Les céramides sont des lipides de la classe des sphingolipides issus de la N-acylation d’une base sphingoide par un acide gras. Ces lipides et leurs analogues suscitent un grand intérêt comme composants actifs dans les industries pharmaceutique et cosmétique. Parmi les biocatalyseurs capables de réaliser la synthèse de ce type de lipide, la lipase B de Candida antarctica semble être l’enzyme la plus adaptée à la production de « pseudo-céramides » à partir d’amino-polyols. Dans ce contexte, nous avons abordé l’étude de l’acylation de composés de type « amino-alcool »catalysée par la lipase B de Candida antarctica, en gardant à l'esprit une approche fondamentale afin d’élargir les connaissances actuelles sur ce sujet. La première partie de notre travail a ainsi traité de l’étude cinétique de l’acylation de composés monofonctionnels afin de déterminer les mécanismes réactionnels et l’énantio sélectivité de la lipase B de Candida antarctica pour les réactions de N-acylation et de O-acylation. Les parties suivantes de notre travail ont porté sur une étude structure-réactivité du substrat accepteur d’acyle et sur l’étude de l’influence du solvant utilisé (solvant organique ou liquide ionique) afin de déterminer les facteurs clés influençant la chimio sélectivité et la régio sélectivité de la lipase B de Candida antarctica lors de l’acylation de composés multifonctionnels de type « amino-alcool ». Finalement, à partir des connaissances acquises dans les différentes parties, nous avons développé et optimisé un procédé de synthèse enzymatique de « pseudo-céramides » (O,N-diacyl aminopropanediols) mis en oeuvre en réacteur continu à « lit fixe ». / Ceramides are lipids from the sphingolipide class derived from the N-acylation of a sphingoid base from a fatty acid. These lipids and their analogs are compounds of interest used as active components in pharmaceutical and cosmetic industries. Among biocatalysts able to synthesize this type of lipids, Candida antarctica lipase B appears to be the most appropriate enzyme for the production of "pseudo-ceramides" derived from amino-polyols. In this context, we have studied the acylation of amino-alcohol-like compounds catalyzed by Candida antarctica lipase B, keeping inmind a fundamental approach to expand the current knowledge on this subject. The first part of our work aimed to determine the reaction mechanisms and the enantio selectivity exhibited by Candida antarctica lipase B during O-acylation and N-acylation reactions, by conducting a kinetic study of mono functional compound acylation. In the following parts of our work, we performed a structurere activity study of the acyl acceptor substrate and evaluated the effect of the solvent used (organic solvent or ionic liquid) to determine the key factors influencing the chemo selectivity and the regio selectivity of the Candida antarctica lipase B-catalyzed acylation of polyfunctional amino alcohol compounds. Finally, starting from the knowledge acquired in the previous parts, we have developed and optimized an enzymatic process of “pseudo-ceramide” (O,N-diacylaminopropanediol) synthesis performed in a continuous packed-bed reactor.

Iron platinum (FePt) has attracted growing interest because of its high Curie temperature, magneto-crystalline anisotropy and chemical stability. Nanoparticles (NPs) made of this alloy are promising candidates for a wide range of biomedical applications including magnetic separation, magnetic targeted drug delivery, hyperthermia for cancer therapy and also as magnetic resonance imaging (MRI) contrast agents. This thesis presents the synthesis, functionalization and characterization of FePt NPs along with a toxicity study and an investigation into their application as MRI contrast agents. Regarding their synthesis, different approaches have been explored including the co-reduction of Fe and Pt precursors in an aqueous media, the thermal decomposition in a conventional high-boiling solvent such as benzyl ether, and in low-melting organic salts (ionic liquids). The data revealed an inhomogeneous composition distribution of Fe and Pt between particles obtained in aqueous media, due to the iron salts hydrolysis, and a mismatch in the co-reduction kinetic of the two metal precursors. While the iron content in the NPs could be increased by using more hydrolytically stable iron precursors or stronger reducing agents, there are remaining limiting parameters which prevent further Fe content increase in NPs. In contrast, by excluding the water from the reaction system and using a Fe²⁻ iron precursor, homogenous 1:1 Fe to Pt ratio NPs can be obtained through a modified thermal decomposition pathway in benzyl ether. Based on the study of synthesis in this conventional chemical, the potential of ionic liquids (ILs) to be used as novel solvents for FePt NPs synthesis was further explored. It was then demonstrated that ionic liquids (ILs) can not only be used as a solvent for synthesis of FePt NPs, but also can provide an exciting alternative pathway to direct synthesis fct-FePt NPs. In the context of the bioapplication of FePt NPs, a family of FePt NPs was specifically designed to enhance their MRI contrast agents properties. In contrast with previous reports, this thesis demonstrates that FePt NPs can be made non-toxic and provides the first data on their cellular uptake mechanisms. A six times increase in the FePt based T₂ contrast properties compared to clinical iron oxide NPs is reported. The relationship between the MRI contrast properties and the NPs architecture is explored and rationalised as the basis for the design of NPs as enhanced MRI contrast agents. Finally, the first observations of cellular and in vivo MR imaging with FePt NPs is also reported. This study opens the way for several applications of FePt NPs such as regenerative medicine and stem cell therapy, thus providing a bio-platform to develop novel diagnostic and therapeutic agents.

L'objectif de ces travaux était de synthétiser, caractériser et étudier le potentiel d'une sélection de liquides ioniques, pour la séparation de l'éthane et de l'éthène. L'influence dans l'absorption de l'éthène de la présence de trois cations métalliques, le lithium (I), le nickel (II) et le cuivre (II) dans un liquide ionique était également étudiée. Les liquides ioniques sélectionnés sont basés sur le cation imidazolium contenant des groupes fonctionnels au niveau de la chaine alkyle latérale. Les anions choisis sont le bis(trifluorométhylsulfonyl)imide, [NTf2], la dicyanamide, [DCA] et le méthylphosphite, [C1HPO3]. Sachant qu'un solvant de séparation idéale doit avoir une capacité d'absorption et une sélectivité de séparation élevées, une faible viscosité, une haute stabilité thermique et une cinétique d'absorption rapide pour le gaz sélectionné. Pour évaluer ces propriétés pour les milieux sélectionnés, plusieurs paramètres ont été déterminés la densité et la viscosité des liquides ioniques ainsi que l'absorption de chaque gaz dans les liquides ioniques. L'absorption de l'éthane et de l'éthène dans les liquides ioniques purs ainsi que dans les solutions de liquide ionique + sel métallique a été mesurée dans une gamme de températures comprises entre 303.15 K et 353.15 K et pour des pressions proches de l'atmosphérique. La sélectivité idéale des liquides ioniques pour l'absorption de l'éthane par rapport à l'éthène a ainsi pu être déterminée. La détermination de l'absorption en fonction de la température a permis d'accéder aux propriétés thermodynamiques de solvatation de ces gaz dans des liquides ioniques et à comprendre la manière dont les liquides ioniques interagissent avec ces solutés comment les liquides ioniques se structurent autour de ces molécules / The goal of this research was to synthesize, characterize and study the potential of selected ionic liquids as solvents for the separation of ethane and ethene. The influence on ethene absorption of the presence of three different metallic cations, lithium (I), nickel (II) and copper (II) in an ionic liquid was also studied. The selected ionic liquids are based in the imidazolium cation containing a functionalization in the alkyl side chain. The chosen anions were the bis(trifluorosulfonyl)imide, [NTf2], the dicyanamide, [DCA] and the methylphosphite, [C1HPO3]. Several parameters were taken into account for this primary evaluation, such as measurements of density, viscosity and absorption of each gas in the ionic liquids, since an ideal separation solvent should have a high absorption capacity and gas selectivity, low viscosity, high thermal stability and fast absorption kinetics for the selected gas. The absorption of the 2 gases in the pure ionic liquids and ionic liquid + metallic salt solutions was measured in the temperature range between 303.15 K and 353.15 K and for pressures close to atmospheric. The ideal selectivity of the ionic liquid for the absorption of ethane compared to ethene was determined. The determination of the gas solubility in function of the temperature allowed access to the thermodynamic properties of solvation of the gases in the ionic liquids, and a deeper understanding of the gas-ionic liquid interactions and the structure of the solution

Abstract The present thesis exploits advanced liquid and gas NMR methods for the characterization of various interesting materials. The methods used to study the structural properties of thermally modified wood, ionic liquids, cements, shales, and porous organic cages include MRI, NMR cryoporometry, Laplace NMR, multidimensional Laplace NMR, as well as ¹²⁹Xe and ¹⁹F NMR. The commonality factor in all the studies is the usage of either inherent or introduced liquid or gas molecules to probe the topical materials. The MRI method was utilized to visualize the water absorption phenomena in the thermally modified pine wood. High-resolution images made it possible to observe the spatial distribution of free water and the changes in the rate of absorption of water in wood samples modified at different temperatures. The images also helped to resolve the individual resin channels. T₂ maps enabled us to observe the changes in the relaxation values of free water in thermally modified wood as compared to their unmodified reference wood samples. The multidimensional Laplace NMR methods were exploited to study the structural and dynamical properties of a novel halogen-free, boron-based ionic liquid (hf-BIL). NMR self-diffusion (D) experiments showed the presence of two coexisting dynamic phases in hf-BIL. Multidimensional D − T₂ correlation experiments made it possible to determine the T₂ relaxation times of the slow and fast diffusing phases. T₂ − T₂ relaxation exchange measurements allowed quantifying the exchange rates of anions and cations between the phases. Moreover, the theoretical modeling of the experimental data revealed that the slow diffusing phase was composed of anion-cation aggregates, while the fast diffusing phase was comprised of free anions and cations. ¹²⁹Xe NMR analysis of the xenon adsorbed in the cements and shales helped us to determine their porous structures. The method exploits the high sensitivity of the chemical shift of ¹²⁹Xe to its local environment. The chemical shift value of ¹²⁹Xe enabled us to estimate the size of the mesopores in the cement samples. The exchange spectroscopy (EXSY) measurements were used to determine the exchange rates between the free gas and mesopores of the cement samples. ¹²⁹Xe NMR spectra of the shale samples provided information about pore sizes and paramagnetic compounds. ¹H NMR cryoporometry measurements of the shale samples immersed in acetonitrile made it possible to analyze the pore size distribution ranging from 10 to over 100 nm. Moreover, T₂ − T₂ exchange measurements helped us to quantify the exchange rates of acetonitrile in the shale samples. Xenon and SF₆ were used as internal reporters to gain versatile information on adsorption phenomena in the cage and window cavities of the crystalline porous organic cages. ¹²⁹Xe NMR analysis of the adsorbed xenon helped us to determine the diffusion coefficients and activation energy of diffusion as well as thermodynamic parameters. With the help of T₂ relaxation time values, it was possible to estimate the exchange rates between cage and window cavities. Chemical exchange saturation transfer (CEST) experiments resolved a window cavity site, which arises from crystal defects in porous organic cages. In addition, ¹⁹F NMR analysis made it possible to estimate the relaxation rates and diffusion coefficients of SF₆ gas in porous organic cages. Modelling of the T₁, T₂ and diffusion data confirmed that the cage to window exchange is the completely dominating mechanism for ¹²⁹Xe T₂ relaxation. T₁ relaxation is dominated by diffusion modulated dipole-dipole relaxation (DDinter) and chemical shift anisotropy (CSA) relaxation due to local cavity mobility. Whereas, in case of SF₆ T₂ data, the dominating mechanism is diffusion modulated dipole-dipole relaxation and for T₁ the local tumbling of SF₆ in cage cavity is the key dynamics behind the dipole-dipole and CSA mechanisms. / Original papers The original publications are not included in the electronic version of the dissertation. Javed, M. A., Kekkonen, P. M., Ahola, S., & Telkki, V.-V. (2015). Magnetic resonance imaging study of water absorption in thermally modified pine wood. Holzforschung, 69(7), 899–907. https://doi.org/10.1515/hf-2014-0183 Javed, M. A., Ahola, S., Håkansson, P., Mankinen, O., Aslam, M. K., Filippov, A., … Telkki, V.-V. (2017). Structure and dynamics elucidation of ionic liquids using multidimensional Laplace NMR. Chem. Commun., 53(80), 11056–11059. https://doi.org/10.1039/c7cc05493a http://jultika.oulu.fi/Record/nbnfi-fe2017102750335 Javed, M. A., Komulainen, S., Daigle, H., Zhang, B., Vaara, J., Zhou, B., & Telkki, V.-V. (2019). Determination of pore structures and dynamics of fluids in hydrated cements and natural shales by various ¹H and ¹²⁹Xe NMR methods. Microporous and Mesoporous Materials, 281, 66–74. https://doi.org/10.1016/j.micromeso.2019.02.034 http://jultika.oulu.fi/Record/nbnfi-fe2019041712678 Komulainen, S., Roukala, J., Zhivonitko, V. V., Javed, M. A., Chen, L., Holden, D., … Telkki, V.-V. (2017). Inside information on xenon adsorption in porous organic cages by NMR. Chemical Science, 8(8), 5721–5727. https://doi.org/10.1039/C7SC01990D http://jultika.oulu.fi/Record/nbnfi-fe201709288804 Håkansson, P., Javed, M. A., Komulainen, S., Chen, L., Holden, D., Hasell, T., … Telkki, V.-V. (2019). NMR relaxation and modelling study of the dynamics of SF₆ and Xe in porous organic cages. Manuscript.

Les matériaux dits de conversion à base de Sb et Sn, utilisés comme électrodes, apparaissent comme des composés particulièrement intéressants compte tenu de leur forte capacité théorique. Le matériau TiSnSb a été récemment développé en tant qu’électrode négative pour batteries lithium-ion. Ce matériau est capable d’accueilir, de façon réversible, 6,5 Li par unité formulaire, ce qui correspond à une capacité spécifique de 580 mAh/g. Dans le domaine des batteries lithium-ion, les propriétés de l’interface électrode/électrolyte (« solid electrolyte interphase », SEI), formant une couche de passivation protectrice à la surface des électrodes sont considérées comme essentielles pour les performances au sens large des batteries. Cet aspect représente le sujet majeur traité dans ce travail de thèse. Dans cet optique, nous avons tout d'abord étudié les propriétés électrochimiques de l'électrode TiSnSb sous divers aspects, dont les effets du régime de cyclage, l’influence de la nature des additifs au sein de l’électrolyte ainsi que l’utilisation de liquides ioniques à température ambiante (RTILs). En particulier, un système d'électrolyte à base de RTILs a été développé et optimisé vis-à-vis des performances électrochimiques. Afin de caractériser l’interface électrode-électrolyte, deux techniques de caractérisation majeures ont été utilisées : la Spectroscopie Photoélectronique à Rayonnement X (XPS) et la Spectroscopie d'Impédance électrochimique (EIS). Cette étude a permis de cibler certains paramètres essentiels liant les aspects performances électrochimiques à la nature de l’interface électrode-électrolyte. / In the past decades, the need for portable power has accelerated due to the miniaturization of electronic appliances. It continues to drive research and development of advanced energy systems, especially for lithium ion battery systems. As a consequence, conversion materials for lithium-ion batteries, including Sb and Sn-based compounds, have attracted much intense attention for their high storage capacities. Among conversion materials, TiSnSb has been recently developed as a negative electrode for lithium-ion batteries. This material is able to reversibly take up 6.5 Li per formula unit which corresponds to a specific capacity of 580 mAh/g. In the field of lithium-ion battery research, the solid electrolyte interphase (SEI) as a protective passivation film formed at electrode surface owing to the reduction of the electrolyte components, has been considered as a determinant factor on the performances of lithium-ion battery. Thus it has been a focused topic of many researches. However, little information can be found about the formation and composition of the SEI layer formed on TiSnSb conversion electrode at this time. With the aim to investigate the influences of the SEI layer on the performances of composite TiSnSb electrode, we first studied the electrochemical properties of the electrode from various aspects, including the effects of cycling rates, electrolyte additives, as well as room temperature ionic liquids (RTILs). Especially, a RTILs-based electrolyte system was developed and optimized by evaluating its physicochemical properties to be able to further improve the performances of TiSnSb electrode. In order to characterize the SEI layer formed at electrode surface, we performed X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). This study allowed to target some essential parameters concerning electrochemical performances linked with the nature of the solid electrolyte interphase.*

Au cours de cette thèse, un nouvel électrolyte polymère gel pour la réalisation de microbatteries au lithium a été développé. Le gel a été préparé par « confinement » d’une phase de N-propyl-N-méthylpyrrolidinium bis(fluorosulfonyl)imide (P13FSI) et de LiTFSI dans un réseau semi-interpénétré (sRip) de polymère (PVdFHFP/ réseau de POE). L’électrolyte gel a tout d’abord été optimisé et étudié en termes de propriétés physicochimiques et de transport ionique en fonction de sa composition. Ensuite, des batteries Li/LiNi1/3Mn1/3Co1/3O2 ont été assemblées en utilisant l’électrolyte sRip. Les performances ont par ailleurs été comparées aux systèmes de références utilisant l’électrolyte à base de POE ou de PVdF-HFP. Outre ses propriétés améliorées par rapport au PVdF-HFP et au réseau de POE (propriétés mécaniques, confinement), l’électrolyte sRip est compatible avec le procédé de dépôt de l’électrode négative en lithium par évaporation sous vide. L’électrolyte sRip optimisé a donc été utilisé pour fabriquer une nouvelle génération de microbatteries en s’affranchissant de l’électrolyte céramique, le LiPON, afin d’abaisser la résistance interne. Les microbatteries Li/sRip gel/LiCoO2 délivrent une capacité nominale stable de 850 μAh à C sur 100 cycles à 25°C. / In this thesis, a new polymer gel electrolyte was prepared and optimized for Li based microbatteries. The gel consisted of an ionic liquid based phase (P13FSI/LiTFSI) confined in a semi-interpenetrating polymers (sIPN) network (PVdF-HFP/crosslinked PEO). sIPN electrolytes were prepared and optimized according to the PVdFHFP/ crosslinked PEO ratio and the liquid phase fraction. Furthermore, the sIPN electrolyte was used as an electrolyte in Li/LiNi1/3Mn1/3Co1/3O2 battery. The performances of the battery (specific capacity, efficiency, cyclability) were determined and compared to batteries using a crosslinked PEO or PVdF-HFP based gel. Such a thin and stable sIPN electrolyte film enabled the preparation of Li based microbatteries using thermal evaporation deposition of lithium directly conducted on the sIPN electrolyte film. This assembly (Li/sIPN) was therefore used to prepare a LiCoO2/sIPN gel/Li quasi solid-state microbattery. This microbattery showed a stable nominal capacity of 850 μAh for over 100 cycles of charge and discharge under 1 C rate at 25°C.

Les liquides complexes sont des matériaux très prometteurs pour réaliser la conversion bon marché et à grande échelle d’énergie thermique en énergie électrique, dans un contexte de réchauffement climatique et de maîtrise de la consommation d’énergie. Nous montrons qu’en présence d’un couple redox, les cellules thermogalvaniques à base de liquides ioniques (NEA et EMIMTFSI) présentent des propriétés remarquables tels des coefficients Seebeck de plus de 5 mV/K (Eu³⁺/Eu²⁺ dans l’EMIMTFSI). De même, ces travaux présentent l’utilisation de ferrofluides, solutions colloïdales (aqueuses ou à base de solvants organiques) de nanoparticules magnétiques (maghémite), pour accroître le coefficient Seebeck et le courant extractible de générateurs thermoélectriques liquides. Les phénomènes réversibles d’adsorption des nanoparticules sur la surface des électrodes jouent également un rôle important sur les propriétés thermoélectriques de ces solutions, et sont modifiés par l’application de champs magnétiques homogènes parallèles ou perpendiculaires au gradient de température.En l’absence d’un couple redox, les liquides ioniques peuvent être utilisés pour fabriquer des supercondensateurs à charge thermique. Ces derniers exploitent les modifications avec la température des double couches électriques aux interfaces liquide/électrode. Nous avons étudié ici ces modifications de double couches dans l’EMIMBF4 par simulations numériques de Monte-Carlo. Les résultats démontrent un accroissement conséquent des propriétés thermoélectriques lors de la dilution du liquide ionique dans un solvant organique, l’acétonitrile, en accord qualitatif avec les résultats expérimentaux. / Complex liquids are promising material for low cost and wide scale conversion of thermal energy to electric energy, within a context of global warming and control of the energy consumption.In this work we showed that with a redox couple, ionic liquid (EAN and EMIMTFSI) based thermogalvanic cells present remarkable thermoelectric properties such as the Seebeck coefficient over 5 mV/K (Eu³⁺/Eu²⁺ in EMIMTFSI). Moreover, we demonstrated for the first time that ferrofluids, colloidal solutions (aqueous or organic solvent based) of magnetic nanoparticles (maghemite), can be used to increase both the Seebeck coefficient and the electric current in liquid thermoelectric generators through unknown physical processes. The importance of reversible adsorption phenomena of the nanoparticles on the electrodes’ surface for the thermoelectric properties of these solutions was revealed. That can be further modified by a homogeneous magnetic field applied perpendicular or parallel to the temperature gradient. Without a redox couple, ionic liquids can be used to build thermally chargeable supercapacitors. They take advantage of temperature dependent electrical double-layer formation at liquid/electrode interfaces. Here, we studied these double-layer modifications in EMIMBF4/platinum through Monte-Carlo simulations. The results show substantial modifications in the thermoelectric properties when the ionic liquid is diluted in an organic solvent, acetonitrile. These results are qualitatively consistent with experimental measurements.

No description available.

L’objectif de ce travail de thèse a été de développer l’ingénierie des polymères liquides ioniques(PILs) de type imidazolium ainsi qu’une nouvelle famille de copolymères à blocs apparentés.Des PILs type imidazolium ont été utilisés en tant que polymères réactifs pour la catalyse organique etla modification chimique par post-polymérisation. Divers composés (homopolymères, copolymèresstatistiques de type styrénique, polymères réticulés) stables à l'air, portant divers contre-anions (bromures,hydrogénocarbonates, carboxylates), ont été spécialement conçus via des stratégies de synthèserelativement simples. La génération de carbènes N-hétérocycliques supportés sur polymères (poly(NHC)s)a permis de comparer les performances catalytiques de tous ces précurseurs à travers des réactions deréférence de la catalyse organique. Spécifiquement, les copolymères statistiques type styrénique peuventégalement être fonctionnalisés de manière stoechiométrique par post-polymérisation avec différentssubstrats électrophiles (e.g. CS2, isothiocyanate, métaux de transition).Une nouvelle famille de copolymère à blocs contenant un bloc poly(acétate de vinyle) et un bloc detype poly(bromure de N-vinyl-3-alkylimidazolium), a été synthétisé par CMRP. La capacité de cescomposés à s'auto-assembler en diverses mésostructures en masse comme en solution a ensuite étédémontrée. Des mesures de conductivité ionique ont montré l’influence de la préparation des échantillonset des conditions de mesures sur les valeurs obtenues. Le comportement en solution par la réactivité ioniquedu bloc PIL et la modification chimique du bloc hydrophobe poly(acétate de vinyle) en hydrophilepoly(alcool vinylique) ont permis la formation de différentes nanostructures micellaires.Mots clés : Polymères liquides ioniques, Copolymères à blocs, Imidazolium, catalyse organique,Modification post-polymérisation, Auto-assemblage, Conductivité ionique, nanoparticules d’or. / The aim of this PhD work is to expand the scope of engineered imidazolium-based poly(ionicliquid)s (PILs) and their related PIL-block copolymers (PIL BCPs).The use of the imidazolium-based PILs as true reactive polymers for organocatalysis and post-chemicalmodification is first described. Miscellaneous air-stable PIL derivatives featuring various counter-anions(e.g. bromides, hydrogen carbonates, carboxylates), including homopolymers, statistical copolymers ofstyrenic-type and crosslinked copolymer networks have been specifically designed by relatively simplesynthetic strategies. The generation of related polymer-supported N-heterocyclic carbenes, poly(NHC)s,enables comparing the catalytic performances in selected organocatalyzed reactions. Specific polystyrenebasedcoPILs can be also stoichiometrically derivatized by post-chemical modification using variouselectrophilic substrates (e.g. CS2, isothiocyanate, transition metals).A novel family of imidazolium-based PIL BCPs, namely poly(vinyl acetate)-b-poly(N-vinyl-3-alkylimidazolium bromide)s synthesized by CMRP, is then described. The ability of these compounds toself-assemble into various types of mesostructures in bulk or in solution has been demonstrated. Ionicconductivity measurements evidenced the influence of sample preparation and measurement conditions.The behavior in solution evidenced via the ionic responsiveness of the PIL block but also by post-chemicalmodification of the hydrophobic poly(vinyl acetate) block into hydrophilic poly(vinyl alcohol) theformation of various micelle-like nanostructures.Keywords: Poly(ionic liquid)s, Block copolymers, Imidazolium, Organocatalysis, Post-polymerizationmodification, Self-assembly, Ionic conductivity, Gold nanoparticles / El objetivo de esta tesis fue el desarrollo de polímeros de ingeniería iónicoslíquidos (pils) y tipo imidazolio una nueva familia de copolímeros de bloques relacionados.Lager tipo imidazolio fueron utilizados como reactivos para la catálisis orgánica ymodificación química de polímeros después de la polimerización. Varios compuestos(homopolímeros, copolímeros aleatorios de tipo estireno, polímeros reticulados) estable en elaire, contra de la realización diversos aniones (bromuros, bicarbonatos, carboxilatos), hansido especialmente diseñadas utilizando estrategias de síntesis relativamente simple. Se utilizóla generación de carbenos N-heterocíclicos soportado sobre polímeros (poli (NHC) s) paracomparar el rendimiento catalítico de estos precursores de referencia a través de reacciones decatálisis orgánica. Específicamente, los copolímeros de tipo estireno también se puedenfuncionalizar sustratos por polimerización posterior estequiométricamente con diferenteselectrófilos (por ejemplo, metales CS2, isotiocianato, de transición).Una nueva familia de copolímero de bloque que contiene un poli (acetato de vinilo) y unbloque de poli (bromuro de N-vinil-3-alquilimidazolio) se sintetizó en CMRP. La capacidadde estos compuestos a auto-ensamblan en varias mesoestructuras como entonces se demostrósolución en masa. Mediciones de conductividad iónica han demostrado la influencia de lascondiciones de preparación y medición de la muestra en los valores obtenidos. Elcomportamiento en solución por el bloque PIL reactividad de iones, y la modificaciónquímica del bloque hidrófobo de poli (acetato de vinilo) hidrófilo poli (alcohol vinílico)permitió la formación de nanoestructuras diferentes micelares.Palabras clave: polímeros líquidos iónicos, copolímeros de bloque, imidazolio, catálisisorgánica, Cambiar post-polimerización, auto-ensamblaje, conductividad iónica, lasnanopartículas de oro.

Three ionic liquids (ILs), trihexyltetradecylphosphonium tetrafluoroborate (TTPT), N-butyl-4-methylpyridinium tetrafluoroborate (BMPT), and 1-methyl-3- octylimidazolium tetrafluoroborate (MOIC), were utilized to prepare sol- gel sorbent coatings. Non-polar polydimethylsiloxane (PDMS) and polar poly(ethylene glycol) (PEG), poly(tetrahydrofuran) (PolyTHF) and bis[(3-methyldimethoxy-silyl)propyl] polypropylene oxide (BMPO) polymers were employed to develop novel ionic liquidmediated sol- gel hybrid organic- inorganic sorbents. The novel sorbents were first tested as coatings for capillary microextraction off-line hyphenated to gas chromatography. To gain an understanding of the role of the ionic liquids in the sol-gel process, the preconcentration abilities of these novel coatings were investigated for several classes of compounds utilizing CME-GC. This was accomplished by comparing GC peak areas of a series of analytes extracted on the ionic liquid mediated sol-gel CME coatings with that of analogous peak areas obtained on sol- gel coatings prepared without the ionic liquid. The morphology of these coatings was compared using scanning electron microscopy (SEM) imaging data. Overall, the ionic liquid-mediated sol- gel coatings had more porous morphologies than the sol-gel coatings prepared without ionic liquid. The PDMS andBMPO sol-gel coatings prepared with ionic liquid in the sol solution provided enhanced extraction sensitivity reflected in higher preconcentration effects and lower detection limits than the sol- gel coatings prepared without the ionic liquid. The polar IL-mediated BMPO sol- gel sorbent was further investigated by exploring the extraction profile and thermal stability of these coatings. A further application of ionic liquid-mediated sol-gel sorbents could be as stationary phases in a microchip-based separation system. Towards this goal, microfluidic channels were fabricated in glass substrates using microelectromechanical engineering. Spiral and serpentine channels were etched in Pyrex and fused silica wafers using wet and deep reactive ion etching (DRIE) techniques. Microfabrication protocols such as the use of hard mask and etching times were investigated for both techniques. DRIE produced microfluidic channels that had an etch quality that was superior to wet etched channels. Thus, the ultimate microchip-based separation system should by fabricated using DRIE.