Différentes membranes conductrices anioniques ont été développées pour protéger une électrode à air fonctionnant dans une batterie Zinc-Air alimentée par de l’air ambiant. Dans ces conditions, le dioxyde de carbone contenu dans l’air, en contact avec l’électrolyte basique, se transforme en carbonate de potassium qui précipite dans la structure poreuse de l’électrode. Cela provoque l’augmentation de sa résistance et la perte de son étanchéité, et l’électrode n’est alors stable que 80 heures. L’objectif de cette étude est donc de rendre stable une électrode à air pendant 3000 heures de fonctionnement.Pour cela, différents réseaux (semi-)interpénétrés de polymères ont donc été développés en associant un polyélectrolyte et un réseau partenaire neutre. La polyépichlorhydrine greffée avec du 1,4-diazabicyclo(2,2,2)octane et un polyélectrolyte fluoré ont été choisis comme polymère conducteur anionique. Des réseaux neutres à base de poly(méthacrylate de 2-hydroxyéthyle), d’alcool polyvinylique et de perfluoropolyéther leur ont été, tour à tour, associés. Les propriétés physico-chimiques des différentes membranes développées ont été caractérisées selon leur densité de charges et leur composition. Les membranes présentant les meilleures propriétés requises (conductivité anionique, prise en masse limitée, sélectivité, …) ont ensuite été assemblées sur des électrodes à air dont le potentiel et la stabilité ont été évalués au cours du fonctionnement en demi-cellule. Ainsi, une électrode à air modifiée avec de telles membranes peut présenter un potentiel stable pendant 6800 heures de fonctionnement à -30mA/cm². / Different anionic conducting membranes have been developed to protect an air electrode operating in a Zinc-Air battery fed with ambient air. Under those conditions, carbon dioxide from atmospheric air reacts with the alkaline electrolyte, and is then transformed into potassium carbonate. The precipitate of this carbonate inside the electrode porous structure leads to the increase of the system resistance and the loss of its sealing after 80 h of operation. The objective of this study focuses on the improvement of the stability of an air electrode for 3000 h of operation, by protecting it from carbonation reaction with a polymer membrane.For this, different (semi-)interpenetrating polymer networks have therefore been developed combining a polyelectrolyte and a neutral network partner. Polyepichlorohydrin grafted with 1,4-diazabicyclo (2,2,2) octane and a fluorinated polyelectrolyte were chosen as anionic conductive polymer. Neutral networks based on poly (2-hydroxyethyl methacrylate), polyvinyl alcohol and perfluoropolyether were then, alternately, associated to the polyelectrolyte. The physico-chemical properties of the various developed membranes were characterized according to their charge density and composition. The membranes with the best required properties (anionic conductivity, limited weight uptake, selectivity ...) were then assembled on air electrodes whose potential and stability have been evaluated during the operation in half-cell. Thus, an air electrode modified with such membranes maintains a stable potential during 6800 hours of running at -30mA / cm².

Orientador: Isabel Cristina Sales Fontes Jardim / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T10:34:05Z (GMT). No. of bitstreams: 1 Ferreira_ClaudiodeCastro_M.pdf: 1652977 bytes, checksum: b266745fcbc738cc97c41fdc4d79a00b (MD5) Previous issue date: 2014 / Resumo: / Resumo: Neste trabalho, prepararam-se fases estacionárias (FE) fluoradas capeadas para utilização em Cromatografia Líquida de Alta Eficiência em Fase Reversa (CLAE-FR). A preparação da FE consistiu na sorção do polímero poli(metil-3,3,3-trifluorproprilsiloxano) (PMTFS) sobre sílica, tipo B, com tamanho de partícula de 5 ?m, seguido de imobilização térmica a 226 oC, por 12 horas e extração com diclorometano, a fim de eliminar o polímero não aderido ao suporte. A FE imobilizada, Si(PMTFS), foi submetida à reação de capeamento com trimetilclorossilano e hexametildissilaxano, para a redução dos grupos silanóis que não foram recobertos pelo polímero. Testes físico-químicos e cromatográficos comprovaram a eficiência da imobilização do polímero e do capeamento. O desempenho cromatográfico da FE fluorada capeada, Si(PMTFS)ec, foi superior ao da não capeada e os testes de Tanaka e colaboradores demonstraram que o capeamento diminuiu a atividade silanofílica da FE e aumentou a sua hidrofobicidade. A FE Si(PMTFS)ec apresentou o mecanismo "U-shape", pois se observou o aumento da retenção de compostos básicos e polares em altas porcentagens do modificador orgânico na fase móvel. As FE de Si(PMTFS)ec apresentaram estabilidade química superior às FE não capeadas, porém, elas mostraram-se mais instáveis que as FE C8, C18 preparadas no grupo. Embora a estabilidade química à fase móvel em meio básica seja uma desvantagem, a mesma possui o mecanismo "U-shape" que pode ser utilizado para aumentar a retenção dos compostos básicos, sem o uso de condições drásticas de pH, além de ser uma FE mais apropriada quando se emprega o espectrômetro de massas, pois a alta concentração de solvente orgânico na fase móvel melhora a ionização dos analitos, aumentando as suas detectabilidades. A FE Si(PMTFS)ec constitui em uma alternativa bem sucedida para emprego em CLAE-FR, devido a sua capacidade em separar vários tipos de compostos / Abstract: / Abstract: In this work, end-capped fluorinated stationary phases (SP) for use in High-Performance Liquid Chromatography on Reversed Phase (RP-HPLC) were prepared. The preparation of the SP consisted in the sorption of the polymer poly(methyl-3,3,3-trifluorproprilsiloxane) (PMTFS) onto type B silica, with particle size of 5 µm, followed by thermal immobilization at 226 °C for 12 h and extraction with dichloromethane to eliminate the polymer that had not interacted with the support. The immobilized SP, Si (PMTFS), was subjected to an end-capping reaction to reduce the silanol groups that were not covered by the polymer. Physical-chemical and chromatographic tests were conducted to evaluate the efficiency of the immobilization of the polymer and of the end-capping reaction. The chromatographic performance of the end-capped fluorinated SP, Si (PMTFS)ec, was greater than that of the non-end-capped phase. The Tanaka tests showed a decrease in silanophilic activity and an increase in hydrophobicity. The Si (PMTFS)ec SP showed a U-shaped mechanism, because of the observed increase in retention of basic compounds at high percentages of the organic component in the mobile phase. The Si (PMTFS)ec SP showed superior chemical stability to non-end-capped SP, however, less stability than C8 and C-18 SP also prepared by the group. Although chemical stability in alkaline mobile phase is a disadvantage, it has a "U-shape" mechanism that can be used to increase the retention of basic compounds without the use of drastic conditions of pH, and is more appropriate for use with a mass spectrometer. Due to the high concentrations of organic solvent in the mobile phase the ionization of the analytes is better, increasing the detectability. The Si (PMTFS)ec SP can be used in RP-HPLC due to its ability to separate various types of compounds / Mestrado / Quimica Analitica / Mestre em Química

Oligomers and polymers based on functionalized Rf-amides were successfully synthesized for the fabrication of hydrophobic surfaces with either linear or network structure. Firstly, new functionalized Rf-amides (RfCONH-, Rf is a perfluoroalkyl segment) were developed in most cases by a one step reaction and a simple work-up procedure. The reaction behaviors of synthesized Rf-amides in polyreactions were well understood. New fluorinated oligoester polyols, blocked IPDI's, and end-hydroxyl terminated oligo(urea urethane)s have been synthesized, the detail structures and properties are well understood. These materials could be suitable components of powder coatings. On the other hand, the end-hydroxyl terminated oligo(urea urethane)s could be used as reactive additives in high solid content and water-borne coatings. Hydrophobic smooth surfaces based on linear polymers, poly(urea urethane)s and alternating MI copolymers, containing fluorinated side groups were successfully constructed. The attachment of fluorinated side groups into polymers can dramatically alter the surfaces of corresponding polymers from more hydrophilic to hydrophobic due to the enrichment of fluorinated side groups on the top of the surface. The backbone configuration, the polarity of backbones, and the thermal treatment on surfaces can influence the surface properties of corresponding materials. Finally, hydrophobic surfaces of cross-linked polyurethanes as model top coatings were constructed under melt condition at high temperature (180 and 190 oC) using the combination of fluorinated oligouretdiones and non-fluorinated oligoester polyols. It was found that the hydrophobicity of resulting cured films is a matter of the competition between the formation of cross-linking network and the segregation of fluoromoieties on the top of the surface.

La maladie d'Alzheimer représente un défi mondial pour la société. Il n'y a pas à ce jour de traitement efficace pour traiter ou ralentir les symptômes de la maladie d'Alzheimer. Cette maladie est caractérisée par une perte de synapses, une augmentation du nombre de plaques extracellulaires d'Abêta et une augmentation de Tau hyperphosphorylée agrégée intracellulaire (neurodégénérescence fibrillaire). Il est communément admis que la maladie d'Alzheimer est principalement liée à l’oligomérisation et à la fibrillation de peptides amyloïdes bêta, et que les oligomères Abêta solubles et les fibres sont des espèces neurotoxiques. Une stratégie pour réduire la présence de ces espèces toxiques de Abêta est l'utilisation de peptides ou de peptidomimétiques pour inhiber l'agrégation de Abêta, soit par interaction avec les oligomères d'Abêta pour empêcher davantage son agrégation en fibres ou en stabilisant les conformations hélicoïdales transitoires de Abêta pour empêcher sa transition vers des structures en feuillets bêta. Dans un premier temps, sur la base des résultats encourageants de glycopeptides contenant un élément polaire casseur de feuillets bêta pour moduler l'agrégation du peptide Abêta, et des propriétés uniques du groupe trifluoromethylhydroxyle, nous avons conçu et synthétisé des mimes de pentapeptides contenant la séquence (Boc) Ala-Val-X-Val-Leu-OMe (X = Ser, Thr, (2S, 3R)-CF3 Thr et (2S, 3S)-CF3 Thr), pour interagir avec le site de nucléation du peptide Abêta dans sa forme monomérique ou oligomérique de manière à perturber l'auto-assemblage en oligomères toxiques. Des études conformationnelles par RMN 2D et par modélisation moléculaire ont indiqué que ces peptides adoptent des conformations étendues dans des solvants polaires (eau et méthanol). Nous avons constaté expérimentalement et théoriquement que les pentapeptides contenant l’acide aminé non naturel (2S, 3S)-CF3-thréonine sont plus étendus que les pentapeptides contenant les acides aminés naturels L-sérine et L-thréonine. Nous avons également observé que les pentapeptides (2S, 3S)-CF3-Thr ont une propension à s’auto-associer en formant des brins bêta intermoléculaires. La capacité de ces pentapeptides à inhiber la formation de fibres amyloïdes a été évaluée sur les peptides Abêta 1-42 et IAPP (impliqué dans le diabète de type II) par des essais de fluorescence à la thioflavine T (ThT). Il a été constaté qu'aucun de ces pentapeptides ont un effet d'inhibition de l'agrégation des peptides Abêta 1-42 et IAPP. Au contraire, certains composés ont montré un effet d'accélération de l'agrégation de IAPP. Accélérer l'agrégation est moins intuitif mais cette stratégie a plus récemment suscité un intérêt. Il pourrait être intéressant d'étudier plus en détail l’intérêt de cette accélération de l'agrégation de IAPP par des techniques complémentaires.Dans une deuxième partie de cette thèse, nous avons assemblé une unité amino acide basée sur un motif CF3-1,4 disubstituted-1,2,3-triazole en homo-oligomères (trimères et tétramères) et en peptidomimétiques. Des études conformationnelles de ces oligomères fluorés ont été menées par RMN 2D et par des simulations de modélisation moléculaire. Nos études préliminaires de modélisation moléculaire prévoient des structures hélicoïdales avec des trimères et des tétramères d'acides aminés à base de ces CF3-triazoles. L'analyse par RMN 2D du tétramère affiche des corrélations NOE très intéressantes, ce qui indique une structure repliée. La capacité de ces oligomères fluorés à moduler la formation de fibres amyloïdes des peptides Abêta 1-42 et IAPP a été évaluée par test de fluorescence à la ThT. Nous avons constaté que le trimère est un faible inhibiteur de l'agrégation de Abêta 1-42, mais aussi un promoteur d'agrégation de IAPP. Le tétramère a été trouvé capable de moduler l'agrégation de Abêta 1-42 et de IAPP, mais non d'une manière classique d'inhibition ou de promotion. / It has been widely recognized that Alzheimer’s disease (AD) represents an unsettling, worldwide challenge for society. By far, there has been no effective cure for AD. Pathologically, AD is characterized by a loss of synapses, an increase in the number of extracellular Abeta plaques and an increase in intracellular aggregated hyperphosphorylated Tau (neurofibrillary tangles). It is commonly believed that AD is primarily linked to oligomerization and fibrillization of amyloid beta peptides, and the soluble Abeta oligomers and fibrils are neurotoxic species.One strategy to reduce the Abeta fibrils is the use of peptides or peptidomimetics to inhibit the Abeta aggregation either by interaction with the Abeta oligomers to prevent its further aggregation into fibrils, or by stabilizing the transient Abeta α-helical conformations to prevent its transition to beta-sheet structures.In the first direction, based on the encouraging results of the glycopeptides containing the polar sugar beta-sheet breaker element to modulate Abeta peptide aggregation and the unique properties of trifluoromethylhydroxyl group, we designed and synthesized pentapeptide mimics with the sequence (Boc) Ala-Val-X-Val-Leu-OMe (X = Ser, Thr, (2S, 3R)-CF3-Thr and (2S, 3S)-CF3-Thr) to interact with the nucleation site of Abeta peptide in its monomeric or oligomeric form so as to disrupt the self-assembly into toxic oligomeric form. Both 2D NMR and molecular modelling studies indicated that these peptides in polar solvent (water and methanol) adopt mainly extended backbone conformations. It is found both experimentally and theoretically that, the (2S, 3S)-CF3-threonine-containing pentapeptides are more extended than the L-serine- and L- threonine-containing pentapeptides. It is also observed that the (2S, 3S)-CF3-Thr pentapeptides have a propensity to self-associate of by forming intermolecular beta-strand contacts. The ability of these pentapeptides to inhibit amyloid fibril formation was evaluated on Abeta1-42 and IAPP peptides by ThT fluorescence assay. It was found that none of these pentapeptides have any inhibition effect in Abeta1-42 peptide and IAPP aggregation. On the contrary, some compounds showed an acceleration effect in IAPP aggregation. Accelerating the aggregation pathways is less intuitive but this strategy has more recently aroused interest. It could be interesting to further study the effect of accelerating IAPP aggregation by complementary techniques.In the other direction, we have assembled novel a CF3-1,4-triazole-based amino acid mimic into homo-oligomers (trimer and tetramer) and peptidomimetics. The fluorinated oligomers were investigated both by NMR conformational studies and molecular modelling simulations. Our preliminary modelling studies predict helical structures with trimer and tetramers of CF3-1,4-disubstituted- 1,2,3- triazole-based amino acid. NMR analysis of tetramer displayed very interesting NOE correlations, indicating a folded structure. The ability of these fluorinated oligomers to modulate the amyloid fibril formation of Abeta1-42 and IAPP peptides were evaluated by ThT fluorescence assay. It was found that trimer was a weak inhibitor of Abeta1-42 aggregation but also a promoter of IAPP aggregation. The tetramer was found able to modulate the aggregation of Abeta1-42 and IAPP but not in a classical inhibition or promotion manner.

Le travail de la thèse est focalisé sur l’ élaboration plasma d’un revêtement multicouches avec une couche supérieure anti-brouillard et une couche inférieure dite barrière sur un polycarbonate. L’ensemble des travaux est divisé en 3 parties: élaborations des deux monocouches barrière ou antibuée puis dépôt de la multicouche barrière - antibuée. La polymérisation plasma de la couche barrière est effectuée à partir d’un mélange de dioxygène et d’un précurseur organosilicié : l’hexaméthyledisiloxane ou le 2,4,6,8-tétraméthylcyclotétrasiloxane ou bien encore le triéthoxyfluorosilane. La caractérisation des couches minces obtenues repose sur la spectroscopie Infrarouge à Transformée de Fourier , la spectroscopie de photoélectrons X et la microscopie à force atomique. L’influence des conditions de dépôt plasma comme la puissance, la proportion monomère/dioxygène, le temps du dépôt sur la structure chimique et l’hydrophobicité de la surface des différents types de couches organosiliciées est étudiée. Les résultats de la perméation avec l’eau liquide ou le dioxygène montrent que la propriété barrière des couches organosiliciées non fluorées est meilleure que pour la couche fluorée. L’élaboration de copolymères anti-buée repose sur l’utilisation de combinaisons entre deux précurseurs hydrophile et hydrophobe en voie plasma pulsé. Les précurseurs tels que le 2-(diméthylamino)éthyl méthacrylate ou l’acide acrylique sont choisis pour leur hydrophile alors que le 1H,1H,2H-perfluoro-1-décène représente la partie oléophobe. La propriété anti-brouillard et sa stabilité à long terme après un vieillissement thermique ou en milieu humide est dépendante de leurs structure et morphologie. / The PhD work is focused on the deposition of a multilayer coating with an anti-fog top layer obtained thanks to the plasma copolymerization of hydrophilic and hydrophobic monomers and an intermediate barrier layer, also obtained by plasma deposition on polycarbonate. The work is divided into 3 parts: the independently preparations of the two monolayers, barrier and anti-fogging ones, then the barrier-antifog multilayer deposition. The characterization of the thin films obtained is based on Fourier Transform Infrared Spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy.The barrier plasma-layer is issued from by the mixture of dioxygen and one of these three organosilicon precursors : hexamethyledisiloxane ; 2,4,6,8-tetramethylcyclotetrasiloxane ; triethoxyfluorosilane. The influence of the plasma conditions such as discharge power, monomer/dioxygen ratio, deposition duration on the chemical structure and the hydrophobicity of the different types of the organosilicon layers was studied. The results of permeation with liquid water or dioxygen show that the barrier property of the organosilicon layer is more efficient than that of the fluorinated layer. Anti-fog plasma-copolymer is synthetized from two hydrophilic and hydrophobic precursors deposited by pulsed plasma mode. The precursors such as 2-(dimethylamino) ethyl methacrylate and acrylic acid were selected for the hydrophilic part while the 1H, 1H, 2H-perfluoro-1-decene will be associated to the oleophobic part. The dependence of the chemical structure and the morphology of the anti-fog layers is studied according to the hydrophilic/oleophobic distribution and the deposition time.

Fluorkemi används på varselkläder i syfte för att skydda textilen mot smuts, vatten, fett och olja. Kemikalierna är skadliga för människor och miljö, de är dessutom mycket svårnedbrutna eller så bryts de inte ner överhuvudtaget. Kemikalierna är utvecklade av människor och delas upp i perfluorerade och polyfluorerade ämnen (PFAS). PFAS klassificeras också som PBT-ämnen, vilket står för att de är persistenta, bioackumulerande och toxiska. Studien är utförd i ett samarbete med Tranemo Textil AB, där behovet av fluorkarbonberedning på varselkläder undersökts. Syftet med studien är att undersöka utifrån användning och tvättprocess om fluorkarbonberedning är essentiell på varselkläder. Genom intervjuer med experter och tvätterier har studien fått fram information om fluorkemi och hur tvättprocessen ser ut. Resultatet från intervjuerna har kombinerats med tester på tyger och på ett bärprov med ett byxben med fluorkarbonberedning och ett byxben utan. Bärprovet har testats av en person i dennes dagliga arbete under sex månader. Studien har sammanställt resultatet och kan konstatera att fluorkemin har negativ påverkan på människa och miljö, vilket ligger till grund för en diskussion kring vad som är nödvändig användning. Vidare kan det konstateras att fluorkarbonberedningens effekt försämras över tid, genom användning, tvätt och annan yttre påverkan. Slitaget sker ojämnt och vissa delar av ett plagg kan ha god avvisande effekt medan andra delar är så kallade öppna friytor. Smuts kan då gå in under beredningen och kapslas in. I resultatet har det också framkommit att rätt skötsel av den här typen av plagg är viktigt och att återaktivering genom värme är väsentlig. Samtidigt belyser respondenterna återkommande en mentalitet hos arbetare att de vill att plaggen ska visa att de arbetar och därför vara smutsiga, vilket medför att många plagg sällan tvättas. Genom utförda intervjuer och tester har studien kommit till slutsatsen att fluorkemi inte är nödvändig på varselkläder. Den yttre påverkan som relativt snabb sliter på beredningen genom användning och tvätt i kombination med att fluorkemin inte fyller någon långvarig avvisande funktion är aspekter som tagits i hänsyn för slutsatsen. / Fluor chemistry is used on high visibility workwear to protect the textile from dirt, water, grease, and oil. The chemicals are harmful to people and the environment, they are also very degraded, or they do not break down at all. The chemicals are developed by humans and divided into perfluorinated and polyfluorinated substances (PFAS). PFAS is also classified as PBT substances, which means that they are persistent, bioaccumulate, and toxic. The study was in collaboration with Tranemo Textil AB, where the need for fluorocarbon finish for high visibility workwear was explored. The purpose of the study is to investigate if a fluorocarbon finish is essential on high visibility workwear, based on the use phase and washing process. Through interviews with experts and laundries, the study has obtained information about fluor chemistry and how the washing process works. The results of the interviews have been combined with tests on fabrics and on a wear test that has been tested in the person’s daily work for six months. The wear test is trousers with one leg with fluorocarbon finish and the other leg without. The study has compiled the results and can find that fluor chemistry has a negative impact on humans and the environment, which forms the basis for a discussion about what is essential use. Furthermore, it can be found that the effect of the fluorocarbon finish impairs over time, through use, washing, and other external impacts. The abrasion is uneven, and some parts of the garment can still have a good repellent effect, while other parts have so-called open surfaces. On the open surfaces, dirt can enter during the fluorocarbon finish and be encapsulated. The study has also emerged that proper care of this type of garment is important and that reactivation through heat is essential. At the same time, respondents repeatedly highlight workers' mentality that the garment should show and reflect high work ethics. This causes that many garments are rarely washed and become very dirty. Through interviews and tests, the study has concluded that fluor chemistry is not necessary for high visibility workwear. The external effects with relatively quickly abrasion on the finish through use and washing, this in combination with that fluor chemistry does not fulfil any long-lasting function are aspects that have been considered in the conclusion.

Au cours de ce travail de thèse, nous nous sommes focalisés sur deux aspects de la RMN du solide: i) la RMN double-résonance de noyaux de fréquences de Larmor proches, ii) la quantitativité des spectres RMN sous polarisation croisée (CPMAS). L’emploi d’une sonde RMN solide prototype multicanaux (1H/19F/X/Y/Z) nous a permis de développer des outils RMN originaux pour la caractérisation de matériaux fluorés et ou hétérogènes (principes actifs, matériaux poreux, polymères), notamment le triple transfert de polarisation (1H, 19F) -13C, le double-transfert en cascade, les découplages multiples, et autres expériences de double-résonance 1H-19F ou 13C-27Al. La séquence multiCP a ensuite été évaluée pour l’obtention de spectre RMN 13C ou 29Si quantitatifs et la caractérisation de matériaux ayant des temps de relaxation contrastés. Nous avons montré que la condition pour obtenir des spectres RMN multiCP quantitatifs est la présence d’un bain de spins 1H dense. Des mesures quantitatives pour des composés purs (acides aminés, principes actifs, excipients, polymères inorganiques) ou en mélanges ont ainsi été obtenues. Le multiCP a ensuite été utilisé pour caractériser la structure locale de polymères siliciés et la nature fine du système de protons dans des membranes de Nafion. Dans la continuité, nous avons étudié une formulation pharmaceutique. Dans ce système hétérogène, nous avons profité des contrastes de temps de relaxation pour distinguer et quantifier les molécules de principe actif à l’intérieur ou en dehors du surfactant. Nous avons également caractérisé les interactions de la molécule avec le surfactant et suivi sa libération dans différents milieux mimant les milieux physiologiques. L’ensemble de ces travaux offre de nouveaux outils RMN pour la caractérisation de la structure locale de matériaux hétérogènes. / During this work, two aspects of solid-state NMR have been investigated: i) double-resonance NMR of nuclei with close Larmor frequencies, ii) quantitative cross-polarization (CPMAS) measurements. The use of a prototype multichannel solid NMR probe (1H/19F/X/Y/Z) has allowed the development of original NMR tools for the structural characterization of fluorinated or heterogeneous materials (active principles, porous solids, polymers), in particular the triple polarization transfer (1H, 19F) -13C, double-transfer ‘en cascade’, multiple decoupling, and other 1H-19F ou 13C-27Al double-resonance experiments. The multiCP experiment has then been evaluated to get quantitative 13C and 29Si NMR spectra and to characterize materials with contrasted relaxation times. We have shown that the presence of dense proton bath was key to get quantitative data. Quantitative measurements were then obtained for pure solids (aminoacids, active principles, excipients, inorganic polymers) and mixtures. The multiCP has then been used to characterize the local structure of siliceous polymers and the nature of the proton spin system in Nafion membranes. Finally, we have studied a pharmaceutical formulation. In this heterogenous system, we have taken benefit from the contrasted relaxation times to distinguish molecules present inside or outside the surfactant. We have also characterized the interactions between the active principle and the surfactant and followed the drug release in various physiological media. The ensemble of this work provides new NMR tools for the characterization of the local structure of heterogeneous materials.

Vorgestellt werden die gezielte mechanochemische sowie die fluorolytische Sol-Gel-Synthese von fluorierten Koordinationspolymeren mit dem Strukturmotiv einer direkten Metall-Fluor Bindung. Im Vorfeld beschränkten sich die mechanochemischen Synthesen von fluorierten Koordinationspolymeren (FCPs) darauf, Fluor über den organischen Linker im Netzwerk zu integrieren. Auch fehlten Studien, welche die Materialeigenschaften bezüglich der unterschiedlichen Fluorpositionen miteinander verglichen. Es wird die erste mechanochemische Synthese eines Koordinationspolymers mit einer direkten Metall-Fluorid-Bindung (Bariumterephthalatfluorid (BaF(p-BDC)0,5)) vorgestellt. Auch das Strontiumacetatfluorid (SrF(CH3COO)), Bariumacetatfluorid (BaF(CH3COO)) und das Bleiacetatfluorid (PbF(CH3COO) konnten durch unterschiedliche Synthesemethoden dargestellt werden. Die Kristallstrukturen wurden aus den Röntgenpulverdiffraktogrammen bestimmt. Unterstützt werden die Strukturlösungen u. a. durch die chemische Verschiebung in den 19F-MAS-NMR-Spektren, aus denen die Metall-Fluor-Abstände berechnet und mit denen aus den Kristallstrukturen verglichen wurden. Die vorgestellten Koordinationspolymere vervollständigen die Reihe der Verbindungen, welche aus Linkern mit gleichem Kohlenstoffskelett, gleichem Metallkation und ähnlicher chemischer Zusammensetzung, jedoch unterschiedlichen Fluorpositionen bestehen. Die gewählten Koordinationspolymere erlaubten damit den Vergleich der thermischen Stabilität, des Wasserabsorptionsverhaltens, sowie die Acidität der sauren Zentren an der Oberfläche bzgl. der unterschiedlichen Bindungsmotive des Fluors. In Abhängigkeit von der Fluorposition zeigen die Lanthanoid-dotierten Koordinationspolymere unterschiedlich lange Lebenszeiten der angeregten Zustände. Durch das Strukturmotiv der direkten Metall-Fluor-Bindung kann die Abklingzeit der angeregten Zustände des angeregten Lanthanoids deutlich verlängert werden. / The targeted mechanochemical and fluorolytic sol-gel synthesis of fluorinated coordination polymers with the structural motif of a direct metal-fluorine bond are presented. Previously, the mechanochemical syntheses of fluorinated coordination polymers (FCPs) were limited to integrating fluorine into the network via the organic linker. There were also no studies comparing the material properties of the different fluorine positions.The first mechanochemical synthesis of a coordination polymer with a direct metal fluorine bond (barium terephthalate fluoride (BaF(p-BDC)0.5)) is presented. Also the strontium acetate fluoride (SrF(CH3COO)), barium acetate fluoride (BaF(CH3COO)) and lead acetate fluoride (PbF(CH3COO)) can be obtained by different synthesis methods. The crystal structures were determined from the X-ray diffractograms. The structural solutions are supported, among other things, by the chemical shift in the 19F MAS NMR spectra, from which the metal-fluorine distances were calculated and compared with those from the crystal structures. The coordination polymers presented complete the series of compounds consisting of linkers with the same carbon skeleton, the same metal cation and similar chemical composition, but different fluorine positions. The selected coordination polymers thus allowed the comparison of thermal stability, water absorption behaviour and acidity of the acid centres on the surface with respect to the different bonding motives of the fluorine. Depending on the fluorine position, the lanthanide doped coordination polymers show different lifetimes of the excited states. Due to the structural motif of the direct metal-fluorine bond, the decay time of the excited states of the excited lanthanidecan be significantly extended.

No description available.

Phosphodiesterase 2A (PDE2A) is highly expressed in distinct areas of the brain, which are known to be related to neuropsychiatric diseases. The development of suitable PDE2A tracers for Positron Emission Tomography (PET) would permit the in vivo imaging of the PDE2A and evaluation of disease-mediated alterations of its expression. A series of novel fluorinated PDE2A inhibitors on the basis of a Benzoimidazotriazine (BIT) scaffold was prepared leading to a prospective inhibitor for further development of a PDE2A PET imaging agent. BIT derivatives (BIT1–9) were obtained by a seven-step synthesis route, and their inhibitory potency towards PDE2A and selectivity over other PDEs were evaluated. BIT1 demonstrated much higher inhibition than other BIT derivatives (82.9% inhibition of PDE2A at 10 nM). BIT1 displayed an IC50 for PDE2A of 3.33 nM with 16-fold selectivity over PDE10A. This finding revealed that a derivative bearing both a 2-fluoro-pyridin-4-yl and 2-chloro-5-methoxy-phenyl unit at the 8- and 1-position, respectively, appeared to be the most potent inhibitor. In vitro studies of BIT1 using mouse liver microsomes (MLM) disclosed BIT1 as a suitable ligand for 18F-labeling. Nevertheless, future in vivo metabolism studies are required.