of the oxidation state by the photocatalyst, which undergo reductive elimination to provide the heterocyclic coupling adduct. Later, we developed a new method for the synthesis of valuable alkynyl benzofuran derivatives devised from o-alkynylphenols and iodoalkynes in the presence of a catalytic mixture of Au(I) and Ir(III) under blue LED irradiation. Under visible light irradiation, the triplet excited state of the vinylgold(I) intermediate and the alkynyl iodide partner readily engaged in a oxidative addition–trans/cis isomerization sequence, deliver Csp2-Csp cross coupling products after reductive elimination. An energy transfer event rather than a redox pathway was demonstrated by the mechanistic and modeling studies. This dual gold/photo catalytic process provides a novel mode of activation in gold homogenous catalysis
He, Jie, and Jie He. "Triazabutadienes and a Glycoprotein-Targeted Photocrosslinker as Protein-Labeling Agents." Diss., The University of Arizona, 2017. http://hdl.handle.net/10150/625629.
Повний текст джерелаAltmann, Lisa-Marie [Verfasser], Markus [Akademischer Betreuer] Heinrich, and Svetlana [Gutachter] Tsogoeva. "Towards biocompatible radical arylations starting from diazonium salts / Lisa-Marie Altmann ; Gutachter: Svetlana Tsogoeva ; Betreuer: Markus Heinrich." Erlangen : Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), 2021. http://d-nb.info/1231077913/34.
Повний текст джерелаCesbron, Marius. "Vers l'élaboration de surfaces modifiées par des monocouches organiques mixtes issues de la réduction de précurseurs diazonium." Thesis, Angers, 2019. http://www.theses.fr/2019ANGE0061.
Повний текст джерелаThe immobilization of mixed organic layers (containing several species) on electrodes allows to confer on the latter the properties of the different species. The electroinduced reduction of diazonium salts is a powerfull grafting method for the formation of robust mixed layers. However, the control of the grafted functionalities ratio, and the thickness of the layers, remain challenging. These limitations are due to the radical reaction mechanisms involved and the difference between the reduction potentials of both diazoniums, generating thick layers which composition is dominated by the most easily reduced precursor. In this context, we tried to control the grafting of these mixed layers. For this two strategies have been developed. The first was to carry out the co-reduction of two diazoniums by chronoamperometry with a redox inhibitor. The chronoamperometry allows to limit the influence of the precursors reduction potentials on the layer composition and the inhibitor limits the grafting to a monolayer. The second strategy was divided into two steps: the generation of an azide platform by electro reduction of 4 azidobenzenediazonium in the presence of a redox inhibitor to limit the thickness of the layers, then a heterogeneous CuAAC between the reactive platform and a mixture of 2 alkynes to form a mixed layer whose composition depends on the alkynes concentrations. The second method was used to form controlled binary organic films. Preliminary studies ont TEMPO and porphyrin based layers was allowed to establich structure-properties and structure-reactivity relationships
Laws, Derek. "Organometallic Electrochemistry: a Study of Diazonium-Based Surface Attachments and the Anodic Chemistry of Piano-Stool Complexes." ScholarWorks @ UVM, 2008. http://scholarworks.uvm.edu/graddis/132.
Повний текст джерелаMateos, Mickaël. "Modifications électrochimiques de surfaces et dispositifs électroniques organiques." Thesis, Bourgogne Franche-Comté, 2018. http://www.theses.fr/2018UBFCK039/document.
Повний текст джерелаOrganic electronics remains a fruitful research field thanks to the diversity of molecular structures reachable by organic synthesis. Molecular materials offer convenient shaping processes, such as solution processing techniques, which can be used for the fabrication of organic devices on plastic substrates.Our works can be summarized as the elaboration of conductometric devices thanks to electrochemistry and the study of their electrical and sensing properties. They deal with two topics: the development of new transducers based on substituted polyanilines and phthalocyanines and the study of the influence of electrochemical modifications on the behavior of known devices.We first developped polymer - phthalocyanine lateral heterojunctions using the properties of polyanilines. Because of their geometry, these new devices differed from the MSDI heterojunction (Molecular Semiconductor - Doped Insulator), a bilayer-based conductometric transducer developed in the laboratory for the detection of gases such as ozone or ammonia. The comprehensive study of poly (2,3,5,6-tetrafluoroaniline) indicated that this material was a poor conducting polymer, compared to polyaniline whose conductivity can be increased by acid-base doping. The presence of fluorine atoms prevented the emergence of the conductive regime found in acidic medium for polyaniline and poly (2,5-dimethoxyaniline). These three polymers, electrodeposited on interdigitated ITO electrodes, allowed us, after sublimation of the lutetium bisphthalocyanine, to build lateral heterojunctions. The electrical behavior of the different devices, studied in particular by impedance spectroscopy, differed according to the nature of the substituents of the electrodeposited polyaniline. Finally, sensing measurements revealed their efficiency to detect ammonia in humid atmosphere, with a sub-ppm limit of detection.Previous works on the development of MSDI emphasized the primary role of interfaces, particularly in the case of n-MSDI that contained a p-n heterojunction. In addition to the modification of the chemical nature of the underlayer, another way to play with the interfaces is to electrochemically modify the surface of the interdigitated electrodes by reducing diazonium salts. Thus, we grafted various substituted benzenes, some of which led to the formation of multilayers as revealed by electrochemical quartz microbalance measurements. The various surface modifications mainly acted as an insulating barrier that amplified the nonlinear behavior of the current-voltage characteristics of MSDI. The grafting of 2,5-dimethoxybenzene significantly improved the ammonia sensitivity of MSDI based on copper hexadecafluorophthalocyanine and lutetium bisphthalocyanine, with a limit of detection of around 200 ppb
Xu, Minrui. "Synthèse et caractérisation de catalyseurs acido-basiques par greffage covalent sur supports carbonés. Application dans le domaine de la valorisation de molécules bio-sourcées." Thesis, Poitiers, 2019. http://www.theses.fr/2019POIT2292/document.
Повний текст джерелаHomogeneous catalyst applications are usually limited in industrial chemical processes because massive wastes are produced and catalyst separation with raw materials and products is inconvenient during industrial production processes. As a result, the heterogenization of homogeneous catalysts onto solid supports was often investigated and proven to be more promising for industrial applications. Nevertheless, not only the tedious catalyst synthesis but also the low catalyst loadings and the resulting low efficiencies contribute to the high cost of supported catalysts. To remedy the deficiency of supported catalysis, scientists have worked on direct functionalization of solid support via covalent bond building. Among the approaches of functionalization being investigated, the chemistry of diazonium developed by Griess is becoming more and more popular and attractive since this promising method enables to graft different organic moieties onto various solid supports. During past few years, the functionalization of carbonaceous materials was widely developed because carbon is an inexpensive and extensively available material. In this study, the spontaneous functionalization of carbonaceous materials (Darco KB-G; Norit SX2 and Vulcan XC72) can lead to basic or acid solids by respectively grafting different aminophenyl groups (phenylimidazole; N,N,dimethylaniline, aniline, phenylmorpholine) for basic solids and phenyl sulfonic group for acid solids, via diazonium chemistry.The functionalized solids were characterized by different technics (elemental analysis, N2 adsorption-desorption, TGA, SEM, FT-IR, XPS and Raman spectroscopy) and used in different model reactions to upgrade bio-resourced platform molecules, especially furfural. For instance, the usefulness and effectiveness of these new basic solids are illustrated with the Knœvenagel condensation between furfural and malononitrile under mild conditions leading to 2-furanylmethylene malononitrile and water. The basic solid Darco-0.5PDA exhibited high activity to the Knœvenagel condensation of furfural and malononitrile under mild experimental conditions (40 °C, Patm). The catalytic performance of functionalized acid solids was assessed in the acetalization reaction of dodecyl aldehyde with ethylene glycol at 60 °C under atmospheric pressure in both conventional and solvent-free PIC (Pickering Interfacial Catalysis) conditions. The experiments evidenced that the synthesized amphiphilic acid solid stabilized dodecyl aldehyde/ethylene glycol Pickering emulsions and demonstrated both good stability and activity in a solvent-free biphasic acetalization
Richard, William. "Nouvelle stratégie de fonctionnalisation de surfaces d'électrodes à base de sels de diazonium : application aux capteurs à antioxydants." Toulouse 3, 2013. http://thesesups.ups-tlse.fr/2231/.
Повний текст джерелаThe work here discussed is a fundamental study of the electrochemical reduction of the 4-nitrobenzene diazonium (NBD). Mechanistic and kinetic studies shed some light on the parts of the NBD reactivity and completed literature data about the subject. An NBD-functionalized antioxidant sensor has been envisaged, allowing the assay of ascorbic acid (AA). In a second time, a combined functionalization using a diazonium salt and a conductive polymer, the polyethylenedioxythiophene (PEDOT) coupled diazonium stability and electrocatalytic properties of PEDOT towards AA and uric acid, two major antioxidants. The modification parameters optimization of the interface and analytical performances determination highlighted the influence of the polymer structure on the sensor response
Nworie, Chimaroke. "Synthesis of a 4-(Trifluoromethyl)-2-Diazonium Perfluoroalkyl Benzenesuflonylimide (PFSI) Zwitterionic Monomer for Proton Exchange Membrane Fuel Cell." Digital Commons @ East Tennessee State University, 2014. https://dc.etsu.edu/etd/2346.
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