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171	Investigations into cyclopropanation and ethylene polymerization via salicylaldiminato copper (II) complexes Boyd, Ramon Cornell 23 January 2007 Two distinct overall research objectives are in this Masters thesis. Very little relates the two chapters apart from the ligands. The first chapter addresses diastereoselective homogeneous copper catalyzed cyclopropanation reactions. Cyclopropanation of styrene and ethyl diazoacetate (EDA) is a standard test reaction for homogeneous catalysts. Sterically bulky salicylaldimine (SAL) ligands should select for the ethyl trans-2-phenylcyclopropanecarboxylate diastereomer. Steric bulk poorly influences trans:cis ratios. Salicylaldiminine ligands do not posses the correct symmetry to affect diastereoselectivity. The SAL ligand belongs to the Cs point group in the solid state. Other ligand motifs are more effective at altering the trans:cis ratios. The second chapter addresses the general route toward successful copper(II) ethylene polymerization catalysts. Catalytic activity of the copper(II) complexes is very low. Polymer chain growth from a copper catalyst is very unlikely. Copper-carbon bonds decompose by homolytic cleavage or C-H activation. Copper-alkyls and aryls readily decompose into brown colored oils and salts with different colors. Ligand transfer to trimethylaluminum (TMA) appears to explain low yield ethylene polymerization. bulky migratory insertion mechanism coordination/insertion methodology d-block metal late transition metal phenolic ring coordination number ketimine precatalysts ketimine nitrogen bis(salicylaldiminato)copper(II) ratio cyclopropane steric bulk salicylaldiminato TMA salt trimethylaluminum aryl oil alkyl copper-aryls copper-alkyls C-H activation homolytic homolytic cleavage copper(II) polymerization ethylene cis trans symmetry diastereomer salicylaldimine SAL EDA ethyl diazoacetate styrene cyclopropanation copper diastereoselective steric protection stable CH(SiMe3)2 intermediate catalytic activity associated TMA free TMA vacant coordination site hydrolysis Lewis acid halogen anionic anionic ligand donor ligand monodentate anionic ligand aluminum(III) monodentate polymer chain polymer chain aluminum-carbon bond bulky SAL ligand open coordination site first row transition metal PE paramagnetic high molecular weight polyethylene alkylate methylaluminoxane MAO anionic ligands arylate aluminum carbon aluminum carbon bond beta-hydrogen elimination beta hydrogen elimination Aufbau reaction Aufbau neutral dialkyl aluminum aluminum-alkyl aluminum alkyl copper(0)
172	Investigations into cyclopropanation and ethylene polymerization via salicylaldiminato copper (II) complexes Boyd, Ramon Cornell 23 January 2007 (has links) Two distinct overall research objectives are in this Masters thesis. Very little relates the two chapters apart from the ligands. The first chapter addresses diastereoselective homogeneous copper catalyzed cyclopropanation reactions. Cyclopropanation of styrene and ethyl diazoacetate (EDA) is a standard test reaction for homogeneous catalysts. Sterically bulky salicylaldimine (SAL) ligands should select for the ethyl trans-2-phenylcyclopropanecarboxylate diastereomer. Steric bulk poorly influences trans:cis ratios. Salicylaldiminine ligands do not posses the correct symmetry to affect diastereoselectivity. The SAL ligand belongs to the Cs point group in the solid state. Other ligand motifs are more effective at altering the trans:cis ratios. The second chapter addresses the general route toward successful copper(II) ethylene polymerization catalysts. Catalytic activity of the copper(II) complexes is very low. Polymer chain growth from a copper catalyst is very unlikely. Copper-carbon bonds decompose by homolytic cleavage or C-H activation. Copper-alkyls and aryls readily decompose into brown colored oils and salts with different colors. Ligand transfer to trimethylaluminum (TMA) appears to explain low yield ethylene polymerization. bulky migratory insertion mechanism coordination/insertion methodology d-block metal late transition metal phenolic ring coordination number ketimine precatalysts ketimine nitrogen bis(salicylaldiminato)copper(II) ratio cyclopropane steric bulk salicylaldiminato TMA salt trimethylaluminum aryl oil alkyl copper-aryls copper-alkyls C-H activation homolytic homolytic cleavage copper(II) polymerization ethylene cis trans symmetry diastereomer salicylaldimine SAL EDA ethyl diazoacetate styrene cyclopropanation copper diastereoselective steric protection stable CH(SiMe3)2 intermediate catalytic activity associated TMA free TMA vacant coordination site hydrolysis Lewis acid halogen anionic anionic ligand donor ligand monodentate anionic ligand aluminum(III) monodentate polymer chain polymer chain aluminum-carbon bond bulky SAL ligand open coordination site first row transition metal PE paramagnetic high molecular weight polyethylene alkylate methylaluminoxane MAO anionic ligands arylate aluminum carbon aluminum carbon bond beta-hydrogen elimination beta hydrogen elimination Aufbau reaction Aufbau neutral dialkyl aluminum aluminum-alkyl aluminum alkyl copper(0)
173	Structure And Dynamics Of Constrained Water : Microscopic Study Of Macromolecular Hydration Using Computer Simulations Pal, Subrata 02 1900 (has links) The thesis, which contains nine chapters, reports extensive large scale atomistic molecular dynamics (MD) simulation studies of water structure and dynamics at the surface of an anionic micelle, hydration layer of two proteins, and in the grooves of a 38-base pairs long DNA. Understanding the structure and dynamics of water molecules at the surfaces of self-organized assemblies and complex biological macromolecules has become a subject of intense research in recent times. Chapter 1 contains a brief overview of the biomolecular hydration dynamics. Relevant experimental, computational, and theoretical studies of biomolecular hydration and the time scales associated with the water dynamics are discussed. In Chapters 2 and 3, the structure, environment, energetics, and dynamics of constrained water molecules in the aqueous anionic micelle of cesium perfluorooctanoate (CsPFO) have been studied using large scale atomistic molecular dynamics simulations. Based on the number of hydrogen bond (HB) that interfacial water molecule makes with the polar head group (PHG) oxygen of the micelle, we find the existence of three kinds of water at the interface. We introduce a nomenclature to identify the species as IBW2 (form two HBs with two different PHG), IBW1 (form one HB with PHG), and IFW (no HB with PHG). Despite of possessing two strong w-PHG bonds, the concentration of the IBW2 species is rather low due to entropic effect. The ion solvation dynamics study at the interface shows the presence of a slow component, with a relaxation time 1-2 order of magnitude slower than that in the corresponding bulk solvent in agreement with the experimental results. Both the translational and orientational dynamics of the water molecules near the micellar surface is found to be much slower than those in the bulk. The HB between the PHG of the micelle and the water molecule has almost 13 times longer life time than that in the bulk between two tagged water molecules. In Chapter 4, we present results of extensive atomistic MD simulation studies of the structure and dynamics of aqueous protein solution of the toxic domain of Enterotoxin (1ETN) and the chicken villin headpiece sub-domain containing 36 amino acid residues (HP-36). Reduced water structure and the faster water dynamics around the active site of these proteins have been observed which may have biological significance. Chapter 5 presents an extensive atomistic molecular dynamics simulations study of water dynamics in the hydration layer of a 38 base long hydrated DNA duplex. The computed rotational time correlation function (TCF) of the minor groove water dipoles is found to be markedly non-exponential with a slow component at long time. The constrained water molecule is also found to exhibit anisotropic diffusion in both the major and minor grooves. At short-to-intermediate times, translational motion of water molecules in minor groove is sub-diffusive. Chapter 6 presents the study of water entropy in both the grooves DNA. The average values of the entropy of water at 300K in both the grooves of DNA are found to be significantly lower than that in bulk water. We propose that the configurational entropy of water in the grooves can be used as a measure of the mobility (or micro viscosity) of water molecules in a given domain. In Chapter 7, we study the specific DNA base-water hydrogen bond lifetime (HBLT) dynamics at the major and the minor grooves of a hydrated duplex. The base-water HBLT correlation functions are in general multi-exponential and the average lifetime depends significantly on the specificity of the DNA sequence. The average HBLT is longer in the minor groove than that in the major groove by almost a factor of 2. Chapter 8 presents the solvation dynamics of constituent bases of aqueous DNA duplex. The solvation TCFs of the four individual bases display highly non-exponential decay with time. An interesting negative cross-correlation between water and counterions is observed which makes an important contribution to relaxation at intermediate to longer times. In the concluding note, Chapter 9 presents a brief summary of the outcome of the thesis and suggests several relevant problems that may prove w orthwhile to be addressed in future Water Chemistry - Computer Simulation Macromolecular Hydration Anionic Micelle Biomolecular Hydration Dynamics Water Dynamics Protein - Water Dynamics DNA Hydration Dynamics 1ETN Protein Aqueous Micelle Aqueous Miceller Surface Aqueous Micellar Solution Solvation Dynamics Inorganic Chemistry
174	Synthesis and characterization of stimuli-responsive microgels based on poly(glycidol)block copolymers / Synthese und Charakterisierung von stimuli-sensitiven Mikrogelen basierend auf Polyglycidol-Blockcopolymeren Mendrek, Sebastian 24 April 2006 (has links) (PDF) New water soluble, attainable to ATRP polymerization Cl-terminated poly(glycidol) macroinitiators were prepared by modification of (Omega)-hydroxyl group of poly(glycidol acetal) using 2-chloropropionyl chloride fallowed by selective acidic deprotection of acetal groups. The obtained macroinitiators of different molar masses were successfully employed in ATRP of NIPAM and 4VP to give well-defined stimuli sensitive block copolymers of targeted molar ratio of blocks. The results obtained from light scattering methods showed formation of stable aggregates upon stimuli (pH or temperature) by all the obtained polymers. Additionally, photocrosslinkable block copolymers of glycidol and NIPAM having incorporated moieties of chromophore (2-(dimethyl maleinimido)-N-ethyl-acryl amide) were prepared using macroinitiator technique and used to synthesis of temperature sensitive microgels. Conjunction points have been successfully formed by UV irradiation of polymer water solution above cloud point. The influence of such parameters like block ratio, block length, amount of chromophore, concentration, irradiation time, temperature and heating rate on the properties of obtained microgels was investigated. The obtained core-shell structures were stable under critical conditions and showed continuous volume phase separation process upon increase of temperature, fully reversible and reproducible (no hysteresis effect). Thus, the proposed method not only gave the opportunity to control size or swelling degree of microgels, but also diminished gradient in crosslinking density (random chromophore distribution in polymer backbone), improved colloid stability (poly(glycidol) shell) and completely eliminated additives (surfactants, initiators, stabilizers). ATRP Anionische Polymerisation Blockcopolymere Makroinitiator stimuli-sensitiv ATRP Anionic Polymerisation Macroinitiator block copolymers stimuli-sensitive ddc:540 rvk:VK 8007 Anionische Polymerisation Atom-Transfer-Polymerisation Blockcopolymere Initiator &lt;Chemie&gt; Mikrogel
175	Développement de tensioactifs à base d’acides biliaires pegylés pour des applications pharmaceutiques Le Dévédec, Frantz 03 1900 (has links) Les acides biliaires sont reconnus comme des tensioactifs d’origine biologique potentiellement applicables dans le domaine pharmaceutique. Leurs structures en font une plateforme idéale pour l’obtention de nouvelles architectures polymères. Des composés synthétisés par polymérisation anionique de dérivés d’oxirane comme l’oxyde d’éthylène, offre des dérivés amphiphiles pegylés démontrant des propriétés d’agrégation intéressantes en vue d’une amélioration de la biocompatibilité et de la capacité d’encapsulation médicamenteuse. Une large gamme d’acides biliaires pegylés (BA(EGn)x) a été préparée avec comme objectif premier leurs applications dans la formulation de principes actifs problématiques. Pour cela, une caractérisation rigoureuse du comportement de ces dérivés (modulation de la longueur (2 < n < 19) et du nombre de bras (2 < x < 4) de PEG) en solution a été réalisée. Dans le but d’améliorer la biodisponibilité de principes actifs lipophiles (cas de l’itraconazole), des nanoémulsions spontanées, composées de BA(EGn)x et d’acide oléique, ont été développées. L’évaluation in vitro, de la toxicité (cellulaire), et de la capacité de solubilisation des systèmes BA(EGn)x, ainsi que les paramètres pharmacocinétiques in vivo (chez le rat), suggèrent une livraison contrôlée par nos systèmes auto-assemblés lors de l’administration orale et intraveineuse. Aussi, la synthèse de copolymères en blocs en étoile à base d’acide cholique pegylés a été effectuée par polymérisation anionique par addition d’un second bloc au caractère hydrophobe de poly(éther d’allyle et de glycidyle) (CA(EGn-b-AGEm)4). Selon le ratio de blocs hydrophiles-hydrophobes CA(EGn-b-AGEm)4, des réponses thermiques en solution (LCST) ont été observées par un point de trouble (Cp) entre 8 oC et 37 oC. Un mécanisme de formation d’agrégats en plusieurs étapes est suggéré. La thiolation des allyles des PAGE permet une fonctionnalisation terminale à haute densité, comparable aux dendrimères. Les caractérisations physico-chimiques des CA(EGn-b-AGEm-NH2)4 et CA(EGn-b-AGEm-COOH)4 indiquent la formation de structures auto-assemblées en solution, sensibles à la température ou au pH. Cette fonctionnalisation élargie le domaine d’application des dérivés d’acides biliaires pegylés en étoile vers la transfection d’ADN, la livraison de siRNA thérapeutiques ou encore à une sélectivité de livraison médicamenteux (ex. sensibilité au pH, greffage ligands). / Bile acids are natural compounds and may have potential for pharmaceutical applications. Their structures provide an interesting platform for polymerization to obtain well-defined architectures. The anionic polymerization of oxirane derivatives, mainly PEG derivatives, endowed new aggregation properties and improvement of biocompatibility of the new amphiphilic polymers based on bile acids. A library of pegylated bile acids (BA(EGn)x) was prepared for the formulation of lipophilic drugs. The aqueous physicochemical behaviors of these derivatives (modulation of the length (2 < n < 19) and the number (2 < x < 4) of PEG arm) were investigated. In order to improve the bioavailability of insoluble active compounds (itraconazole, an antifungal drug), a binary system based on the association of BA(EGn)x and oleic acid, formed self-emulsifying drug delivery systems. The in vitro evaluation of cell toxicity and solubilization capacities of the BA(EGn)x systems followed by the in vivo evaluation in rats of the pharmacokinetic parameters demonstrated the advantages of our self-assembled system for controlled drug delivery for both oral and intravenous administration. Star-shaped block copolymers of pegylated cholic acid (CA(EGn-b-AGEm)4) were prepared by the introduction of a second hydrophobic block of PAGE poly(allyl glycidyl ether). They demonstrated thermosensitivity (8 oC < LCST < 37 oC) in aqueous solution, suggesting a mechanism based on the formation of aggregates in two steps. The PAGE block with pendant groups may facilitate futher functionalization. The thiolation of allyl yields a new class of charged PEGylated star polymers (with multiple amines or carboxylic groups). CA(EGn-b-AGEm-NH2)4 and CA(EGn-b-AGEm-COOH)4 derivatives showed self-assembled structures in solution with temperature and pH responsiveness, respectively. This functionalization may lead to broader application of pegylated star derivatives in DNA transfection systems, siRNA delivery systems or as selective delivery system (pH-dependent). Acides biliaires PEG Polymère en étoile Polymérisation anionique Système de relargage de médicaments Bile acids Star polymers drug delivery system anionic polymerization itraconazole thermo responsive polymers
176	Pyridine and amine functionalized polymers by anionic and controlled free radical polymerization methods Ndawuni, Mzikayise Patrick 07 1900 (has links) The synthesis of dipyridyl functionalized polysulfones with improved hydrophilicity, enhanced membrane morphology and excellent ATRP polymeric ligand properties was conducted by the following method: (a) the formation of lithiated polysulfone from unmodified polysulfone and the subsequent reaction with 2,2'-vinylidenedipyridine in tetrahydrofuran at -78 oC under argon atmosphere to afford the corresponding dipyridyl functionalized polysulfone. The stoichiometry of the reaction affects the degree of functionalization of the product. When equimolar amounts of 2,2'-vinylidenedipyridine are added to the lithiated polysulfone, the degree of functionalization obtained was 45%. However, the addition of 10% and 20% molar excess of 2,2'-vinylidenedipyridine to the corresponding lithiated polysulfone produced dipyridyl functionalized polysulfones with degrees of functionalization of 80% and 95%, respectively; and (b) the membranes obtained from unmodified polysulfone as well as dipyridyl functionalized polysulfones were characterized by atomic force microscopy, scanning electron microscopy, pure water permeation measurements and contact angle measurements. Amine chain end functionalized polystyrene and poly(methyl methacrylate) were prepared by Atom Transfer Radical Polymerization (ATRP) methods as follows: (a) •-Aminophenyl functionalized polystyrene was prepared in quantitative yields by ATRP methods using a new primary amine functionalized initiator adduct, formed in situ by the reaction of 1-(4-aminophenyl)-1-phenylethylene and (1-bromoethyl)benzene in the presence of copper (I) bromide/2,2'-bipyridyl as catalyst in diethyl ether at 110 oC, for the polymerization of styrene.(b) New •-bis(aminophenyl) and •,ω-tetrakis(aminophenyl) functionalized polymers were prepared in quantitative yields by the ATRP method using the following synthetic strategy: (i) the initiation of styrene polymerization with a new primary diamine functionalized initiator adduct, generated in situ by the reaction of stoichiometric amounts of 1,1-bis(4-aminophenyl)ethylene with (1-bromoethyl)benzene in the presence of copper (I) bromide/2,2'-bipyridyl as catalyst, afforded •-bis(aminophenyl) functionalized polystyrene; and (ii) •-bis(aminophenyl) functionalized poly(methyl methacrylate) was prepared by the ATRP method using the primary diamine functionalized initiator adduct as initiator for methyl methacrylate polymerization; and (iii) well defined •,ω-tetrakis(aminophenyl) functionalized polystyrene was prepared by the post ATRP chain end modification reaction of •-bis(aminophenyl) functionalized polystyrene with 1,1-bis(4-aminophenyl)-ethylene at the completion of the polymerization reaction. (c) Similarly, •-bis(4-dimethylaminophenyl) functionalized polystyrene was prepared by using a new tertiary diamine functionalized initiator adduct, formed in situ by treatment of equimolar amounts of 1,1-bis[(4-dimethylamino)phenyl]-ethylene with (1-bromoethyl)benzene in the presence of copper (I) bromide/2,2'-bipyridyl as the catalyst in diphenyl ether at 110 oC for the initiation of styrene polymerization by the ATRP method. Furthermore, the ATRP of methyl methacrylate, initiated by the new tertiary diamine functionalized initiator adduct, produced •-bis(4-dimethylaminophenyl) functionalized poly(methyl methacrylate). In addition, •,ω-tetrakis(4-dimethylaminophenyl) functionalized polystyrene was synthesized via a post ATRP chain end modification reaction of •-bis(4-dimethylaminophenyl) functionalized polystyrene with equimolar amounts of 1,1-bis[(4-dimethylamino)phenyl]ethylene at the completion of the polymerization process. vi Quantitative yields of the different amine functionalized polymers with predictable number average molecular weights (Mn = 1.3 x 103 – 16.4 x103 g/mol), narrow molecular weight distributions (Mw/Mn = 1.03 – 1.29) and controlled chain end functionality were obtained. Polymerization kinetics data was employed to determine the controlled/living character of each ATRP reaction leading to the formation of the different amine chain end functionalized polymers. The polymerization processes were monitored by gas chromatographic analyses. Polymerization kinetics measurements for all reactions show that the polymerizations follow first order rate kinetics with respect to monomer consumption. The number average molecular weight of the amine functionalized polymers increases linearly with percentage monomer conversion and polymers with narrow molecular weight distribution were obtained. The ATRP of styrene, catalyzed by a novel dipyridyl functionalized polysulfone/CuBr supported catalyst system, afforded well defined polystyrene with predictable number average molecular weight and narrow molecular weight distribution in a controlled/living free radical polymerization process. The substituted 1,1-diphenylethylene initiator precursor derivatives and the functionalized polymers were characterized by nuclear magnetic resonance spectrometry, fourier transform infrared spectroscopy, thin layer chromatography, column chromatography, size exclusion chromatography, non-aqueous titrations, differential scanning calorimetry and thermogravimetrical analysis. / Chemistry / M. Sc. (Chemistry) Anionic polymerization Polymer membranes Controlled/living polymerization Telechelic polymers 1-diphenyl-ethylene derivatives Supported catalyst Amine functionalized polymers Polysulfone Atom transfer radical polymerization Amine substituted 1 547.7 Addition polymerization Polymers
177	Functionalized Layered Double Hydroxides and Gold Nanorods Dutta, Dipak January 2011 (has links) (PDF) The reversible and topotactic insertion of guest species within layered host lattices, known as intercalation is a widely studied phenomena. The Layered Double Hydroxides (LDHs) or Anionic Alloys are important class of layered solids with its own distinct ion-exchange host-Guest Chemistry. The LDH structure may be derived from that of Brucite, Mg(OH)2, by random isomorphous substitution of Mg2+ ions by trivalent cations like Al3+, Ga3+ etc. This substitution leaves an excess positive charge on the layers, which is compensated by interlamellar anions. These ions are exchangeable and thus new functionalities can be introduced to ion exchange reactions. Insertion of neutral, non-polar or poorly water-soluble guest molecules remains a challenge. In the present study, two methodologies were adopted to extend the host-guest chemistry of LDHs to neutral and non-polar species, first by using Hydrophobic interaction and second, charge transfer (CT) interaction as driving force. Hlydrophobic interaction as driving force involves functionalization of the Mg-Al-LDH galleries as bilayers, thus covering the essentially hydrophilic interlamellar space of the LDH to one that is hydrophobic and able to solubilize neutral molecules like Anthracene. CT interaction as driving force, involves pre-functionalization of the galleries of the LDH with a donor species e.g. 4-aminobenzoic acid by conventional ion exchange methods to form a LDH-donor intercalated compound. This compound can selectively adsorb acceptor species like Chloranil, Tetracyanoquinodimethane etc. into the interlamellar space of the solid by forming donor-acceptor complexes. The confined donor-acceptor complexes have been characterized by X-Ray Diffraction, UV-Visible, Fourier Transformed Infra-Red and Raman Spectroscopy, Molecular Dynamics Simulations were able to reproduce the experimental results. One dimensional gold nanostructure like nanorods (AuNRs) have received great attention due to their size dependent optical properties, Extending these applications requires assembling the AuNRs into one-, two- and if possible three-dimensional architectures. Several approaches have been developed to assemble AuNRs in two-orientation modes namely end-to-end and side-to-side. The present study self-assembly of the AuNRs has been achieved by anchoring β-cyclodextrin (β-CD) cavities to the nanorods surface. The host-guest chemistry of β-CD has been exploited to assemble the AuNRs. Our strategy was to use a guest molecule that is capable to link β-CD into 1:2 host-guest fashions to link up two β-CD capped nanorods. The guest molecule chosen for the present study was 1,10-phenanthroline. Linkage between the ends of rods leading to V-shaped rods dimmer assembly and side-to-side assembly was achieved by varying the extent of cyclodextrin capping of the AuNRs followed by the addition of linker, 1,10-phenanthroline. The formation of the assembly was characterized using UV-Visible-Near-IR Spectoscopy and Transmission Electron Microscopy. Layered Double Hydroxides (LDHs) Gold Nanorods (AuNRs) Charge Transfer Anionic Clays Mg-Al LDH-DDS Gold Nanorod Hybrids Charge-Transfer Complexes Inorganic Chemistry
178	Couplage RMN et rayonnement synchrotron à haute température pour l’étude de fluorures fondus : application aux fluorures de zirconium / Coupling NMR with Synchrotron radiation at high temperature for the study of molten fluorides : applied to zirconium fluorides Maksoud, Louis 14 October 2013 (has links) Les fluorures fondus sont utilisés dans les Réacteurs à Sels Fondus tels que le réacteur non modéré, à neutrons rapides, MSFR où le sel fondu LiF-ThF4 joue le rôle du combustible et du liquide caloporteur. La formation des produits de fissions (PF) tels que les lanthanides, au cours du fonctionnement de ce réacteur, peut modifier les propriétés physicochimiques du bain fondu. Il est ainsi important de caractériser le bain fondu de point de vue structural et dynamique afin de remonter à ses propriétés. En raison des problèmes de radioactivité liés au thorium, et des conditions requises liées aux méthodes spectroscopiques utilisées, le système étudié dans ce manuscrit est le LiF-ZrF4-LaF3 (le zirconium et le lanthane étant des PF potentiels). L'approche développée dans cette thèse combine des mesures par spectroscopies RMN et EXAFS à 850 °C avec des simulations de dynamique moléculaire. Dans le bain fondu, nous avons montré la coexistence de complexes à base de zirconium et de lanthane de différentes coordinences, dont les proportions et les interactions dépendent de la composition. En fonction de la teneur en ZrF4, les espèces [ZrF7]3- majoritaires évoluent peu mais se connectent davantage via des fluors pontants. L’ajout de LaF3 au mélange stabilise la coordinence 7 autour du zirconium et tend à enrichir l’environnement du lanthane en fluors. Un ordre à moyenne portée s’établit entre les différents complexes à base de zirconium et de lanthane par l’intermédiaire des fluors pontants. La dynamique des espèces est ralentie en fonction de l’ajout de ZrF4 et LaF3. Nous avons noté un effet important sur la structure et la dynamique des espèces à partir de 10% mol. LaF3 ajouté au mélange. Les données obtenues par cette approche originale de la chimie du bain fondu dans le RSF en présence des PF, sont fondamentales pour améliorer la séparation de ces derniers et optimiser le procédé. / Molten fluorides are used in Molten Salt Reactors MSR such as the non moderated fast reactor MSFR, where the molten salt LiF-ThF4 is the fuel and the coolant. The formation of fission products (FP) such as lanthanides, during the reactor operation, possibly modifies the physicochemical properties of the melt. It is therefore important to characterize the melt from the structural and the dynamics point of view in order to determine its properties. Because of problems related to the radioactivity of thorium, as well as requirements related to spectroscopic methods, the system studied in this thesis is the LiF-ZrF4-LaF3 (zirconium and lanthanum are possible FP). The approach followed in this thesis combines measurements by NMR spectroscopy and EXAFS at 850 °C with molecular dynamics simulations. In the molten salt, we have shown the existence of zirconium and lanthanum complexes with different coordination numbers, whose proportions depend on the composition. Depending on the content of ZrF4, [ZrF7]3- species are dominant but change slightly and are further connected between each other’s via bridging fluorine. The addition of LaF3 to the mixture stabilizes the 7 coordination number around the zirconium and tends to enrich the environment of lanthanum with fluorides. A medium-range order is established between the various complexes containing zirconium and lanthanum due to bridging fluorine. Species dynamics is slower when the amount of either ZrF4 or LaF3 is higher. We noted a significant effect on the structure and dynamics of species starting 10 mol%. LaF3 added to the medium. The data obtained by this novel approach concerning the chemistry of the molten salt in MSR containing FP, are fundamental to improve the separation of these products and optimize the process. Fluorures fondus MSFR Produits de fission RMN EXAFS Dynamique moléculaire Haute température Propriétés physicochimiques Structure Dynamique Complexes anioniques Molten fluorides MSFR Fission products NMR EXAFS Molecular dynamics High temperature Physicochemical properties Structure Dynamics Anionic complexes
179	Estudo da aplicação de hidróxidos duplos lamelares na remoção e liberação lenta de pesticidas / Study of aplication of Layered Double Hydroxides in removal and slow release of pesticides Lucelena Patricio Cardoso 13 September 2006 (has links) A extensa utilização de pesticidas na agricultura moderna tem contribuído para um aumento na contaminação do meio ambiente. Os Hidróxidos Duplos Lamelares (HDLs) ou argilas aniônicas, apresentam uma estrutura lamelar na qual uma variedade de ânions podem ser intercalados entre as lamelas através de interações eletrostáticas. Estes materiais lamelares podem ser utilizados em processos de adsorção/sorção e como suporte para a liberação lenta de compostos químicos. Assim, os principais objetivos deste trabalho foram: o estudo da sorção de ânions orgânicos de herbicidas ácidos 2,4-D, MCPA e Picloram utilizados na agricultura nacional, pela regeneração de HDLs de Mg-Al-CO3 calcinado e por troca aniônica em HDLs de Mg-Al-Cl. Para isso foram investigados a cinética do processo de sorção, além da determinação das isotermas em dois valores diferentes de pH. Assim, estes herbicidas foram intercalados em HDLs de Mg-Al, utilizando dois métodos de síntese indireta: regeneração do material calcinado e troca aniônica em solução, além do método de síntese direta por coprecipitação, sendo os materiais devidamente caracterizados. Todos os materiais obtidos, intercalados com cada um dos herbicidas, foram utilizados para o estudo da cinética de liberação dos mesmos em água. Os materiais obtidos por regeneração contendo cada um dos três herbicidas foram utilizados também no estudo da lixiviação em colunas de solo e no estudo de bio-ensaio com plantas, para testar a eficiência dos HDLs como suportes na liberação lenta dos herbicidas. A partir do estudo da cinética do processo de sorção dos ânions orgânicos presentes em solução utilizando HDLs de Mg-Al contendo cloreto ou carbonato após a calcinação, observou-se que a remoção dos ânions ocorreu através dos processos de troca aniônica no caso do HDL contendo cloreto, ou de regeneração da estrutura lamelar no caso do HDL calcinado. A intercalação dos ânions orgânicos na posição vertical foi verificada no processo de adsorção/sorção, e se mostrou dependente da concentração do herbicida em solução. O HDL calcinado apresentou a maior eficiência na remoção dos ânions da solução. Os herbicidas suportados em HDLs, apresentaram uma liberação em água mais lenta do que os mesmos em sua forma livre, e não se mostrou dependente do método de preparação da matriz utilizada. Os resultados dos estudos de lixiviação utilizando como matriz o HDL obtido por regeneração, demonstraram que os HDLs são bons suportes para os herbicidas pois apresentaram uma liberação lenta do ingrediente ativo, principlamente para o herbicida Picloram. O bio-ensaio mostrou que a forma de liberação dos herbicidas suportados foi eficiente no controle da germinação das sementes de plantas em aplicações pré-emergenciais. / The extensive use of pesticides in modern agriculture has been contributing to an increase in environmental contamination. Layered Double Hydroxides (LDHs), or anionic clays, bear a layered structure, and a variety of anions can be intercalated between these layers through electrostatic interactions. These layered materials can be used in adsorption/sorption processes and in the slow release of chemical compounds. So this work aims at studing the sorption of the acid herbicides bearing organic anions 2,4-D, MCPA and Picloram, used in national agriculture, through regeneration of calcined Mg-Al-CO3 LDH and anion exchange of Mg-Al-Cl ? LDH. For this purpose, the kinetics of the sorption process was investigated, and the determination of isotherms in two different pH values was carried out. The herbicides were intercalated in Mg-Al ? LDH using two indirect synthesis methods: regeneration of the calcined material and anion exchange in solution; besides the direct synthesis method by coprecipitation. The obtained materials were properly characterized. All the obtained materials, intercalated with each of the herbicides, were used in a kinetic release study in water. The materials obtained by regeneration were also used in a leaching and in a bioassay study, to test the efficiency of LDHs as supports for the slow release of herbicides. From the kinetic sorption process of the organic anions in solution using Mg-Al ? LDH containing chloride or carbonate after calcination, it was observed that the removal of anions occurred through an anionic exchange process in the case of the LDH containing chloride, or through regeneration of the layered structure in the case of the calcined LDH. The intercalation of organic anions in a vertical position was observed in the adsorption/sorption process, and it was shown to be dependent on the herbicide concentration in solution. The calcined LDH was the most efficient for removal of anions in solution. The herbicides supported on LDHs, presented a slower release in water than the same compounds in their free form, and the release behavior was not dependent on the methodology used for the preparation of the matrix. Leaching study results using the LDH obtained by regeneration as matrix demonstrated a slow release of the active ingredient, mainly for the Picloram herbicide. The bioassay showed that the release behavior of the supported herbicides was efficient in the control of plant seeds germination at preemergence applications. 24-D argilas aniônicas efeito memória herbicidas ácidos Hidróxidos Duplos Lamelares liberação lenta MCPA Picloram regeneração 24-D acid herbicde anionic clays Layered Double Hydroxides MCPA memory effect Picloram regeneration slow release
180	Synthesis And Environmental Applications Of Polyaniline And Its Nanocomposites Mahanta, Debajyoti 01 1900 (has links) (PDF) The present thesis is focused on the synthesis and environmental applications of polyaniline and its nanocomposites. It is organized in six chapters and brief discussions of the contents of the individual chapters are given below. Chapter 1 reviews two important water purification methods: adsorption and photocatalysis, which are widely discussed in literature. A general introduction to conducting polymers has been given and their photocatalytic activity has been described. Chapter 2 reports the application of polyaniline emeraldine salt for the removal of anionic dyes from aqueous solutions by adsorption. A possible mechanism for the anionic dye adsorption by PANI emeraldine salt has been proposed. The electrostatic interaction between the positively charged PANI backbone and dye anions is responsible for significant dye adsorption. The kinetic parameters for the adsorption of anionic dyes on PANI have also been determined. In Chapter 3, we investigate the adsorption and desorption of anionic dyes from aqueous solution by PANI doped with different protonic acids. PANI with three dopants, namely p-toluene sulfonic acid (PTSA), camphor sulfonic acid (CSA) and dodecyl benzene sulfonic acid (DBSA) were used to adsorb various dyes. The adsorbed dyes were desorbed from the polymer by using a basic aqueous solution. It was found that the adsorption of dye is dependent on the size and nature of the dopant acids. The influence of different dopants on the adsorption and desorption kinetic parameters was also examined. In chapter 4, the inherent property of PANI to adsorb dyes has been explored for the detection of dyes by electrochemical method. The changes in the CV of PANI film coated on Pt electrodes on addition of dye have been employed for detection of dye in aqueous solution. Furthermore, PANI coated stainless steel (SS) electrodes show a change in current intensity of Fe2+/Fe3+ redox peaks due to addition of dye in the electrolyte solution. Chapter 5 describes the synthesis and characterization of polyaniline-grafted-chitosan (CPANI) with different grafting ratios. The mechanical properties and the crystallinity of CPANI were investigated by means of nanoindentation and X-ray diffraction experiments, respectively. CPANI has been further self-assembled into multilayer thin film via versatile and simple layer-by-layer (LbL) approach. Negatively charged hyaluronic acid (HUA) was used as complementary polyelectrolyte for the self-assembly. LbL growth of the multilayer thin films has been monitored with UV-vis spectral analysis as well as by AFM. The formation of thin film has been further characterized by SEM. The pH responsive behavior of CPANI/HUA multilayer thin film has been investigated. Reusability of this thin film has been investigated by repeating the pH responsive experiments for 10 cycles. Chapter 6 is focused on the preparation of nanocomposite thin films of CPANI/PSS/TiO2 via LbL approach. LbL growth of this self-assembly was monitored by UV-vis spectral analysis and porous nature was observed from SEM images. Poly (styrene sulfonate) (PSS) was used as bridging layer between TiO2 nanoparticles and CPANI for the multilayer self-assembly. Incorporation of CPANI within this LbL self-assembly enhanced the dye degradation ability of the thin film by increasing the availability of dye molecules around the TiO2 nanoparticles. Furthermore, CPANI may act as a sensitizer to enhance the photocatalytic activity of TiO2. The effects of surface area of the multilayer thin film and amount of catalysts (TiO2 nanoparticles) incorporated in the self-assembly were described based on the kinetics of the dye degradation reactions. The same multilayer thin film can be efficiently used for dye degradation several times. The work presented in this thesis utilizes unique dye adsorption properties of PANI and its copolymers. The change in conductivity of PANI after dye adsorption and the electrochemical dye detection in aqueous medium promise the potential of PANI as a dye sensing material in waste water at very low concentration. The nanocomposites of CPANI/PSS/TiO2 present a novel material for photocatalysis. Polyaniline (PANI) Polyaniline Nanocomposites Anionic Dyes Polyaniline-Grafted-Chitosan (CPANI) Adsorption Photocatalysis Dyes - Detection Dyes - Adsorption Dye Contaminated Water - Purification Polyaniline - Adsorption Properties Polyaniline-Grafted-Chitosan Copolymer TiO2 Nanoparticles TiO2 Composites Chemical Engineering

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