Tesis sobre el tema "Résonance magnétique nucléaire de l'état solide"
Crea una cita precisa en los estilos APA, MLA, Chicago, Harvard y otros
Consulte los 50 mejores tesis para su investigación sobre el tema "Résonance magnétique nucléaire de l'état solide".
Junto a cada fuente en la lista de referencias hay un botón "Agregar a la bibliografía". Pulsa este botón, y generaremos automáticamente la referencia bibliográfica para la obra elegida en el estilo de cita que necesites: APA, MLA, Harvard, Vancouver, Chicago, etc.
También puede descargar el texto completo de la publicación académica en formato pdf y leer en línea su resumen siempre que esté disponible en los metadatos.
Explore tesis sobre una amplia variedad de disciplinas y organice su bibliografía correctamente.
Camus, Lydie. "Caractérisation par résonance magnétique nucléaire à l'état solide de silices hybrides". Paris 6, 2003. http://www.theses.fr/2003PA066415.
Texto completoBoukadir, Saïd. "Caractérisation par résonance magnétique nucléaire des noyaux quadrupolaires à l'état solide". Lille 1, 1989. http://www.theses.fr/1989LIL10100.
Texto completoCharmont, Patrick. "Contributions à l'amélioration de la résolution en résonance magnétique nucléaire à l'état solide". Lyon, École normale supérieure (sciences), 2001. http://www.theses.fr/2001ENSL0187.
Texto completoHerbert-Pucheta, José-Henrique. "Aspects structuraux, dynamiques et méthodologiques de la résonance magnétique nucléaire à l'état solide de biomolécules". Paris 6, 2012. http://www.theses.fr/2012PA066584.
Texto completoAn important number of molecular systems of biological interest like proteins cannot be studied by x-ray diffraction or liquid-state nuclear magnetic resonance methods because of lack of single crystals or intrinsic insolubility. Solid-state NMR spectroscopy offers the potential to provide precious information about the secondary structure of proteins, protein-protein interactions, folding and internal dynamics. Extensive solid-state NMR studies have been done on microcrystalline proteins, amyloid fibrils, membrane proteins or micelle-protein suspensions. Yet methodological developments in sample preparation of microcrystalline proteins, as well as further development in high-resolution solid-state NMR techniques are necessary. This thesis focuses on a number of structural, motional and methodological aspects encountered in the studies of biomolecules by solid-state NMR. An insight into the structural and motional features of C-terminal domain of the Human Centrin 2 (C-ter HsCen2) complex in a microcrystalline state is presented in the first part of the dissertation. In the second part, it is shown how one- and two-dimensional solid-state NMR experiments can help to disentangle spectral features in systems containing a mixture of different crystallographic forms with crystallographically inequivalent molecules in the unit cell of L-arginine hydrochloride. Polymorphism of L-glycine samples obtained by laser-induced crystallization methods is also studied. The final chapter presents an approach for removing the intrinsic asymmetry of 2D solid-state homonuclear correlation spectra of uniformly labelled biomolecules by equilibrating the magnetization in the initial stage of exchange experiments. It is also shown that the requirements needed for symmetrising the 2D exchange spectra are similar to the requirements needed to record quasi-quantitative cross-polarization magic-angle spinning spectra
Hu, Bingwen. "Manipulations des interactions dipole-dipole en RMN de l'état solide". Thesis, Lille 1, 2009. http://www.theses.fr/2009LIL10062/document.
Texto completoThis thesis deals with the recoupling and decoupling of dipolar homonuclear and heteronuclear interactions in solid-state NMR.First, two kinds of techniques for establishing the through-space correlations between quadrupolar nuclei and spin 1/2 nuclei are presented. One is MPCP (Multiple-pulse Cross-Polarization) recoupling sequence and the other one is D-HMQC (Dipolar assisted- Heteronuclear Multiple Quantum Coherence) sequence. We evaluate different kinds of dipolar recoupling techniques such as SFAM, SR41², that are used in our D-HMQC. Second, we propose a new 1H homonuclear dipolar decoupling technique labeled SAM (Smooth Amplitude Modulation). This method that is a symmetry-based sequences, works mainly at fast or ultra-fast Magic Angle Spinning (MAS) rates (vR > 25 kHz) and is complementary to previous methods, such as DUMBO, FSLG/PMLG. Third, a novel symmetry-based homonuclear recoupling method (SPIP) that excites double-quantum (DQ) coherences between spin-1/2 nuclei, such as 1H, is presented. Compared to previous 1H DQ-recoupling techniques, this pulse sequence requires moderate rf field, even at ultra-fast MAS speed. Furthermore, it displays higher robustness to both chemical shift anisotropy and spreads in resonance frequencies.Fourth, a new processing scheme, called covariance, is employed in solid state NMR to produce homo-nuclear correlation (HOMCOR) 2D spectra. It can accommodate signal truncation much better than the usual 2D-FT data treatment, without any previous knowledge of the positions and line-widths of the resonances. Besides, covariance methods can be applied to HETCOR NMR data to generate two HOMCOR indirect-covariance spectra
Quoineaud, Anne-Agathe. "Caractérisation et quantification de l'aluminium dans les zéolithes désaluminées par RMN haute-résolution à l'état solide". Caen, 2002. http://www.theses.fr/2002CAEN2049.
Texto completoGerbaud, Guillaume. "Etude des facteurs qui influencent la qualité du découplage hétéronucléaire en résonance magnétique nucléaire de l'état solide". Aix-Marseille 1, 2004. http://www.theses.fr/2004AIX11012.
Texto completoSahour, Mohamed Elhaddi. "Application de la résonance magnétique nucléaire à l'étude des mouvements moléculaires à l'état solide : cas du 1-cyanoadamantane". Lille 1, 1986. http://www.theses.fr/1986LIL10021.
Texto completoLacoste, Jean-François. "Élaboration de fibres de poly(éthylène téréphtalate) à propriétés thermomécaniques améliorées par modification chimique à l'état fondu et à l'état solide". Lyon 1, 2004. http://www.theses.fr/2004LYO10045.
Texto completoThe aim of this thesis is to enhance the thermomechanical properties of PET fibers trialkoxysilane end-group crosslinking (hydrolysis-condensation) after the functionalization the alcohol and acid PET end-groups with bifunctional reagents. OH groupes were reacted with anhydride or isocyanate and COOH groups with epoxide. Reaction kinetics were studied by NMR on end-group model compounds. During melt modification many degradation and side reactions were observed and crosslinking occurred after hydrolysis-condensation. Thus we preferred to study the solid-state functionalization by diffusion of reagents at temperatures below 256°C. After solid-state modification, crosslinking finally occured giving maximum gel contents of 70°C. Mechanical properties of partially crosslinked samples were maintained up to 320°C
El, Alaoui El Abdallaoui Habib. "Étude de la structure et de la dynamique de molécules phosphorylées et de leurs complexes métalliques par mesures du temps de relaxation spin-réseau des noyaux #3#1p, #1#3c et #1#7o en solution et RMN à l'état solide". Nancy 1, 1992. http://www.theses.fr/1992NAN10184.
Texto completoPorcino, Marianna. "La spectroscopie de résonance magnétique nucléaire à l'état solide : un outil pour la caractérisation des systèmes poreux de délivrance de médicaments". Thesis, Orléans, 2020. http://www.theses.fr/2020ORLE3054.
Texto completoDrug delivery systems (DDSs) are formulations used to improve the performance of drugs with low efficacy and safety. Nanosized porous Metal-Organic Frameworks (MOFs) are considered as promising drug carriers, as large amount of drug can be incorporated in their pores and their surface can be coated with specific ligand, increasing their stability and efficacy. Analysis of the structure of a DDS is an essential step to guide the synthesis efforts towards particles with improved properties. Solid-state NMR spectroscopy is uniquely suited to study these supramolecular assemblies as it provides information at the atomic scale about drug location, drug-carrier interaction, and carrier structure and about the process of degradation, which allows the delivery of the drug. In this thesis, we have explored the potential of ssNMR spectroscopy associated to, when required, isotope labeling for the in-depth characterization of selected MOF-based DDSs. A particular focus was put on the use of heteronuclei (19F, 27Al, 31P, 13C, 17O) that are present in the drug and/or the carrier, and which, at the cost of severe sensitivity drop, provide much more information than 1H nucleus
Weingarth, Markus. "Découplage et recouplage en RMN haute résolution à l'état solide en présence d'une rotation à l'angle magique très rapide et dans les champs statiques élevés : aspects méthodologiques et applications". Paris 6, 2010. http://www.theses.fr/2010PA066549.
Texto completoPizzala, Hélène. "Etude structurale et dynamique par résonnance magnétique nucléaire de salicylidèneamines substituées à l'état solide : transfert de proton et polymorphisme". Aix-Marseille 1, 1999. http://www.theses.fr/1999AIX11032.
Texto completoGardiennet-Doucet, Carole. "Exploitation de l'anisotropie de déplacement chimique pour l'étude de la géométrie moléculaire et des contacts intermoléculaires par résonance magnétique nucléaire à l'état solide". Nancy 1, 2005. http://www.theses.fr/2005NAN10010.
Texto completoThis work presents various methodologies to probe the molecular geometry and the nature of intermolecular contacts in organic and inorganic solids. The first part gives a brief description of basic principles of solid-state NMR that are used through these studies. In the second part, the variation of chemical shielding tensor principal values of carboxy carbon-13 and phosphate phosphorus-31 upon deprotonation is correlated with ionisation state, conformation and nature of the intermolecular interactions. The third part deals with the characterisation of the strong hydrogen bond involving the silanols of sodium hydrous polysilicates, using complementary methods such as 1H-29Si cross-polarisation dynamics and dipolar modulation of the 29Si chemical shift anisotropy at slow spinning frequency
Ziarelli, Fabio. "Applications et développements des méthodes de résonance magnetique nucléaire haute résolution à l'état solide pour les matériaux organiques et inorganiques". Aix-Marseille 1, 2004. http://www.theses.fr/2004AIX11004.
Texto completoTruflandier, Lionel. "Détermination de paramètres RMN par la théorie de la fonctionnelle de la densité : application aux éléments 3d en RMN de l'état solide". Nante, 2007. http://www.theses.fr/2007NANT2083.
Texto completoBesides Zeeman levels perturbation, nuclear magnetic resonance spectroscopy (NMR) applied to solid state allows the observation of numerous coupling interactions that are not accessible in liquid state. Despite sequential developments for high resolution measurements, interpretation of resonance spectra remains delicate. .
Chandrappa, Ravi Kumar. "Caractérisation de formulations pharmaceutiques par RMN de l'état solide : polymorphisme et déformulation". Versailles-St Quentin en Yvelines, 2011. http://www.theses.fr/2011VERS0058.
Texto completoThis thesis reports on the use of solid-state NMR in the quality control of pharmaceutical formulations. Polymorphism structural studies were done on two active principle components of pharmaceutical drugs, Xaliproden and Irbesartan. A process of deformulation is proposed and validated, aiming at controlling drug quality and detecting counterfeits. The effects of processing on the stability of the drugs and the individual ingredients are followed and described by use of high-resolution NMR techniques. Finally, the quantitative aspects of the NMR measurements by 13C CPMAS techniques are investigated. Common techniques are evaluated for 13C enriched or naturally abundant samples, and another method is proposed in view of these applications
Udupi, Seetharamacharya Sudheendra. "Solid-state NMR studies of membrane associated polypeptides : Applications to channel-forming peptides". Université Louis Pasteur (Strasbourg) (1971-2008), 2005. https://publication-theses.unistra.fr/public/theses_doctorat/2005/UDUPI_SEETHARAMACHARYA_Sudheendra_2005.pdf.
Texto completoRichard, Julie-Andrée. "Étude de l'interaction entre le dimyristoylphosphatidylglycérol et la purothionine-ß par spectroscopies infrarouge et de résonance magnétique nucléaire du phosphore-31 à l'état solide". Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2001. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/MQ57837.pdf.
Texto completoCalin, Nathalie. "Etude thermique de quelques sels d'hétéropolymolybdates : mise en évidence d'interactions anion-anion et anion-cation à l'état solide". Lille 1, 2001. https://pepite-depot.univ-lille.fr/LIBRE/Th_Num/2001/50376-2001-119.pdf.
Texto completoCoelho, Cristina. "Matériaux silicophosphate et RMN en phase solide : apport des expériences dipolaires (D) et scalaires (J)". Paris 6, 2007. http://www.theses.fr/2007PA066129.
Texto completoAlexis, Marie. "Effet du feu sur le stockage de carbone dans un écosystème subtropical : dynamique des charbons". Paris 6, 2006. http://www.theses.fr/2006PA066332.
Texto completoYaakoub, Mfeddel. "Synthèse et caractérisation d'oxo-carboxylates de titane (IV) par diffraction des RX et RMN en solution ou à l'état solide". Université Louis Pasteur (Strasbourg) (1971-2008), 2008. https://publication-theses.unistra.fr/public/theses_doctorat/2008/YAAKOUB_Mfeddel_2008.pdf.
Texto completoThis PhD thesis is devoted to a structural study of some titanium(IV) oxocarboxylate species synthesized by reacting titanium(IV) alkoxides with various carboxylic acids. The manuscript is made of three parts describing results obtained with saturated, unsaturated and halogenated carboxylic acids respectively. A new nomenclature is proposed allowing to classify with logic and rigor all the structures described both in literature and in this thesis. All the reported new compounds (a grand total of 27) were characterized through single-crystal X-ray diffraction and structurally described. Another major improvement was to perform in each case a detailed NMR study involving a wide range of techniques : solution NMR (1H and 13C), solid-sate NMR with cross-polarization and magic angle spinning (13C CP-MAS) as well 2D spectroscopies such as 1H DOSY and 1H-1H COSY. It was thus possible to check the stability or instability of the structures observed in the solid state after dissolution of crytalline species in CDCl3
Saito, Kazuko. "Analyse quantitative par RMN de l'état solide C-13 par polarisation croisée et en rotation à l'angle magique "CPMAS" de formulations galéniques en vue de l'identification de contrefaçons". Versailles-St Quentin en Yvelines, 2011. http://www.theses.fr/2011VERS0003.
Texto completoThis thesis undertakes a reinvestigation of the solid state NMR CPMAS measurement for pharmaceutical materials, in order to assess their quality: original drugs, generics of counterfeits. The pulse sequence RAMP-CPMAS was revisited in order to evaluate its performances for quantification. Combining RAMP-CPMAS with a forced return to equilibrium with a “flip-back” pulse allows obtaining a measurement in a reasonable and constant time, suppressing one of the limitations for the implementation of solid state NMR in the industry. All the parameters of the magetization transfert du ring CPMAS can therefore be under experimental control, including those described to be intrinsically sample dependent, , TCH et T1, by using a good choice of experimental parameters. Therefore, CPMAS measurement can be made quantitative. Base upon these results, recommandations for quantitative measurements are suggested for different types of situations
Nagendrachar, Garaga Mounesha. "Structure locale autour d'hétéroatomes dans des matériaux alumino- et borosilicates pour la catalyse". Phd thesis, Université d'Orléans, 2013. http://tel.archives-ouvertes.fr/tel-00919192.
Texto completoWang, Qiang. "Recouplage dipolaire en RMN des solides en rotation à l'angle magique". Thesis, Lille 1, 2010. http://www.theses.fr/2010LIL10159/document.
Texto completoSolid state NMR as a powerful analysis tool is extensively used in many fields such as catalysis science, polymer materials, and biological molecules. This thesis work mainly describes the development of new NMR methods to recover dipolar coupling of rotating solids and their applications for spectral assignment and structural investigation by solid state NMR. First, a new broadband homo-nuclear Double Quantum (DQ) dipolar recoupling sequence which can be used at high field and ultra-fast magic-angle spinning was introduced. To improve the spectral resolution, 1H homonuclear decoupling technique were applied during the acquisition time, t2 and indirect evolution time, t1. Then, a comparison between different symmetry sequences with and without composite pulses which also can be used at ultra fast spinning for DQ coherence excitation was discussed. Moreover, these homonuclear DQ dipolar recoupling sequences were the employed for the unambiguous assignment of 19F spectra of inorganic fluorides at high field (18.8 T) and ultra-fast magic-angle spinning (65 kHZ). To expand DQ dipolar recoupling methods on half-integer quadrupolar nuclei, a low radiofrequency (RF) pulse sequence with block cycling to selectively excite homo-nuclear DQ coherence of central transition (CT) was proposed. Last, a scheme for rapid analysis of natural abundance amino acid by high-resolution 14N filtered high resolution 1H-13C correlation was designed in the NMR of rotating solid
Caron, Matthieu. "Réexamen du mécanisme de l’intumescence : application au système modèle PP/APP/PER/4A". Electronic Thesis or Diss., Centrale Lille Institut, 2024. http://www.theses.fr/2024CLIL0001.
Texto completoThis work deals with the re-investigation of the thermal decomposition of a model intumescent polypropylene (PP) containing ammonium polyphosphate (APP), pentaerythritol (PER) and zeolite 4A as a synergy agent. The fire performances of PP/APP/PER/4A formulations are studied to determine the optimal mass fraction of 4A (1 wt%). The decomposition steps of PP/APP/PER/4A formulations with and without PP or 4A are determined by thermogravimetric analyses (TGA). Then, the chemical structure of the materials and the evolution of the free radicals are studied as a function of temperature by ex-situ 27Al, 29Si, 13C and 31P nuclear magnetic resonance (NMR) andelectron paramagnetic resonance (EPR) analyses respectively. Besides, ex-situ hyperfine correlation (HYSCORE) pulsed EPR analyses are done to follow the evolution of the chemical environments of free radicals in the materials in a precise and innovative way. It is showed that materials undergo a structural shift between 350 and 400 °C from a predominantly carbonaceous residue with a high concentration of free radicals to a predominantly phosphorated residue
Kunjir, Shrikant. "Study of new porous materials by NMR". Thesis, Normandie, 2018. http://www.theses.fr/2018NORMC211/document.
Texto completoThe zeolites are ‘molecular sieves’ known for their numerous applications in adsorption, ion exchange, and catalysis. In this thesis, we focused on the study of some questions related to zeolite synthesis and post-synthesis, which are not yet resolved by other techniques. NMR was the primary tool in this work, as it gives access to local structural information on nanocrystals even when diffraction techniques found their limits. NMR can also be used to study porosity using probe molecules adsorption, and in particular, xenon is known as a good molecule for this purpose. Indeed, the isotope 129Xe can be hyperpolarized to increase the detection sensitivity, and interestingly it presents a wide chemical shift range depending on its confinement and thus the porosity of studied material. Two studies are reported in this manuscript: (i) In the first study, the initial steps during the crystallization of nano-faujasite (FAU) type materials were investigated using classical NMR (mainly by 29Si and 23Na MAS NMR) and advanced NMR (129Xe HP NMR). It was shown that crystallization starts at much earlier synthesis stages than those observed by other classical techniques (XRD, SEM, N2 adsorption…). The first SBU seems to be the hexagonal prisms, prior to the sodalite cages, which rapidly form confined environment and then supercages. Moreover, it has been proved by 129Xe HP NMR and 2D EXSY that nano-faujasite zeolite presents opened sodalite cages and a more flexible structure than in micro-faujasite zeolite. (ii) The second study is an investigation on the recrystallization phenomena occurring during hierarchization process of zeolite and which could explain the homogenous distribution of the mesopore sizes. As a remarkable result, it has been shown in this work that during the hierarchization of beta zeolite with TPAOH, the recrystallization lead to the formation of tiny MFI particles, formed at the surface of the mesopores (1H MAS NMR, 129Xe HP NMR and 2D EXSY)
Matthes, de Schwalmstadt Jochen. "Utilisation de la spectroscopie RMN à l'état gazeux, liquide et solide pour l'étude de la mobilité du dihydrogène et de l'interaction hydrogène métal dans des complexes des métaux de transition". Toulouse 3, 2004. http://www.theses.fr/2004TOU30044.
Texto completoZagdoun, Alexandre. "Dynamic Nuclear Polarisation Surface Enhanced NMR Spectroscopy". Phd thesis, Ecole normale supérieure de lyon - ENS LYON, 2014. http://tel.archives-ouvertes.fr/tel-01065554.
Texto completoSchahl, Adrien. "Interactions polysaccharides-lipides : étude théorique et expérimentale combinant calculs de dynamique moléculaire, calculs quantiques de spectres RMN 13C et RMN 13C à l'état solide". Thesis, Toulouse 3, 2020. http://www.theses.fr/2020TOU30178.
Texto completoPolysaccharide-lipid interactions now form a vast domain of study, of particular interest to the pharmaceutical and food industries. We already know that amylose, an essentially linear polysaccharide composed of [alpha 1→4]-linked glucose moieties, can form helices around small hydrophobic molecules and lipidic chains. These helical structures are called V polymorphs and their study may allow the development of new ways to deliver bioactive compounds, or of new vaccine adjuvants. This type of interaction might also be found in other biological systems, such as in the capsule of Mycobacterium tuberculosis. Indeed, this external layer covering the bacillus is composed mostly of a large branched polysaccharide analogous to amylose, called alpha-glucan, but it also contains numerous lipids, such as phtiocerol dimycocerosates or trehalose dimycolates, known to be virulence factors of the mycobacterium. Demonstration of the existence of such interactions and their study may lead to a better understanding of the capsule and its biological functions. This manuscript describes a study combining theoretical and experimental methods to characterize the interactions amongst amylose complexes formed in the presence of classical and mycobacterial lipids and in systems composed of branched polysaccharides. The first part of this work describes two purely theoretical studies on amylose complexed with palmitic acid and on amylose double helices called B polymorphs. Using molecular dynamics (MD) simulations and calculations of Nuclear Magnetic Resonance (NMR) parameters at the Density Functional Theory (DFT) level, we were able to define the minimum number of glucose residues needed to former a stable V polymorph around a palmitic acid molecule. We could also show that the number of residues has a direct impact on the calculation of NMR parameters and that it is crucial to consider the dynamic behavior of these polymers to obtain results that fit well to experimental data. Regarding the B polymorph, we showed that it is essential/necessary to consider the periodic conditions of the system to be able to characterize two different residue positions, as has been observed experimentally. To the best of our knowledge, no V polymorph has been characterized in the presence of lipids composed of several lipidic chains. The second part of this manuscript describes several such complexes, formed in the presence of classical and mycobacterial lipids composed of 1, 2 or 4 lipidic chains, and their analysis by solid-state NMR. We elaborated a model describing the different equilibria implicated in the complexation process and could demonstrate that the primary structure of the lipids was one of the key factors. [...]
Pitard, Domitille. "Étude de l'organisation à l'état solide et de la dynamique des chaines polymères dans les nanocomposites polyéthylène/POSS". Phd thesis, Université Paris-Est, 2008. http://tel.archives-ouvertes.fr/tel-00461664.
Texto completoDekhil, Myriam. "RMN cristallographique : mesure de distances internucléaires sur des échantillons de poudre par RMN du solide". Electronic Thesis or Diss., Aix-Marseille, 2016. http://www.theses.fr/2016AIXM4734.
Texto completoMeasurment of dipolar coupling provides 3D structural information of powder samples. However, in practice, the high density of spins in organic compounds prevents the measurements of long-range dipolar couplings in solid-state NMR by the so-called dipolar truncation effect. The study of rare spins on natural abundance allows to overcome this problem. In fact, with a natural abundance of 1.1 %, the probability for three 13C to be coupled is negligible. We developed a methodology based either on the dipolar recoupling NMR pulse sequence POST-C7 or on the dramatic increase in sensitivity provided by dynamic nuclear polarization. We demonstrated that its methodology provides a measure of 13C-13C dipolar couplings in natural abundance powder samples and that the so-obtained distance information is sensitive to both molecular conformation and crystal packing of powder samples. Moreover, we show that the recoupling pulse sequence R20_9_2 is more robust to strong chemical shift anisotropy and also to strong 1H-13C heteronuclear dipolar couplings than POST-C7. The second challenge involves 13C signal assignment for natural abundance. In fact, there are only a few examples of 13C-13C correlation spectra obtained for natural abundance samples. Here, we show that 13C-13C correlation spectra sequence based on the reintroduction of 13C−13C dipolar couplings can be obtained with standard MAS probe and within few days using R20_9_2 pulse sequence. Contrary to pulse sequences based on 13C-13C J coupling, our pulse sequence requires shorter DQ excitation time and hence, is more suitable for samples having short T2 relaxation times such as amorphous solids
Bertani, Philippe. "Mesures de distances internucléaires par résonance magnétique nucléaire du solide haute résolution". Université Louis Pasteur (Strasbourg) (1971-2008), 2001. http://www.theses.fr/2001STR13125.
Texto completoWang, Shishan. "Production, assembly and solid-state NMR analysis of various hepatitis B virus capsids". Thesis, Lyon, 2019. http://www.theses.fr/2019LYSE1146.
Texto completoHepatitis B is a widely spread liver disease which causes a heavy burden for human health, with 257 millions of people affected by chronic infection and about 780,000 deaths per year. Yet, infected patients can not be completely cured by current treatments using notably nucleos(t)ide analogues and interferons. In order to achieve the goal of the World Health Assembly (WHA), who wishes to eliminate hepatitis B by 2030, new therapies need to be developed. Given its critical role for the Hepatitis B virus (HBV) life cycle, the core protein (Cp) is today one of the antiviral targets with the highest potential. Our research focuses on the characterization of HBV capsids in different conformational states using biochemistry and solid-state NMR, aiming at revealing their precise conformation under different conditions, including the interaction of capsids with antivirals, and the correlation between capsid conformation and viral maturation. For sample preparation, both a bacterial expression system and a wheat germ cell-free protein synthesis system have been established in the laboratory to produce HBV capsids, and protocols to disassemble and reassemble capsids with different nucleic acids have been implemented. Both capsids preformed in E. coli and capsids reassembled in vitro were addressed to NMR studies. Different capsids forms include the truncated versions Cp140 and Cp149, the full length protein Cp183, the phosphorylated P-Cp183 and mutant forms. First, we have prepared samples for the sequential assignment of the protein using solid-state NMR. The use of carbon-13 detection asks for several tens of milligrams of sample, which were produced using labeled isotopes and bacterial expression in minimal media. Sequential assignments were performed using the truncated capsid Cp149, which showed highly similar spectra to Cp183. This sample was also used to identify conformational differences between the four different monomers in the capsid, which are due to the T=4 icosahedral symmetry. Then, the main body of the thesis is the investigation and comparison of a variety of different capsid forms, including Cp183, P-Cp183, Cp149, Cp140, another truncated form resulting in mainly T=3 icosahedral assemblies, and Cp140 C61A and Cp183 F97L mutants. We investigated all samples in both the E. coli-produced and reassembled forms, which needs for the full-length protein the presence of nucleic acids, of which we tested several, including the viral pregenomic RNA. We investigated different symmetries, as well as oxidation states of the capsid, and compared the differences via chemical shift perturbations observed in NMR spectra. We reported in a site-specific manner the major conformational changes observed between the different preparations. Proton-detected solid-state NMR at 100 kHz has recently emerged as a tool for analyzing proteins with the need of less sample amount. We have applied this strategy to the analysis of the Cp149 capsids, in order to obtain sequential assignments of the amide proton resonances. For this, deuteration of the protein in bacteria was used as well, needing adaptation of sample preparation protocols. Proton detection can be successfully combined with cell-free protein synthesis, which gives low yields compared to bacterial expression. This approach is of potential interest to analyze capsid assembly modulation induced by the presence of drugs. While we have started in the framework of this thesis to analyze the capsid in presence of different capsid assembly modulators by carbon-13 detected NMR on E. coli and reassembled capsids (preliminary results not reported here), proton detection opens the way to an analysis of the impact of capsid modulation directly on the exit of the core proteins from the ribosome, on assembly. We showed that cell-free expression combined with proton-detection solid-state NMR can be used to analyze capsid chemical shifts, and thus in future work the conformational modulations
Imbach, Juliette. "Etude de la solution solide hydroxylapatite-britholite : apport de la résonance magnétique nucléaire du solide". Paris 11, 2001. http://www.theses.fr/2001PA112194.
Texto completoDekhil, Myriam. "RMN cristallographique : mesure de distances internucléaires sur des échantillons de poudre par RMN du solide". Thesis, Aix-Marseille, 2016. http://www.theses.fr/2016AIXM4734.
Texto completoMeasurment of dipolar coupling provides 3D structural information of powder samples. However, in practice, the high density of spins in organic compounds prevents the measurements of long-range dipolar couplings in solid-state NMR by the so-called dipolar truncation effect. The study of rare spins on natural abundance allows to overcome this problem. In fact, with a natural abundance of 1.1 %, the probability for three 13C to be coupled is negligible. We developed a methodology based either on the dipolar recoupling NMR pulse sequence POST-C7 or on the dramatic increase in sensitivity provided by dynamic nuclear polarization. We demonstrated that its methodology provides a measure of 13C-13C dipolar couplings in natural abundance powder samples and that the so-obtained distance information is sensitive to both molecular conformation and crystal packing of powder samples. Moreover, we show that the recoupling pulse sequence R20_9_2 is more robust to strong chemical shift anisotropy and also to strong 1H-13C heteronuclear dipolar couplings than POST-C7. The second challenge involves 13C signal assignment for natural abundance. In fact, there are only a few examples of 13C-13C correlation spectra obtained for natural abundance samples. Here, we show that 13C-13C correlation spectra sequence based on the reintroduction of 13C−13C dipolar couplings can be obtained with standard MAS probe and within few days using R20_9_2 pulse sequence. Contrary to pulse sequences based on 13C-13C J coupling, our pulse sequence requires shorter DQ excitation time and hence, is more suitable for samples having short T2 relaxation times such as amorphous solids
Roux-Da, Silva Mélanie. "Caractérisation structurale, en particulier par resonance magnétique nucléaire du solide, d'aluminophosphates microporeux bruts de synthèse et traités en température". Mulhouse, 2002. http://www.theses.fr/2002MULH0707.
Texto completoThe aim of this work is to characterize microporous aluminophosphate materials by various solid-state NMR and powder X-ray diffraction techniques. Three aluminophosphates were chosen: AlPO4-SOD, AlPO4-ZON and AlPO4-40. These materials were recently synthesized in the Laboratoire de Matériaux Minéraux and their frameworks can be described by the same SBU (Secondary Building Units) 6-2 or 4. Structural modifications induced by various thermal treatments and the effect of rehydration were particularly investigated for AlPO4-SOD and AlPO4-ZON. The AlPO4-40 synthesis was also optimized in the presence of fluorine, the corresponding material was compared to that synthesized from an alkaline medium
Dhalluin, Christophe. "Etude par résonance magnétique nucléaire à l'angle magique de molécules sur support solide". Lille 1, 1997. http://www.theses.fr/1997LIL10141.
Texto completoHamdouna, Lama. "Caractérisation RMN et activité antimicrobienne de complexes organométalliques préparés par mécanosynthèse". Electronic Thesis or Diss., Université de Lille (2022-....), 2023. https://pepite-depot.univ-lille.fr/ToutIDP/EDSMRE/2023/2023ULILR048.pdf.
Texto completoThe extensive use of solvents in modern chemical synthesis has posed significant economic and environmental challenges. To address these concerns, it is crucial to reduce solvent usage and embrace eco-friendly synthesis methods. One promising solution to these challenges is mechanochemical synthesis, which employs mechanical forces to drive chemical reactions without traditional solvents. However, many aspects of the reaction mechanisms involved in mechanochemistry remain poorly understood. Solid-state nuclear magnetic resonance (ssNMR) spectroscopy, capable of providing atomic-level resolution, holds great promise in unraveling the mechanisms of mechanochemical reactions. In this dissertation, we applied ssNMR spectroscopy to investigate the mechanochemical synthesis of transition metal-N-heterocyclic carbene (NHC) complexes through the weak base approach. These complexes, such as [Cu(Cl)(NHC)], [Ag(Cl)(NHC)], and [Rh(acac)(CO)(NHC)], have applications in catalysis and as anti-infective coatings for medical devices. Our research primarily focuses on exploring the impact of different workup protocols used during the preparation of these complexes. To explore these processes, we conducted a series of multinuclear ssNMR experiments, involving spin-1/2 (1H, 13C, 15N, 109Ag) and quadrupolar (35Cl, 63Cu) nuclei, at static magnetic field strengths of 9.4, 18.8, and 28.2 T. This approach allowed us to monitor the consumption of reactants and the formation of intermediate and final products across various synthetic routes and workup protocols. We leveraged the high resolution and sensitivity offered by a 1.2 GHz NMR magnet to observe isotopes subject to substantial quadrupolar interactions, such as 35Cl and 63Cu. Signal assignment in the NMR spectra was achieved through 2D heteronuclear correlation techniques in conjunction with Density Functional Theory (DFT) calculations of NMR parameters. Additionally, we complemented our ssNMR studies with techniques such as powder X-ray diffraction (XRD) and vibrational spectroscopy. Moreover, we extended our investigation to the mechanochemical synthesis of chalcogen-NHC derivatives, specifically thioureas (NHC=S) and selenoureas (NHC=Se), known for their unique electronic properties and biological activities. Using multinuclear ssNMR experiments, including spin-1/2 (1H, 13C, 15N, 77Se) and quadrupolar (33S) nuclei at static magnetic fields of 9.4 and 18.8T, along with DFT calculations of NMR parameters, we unveiled the mechanisms underlying these transformations. Our findings unequivocally confirm that the studied transition metal-NHC complexes and chalcogen-NHC derivatives are indeed formed in the solid state during ball milling, dispelling any doubts regarding solvent-driven reactions during subsequent workup or characterization. However, this assertion does not apply to the [Rh(acac)(CO)(NHC)] complexes, where mechanical forces during ball milling facilitated the reaction but necessitated the presence of solvents to complete it. Additionally, our study identified intermediate compounds, unreacted reagents, and by-products, providing a comprehensive understanding of the reaction outcomes. In conclusion, our research provides valuable insights into the mechanisms of mechanochemical processes and highlights the potential of ssNMR spectroscopy as a powerful technique for investigating and optimizing sustainable synthesis routes. This work contributes to the development of environmentally friendly and economically viable methods for chemical synthesis, addressing the pressing challenges posed by solvent usage in modern chemistry
Tembou, Nzudie Denis. "Etude de l'interphase des latex core-shell par la RMN du solide à haute résolution". Mulhouse, 1992. http://www.theses.fr/1992MULH0234.
Texto completoDe, Paëpe Gaël. "Découplage hétéronucléaire en RMN solide". Lyon, École normale supérieure (sciences), 2004. http://www.theses.fr/2004ENSL0280.
Texto completoKolokolov, Daniil. "Dynamique d'espèces adsorbées dans des matériaux poreux étudiée par ²H NMR et spectroscopie neutronique". Phd thesis, Université Claude Bernard - Lyon I, 2010. http://tel.archives-ouvertes.fr/tel-00833374.
Texto completoDuweltz, David. "Etudes de l'organisation en masse du polypropylène isotactique par RMN du solide". Paris 12, 2002. http://www.theses.fr/2002PA120013.
Texto completoThe iPP M a great industrial polymer whose properties are related to his semi-crystallin character. The iPP tends to crystaffise under lamellar form, the crystallites being separated by amorphous regions. The degree of crystallinity, as well as the structural forms, largely depend on the crystallisation conditions. The macroscopic properties of the crystalline homopolymers are greatly related to the amorphous and crystalline spatial distribution and to the respective mobilities. The aim of this work is to study these features with the use of the 1H and 13C NMR techniques. The nature of the crystalline form has been studied by solid-state 13C NMR. The values of the relaxation times, T1 (1H) and T1p(1H), in the crystalline regions reflect the size and the perfection of the crystallites. Thus, we have monitored the transformation of the smectic phase of a quenched sample to the alpha-form. The 1H NMR made it possible to obtain quantitative information on the different phases. We have evidenced, by 1H NMR, three distinct regions in the iPP: a crystalline phase, a free amorphous phase and a constraint amorphous phase. A good correlation has been obtained between the percentage of the different regions, measured by NMR, and the rate of the crystalline regions measured by X-ray scattering. The mobility of the free amorphous phase depends on the annealing temperature. An annealing at high temperature indeed allows to relax the constraints of this phase. The influence of the regio-defects on the bulk organisation of the iPP has been studied by means of iPP synthesized by metallocene catalysis exhibiting tail-to-tail linking defects and iPP/Ethylene copolymers. The presence of defects induces a noticeable decrease of the crystalline degree. The localisation of the defects in the iPP has been realised by 13C NMR. The major part of the defects is in the amorphous phase. However, we have highlighted that a little fraction of these defects are included in the crystallites
Fruchart, Jean-Sébastien. "Nouvelles méthodologies de synthèse en phase solide et apport de la RMN à l'angle magique pour la caractérisation d'intermédiaires sensibles". Lille 2, 2001. http://www.theses.fr/2001LIL2P012.
Texto completoGiraud, Nicolas. "Développements méthodologiques pour l'analyse structurale et dynamique de protéines par résonance magnétique nucléaire du solide". Lyon 1, 2005. http://www.theses.fr/2005LYO10165.
Texto completoWarnet, Xavier. "Études des membranes biologiques par RMN du solide in cellulo". Sorbonne Paris Cité, 2015. http://www.theses.fr/2015USPCC177.
Texto completoNuclear Magnetic Resonance (NMR) spectroscopy has revealed efficient for in situ (and in vivo) structural studies of biological macro-molecules. The first studies focused on small soluble molecules, and quickly, the interest shifted toward the study of soluble proteins. For few years now, magie-angle spinning (MAS) solid-state NMR has appeared as a technique of choice to obtain structural information about membrane proteins in their native environment (biological membranes). It is now well established that the two major components of biological membranes, that is to say: lipids and membrane proteins, are intimately connected, and the study of their mutual influences constitute a crucial step in die comprehension of biological membranes as a whole. In order to bring some dues regarding this question we have chosen a particular system: the strain C43(70E3) and its network of proliferating membranes, formed after the over-expression of the b subunit of the ATP synthase F1F0 of E. Coli. The analysis of the organisation of this network, and the involvement of the b subunit (via MAS NMR 13C/15N) and lipids (via mass spectrometry and MAS NMR 31P) allowed us to obtain some information regarding the importance of these two components in the establishment and stabilisation of this membrane network. Moreover, during this project, the combination of 2H NMR and MAS appeared as a technique particularly suited for die study of biological membranes of whole cells (alive) under various growth conditions. Also, the methods used and developed during this project could prove beneficial in the study of various biological membranes, from a proteic and lipidic stand point
Paris, Michael. "Etude de l'ordre local dans les biopolymères par RMN du solide : applications aux traitements physico-chimiques de l'amidon". Le Mans, 2000. http://cyberdoc.univ-lemans.fr/theses/2000/2000LEMA1017.pdf.
Texto completoThe 13C high resolution solid state NMR spectra of well defined starchy substrates - native and recrystallized starches - were recorded. For both A and B crystalline polymorphs, the decomposition of these spectra showed the existence of three phases in natives starches (amorphous, intermediate and crystalline) and only two in recrystallized starches (intermediate and crystalline). The plasticizing/structuring role of water was evidenced for each phase. Moreover, the comparison of the crystalline phase amount determined by NMR and X-ray diffraction showed the simultaneous water molecules effects at both local and microscopic scales. The non-crystalline phase rnultiplicity led us to the first experimental study of amorphous state characterization in starches. Decomposition of the13C high resolution solid state NMR spectra of amorphous samples prepared from various starchy substrates with different techniques showed the heterogeneous reproducible character of these amorphous samples. Indeed, only 4 main types of well identified and stable of (1-4) linkages exist in these substrates. Moreover, two of them are dependent on the sample history (technique of preparation and branching points). In addition to the spectral decomposition characterization, a dynamical approach was undertaken. For the amorphous starchy substrates, the magnetization curves versus crosspolarization contact time were plotted for each individual component evidenced by the spectral decomposition. In agreement with 2D NMR WISE experiments, the fitting of these curves need a two proton reservoirs model of cross-polarization. The determination and the interpretation of the characteristic parameters of this model yielded informations about water molecules distribution inside the samples. Moreover, this dynamical approach confirmed some of our previous results obtained by spectral decomposition. Finally, the 13C chemical shift anisotropy versus glycosidic angles (D,Y) was predicted from ab initio calculations (Gaussian 98). This anisotropy was also determined by 2D NMR chemical shift recoupling experiments. The comparison of both allowed to estimate the glycosidic angles values associated to the different types of the c(1-4) linkages. The first results of this method were discussed
Stein, Paul Christiaan. "Contribution à l'étude des conducteurs organiques par la RMN". Paris 11, 1985. http://www.theses.fr/1985PA112182.
Texto completoThis thesis presents a nuclear magnetic resonance (NMR) investigation of the organic conductors (TMTSF)₂Clo₄ and (TMTSF)₂PF₆. NMR results on the proton and carbon atoms are correlated to the physical and structural properties of these conductors. At ambient temperature the effective dimensionality has been studied by proton NMR. The salts exhibit a cross-over from a two-dimensional regime to a one-dimensional regime as a function of the timescale of the measurements, which is fixed by the magnetic field. High resolution ¹³C CP-MAS NMR experiments have allowed resolution of all individual carbon sites. The different sites exhibit strong, anisotropic deviations from Korringa's law. At law temperatures the metal-insulator (spin density wave) transition in TMTSF) PF has been studied by proton NMR as a function of orientation and temperature at various magnetic fields in the neighborhood of the spin-flop field. The spin-lattice relaxation rate exhibits a divergence at the transition temperature, which is well described by a three-dimensional coupling to critical fluctuations. In order to estimate the influence of molecular motion on the proton relaxation time, a study of methylgroup rotation has been performed by proton NMR between 20 K and 300 K
Colsenet, Roxane. "Étude par RMN de la diffusion moléculaire : influence de la structure des protéines laitières à l'état liquide et gélifié". Nantes, 2005. http://www.theses.fr/2005NANT2111.
Texto completo