Les peptides de la famille du LAH4 sont des peptides cationiques capables de se replier en hélice α amphiphile. Ces peptides sont riches en histidines ce qui permet de moduler les interactions de ces peptides de manière pH dépendante et dans une gamme physiologique. Leurs capacités à interagir et perturber les membranes ont été utilisées pour divers applications biologique, et notamment pour l'amélioration de systèmes de transport de gènes.Le travail de cette thèse a été divisé en trois parties dans le but de caractériser de manière biophysique les différentes interactions ayant lieu lors de la livraison du système de transport de gènes à l’intérieur d’une cellule. L’interaction peptide-peptide : avec l’étude de l’agrégation en fibrilles de la VF1 ; l’interaction peptide-membrane : avec l’effet du LAH4L1 en présence de membranes ; et l’interaction peptide-ADN : avec le suivit de l’interaction entre le LAH4L1 et de l'ADN. / The LAH4 family consists of cationic amphiphilic peptides with propensity to fold in α-helical secondary structures. They contain histidines allowing the modulation of their interactions in a pH dependent manner in the physiological range. In membranes, at neutral or acidic pH the peptide assumes a transmembrane or an in planar configuration, respectively.In the field of gene delivery systems, peptides like LAH4 are used. They are able to firstly interact with different cargoes in order to form stable complexes, then interact with the cell membrane, and finally, promote to escape from the endosome.This PhD has been divided into three parts in order to characterize, with biophysical methods, the interactions occurring during the delivery of these gene systems: peptide-peptide interactions with a focus on the study of VF1 fibre formation; peptide-membrane interactions: with the investigation of the effect of LAH4L1 in different membranes; and peptide-DNA interactions, where the interactions of LAH4L1 with a small DNA fragment were measured.

Les oxydes fonctionnels sont des matériaux qui manifestent des propriétés intéressantes. L'étude de l'environnement local par rapport à la structure moyenne idéale est essentiel et peut être fourni par l'utilisation de techniques modernes de résonance magnétique nucléaire (RMN). Le travail présenté dans cette thèse suit et développe ces approches combinées pour l'enquête de trois classes différentes d'oxydes fonctionnels qui trouvent des applications dans des domaines d'intérêt technologique pertinente, comme l'optique et de l'énergétique : système perovskite LaSrAlO4, mélilite LaSr(Ga/Al)3O7 et la famille de orthosilicates Li2(Fe/Mn)SiO4. / The functional oxides are performing materials showing interestant properties. The study of the local environment respect to the average struvture is essential for the deep understanding of the correlations between structure and properties ; this investigation of short and medium range can be performed with the use of solid state NMR techniques. In particular in this thesis three different classes of materials for applications in fields of optic and energy are considered : perovskite structure LaSrAlO4, the melilite system LaSr(Ga/Al)3O7 and the family of orthosylicates Li2(Fe/Mn)SiO4.

No description available.

L’objectif de cette thèse est de développer un concept inédit permettant l’utilisation de silices mésoporeuses pour encapsuler des principes actifs cosmétiques de façon permanente, ce qui permet d’améliorer leur tolérance cutanée, d’optimiser leur stabilité à la lumière tout en préservant leur efficacité et de faciliter leur formulation au sein de produits cosmétiques. Pour cela, la voie consistant à encapsuler des filtres UV à usage cosmétique au sein de silices mésoporeuses de type MCM-41 de façon in-situ a été choisie car elle semblait la plus propice à l’encapsulation d’une grande quantité de principes actifs de façon permanente. Deux filtres UV ont été étudiés un lipophile, nommé Parsol MCX, et un hydrophile, appelé Parsol HS. Pour l’ensemble des principes actifs étudiés, un taux d’encapsulation approprié a été obtenu et les caractérisations, effectuées notamment par RMN du solide, ont permis de montrer que l’encapsulation est effective au sein des pores ce qui, couplé à la bonne stabilité de l’encapsulation dans le cas de l’actifs hydrophile, garantit un contact minimum entre l’actif et la peau du consommateur. En revanche, un relargage important de filtre UV lipophile a été constaté. Il a été établi que les propriétés physico-chimiques des matériaux diffèrent significativement suivant que les principes actifs encapsulés soient lipophiles ou hydrophiles. Dans tous les cas, l’organisation poreuse, l’ordre structural et la morphologie des particules contenant des principes actifs varient significativement par rapport aux silices mésoporeuses de référence de type MCM-41, synthétisées sans principe actif. La présence de principe actif au sein du milieu réactionnel a donc une influence sur la structure et la texture des matériaux obtenus, ce qui est dû aux interactions entre les molécules de principe actif, les espèces silicate et les molécules de tensioactif au sein du milieu réactionnel. / The objective of this thesis is to develop a new concept that consists to permanently encapsulate cosmetic active ingredients into mesoporous silica. The encapsulation of these active molecules improves their skin tolerance, optimizes their light stability while preserving their effectiveness and facilitates their formulation in cosmetic products. Thus, UV filters have been encapsulated in MCM-41 type mesoporous silica by using in-situ route because it seemed the most efficient route to achieve permanently encapsulation of large quantities of active. Two UV filters have been studied. One is lipophilic (Parsol MCX) and the other is a hydrophilic (Parsol HS). For all the active molecules studied, an appropriate encapsulation rate was obtained and the characterizations, particularly these performed by solid-state NMR, have shown that the encapsulation is effective within the pores which, coupled with the good stability of encapsulation in the case of hydrophilic actives, ensures minimal contact between the active and the consumer's skin. In contrast, a significant release of lipophilic UV filter was found. It was established that the physico-chemical properties of the synthesized materials differ significantly according to the lipophilic or hydrophilic nature of the encapsulated molecules. In all cases, the porous organization, the structural order and the morphology of the particles containing active ingredients vary significantly compared to the reference MCM-41 type mesoporous silica, synthesized without active ingredient. Thus, the presence of the active ingredient in the reaction medium has an influence on the structure and the texture of the synthesized materials, which is due to interactions between the actives molecules, the silicate species and the surfactant molecules in the reaction medium.

Dipolar couplings are one of the major source of structural information. Due to their dependence on the distance between the nuclei and the angle of orientation of the dipolar vector with respect to the magnetic field, they provide significant insight into the geometry and topology of molecules. As the dipolar interactions are in general present in the solid phase of the compounds, solid state NMR experiments have gained significant popularity and is widely used. Separated Local Field NMR spectroscopy based on cross-polarization technique has been used to measure the heteronuclear dipolar couplings in solid state. However, the technique undergoes many experimental challenges and requires further development. This thesis is concerned mainly with the development of techniques to measure the dipolar couplings accurately in oriented molecules. In this regard, a method for fast data acquisition is also proposed. The first chapter briefly introduces the basics of NMR spectroscopy, methodologies applied for obtaining a high resolution NMR spectrum in the solid state. An introduction to liquid crystals is presented and the nature of NMR interaction in the liquid crystalline phases is described. In chapter-2, a new pulse scheme has been proposed that includes the X-nucleus polarization in the SLF experiments and is shown to provide better sensitivity and resolution. A quantitative analysis with simulation and experimental results are also presented. In chapter-3, the performance of various homonuclear decoupling pulse schemes incorporated into SLF experiments tested on oriented systems are compared. The proposed pulse schemes are shown to provide high resolution spectrum with accurate dipolar coupling measurement for natural abundant samples and for uniformly labeled compounds as well. Theoretical description with simulation and experimental results shown here are found to provide optimum results under several technical complications seen with respect to the conventional methods used for SLF experiments. Chapter-4, an attempt is made to reconstruct 2D J-resolved and 2D- SLF spectra from several 1D experimental data. This is achieved with the help of projection reconstruction method and is shown to provide high resolution 2D spectrum with saving of experimental time by an order of two. Chapter-5, high resolution spectra from SLF experiments under phase alternating pulses and using amplitude and time averaged nutation techniques are shown for accurate dipolar coupling measurement with a dramatic reduction in rf power. This is important as the use of low rf power leads to low sample heating and can be applied suitably for the study of liquid crystals and salty biomolecules. Chapter-6, attempts are made to characterize two novel thiophene based liquid crystals using both solution and solid state NMR spectroscopy. C-H dipolar couplings measured from SLF experiments are mainly used to find the order parameters and geometry of the molecules.

Die Copolymerisation wurde mit dem Ziel untersucht, polymere Materialien zu synthetisieren, die die individuellen Eigenschaften der entsprechenden Homopolymere kombinieren. Die Dissertation konzentrierte sich auf die Elektrosynthese und Charakterisierung von leitfähigen Copolymerfilmen auf Basis von Pyrrol- und Thiophenderivaten. Mit einer Reihe von elektrochemischen, spektroskopischen und mikroskopischen Untersuchungsmethoden (Zyklovoltammetrie, elektrochemische Impedanz-spektroskopie, photoelektrochemische Spektroskopie, Elektrospray- Ionisations-Massenspektroskopie, Festkörper- NMR, Raman-Spektroskopie, Thermoanalyse und Rasterelektronenmikroskopie) wurde die Bildung echter Copolymere von Pyrrol mit Bithiophen und von 3-Methylthiophen mit Ethyl-3-thiophenazetat nachgewiesen. Die analytischen Ergebnisse bestätigen, dass Random- Copolymere und keine Block-Copolymere gebildet wurden. Die elektronischen und strukturellen Eigenschaften der Copolymerfilme liegen zwischen denen der jeweiligen Homopolymere und sind abhängig von der Copolymerzusammensetzung. Insbesondere die Halbleiterparameter der Copolymerfilme von Pyrrol mit Bithiophen wie Flachband-Potential, Bandlücken-Energie und Ladungsträgerdichte verschieben sich von denen des reinen Polypyrrols bis zum Polybithiophen, wenn der Gehalt an Bithiophen im Copolymerfilm vergrößert wird. Diese Parameter sind einstellbar durch Variation des Monomerverhältnisses oder des Polymerisationspotentials. Außerdem konnten die strukturellen und elektronischen Eigenschaften des funktionalisierten Polymers Ethyl-3-thiophenazetat durch Copolymerisation mit 3-Methylthiophen deutlich verbessert werden. Die synthetisierten leitfähigen Copolymerfilme können in der Sensorik Anwendung finden. / The copolymerization has been studied as a new strategy to synthesize polymer materials by combining interesting properties of the respective homopolymers. In this dissertation, the work focused on the electrosynthesis and characterization of conducting copolymer films based on pyrrole and thiophene derivatives. A variety of electrochemical, spectroscopic and microscopic techniques such as cyclic voltammetry, electrochemical impedance and photoelectrochemical spectroscopy, electrospray ionization mass spectroscopy, solid state NMR and Raman spectroscopy, thermal analysis and scanning electron microscopy supported the formation of true copolymers of pyrrole with bithiophene and 3-methylthiophene with ethyl-3-thiophene acetate. The analytical results exhibited that random copolymers were produced rather than block copolymers. The electronic and structural characteristics of the copolymer films were intermediate between those of the respective homopolymers and they were dependent on the copolymer composition. In particular, the semiconducting parameters of the copolymer films of pyrrole and bithiophene such as flat band potential, band gap energy and charge carrier density shifted from those of polypyrrole to polybithiophene with increasing bithiophene content of the copolymer films. Such parameters were controlled precisely by alternating either the monomer ratio or the polymerization potential. In addition, the morphological and electronic properties of the functionalized polymers of ethyl-3-thiophene acetate were increased significantly by copolymerization with 3-methylthiophene. The obtained conducting copolymer films were able to be applied in the field of sensoric.

No description available.

No description available.

Dans les piles primaires au lithium, l'anode de lithium peut être couplée principalement à quatre matériaux de cathode (MnO2, SO2, SOCl2 et des composés fluorés CFx). Les piles Li/CFx présentent de nombreux avantages tels qu’une densité d'énergie élevée (jusqu'à 2200 Wh.kg-1), un potentiel de décharge relativement élevé (environ 2,4 V vs Li+/Li) et une longue durée de vie (plus de 10 ans à la température ambiante). Au cours de ce travail, nous avons intensément étudié les propriétés électrochimiques des carbones fluorés nanostructurés. Pour plus de performances, des précurseurs nanocarbonés de dimensionnalité différentes, et des procédés de synthèse gaz-solide variés ont été employés. Ainsi, des structures fermées comme les nanofibres de carbone (1D, tubulaire), ouvertes comme les nanodisques / nanocônes (2D en majorité, discotiques) et intermédiaires avec les noirs de carbone graphitisés. Chaque mode de synthèse a été optimisé en fonction du précurseur de départ (son facteur de forme, sa dimensionnalité, son degré de graphitisation ...). Pour remédier aux limitations des carbones fluorés commerciaux, leur mécanisme de décharge a été finement étudié afin d'améliorer notre compréhension sur la défluoration électrochimique d'une cathode CFx, et de les comparer aux CFx synthétisés au laboratoire, le but principal étant de dépasser les performances actuelles et de synthétiser des matériaux inédits pour la pile primaire au lithium. Des extracapacités par rapport aux valeurs théoriques dans les batteries Li/CFx ont été obtenues avec de nanocarbones fluorés spécifiques et le phénomène électrochimique à l’origine de cette extracapacité a été clairement expliqué. / For primary lithium batteries, the lithium anode can be coupled mainly four cathode materials (MnO2, SO2, SOCl2 and fluorinated carbons CFx). Li/CFx batteries have many inherent advantages such as high energy density (up to 2200 Wh.kg-1), a moderately high discharge potential (about 2.4 V vs. Li+/Li) and a long life (over 10 years at room temperature). During this work, the electrochemical performances in primary lithium battery of nanostructured fluorinated carbons were investigated. To improve their performances, carbonaceous precursors with different dimensionalities, and various gas-solid fluorination methods were selected. Thus, a closed structure such as carbon nanofibres (1D, tubular), opened such as carbon nanodiscs/nanocones (2D in majority, discotic) and intermediate with graphitized carbon blacks have been chosen. Each synthesis route was optimized based on the starting material and their specificities, i.e. the shape factor, dimensionality, graphitization degree, stacking mode. To address to the limitations of commercial CFx materials, their discharge mechanism has been studied in order to improve the understanding about the electrochemical defluorination of a CFx cathode, and to compare it to original CFx synthesized in our laboratory, the main purpose is to exceed the current performances and to synthesize unrealized materials for primary lithium battery. Extracapacities in Li/CFx batteries were obtained with some specific fluorinated nanocarbon materials and their explanation was discussed.

This thesis describes applications of advanced multinuclear solid-state nuclear magnetic resonance (NMR) experiments to the characterisation of industrially-relevant catalyst materials. Experiments on γ-Al₂O₃ introduce the use of solid-state NMR spectroscopy for the investigation of disordered solids. The existence of Al(V) sites on the surface of this material is demonstrated, showing that removal of adsorbed H₂O may facilitate a rearrangement effect in γ-Al₂O₃ that promotes the formation of these Al environments. A range of aluminium oxide-based supported metal catalysts has been investigated. Studies of these systems by ¹H and ²⁷Al solid-state NMR spectroscopy indicate that a metal-support interaction (MSI) exists between surface cobalt oxide crystallites and the γ-Al₂O₃ support, and is strongest for materials containing small, well dispersed Co oxide crystallites. It is shown that the hygroscopic nature of γ-Al₂O₃ allows the extent of the MSI to be visualised by ¹H MAS NMR, by observing the extent of the proton-metal oxide interaction resulting from the presence of adventitious adsorbed H₂O. The surface/bulk chemistry of Co spinel aluminate materials is also investigated. ¹H, ²⁹Si, ²⁷Al and ¹⁷O solid-state NMR techniques are used to gain insight into the structural nature of silicated alumina catalysts. The combination of isotopic enrichment and dynamic nuclear polarisation (DNP) surface-enhanced NMR spectroscopy can provide a definitive and fully quantitative description of the surface structure of Si-γ-Al₂O₃ (1.5 wt% Si), and the role of adventitious surface water is highlighted. Analysis of silicated aluminas prepared by “sequential grafting” and “single shot” approaches shows that silica growth on γ-Al₂O₃ follows two distinct morphologies. ¹⁷O gas exchange enrichment is also shown to be successful in facilitating ¹⁷O solid-state NMR studies of these materials. It is demonstrated that double (²⁹Si and ¹⁷O) enrichment of Si-γ-Al₂O₃ (1.5 wt% Si) can facilitate access to ²⁹Si-¹⁷O 2D correlation experiments, even at low silica loading. An exploratory investigation of Ti-alumina model catalysts has also been carried out using ¹H, ²⁷Al and ¹⁷O solid-state NMR spectroscopy. These studies indicate that Ti-γ-Al₂O₃ and Ti-Al M50 may be structurally distinct materials.