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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
41

Compréhension de la formation des suies : étude de la combustion de précurseurs des cycles aromatiques en flamme laminaire prémélangée / Comprehension of soot formation : study of the combustion of soot precursors in laminar premixed flat flames

Gueniche, Hadj Ali 08 June 2007 (has links)
Les suies et les hydrocarbures polyaromatiques, qui sont émis à l’échappement des moteurs Diesel, constituent une part importante de la pollution urbaine. Depuis plusieurs années, de nombreuses recherches ont permis de progresser dans le domaine de la cinétique de la combustion des hydrocarbures qui est maintenant relativement bien connue. Il reste néanmoins des zones d’ombre concernant la formation des composés aromatiques (benzène, toluène,…) et des hydrocarbures aromatiques polycycliques (HAP) dont la formation provient d’espèces composées de deux à six atomes de carbone et qui mènent directement ou indirectement à la formation des suies.L’allène, le propyne, le butadiène et le cyclopentène sont des produits intermédiaires importants de la combustion dans les moteurs. Dans ce contexte, ce travail de thèse a permis de mieux comprendre les voies réactionnelles importantes dans la formation du benzène et du toluène. Le chapitre I de ce mémoire présente une revue bibliographique des travaux antérieurs sur l’oxydation du méthane, de l’allène, de propyne, de 1,3-butadiène et du cyclopentène. Le chapitre II présente une description détaillée du montage expérimental utilisé durant cette étude afin d’étudier la structure de la flamme laminaire de prémélange. Les chapitres III, IV et V présentent les résultats expérimentaux obtenus en flamme laminaire de prémélange, ainsi qu’une comparaison avec des simulations effectuées à l’aide de mécanismes réactionnels élaborés durant ce travail de thèse / Soots and polyaromatic hydrocarbons (PAH), which are present in the exhaust gas of diesel engines, represent a large part of the urban pollution. Many efforts have then been focused on reducing the emissions of these compounds. The formation of soot precursors and PAH in combustion involves small unsaturadted hydrocarbons the chemistry of which is still very uncertain. Allene, propyne, 1,3-butadiene and cyclopentene are intermediate products in the combustion in cars engines. This work has led to a better understanding of several important paths in the formation of benzene and toluene. The chapter I of this report presents a bibliographic review of former work on the oxidation of methane, allene, propyne, 1,3-butadiene and cyclopentene. Chapter II gives a detailed description of the experimental set up used during this work to study the structure of the premixed flat laminar flames. Chapters III, IV and V present our experimental results obtained in laminar premixed flat flames and also the comparison with simulations
42

The development of nitro-Mannich/hydroamination cascades for the synthesis of substituted N-heterocycles

Barber, David M. January 2013 (has links)
This thesis describes the development of nitro-Mannich/hydroamination cascade reactions for the synthesis of N-heterocycles, which are important motifs found in a variety of biologically active natural products and pharmaceuticals, such as atorvastatin (Lipitor®). Chapter 2 outlines the development of an efficient synthesis of 2,5-disubstituted pyrroles using a nitro-Mannich/hydroamination cascade. Starting from easily prepared N-protected imines and nitroalkyne substrates, a compatible combination of KOtBu (10 mol%) and AuCl3 (5 mol%) was used to afford the desired pyrrole products, after an alkene isomerisation/HNO2 elimination reaction sequence. Chapter 3 describes the extension of this methodology to the diastereo- and enantioselective synthesis of 1,2,3,4-tetrahydropyridine derivatives using a nitroalkyne substrate with an extended carbon chain. The sequential addition of a bifunctional Brønsted base/H-bond donor organocatalyst and a gold complex was found to facilitate the desired cascade reaction affording substituted 1,2,3,4-tetrahydropyridine products. We then established that highly substituted pyrrolidine compounds could be prepared by replacing the nitroalkyne substrate with a nitroallene substrate (Chapter 4). The combination of KOtBu (5 mol%) and a gold catalyst derived from Au(PPh3)Cl (10 mol%) and AgSbF6 (20 mol%) was found to give an efficient diastereoselective synthesis of pyrrolidine derivatives after an additional nitro group epimerisation step. In addition, the nitro-Mannich/hydroamination cascade using nitroallene substrates was developed into an enantioselective variant using the previously employed bifunctional Brønsted base/H-bond donor organocatalyst. This afforded enantioenriched pyrrolidine derivatives.
43

Novel Fatty Acid Dioxygenases of Human and Plant Pathogenic Fungi : Studies by Gene Deletion and Expression

Jernerén, Fredrik January 2011 (has links)
The dioxygenase-cytochrome P450 fusion proteins (DOX-CYP) comprise a heme-containing enzyme family that shares structural and catalytic properties with mammalian prostaglandin H (PGH) synthases. 7,8-Linoleate diol synthase (7,8-LDS) of Gaeumannomyces graminis was first characterized, and DOX-CYP enzymes are of mechanistic and biological interest. The growing number of fungal genome sequences has revealed DOX-CYP homologues in medically and economically important species. The aim of this thesis was to identify novel members of the DOX-CYP fusion protein family. The devastating rice pathogen Magnaporthe oryzae contains two DOX-CYP genes. The fungus synthesizes 7S,8S-dihydroxyoctadecadienoic acid (7,8-DiHODE) by dioxygenation of linoleic acid to 8R-hydroperoxyoctadecadienoic acid (8R-HPODE), and subsequent isomerisation to the diol. 7,8-LDS of M. oryzae was identified by gene deletion, but the infection and reproduction processes of the Δ7,8-LDS strain were not altered. A mutant with constitutive protein kinase A activity profoundly changed the oxygenation profile, possibly due to post-translational modification. The human pathogens Aspergillus fumigatus and A. clavatus contain three DOX-CYP, designated psi producing oxygenase A (ppoA), ppoB, and ppoC, and form three oxylipins: 5S,8R-DiHODE, 8R,11S-DiHODE, and 10R-hydroxyoctadecadienoic acid.  PpoA was identified as 5,8-LDS, and ppoC as 10R-DOX. The 8,11-linoleate hydroperoxide isomerase activity was reduced by two imidazole-containing P450 inhibitors, miconazole and 1-benzylimidazole. PpoB could not be linked to the biosynthesis of 8,11-DiHODE for the following reasons: First, the 8,11-hydroperoxide isomerase activity was retained in A. fumigatus ΔppoB strains. Second, the P450 domain of the deduced ppoB of A. clavatus lacks a heme-thiolate cysteine ligand, presumably essential for hydroperoxide isomerase activity. Linoleate 9R-DOX activities of Aspergillus terreus and Lasiodiplodia theobromae were discovered. 9R-HPODE was further converted into unstable allene oxides, as judged by the accumulation of their hydrolysis products, α- and γ-ketols. These allene oxide synthase activities were specific for 9R-hydroperoxides. The 9R-DOX and AOS were found to have unique characteristics. In conclusion, novel DOX-CYP enzymes were identified in human and plant pathogenic fungi. These enzymes might be involved in biological processes, and show interesting catalytic similarities to human PGH synthase and thromboxane synthase (CYP5A).
44

Formation de composés polycycliques par activation de doubles liaisons : approche catalytique intra et intermoléculaire de réactions de type Friedel-Crafts : applications au domaine des arômes et parfums / Non disponible

Cacciuttolo, Bastien 14 February 2013 (has links)
L’utilisation de méthodologies de synthèse toujours plus performantes et respectueuses de l’environnement est un axe de recherche majeur de la chimie moderne. L’apport de la catalyse, avec l’utilisation de superacides de Lewis, a permis d’améliorer de nombreux processus synthétiques. Nous avons pu développer dans ce manuscrit des réactions de cycloisomérisation de type réaction de Friedel-Crafts qui donnent accès à un ensemble de structures polycycliques intéressantes avec de bons rendements et sélectivités. L’utilisation d’une quantité catalytique, entre 1 et 10 mol% de Bi(OTf)3, permet l’activation d’oléfines et d’allènes non activés ainsi que de systèmes 1,3-diéniques. Ce type de méthodologie, à économie d’atomes maximale, a permis de limiter la formation de sous-produits, le catalyseur pouvant être recyclé et réutilisé sans perte d’activité. Des approches intra- et intermoléculaires, des réactions cascades et tandems ainsi qu’une étude mécanistique ont été effectuées afin de mieux comprendre la réactivité et ses limitations, et ainsi atteindre une plus large gamme de structures. Les méthodologies développées ont été appliquées au domaine des arômes et parfums pour la synthèse d’analogues de la Calone 1951®, de chromanes, d’indanes et de tétralines fonctionnalisés, posant les bases de travaux futurs pour une meilleur compréhension des relations structures-odeurs / Efficient and ecofriendly synthetic methodologies have always constituted an important area of research in modern organic chemistry. Lewis superacid catalysis has contributed in the improvement of many synthetic processes. We have developed some cycloisomerization reactions including Friedel-Crafts type reaction, giving access to a set of interesting polycyclic structures with good yields and selectivities. The use of a catalytic amount of Bi(OTf)3 (1 to 10 mol%), has allowed the activation of olefins, non-activated allenes and of 1,3-dienic systems. This atom economy methodology can prevent the formation of by-products and the catalyst can be recycled without loss of activity. Intra- and intermolecular approaches, tandem and cascades reactions, as well as mechanistic studies were conducted to enable a better understanding of the reactivity and its limitations to reach a wider range of structures. The developed methodologies were applied to the field of flavors and fragrances in the synthesis of Calone 1951® analogues, and for the preparation of chromans, indanes and tetralins type functionalized structures, for a better understanding of the structure/odor relationship.
45

Vers la synthèse totale de la Thapsigargine inhibiteur de l’enzyme SERCA / Toward the total synthesis of thapsigargin, an inhibitor of SERCA enzyme

Tap, Aurélien 16 December 2013 (has links)
La thapsigargine (Tg) est une lactone sesquiterpène polyoxygénée appartenant à la famille des guaianolides, isolée de Thapsia (Apiacae), une plante poussant communément dans le basin méditerranéen. Son intérêt dans le traitement du cancer de la prostate est basé sur son potentiel inhibiteur de l’enzyme endo/sarcoplasmique calcium ATPase (SERCA). Ce phénomène conduit à une augmentation de la concentration du calcium dans le lumen du réticulum endoplasmique et engendre une apoptose cellulaire. Dans un premier temps, un modèle 8-desoxy-bicyclo[5.3.0]decadiénone, de structure proche du squelette de la Tg, a été synthétisé par le biais d’une réaction clé de Pauson-Khand allène-yne catalysée par un complexe de rhodium. L’approche directe développée est robuste avec de hautes sélectivités et rendements. Cette voie a ensuite été appliquée à la synthèse du produit naturel. A partir d’un époxyde optiquement enrichi, la partie Sud de la Tg (le motif lactonique) est tout d’abord mise en place. Les centres C6 et C8 sont ensuite construits respectivement par alcynylation/réduction asymétrique et par propargylation énantiosélective. Cette première approche a permis d’isoler un produit énantiopure possédant les centres chiraux C6, C7 et C8 ainsi que du motif lactonique en dix-sept étapes. Une seconde voie a été initiée permettant la mise en place plus rapide de la partie Sud de la molécule incluant les centres asymétriques C6, C7, C8 et C11 par le biais d’une réaction de dihydroxylation. Cette seconde voie a permis d’isoler un produit racémique possédant les centres chiraux C6, C7, C8 et C11 ainsi que du motif lactonique en dix étapes. Parallèlement, une étude méthodologique a été menée sur la réaction de Pauson-Khand allénol-yne intramoléculaire. Treize composés bicycliques ont été synthétisés en série acétal et NTs. / Thapsigargin (Tg) is a highly oxygenated sesquiterpene lactone belonging to the guaianolide family, isolated from the Mediterranean plant species Thapsia (Apiaceae). Its interest towards treatment of prostate cancer is based on the potency of this compound as an inhibitor of the endo/sarcoplasmic calcium ATPase (SERCA) inducing an increase in cytosolic calcium concentration and leading to apoptotic cell death. A straightforward approach to a highly functionalized 8-desoxy-bicyclo[5.3.0]decadienone model close to the Tg framework has been achieved through a key Rh(I) allenic Pauson-Khand reaction (APKR). The synthetic route developed therein is robust and the yields and selectivities are high. This approach was used in the synthesis of the natural compound. Starting from the same chiral epoxide, the bottom portion of the Tg (lactone core) is first built, then C6 and C8 carbons are functionalized respectively by asymmetric reduction and enantioselective propargylation. This first way allowed to synthesize a seventeen steps-enantiopure product with C6, C7, C8 chiral centers and the lactone core. A second way is performed to set up faster the bottom part of the molecule included C6, C7, C8 and C11 asymmetric centers through a dihydroxylation step. This second approach allowed to synthesize a ten steps-racemic product with C6, C7, C8, C11 chiral centers and the lactone core. Meanwhile, a methodological study was conducted on the intramolecular allenol-yne Pauson-Khand reaction. Thirteen bicyclic compounds were synthesized in acetal and NTs series.
46

Structure and Dynamics of Core-Excited Species

Travnikova, Oksana January 2008 (has links)
<p>In this thesis we have performed core-electron spectroscopy studies of gas phase molecular systems starting with smaller diatomic, continuing with triatomic and extending our research to more complex polyatomic ones. We can subdivide the results presented here into two categories: the first one focusing on electronic fine structure and effect of the chemical bonds on molecular core-levels and the other one dealing with nuclear dynamics induced by creation of a core hole. In our research we have mostly used synchrotron radiation based techniques such as X-ray Photoelectron (XPS), X-ray Absorption (XAS), normal and Resonant Auger (AES and RAS, respectively) and Energy-Selected Auger Electron PhotoIon COincidence (ES-AEPICO) spectroscopies.</p><p>We have demonstrated that resonant Auger spectroscopy can be used to aid interpretation of the features observed in XAS for Rydberg structures in the case of Cl<sub>2</sub> and C1s<sup>−1</sup>π*<sup>1</sup> states of allene molecules. The combined use of high-resolution spectroscopy with <i>ab initio</i> calculations can help the interpretation of strongly overlapped spectral features and disentangle their complex profiles. This approach enabled us to determine the differences in the lifetimes for core-hole 2p sublevels of Cl<sub>2</sub> which are caused by the presence of the chemical bond. We have shown that contribution in terms of the Mulliken population of valence molecular orbitals is a determining factor for resonant enhancement of different final states and fragmentation patterns reached after resonant Auger decays in N<sub>2</sub>O.</p><p>We have also performed a systematic study of the dependence of the C1s resonant Auger kinetic energies on the presence of different substituents in CH<sub>3</sub>X compounds. For the first time we have studied possible isomerization reaction induced by core excitation of acetylacetone. We could observe a new spectral feature in the resonant Auger decay spectra which we interpreted as a signature of core-excitation-induced keto-enol tautomerism.</p>
47

Untersuchungen zur Oxygenierung organischer Substrate durch Oxo-Verbindungen der Elemente Vanadium und Mangan

Brandt, Marcus 13 August 2007 (has links)
Die vorliegende Arbeit beschäftigt sich mit der Oxygenierung von ungesättigten Kohlenwasserstoffen durch Übergansmetalle und katalytischer Oxidation von Olefinen und Aliphaten. Sie ist in die folgenden drei Teile gegliedert: 1. Matrixisolationsstudien zum System MnO3Cl/Allen: Das System Permanganylchlorid/Allen wurde in einer Argonmatrix durch Photolyse (546 nm) zu Reaktion gebracht. Die entstandenen Komplexe (O=)2MnCl(O=CCH2CH2) 37R und (O=)2MnCl(H2COCCH2) 38R wurden mit Hilfe der IR-Spektroskopie, Isotopenmarkierungs-Experimenten (18O, D) und DFT-Rechnungen (B3LYP/LANL2DZ) zweifelsfrei identifiziert und der Reaktionsmechanismus Hilfe von mit weiteren DFT-Rechnungen (B3LYP/6-311Gd) aufgeklärt. 2. Synthese eines neuen dinuklearen Vanadium-Silsesquioxan-Komplexes Silika geträgerte Vanadium-Komplexe sind vor allem als Katalysatoren für die Oxidation von Kohelnwasserstoffen interessant. Man geht davon aus, dass vor allem die tetraedrisch koordinierten VO4-Spezies für die katalytische Aktivität bzw. Selektivität verantwortlich sind. Da nur eine Vanada-Silsesquioxan-Modellverbindung bekannt war, wurden Versuche unternommen weitere zu synthetisieren. Es konnte eine neue Verbindung erhalten werden, die vollständig charakterisiert wurde und auf ihre katalytische Aktivität getestet wurde. 3. Quantenmechanische Rechnungen zur Lösung ausgewählter Fragestellungen des Systems Mo/Bi Mit Hilfe von DFT-Rechnungen wurden verschiedene Mo-Bi-Verbindungen, die im Rahmen der mechanistischen Aufklärung des SOHIO-Verfahrens durch Synthese von Modellverbindungen erhalten wurden, auf ihre besondere Bindungssituation hin untersucht. Dazu wurden unter anderem die Bader sowie die NBO-Analyse verwendet. / Submitted thesis deals with the oxygenation of unsaturated hydrocarbons by transition metals and catalytic oxidations of olefins and aliphats. It is divided into the following three parts: 1. Matrixisolationstudies of the system MnO3Cl/allene: The light-induced (546 nm) reaction of MnO3Cl with allene has been investigated in low-temperature argon matrices at 11 K. IR spectroscopic studies in combination with isotopic enrichment experiments (18O, D) and DFT calculations (B3LYP/LANL2DZ) allowed the identification of (O=)2MnCl(O=CCH2CH2), 37R, and (O=)2MnCl(H2COCCH2), 38R as products. First of all, possible ways for their formation are discussed qualitatively in the context of the literature available, and then quantitatively with the background of DFT data (B3LYP/6-311G(d)) obtained for starting materials, products, transition states and intermediates. Based on the results a reaction mechanism was proposed. 2. Synthesis of a novel dinuclear vanadium-silsesquioxane-complex Silica-supported vanadium complexes have attracted the interest as catalyst for the oxidation of hydrocarbons. Especially tetrahedrally coordinated VO4-Spezies are supposed as active/selective sites. To investigate the chemical behaviour and –properties of such species, Feher et al. synthesized a vanadium-silsesquioxane-complex in 1991 since silsesquioxanes are known to be excellent structural models for the silica surface. The synthesis and catalytic activity of a new complex, that was successfully synthesised, is reported here. 3. Quantum mechanical calculations for solving selected problems at Mo/Bi-systems. During the investigation of the reaction mechanism of the SOHIO-process some very unusual Mo-Bi-complexes could be isolated in the workgroup of Prof. Dr. Ch. Limberg. The bonding situation of four special complexes was analysed by means of calculations based of density functional theory (DFT) in combination with natural bond orbital analysis (NBO) respectively Bader-theory. 1
48

Evaluation of The Electronic Properties of Carbon(0)-Based Compounds Through Gold Catalysis and X-Ray Structure Analysis / Évaluation des propriétés électroniques des composés à base de carbone(0) par la catalyse a l’or et analyse des structures aux rayons-X.

El hellani, Ahmad 23 November 2012 (has links)
La plupart des composés organiques ont un atome de carbone tétravalent, où tous les électrons de valence sont utilisés pour former des liaisons covalentes. En parallèle, la chimie des composés divalents ayant un carbone(II) s’est développée après l’isolement de carbènes stables par Bertrand en 1985. Auparavant, en 1961, Ramirez a rapporté l’isolement de l’hexaphénylcarbodiphosphorane, que l’on peut considérer comme un composé présentant un carbone(0) avec ses deux doublets libres, lui permettant de coordiner jusqu’à deux acides de Lewis. A partir de 2006, les propriétés électroniques de ces ligands ont été étudiées au travers d’études théoriques par Frenking ; ce qui a permis à Bertrand et Fürstner d’isoler et d’ajouter des nouveaux membres à cette famille. Cette classe de ligand est aujourd’hui connue sous le nom de “carbônes”, avec comme formule générale CL2 (L = PR3 ou carbène).Cette famille n’a jamais été utilisée dans le domaine de la catalyse. C’est pourquoi nous avons, décidé d’etudier les propriétés électroniques de ce ces composés au travers de la catalyse à l’or, afin de les comparer aux NHC, phosphines, et phosphites. Récemment, nous avons utilisé ces composés pour générer des complexes donneur accepteur avec du GaCl3, et de corréler leurs différentes caractéristiques géometriques à leurs propriétés électroniques en utilisant les règles de Gutmann sur des adduits acide/base de Lewis. De plus, nous avons isolé des “dimères” ioniques dont la formation peut être expliquée par les propriétés intrinsèques des ligands. Nous avons ainsi démontré par ces deux approches que les “carbônes” sont de meilleurs donneurs que les NHC. / Most organic compounds which are stable in the condensed phase contain tetravalent carbon atoms, where all four valence electrons are being engaged in chemical bonds. On the other hand, the chemistry of divalent carbon(II) was only recognized after the isolation of a stable persistent carbene by Bertrand and co-workers in 1985. Such products display one s-type lone pair orbital and are thus good ligands. Earlier on, concern was also paid to a new family of compounds, first reported in 1961 by Ramirez and co-workers. They can be considered as divalent carbon(0) derivatives with two lone pairs at the central carbon, with a possibility of double coordination of two Lewis acids to this carbon. This feature was proposed by Kaska in 1973, and verified later by the isolation of di-metalated adducts. From 2006, these compounds were the centre of extensive theoretical investigations by Frenking, which led to the isolation of new members of this family by Fürstner and Bertrand. This family is now referred to as “carbones”, of general formula CL2 (L =PR3 or carbene).“Carbones” are still virtually unused in catalysis. Thus, we have decided to study these derivatives, especially in the field of gold catalysis, and to compare them with well-known ligands such as NHCs, phosphines and phosphites. Recently, we were able to synthesize their corresponding GaCl3 complexes and to rationalize their electronic properties through Gutmann’s rules for Lewis acid/Lewis base adducts. In addition, we obtained some ionic “dimers” and we explained their formation on the basis of ligand’s electronic properties. We have shown through these two approaches that carbones are far better donors than NHCs.
49

Structure and Dynamics of Core-Excited Species

Travnikova, Oksana January 2008 (has links)
In this thesis we have performed core-electron spectroscopy studies of gas phase molecular systems starting with smaller diatomic, continuing with triatomic and extending our research to more complex polyatomic ones. We can subdivide the results presented here into two categories: the first one focusing on electronic fine structure and effect of the chemical bonds on molecular core-levels and the other one dealing with nuclear dynamics induced by creation of a core hole. In our research we have mostly used synchrotron radiation based techniques such as X-ray Photoelectron (XPS), X-ray Absorption (XAS), normal and Resonant Auger (AES and RAS, respectively) and Energy-Selected Auger Electron PhotoIon COincidence (ES-AEPICO) spectroscopies. We have demonstrated that resonant Auger spectroscopy can be used to aid interpretation of the features observed in XAS for Rydberg structures in the case of Cl2 and C1s−1π*1 states of allene molecules. The combined use of high-resolution spectroscopy with ab initio calculations can help the interpretation of strongly overlapped spectral features and disentangle their complex profiles. This approach enabled us to determine the differences in the lifetimes for core-hole 2p sublevels of Cl2 which are caused by the presence of the chemical bond. We have shown that contribution in terms of the Mulliken population of valence molecular orbitals is a determining factor for resonant enhancement of different final states and fragmentation patterns reached after resonant Auger decays in N2O. We have also performed a systematic study of the dependence of the C1s resonant Auger kinetic energies on the presence of different substituents in CH3X compounds. For the first time we have studied possible isomerization reaction induced by core excitation of acetylacetone. We could observe a new spectral feature in the resonant Auger decay spectra which we interpreted as a signature of core-excitation-induced keto-enol tautomerism.
50

Allene, Dihydronaphthalenon-Derivate und andere Sekundärmetabolite aus Pilzen mariner Habitate sowie Beiträge zu deren Biosynthese / allenes, dihydronaphthalenone-derivatives and further secondary metabolites from marine fungi as well as contributions to their biosynthesis

Wolff, Diana 03 November 2004 (has links)
No description available.

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