Teses / dissertações sobre o tema "Synthèse organique – Analyse"
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Gastaldi, Stéphane. "Les radicaux sulfonyle en synthèse organique : application à la synthèse de l'acide kai͏̈nique". Aix-Marseille 3, 1997. http://www.theses.fr/1997AIX30091.
Texto completo da fonteHoudier, Stéphane. "Cycloisomaltodextrines : synthèse, stéréosélectivité, analyse conformationnelle". Grenoble 1, 1993. http://www.theses.fr/1993GRE10046.
Texto completo da fonteDeschrevel, Brigitte. "Réversibilité de réactions enzymatiques de type hydrolyse/synthèse en milieu partiellement aqueux/partiellement organique". Rouen, 1993. http://www.theses.fr/1993ROUES006.
Texto completo da fonteGirard, Nicolas. "Cyanation anodique d'amines tertiaires aromatiques : application à la synthèse de la solenopsine A, de l'alcaloïde 241D et de la pumiliotoxine C". Rennes 1, 2005. http://www.theses.fr/2005REN1S088.
Texto completo da fonteLieber, Jean. "Raisonnement à partir de cas et classification hiérarchique : application à la planification de synthèse en chimie organique". Nancy 1, 1997. http://www.theses.fr/1997NAN10215.
Texto completo da fonteThis thesis describes an approach to case-based reasoning based on hierarchical classification. A case consists of a problem and a solution to this problem. Case-based reasoning consists in exploiting a case base in order to solve a problem called the target problem. In the framework of this thesis, such a reasoning takes two main steps: retrieval and adaptation. Retrieval consists in searching the case base for a case similar to the target problem. Adaptation uses the retrieved case in order to build up a solution to the target problem. The case base is organised in a hierarchy. Retrieval is performed by a "strong" classification step followed -if needed- by a "smooth" classification step. Strong classification consists in searching in the case base hierarchy for a case more general than the target problem, i. E. A generic case the solution of which can be specialised into a solution of the target problem. If this search succeeds, the adaptation of such a case can be performed by specialised of the generic case found. Otherwise, the role of smooth classification is to make sorne modifications on the cases of the hierarchy and on the target problem within the objective of having one of these modified cases more general than the modified target problem. Then the adaptation step takes these modifications into account. The application of this thesis takes place in the domain of planning in organic synthesis. In this application, a problem is given by a molecule and a solution is a synthesis plan, Le. The description of a chemical method for building up a molecule
Deleuze, Hervé. "Réaction des lipases en milieu organique : synthèse de composés à partir de diols et diesters meso : analyse et modélisation cinétiques". Aix-Marseille 3, 1987. http://www.theses.fr/1987AIX30061.
Texto completo da fonteLafarge, David. "Analyse didactique de l'enseignement-apprentissage de la chimie organique jusqu'à bac+2 pour envisager sa restructuration". Phd thesis, Université Blaise Pascal - Clermont-Ferrand II, 2010. http://tel.archives-ouvertes.fr/tel-00578419.
Texto completo da fonteVismara, Philippe. "Reconnaissance et représentation d'éléments structuraux pour la description d'objets complexes : application à l'élaboration de stratégies de synthèse en chimie organique". Montpellier 2, 1995. http://www.theses.fr/1995MON20253.
Texto completo da fonteGicquiaud, Julien. "Activation électrophile des alcynes vis-à-vis de l'attaque de nucléophiles carbonés catalysée par les acides de Bronsted : éco-conception et analyse du cycle de vie d'une nouvelle voie catalytique". Thesis, Bordeaux, 2019. http://www.theses.fr/2019BORD0446.
Texto completo da fonteThis manuscript presents a study of cycloisomerization reactions, in accordance with the principles of green chemistry, based on the electrophilic activation of alkynes in the presence of achiral and chiral Brønsted acids via the formation of vinyl cation intermediates and the attack of the latter by carbon nucleophiles. The use of a catalytic amount of Brønsted acid with 2-alkynylbiaryl substrates delivered phenanthrene derivatives in good to excellent yields under mild reaction conditions. High catalytic activities, along with differences of chemo- and regioselectivity were observed when comparing to carbophilic metallic Lewis acid catalysts.The use of a directing group substituting the alkyne function, the 2-naphtholyle moiety, resulted in increased basicity of the alkyne, increased regioselectivity of the protonation step and the creation of hydrogen bonding with the catalyst, paving the way for the development of an asymmetric version of cycloisomerization reactions. In the presence of chiral Brønsted acids, such as N-triflylphosphoramides, the enantioselective synthesis of atropisomeric phenanthrenes was achieved with excellent yields and good enantiomeric excesses. An intermolecular reaction of hydroarylation of alkynes in the presence of the same catalysts delivered atropisomeric alkenes in excellent yields and enantioselectivities.The use of a directing group on the alkyne also allowed for the first time the development of Brønsted acid-catalyzed enyne cycloisomerization reactions involving the initial, selective protonation of the alkyne function. A variety of polycyclic scaffolds were obtained by this methodology with high yields and moderate enantioselectivities.The cycloisomerization catalytic reaction is known to chemists as a model reaction respecting several principles of green chemistry such as atomic economy, waste limitation and the principle of catalysis.However, no quantitative evidence is provided by chemists to promote the sustainability of the methodologies developed in their laboratories. Several monocriteria parameters and multi-criteria methods have been developed to try to address this environmental quantification issue. However, the interest in developing new catalytic systems should be associated with the development of more environmentally efficient processes in addition to knowing if it is more chemically efficient.Life cycle assessment (LCA) is the standardized reference method for quantifying the environmental impacts (e. g. climate change, toxicity, resource use) of a product over its life cycle. LCA has already been applied to green chemistry developments to compare the durability of chemical reactions, or for eco-design applications. However, it is not trivial to use LCA at the laboratory scale because it requires (i) data that are difficult for the chemist to access (ii) additional modeling steps to estimate potential impacts at the industrial scale (iii) requires the expertise of a LCA practitioner. [...]
Berrah, Yacine. "Etude de différentes stratégies de modélisation de réactions complexes dans un réacteur fermé en synthèse organique : application à la réaction de cyanoéthylation du malonate de diméthyle". Lyon 1, 1991. http://www.theses.fr/1991LYO10216.
Texto completo da fonteGenève, Stéphane. "Synthèse et structure tridimensionnelle de peptides vinylogues cis et trans : application à la préparation d'hétérocycles azotés chiraux originaux". Nancy 1, 2000. http://www.theses.fr/2000NAN10078.
Texto completo da fonteLoison, Aurélie. "Recherches sur l’origine de la vie : synthèse prébiotique de composés organiques simples dans des conditions simulant des sources hydrothermales sous-marines". Strasbourg, 2010. https://publication-theses.unistra.fr/public/theses_doctorat/2010/LOISON_Aurelie_2010.pdf.
Texto completo da fonteThe aim of this thesis was to evaluate the potential for prebiotic chemistry of the conditions prevailing in the vicinity of black smoker-type hydrothermal vents, which are deep sea environments rich in H2S and transition metal sulfides. We have studied and disclosed a complex pathway, which could be involved in the first steps of life on earth, by means of laboratory simulation experiments involving the constituents of the fluids emitted at these vents, CO, H2S, NiS and NH4+, some simple raw materials and prebiotic plausible compounds. The abiotic synthetic process elucidated in this thesis leads to organic compounds of prebiotic interest comprising mono or bi-functionalized molecules, potentially with any chain length, such as thiols, alkyl sulfides, aldehydes, ketones, thioesters, thioacids, dithioacetals, alpha-sulfido carboxylic acid derivatives, amino acids with various alkyl chains and carboxylic acids with linear or branched chains. Besides, the highlighted synthesis of n-carboxylic acids containing up to four carbon atoms opens a pathway for the prebiotic formation of linear lipidic amphiphilic compounds, which are potential precursors of membrane constituents. On the basis of experiments involving organic compounds with key chemical functionalities, in addition to CO, H2S, NiS and NH4+, we suggest an iterative mechanism based on homogeneous catalysis with nickel carbonyl complexes. The crucial step of the disclosed synthetic process leads to the abiotic C-C bond formation, via the insertion of CO in C-S bonds. Aldehydes and ketones are the key intermediates of this pathway
Braganti, Jean-Philippe. "Synthèse d'alliages amorphes AI-Ni-Zr par broyage mécanique : étude de la cinétique de cristallisation par calorimétrie : analyse du chemin réactionnel par diffraction des rayons X". Nancy 1, 2000. http://www.theses.fr/2000NAN10124.
Texto completo da fontePicard, Baptiste. "Maîtrise de la sélectivité par application de la technologie microfluidique à des réactions rapides concurrentes : application à la génération de carbénoïdes vinyliques et à la neutralisation d'agents chimiques de guerre". Thesis, Normandie, 2018. http://www.theses.fr/2018NORMR165.
Texto completo da fonteThe goal of this work was to put in application the unmatched properties of fluidic microreactors in the field of organic synthesis. Those particular properties are discussed in this document, in an attempt to rationalize their effects on reaction courses. The first part of this work is dedicated to exploiting unstable vinylic carbenoids as nucleophiles despite their very short half-lives (often inferior to the second). Even if some results show efficient trapping of those elusive intermediates, applicability in synthesis remains very limited because of the extreme nature of the kinetics involved. The second part describes the application of microreactors to neutralization of chemical warfare agent (CWA) with an emphasis on scalability and safety. Oxidative neutralization pathways were explored on half-mustard thioethers (2-chloroethyl sulfides), as yperite simulants. The developed method allows their full conversion to sulfoxides, and only produces non-toxic effluents. This oxidative method was easily scaled up to 25g of half-mustard, and was successfully coupled with an in-line NMR analysis.Effectiveness of this method on phosphonothioates was also explored. These neurotoxic organophosphorus molecules, which are the majority constituents of the V series, can also be neutralized by the selective oxidation of a sulfur atom. To perform this study, a new pathway to phosphonothioate moiety was successfully explored. This allowed a new synthetic path for PhX (a close, phenyl analogue of VX), along with other relevant V series analogues. This method offers good yields at lab scale, in an expedient fashion. Reactivity of these CWA simulants was then evaluated against multiple oxidants. Even if a unified method could not yet be developed, a better understanding of the involved oxidative mechanisms could allow to address this challenge
Vasseur, Alexandre. "Fonctionnalisation C-H d’hétérocycles dérivés de la biomasse : réactions pallado-catalysées de Heck déshydrogénantes". Thesis, Reims, 2012. http://www.theses.fr/2012REIMS017/document.
Texto completo da fonteThis thesis describes Pd-catalyzed dehydrogenative Heck reactions of heteroarenes that could be derived from the biomass with electron-rich alkenes such as styrenes. The first chapter presents a new methodology enabling cross coupling dehydrogenative Heck Reactions of furans and thiophenes with styrenes under Mild conditions and discusses the Influence of the oxidizing agent on the reaction rate. The second chapter focuses on ESI-MS studies of the dehydrogenative Heck reactions of furans with acrylates using benzoquinone as reoxidant and DMSO as solvent. The presentation of a new methodology for aerobic dehydrogenative Heck reactions of heterocycles with styrenes and the explanation about the negative effect of metallic co-oxidants represent the third chapter
Imani, Zeynab. "Le rôle d’interactions N-H···S proximales dans des peptides". Thesis, université Paris-Saclay, 2021. http://www.theses.fr/2021UPASF015.
Texto completo da fonteNon-covalent interactions play a key role in chemical biology phenomena such as the stabilization of protein tertiary and quaternary structure or protein-protein and protein-substrate recognition. Among these interactions, the classical amide-type NH···O=C hydrogen bond has been thoroughly studied. The study of other types of non-covalent interactions implicating peptide backbone NH groups is much rarer. This work focused on the impact of NH···S hydrogen bonding on the conformational preferences of thioether amino acid residues and their short oligomers. A panel of capped derivatives of the following non-canonical sulfur-containing amino acids was prepared: Cys(Me) (acyclic), Attc (thietane), Atlc (thiolane), Atc (thiane). These derivatives were characterized computationally, by IR/UV double resonance laser spectroscopy in the gas phase, by IR and NMR spectroscopy in solution, and in the solid state. We demonstrated the concomitant existence of inter-residue C6ˠ NH···S hydrogen bonds and C5 NH···O=C interactions in each of these four compounds. This combined stabilizing feature was also prevalent in Attc oligomers. A different intra-residue C5ˠ NH···S hydrogen bond was characterized in short oligomers of Atlc and Atc, in some cases associated with a ˠ-turn NH···O=C interaction. The significance of NH···S bonding in the combined C5-C6ˠ structural feature of Attc was evaluated by comparison with capped derivatives of other four-membered ring amino acids: Ac4c (cyclobutane), Aatc(Me) (azetidine), Aotc (oxetane). The C5–C6ˠ feature was present in the three heterocyclic residues: comparison of their IR spectra in gas phase and in solution, aided by theoretical calculations, allowed us to identify an increasing strength of NH···X hydrogen bonding from X=O to X=S to X=N
Akoumany, Katy. "Dérivés de l'exopolysaccharide d’Alteromonas infernus, mimétiques de glycosaminoglycanes, et développement d'une stratégie pour leur analyse structurale". Thesis, Nantes, 2019. http://www.theses.fr/2019NANT4082.
Texto completo da fonteIn search of new bioactive compounds, marine bacteria constitute a considerable source of innovative molecules. The bacterial exopolysaccharide (EPS), produced by the deep-sea hydrothermal vent strain Alteromonas infernus, is a high molecular weight, highly branched and anionic heteropolysaccharide with a nonasaccharide repeating unit. This macromolecule and its low-molecular-weight derivatives obtained through a chemical process have previously displayed interesting GAG-like properties such as anti-metastatic and anti-coagulant (heparin-like) ones; they can also improve stem cell differentiation.To investigate the molecular bases of the biological activity and to facilitate the structural analysis of the bioactive derivatives (~20 000 g/mol), fragments of the native EPS molecule have been prepared by organic synthesis and enzymatic depolymerisation.The first part of this thesis is dedicated to the synthesis of the disaccharides composing the repeating unit of the EPS. The synthetic pathways to acceptor and donor glycosyls have been developed and two protected disaccharides have been synthetized.The second part is devoted to the preparation of oligosaccharides and low molecular weight derivatives by enzymatic depolymerization of the native EPS. A new generation of low molecular weight derivatives has been produced and a new bisulfated octasaccharide has been characterized by mass spectrometry
Aubry, Carine. "Synthèse, analyse structurale et activité biologique d'analogues rigides d'un antagoniste de l'octadécaneuropeptide ODN". Rouen, 2003. http://www.theses.fr/2003ROUES002.
Texto completo da fonteODN is a member of the family of peptides (endozepines), able to link up with benzodiazepine receptors, and with a new receptor, not again characterized. Relationship-activity studies carried out on many synthesized analogs of ODN have proved that octapeptide (OP) Ct of ODN, had the same activity to ODN itself. In the same time, the first complete antagonist of the new receptor, corresponding to cyclic OP with a D-Leucine in 5 position has been synthesized. This modified OP has been studied in NMR, and it had been proved that it exist under two forms due to the cis-trans isomery induced by the proline. In a first time, we synthesized severals proline analogs, and then, introduced them in OP, modified en 5 position, in order to prevent the isomerization process induced by the proline. The obtained pseudo-peptides, have been analyzed by NMR spectroscopy, and, tested on rat astrocytes in order to know their potential activity
Geng, Lopez Joaquin. "Synthèse et caractérisations électrochimiques vis-à-vis du lithium de structures organiques polycarbonylées et/ou azotées pour application au stockage électrochimique de l’énergie". Amiens, 2011. http://www.theses.fr/2011AMIE0117.
Texto completo da fonteTo satisfy our electrical needs and being faced with a total lack of universal solution, any safe and reliable way to generate operative electricity could find a practical application. From this point of view efficient electrical storage technologies such as Li-ion batteries will have a crucial role to play. However, current technology nearly exclusively operates on inorganic insertion compounds synthesized from high temperature reactions and non renewable resources. The abundance and material life cycle costs of such batteries may present issues in the long term with foreseeable large scale applications. As possible alternative, we have put forward a radically different approach by developing low emission materials based on organic typically deriving from biomass. However, promoting organic-based electrode materials involves the difficult task of identifying stable redoxorganic materials able to reversibly react at both high and low potentials vs. Li. In this context we decided to synthesize and study the electrochemical properties of polycarbonylated compounds, and evaluate different structures. First we studied some nitrogen based derivatives, such as tetraketopiperazines and two derivatives of hexaazatriphenylene (HAT), then we have studied the substituant effect on the p-benzoquinone core and we tested vs Li the pyromellitic diimide dilithium salt. We were looking forward to create a robust experimental database of potential chemical structures in relation with their solid state electrochemical behavior towards lithium. We hope that these results will help us to develop new electro-active organic materials able to satisfy the present and future electrical needs
Chakroune, Said. "Synthèse et étude de nouveaux matériaux organiques issus de précurseurs du type tétrachalcogénofulvalènes fonctionnalisés". Montpellier 2, 1993. http://www.theses.fr/1993MON20123.
Texto completo da fonteTursun, Ahmatjan. "Synthèse asymétrique de spirohétérocycles : un accés modulaire à des spiroacétals, une approche originale des spiroaminoacétals". Phd thesis, Université Blaise Pascal - Clermont-Ferrand II, 2006. http://tel.archives-ouvertes.fr/tel-00688834.
Texto completo da fonteSoulairol, Florence. "Contribution à l'étude d'espèces organosiliciées insaturées stabilisées par coordination nucléophile intramoléculaire". Montpellier 2, 1993. http://www.theses.fr/1993MON20251.
Texto completo da fonteVoirin, Stéphane. "Connaissance de l'arôme du raisin : analyses et synthèses de précurseurs hétérosidiques". Montpellier 2, 1990. http://www.theses.fr/1990MON20074.
Texto completo da fonteJavidan, Azarang. "Synthèse et étude de nouveaux matériaux organiques cristallins conducteurs issus de précurseurs de type tétrachalcogénofulvalène". Montpellier 2, 1997. http://www.theses.fr/1997MON20128.
Texto completo da fonteLI, Hong Shi. "Synthèse et caractérisation du poly[(dioxa 3,6 heptyl)-3-thiophene], vers une électrode iono-sélective". Paris 13, 1992. http://www.theses.fr/1992PA132009.
Texto completo da fonteBellet, Brice. "Synthèses de structurants organiques originaux pour la préparation de nouvelles structures zéolithiques". Thesis, Mulhouse, 2016. http://www.theses.fr/2016MULH8472/document.
Texto completo da fonteSeveral synthetic strategies have emerged such as the use of fluoride, the introduction of germanium and the development of new organic structure directing agents (SDAs) to obtain zeolites, which have led to significant structural diversity. Previous works at the laboratory enable us to develop a new range of non-commercial SDAs that have been designed to produce novel extra-large pores zeolites (>10 TO4 units). Elaborated organic structure directing agents (pyrrolidine derivatives) were first synthesized by a concise route and then engaged in hydrothermal synthesis. Eight non-commercial and original SDAs were produced which led to the synthesis of several known zeolites such as octadecasil (AST), ITQ-7 (ISV), ITQ-17 (BEC) and ITQ-21. The use of the cations N,N-dimethylperhydro-dicyclopenta[b,d]pyrrolium and N,N-dimethyldicyclopentyl-ammonium, allowed us to discover two new silicogermanates named cloverite of known topology -CLO and the novel one Mu 43. Each of these two materials possesses a three-dimensional channel system with 12-membered ring pores (Mu-43) or 20-membered ring pores (cloverite)
Catana, Dan-Andrei. "Synthèse et caractérisation de dinucléotides contraints par des cycles dioxaphosphorinane et phostone". Toulouse 3, 2012. http://thesesups.ups-tlse.fr/1897/.
Texto completo da fonteOur team is interested in preorganizing nucleic acid strands in adopting non-canonical conformations, present in secondary structures of DNA and RNA. In this context, several families of dinucleotides called D-CNAs having a (1,3,2)-dioxaphosphorinane ring, have already been synthesized and characterized. A,béta-P-CNAs (Phostone Constrained Nucleic Acids, a and béta angles constrained) have been synthesized as alternatives to a,béta-D-CNAs and give access to two new diastereoisomers having the constrained torsion angles alpha and beta equal to (t, t) and (t, t). The a,béta-P-CNAs synthesis uses a diastereoselective intramolecular Arbuzov reaction optimized by lithium bromide adduct and micro-wave irradiation. The synthesis of ribo-a,béta-D-CNAs (g+, t) and (g-, t) diastereoisomers was realized in order to complete the previous work carried out by our team regarding the mixed dimers ribo / 2'-deoxyribo and 2'-deoxyribo / ribo and allowed us to study the influence of the two 2'-hydroxiles groups on the stability and conformation of the whole molecule. For the synthesis of Epsilon,Zêta-D-CNAs (Epsilon and Zêta angles constrained), we propose a new strategy that uses a pentose as reagent instead of a hexose, thus avoiding the steps involving the cleavage of the extra carbon atom. This strategy also affords a new approach for the synthesis of Epsilon,Zêta-DCNAs which will allow to introduce different nucleic bases on a disaccharide scaffold having the dioxaphosphorinane modification
Tanrıver, Gamze. "Modélisation moléculaire des modifications post-translationnelles dans Bcl-xL et des sels de céténiminium". Electronic Thesis or Diss., Université de Lorraine, 2021. http://www.theses.fr/2021LORR0302.
Texto completo da fonteIn recent years, computation chemistry plays important role in order to understand and give insight on structural properties of systems (protein, small molecules etc.) by mimicking their environment. This dissertation consists of two main topics, namely understanding impact of Bcl-xL deamidation by means of molecular dynamics (MD) simulations and investigation of keteniminium salt (KI) by quantum mechanical (QM) methods. Investigation of post-translational modifications (PTMs) gains importance to understand their roles on structure and functions of proteins. Deamidation, one of the post-translational modifications is a crucial switch used for regulating the biological function of anti-apoptotic Bcl-xL. In the first part of the thesis, deamidation-induced conformational changes in Bcl-xL were explored to gain insight into its loss of function by performing molecular dynamics (MD) simulations. The outcomes of this study will provide a unique perspective on the underlying mechanism of Bcl-xL deamidation-induced cell death.Keteniminium salt, nitrogen analog of ketene is widely used intermediate for the synthesis of various scaffolds/substances due to its higher electrophilicity, reactivity and regioselectivity. In the second part of the thesis, keteniminium salt was scrutinized from formation to its involved reactions by means of DFT study. Experimentally observed reactivity differences in the [2 + 2] cycloaddition and electrocyclization reactions were rationalized via a range of different analysis techniques. The outcomes of this study are expected to contribute to the understanding of formation and reactivity differences of keteniminium salt and aid synthetic applications
Deleuze, Hervé. "Réactions des lipases en milieu organique synthèse de composés chiraux à partir de diols et diesters méso : analyse et modélisation cinétiques /". Grenoble 2 : ANRT, 1987. http://catalogue.bnf.fr/ark:/12148/cb37604362q.
Texto completo da fonteAndrianome, Marc. "Contribution à l'étude d'allylétains terpéniques : synthèse et réactivité". Bordeaux 1, 1985. http://www.theses.fr/1985BOR10514.
Texto completo da fonteEvlyukhin, Egor. "Synthèse avancée de matériaux hybrides pHEMA-TiO₂ par méthode sol-gel et polymérisation induite par hautes pressions, analyse de leurs propriétés optiques". Thesis, Sorbonne Paris Cité, 2015. http://www.theses.fr/2015USPCD060.
Texto completo da fonteThe specific functional properties of the organic-inorganic hybrid materials depend on their microstructure and the nature of the interface between their organic and inorganic components. The production of hybrid materials with an optimum combination of mechanical and functional properties is a major problem in hybrid materials science. In this thesis we adress this issue by studing and proposing a new approach for synthesizing of photosensitive pHEMA-TiO₂ hybrid materials in wich inorganic nanoparticles are dispersed in a polymer. The method that we propose is based on the high pressure (HP) induced polymerization of the organic phase in the absence of a chemical initiator. We first observed the spontaneous polymerization of HEMA under static pressure. The polimerization process takes place in pressure range below the glass transition point (0.1-1.6 GPa) and after 41 days monomer conversion yield (CY) does not exceed 28%. The reaction may be significantly accelerated when the pressurized sample is irradiated in the UV range. We then developed an original approach based on compression-decompression cycle. During the compression step (>6.5 GPa) the biradicals formed from the excited monomers HEMA (T1) lead to the formation of small oligomers. The polimerization occurs in the second step when the sample decompressed at pressures between 0.1 and 2 GPa. The CY of 90% in less than 5 min is achieved. The new HP approach allows multiply by a factor of 3 the contration of nanoparticles in hybrids without damaging of their polimerization state. These hybrids exhibit a quantum efficiency of photoinduced charge separation of 15% and an electron storage capacity of 50%
Debieu, Sylvain. "Synthèse in situ de fluorophores organiques : formation de liaisons covalentes par déclenchement enzymatique et applications en biodétection". Thesis, Bourgogne Franche-Comté, 2017. http://www.theses.fr/2017UBFCK051/document.
Texto completo da fonteFluorescence imaging is a growing field of biology over the past decades. Intensive works mainly focused on instrumental developments and chemistry of contrast agents (probes), were already done to improve such bioanalytical technique. The main goal of this Ph. D. thesis was to explore various fluorogenic molecular platforms responsive to various (bio)chemical stimuli and capable of releasing organic fluorophores in the biological medium to analyze. This approach named "in-situsynthesis" is based on domino reactions belonging to the repertoire of "covalent chemistry", triggered by the target (bio)analyte. This kind of process should provide advanced fluorogenic probes with high signal-to-noise ratio. Another purpose of this work was to investigate some dualtriggering events to access to fluorogenic molecules acting as "AND-type" molecular logic gates for dual-analytes detection applications. To establish this approach, the formation of highly fluorescent7-hydroxy-2-iminocoumarin scaffolds triggered by several enzyme pairs (hydrolase and nitroreductase) was studied and now described in the first chapter of this manuscript. The second part of this work, described in chapters II and III, was devoted to the development of original "caged" precursors able to release fluorophores whose absorption / emission maxima are dramatically redshifted compared to those of coumarin derivatives. The first achievement concerned the detection of protease or nitroreductase activities through in-situ formation of a pyronin scaffold. Further works, currently in progress, are focused on "caged" precursors whose the dual reaction with a model protease should lead to the release of a benzophenoxazine derivative. Finally, some chemistry aspects related to an emerging and promising class of NIR fluorophores (dihydroxanthene-hemicyanine hybrids) are presented and the opportunity to form them in biological media, upon enzymatic triggering is also discussed
Zitoun, David. "Synthèse et magnétisme de nanoparticules de cobalt/rhodium et cobalt/ruthénium". Toulouse 3, 2003. http://www.theses.fr/2003TOU30078.
Texto completo da fonteOllivier, Anthony Gabriel André. "Synthèse asymétrique de spiroacétals : vers la broussonétine H". Thesis, Clermont-Ferrand 2, 2011. http://www.theses.fr/2011CLF22109/document.
Texto completo da fonteSpiroketal pattern appears in the skeleton of many natural products exhibiting various biological activities, and several synthetic routes to it have been reporting. Contrarily, spiroaminal moiety, its nitrogen analogue, has been less studied. The first of our objectives consisted to develop the most general enantioselective synthetic pathway to this framework. The adopted strategy is based on a key step acid-catalysed spirocyclisation of aminohydroxyketones, resulting from the sequential alkylation of acetone N,N-dimethylhydrazone by various iodide derivatives. If targeted spiroaminals could not be obtained, these polyfunctionalized ketones permit an efficient access to original spiroketals skeletons like 1,6-dioxaspiro [4.6] undecanes and 1,7-dioxaspiro [5.6] dodecanes. In a second part, we focused on the total synthesis of broussonetine H, a natural spiroketal possessing powerful inhibitory activities against β-glycosidases. Its elaboration was envisaged through the coupling between two key fragments : the 2-ethynyl-1,7-dioxaspiro [5.5] undecane and an iminocyclitol substitued by an epoxide. The synthesis of these two compounds was realized in few steps with good overall yelds.Their coupling led to a protected form of broussonetine H. The final deprotection step remains to be optimized to allow the final isolation of the natural product
Béal, Patricia. "Utilisation de l'acroléine dans la synthèse de nouveaux composés odorants : étude de la réactivité de l'acroléine ou de diènes activés dans des réactions d'hétéro Diels-Alder avec des systèmes norbornéniques". Le Havre, 2001. http://www.theses.fr/2002LEHA0004.
Texto completo da fonteThe aims of this work was to prepare in two steps new compounds incorporating one or two acrolein moieties and then to study their olfactory properties. In the first past, we studied the structure and reactivity of trivertal 1. We prepared several esters from trivertal 1 either by conversion in aldehyde group or by Wittig reaction with phosphoranes leading to a,b-unsaturated esters. The synthesis of two aldehydes from trivertal 1 was also carried out. The Grignard reaction between trivertal 1 and acrolein leads to compound 19 allowing us to obtain three other derived products. In a last part, dehydration of trivertanol 2 was performed to produce the corresponding diene 24 wich was allowed to react with acrolein in a catalysed Diels-Adler reaction. All the prepared compounds have been submitted to an olfactory analysis. In the second part, we studied the hetero Diels-Alder reaction between acrlein and several substituted norbonenes. The results have shown that the compounds bearing an exocyclic double bond at the position a of the were not subjected to the Diels-Adler reaction and thus gave the desired products with moderate yields. The olfactory characteristics of all the obtained products were determined. In a last part, we looked for a valuable precursor or equivalents of acrolein. Our research followed two directions. The first one dealt with synthesis and reactivity of 1,3-dioxene 55 wich could be considered as an effective precursor of acrolein. The second one descrinbed the syntheses of several potential synthetic equivalents of acrolein bearing an electron withdrawing group at the position. The hetero Diels-Alder reactions of these compounds with ethylidene norbornene 35 was studied and the best result was obtained with the compound 63 bearing a CH2SO2Ph group. Among all the synthesised products, three of them have been selected by evaluation panel and their synthesis has been reproducted in a higher scale
Legros, Jean-Yves. "Alkylation allylique catalysée par les complexes de palladium : analyse du déroulement stéréochimique, synthèse énantiosélective de composés à chiralité axiale". Paris 11, 1988. http://www.theses.fr/1988PA112178.
Texto completo da fonteThe present work deals with synthetic and mechanistic aspects of the palladium - catalyzed nucleophilic substitution of allylic acetates. In the first part, model substrates are devised and synthesized; they allow a determination of the stereochemical course of the reaction. Nucleophiles are classified according to their reaction mode with the intermediate palladium complex. An approach of the kinetics of the oxidative addition of allylic substrates to palladium complexes through 31 phosphorus NMR study is reported. The last port described the first catalytic enantioselective synthesis of axially dissymetric compounds. Through asymetric palladium catalyzed substitution using chiral phosphine ligands, allylic acetates of suitable structure and geometry lead to chiral 4-substitutedcyclohexylidenes. This alkylation proceeds with excellent regioselectivity and enantioselectivity up to 40%. These substrates were used in palladium(II)and palladium(O) catalytic isomerization of allylic acetates; place with 15% enantiomeric excess: catalyzed asymetric isomerization. In the latter case, isomerization took this result is the first palladium
Auger, Jacques. "Analyse et synthèse de substances allélochimiques des allium (liliacées) et synthèse d'analogues : applications à quelques comportements d'insectes inféodés ou non au poireau (allium porrum L.)". Tours, 1987. http://www.theses.fr/1987TOUR4012.
Texto completo da fonteErades, Laurent. "Nanoparticules d'oxydes semi-conducteurs : synthèse, caractérisation et application à la détection sélective de gaz". Toulouse 3, 2003. http://www.theses.fr/2003TOU30031.
Texto completo da fonteBinet, Laurent. "Synthèse de tétrathiafulvalènes polychalcogènes et/ou fonctionnalisées : préparation et étude de leurs complexes, sels, films et intercalats comme matériaux conducteurs". Montpellier 2, 1997. http://www.theses.fr/1997MON20124.
Texto completo da fonteSemenzin, Delphine. "Réactions "d'hydrophosphoration". Etude comparée de différentes méthodes d'activation". Toulouse 3, 1994. http://www.theses.fr/1994TOU30210.
Texto completo da fonteVahirua-Lechat, Isabelle. "Contribution à l'étude des composés organiques volatils d'huiles essentielles de plantes aromatiques médicinales polynésiennes". Montpellier 2, 1994. http://www.theses.fr/1994MON20120.
Texto completo da fonteZénone, François. "Synthèse et étude conformationnelle par RMN du carbone 13 d'arylcyclohexylamines douées de sélectivité pour le récepteur PCP/NMDA ou pour le système dopaminergique". Montpellier 2, 1990. http://www.theses.fr/1990MON20235.
Texto completo da fonteZouikri, Mohamed. "Le résidu aza-prolyle, son introduction dans un peptide : modifications structurales dues à la substitution AzPRO/PRO". Vandoeuvre-les-Nancy, INPL, 1996. http://www.theses.fr/1996INPL079N.
Texto completo da fonteBédat, Joëlle. "Synthèses et études spectroscopiques de modèles biomimétiques chiraux du NADH : évaluation des facteurs conformationnels qui gouvernent le transfert énantiosélectif de l'hydrogène". Rouen, 1995. http://www.theses.fr/1995ROUES024.
Texto completo da fonteToquer, Guillaume. "Couplages originaux entre Surfactants et Cristaux Liquides Thermotropes : Microémulsions inverses et émulsions directes". Phd thesis, Université Montpellier II - Sciences et Techniques du Languedoc, 2006. http://tel.archives-ouvertes.fr/tel-00142098.
Texto completo da fonteLa première étude porte sur l'organisation de systèmes lyotropes (surfactants et eau) dans un solvant thermotrope anisotrope (cristal liquide). L'existence d'une phase baptisée « nématique transparente » dans un tel système mixte thermotrope-lyotrope de type microémulsion a été en effet récemment débattue. Des expériences de diffusion dynamique de lumière, au voisinage de la transition isotrope-nématique, laissait supposer l'apparition d'une phase intermédiaire, résultant de la compétition entre l'apparition d'un ordre nématique dans le solvant et des effets d'ancrages sur les agrégats.
Nous avons caractérisé, dans un premier temps, par diffusion de rayonnement X et neutrons, la morphologie et les interactions d'agrégats, composés de bromure de didodecyldimethylammonium (DDAB) et d'eau, dans le cristal liquide 4-n-pentyl-4'-cyanobiphenyl (5CB) en phase isotrope. L'étude de l'évolution des diagrammes de phases couplée à des expériences de diffusion (X, Lumière et neutrons) a permis de montrer que l'ajout de cosurfactants permettait de faire varier continûment la taille des nanoagrégats. L'ensemble de nos données expérimentales s'explique bien par la présence d'interactions fortes de Van der Waals entre micelles, ce qui justifie en particulier l'absence de transition microémulsion/ lamellaire gonflée dans ce système. L'analyse des facteurs de structure a permis par ailleurs de mettre en évidence une seconde interaction attractive entre micelle, causée par les fluctuations paranématiques du cristal liquide, intervenant essentiellement à l'approche de la transition isotrope-nématique du cristal liquide. Nous discutons de cette nouvelle interaction à la lumière des résultats de nos expériences de diffusion.
La deuxième étude porte sur les émulsions directes eau-cristal liquide en présence de surfactants amphotropes que nous avons synthétisés et caractérisés par RMN. La formulation de ces surfactants visait à renforcer leur localisation exclusive à l'interface eau-cristal liquide. Les émulsions obtenues montrent la formation spectaculaire de gouttes allongées cylindriques de type filaments. Les propriétés statiques et dynamiques de ces objets ont été explorées et l'origine de cette instabilité est explicitée. La longueur des microtubes est modifiable par des gradients de concentration ou des variations de température ce qui nous a permis de discuter du mécanisme régissant leur morphologie.
Géniès, Sylvie. "Étude de la passivation de l'électrode carbone-lithium". Grenoble INPG, 1998. http://www.theses.fr/1998INPG0008.
Texto completo da fonteBorta, Ana. "Matériaux magnétiques moléculaires : chimie de coordination de systèmes polymétalliques à base d’éléments d et f : synthèses, structures cristallines, magnétisme et relations magnéto-structurales". Thesis, Lyon 1, 2009. http://www.theses.fr/2009LYO10168.
Texto completo da fonteMolecular magnetism is a field which gathers the magnetism of the simplest molecules but also that of very complex systems : high-spin molecules, molecular-based magnets, single molecule magnets, magnetic supramolecular buildings. Coordination chemistry is one way to obtain compounds with specific magnetic properties : ferromagnetic exchange interactions, uniaxial anisotropy, slow relaxation and quantum tunnelling of magnetization. In this context, the work presented here reports the synthesis and the detailed study of the crystal structures and interest of this study is the understanding of the magneto-structural relationships. In the fist chapter we give some elements of molecular magnetism. In the second chapter we present the results obtained by the association of 2-hydroxypyridine lignad, with cuII et LnIII ions. The syntheses lead to two different series of compounds : [Tu4Ln2] and [Cu8Ln2]. In the third chapiter we foaclized our attention on synthesis and study of new heptanuclear mixed-valence manganese complex with 2-OHBzIm ligand (2-hydroxybenzimidazole). The structure is formed by [Mn7(L]12]5+ core, consisting in a nearly planar Mn7 unit comprising a central Mn held within a Mn6 hexagon. The magnetic properties of this compound show a single molecule magnet behaviour. In the last chapter we report the results of the theoretical and experimental study of the antiferromagnetic exchange interactions ad the anisotropy in a dinuclear CoII complex from measurements made on large size single crystal. This study was completed with a polarized neutron diffraction study
Ivol, Flavien. "Formulation d'électrolytes sécuritaires pour supercondensateurs". Thesis, Tours, 2019. http://www.theses.fr/2019TOUR4020.
Texto completo da fonteThe main objective of this PhD thesis is to design and optimize an efficient and safe organic electrolyte for capacitive supercapacitor applications. The benchmark electrolyte currently used in these particular systems presents a significant safety drawback, due to its high flammability. To overcome this issue, several nitrile and dinitrile solvents have been used to formulate alternative electrolytes for supercapacitors. These solvents were initially identified based on their relatively high thermal stability and low volatility. Furthermore, it was also proposed to substitute the reference molten salt with commercially available aprotic ionic liquids, or ones synthetized in the laboratory. The substitution was found to enhance the salt miscibility and compatibility when combined with selected organic solvents, allowing for the formulation of highly concentrated electrolytes with improved electric double-layer storage process. In addition, the ionic liquid-based electrolytes have a larger liquidus temperature range than that of the benchmark molten salt. More importantly, this work presents a clear strategy led by a multi-parametric experimental approach supported by theoretical calculations to optimize the formulation of safer electrolytes for supercapacitors
Jobin, Donald. "Approche de synthèse d'analogues du sialyl Lewis X". Thèse, 2004. http://hdl.handle.net/1866/14355.
Texto completo da fonteTurcotte, Stéphane. "Les azasulfurylpeptides : synthèse, analyse conformationnelle et applications biologiques". Thèse, 2015. http://hdl.handle.net/1866/12321.
Texto completo da fonteThe azasulfurylpeptides are peptide mimics in which the alpha carbon and the carbonyl of an amino acid residue are respectively replaced by a nitrogen atom and a sulfonyl group (SO2). The primary goal of this doctorate project was to develop a new effective method for the synthesis of these motifs, also called N-aminosulfamides. Towards this aim, the use of 4-nitrophenyl sulfamidates turned out to be important in the synthesis of azasulfuryltripeptides, allowing hydrazide couplings under micro-wave irradiation (Chapter 2). Side-chain diversity was then added using a stoichiometric amount of base and different alkyl halides to alkylate chemoselectively the azasulfurylglycine (AsG) residue. The conformational properties of the N-aminosulfamides in the solid state were studied using X-Ray crystallography, which showed a tetrahedral geometry about the sulfur atom, features of azapeptides and sulfonamides, as well as potential to favor the formation of gamma turns (Chapter 3). Following the development of the synthesis of these N-aminosulfamides in solution, a combinatorial approach on solid support was elaborated on Rink amide resin to generate a library of azasulfurylpeptides. The study was performed using the Growth Hormone Releasing Peptide 6 (GHRP-6, His-D-Trp-Ala-Trp-D-Phe-Lys-NH2). The latter is a hexapeptide that has affinity for two receptors, the Growth Hormone Secretagogue Receptor 1a (GHS-R1a) and the Cluster of Differenciation 36 (CD36) receptor. Selective binding to the CD36 receptor has therapeutic potential in the treatment of age-related macular degeneration (AMD). Six azasulfurylpeptide analogs were synthesized on solid support by replacing tryptophan at the 4th position of GHRP-6 with different N-aminosulfamide residues (Chapter 4). The GHRP-6 analogs were tested for their ability to mediate the effects of receptor-specific ligands on the function and downstream signaling of the Toll-Like Receptor 2 (TLR2), in collaboration with Professor Huy Ong at the department of Pharmacology in the Faculty of Pharmacy at the Université de Montréal. The TLR2-TLR6 complex is known to be co-expressed and modulated by CD36. On binding to CD36, certain GHRP-6 ligands exhibited effects on the signaling of TLR2. For example, the azasulfurylpeptides [4-F-AsF4]- and [4-MeO-AsF4]-GHRP-6 prevented the overproduction of nitric oxide (NO), a reactive oxygen species formed following the induction of signal in macrophages on binding of TLR2-specific ligands, such as the Fibroblast-Stimulating Lipopeptide 1 (R-FSL-1) and lipoteichoic acid (LTA). Furthermore, the secretion of the Tumor Necrosis Factor Alpha (TNFa) and Monocyte Chemoattractant Protein 1 (MCP-1), as well as the activation of the Nuclear Factor Kappa-light-chain-enhancer of activated B cells (NF-kB), all were reduced. These results offer promise for regulating Toll-like receptor roles in triggering innate immunity and inflammatory responses (Perspectives). Finally, the potential of the azasulfurylpeptides to inhibit metallo-bêta-lactamases, such as the New-Delhi Metallo-β-lactamase 1 (NDM-1), IMP-1 and the Verona Integron-encoded Metallo-bêta-lactamase 2 (VIM-2), has been studied in collaboration with Professor James Spencer at the University of Bristol (United-Kingdom). Some analogs were micromolar inhibitors of IMP-1 (Perspectives). These new approaches for the synthesis of azasulfurylpeptides in solution and on solid support should enable their use in studies of structure-activity relationships with different biologically active peptides. In addition to expanding the application of azasulfurylpeptides as enzyme inhibitors, this thesis has revealed the potential of these N-aminosulfamides to mimic the peptide secondary structures, such as gamma turns. Application of azasulfurylpeptides in this respect has been demonstrated by the synthesis of CD36 ligands exhibiting modulatory effects on the TLR2. Considering their effective synthesis and potential as inhibitors, azasulfurylpeptides should find broad use in peptide science for applications in medicine and chemical biology.