Дисертації з теми "Photosensibilisateur à base de ruthénium"
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Gueret, Robin. "Systèmes moléculaires pour la production d'hydrogène photo-induite dans l'eau associant des catalyseurs de cobalt à un photosensibilisateur de ruthénium ou un colorant organique." Thesis, Université Grenoble Alpes (ComUE), 2017. http://www.theses.fr/2017GREAV074/document.
The work of this manuscript is focused on the design of molecular systems in homogeneous solution for photocatalytic production of molecular hydrogen in water using cobalt catalysts with pentadentate tetrapyridinic and tetra- and pentaza macrocyclic ligands. In association with [Ru(bpy)3]2+ as photosensitizer and sodium ascorbate as sacrificial electron donor, the macrocycle based catalysts display high performances for H2 production, far exceeding those of the polypyridine based catalysts, both in terms of activity and stability, because of the stability of their reduced state «Co(I)». Finally, [Ru(bpy)3]2+ was successfully substituted with a robust organic dye belonging to the triazatriangulenium family, leading to an even more efficient photocatalytic system. These results demonstrate well that organic dyes are a truly efficient alternative to noble metal based photosensitizers, even in acidic aqueous medium
Nguyen, Thi Quyen. "Développement de photoélectrodes hybrides via l'assemblage d'un photosensibilisateur à base de ruthénium et d'un nanocatalyseur métal-oxyde métallique pour la génération d'O2 solaire." Thesis, Toulouse 3, 2021. http://www.theses.fr/2021TOU30046.
In this work, different nanostructured catalytic systems have been synthesized by an organometallic approach to produce nanoparticles (NPs) of small size and narrow size distribution, and their catalytic activity in the water oxidation reaction has been evaluated. First Fe NPs stabilized by oleic acid were synthesized that displayed an average size of ca. 10 nm ± 1.1 nm. A gamma-Fe_2O_3 oxide layer ca. 2.6 nm thick has been formed at their surface to obtain Fe@FeOx core-shell structure of ca. 11.5 ± 2.3 nm in diameter. Despite their hydrophobicity, these nanoparticles showed good electrocatalytic activity in alkaline conditions. As the gamma-Fe_2O_3 oxide shell is well adapted to the grafting of phosphonic groups, these Fe@FeOx NPs were grafted with different aminophosphonic acids in order to transfer them into water. Preliminary assessment of their catalytic activity showed improved activity for the NPs functionalized by 3-aminopropylphosphonic acid which opens promising prospects. Subsequently, a Ru-phenanthroline light-harvester with a pendant phosphonate group was synthesized and grafted onto the Fe@FeOx core/shell NPs to afford a novel hybrid photoanode for solar-driven water splitting. Mono- and biphasic processes were investigated to graft the Ru-complex at the surface of the NPs. The monophasic process was found to be more efficient as it provided a higher grafting density at the surface of the NPs (respectively 56 and 9 Ru per nanoparticles for the mono and biphasic processes). Photoelectrochemical measurements showed that the hybrid nanocatalyst comprising the highest Ru content was ca. 9-fold more catalytically active than a simple mixture between a ruthenium polypyridyl photosensitizer bearing no grafting group and the Fe@FeOx nanoparticles, and 40-fold more active than the pristine Fe@FeOx NPs. The performance enhancement could be attributed to a more efficient electron transfer between the ruthenium polypyridyl photosensitizer and the Fe@FeOx water oxidation catalyst thanks to the covalent bonding between these two components. The covalent grafting was found to improve not only the photocatalytic activity but also the stability of the system. Finally, amorphous NiFe NPs (diameter ca. 4 nm) with two different ratios between Ni and Fe (Ni_0.5Fe_0.5 NPs and Ni_0.68Fe_0.32 NPs) were synthesized, oxidized in air and grafted with 3-aminopropylphosphonic acid in order to obtain hydrophilic systems. The electrocatalytic activity of these water-soluble NPs was studied in alkaline solution, in comparison with that of crude NiOx NPs, FeOx NPs, and Ni_0.1Fe_0.9Ox NPs. The water soluble NPs containing 32 % of Fe (Ni_0.68Fe_0.32Ox) showed the highest activity and a good durability in alkaline solution. These characteristics make these amorphous NPs potentially applicable in photoelectrochemical cells for water splitting
Schneider, Ludovic. "Systèmes hybrides photosensibilisateur-laccase pour la catalyse d'oxydation de composés organiques." Thesis, Aix-Marseille, 2014. http://www.theses.fr/2014AIXM4372.
Laccases are oxidases that efficiently perform the reduction of dioxygen into water. Studies in the laboratory have allowed to show that irradiation under inert atmosphere of a EDTA/[Ru(bpy)3]2+/laccase system, lead to the photoreduction of the enzyme via the irradiation of [Ru(bpy)3]2+*. The substitution of EDTA by the alkene p-styrene sulfonate results similarly in a photoreduction of the enzyme. Opening the system to air allows a dioxygen consumption with a simultaneous detection of oxidation products such as the epoxide, diol and p-benzaldehyde sulfonate detected by NMR. The influence of the concentration of the partners, the irradiation source and pH on the efficiency of the reaction was evaluated. Other alkenes such as styrene, cyclohexene and cyclooctene are also substrates. Isotopic labeling experiments in the presence of either H218O or 18O2, as well as the use of reactive oxygen species generators, allowed us to propose a main mechanism where the laccase assisted RuIII photogenerated specie would withdraw an electron from the substrate which in turn would react with dioxygen to yield the products observed. Other ruthenium and manganese photosensitizers were also used. To address the control of the reactivity, a covalent grafting of a ruthenium photosensitizer, on a unique lysine nearby the substrate oxidation site of the laccase was done
Pernot, Marlène. "Amélioration de l'efficacité en thérapie photodynamique par couplage d'un photosensibilisateur à des molécules actives." Thesis, Université de Lorraine, 2012. http://www.theses.fr/2012LORR0195/document.
To improve tumor cells selectivity and/or photodynamic therapy (PDT) anti-tumor efficiency, active molecules (peptides, pseudopeptides, alkylating agents) have been conjugated to the photo-activable molecule. In a first part, vascular effect of PDT has been promoted by targeting the tumor vasculature with angiogenic phenotype. A chlorine-type photosensitizer have been coupled to a neuropilin-1 (NRP-1)-targeting peptide and has shown its in vitro and in vivo anti-tumor efficiency for PDT. However, the peptidic sequence has been degraded in vivo. Clivage site-modified pseudopeptides have been synthesized and tested in vitro, conjugated to TPC or not. Chlorine cellular uptake has been improved after coupling with pseudopeptides. A technique of RNA interference-mediated silencing of NRP-1 in MDA-MB-231, over-expressing NRP-1, has highlighted the receptor-dependent uptake of the conjugates and their cellular selectivity. Pseudopeptides and conjugates have shown their NRP-1 affinity and their in vivo stability. Ruthenium (Ru) is considered as an interest therapeutic molecule in oncology. In a second part, we have studied the in vivo interest of coupling an alkylating agent with porphyrine and chlorine-type photosensitizers. The in vivo efficiency studies on nude mice xenografted ectopically with KB cells have been carried using experimental design approach. Two in vitro efficient conjugates [Ru(_6-p-PriC6H4Me)(5-(3-pyridyl)-10,15,20-triphenylporphyrin)Cl2, or Rut1, and Ru4(_6-p-PriC6H4Me)4(5,10,15,20-tetra(3-pyridyl)porphyrin)Cl8, or Rut4] have been compared in vivo. Rut4 conjugate has appeared to be more efficient than Rut1. Biodistribution studies using fiber spectrofluorimeter and classic pharmacokinetic studies have shown an optimal drug-light interval of 24h. However, after PDT parameters optimization, the Ru coupling with a photo-activable molecule (porphyrin or chlorine) hasn?t shown any significant in vivo anti-tumor efficiency
Zhang, Lei. "Catalyseurs à base de ruthénium pour la transformation des bio-alcools." Thesis, Lille 1, 2014. http://www.theses.fr/2014LIL10182/document.
Acceptorless dehydrogenation of alcohols to corresponding ester or acid are environmentally friendly and atom-economic transformation pathways; Selective deuteration of alcohols using heavy water as deuterium source is a novel and interesting reaction.In the present thesis, two types of ruthenium-based catalysts (in situ formed and isolated) are used for above mentioned three reactions. It is proven that for all three reactions, the catalysts show high activities. Dehydrogenation of ethanol under neat and neutral conditions is performed; a recyclable catalytic process for butyric acid formation from butanol dehydrogenation is established; ethanol-d6 can be obtained when the selective deuteration is performed in a closed system. These three reactions have similar reaction pathways, which might be the reason why they can share same catalysts
Guillo, Pascal. "Développement de nouveaux catalyseurs à base de ruthénium pour l'oxydation : vers des systèmes photoactivables." Grenoble, 2010. http://www.theses.fr/2010GRENV042.
This the sis deals with the development of new homo and heterodinuclear complexes. At fIrst, with the objective to use chiral properties of tris-diimine ruthenium complexes in asymmetric catalysis, modifIed manganese salen complexes constituted by the assembly of a ruthenium and Mn or Zn-salen fragments were synthesized and fully characterized. More particularly, a Ru(II)-Mn(IV) species was characterized and a very efficient electron transfer has been also observed from the excited state of the ruthenium to the manganese. Ln the second part of the thesis, the photo sensitive and the catalytic properties of ruthenium complexes were both associated within a unique complex. Two chromophore catalyst dyad families were synthesized and fully characterized. Both of them showed high abilities to convert sulfIdes into sulfoxides under light exposure, using water as the only source of oxygen atom and a Co(III) salt as electron acceptor. Ln the context of sustainable development, we have shown that the association of a photosensitizer and solar energy allow soft conditions to perform oxidation reactions
Lebedeva, Anastasia. "Nanomatériaux à base de ruthénium et de manganèse pour l'oxydation catalytique d'hydrocarbures dans l'eau." Thesis, Rennes 1, 2017. http://www.theses.fr/2017REN1S099/document.
The activation of the Csp3-H bond and its transformation into a carbon-heteroatom bond remains a great challenge for the organic chemistry. An example of industrial application is the oxidation reaction of cyclohexane, leading to the production of the corresponding ketone and alcohol, key intermediates of Nylon-6 and Nylon-6,6 polyamides. Among the strategies to activate this unreactive bond, catalysis affords a relevant and sustainable tool. In this work, aqueous suspensions of metal nanoparticles were evaluated in terms of their stability and catalytic performances. Firstly, ruthenium colloids were synthesized from RuCl3.3H2O and fully characterized by various physico-chemical analyses (TEM, XPS, SAXS, UV-visible, etc.). Ru+3 active species were obtained, with a Ru(OH)3-xClx structure. After optimization of the reaction conditions, high conversions, combined with pertinent selectivities towards the ketone (up to 98%), were achieved. The presence of radical species was proved through kinetic and mechanistic studies. Furthermore, these easily recyclable Ru colloids were also evaluated in the oxidation of several saturated and unsaturated hydrocarbons. Secondly, a catalyst based on manganese dioxide, a cheap and abundant metal, was synthesized by an original redox process, starting from KMnO4 and in the presence of a hydroxylated quaternary ammonium (HEA16Cl), which plays the role of a reducing and stabilizing agent. This system proved to be a relevant alternative to methodologies based on noble metals. The MnO2 nanorods showed a good activity in the cyclooctane oxidation with a 100% selectivity towards the ketone
Shaw-Taberlet, Jennifer. "Dispositifs moléculaires fonctionnels à base organométallique." Rennes 1, 2006. https://tel.archives-ouvertes.fr/tel-00116762.
The synthesis of molecules whose properties undergo photo- or redox-induced variations must precede the elaboration of molecular electronic devices. This PhD thesis aims at the realization of nanoscopic molecular components to assemble carbon-rich organic fragments complexations onto transition metals. In this vein, we have shown that regioselective complexation onto substituted naphthalenes by the arenophile yields heterobinuclear compounds in which the redox-active organoiron end-group is conjugated with a terminus of variable (i) aromaticity, (ii) steric encumbrance and (iii) polarizability. The electronic properties of the iron atom were found to depend upon the coordination site of the arenophile: either on the substituted (collinear) or on the free (orthogonal) naphthyl ring. Remarkably, the arenophile underwent inter-ring haptotropic rearrangement (IHR) from the free naphthyl ring to the substituted one
Yuan, Shibin. "Etude de l'activation de l'hydrogène sur des catalyseurs à base de ruthénium (sulfure ou métal)." Lyon 1, 1992. http://www.theses.fr/1992LYO10169.
Charrier, Florian. "Utilisation de ressources issues de la biomasse pour la synthèse de complexes de ruthénium à ligands 2,2’ : 6’,2’’-terpyridines comme colorants au sein de cellules solaires DSSC." Thesis, Bourgogne Franche-Comté, 2017. http://www.theses.fr/2017UBFCD081/document.
Throughout this thesis, new organometallic dyes have been developed to use them as photosensitizers in dye-sensitized solar cells (DSSCs), whose simplicity of implementation, low cost production and attractive design are major assets. Black dye analogues were first developed, a thorough study of DFT calculations allowed a more constructive approach to the choice of molecular designs. Biomass-derived aldehydes such as vanillin, syringaldehyde or 5-hydroxymethylfurfural have been used to substitute the terpyridine ligand by different (hetero)aromatic groups in the 4’ position in order to modulate charge transfers. In a second step, a hexyloxymethyl chain was introduced in the 4'' position with the aim of reduce charge recombination during the solar cell operation and in the same time to place the LUMO closer to the anchoring groups for better charge injections to the semiconductor. The use of cyanoacrylate groups was also considered in place of the carboxylic acids in order to obtain more panchromatic absorptions. [Ru(tpy)2] and [Ru(tpy)(bpy)NCS] complexes have also been synthesized and studied for their increased stability over time in the solar cell compared to the NCS ligand complexes. Some dyes have been tested in solar cells in combination of titanium dioxide as the semiconductor and the I3-/I- couple as the redox mediator
Luc, Jérôme. "Propriétés optiques non linéaires et structuration photo-induite de nouveaux complexes organométalliques à base de ruthénium." Phd thesis, Université d'Angers, 2008. http://tel.archives-ouvertes.fr/tel-00351578.
Nous déterminons, à l'aide de diverses techniques expérimentales (DFWM, SHG, THG, Zscan), l'influence de la fonctionnalisation de ces structures moléculaires sur l'amélioration de leurs propriétés ONL du deuxième et troisième ordre en jouant notamment sur la nature du fragment accepteur et du transmetteur π-conjugué. Nous présentons les résultats de calculs théoriques de chimie quantique afin de proposer une étude ONL de ces complexes à l'échelle moléculaire. Enfin, nous complétons ce travail sur des complexes ruthéniumacétylure contenant un fragment azobenzène dans leur système organique p-conjugué, par la diffusion des rayons X aux grands angles (WAXS) et par l'étude, en régime picoseconde, de la dynamique de formation de réseaux de surface photo-induits (SRGs) en utilisant une technique d'holographie en transmission et la microscopie à force atomique (AFM).
Vignon, Paul. "Catalyseurs homogènes et hétérogènes à base de ruthénium pour la métathèse d’oléfines issues de ressources renouvelables." Thesis, Lille 1, 2013. http://www.theses.fr/2013LIL10037.
Production of materials from renewable raw materials is urgent by the decreasing availability of fossil fuels. This need has motivated the emergence of the concept of bio-refinery that certain products obtained in large quantities are derivatives of fatty acids (Fatty Acid Methyl Ester, FAME). These FAMEs are mainly produced by hydrolysis of triglycerides and have already found many application areas. In the context of optimal use of different products by bio-refineries, FAMEs modifications can be implemented thanks to catalysis, including olefin metathesis, taking advantage of the internal double bond present in these compounds. Significant efforts have been made on the ethenolysis of [Delta]9 FAME into [Alpha]-olefins, as these have a wide range of applications, but also on reducing the carbon chain size by reaction with small olefins (C4). Moreover, in order to limit metal contamination of products and to allow catalyst recycling, the use of heterogeneous catalyst is of high interest. We thus prepared heterogenized commercial ruthenium catalysts. These heterogeneous catalysts were prepared in a two-step procedure: modification of the catalyst or the silica and catalysts grafting by ligand exchange on silica. The reactions studied in this thesis concern self-metathesis, ethenolysis and various cross-metatheses of methyl oleate and FAME bio-derived sources using homogeneous catalysts and their grafted analogs. Despite the impossibility of recycling performance, heterogeneous catalysts have achieved our reactions efficiently and some of these reactions are the first example of such transformations with heterogeneous catalysis
Le, Pleux Loïc. "Conception de cellules photovoltaïques à base de semi-conducteurs de type p sensibilisés par un colorant." Nantes, 2010. http://www.theses.fr/2010NANT2048.
This work deals with the sensitization of p-type semi-conductors for photovoltaic conversion. New organic dyes were synthetised and characterised, which allow us to enhance NiO sensitized solar cells photoconversion yield. Moreover, the first organometallic dyes for ptype semi-conductors sensitization were prepared, which gave us a way to identify an optimal anchoring group instead of a carboxylic acid group which is usually used. New redox mediators were alos studied, and a tandem dye solar cell with a Voc of 950 mV was built. Nickel oxide is by far the major semiconductor used for the fabrication of p-DSSCs. It enables the development of this new type of research field, but it possesses a too accessible valence band potential to permit the fabrication of solar cells delivering a high voltage. Therefore, the use of new p-SCs with deeper valence band potentials would be most certainly beneficial to develop p-DSSCs with much higher solar energy conversion efficiencies. Results which were obtained with CuGaO2 delafossite are very encouraging. Taking into account that we have barely started to explore this new research field and the number of adjustable parameters, there are certainly plenty of exciting discoveries to be made and we can anticipate that important progresses will be achieved in the near future
Legrand, Christophe. "Hydroestérification d'oléfines par les formiates d'alkyle catalysée par les complexes du ruthénium." Lille 1, 1991. http://www.theses.fr/1991LIL10075.
Delime, Fabien. "Etude d'électrocatalyseurs dispersés à base de platine pour l'oxydation de l'éthanol en vue d'une application à une pile à combustible pour le véhicule électrique." Poitiers, 1997. http://www.theses.fr/1997POIT2350.
Dussarrat, Christian. "Caractérisations cristallographiques et magnétiques de nouvelles phases oxygènées a base de ruthénium. Filiations structurales avec les perovskites." Phd thesis, Université Sciences et Technologies - Bordeaux I, 1996. http://tel.archives-ouvertes.fr/tel-00153325.
Dussarat, Christian. "Caractérisations cristallographiques et magnétiques de nouvelles phases oxygénées à base de ruthénium : filiations structurales avec les perovskites." Bordeaux 1, 1996. http://www.theses.fr/1996BOR10596.
Halluin, Yann. "Catalyseurs à base de ruthénium modifié pour la synthèse d'alcools lourds à partir du gaz de synthèse." Lille 1, 1998. https://pepite-depot.univ-lille.fr/LIBRE/Th_Num/1998/50376-1998-285.pdf.
Ferris, Anaïs. "Structuration de collecteurs de courant d'or pour la réalisation de micro-supercondensateurs à base d'oxyde de ruthénium." Thesis, Toulouse 3, 2017. http://www.theses.fr/2017TOU30022/document.
The increasing importance of portable and wearable electronics as well as embedded wireless sensor networks has made energy autonomy a critical issue. Micro-energy autonomy solutions based on the combination of energy harvesting and storage may play a decisive role. However, the short lifetime of micro-batteries is problematic. Micro-supercapacitors are a promising solution in terms of energy storage for embedded systems on the account of their important lifetime. In this work we have focused on the optimization of the performances of micro-supercapacitors in terms of energy and power density. As the capacitance is directly related to the accessible surface area of the electrodes, we have investigated the structuration of the current collectors in order to improve the performances of ruthenium oxide-based micro-supercapacitors. Two mains technics have been studied to obtain three dimensional structures. In a first phase, the oblique angle physical vapor deposition (OAD) has been investigated to fabricate a columnar gold structure, subsequently covered by an electrochemical ruthenium oxide. In a second phase, a highly porous gold architecture has been studied using electrodeposition via a hydrogen bubbles dynamic template. The ruthenium oxide electrodeposited on the resulting mesoporous gold structure shows good compatibility, in terms of homogeneous deposition, with a significant capacitance at slow rate (> 3F.cm-2) and an important cyclability. As proof of concept, a device has been designed in a stack configuration with good performances. Moreover, the technology finalized for electrodes fabrication has been transferred to the micro-scale on planar interdigitated devices using a suitable photolithography process
Blasius, Romain. "Interactions et photoréactions de complexes du ruthénium (II) à base du ligand HAT avec des acides nucléiques." Doctoral thesis, Universite Libre de Bruxelles, 2003. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/211309.
Ramlot, Diane. "Synthèse et étude photophysique de nouveaux complexes de Rh, Ir et Ru à base de dérivés du dipyrrométhène." Doctoral thesis, Universite Libre de Bruxelles, 2011. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/209945.
Notre travail s’est concentré plus particulièrement sur des complexes de Rh(III), Ir(III) et Ru(II) incorporant un ou plusieurs dérivés du dipyrrométhène. Le premier volet de cette thèse est consacré à la synthèse de quatre complexes mononucléaires [Rh(dipy)3], [Rh(ppy)2dipy], [Ir(ppy)2dipy], [Ru(phen)2dipy]+ dont nous avons ensuite étudié les propriétés photophysiques et électrochimiques. Des calculs théoriques TD-DFT ont également permis de conforter l’attribution de la nature des différents états excités responsables de la luminescence de ces composés.
Le second volet de cette thèse est consacré à la mise au point de complexes dinucléaires à l’aide d’un dérivé pontant du dipyrrométhène, avec lequel deux composés ont été obtenus :[Ir2(ppy)4µdipy] et [Rh2(ppy)4µdipy]. Une étude complète du composé d’iridium nous a permis de déterminer ses propriétés. Les nombreux problèmes de solubilité que nous avons rencontrés avec le composé de rhodium ne nous ont pas permis de mener des études approfondies de ce composé.
Lors d’un essai de synthèse du composé dinucléaire d’iridium, nous avons isolé le complexe mononucléaire pontant [Ir(ppy)2µdipyH]. Afin de l’engager dans la préparation d’un complexe hétérodinucléaire de type Bodipy, nous avons préalablement mis au point la synthèse d’un bodipy mononucléaire et nous avons examiné ses propriétés optiques. Nous nous sommes dès lors basé sur les conditions de synthèse de ce bodipy mononucléaire pour tenter de réaliser, sans succès, la synthèse du complexe hétéronucléaire [Ir(ppy)2µdipyBF2].
L’ensemble des résultats obtenus au cours de ce travail, nous ont permis de comprendre l’effet du métal de transition et celui de la dérivatisation du dipyrrométhène sur les propriétés photophysiques des complexes formés. Il serait dès lors intéressant de tirer parti de l’ensemble de ces résultats pour mettre au point un nouveau dérivé pontant du dipyrrométhène afin d’optimiser les propriétés des complexes formés, et à terme permettre la préparation de réseaux organométalliques performants et exploitables dans des dispositifs électroluminescents.
Doctorat en Sciences
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Mikulová, Jana. "Oxydation voie humide de l'acide acétique catalysée par les métaux (Pt, Ru) déposés sur oxydes à base de cerium." Poitiers, 2007. http://www.theses.fr/2007POIT2287.
Ghesquière, Jonathan. "Ingénierie biomoléculaire de systèmes photo-activables à base de complexes de RuII." Doctoral thesis, Universite Libre de Bruxelles, 2011. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/209811.
de nombreux domaines. Dans, le présent travail, nous avons combiné l’utilisation conjointe de ces
complexes et de biomolécules en vue de leur utilisation dans différents domaines liés à la biologie.
Les trois premiers chapitres sont consacrés à l’étude de la photoréaction entre les complexes
[Ru(TAP)3]2+ et [Ru(TAP)2(phen)]2+ en présence des acides aminés tryptophane et tyrosine. Ces
études ont permis d’améliorer la compréhension des processus photo-induits entre le complexe
de RuII et le tryptophane, menant notamment à la mise en évidence d’une réaction de fuite au
transfert d’électron en retour entre les deux espèce radicalaires photo-produites. Cette réaction a
pu être identifiée comme étant le processus de dimérisation de deux unités tryptophanes. Cette
dimérisation ainsi que la formation de double photo-adduit impliquant deux tryptophanes et un
complexe de RuII ont été mises en évidence et étudiées en utilisant un support oligonucléotidique
double brin sur lequel sont attachées les espèces réactives.
Le quatrième chapitre concerne l’étude d’un conjugué formé entre le complexe de RuII ,
[Ru(TAP)2(phen)]2+, et le peptide de transfection TAT. La photoréactivité de cette entité a
été examinée et confirmée en présence de l’acide aminé tryptophane et de la base guanine. Pour
cette dernière, une étude plus poussée a été réalisée afin de caratériser au mieux l’interaction
existant entre le conjugué Ru-TAT et un oligonucléotide comportant une guanine. Cette étude
rassemble des observations expérimentales et une approche théorique par modélisation moléculaire.
Le cinquième chapitre consiste en l’étude du comportement photophysique du complexe
[Ru(TAP)2(pytz)]2+ sous illumination en présence de la base guanine. Cette étude vise à déterminer
si ce complexe possède les qualités d’agent photo-oxydant satisfaisantes pour envisager
son ancrage sur diverses biomolécules. L’étude a permis de montrer que l’utilisation du ligand pytz
comme point d’ancrage du complexe de RuII est partiellement compromise à cause de l’instabilité
du complexe sous illumination.
Le sixième et dernier chapitre résume les efforts effectués dans le cadre de la synthèse d’un
complexe de RuII ,le [RuII(phen”-ODN)3] devant mener à la formation de réseaux tridimensionnels
mixtes ADN-complexes. Bien qu’une caractérisation complète de ce produit n’ait pu être réalisée,
certaines mesures indiquent que ce complexe pourrait avoir été obtenu.
Doctorat en Sciences
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Sousa, Joao Fernandes De. "Valorisation chimique de l'amidon de mais par hydrolyse et hydrogenolyse sur un catalyseur solide a base de ruthénium." Vandoeuvre-les-Nancy, INPL, 1993. http://www.theses.fr/1993INPL090N.
Migalska-Zalas, Anna. "Etude des effets optiques du deuxième et troisième ordre photo induits dans des complexes alkynyls à base de ruthénium." Angers, 2006. http://www.theses.fr/2006ANGE0022.
The thesis is devoted to the theoretical and experimental studies of Photo-induced second and third order optical effects in ruthenium alkynyl push pull complexes. The main goal of this work was to determine the influence of the chemical structures of the organometallic compounds on the second and third-order nonlinear optical properties using optically and acoustically induced second harmonic generation (AISHG) and degenerate four wave mixing (DFWM) experiments. The investigation of kinetics of the third order nonlinear optical processes in organometallic complexes is also presented. The alkynyl ruthenium derivatives were embedded in polymethyl methacrylate (PMMA) and polyvinylcarbazole (PVK) polymer matrix. We showed that the influence of the polymer matrix play crucial role for the kinetics of the observed behaviour in the Ru-containing chromophore. The originality of this work consists especially on judicious choice of studied compound according to their potential applications in optoelectronics. We showed a good correlation between the chemical structures and the nonlinear optical properties. We also demonstrate their potentiality for the applications in nonlinear optics (SHG, AISHG,THG) and recently as like optical memories in picoseconds regime
Nasrallah, Houssein. "Immobilisation de complexes à base de ruthénium par des interactions non-covalentes pour le recyclage en métathèse des oléfines." Thesis, Université Paris-Saclay (ComUE), 2015. http://www.theses.fr/2015SACLS005.
Ruthenium complexes immobilization by non-covalent interactions for the recycling in olefin metathesisAbstractThe aim of this thesis is the development of new ruthenium complexes immobilization strategies onto insoluble supports by non-covalent interactions, for their easy recycling in olefin metathesis reactions.First, a bibliographic part is devoted to the development of the olefin metathesis from the discovery until now. Then, three different approaches of metathesis catalysts immobilization are described in order to achieve efficient recycling, considering the important challenges associated to this reaction. Firstly, an immobilization procedure of catalysts by formation of reversible charge transfer complexes (CTC) is described between the appropriated tagged catalyst and the support. Based on the results obtained in these conditions, a more economical approach involved the immobilization of a commercially available catalyst by formation of hydrogen bonds with the silanol sites present in silica. Finally, another type of support namely a structured carbon based support (rGO), was used for the pyrene tagged ruthenium complexes immobilization via formation of non-covalent π- π interactions (π-stacking).The catalytic performances of these solid materials were firstly evaluated in the benchmark reaction of olefin metathesis (RCM of DEDAM). Then, other olefin metathesis reactions were applied to extend the application of these materials (enyne, CM, self-metathesis of methyl oleate).The development of these approaches has also been accompanied by mechanistic studies, based on the boomerang effect, already known for these reactions.This work was performed as part of the ANR project CD2I CFLOW-OM, in collaboration with academic (ENSC-Rennes, LGPC Lyon, CPE Lyon-Caen LCMT) and industrial (ITERG, NOVANCE, OMEGA-CAT- SYSTEM) partners
Nowakowski, Pawel. "Systèmes micro-nano-structurés et couches minces multifonctionnels, à base de dioxyde de ruthénium : élaborations et propriétés catalytiques et électriques." Phd thesis, Université du Sud Toulon Var, 2008. http://tel.archives-ouvertes.fr/tel-00343499.
Duval, Marion. "Procédés originaux d’hydrogénation à base de nanoparticules de palladium et ruthénium pour la valorisation de dérivés terpéniques en catalyse multiphasique." Thesis, Rennes, Ecole nationale supérieure de chimie, 2020. http://www.theses.fr/2020ENCR0069.
Tran, Ngoc Dung. "Catalyseurs monométalliques ou bimétalliques à base de Ru et Au pour l'oxydation de composés organiques dans l'eau." Phd thesis, Université Claude Bernard - Lyon I, 2008. http://tel.archives-ouvertes.fr/tel-00349315.
Miousse, Danielle. "Mécanisme et cinétique de la réaction de dégagement d'hydrogène sur des électrodes à base d'alliages de nickel et d'oxyde de ruthénium." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1997. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/nq26391.pdf.
Claessens, Nicolas. "Synthèse de complexes du ruthénium (II) comportant un ligand chiral base de Tröger bisphénanthroline et étude de leurs comportements en présence d'ADN." Doctoral thesis, Universite Libre de Bruxelles, 2008. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/210472.
Résumé
Dans la recherche de traitements thérapeutiques spécifiques, l’ADN, centre de stockage de l’information génétique, occupe une place privilégiée. Dans ce cadre, le service de Chimie Organique et Photochimie s’est focalisé sur l’étude de l’interaction des complexes polyazaaromatiques du Ru(II) avec la double hélice. La mise au point de nouveaux ligands ou la fonctionnalisation de ligands existants permet de moduler tant les propriétés photophysiques des complexes que leur interaction avec l’ADN. Dans cette optique, notre thèse de doctorat consiste à développer deux nouveaux complexes de Ru(II) contenant un ligand chiral Base de Tröger bisphénanthroline (BTphen2) :le [Ru(phen)2BTphen2]2+ et le [Ru(TAP)2BTphen2]2+. L’objectif de ce travail consiste plus particulièrement à examiner l’influence de la chiralité et de la structure particulière du ligand BTphen2 sur l’interaction des complexes résultants avec l’ADN.
La première partie de ce travail a été consacrée à l’étude du [Ru(phen)2BTphen2]2+. Trois des quatre stéréoisomères du [Ru(phen)2BTphen2]2+ (les complexes Lambda-R, Lambda-S et Delta-S) ont été isolés pour la première fois avec une pureté optique acceptable à l’aide d’une nouvelle stratégie de synthèse basée sur l’utilisation de blocs de construction optiquement purs. La caractérisation de chacun de ces stéréoisomères par RMN1H et dichroïsme circulaire a ensuite permis de lever toute ambiguïté concernant leur stéréochimie. L’étude des différents stéréoisomères du [Ru(phen)2BTphen2]2+ seuls en solution a montré que l’introduction du ligand BTphen2 modifie les propriétés du complexe par rapport au complexe parent [Ru(phen)3]2+ (allongement de la durée de vie de l’état électronique excité, déplacement bathochrome des maxima d’émission et d’absorption). Par contre, la chiralité du complexe n’induit quant à elle aucune différence significative au niveau des propriétés photophysiques des différents stéréoisomères.
L’étude du [Ru(phen)2BTphen2]2+ en présence d’ADN de thymus de veau a montré que, contrairement au complexe [Ru(phen)3]2+, l’intercalation partielle d’un des ligands phénanthrolines du complexe entre les paires de base de l’ADN est empêchée par la structure coudée du BTphen2. D’autre part, l’introduction du BTphen2 augmente l’affinité du complexe [Ru(phen)2BTphen2]2+ pour la double hélice par rapport au complexe [Ru(phen)3]2+.
La chiralité du [Ru(phen)2BTphen2]2+ influence fortement l’interaction du complexe avec l’ADN-B. Ainsi, la quantification des modifications d’intensité d’émission des différents stéréoisomères en présence d’ADN a permis de mettre en évidence une grande sélectivité d’interaction. Ces études montrent que si la chiralité du centre métallique assure une influence prépondérante dans la stéréosélectivité d’interaction des différents stéréoisomères, cette dernière est néanmoins exacerbée en présence du ligand BTphen2. Ainsi, comme pour la majorité des complexes, le [Ru(phen)2Btphen2]2+ présente une énantiosélectivité d’interaction avec l’ADN-B en faveur des isomères de centre métallique Delta. Par contre, l’introduction du ligand BTphen2 engendre une différence d’affinité entre les stéréoisomères Delta et Lambda plus de 30 fois supérieure à celle observée pour le [Ru(phen)3]2+ ou d’autres complexes de ruthénium(II). La chiralité du ligand BTphen2 se traduit principalement par une différence d’orientation entre la sous-unité phénanthroline non complexée de la BTphen2 (phen’) et le ligand phénanthroline qui lui fait face. Cette différence d’orientation des sous-unités phen’ et phen influence l’adsorption du complexe dans les sillons de la double hélice. Ainsi, lorsque l’on conserve une chiralité identique pour le centre métallique, les stéréoisomères présentant deux sous-untités phen’ et phen sécantes (le Delta-R ou le Lambda-S) s’adsorbent plus profondément dans les sillons de l’ADN que les isomères avec des sous-unités parallèles (le Delta-S ou le Lambda-R).
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Doctorat en Sciences
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Stallivieri, Aurélie. "Synthèse de systèmes à base de photosensibilisateurs pour l'amélioration de la sélectivité tumorale en thérapie photodynamique." Thesis, Université de Lorraine, 2015. http://www.theses.fr/2015LORR0128/document.
One limitation of photodynamic therapy is the low selectivity of photosensitizers (PS) to tumour tissue. The search of new PS more selective began to focus on the synthesis of PS coupled with substrate specific of the membrane receptors overexpressed in certain cancers. The acid folic receptor is overexpressed in ovarian carcinomas and PS were conjugated with folic acid. PS were also coupled with a specific peptide of neuropilin 1 overexpressed in tumoral cells of medulloblastoma. Another strategy for increasing the selectivity of the treatment is to produce reactive oxygen species specifically at the tumor site. The activity of enzymatic cleavage of biomarkers overexpressed in tumour areas is used. The gelatinases (MMP-2 and MMP-9) and their activator MMP-14 are known to play a key role in tumour angiogenesis and the growth of glioblastoma multiform. Different photodynamic molecular beacons (PMB), composed of a photosensitizer and a quencher linked together by a peptide substrate of gelatinases or MMP-14, were designed
Orlewski, Jacek Paul. "Préparation et caractérisation de clusters hydrosolubles du ruthénium, de l'osmium et de l'iridium : hydrogénation du citral en phase aqueuse." Lyon 1, 1989. http://www.theses.fr/1989LYO10147.
Grasset, Fabien. "Propriétés structurales, magnétiques et catalytiques de nouveaux oxydes à base de ruthénium ou de platine à empilements mixtes dérivés de la structure perovskite." Phd thesis, Université Sciences et Technologies - Bordeaux I, 1998. http://tel.archives-ouvertes.fr/tel-00007279.
Zhao, Jingpeng. "Oxydation catalytique sélective des alcools en composés carbonylés par des catalyseurs à base de Ru." Thesis, Lille 1, 2019. http://www.theses.fr/2019LIL1R062.
Selective aerobic oxidation of alcohols to carbonyl compounds is a fundamental and practicable transformation for many biological and organic reactions providing key intermediates and valuable pharmaceuticals. The intrinsic reactivity and selectivity challenges in green chemistry for oxidation using oxygen as terminal oxidant significantly restrict its application in industry. Traditionally used metallic catalysts provide low selectivity due to over-oxidation of aldehydes further to acids. The recently developed combination of organic hydrogen scavengers (DDQ, TEMPO) and inorganic regeneration agents (Fe3+, NO) have been used as a catalyst for mild selective oxidation of alcohols in the presence of oxygen. However, homogeneous nature of the catalyst and use of toxic and non-environmentally friendly chemicals require further development of this concept for oxidation of alcohols. To solve these problems, we propose application of heterogeneous nano-electrocell concept inspired from electrocatalysis. The catalysts contain nano-anode and nano-cathode sites arranged in core-shell structure at nano-scale level. The alcohol is oxidized over the non-metallic quinones shell sites, with subsequent migration of hydrogen to the metallic Ru nanoparticles as core for oxidation to water. In this thesis, we have found the appropriate “core” and “shell” materials, on the basic of metallic Ru and non-metallic quinones species, respectively, and applied it for oxidative dehydrogenation of alcohols and O2 reduction. Meanwhile we propose oxidation combined with acetalization using Ru@MOF tandem catalyst containing ultra-fine Ru nanoparticles (< 2 nm) in the MOF structure
Saadallah, Dounia. "Synthèse de complexes originaux de ruthénium(II) à base de ligands étendus dérivés de phénanthroline, caractérisation photophysique et propriétés d'interaction avec les G-quadruplexes." Thesis, Université Grenoble Alpes (ComUE), 2016. http://www.theses.fr/2016GREAV036/document.
The interest for some unusual structures of DNA, the G4 quadruplexes was growing these past few years. Those structures were extensively studied in vitro, but a lot remains unkwown about their existence in vivo. Intererstingly, G4 structures seem to play key regulatory roles in gene expression and are therefore potential therapeutic targets for diseases such as cancer. Consequently, visualisation of those structures in cells is the present challenge today, and the use of small molecules with luminescent properties is promising in this context.In this framework, we designed a series of new rutheniumII complexes chelating a large planar aromatic ligand, (heptacycle dpqp or octacycle dppqp). The combination of the photophysical properties of RuII complexes with proposed favorable stacking properties of the ligand with G4, would make these complexes promising molecular tools for G4 visualization.The first part of this project focusses on the synthesis of ruthenium complexes and their specific ligands. One particular ligand is formed by the condensation between acridine and phenanthroline moieties. A chemistry on the complex approach enabled us 1) to functionnalize the chelated ligand by a triple bond that will be used for the formation of an heterodimer by click chemistry, and 2) to build an additional cycle on the chelated ligand. Photophysical properties were evaluated and only two complexes, [Ru(phen)2dpqp-Cl]2+ and [Ru(TAP)2dpqp-Cl]2+, exhibit the same photophysical behaviour than the reference complexes. Indeed, the quantum yields are in the same order of magnitude than for [Ru(bpy)3]2+ and the excited state lifetime are of a few hundred nanosecondes. The other complexes are non-luminescent and a quenching by excited state proton transfer was hypothesised to explain this unusual behaviour. Interaction properties with G4 DNA were evaluated. All complexes display good affinity towards G4 and as expected, the complexe bearing the octacyclic ligand shows a strong selectivity towards G4 compared to dsDNA. Two of the complexes were proven to be potential luminescent light-switch ON probes for G4 detection in cells. In conclusion, this work highlights the possibility to use some of the newly synthetized complexes as efficient molecular tools for G4 visualization in cells
Saadallah, Dounia. "Synthèse de complexes originaux de Ruthénium(II) à base de ligands étendus dérivés de phénanthroline, caractérisation photophysique et propriétés d’interaction avec les G-quadruplexes." Doctoral thesis, Universite Libre de Bruxelles, 2016. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/242038.
Doctorat en Sciences
info:eu-repo/semantics/nonPublished
Combemale, Lionel. "Elaboration et réactivité interfaciale d'oxydes pérovskites à base de Lanthane Strontium Chrome Ruthénium (LSCrRu) comme composés d'anode de piles à combustible à température intermédiaire (ITSOFC)." Dijon, 2005. http://www.theses.fr/2005DIJOS052.
New data on the interest of ruthenium doped lanthanum strontium chromite La1-xSrxCr1-yRuyO3δ (LSCrRu) as anode in ITSOFC are presented. Microwave synthesis of mixed oxides allowed shaping of half-cells and complete cells using sputtering and screen printing methods. LSCrRu methane reforming property had been studied in a mono-chamber system coupled with a mass spectrometer in collaboration with Institut de REcherche Hydro-Québec. Anode/electrolyte interfacial reactivity had been analysed using SIMS and XRD on half cells models after ageing under H2 at 800°C. This experiment gave the chemical composition of the film after treatment. Complete cells, tested under working conditions, highlighted, after selective dissolution of LSCrRu film, a microstructure modification at anode/electrolyte interface. XPS and SEM-EDX techniques did not show chemical reactivity
Combemale, L. "Elaboration et réactivité interfaciale d'oxydes pérovskites à base de Lanthane Strontium Chrome Ruthénium (LSCrRu) comme composés d'anode de piles à combustible à température intermédiaire (ITSOFC)." Phd thesis, Université de Bourgogne, 2005. http://tel.archives-ouvertes.fr/tel-00452892.
Lachaud, Fabien. "Vers la photoxydation de l'eau. Systèmes biomimétiques de la paire His190/TyrZ du photosystème II. Complexes à base de ruthénium et de métaux de transition." Paris 11, 2007. http://www.theses.fr/2007PA112151.
The use of fossil energy is one of the nowadays important problems. Hydrogen is one of the possible answer of that problem. To produce hydrogen, one can imagine a system that oxydise water like in photosynthesis, and reduce proton like in hydrogenase. To mimic the electrons transfer that occur in photosystem II, we've synthesised and studied a ruthenium(+II) complex. That complex shows two photoinduced electron transfer in presence of an electron acceptor, in neutral and basic pH. In acidic pH, only one transfer has been observed. We've modified that complex to add a phenol fonction. The two new ruthenium complexs have been studied. They've shown two photoinduced electron transfer, and the resulting radical has been caracterised by EPR. We've also synthesised two plynuclear complexs, with one ruthenium(+II) moity and a dimer of manganese (+II) or copper(+II) ions. The preliminary studies of those two complexs make us hope they could accumulate more than one oxydative equivalent
Louessard, Pierrick. "Etude des catalyseurs bimétalliques Ru-Sn-SiO2 préparés par interaction du tétrabutyl-étain avec le précurseur monométallique Ru-SiO2 : application à l'hydrogénation de l'acétate d'éthyle." Lyon 1, 1988. http://www.theses.fr/1988LYO10113.
Monnier, Florian. "Applications du catalyseur RuCl(COD)C5Me5 en chimie fine : transformations sélectives d'alcynes en diènes fonctionnels, alcénylcyclopropanes et vinylphosphines." Rennes 1, 2003. http://www.theses.fr/2003REN10095.
Awada, Ali. "Etude des propriétés de coordination de ligands tridentés à base d'acridine sur le ruthénium New Acridine-Based Tridentate Ligand for Ruthenium(II): Coordination with a Twist." Thesis, Université Grenoble Alpes (ComUE), 2019. http://www.theses.fr/2019GREAV072.
Light-induced electron and energy transfer in molecular arrays is being extensively studied in view of artificial photosynthesis. In this context, [Ru(bpy)3]2+ derivatives have been widely used, due to their favorable photophysical properties, i.e. lifetimes in the µs range at room temperature, high emission quantum yields, and strong oxidizing and reducing capability. The electronic structural design of most ruthenium(II) complexes is of great importance by specifying the complexes’ photophysical, photochemical, and electrochemical properties. As a consequence, the main theme of this thesis is to explore the coordination properties of new tridentate ligands on the ruthenium cation. This work describes the synthesis of these new tridentate ligands based on the acridine heterocycle with different moieties at positions 4 and 5. Octahedral ruthenium(II) complexes were then constructed around these acridine-based ligands, with tuned energy levels of the functionally active 3MC and 3MLCT excited states. Very few acridine derivatives are substituted at positions 4 and 5. The synthetic strategy for the target ligands starts from acridone. The 4,5-dibromoacridine was obtained in four synthetic steps and this common precursor was subsequently used for the construction of tridentate (NNN) ligands with pyridine and pyrazole. In addition, a thioether acridine-based tridentate ligand (SNS) analogue was synthesized, and another tridentate thioether (SNS) ligand, without an acridine heterocycle, was prepared to gain some flexibility within the ligand scaffold. The corresponding homoleptic complexes with 6-membered metallacycles only adopted a facial octahedral geometry. Thus, the heteroleptic complexes were prepared in combination with a planar terpyridine ligand in order to force the constrained and rigid ligands to coordinate in a meridional fashion on the metal. The electrochemical, photophysical, and photochemical properties of all complexes were studied and the structure for most of these Ru(II) complexes was deduced by X-ray diffraction crystallography experiments. The bis-tridentate Ru(II) complexes based on the flexible (SNS) thioether ligand were photoactive: they were able to undergo a photosubstitution reaction, by replacing the tridentate thioether ligand with monodentate ligands, upon white light exposure
Moraes, de Abreu César Augusto. "Hydrogénolyse sur catalyseurs à base de ruthénium de solutions et de suspensions de mono, di et polysaccharides : application à la valorisation de la pulpe de betterave déshydratée." Compiègne, 1985. http://www.theses.fr/1985COMPD010.
Giordano, Laurent. "Nouvelles réactions catalytiques entre les Bicycles [2. 2. 1] insaturés et les alcynes induites par le palladium et le ruthenium." Aix-Marseille 3, 2002. http://www.theses.fr/2002AIX30006.
In our research work, we have been involved in the development of new catalytic reactions of unsaturated bicyclic[2. 2. 1] compounds and alkynes. An efficient palladium catalysed addition of terminal alkynes across one double bond of norbornadiene resulting in the selective formation of exo-5-alkynyl-bicyclo[2. 2. 1] hept-2-enes is reported. The reaction show general applicability to various functionalized alkynes and bicyclo[2. 2. 1]hepta-2,5-dienes. Mechanistic insights into these reaction are also provided on the basis of labelling experiments. A new synthesis of 8,9-disubstituted deltacyclenes via a [2+2+2] cycloaddition of norbornadiene with disubstituted alkynes has been achieved with ruthenium catalyst systems. The reaction is applicable to various disubstituted alkynes and 7-substituted norbornadienes. The Homo-Diels Alder Reaction becomes more efficient when the C7-substituent is an aryl or alkyl group. Finally, an efficient catalyst system combining CpRuCl(PPh3)2 and MeI allow the [2+2] cycloaddition of norbornadiene or norbornene with various disubstituted alkynes providing functionalized tricyclic compounds. We have shown that the activation of CpRuCl(PPh3)2 with methyl iodide generates in situ CpRuI(PPh3)2 as the key catalyst
Aouad, Samer. "Etude des propriétés physico-chimiques et catalytiques des solides à base de ruthénium : applications dans des réactions d'intérêts environnementaux : oxydation des suies, des COV et vaporeformage du méthanol." Littoral, 2007. http://www.theses.fr/2007DUNK0202.
Ruthenium supported on ceria, alumina and mixed supports catalysts are studied in carbon black combustion, VOC oxidation and steam reforming of methanol. Ruthenium supported on ceria catalysts are active and selective for CO2 formation in oxidation reactions. This is correlated to the presence of two different species of ruthenium oxides in interaction with ceria. These two species are easily reducible at low temperature. It is also showed that the optimal content of ruthenium on ceria is about 1,5wt. %. For higher contents, the reactivity is no more improved due to the formation of RuO2 agglomerates which are less reactive than ruthenium oxides in interaction with ceria. The carbon black oxidation mechanism in the presence of our catalysts begins with the reduction of ruthenium oxide species in interaction with ceria. These species are then oxidized again by reaction with the oxygen present in the gaseous phase. A similar mechanism is envisaged in the oxidation of the VOCs. The thermal effect related to the catalytic oxidation of VOC is then evidenced in the simultaneous combustion of soot and VOC. This result confirms that it is possible to use our catalysts to eliminate soot emitted by Diesel engines and some industries. The positive role of ceria support is pointed out in the steam reforming of methanol reaction. The interaction between ceria and ruthenium seems to be also responsible for the carbon monoxide elimination from reaction products. The presence of palladium improves the H2 selectivity in the reaction
Riegel, Gilles. "Rôle de la voie du stress du réticulum et de la biosynthèse du glutathion dans l’activité anticancéreuse de composés organométalliques à base de ruthénium dans le cancer gastrique." Thesis, Strasbourg, 2019. http://www.theses.fr/2019STRAJ071.
Cancer treatment is still based on surgery associated with platinum-based chemotherapy. These drugs induce side effects and are sensitive to resistance mechanisms. This shows the need to develop new anticancer therapies among which ruthenium compounds display promising properties.This study demonstrates the implication of metabolism, namely, the transsulfuration pathway and glutathione biosynthesis in the activity of the RDC11 (ruthenium derived compounds). These metabolic regulations are mediated by the effect of RDC11 on the ER stress pathway. Furthermore, I characterized the role of the metallic atoms in the sensitivity of cancer cells towards these drugs. More precisely, replacement of ruthenium by osmium reduces strongly the efflux of these drugs, increasing their intracellular concentration and efficiency.This work characterises the role of cellular metabolism for the anticancer activity of organometallic compounds, opening the way for the investigation of these compounds mode of action looking forward entry in clinical trials
D'Ornelas, Lindora. "Chimie organométallique de surface, réactivité des clusters moléculaires de ruthénium et d'osmium à la surface des oxydes divisés : structure et réactivité des analogues moléculaires des complexes de surface : applications en catalyse d'hydrogénation et d'isomérisation des oléfines." Lyon 1, 1986. http://www.theses.fr/1986LYO10006.
Roesyadi, Achmad. "1ère Partie : Valorisation de la sciure de bois de peuplier par autohydrolyse, hydrolyse acide et hydrogénolyse sur des catalyseurs à base de ruthénium imprégné sur charbon actif : 2ème Partie : Étude d'un réacteur triphasé d'hydrogénolyse du type Verlimob à base d'un venturi à émulsion : application du réacteur à l'hydrogénolyse de solutions aqueuses de glucose." Compiègne, 1987. http://www.theses.fr/1987COMPD089.
Valorisation of poplar flour is studied by hydrogenolosys on ruthenium catalyst deposited on active carbon. Hemicelluloses and cellulose obtained by auto hydrolysis and delignification of auto hydrolysis residue are hydrogenolysed directly (hemicellulose) or after an acid hydrolysis (hemicelluloses and cellulose). At 200°C and 50 bar total pressure, hydrolysis solutions after neutralisation are converted into polyalcohols, and monoalcohols. For the hemicelluloses solution, the cleavage of C-C bonds on all carbon atoms is possible ; also, among the products, ethylene glycol and glycerol are not negligible comparatively with methanol. In the case of the valorisation of residual cellulosic, a triphase reactor Verlimob type had been developed, where the gaseous phase and liquid phase contact in the emulsing venture. The rate of the auto-aspirated gas flow is given by the relation : O-G (l/h) (TPN) =5,82 PtO,61 O-L 0,547 and the energy dissipation in the liquid phase is proportional to the total pressure and increase with the flow of circulating liquid. The estimation of the coefficient of the gas-liquid transfer KLS and the surface exchange S, affected by the oxidation reaction of sodium sulphite in the absence and the presence of cobalt sulphate, showed that KLS increases with Pt and O-L and S depends only on the flow of the recirculating liquid. Then the transfer coefficient KL can be evaluated at +- 20 % by the relation : kL (m/s) =19,13 10-3 (O-G/O-L)-1,694 (O-L-O-G)-0,796. The reaction of the hydrogenolysys of glucose on ruthenium catalyst deposited on active carbon, had been carried out at 200 °C and the operational parameters O-L and Pt were modified. The glucose is completely converted during 4 hours into polyalcohols, diols and monoalcohols. The production of methanol reached 54 % of the initial amount of glucose at Pt=80bars, and O-L=1000 l/h
Troian, Gautier Ludovic. "Synthèse et étude de nouveaux complexes de ruthéniumII à base de ligands polyazaaromatiques étendus en vue d'applications dans le domaine de l'opte-électronique." Doctoral thesis, Universite Libre de Bruxelles, 2014. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/209186.
Les ligands π-accepteurs permettent également de diriger et de localiser le transfert d’électron à l’état excité. Lorsque le complexe absorbe un rayonnement lumineux de bonne énergie, un électron peut être transféré du centre de ruthéniumII vers un des ligands ancillaires. Ce transfert d’électron aura lieu vers le ligand qui est le plus avide en électrons. Ce phénomène trouve des applications directes en photo-conversion d’énergie solaire. En effet, afin de convertir de l’énergie solaire, il est important d’absorber le rayonnement lumineux, mais également de pouvoir transférer cette énergie en un lieu donné. L’utilisation de ligands avides en électrons permet donc de diriger cette énergie en un lieu précis.
Dans le cadre de cette thèse de doctorat, nous nous sommes focalisés sur la synthèse de nouveaux ligands polyazaaromatiques qui devraient conférer des propriétés inédites aux complexes résultants. La première partie de cette thèse de doctorat a donc consisté à synthétiser des ligands polyazaaromatiques possédant un plan aromatique étendu. Nous avons mis au point une voie de synthèse pour obtenir des ligands tels que la 1,4,5,8-tétraazaphénanthrène-9,10-dione, précurseur du ligand 1,4,5,8-tétraazaphénanthrèno[9,10-b]1,4,5,8,9,12-hexaazatriphénylène (TAPHAT). Au cours de la synthèse de la 1,4,5,8-tétraazaphénanthrène-9,10-dione, nous avons également pu mettre au point une nouvelle méthode d’oxydation de noyaux de type quinoxaline à l’aide de dérivé d’iode hypervalent. Une fois la synthèse du ligand TAPHAT et des différents précurseurs effectuée, nous avons pu procéder à la synthèse des complexes de ruthéniumII. Le ligand TAPHAT, étant fortement insoluble et possédant quatre sites de chélation, nous avons décidé de procéder à la synthèse de complexes précurseurs pour préparer des complexes porteurs de ce ligand. Nous avons dès lors tenté d’obtenir les complexes précurseurs [Ru(TAP)2(diNH2TAP)]2+ et [Ru(TAP)2(tapdione)]2+. La synthèse de ces précurseurs a présenté de nombreux problèmes de chélation, donnant lieu cependant à des complexes très intéressants. Face à ces problèmes, nous nous sommes donc uniquement focalisés sur la synthèse du [Ru(TAP)2(diNH2TAP)]2+. Ce complexe précurseur a ensuite permis d’accéder à des complexes tels que le [Ru(TAP)2(HATPHE)]2+. Les complexes à base du ligand 9,10-diamino-1,4,5,8-tétraazaphénanthrène, à savoir le [Ru(TAP)2(diNH2TAP)]2+ et le [Ru(phen)2(diNH2TAP)]2+ ont ensuite été utilisés pour accéder aux complexes mono- et binucléaires symétriques du TAPHAT. Nous avons ensuite étudié les complexes à base du ligand PHEHAT ainsi que ceux à base du ligand TAPHAT et comparé leurs propriétés photophysiques, photochimiques et électrochimiques.
En plus de ces complexes à base de ligands PHEHAT et TAPHAT, nous avons également eu l’occasion de synthétiser des ligands analogues au ligand DPPZ. Nous avons synthétisé deux ligands plus étendus que le DPPZ, à savoir le DPQQX, dont la synthèse avait déjà été rapportée dans la littérature, et le PDPPZ. Bien que les complexes à base du ligand PDPPZ n’aient pas pu être purifiés au cours de cette thèse, nous avons tout de même pu obtenir les complexes [Ru(TAP)2(DPQQX)]2+ et [Ru(phen)2(DPQQX)]2+. Les études photophysiques, photochimique et électrochimiques ont permis de mettre en évidence de nombreuses propriétés intéressantes. De plus, des études poussées en résonance magnétique nucléaire 1H ainsi qu’en dichroïsme circulaire ont permis de montrer un processus d’auto-assemblage en solution.
Finalement, en plus de la synthèse de ligands polyazaaromatiques et de leurs complexes de ruthéniumII, nous avons également exploité la technique d’absorption transitoire dans le cadre d’une collaboration avec le laboratoire de résonance magnétique nucléaire. Cet axe de recherche s’est articulé autour de l’utilisation de deux complexes de ruthéniumII à savoir le [Ru(TAP)3]2+ et le [Ru(TAP)2(HAT)]2+. Ces complexes sont capables, sous illumination, de réaliser un transfert d’électron avec un réducteur. Ces processus de transfert d’électron photo-induit entre des réducteurs tels que la GMP, la N-acétyl-tyrosine, l’hydroquinone et les deux complexes de ruthéniumII ont été étudiés par les membres du laboratoire de résonance magnétique nucléaire à l’aide d’une technique dite Photo-Chemically Induced Dynamic Nuclear Polarization (Photo-CIDNP). Notre contribution a été d’investiguer les paramètres de quenching entre ces complexes et les différents réducteurs à l’aide de techniques classiques telles que la détermination de constantes de quenching via des analyses de type Stern-Volmer ainsi qu’à l’aide de techniques plus pointues telles que la photolyse éclair laser.
Doctorat en Sciences
info:eu-repo/semantics/nonPublished