Дисертації з теми "Immobilisation of the catalyst"
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Scruton, S. L. "Ionic immobilisation of an anionic carbonylation catalyst." Thesis, University of Southampton, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.380592.
Повний текст джерелаGoldys, Anna M. "Immobilisation and application of bifunctional iminophosphorane organocatalysts." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:f4f28a47-0373-4b66-8537-d4e7028d4d63.
Повний текст джерелаZhang, Liping. "Immobilisation de catalyseurs moléculaires de polymérisation d’oléfines sur nanomatériaux." Thesis, Toulouse, INPT, 2014. http://www.theses.fr/2014INPT0013/document.
Повний текст джерелаThis present thesis deals with the development of active olefin polymerization catalysts based on late transition metal (nickel and iron) imino-pyridine complexes supported on nanomaterial. Chapter I gives a comprehensive literature review of unsupported and supported ethylene polymerization catalyst. In Chapter II we report the ethylene polymerization studies using nickel complexes containing an –NH2 group for covalent immobilization on multi-walled carbon nanotubes (MWCNTs) of the corresponding precatalysts. Comparison of the homogeneous catalysts with their supported counterparts evidenced higher catalytic activity and higher molecular weights for the polymers produced. In Chapter III, iron complexes containing a pyrene group have been synthesized and immobilized on MWCNTs through non-covalent π-π interactions between pyrene group and surface of MWCNTs. Activated by MMAO, both the iron complexes and immobilized catalysts show high activities for ethylene polymerization. It was possible to evidence that MWCNTs have a great influence on the catalytic activity and on the structure of the resulting polyethylenes. Imino-pyridine nickel complexes containing various kinds of aromatic groups have been synthesized in Chapter IV and polymerization conditions in the presence and in the absence of nanocarbon materials, such as MWCNTs or few layer graphene (FLG), are discussed. For those nickel catalysts bearing 1-aryliminoethylpyridine ligands, the presence of MWCNTs in the catalytic mixture allows the formation of waxes of lower molecular weight and polydispersity, whereas the presence of FLG proved to be beneficial for the catalytic activity. In Chapter V, isoprene polymerization catalyzed by iron complexes containing polyaromatic groups and non-covalently supported on nanoparticles and confined into the inner cavity of MWCNTs (Cat@NPs and Cat@NPs@MWCNTs) are investigated. Iron complexes show excellent activity for the isoprene polymerization and produced high glass temperature polyisoprene with a high trans-1,4-polyisoprene selectivity. Polymer nanocomposites are produced by supported catalysts and, transmission electron microscopy (TEM) evidenced efficient coating of the resulting polyisoprene around the oxygen sensitive iron nanoparticles
Ben, Osman Chirine. "Synthèse et utilisation de nouveaux matériaux hybrides pour la catalyse en ATRP supportée du méthacrylate de méthyle." Thesis, Paris 6, 2014. http://www.theses.fr/2014PA066564/document.
Повний текст джерелаThe aim of this project is to develop hybrid nanoparticles bearing well definedpolymer arms as supported catalyst for the atom transfer radical polymerization of methylmethacrylate. This new generation of “semi heterogeneous" catalysts was prepared by twostrategies. The first consisted of immobilizing the polymer arms bearing the ligands enablingcoordination of copper bromide onto silica particles by covalent bonds. Hybrid nanoparticleswith low polymer grafting density were targeted to prevent the overlapping of chains on thesurface. Unfortunately, the polymerizations were not controlled probably due to a lack ofaccessibility of the initiator and propagating radicals to the copper complexes. To improve theaccessibility, a reversibly supported catalyst was developed via self-assembly using hydrogenbonding between chains α-functionalized by a proton donor-acceptor unit (DAD) and acomplementary unit (ADA) anchored on silica particles. These new hybrid materials wereefficient in the controlled radical polymerization of MMA, yielding polymers with controlledmolecular weights and dispersities narrower than those obtained for homogeneous ATRP.Moreover, after catalyst separation from the reaction medium by centrifugation, more than96% of the originally used copper was recovered
Smith, Graham Michael. "Enzyme immobilisation and catalysis in ordered mesoporous silica /." St Andrews, 2008. http://hdl.handle.net/10023/573.
Повний текст джерелаSmith, Graham Murray. "Enzyme immobilisation and catalysis in ordered mesoporous silica." Thesis, University of St Andrews, 2008. http://hdl.handle.net/10023/573.
Повний текст джерелаLaunez, Rémy. "Immobilisation d'organocatalyseurs sur supports inorganiques et évaluation de leur activité en condition de flux continu." Thesis, Université Paris-Saclay (ComUE), 2015. http://www.theses.fr/2015SACLS212/document.
Повний текст джерелаThe aim of our project was to develop an eco-friendly process based on heterogeneous asymmetric organocataysis in continuous flow conditions. To succeed in this development, we chose to use a quinine-derived bifunctional organocatalyst: cupreine. Silica, a mesoporous inorganic material, was chosen as the support to immobilize this organocatalyst. The grafted cupreine was then tested as catalyst for the asymmetric Michael addition between the trans-β-nitrostyrene (Michael acceptor) and the dimethyl malonate (Michael donor) in continuous flow condition.First, we immobilized the catalyst on two types of silica, following three different strategies. The various cupreine-grafted silicas we obtained were functionnalized with 0.2 to 0.4 mmol of cuprein per gram of silica. Each one of them possessed specific characteristics depending of the followed strategy.The assessment of the catalytic activity of immobilized silica was then performed in batch condition. Different bio-based solvents were used for the Michael addition. 2-MeTHF was chosen as the best solvent among those tested and used in continuous flow. Immobilized cupreine proved to be as efficient in heterogenous condition as in homogenous (enantiomeric excess was superior or equal to 85 % and conversion better than 96 %), except for turn over frequency (TOF, mol of converted substrate/mol of catalyst/reaction time) which is three times lower in hetereogeneous condition (0.2h-1 to 0.6 h-1 in homogenous condition).Michael addition of trans-β-nitrostyrene to dimethyl malonate was then realized in continuous flow condition, using the various silica-supported catalysts. Turn over frequency of cupreine was doubled (0.4 h-1) and the turn over number (mol of converted substrate/mol of catalyst) increased from 16 to 63 in continuous flow condition. Derivatives of trans-β-nitrostyrene (chlorinated, phenolic and methoxylated in position 4) were successfully tested in continuous flow.To the best of our knowledge, we realized the first asymmetric Michael addition between trans-β-nitrostyrene and the dimethyl malonate, catalysed by silica-supported cupreine in batch and in continuous flow, using a bio-based solvent.We successfully developed an eco-friendly process based on heterogeneous organocatalysis in continuous flow. This process favorited an efficient recycling of the supported catalyst, and increased the productivity of grafted cupreine compare to the heterogeneous condition in batch. The enantioselectivity of the cupreine for this reaction was similar in both homogeneous and heterogeneous conditions
Parnham, Benjamin L. "Modification of bis(ditertiarybutylphosphinomethyl)benzene for improved catalyst separation and stability." Thesis, University of St Andrews, 2007. http://hdl.handle.net/10023/325.
Повний текст джерелаNieczypor, Piotr. "Immobilisation of Ru-based metathesis catalysts and related aspects of olefin metathesis." [S.l. : Amsterdam : s.n.] ; Universiteit van Amsterdam [Host], 2004. http://dare.uva.nl/document/74260.
Повний текст джерелаSouron, Elodie. "Immobilisation de liquides ioniques au sein de matrices polymères et applications." Caen, 2012. http://www.theses.fr/2012CAEN2051.
Повний текст джерелаThis work deals with the development of new ways of immobilization of ionic liquids in polymer matrices. Three ways of immobilization were tested. In the first one, the ionic liquid was encapsulated in polyelectrolyte microcapsules. In the second one, the combination of Pickering emulsion and layer by layer techniques were tested to immobilize ionic liquid. Finally, in the third one, the ionic liquid was entrapped in biopolymer matrices. For the first way, the study of the stability of polyelectrolyte microcapsules in ionic liquid showed that a cross-linking step was necessary to get stable microcapsules in this ionic media. The cross-linked microcapsules were used as microreactors for the synthesis of PMMA, a hydrophobic polymer, in ionic liquid media. Then, microcapsules containing ionic liquid were prepared and applied to metallic depollution. The second way based on the combination of Pickering emulsion and the layer by layer techniques was unsuccessfully applied to the emulsion “ionic liquid in water” and did not allow the immobilization of the ionic liquid phase. In the third way, ionic liquid immobilization proceeded by confinement of an ionic liquid phase in chitosan or alginate beads. The prior solubilisation of an organometallic catalyst in the ionic liquid phase led to catalytic materials which were tested with the Tsuji-Trost reaction
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.
Повний текст джерелаRuthenium 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
Anderson, Amanda E. "Strategic immobilisation of catalytic metal nanoparticles in metal-organic frameworks." Thesis, University of St Andrews, 2017. http://hdl.handle.net/10023/10816.
Повний текст джерелаEl, Khamlichi Aicha. "Immobilisation de catalyseurs dans des phyllosilicates et leurs applications dans des réacteurs continus." Rennes 1, 2010. http://www.theses.fr/2010REN1S138.
Повний текст джерелаThis thesis is related to the development of environmentally friendly chemical processes. It contributes to the general effort towards a greener chemistry by reducing matter and energy costs. Our approach uses the montmorillonite as a support for heterogeneous catalysis. This natural lamellar material can be modified easily by exchanging cation contained in the interlayer space. Palladium complexes with or without ligands have been immobilized onto these support using a methodologies developed in our laboratory. Sevral analyses confirmed the effectiveness of the palladium intercalation. These hybrids materials have subsequently been implemented in continuous reactors. These techniques greatly increase the energetic efficiency of the process. Furthermore, they allow for a better control of operating conditions leading to better yield and selectivities. In the case of Heck-Mizoroki cross coupling, we observed a good activity and excellent selectivities. The system displayed an excellent stability with limited leaching which allowed more than 60 h of continuous use
Skalli, Abdelmajid. "Catalyse enzymatique en milieu organique immobilisation des protéases et leurs utilisations en synthèse peptidique /." Grenoble 2 : ANRT, 1986. http://catalogue.bnf.fr/ark:/12148/cb376012485.
Повний текст джерелаMichelot, Audric. "Immobilisation de catalyseurs sur un support solide inorganique à l'aide d'une chaîne moléculaire afin de permettre leur recyclage." Thesis, Toulouse 3, 2015. http://www.theses.fr/2015TOU30345/document.
Повний текст джерелаThe asymmetric catalysis in homogeneous phase experienced a rapid development over the past decades and many complexes or ligands have been described in the literature. The separation and effective recycling of the catalyst (or ligands) appears expensive and as one of the challenges that combines both expectations of industrial organic synthesis and green chemistry. Among the various solutions proposed, immobilization of the catalyst on a solid support (powder) using a "molecular chain" appears as a seductive answer: the catalyst (metal-ligand pair) is recovered by simple filtration and can be reused. Our project is centered on chiral catalysts developed by our team and applied under Suzuki-Miyaura reactions and asymmetric hydrogenation. The use of hydroxyapatite (HAP) as organometallic catalysts inorganic support is a virtually unexplored field which nevertheless anchored in a process of sustainable development by responding to environmental and economic concerns: biocompatible synthetic materials in aqueous media (no organic solvent). We focused in particular grafting the HAP surface with functionalized alkoxysilanes (R-Si(OR')3). The nature of the interaction has been studied by various techniques (FTIR spectroscopy, Raman, NMR, XRD, SEM, TEM, etc.). These supports have shown moderate results in the Suzuki-Miyaura reaction. The use of mesoporous silica as a support has also been studied. We synthesized a variant of a functionalized ligand P,S ferrocenic have demonstrated good activities and enantioselectivities in homogeneous catalysis. Grafted on different media (HAP, silica, ...), we have made the first tests in catalysis of asymmetric hydrogenation and compared the influence of the media on activity
Goux, Jérôme. "Combinaisons "early-late" : synthèse, tests catalytiques et extension vers une immobilisation par voie électrochimique." Dijon, 2003. http://www.theses.fr/2003DIJOS038.
Повний текст джерелаMatzen-Fredel, Anna. "Immobilisation of metathesis catalysts on mesoporous materials for the conversion of bio sourced fatty compounds." Thesis, Lille 1, 2012. http://www.theses.fr/2012LIL10174.
Повний текст джерелаAs fossil resources constantly decrease, the concept of bio-refinery is a most attractive approach to generate chemicals from renewable resources. In this context, unsaturated fatty acids derived from the hydrolysis of crops extracted-triglycerides are a major class of substrates. These must be converted to high added-value derivatives: catalytic transformations can play a key role in this, by converting such compounds into other functionalized derivatives. A most attractive reaction to meet this challenge is olefin metathesis. Based on product/catalyst separation and catalyst recycling issues, use of heterogeneous catalysts is of high interest.We thus prepared heterogenized commercial ruthenium catalysts. The hybrid materials were prepared in a two-step procedure: after silver salt-mediated cationization, the organometallic species were immobilized by ion exchange on mesoporous aluminosilicates of the MCM-41 family. The novel catalysts were characterized by solid-state NMR, IR, XRD, BET, elemental analysis and TGA. They were successfully applied in several metathesis reactions involving the archetypic methyl oleate, a C18 unsaturated ester, with different grades of purity. The probed reactions were self-metathesis, ethenolysis and cross-metathesis with functionalized olefins derived from acrylic and crotonic acids. Though recycling was not completely successful, the supported catalysts were able to efficiently catalyze all these transformations, providing in some instances the first heterogeneously examples of such reactions with high activity and selectivity
Benyahya-Bouayad, Sofia. "Immobilisation de ligands par voie sol-gel pour l'arylation de nucléophiles oxygénés catalysée au cuivre." Montpellier 2, 2009. http://www.theses.fr/2009MON20082.
Повний текст джерелаOur aim was to develop a way to synthesize diarylethers using copper catalyted ligands immobilized on silyl-organic inorganic materials prepared by sol-gel. The interest of these heterogeneous systems is that they are recyclable and reusable, less polluting and less toxic due to their ability to sequester metal catalyst. This is particularly important for use of diaryléthers obtained in pharmaceutical industry. We managed to synthesize by sol-gel process materials incorporating bipyridine or β-dicarbonyl type ligands. These materials were then applied in copper-catalyzed arylation of phenols by aryl iodides and bromides. The new heterogeneous catalysts have yielded good results in arylation of oxygen nucleophilies and also in terms of recovery and reuse. In addition, diaryléthers products are obtained "clean" of copper traces used in catalysis. The method we developed is therefore particularly competitive in terms of cost, pollution and residual toxicity. It is to our knowledge the first example of ligand supported on silica by sol-gel and applied in copper-catalyzed arylation of phenols
Hodgson, Ben Joseph. "Immobilisation of bio-molecules on magnetisable solid supports for applications in bio-catalysts and bio-sensors." Thesis, University of Central Lancashire, 2014. http://clok.uclan.ac.uk/10425/.
Повний текст джерелаBenyahya, Sofia. "Immobilisation de ligands par voie sol-gel pour l'arylation de nucléophiles oxygénés catalysée au cuivre." Phd thesis, Université Montpellier II - Sciences et Techniques du Languedoc, 2009. http://tel.archives-ouvertes.fr/tel-00690537.
Повний текст джерелаPachariyanon, Pavadee [Verfasser], David W. [Akademischer Betreuer] Agar, and Rolf [Gutachter] Wichmann. "Immobilisation of non-selective catalysts in permselective microcapsules / Pavadee Pachariyanon. Betreuer: David W. Agar. Gutachter: Rolf Wichmann." Dortmund : Universitätsbibliothek Dortmund, 2012. http://d-nb.info/1109055374/34.
Повний текст джерелаMatzen, Anna Katharina [Verfasser]. "Immobilisation of metathesis catalysts on mesoporous materials for the conversion of bio sourced fatty compounds / Anna Katharina Matzen." Aachen : Hochschulbibliothek der Rheinisch-Westfälischen Technischen Hochschule Aachen, 2014. http://d-nb.info/1049350359/34.
Повний текст джерелаAbis, Laura. "Gold and gold-palladium catalysts synthesized by a modified sol-immobilisation method for thermal and plasmonic glycerol oxidation." Thesis, Cardiff University, 2018. http://orca.cf.ac.uk/114039/.
Повний текст джерелаHonnoraty, Anne-Marie. "Synthèse et immobilisation par copolymérisation d'analogues du pyridoxal - étude de leur activité comme catalyseur de racémisation d'alpha-aminoesters." Montpellier 2, 1994. http://www.theses.fr/1994MON20031.
Повний текст джерелаBacchi, Philippe. "Immobilisation de la glucose oxydase au sein de gels hydrophobes de nafion. Application au dosage du glucose par amperometrie." Université Joseph Fourier (Grenoble), 1996. http://www.theses.fr/1996GRE10246.
Повний текст джерелаEvoung-Evoung, Ferdinand. "Immobilisation des systèmes cavitaires métalliques bio-inspirés sur électrode d'or via les monocouches auto-assemblées pour la détection et la catalyse." Thesis, Brest, 2016. http://www.theses.fr/2016BRES0053/document.
Повний текст джерелаThis work depends on functionalized surface theme using modification of selfassembled monolayers (SAMs). The main objective consists to elaborate a new general pathway to modify monolayers with miscellaneous objects of interest. For this, we decide to focus our work to synthesize a versatile platform handling two ethynyl arms. These functions are available to operate two CuAAC reactions. The first one is use for linking platform with object of interest (in general ferrocenyl derivatives). Ligands obtained by that way were used for complexation of Cu2+ and Zn2+ ions. Electrochemical and spectroscopic (UV-Visible and EPR) studies were performed on these compounds. The second CuAAC reaction is used to immobilize copper complexes on azide modified electrode (azide derivatives SAMs on gold and ITO or direct functionnalization of glassy carbon surface). The grafting is operating through “self-induced electroclick” method; this means the CuAAC reaction is catalysed by the copper complex which is immobilized. Functionalized electrodes were characterized by cyclic voltammetry. It appears that similar complexes have closed grafting kinetic. These studies also demonstrate the both influence of copper and spacer on a second electroactive site (ferrocene moieties). The reactivity of copper centre is evaluated for complexes in solution and immobilized on surface with electrocatalytic reduction of nitrite ions by copper (I) species. The catalytic efficiency strongly depends on potential of copper reduction. Also, similar complexes show a loss of catalytic power with immobilization on surface
Yazidi, Dounia. "Immobilisation controlée de la peroxydase du raifort à la surface d' électrode et analyse quantitative de son comportement par voltamétrie cyclique." Paris 7, 2005. http://www.theses.fr/2005PA077087.
Повний текст джерелаBalistreri, Noémie. "Conception de systèmes catalytiques hétérogènes chimioenzymatiques pour l'époxydation." Thesis, Paris 6, 2016. http://www.theses.fr/2016PA066290/document.
Повний текст джерелаThe objective of this work was to develop an heterogeneous catalyst system supplied by dioxygen, rather than commercial H2O2, in order to carry out epoxidation reactions. Our strategy was to couple the in situ production of H2O2, catalyzed by glucose oxidase (GOx), with a Ti-based catalyst. The enzyme was covalently grafted onto a silicic mesocellular foam (MCF) functionalized by aminopropyle groups, then the thermal stability and behavior in organic solvents of the resulting material were investigated. The approach aiming at anchoring Ti, then GOx on the same support did not result in an effective tandem catalyst because of a too high –NH2 surface coverage. Hydrophilicity of MCF makes the oxidation of organosoluble alkenes unefficient. An alternative approach consisted in using the hydrophobic TS-1 zeolite known to operate in aqueous medium but whose micropores do not allow GOx hosting. However, TS-1 combined in a mechanical mixture with GOX immobilized on MCF turned out to be effective for the oxidation of cyclohexene in MeOH/acetate buffer 50:50 at 35°C (50% yield of epoxide and its derivatives). Even better performances were obtained for prop-2-ene-1-ol oxidation in aqueous medium at 40°C (87 % yield of glycerol). The basic attack of TS-1 has created mesoporosity to host GOx but damaged active Ti sites. On the other hand, TS-1 coated MCF appeared to be a good option having a beneficial effect on the oxidation of prop-2-en-1-ol in water by H2O2. Finally, a manganese porphyrin, Mn-TCPP, was also tested successfully as alkene oxidation catalyst in combination with GOx but, in case of immobilization, the presence of the silicate support lead to a deactivated catalyst
Roche, Jérôme. "Régénération continue du cofacteur NADH catalysée par la formate déshydrogénase immobilisée en réacteur filtre-presse." Toulouse 3, 2011. http://thesesups.ups-tlse.fr/1310/.
Повний текст джерелаThe cofactor nicotinamide adenine dinucleotide (NADH) is used during enzymatic reactions catalyzed by the enzymes of the dehydrogenase group. Those reactions can lead to optically active compounds with high value added and an enantiomeric excess of more than 99%. However, the high cost of NADH does not allow its use in stoechiometric amount during enzymatic synthesis; it has to be regenerated in situ during the reaction. A regeneration pathway using formate dehydrogenase immobilized in a filter press reactor is developed from the enzyme immobilization to the process implementation in situ for the synthesis of a model compound, the L-lactate. The behavior of the system in a continuous flow micro-structured reactor is studied and a simulation of the concentration profile in the reactor is used to determine the reaction limitation
Jacoby, Jonathan. "Lipase Mucor miehei immobilisée dans des matériaux poreux silicatés : bioréacteurs pour la synthèse d'esters méthyliques à partir d'huiles végétales." Thesis, Université de Lorraine, 2013. http://www.theses.fr/2013LORR0217/document.
Повний текст джерелаThis work was to prepare catalysts by immobilizing Mucor miehei lipase into silicate porous materials for the biodiesel production from vegetable oils. To develop this study, several systems based on surfactants were used to synthesize silicate materials with controlled porosity by taking protocols described in the literature or developed in the laboratory. The common point of these materials, whether mesoporous or meso-macroporous, is a hexagonal organization of their mesopores. Meso-macroporous materials were prepared from oil-in- water emulsions (O/W) and from double emulsions (W/O/W) or from solid lipid nanoparticles(SLN). These different materials served as a matrix for immobilization of the lipase. Several methods of immobilization were investigated. Firstly, the lipase was fixed into support by physisorption by immersing material in an enzymatic solution. Secondly, the lipase was linked covalently to matrix with urea bonds. In our case, the material had to be functionalized after this synthesis. Finally, the encapsulation method of the enzyme was carried out only with materials prepared form double emulsions and SLN. All bioreactors were tested by performing a transesterification reaction with methanol. The conditions of this methanolysis were optimized with an experimental design
Delahaye, Yannick. "Dynamique et catalyse dans des modèles photosynthétiques de chromatophores reconstitués." Compiègne, 2006. http://www.theses.fr/2006COMP1610.
Повний текст джерелаThis work fits into the implementation of a new method of study of the dynamics of the exchanges of electrons in the biological membranes, and corresponds to the phase of progressive introduction of various biological elements in a biomimetic membrane model. Notably, it consisted in realizing the incorporation and the electrochemical detection of the photosynthetic chain of the purple bacteria Rhodobacter sphaeroides, in a model of artificial bilayer supported by an electrode. The strategy proposed to create this biomimetic structure is to accumulate proteoliposomes inside the electrode of microporous alumina, the surface of pores of which was beforehand functionalized, and to cause their fusion by an outside agent. Rather than to envisage the reconstruction of every oxydoreductase in an individual way, proteoliposomes is formed by the structural rearrangement of chromatophores (bacterial vesicles), the wall of which contains the totality of the photosynthetic chain, with lipid vesicles. Besides, electrochemical measures allowed bringing to light the functionality of a party of the reaction centers so reconstituted
Gkaniatsou, Effrosyni. "Elaboration of novel enzymatic immobilization matrices, based on Metal-Organic Frameworks for the catalytic degradation of environmental pollutants." Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLV005.
Повний текст джерелаThe use of enzymes in biocatalytic processes has been a challenging goal over the years. While enzymes present exceptional catalytic properties, their fragility hinders their industrial application. Their stabilization and protection are therefore of paramount importance. This can be effectively addressed through their immobilization within host solid matrices. Traditional materials (silica, clays, polymers, biopolymers, porous carbons…) have been widely studied as supports. Their pure organic or inorganic nature often requires a compromise between affinity with enzymes and robustness of the matrix. Besides, most of them have non-ordered porosity, with non-homogenous pore size distributions, unsuitable for homogeneous immobilization. Metal-Organic Frameworks (MOFs) have been recently introduced as alternative supports, thanks to their hybrid nature and their crystalline and highly porous structures.The aim of this PhD was to combine Metal-Organic Frameworks (highly porous and chemically stable polycarboxylate MOFs) and a mini-enzyme, microperoxidase 8 (MP8) to obtain multifunctional biocatalysts. In a first part, the mesoporous MIL-101(Cr) was used as a host matrix to encapsulate MP8. The encapsulation led to an increased catalytic activity under conditions (acidic conditions, high concentration of H2O2) detrimental to the catalytic activity of MP8, thereby demonstrating the protecting effect of MIL-101(Cr) matrix. The biocatalyst was also efficiently recycled. The selectivity of MP8 for the degradation of the harmful negatively charged organic dye methyl orange was also enhanced, thanks to the charged-based selective adsorption of the dye in MIL-101(Cr) porosity. A second part of the work was devoted to the use of functionalized MIL-101(Cr) analogs. First, functionalized ligands (bearing –NH2 and –SO3H groups) were used, and their influence on MP8 encapsulation was evaluated. The catalytic activity toward sulfoxidation reactions was also studied. The successful encapsulation of MP8 was strongly dependent on charge matching between the enzyme and the MOFs particles, while its catalytic activity was affected by the specific microenvironment of the pores. The MOF frameworks also modified the reactivity of MP8 toward different thioanisole derivatives. Then, a mixed metal MOF (MIL-101(Cr/Fe)), selected for its stable catalytic properties, was synthesized and characterized. Finally, the last part was devoted to the in-situ synthesis of MOFs (microporous MIL-53(Al)-FA) in presence of biomolecules (BSA) under compatible conditions with the preservation of the protein’s quaternary structure (aqueous media and room temperature). The resulting hybrid materials were thoroughly characterized and presented high loadings of BSA. A preliminarily study was performed with the enzyme, Horseradish Peroxidase, which retained its catalytic activity after immobilization
Dettori, Léna. "Approche multi-échelle pour l’étude de la réaction de N-acylation enzymatique d’acides aminés." Thesis, Université de Lorraine, 2017. http://www.theses.fr/2017LORR0346/document.
Повний текст джерелаN-acylation of amino acids or peptides results in bioactive and/or functional molecules showing increased bioavailability, hydrophobicity and stability. Acylated amino acids have been broadly described as being a kind of surfactant with great surface chemistry properties, interesting biological activities, weak toxicity and low environmental impact. Acylation of amino acids or peptides is being performed chemically at industrial scale. It creates constraints in term of reaction selectivity, environmental safety and cost of polluted wastewater treatment. Enzymatic catalysis is an alternative to chemical acylation reaction. Several enzyme/solvent pairs have already been described in the literature. Their performance are however somewhat limited. The objective of this thesis work was thus to improve the capacity of acylation processes at different scales. At the molecular scale, a study was performed using Candida antarctica’s (CALB) lipase B. Molecular modeling was used to create a methodology coupling docking simulation and interaction calculus that would allow for a better understanding of CALB regioselectivity during lysine acylation by different fatty acids. Studies were also conducted at the reaction level, especially by searching for new aminoacylase-type of biocatalysts in Streptomyces ambofaciens raw extract. Regioselectivity and performance of these enzyme’s catalytic reactions were compared to those of CALB. Results brought into light a promising potential from S. ambofaciens’ aminoacylases in synthesizing acylated amino acids/peptides. Indeed, on top of their ability to catalyse acylation reaction in aqueous solution, these enzymes have a different regioselectivity compared to CALB’s. Regioselectivity targeting N-terminal groups is a rarely researched phenomenon allowing acylation to be performed without modifying amino acids or peptides lateral chains and hence their functionality. In the last part part of this work, studies at process scale were performed. Aminoacylase were first immobilized on mesoporous silicates and several immobilisation methods were compared. Using physisorption, a method for the immobilisation of S. ambofaciens’ aminoacylases was developed to reach a conserved specific activity during 3 cycles. Finally, intensification of acylation reaction was examined in microwave or microstructured reactors. First, an experimental set up was performed in an heated reactor using microwaves irradiation. This kind of reactor was demonstrated as being adapted to acylation reaction using a commercial immobilized form of CALB (Novozym435®) as catalyst in organic solvent. The microwave reactor was however not suited for free S. ambofaciens aminoacylase in aqueous solution. For that latter reaction, intensification had to be approached through other aspects of the process. Hydrodynamic appeared indeed as an important aspect for this reaction occurring in a biphasic medium composed of fatty acids and aqueous solution. A microstructured microfluidic reactor was hence tested. Conversion yield were increased with this system. This study demonstrated how mixing quality was an important factor for acylation reaction and could be a way to intensify the enzymatic process at larger scale
Gairola, Priyanka. "Association of Metal-Organic Framework and Transaminase for chemoenzymatic production of amines." Electronic Thesis or Diss., Sorbonne université, 2019. http://www.theses.fr/2019SORUS107.
Повний текст джерелаDue to the scarcity of fossil resources, the chemical industry must today evolve to turn to new sources of raw material. Added to this are the ever-increasing environmental pressures that impose a reduction in the ecological and energy impact of the processes. Responding to these major technological challenges involves the design of new chemical processes making it possible, in particular, for the massive transformation of natural chemical resources (cellulose, lignin, algae, etc.) into high value-added chemicals that meet the so-called "Green chemistry" i, ii. In this context, heterogeneous catalysis is an essential tool since it makes it possible to accelerate the chemical reactions under sustainable conditions by making it possible to recycle the active phases ii. The development of processes that are increasingly adapted to today's industrial and environmental challenges, however, requires the development of new catalysts, in particular capable of reducing energy consumption even more, of saving atoms and of reducing as much as possible the quantities of reagents and solvents used as well as the waste produced. To do this, heterogeneous catalysts capable of catalyzing several chemical reactions in one step "in cascade" are particularly promising. [...] The overall goal of this thesis was to build a chemoenzymatic system capable of carrying out a cascade of two reactions allowing the transformation of alcohols into amines. For that it was proposed to immobilize on a crystalline organic-inorganic hybrid material called MOF (Metal-Organic Framework), a chemical catalyst, responsible for a first step of oxidation of alcohol to carbonyl compound, and a transaminase enzyme catalyzing the subsequent amine transfer step. The implementation of such a sophisticated system was a real challenge, especially because it was a question of finding reaction conditions (solvent, temperature, pH, and choice of chemical reagents) that are compatible with the working conditions of transaminases (mild reaction temperatures ≤ 60 ° C, at least partially aqueous solvents). This was a prerequisite for carrying out "one-pot" syntheses, where the two targeted reactions were to be catalyzed consecutively by the chemical catalyst and the enzyme in the same reaction medium without isolation of the intermediate carbonyl. It was also necessary to ensure the stability of the MOF in the reaction medium, and in particular the integrity of its structure in solvents containing the aqueous buffer solutions necessary for the stability of the enzymes. [...]
Thomasset, Brigitte. "Stabilisation de membranes chloroplastiques approche structurale et fonctionnelle /." Grenoble 2 : ANRT, 1986. http://catalogue.bnf.fr/ark:/12148/cb37601535n.
Повний текст джерелаDüskünkorur, Hale. "Biopolyester synthesis by enzymatic catalysis and development of nanohybrid systems." Phd thesis, Université de Strasbourg, 2012. http://tel.archives-ouvertes.fr/tel-00864276.
Повний текст джерелаCitadelle, Cécilia. "Synthèses de nouveaux catalyseurs de ruthénium pour la métathèse des esters méthyliques d'huiles végétales." Phd thesis, Université Claude Bernard - Lyon I, 2009. http://tel.archives-ouvertes.fr/tel-00817291.
Повний текст джерелаJoseph, Virginia. "Nanopartikel auf Oberflächen." Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät I, 2012. http://dx.doi.org/10.18452/16553.
Повний текст джерелаWithin this work nanostructured surfaces were generated by immobilization of gold and silver nanoparticles with organosilanes and characterized regarding their suitability as substrates for Surface-enhanced Raman scattering (SERS). Essential knowledge for the optimization of SERS-active nanostructures could be found by experimental invest-igations on the influence of particle size and assembly on the plasmonic properties. Through combined experimental investigations, including spectroscopic and imaging techniques, and electrodynamic simulations of local fields, the plasmonic and nanoscopic properties of particles on surfaces were related to their SERS-properties. The nanostructured surfaces exhibit high and, over a wide range of analyte concentration, stable enhancement factors with high microscopic homogeneity. Therefore immobilized nanostructures are suitable substrates for quantitative SERS. The potential for the use of the nanostructured surfaces in analytical problems was shown in various applications. Signal fluctuations that can occur in the detection of complex analyte mixtures can be significantly reduced by immobilization of the nanoparticles. This offers the possibility to use multivariate statistical methods for automated classification and identification of molecule mixtures but also for multiplexing and imaging by SERS. Simultaneous immobilization of gold and silver nanoparticles and gold and platinum nanoparticles using the same linker molecule allowed for the first time to generate surfaces with defined plasmonic and functional properties with low cost and high reproducibility. These new mix and match-substrates were used to follow catalytic reactions and determine reaction constants of such reactions for the first time using SERS. The outcome of this work suggests a wide range of applications of plasmonic nanostructured surfaces in the future. This includes the investigation of catalysis, microscopic applications of SERS and clinical diagnosis.
Brocklebank, Simon Pearson. "Rational immobilisation of enzymes : immobilisation of transketolase for carbon-carbon bond synthesis." Thesis, University College London (University of London), 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.322288.
Повний текст джерелаRossell, Jacqueline. "Protein immobilisation for AFM." Thesis, University of Nottingham, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.404144.
Повний текст джерелаCoote, Alexander Stuart. "Polyurethanes for enzyme immobilisation." Thesis, Imperial College London, 1989. http://hdl.handle.net/10044/1/47386.
Повний текст джерелаCitadelle, Cécilia. "Synthèses de nouveaux catalyseurs de ruthénium pour la métathèse des esters méthyliques d’huiles végétales." Thesis, Lyon 1, 2009. http://www.theses.fr/2009LYO10083/document.
Повний текст джерелаThe development of efficient ruthenium based catalysts has contributed to the development of olefin metathesis. This reaction catalyzed by tungsten, rhenium or molybdenum complexes, was applied, until now, to non-fonctionalized olefins. The use of ruthenium precursors allowed to broaden range of applications of olefin metathesis owing to their high tolerance to various organic functions. Indeed, methyl esters of vegetable oils can be converted into chemical base by metathesis in the presence of ruthenium based catalysts. In this study, we report ruthenium complexes reactivities for ethenolysis of methyl oleate as well as the design and the characterization of new systems. We describe the synthesis of new ruthenium catalysts containing cyclic alkyl(amino)carbenes and the evaluation of their performances. We show that these precatalysts display interesting catalytic properties for the ethenolysis of methyl oleate. Modifications of the carbenes ligands architecture provide the possibility to create novel catalysts as the functionalization of the isopropoxybenzylidene ligand which allowed immobilization of catalysts in ionic liquid. Besides, attempts to coordinate other ligands, such as fluorenylidène and silylene, able to afford active complexes will be discuss
Hulak, Deschamps Isabelle. "Immobilisation d'anticorps sur polymères fonctionnalisés." Paris 13, 1990. http://www.theses.fr/1990PA132001.
Повний текст джерелаOloo, Fiona Angela. "The immobilisation of enzymes on colloidal liquid aphrons (CLAs) : stability, immobilisation parameters and protein structural conformation." Thesis, Imperial College London, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.412714.
Повний текст джерелаWolowacz, Sorrel Elizabeth. "Novel immobilisation techniques for amperometric biosensors." Thesis, University of Cambridge, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.319586.
Повний текст джерелаEl-Kholy, Amany Osama Amin. "Immobilisation and labelling chemistries of DNA." Thesis, Imperial College London, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.339190.
Повний текст джерелаGreen, Christopher A. "Covalent immobilisation of Langmuir-Blodgett films." Thesis, University of Salford, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.386420.
Повний текст джерелаMahmood, Nadia. "Novel immobilisation matrices for amperometric biosensors." Thesis, University of Huddersfield, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.368306.
Повний текст джерелаDickson, Catherine Louise. "Immobilisation of actinide simulants in cement." Thesis, University of Aberdeen, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.300954.
Повний текст джерелаCaruana, Daren Joseph. "Electrochemical immobilisation of enzymes on microelectrodes." Thesis, University of Southampton, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.240238.
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