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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

Pyridinium Salts: from Photoinduced Through-Space Electron Delocalization to Novel Spontaneous Reactions Causing Thermal DNA Damage

Tcyrulnikov, Nikolai 06 August 2019 (has links)
No description available.
42

Heterogen katalysierte Gasphasen-Epoxidation von Propen an FeOx/SiO2-Katalysatoren

Duma, Viorel 14 August 2001 (has links) (PDF)
Im Rahmen der vorliegenden Arbeit wurde eine neuartige Methode und die entsprechenden Katalysatoren für die heterogen katalysierte Gasphasen-Epoxidation von Propen entwickelt und optimiert. Das Propen wurde an FeOx/SiO2-Katalysatoren mit N2O als Oxidationsmittel epoxidiert. Die Katalysatoren wurden mittels XRD, TEM, XPS, Physi- und Chemisorption, TPR/TPO, TPD und IR untersucht und charakterisiert. Der Einfluß der Reaktionsbedingungen auf die Oxidationsergebnisse wurde bestimmt und Untersuchungen zum Reaktionsablauf durchgeführt. Es wurden Selektivitäten zu Propenoxid von 40-70%, bei Propenumsätzen von 3-12%, erreicht. Die maximalen erzielten PO-Ausbeuten betrugen über 5%, und sind damit den berichteten Ergebnisse aus der Literatur überlegen.
43

Développement et évaluation de nouveaux systèmes catalytiques pour une chimie plus respectueuse de l'environnement / Development and evauation of new catalytic systems for more environmentally chemistry

El Kadiri, Moulay Youness 11 October 2012 (has links)
La fonctionnalisation sélective de BINOL en position 6 ou 6 et 6' par des groupements 3 - (diméthylamino)prop-1-yn-1-yl est décrite. Cette méthode constitue une stratégie prometteuse pour le développement de nouveaux ligands recyclables. Les complexes de La et Yb correspondants ont été testés dans la réaction d’époxydation des cétones α, β-insaturées. Les complexes d’ytterbium sont les plus efficaces, fournissant les époxydes chiraux attendus avec 90 ou 93% d’excès énantiomérique en conditions homogène et hétérogène, respectivement.Dans le cadre de nos études, nous avons également évalué de nouveaux catalyseurs comportant un ion de manganèse penta-coordinnée [LMn(III)OH]ClO4 et [LMnCl](MnCl4)0,5. Ces complexes ont été testés dans la réaction d’époxydation des oléfines terminales utilisant H2O2/NaHCO3 et PhIO comme oxydant. Il s'avère que le complexe [LMn(III)OH]ClO4 est le catalyseur le plus efficace de la série. Une autre approche également été envisagée : oxyder une molécule d’eau présente dans la sphère de coordination du métal par le Cerium Ammonium Nitrate (CAN) et utiliser l’espèce oxydante ainsi générée pour oxyder des substrats. Nos études ont montré que cette stratégie était possible et permettait d’oxyder des substrats organiques. / The selective functionalization of BINOL in position 6 or 6 and 6’ with 3-(dimethylamino)prop-1-yn-1yl is described, and it constitutes a promising strategy for the development of a recyclable ligands. The corresponding La and Yb complexes were evaluated towards the epoxidation of α,β-unsaturated ketones. The Yb-complexes displayed an efficient activity, affording the expected chiral epoxides in up to 90 or 93% ee in homogeneous and heterogenous catalysis, respectively.As part of our studies, we also evaluated new catalysts with a penta-coordinated manganese ion [LMn(III)OH]ClO4 and [LMnCl](MnCl4)0.5. These complexes were tested in the epoxidation reaction of terminal olefins using H2O2/NaHCO3 and PhIO as an oxidant. It turns out that the complex [LMn (III) OH] ClO4 is the most efficient catalyst of the series. Another approach was also considered: oxidize a molecule of water present in the coordination sphere of the metal by Cerium Ammonium Nitrate (CAN) and use the generated oxidizing species to oxidize substrates. Our studies have shown that this strategy was feasible and allowed to oxidize organic substrates.
44

Epoxidation and di-hydroxylation of camelina sativa oil

Kim, Namhoon January 1900 (has links)
Master of Science / Department of Grain Science and Industry / Xiuzhi Susan Sun / Plant oil-based raw materials have become more attractive alternatives in polymer industry as fossil resources depletion and environmental concerns continue to arise. Camelina (camelina sativa L.) seed contains about 45% of oil and about 90% of the oil is unsaturated fatty acids such as linoleic acid, α-linolenic acid, and erucic acids. It also provides the advantages of low cost and low fertilizer demand. Functionalized oils such as epoxidized camelina oil (ECO) and di-hydroxyl camelina oil (DCO) can be used for resins, adhesives, coatings, etc. The objectives of this work were to synthesize and characterize ECO and DCO from camelina oil. The epoxidation reaction of camelina oil was completed with formic acid and hydrogen peroxide. Catalyst ratio, reaction time, and temperature effects on the epoxidation reaction were studied. The optimum epoxy content of 7.52 wt% with a conversion rate of 76.34% was obtained from camelina oil using excess hydrogen peroxide and a molar ratio of formic acid of less than 1 for 5 hours in 50 °C. Camelina oil yields higher epoxy content (7.52 wt%) than soybean oil (6.53 wt%); however, soybean oil had a higher conversion rate of 80.16% compared to camelina oil because of uniform fatty acids distribution. In this study, we found that epoxidation efficiency is significantly affected by fatty acids composition, structure, and distribution. DCO was synthesized from ECO with different reaction parameters. The ring opening of ECO was performed with water, perchloric acid, and THF as proton donor, catalyst, and solvent respectively. Hydroxyl value of DCO was measured, and the maximal hydroxyl value was 369.24 mg KOH/g. physical properties of DCO were characterized by acid value and moisture content; thermal properties of DCO were obtained using different scanning calorimeter (DSC), thermalgravimetric analysis (TGA). Amount of solvent and acid catalyst addition affected the hydroxyl value and residual acid in DCO. Heat capacity, phase transition temperatures, and thermal stability of DCO were obtained and showed higher values than ECO’s. The DCO showed higher peel adhesion when it was formulated with epoxidized soybean oils through UV curing because camelina oil allows higher epoxy content, which results in higher hydroxyl values.
45

Određivanje optimalnih uslova izvođenja procesa epoksidovanja biljnih ulja persirćetnom kiselinom / Determination of the Optimal Process Conditions for the Epoxidation of Vegetable Oils with Peracetic Acid

Govedarica Olga 31 March 2017 (has links)
<p>Hemijskim transformacijama se iz biljnih ulja dobijaju vredni &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; derivati, poput epoksidovanih biljnih ulja, koji se<br />koriste u hemijskoj i polimernoj industriji. Kvalitet, pa<br />time i primena epoksidovanih biljnih ulja, zavise od<br />sadržaja epoksidnih grupa u derivatizovanom ulju, koji bi<br />trebalo da je &scaron;to veći. Kako epoksidne grupe nastaju<br />oksidacijom dvostrukih veza u trigliceridima kao<br />dominantnoj grupi jedinjenja u biljnim uljima, pogodna<br />sirovina za epoksidovanje su visoko nezasićena ulja,<br />kakvo je laneno.<br />Proizvodnja epoksidovanih biljnih ulja zahteva izbor<br />takvih procesnih uslova pri kojima bi se postigli &scaron;to<br />potpunija konverzija dvostrukih veza i &scaron;to veća<br />selektivnost procesa u odnosu na epoksidnu grupu. Zato je<br />kao cilj ove doktorske disertacije postavljeno određivanje<br />optimalnih vrednosti procesnih uslova epoksidovanja<br />lanenog ulja persirćetnom kiselinom formiranom in situ iz<br />sirćetne kiseline i 30% vodenog rastvora vodonik<br />peroksida u prisustvu jonoizmenjivačke smole kao<br />katalizatora. Određivanje je izvedeno primenom<br />metodologije odzivne povr&scaron;ine, kao i kori&scaron;ćenjem u ovoj<br />disertaciji predloženih kinetičkih modela ispitivanog<br />reakcionog sistema, u oba slučaja sa maksimumom<br />relativnog prinosa epoksida kao funkcijom cilja.<br />Ispitivanje uticaja procesnih uslova, i to temperature,<br />molskog odnosa reaktanata, količine katalizatora i brzine<br />me&scaron;anja, na tok procesa epoksidovanja je bilo osnov za<br />definisanje graničnih vrednosti procesnih uslova unutar<br />kojih je tražen maksimum prinosa epoksida. Oblast dugih<br />vremena reagovanja, koja nije od interesa za industriju, je<br />izbegnuta adekvatnim izborom temperature.<br />Pri optimalnim vrednostima procesnih uslova<br />epoksidovanja lanenog ulja, određenim primenom<br />metodologije odzivne povr&scaron;ine, postignuto je dobro<br />slaganje očekivane i eksperimentalno određene vrednosti<br />maksimalnog relativnog prinosa epoksida, sa odstupanjem<br />od 3,28%.<br />Za potrebe određivanja optimalnih uslova izvođenja<br />procesa epoksidovanja biljnih ulja kori&scaron;ćenjem kinetičkih<br />modela, razvijena su tri pseudohomogena modela<br />ispitivanog trofaznog multireakcionog sistema. Pored<br />kinetike osnovnih reakcija formiranja persirćetne kiseline i&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; reakcije epoksidovanja dvostrukih veza triglicerida biljnog ulja,&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; kao i kinetike sporedne reakcije otvaranja epoksidne<br />grupe sa sirćetnom kiselinom, u predloženim modelima je<br />uzeta u obzir i raspodela sirćetne i persirćetne kiseline<br />između uljne i vodene faze sistema. Opisan je i uticaj<br />masno-kiselinskog sastava ulja, odnosno broja dvostrukih<br />veza u masno-kiselinskim lancima triglicerida, na kinetiku<br />reakcija. Za koeficijent raspodele sirćetne kiseline između<br />tečnih faza reakcionog sistema predložena je empirijska<br />korelacija koja je dala dobro slaganje izračunatih<br />vrednosti sa eksperimentalnim podacima. Kinetički<br />parametri modela su određeni fitovanjem<br />eksperimentalnih podataka o promenama količina<br />dvostruke veze i epoksidne grupe sa vremenom izvođenja<br />procesa epoksidovanja. Na osnovu statističkih pokazatelja<br />uspe&scaron;nosti fitovanja eksperimentalnih podataka, potvrđena<br />je prepostavka da je pseudohomogeni model publikovan u<br />literaturi unapređen uzimanjem u obzir pomenutih<br />fenomena raspodele komponenata reakcione sme&scaron;e i<br />masno-kiselinskog sastava sirovine pri modelovanju<br />reakcionog sistema epoksidovanja biljnih ulja<br />persirćetnom kiselinom.<br />Kori&scaron;ćenjem predloženih pseudohomogenih modela<br />reakcionog sistema za određivanje optimalnih uslova<br />izvođenja procesa epoksidovanja lanenog ulja in situ<br />formiranom persirćetnom kiselinom u prisustvu<br />jonoizmenjivačke smole, dobijeno je odstupanje od 5,51%<br />očekivane od eksperimentalno određene vrednosti<br />relativnog prinosa epoksida.<br />Bolje slaganje predviđene sa eksperimentalno određenom<br />vredno&scaron;ću relativnog prinosa epoksida u kontrolnom<br />eksperimentu je dobijeno primenom metodologije odzivne<br />povr&scaron;ine u poređenju sa kori&scaron;ćenjem kinetičkih modela pri<br />određivanju optimalnih vrednosti procesnih uslova. To je i<br />očekivano, s obzirom da regresiona jednačina kori&scaron;ćena u<br />okviru metodologije odzivne povr&scaron;ine bolje fituje relativni<br />prinos epoksida. Standardna devijacija relativnog prinos<br />epoksida za regresionu jednačinu je 8,9 puta niža od one<br />izračunate za kinetički model koji najbolje predviđa<br />optimalne procesne uslove epoksidovanja lanenog ulja<br />persirćetnom kiselinom.</p> / <p>Vegetable oils can be transformed into added value<br />products by various chemical modifications, such as<br />epoxidation. The epoxidized vegetable oils have a<br />wide range of applications in the chemical and<br />polymer industry. The quality, and consequently the<br />application, of epoxidized vegetable oil is influenced<br />by the epoxy group content. Since the epoxy groups<br />are formed by the oxidation of double bonds in<br />triglycerides, the main constituent of vegetable oils,<br />highly unsaturated vegetable oils, such as linseed<br />oil, are desirable raw materials.<br />The manufacturing of epoxidized vegetable oils<br />requires the optimization of the process conditions<br />in order to achieve complete conversion of double<br />bonds and high selectivity of the process in respect<br />to the epoxy groups. Therefore, the aim of this<br />doctoral thesis is to determine the optimal process<br />conditions for the epoxidation of linseed oil with<br />peracetic acid, formed in situ from acetic acid and<br />30% hydrogen peroxide in the presence of an ion<br />exchange resin as the catalyst. The optimal process<br />conditions were determined by response surface<br />methodology, as well as by using developed pseudohomogeneous<br />kinetic models that describe the<br />investigated reaction system. For both optimization<br />methods, the relative epoxy yield was selected as an<br />objective function to be maximized.<br />The effects of process conditions, such as<br />temperature, molar ratio of reactants, catalyst<br />amount and steering speed, on the kinetics of the<br />epoxidation were studied in order to define<br />constraints for the optimization. To avoid long<br />reaction times, which are not of interest in<br />manufacturing, an adequate temperature range was<br />selected. Under the optimized process conditions for the<br />epoxidation of linseed oil, which were determined<br />by response surface methodology, good agreement<br />between the calculated and experimentally<br />determined relative epoxy yields was achieved<br />within 3.28%.<br />Three models describing the three-phase multireaction<br />system of vegetable oil epoxidation with<br />peracetic acid were developed and further used for<br />the optimization. The models are pseudohomogeneous<br />with respect to the catalyst. Besides<br />the kinetics of the main reactions of peracetic acid<br />and epoxy group formation, the models take into<br />account the side reaction of the epoxy group opening<br />with acetic acid. The partitioning of the acetic acid<br />and peracetic acid between the oil and aqueous<br />phases is considered. In two proposed models, the<br />effect of fatty acid composition on the kinetics of the<br />process is also described by considering the number<br />of double bonds in the fatty acid chains. The<br />developed empirical correlation for the partition<br />coefficient for acetic acid between the liquid phases<br />shows good agreement between the calculated and<br />experimental data. The kinetic parameters of the<br />proposed pseudo-homogeneous models were<br />determined by fitting the experimentally determined<br />changes of the double bond and epoxy group<br />amounts with reaction time of the epoxidation.<br />Statistical values of the models` parameters<br />determination confirmed the hypothesis that the<br />pseudo-homogeneous model proposed in the<br />literature can be improved by considering the<br />partitioning phenomena and the effect of the oil fatty<br />acid composition on the kinetics of the vegetable<br />oils epoxidation with peracetic acid.<br />Under the optimized process conditions for the<br />epoxidation of linseed oil with peracetic acid formed<br />in situ in the presence of the ion exchange resin,<br />which were determined by using proposed pseudohomogeneous<br />models, the experimentally<br />determined relative epoxy yield was 5.51% lower<br />than the calculated.<br />Better agreement between the calculated and<br />experimentally determined values for the relative<br />epoxy yield, achieved under the optimal process<br />conditions, is obtained when the response surface<br />methodology (RSM) was applied as opposed to<br />when the kinetic models were used for the<br />determination of the optimal process conditions.<br />This is in accordance with better fitting of the<br />relative epoxy yield by RSM regression equation<br />than by kinetics models. Standard deviation of the<br />relative epoxy yield for RSM regression equation is 8.9 times lower than the standard deviation for the<br />most successful kinetic model used for prediction of<br />the optimal process conditions for the epoxidation of<br />the linseed oil by peracetic acid.</p>
46

Síntese e propriedades do óleo de soja funcionalizado com grupos hidroxílicos para aplicação em poliuretanos / Synthesis and properties of hydroxyl-functionalized soybean oil for application in polyurethanes

Pontel, Carlos Eduardo 27 January 2017 (has links)
Este trabalho teve como objetivo a modificação de óleo de soja por meio da sua funcionalização com grupos hidroxílicos visando seu uso na síntese de poliuretanos. As reações de funcionalização foram conduzidas em duas etapas, uma de epoxidação seguida de hidroxilação utilizando álcoois de baixo peso molecular como agente hidroxilante. Na primeira etapa do processo, a epoxidação, duas amostras foram obtidas variando o grau de funcionalidade de aproximadamente 2 mol de epóxido por mol de óleo epoxidado (F2) e, aproximadamente, 2,5 mol de epóxido por mol de óleo epoxidado (F2,5). Na segunda etapa, variou-se os álcoois utilizados como agentes hidroxilantes da amostra F2 entre metanol, etanol, isopropanol e 1-butanol; enquanto que a amostra F2,5 foi hidroxilada apenas com etanol. Os óleos modificados foram caracterizados por meio de espectroscopia na região do infravermelho (FTIR), espectroscopia de ressonância magnética nuclear de prótons (RMN 1H); determinação do percentual de epóxido, índice de hidroxila e de acidez, distribuição de massa molar e viscosidade dinâmica. Os resultados obtidos foram comparados com os valores típicos do óleo de mamona que por ser naturalmente hidroxilado é muito usado na síntese de poliuretanos. A caracterização estrutural permitiu comprovar a eficácia da síntese, apresentando evidências claras quanto às diferenças estruturais existentes entre as amostras funcionalizadas e o óleo de mamona. As técnicas de FTIR e RMN 1H mostraram a formação do grupo beta-hidroxi-éter, vicinal à hidroxila, de acordo com o tipo de álcool usado na hidroxilação de cada uma das amostras. Variações entre a estimativa do índice de hidroxila, através do percentual de epóxido e o índice de hidroxila experimental sugeriram reações paralelas durante a síntese. A influência da acidez durante o processo e a acidez final de cada uma das amostras também foi determinada. As curvas de GPC comprovaram umas das vias paralelas sugeridas com a formação de fases oligoméricas entre os triglicerídeos. A viscosidade final apresentou grande variação, principalmente em função do grupo beta-hidroxi-éter formado em cada caso, do grau de funcionalidade, além da redução do teor de insaturações do óleo modificado. Dados sobre a energia de ativação de escoamento do fluido em função da temperatura mostraram que o fator mais significativo na variação da viscosidade é o índice de hidroxila final das amostras. As amostras sintetizadas foram usadas na polimerização de poliuretanos. A reatividade das amostras foi determinada através de ensaios de cura acompanhados por FTIR, além de uma caracterização mecânica dos poliuretanos finais feita por Análise Dinâmico Mecânica (DMA). As amostras apresentaram uma alta variação quanto à reatividade no processo de polimerização. Os ensaios de DMA mostraram a relação direta entre a temperatura de transição vítrea e o grau de funcionalidade, além do efeito plastificante gerado pelas cadeias livres contidas na fase flexível formada pelos triglicerídeos parcialmente funcionalizados. / The objective of this work was the modification of soybean oil by its functionalization with hydroxyl groups for its use in the synthesis of polyurethanes. Functionalization reactions were conducted in two steps, one epoxidation followed by hydroxylation using low molecular weight alcohols as hydroxylating agent. In the first step, two samples were obtained varying the degree of functionality of approximately 2 moles of epoxide per mole of epoxidized oil (F2) and approximately 2.5 moles of epoxide per mole of epoxidized oil (F2,5). In the second step, the process was varied using different alcohols as hydroxylating agents of the F2 sample, which were methanol, ethanol, isopropanol and 1-butanol; while the F2.5 sample was hydroxylated only with ethanol. The modified oils were characterized by Infrared Spectroscopy (FTIR), Proton Nuclear Magnetic Resonance Spectroscopy (1HNMR), determination of the percentage of epoxide, hydroxyl and acidity index, molar mass distribution and dynamic viscosity (Brookfield viscosity). The obtained results were compared to the typical values of castor oil which, because it is naturally hydroxylated, is widely used in the synthesis of polyurethanes. The structural characterization allowed proving the efficacy of the synthesis, presenting clear evidence regarding the structural differences between the functionalized samples and castor oil. The results from FTIR and 1HNMR techniques showed the formation of the beta-hydroxyl ether group, side to the hydroxyl, according to the type of alcohol used in the hydroxylation of each of the samples. Variations between the estimation of the hydroxyl number, through the percentage of epoxide and the experimental hydroxyl number, suggested parallel reactions during the synthesis. The influence of the acidity during the process and the final acidity of each of the samples were also determined. The GPC curves confirmed one of the parallel pathways suggested with the formation of oligomeric phases between the triglycerides. The final viscosity showed great variation according to the beta-hydroxyl ether group formed in each case, the degree of functionality and the reduction of unsaturation content in the modified oil. Activation energy values of fluid flow as a function of temperature showed that the most significant factor in the viscosity variation is the final hydroxyl number of samples. The synthesized samples were used in the polymerization of polyurethanes. The reactivity of the samples was determined by curing tests monitored by FTIR technique, in addition to a mechanical characterization of final polyurethanes by Dynamic Mechanical Analysis (DMA). The samples showed a high variation in reactivity in the polymerization process. The DMTA tests showed the relationship between the glass transition temperature and the degree of functionality in addition to the plasticizing effect generated by free chains contained in the flexible phase formed by the partially functionalized triglycerides.
47

Nanolithographie catalytique par microscopie à force atomique : étude des paramètres physico-chimiques / Catalytic atomic force microscopy nanolithography : study of physico-chemical parameters

Mesquita, Vincent 03 November 2016 (has links)
Les procédés lithographiques sont de nos jours très utilisés au sein de l’industrie de la microélectronique pour réaliser des matériaux fonctionnels de taille nanométrique. L’obtention de composants de taille de plus en petite (<100 nm) nécessite la mise en œuvre de nouveaux procédés de fabrication. Les travaux de recherches réalisés dans cette thèse portent sur l’étude d’un nouveau concept de lithographie par microcopie à force atomique (AFM). L'objectif principal est d'utiliser la pointe d’un AFM comme outil pour promouvoir des réactions catalysées sur une zone bien définie d’une surface greffée. De cette manière, diverses molécules ont pu être greffées sélectivement et spatialement pour conduire à des objets finis en 3 dimensions. Afin de mieux comprendre le mécanisme réactionnel, différents paramètres physico-chimiques ont été étudiés dans la première partie : vitesse de balayage de la pointe, force appliquée, distance interligne lors de la gravure du motif, largeur de lignes limites, durée de vie de la pointe catalytique et influence de la flexibilité du catalyseur présent sur la pointe. La deuxième partie consiste à la réalisation de nanostructures avec des molécules aux propriétés physico-chimiques particulières (optique, électrique, catalytique) ainsi qu’à la construction de nanostructures tridimensionnelles. Quelques résultats marquants sont l’obtention d’une largeur de ligne limite de 25 nm, d’une surface de greffage minimum de 480 µm² et d’une structure de forme pyramidale composée de trois niveaux moléculaires distincts. / Lithography processes are widely used in the microelectronics industry for the realization of functional materials of nanometric size. To obtain components increasingly small (<100 nm) the development of new manufacturing processes is requires. The research presented in this thesis concerns the study of a new concept of lithography by Atomic Force Microscopy (AFM). The main objective is to use the tip of an AFM as a tool to promote catalysed reactions on a well defined zone of a grafted surface. In this way, diverse molecules could be grafted selectively and spatially to form three dimensioned objects. To better understand the reaction mechanism, different physico-chemical parameters were studied in the first part: the scanning speed of the tip, the strength applied, the interline spacing during the engraving pattern, the width lines limits, the life time of the catalytic tip and the influence of the catalyst flexibility coated to the tip. The second part consists in the realization of nanostructures with molecules that have particular physico-chemical properties (optical, electric, catalytic) and the construction of three-dimensional nanostructures. Some pertinent results are the achievement of line width of 25 nm, a minimum grafted surface of 480 µm² and the formation of a structure of pyramidal shape constituted of three different molecular levels.
48

Elaboration de nouvelles métalloenzymes artificielles pour des réactions d'oxydation sélectives selon différentes stratégies / Elaboration of new artificial metalloenzymes for selective oxidation reactions with various strategies

Allard, Mathieu 20 October 2011 (has links)
Devant la nécessité de préservation de l’environnement, la chimie devra de plus en plus devenir « verte ». Le développement de catalyseurs bio-hybrides est une voie prometteuse vers une chimie verte. En effet, ces catalyseurs combinent à la fois les avantages de la catalyse homogène (large gamme de réactivité) et ceux de la catalyse enzymatique (réaction en milieux aqueux, optimisation possible par génie biotechnologique). Ces nouveaux types de catalyseurs éco-compatibles semblent être à ce jour une alternative intéressante à la catalyse chimique classique.Cette thèse s’inscrit dans le cadre du développement de nouveaux catalyseurs bio-hybrides appelés Hémozymes, basés sur l’insertion non covalente de complexes métalliques hydrosolubles (responsables de l’activité catalytique), au sein d’une protéine hôte : la Xylanase A (pouvant induire une régio/stéréo/chimio-sélectivité).Pour cette étude, nous avons synthétisé différents complexes métalliques de taille variable (porphyrines, salens et salophens) métallés soit par du fer soit par du manganèse. L’étude de leur association avec la Xln A ainsi que les essais de leur activité catalytique nous ont permis d’aboutir à des résultats intéressants, d’une part pour la réaction d’oxydation du thionanisole par le peroxyde d’hydrogène, d’autre part pour l’oxydation d’alcènes aromatiques par l’oxone (KHSO5). Nous avons ainsi obtenu deux métalloenzymes artificielles remarquables, l’une capable de catalyser l’oxydation énantiosélective du thioanisole par le peroxyde d’hydrogène (84% de rendement, 40% d’excès énantiomérique en faveur de l’isomère S), l’autre capable de catalyser l’époxydation asymétrique du paraméthoxy-styrène par KHSO5 (17% de rendement, 80% d’excès énantiomérique en faveur de l’isomère R). Enfin, de nouvelles stratégies pour concevoir des catalyseurs bio-hybrides ont également été envisagée comme le greffage covalent de complexes métalliques au sein d’une protéine hôte, ou encore l’utilisation d’une forte affinité ligand-protéine (comme les interactions de type inhibiteur) pour enfouir un cofacteur métallique au sein d’une protéine. / In those days, the preservation of the environment is a huge challenge, so chemistry has to become more "Green". The development of bio-hybrid catalysts is a promising way towards a green chemistry. Indeed, these catalysts both combine the benefits of homogeneous Catalysis (wide range of reactivity) and those of enzyme catalysis (reaction in aqueous media, possible optimization by biotechnological engineering). These new kind of eco-compatible catalyst seem to be an interesting alternative to classical chemical catalysis to this day.For this study, we have synthesized various complexes with various size (porphyrins, salens and salophens) metalled by iron or manganese. The study of their association with Xln A and the catalytic activity assays allowed us to achieve interesting results, on the one hand to the oxidation of the thionanisole by hydrogen peroxide, on the other hand for the oxidation of aromatic alkenes by the oxone (KHSO5).This thesis is about the development of new bio-hybrid catalysts called Hemozymes, based on the non-covalent insertion of water-soluble metal complexes (responsible for the catalytic activity), inside a host protein: Xylanase A (which can induce a regio/stereo/chemo-selectivity).We have thus obtained two remarkable artificial metalloenzymes, one able to catalyze the enantioselective oxidation of thioanisole by hydrogen peroxide (84% yield, 40% of enantiomeric excess for the S isomer), the other able to catalyze the asymmetric epoxidation of paramethoxy-styrene by KHSO5 (17% yield, 80% enantiomeric excess for the R isomerFinally, new strategies to develop bio-hybrid catalysts have also been considered, such as covalent linkage of metal complexes within a host protein or the use of a high ligand-protein affinity (such as the interactions of inhibitor with proteins) to introduce the metal cofactor inside the protein pocket.
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Surface Engineering of Mesoporous Silica for Ti-Based Epoxidation Catalysts / Ingénierie des Surfaces de Silice Mésoporeuse pour Ti-Based catalyseurs d'époxydation

Fang, Lin 13 November 2012 (has links)
Les sites actifs de l’époxydation des alcènes dans les catalyseurs au titane supporté sur silice sont des ions Ti(IV) isolés. La stratégie d’isolation de site adoptée ici consiste à greffer l’isopropoxyde de titane par réaction avec les groupements silanol de surface dont la densité est diminuée par « capping » chimique remplaçant le traitement thermique usuel, très énergivore. La technique du pochoir moléculaire à motifs périodiques (PMP) a été appliquée pour forcer l’isolation de site. Dans les silices poreuses mesostructurées par un tensio-actif, c’est ce dernier, partiellement extrait, qui génère l’effet PMP lors du capping. Son élimination à l’étape suivante libère des îlots de groupements silanol sur lesquels sont greffés les ions Ti(IV). Une étude spectroscopique quantitative menée en parallèle par FT-IR et par RMN du solide du 29Si démontre que le pochoir organique inverse formé de groupement organosilyls greffés est conservé à toutes les étapes de synthèse. La spectroscopie UV en corrélation avec l’activité catalytique en époxydation du cyclohexene montent que ces surfaces originales favorisent un nombre beaucoup plus grand de sites mononucléaires isolés que les surfaces de silice non modifiées. La démonstration est faite avec une fonction de capping dipodale, 1-2-ethanebis(dimethylsilyl) (EBDMS), beaucoup plus stable que le monopodal classique, trimethylsilyl (TMS). Par ailleurs, le pochoir organique inverse issu du TMS ou de EBDMS voit sa stabilité augmentée par traitement thermique tout en préservant son effet dispersant pour le titane. Pour ce faire, un suivi quantitatif de la décomposition des organosilanes greffés a été réalisé par RMN du solide du 29Si. Finalement, une description affinée et quantitative du mode de greffage du titane a été réalisée par simulation des spectres UV sur une série de catalyseurs supposant 5 types d’espèces comprenant les sites isolés et les clusters, les derniers se différenciant par leur gamme de taille. / The active sites for epoxydation of alkenes in silica supported titanium catalysts are isolated Ti(IV) ions. The strategy for site isolation consists here to graft titanium isopropoxyde by reaction with surface silanol groups, the density of which is decreased by chemical capping instead of the energy consuming thermal treatment. The molecular stencil patterning technique (MSP) is applied to enforce site isolation. In mesostructured porous silicas, the partly extracted templating surfactant plays the role of a MSP mask during capping. Then, the elimination of the remaining surfactant liberates silanol islands for the grafting of Ti(IV) ions. Quantitative FT-IR and 29Si MAS-NMR studies reveal that the inverse organic stencil made of grafted organosilyls groups is maintained at each synthesis steps. Diffuse reflectance UV spectroscopy in correlation with the catalytic activity in epoxidation of cyclohexene show that these original surfaces favor the formation of a much larger number of isolated mononuclear sites than the unmodified silica surfaces. The demonstration is obtained using a dipodal organosilyl function, 1-2-ethanebis (dimethylsilyl) (EBDMS) that is much more stable than the classic and monopodal, trimethylsilyl (TMS). Besides, it is shown that the inverse organic stencil (from EBDMS or TMS) is stabilized further by thermal treatment while its dispersive effect on titanium can be preserved. The proof relies on a quantitative 29Si solid State NMR study. Finally, a refined description of the grafting mode of titanium was realized by simulation of the UV spectra of a large series of catalysts assuming only 5 different types of species including isolated species and clusters differentiated by the range of sizes.
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Reações químicas em óleo de soja utilizando celadonita

Zarth, Cíntia Salomão January 2008 (has links)
Neste trabalho foi realizado o estudo de transformações de óleo de soja com o catalisador VO(acac)2 em meio homogêneo e heterogêneo. Estes processos catalíticos estão de acordo com os conceitos de química limpa, no sentido de economia de reagentes e diminuição de subprodutos, enquanto que a matéria-prima, óleo vegetal, foi escolhida por ser de fonte renovável, sustentável e abundante no Rio Grande do Sul e no Brasil. A reação de transesterificação do óleo de soja foi realizada através do sistema VO(acac)2 e VO(acac)2 suportado em uma argila celadonita, cujo depósito localiza-se na região de Ametista do Sul – RS. O sistema heterogêneo foi caracterizado pelas técnicas de DRX, BET, BJH, ATG, FTIR, CHN, MEV/EDS e ICP/OES. O teor de vanádio impregnado na argila foi de 1,06 %. O melhor rendimento das reações de transesterificação foi de 36 % e 30 % para os sistemas homogêneo e heterogêneo, respectivamente, para as condições de 2 % em mol e 5 % em mol de vanádio, a 65 ºC de temperatura e 48 horas de reação. Alguns testes foram realizados em reações de epoxidação. Do sistema celadonita/VO(acac)2 foi obtido conversão de 44 %, 15 % de monoepóxido e 34 % de seletividade, em 3 horas de reação. A avaliação quantitativa das reações foi realizada por RMN de 1H. / This work presents the study of soybean oil reactions with VO(acac)2 in homogeneous and heterogeneous catalytic systems. The catalytic systems follow the green chemistry principles of economy of reagents and reduction in sub-products of the reaction while the starting material, soybean oil, was chosen as a renewable source, sustainability of its crop and abundancy. Soybean oil transesterification reactions were done with the catalytic system VO(acac)2 and VO(acac)2 supported in celadonita, which is a mineral found in Ametista do Sul / RS. The heterogeneous system was characterized by the XRD, BET, BJH, TGA, FTIR, CHN, SEM/EDX and ICP/OES techniques. The amount of vanadium impregnated in the clay it was 1,06%. The best conditions for transesterification reaction gave 36 % yield for homogeneous system and 30 % yield for heterogeneous system, using 2 % molar and 5 % molar of vanadium, respectively, at 65 ºC of temperature and 48 hours of reaction. Some tests on epoxidation reactions were performed. With celadonita/VO(acac)2 system it was obtained a conversion of 44%, 15% of monoepoxide and 34 % of selectivity after 3 hours of reaction. The quantitative evaluation of the reactions was made by 1H NMR.

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