A tese de doutorado tem como foco o desenvolvimento de nanopartículas superparamagnéticas (Fe3O4 - magnetita) hidrofílicas e lipofílicas aplicadas à nanotecnologia do petróleo. Inicialmente, os objetivos foram voltados para a elaboração e transferência de tecnologia envolvendo uma rota de síntese de nanopartículas lipofílicas, em escala semi-industrial. Para isso, foram realizados ensaios piloto num reator com capacidade de uma tonelada, visando a produção de nanopartículas magnéticas recobertas com ácido esteárico. Mais tarde, esse trabalho foi otimizado, permitindo sua execução em laboratório, prosseguindo depois, com um escopo mais amplo, incluindo a síntese de nanopartículas recobertas com polímero hidrofílico. Nesse sentido, foram desenvolvidas duas rotas inéditas para produção desses nanomateriais. Em um segundo estágio, as investigações foram voltadas para a utilização das nanopartículas sintetizadas, em estudos de avaliação das condições dos reservatórios de petróleo. Para isso, a técnica de ressonância magnética nuclear (RMN) foi explorada, monitorando o efeito da concentração dessas nanopartículas superparamagnéticas sobre o tempo de relaxação dos prótons, e o consequente efeito de contraste nas imagens em função da magnetização. A aplicação desse tipo de ferramenta (RMN) já vem sendo feita (sem nanopartículas magnéticas) pelas empresas prestadoras de serviço ao setor de petróleo e gás, na avaliação e perfilagem de reservatórios. Isso motivou o estudo dos nanomateriais magnéticos como sondas para melhorar o mapeamento de fluidos em meio poroso. Eles seriam aplicados como aditivos em fluidos de injeção em reservatórios, tanto para imageamento, como para a obtenção de parâmetros petrofísicos. Por fim, devido à presença de grupos carboxílicos na superfície das nanopartículas hidrofílicas, foram investigadas suas interações com microcristais de carbonato de cálcio, pensando no modelo de reservatório petrolífero do tipo carbonáceo. Explorando técnicas de microscopia eletrônica de varredura (MEV) e de microscopia Raman confocal, a presença das nanopartículas magnéticas sobre a superfície da matriz mineral foi constatada, confirmando sua interação efetiva com o CaCO3. Abordando a síntese, caracterização e aplicações das nanopartículas superparamagnéticas, esta tese proporciona uma base para estudos de aplicação de nanomateriais, assunto cada vez mais relevante, diante dos inúmeros problemas e desafios enfrentados pelo setor de petróleo e gás. / The Ph.D thesis is focused on the preparation of hydrophilic and lipophilic superparamagnetic nanoparticles (Fe3O4 - magnetite) for application in oil nanotechnology. The initial efforts have been directed to the upscaling of a laboratory route of synthesis of lipophilic nanoparticles, aiming technology transfer to the industry. Accordingly, a pilot process, involving a one ton reactor, has been tested for the production of magnetic nanoparticles coated with stearic acid. After this, the research has evolved, allowing the production in the laboratory scale, and continued, pursuing the development of nanoparticles coated with a hydrophilic polymer. Two new routes for the production of these nanomaterials have been developed. In a second step, the investigations were directed to the application of these nanoparticles to the evaluation of oil reservoirs, by monitoring the proton relaxation times, using nuclear magnetic resonance (NMR), and the consequent contrasting effects observed on the images, as a function of the magnetization and the concentration of these particles. Currently, NMR tools are being employed in the oil and gas sector for the evaluation and profiling of reservoirs. This fact has stimulated the use of such nanomaterials for improving the mapping of the fluids in porous media. Introduced as additives for fluid injection into reservoirs, they can enhance the imaging and also perform the rating of petrophysical parameters. Finally, the presence of carboxylic groups on the surface of the hydrophilic nanoparticles has been explored in studies of interaction with calcium carbonate, simulating a carbonaceous type reservoir. Based on electron microscopy (SEM) and confocal Raman microscopy, the presence of magnetic nanoparticles on the surface of the mineral matrix has confirmed the interaction of these particles with the CaCO3 surface. By developing the synthesis, characterization and application of superparamagnetic nanoparticles, this work provides a useful starting point for further research on the use nanoparticles, for solving problems and challenges in the oil and gas sector.

En dépit de leur importance, la caractérisation des communautés bactériennes dans l’environnement reste encore très incomplète. Les principales raisons sont, d’une part, la difficulté d’appréhender la totalité de la communauté bactérienne quand plus de 99% des bactéries demeurent récalcitrantes à la culture in vitro et ne peuvent donc être étudiées par les approches classiques de microbiologie. D’autre part, la métagénomique, censée contourner cette méthode de culture en s’intéressant à l’ensemble des génomes extraits des milieux d’études, demeure elle aussi imparfaite du fait de limitations techniques (biais d’extraction de l'ADN, de clonage, de PCR, de séquençage et d’assemblage des génomes etc.) et conceptuelles, inhérentes à la complexité et l’hétérogénéité des environnements. Pour compenser les limites de chacune de ces techniques, des méthodes de tri cellulaire appliquées en conjonction avec les deux premières pourraient aider à un meilleur décryptage de la diversité microbienne. Basée sur la sélection spécifique (taxonomique et/ou fonctionnelle) et l’isolement direct des cellules bactériennes ciblées à partir d’un échantillon environnemental complexe, l’étude est restreinte à une population spécifique, voire à une cellule isolée. Pourront alors être appliquées les approches classiques de mise en culture ou d’extraction de l’ADN pour une étude restreinte à l’ADN ou l’ARN, leur répétition sur les différentes populations devant à terme (lointain) approcher l’exhaustivité. C’est dans ce contexte que s’est positionné ce travail de thèse visant dans un premier temps à mettre au point un nouvel outil de tri cellulaire basé sur l’intégration de micro-aimants permanents dans un canal microfluidique. A partir de ce système de tri magnétique miniaturisé, offrant de nombreux avantages (dispositif portable, peu coûteux, nécessitant de faibles volumes réactionnels et potentiellement intégrable en « laboratoire sur puce »), une technique d’isolement sélectif de cellules bactériennes marquées magnétiquement a alors été développée. Ciblées sur des critères taxonomiques après hybridation in situ avec des sondes d’acides nucléiques biotinylés complémentaires d’une région spécifique du gène 23S rRNA, des cellules bactériennes ont été marquées magnétiquement après réaction de la sonde avec des nanoparticules magnétiques fonctionnalisées par des molécules de streptavidine. Les premiers résultats montrent l’établissement d’une méthode de tri suffisamment spécifique et sensible pour piéger les cellules marquées diluées (0,04%) au sein d’une suspension, à des niveaux compatibles avec l’isolement futur de populations d’intérêt à partir de communautés d’environnements complexes. Sur un principe comparable, l’approche a été adaptée à l’étude des transferts horizontaux de gènes in situ. Les applications d’un tri cellulaire grâce au marquage par des nanoparticules magnétiques et l’emploi de micro-aimants intégrés dans des microsystèmes fluidiques semblent donc très prometteuses pour le développement de la microbiologie environnementale. / Despite their importance, bacterial communities in the environment remain poorly characterized. On the one hand, it is difficult to gain knowledge of the community as a whole because over 99% of bacteria are recalcitrant to in vitro culture, rendering classic microbiological approaches imposible to carry out. On the other hand, metagenomics, which can be used to circumvent culture-based approaches by extracting all the genomes from a given environment, is also problematic given the associated technical limitations (biases related to DNA extraction, cloning, PCR, genome sequencing and assembling etc.), and conceptual difficulties related to the complexity and the homogeneity of the environments. In order to overcome some of the limitations of these approaches, bacterial cell selection methods have been developed and can be used to improve our understanding of microbial diversity. Based on taxonomic and/or functional selection and the direct isolation of bacterial cells from an environmental sample, bacterial cell selection can be used to reduce microbial community complexity by targeting specific populations, or even an isolated cell. A variety of classic approaches such as cultivation or DNA/RNA extraction can then be carried out. This cycle can theoretically be repeated until all members of the community are characterized. The aim of this doctoral thesis was to design a novel cell selection tool based on the permanent integration of micro-magnets into a microfluidic canal. In conjunction with a new miniaturized magnetic selection system that provides several advantages over larger systems (portable, low cost, requiring smaller reaction volumes and can be potentially integrated on “laboratory on a chip” systems), a method for selective bacterial cell isolation using magnetic labeling was developed. The bacterial cells were targeted based on taxonomic criteria; biotin-labeled probes were developed for a specific region of the 23S rRNA gene. Following in situ hybridization with the probes, baceterial cells were labeled with streptavidin-functionalized magnetic nanoparticles. First results showed that the tool was specific and sensitive enough to trap labeled and diluted (0,04%) cells from a suspension at levels that are comparible to populations of interest found in complex environmental communities. This tool has also been adapted to study in situ horizontal gene transfer as well. The application of a cellular selection tool that labels targets with magnetic nanoparticles coupled to fluidic microsystems with integrated nano-magnets looks very promising for future studiesin environmental microbiology.

The study of bulk and nanoparticles of perovskite rare earth manganites has been an extensive area of research in the recent past due to their rich and interesting physics and potential applications [1-5]. Manganites have potential applications in the emerging field of spintronics because of their colossal magnetoresistance (CMR) [6] and half-metallic [7] properties. Nano sized materials exhibit enhanced and different electronic and magnetic properties and expected to behave quite differently compared to their bulk counterparts due to quantum confinement effects and high surface/volume ratio. Magnetic nanoparticles in particular have great potential for use in a wide range of applications including magnetic recording media, various sensors, catalysts, magnetic refrigeration, medicine etc. In this thesis we study changes in the magnetic ordering of certain bismuth based manganites Bi1-xAxMnO3 (A = Ca and Sr) using various experimental probes when we reduce their particle size to nano scale. The general formula for doped manganites is R1-xAxMnO3 where R is a trivalent rare-earth ion such as La, Nd, Pr, Sm and A is a divalent alkaline earth ion such as Ca, Sr, Ba, Pb. They became interesting due to their many intriguing properties like CMR (Colossal Magnetoresistance), phase separation, charge ordering (CO), orbital ordering (OO) and many more. These properties depend sensitively on many factors like temperature, magnetic field, pressure and doping concentration x. There is a strong coupling of spin, orbital and lattice to each other in manganites. The complex interplay of all these couplings make them strongly correlated systems. In the parent compound RMnO3 Mn ion is in Mn3+ state while it is present as Mn4+ in the compound AMnO3. The manganites with x = 0 and x = 1 are both antiferromagnetic insulators, magnetism in them being mediated by superexchange through oxygen. On doping with a divalent alkaline earth ion in RMnO3, there is a transition The properties of nanoparticles of manganites show strong surface effects. The magnetic behavior is strongly governed by the free surface spins in nanoparticles. And as the size reduces, there is suppression of charge ordering which can also disappear in very small particles [11]. Antiferromagnetism in bulk gives way to ferromagnetism in nanoparticles [12-14]. In the following we give a chapter wise summary of the results reported in the thesis. Chapter 1: This chapter of the thesis consists of a brief introduction to the physics of manganites. Further we have written a detailed overview of bismuth based manganites, properties of nano manganites and the technique of EPR. There is a section about different line shapes observed in EPR of manganites, their origin and how to fit them to appropriate lineshape function [15]. This chapter also includes a detailed account of experimental methodologies used in thesis which are: EPR spectrometer, SQUID magnetometer, X-ray diffractometer and TEM and the analysis procedure adopted in this work. Chapter 2: This chapter deals with the magnetic and EPR studies of nanoparticles (average diameter ~ 30 nm) of Bi0.25Ca0.75MnO3 (BCMO) and their comparison with the results on bulk BCMO. Bulk Bi0.25Ca0.75MnO3 (BCMOB) shows charge ordering at 230 K followed by a transition to an antiferromagnetic phase at 130 K [16]. The bulk and the nanoparticles (D ~ 30 nm) of Bi0.25Ca0.75MnO3 were prepared by solid-state reaction method and sol-gel method respectively. The two samples were investigated by using XRD, TEM, SQUID and EPR techniques. Our magnetization and EPR results show that the charge ordering disappears in nanoparticles of this composition and there emerges a ferromagnetic phase similarly to the rare earth manganites. The nanoparticles of the rare earth based manganites are found to consist of an antiferromagnetic core and a ferromagnetic shell/surface region [3, 17] and thus are expected to exhibit the ‘exchange bias (EB) effect’ [18-22] resulting in a shift of the magnetic hysteresis loop. Indeed many nanomanganites do show EB effect. However, contrary to this expectation, we find that in BCMON samples the EB effect is absent. Chapter 3: In this chapter, we report the results of temperature dependent magnetization and electron paramagnetic resonance studies on bulk and nanoparticles of electron (x = 0. 6, BCE) and hole (x = 0.4, BCH) doped Bi1-xCaxMnO3 (BCMO) and the effect of the size reduction on the electron-hole asymmetry observed in the bulk sample. Bulk sample of Bi0.4Ca0.6MnO3is a paramagnetic insulator at room temperature with Tco = 330 K and TN ~ 120 K while BiCaMnO3 undergoes a charge ordering transition at TCO = 315 K with TN ~ 150 K [16]. All the four samples were investigated by using XRD, TEM, SQUID and EPR techniques. It is shown that antiferromagnetism and charge order persist in the hole doped nano sample while ferromagnetism has emerged in the electron doped nano sample. Our magnetization and EPR results show that spin glass phase exists in bulk BCE, bulk BCH and nano BCE whereas no sign of either spin glass state or ferromagnetism is seen in nano BCH. We have shown that electron-hole asymmetry in terms of ‘g’ parameter has reduced in the nanoparticles but it has not completely disappeared in contrast with the results on Pr1-xCaxMnO3 [23]. We understand these interesting results in terms of the presence of the highly polarizable 6s2 lone pair electrons on bismuth which is known to cause many interesting departures from the behavior of rare earth manganites. We study the temperature dependence of the linewidth behavior by fitting it to the different models [24¬27] and find that Shengelaya’s model [25, 26] fits well to all the four samples describing the spin dynamics satisfactorily in the present samples. Chapter 4: In this chapter, we present the fabrication, characterization and the results obtained from the magnetization and EPR measurements carried out on bulk and nanoparticles of Bi0.1Ca0.9MnO3. We prepared the nanoparticles of BCMO by standard sol¬gel technique and bulk samples by solid state reaction method. We investigated magnetic ordering by doing temperature dependent magnetic and EPR studies on both the samples and compared the properties with each other. Bulk Bi0.1Ca0.9MnO3 (BCMB) shows mixed phase of antiferromagnetism and ferromagnetism without any charge ordered state. Our results show that the ferromagnetism exists in the bulk BCMO which is present in the nano sample as well but with somewhat weakened strength with the size reduction. The nanoparticles of the rare earth based manganites are found to consist of an antiferromagnetic core and a ferromagnetic shell/surface region and thus are expected to exhibit the more uncompensated spins on the surface which reduce the magnetization in the nanoparticles. We calculated activation energy for the two samples by fitting the intensity behavior to the Arrhenius equation [28]. Activation energy was found to decrease for nano BCMO which indicates the weaker intracluster double-exchange interaction in it. Chapter 5: This chapter deals with the comparative study of the temperature dependent magnetic properties and EPR parameters of nano and bulk samples of Bi0.2Sr0.8MnO3 (BSMO). Nanoparticles and bulk sample of BSMO were prepared by sol-gel technique and solid state reaction method respectively. Bulk BSMO has high antiferromagnetic transition temperature TN ~ 260 K and robust charge ordering (TCO ~ 360 K) [29]. We confirm that the bulk sample shows an antiferromagnetic transition around ~ 260 K and a spin-glass transition ~ 40 K. For nano sample we see a clear ferromagnetic transition at around ~ 120 K. We conclude that mixed magnetic state exists in the bulk sample whereas it is suppressed in the nano sample and strong ferromagnetism is induced instead. Chapter 6: This chapter summarizes the main conclusions of the thesis, also pointing out some future directions for research in the field.

La fabrication d’aimants permanents nano-structurés est l’une des solutions envisagées pour remplacer les aimants actuels à base de terres rares, pour lesquelles se posent des problèmes géopolitiques et environnementaux. Dans le but d’élaborer de tels matériaux, nous avons suivi une approche bottom-up utilisant des méthodes chimiques.Nos travaux ont visé dans un premier temps à synthétiser des nanoparticules (NPs) magnétiques dures qui peuvent servir de briques élémentaires dans la fabrication d’aimants nano-structurés. Notre étude systématique sur des nanobâtonnets de cobalt (NBs Co) synthétisés par voie polyol, a montré que leur champ coercitif augmente de 3 à 7 kOe avec la diminution du diamètre et l’augmentation du rapport d’aspect structural. Des simulations micro-magnétiques ont montré qu’un mécanisme de retournement d’aimantation par nucléation-propagation de parois rendait compte des résultats expérimentaux. Des NPs bi-métalliques FePt et tri-métalliques FePtX (X = Ag, Cu, Sn, Sb) de structure CFC ont été obtenues par l’adaptation d’une synthèse organométallique ou par la réduction d’acétylacétonates métalliques. Les recuits à haute température (650°C pour FePt, 400°C pour FePtX) ont conduit à la transition de phase FePt CFC L10 et à des champs coercitifs élevés (>12 kOe). La maîtrise d’un procédé multi-étapes, impliquant la protection des NPs FePt CFC par une coquille MgO et un recuit à 850°C, a permis d’obtenir des NPs FePt L10 de taille moyenne 10 nm présentant des champs coercitifs jusqu’à 27 kOe.La seconde partie de nos travaux a porté sur l’assemblage de NPs présentant des anisotropies différentes. Deux systèmes ont été étudiés : FePt CFC+FeCo CC, FePt L10+NBs Co HCP. Dans les deux cas, le contact entre les deux types de NPs a été favorisé par l’utilisation d’un ligand bi-fonctionnel suivi d’un traitement thermique. Dans le système FePt+FeCo, le recuit à haute température (650°C), nécessaire pour obtenir la phase FePt L10, a entraîné l’inter-diffusion des phases et la quasi-disparition de la phase FeCo CC. Dans le second système FePt+Co, un comportement de spring magnet a clairement été identifié, les deux phases étant efficacement couplées. L’inter-diffusion des phases a été limitée par la température modérée du recuit (400°C). Un champ coercitif de 10 kOe a été mesuré pour une teneur en Pt de seulement 25%at., malgré la perte de la forme anisotrope des NBs Co. / The production of nano-structured permanent magnets is a promising alternative to rare earth magnets, which induced geopolitical and environmental issues. In order to elaborate such materials, we followed a bottom-up approach based on chemical methods. A first objective consisted in synthesizing hard magnetic nanoparticles (NPs) as building blocks for nano-structured magnets. The properties of cobalt nanorods (Co NRs) synthesized by the polyol process have been systematically studied. Coercive fields could be raised from 3 to 7 kOe by decreasing the diameter and improving the structural aspect ratio. Micro-magnetic simulations showed that a magnetization reversal following a nucleation and domain-wall propagation process could explain the experimental results. Bi-metallic FePt and tri-metallic FePtX (X = Ag, Cu, Sn, Sb) exhibiting the FCC structure were synthesized following two routes based on the reduction of an organometallic Fe precursor or of metallic acetylacetonates. Annealing at high temperatures (650°C for FePt, 400°C for FePtX) allowed the phase transition FCC  L10 to occur, leading to high coercive fields (>12 kOe). A multi-steps process, involving the protection of FePt NPs with an MgO shell and an annealing at 850°C, was optimized to produce L10 FePt NPs with a mean size of 10 nm and a coercivity up to 27 kOe. In the second part of our study, we worked on assemblies of NPs with different magnetic anisotropies. Two systems were studied : FCC FePt+BCC FeCo, L10 FePt+HCP Co NRs. In both cases, the contact between the two types of NPs was favored by the presence of a bi-functional ligand followed by an annealing step. Concerning the FePt+FeCo system, the high temperature annealing (650°C), required to get the L10 FePt phase, led to the inter-diffusion of the phases and to the dissolution of the BCC FeCo phase. For the FePt+Co system, a spring magnet behavior has been clearly evidenced, the two phases being efficiently coupled The inter-diffusion of the phases was limited thanks to the fairly low annealing temperature (400°C). A coercive field of 10 kOe was measured for a Pt content as low as 25%at., eventhough the Co NRs anisotropic morphology was lost

Le laboratoire LT2C utilise depuis quelques années un procédé sol-gel basse température pour développer un matériau magnéto-optique composite parfaitement compatible avec les technologies d’optique intégrée sur verre. Néanmoins, la qualité actuelle du matériau ne permet pas son utilisation dans l’intégration des composants à effets non-réciproques. Dans le but d’exalter les effets magnéto-optiques et le facteur de mérite du matériau, le laboratoire LT2C s’est orienté vers sa structuration 3D en adaptant une approche basée sur les opales. Cette dernière consiste à fabriquer des opales directes à partir de l’auto-arrangement de microbilles de polystyrène sur un substrat de verre. Les opales sont ensuite infiltrées par une solution sol-gel dopée par des nanoparticules magnétiques de ferrite de cobalt. Après traitement thermique, le polystyrène est dissout dans l’acétate d’éthyle pour obtenir une structure 3D formée de trous d’air dans une matrice de silice dopée. Dans ce cadre, l’objectif des travaux de cette thèse consiste tout d’abord à optimiser au mieux la procédure d’élaboration des opales afin d’améliorer leur qualité structurelle et magnéto-optique. Ensuite, il consiste à réaliser une étude systématique des effets magnéto-optiques dans ces structures 3D pour investiguer le comportement spectral de l’effet Faraday, et ainsi qualifier les modifications apportées au facteur de mérite. Une analyse des images MEB et une caractérisation optique montrent que notre méthode d’élaboration conduit à la fabrication d’opales de bonne qualité structurelle et optique. Les mesures de rotation et d'ellipticité Faraday en fonction du champ magnétique appliqué présentent des cycles d’hystérésis, et mettent en évidence un effet non-réciproque, ce qui surligne le caractère magnéto-optique des opales inverses dopées. Une étude spectrale systématique des effets magnéto-optiques dans ces structures 3D montre deux pics et une atténuation de rotation et d’ellipticité Faraday, respectivement en bords et au centre de la BIP. Cependant, ces modifications spectrales significatives ne conduisent pas à une exaltation de la valeur du facteur de mérite. Cela est principalement dû aux défauts structurels qui diminuent le niveau de transmission de l’opale inverse dopée par rapport la couche de référence / LT2C laboratory uses since recent years a low temperature sol-gel process to develop a magneto-optical composite material that is perfectly compatible with glass integrated optics. However, due to an actual low figure of merit, this material cannot be embedded on integrated non-reciprocal devices. In order to exalt the magneto-optical effects and figure of merit, the LT2C laboratory adopted a process based on opals to 3D structure the material. The selected process consists in elaborating direct opals by self-assembling monodisperse polystyrene microspheres on glass substrate. Those opals are then impregnated with a homogeneous solution of sol-gel silica precursors doped with cobalt ferrite nanoparticles. Resulting samples are later oven dried for 1 hour at 90°C. Finally, polystyrene spheres are dissolved in ethyl acetate to obtain a 3D structure formed by air voids in doped silica matrix. In this context, the objective of this thesis is to optimize the fabrication process of opals in order to improve their structural and magneto-optical quality. Furthermore, it consists in making a systematic study of the magneto-optical effect in these structures in order to investigate the spectral behavior of the Faraday effect and thus quantify the figure of merit. Analysis of SEM images and optical characterization prove that our elaboration process leads to the fabrication of opals with good structural and optical quality. Measurements of Faraday rotation and ellipticity as a function of applied magnetic field show hysteresis loops with an unambiguous non-reciprocal behavior. These observations highlight the magneto-photonic character of the doped inverse opals. A systematic spectral study of the magneto-optical effect in these 3D structures displays two peaks and an attenuation of Faraday rotation and ellipticity, respectively at the edges and the center of the photonic band gap. However, these significant spectral modifications do not increase the value of figure of merit. This ascertainment is primarily due to structural defects that lower the transmission magnitude of the doped inverse opals in comparison to a magneto-optical reference monolayer

Dans les systèmes des télécommunications, beaucoup d’études ont été entreprises pour intégrer des composants passifs non réciproques. Le bon fonctionnement des circulateurs exige souvent des aimants volumineux et lourds qui assurent une orientation uniforme des moments magnétiques du matériau ferrite. Pour tendre vers l’intégration et la miniaturisation des circulateurs, les nanotechnologies peuvent offrir des solutions intéressantes. L’objectif de cette thèse a été de développer un circulateur coplanaire auto-polarisé. L'approche choisie est fondée sur la réalisation de substrats composites à «nano-fil ferrimagnétiques». Elle consiste à faire un dépôt par magnétophorèse ou dip-coating de nanoparticules de ferrite de cobalt dans des membranes d’alumine poreuses et de les orienter sous champ magnétique de manière uniforme. Des substrats composites magnétiques ont été fabriqués à partir de nanoparticules CoFe2O4 dispersées dans une matrice sol-gel de silice en utilisant la technique de Dip-coating avec et sans un champ magnétique appliqué. De nombreuses études ont été faites afin d'étudier le comportement magnétique et diélectrique de ces substrats : VSM, polarimétrie spectrale, MFM et autres. Les cycles d'hystérésis montrent une forte différence des valeurs des champs coercitifs (μ0Hc) et rémanents (Mr/Ms) si, durant la fabrication, un champ magnétique est appliqué ou non, démontrant ainsi l'orientation (ou non) des nanoparticules. Ce nano-composite est un candidat intéressant pour la fabrication de circulateurs même si la concentration et l’orientation des particules sont insuffisantes. Des circulateurs ont été conçus, modélisés et simulés à l'aide du logiciel HFSS. Suite à des résultats de simulation intéressants; un premier prototype a été fabriqué et caractérisé en hautes fréquences. Les résultats de mesure ont montré un phénomène de circulation, qui reste très faible en raison du faible pourcentage de nanoparticules magnétiques dans le composite et de leur orientation imparfaite. Les verrous technologiques ont été clairement identifiés et ne permettent pas, pour l’instant, de réaliser un circulateur opérationnel / In telecommunications systems, many studies have been undertaken to integrate non-reciprocal passive components. The proper functioning of circulators often requires large and heavy magnets that ensure a uniform orientation of the magnetic moments of the ferrite material. To work towards the integration and miniaturization of circulators, nanotechnology can offer interesting solutions. The aim of this thesis was to develop a self-biased coplanar circulator. The approach is based on the production of composite substrates "ferrimagnetic nanowire." It consists in a magnetophoresis or a dip-coating deposition of cobalt ferrite nanoparticles in porous alumina membranes and orienting them in a magnetic field uniformly. Magnetic composite substrates were made from CoFe2O4 nanoparticles dispersed in a matrix of silica sol-gel using the dip-coating technique with and without an applied magnetic field. Many studies have been made to study the magnetic and dielectric behavior of these substrates: VSM, spectral polarimetry, MFM and others. The hysteresis loops show a strong difference in the values of coercive fields (μ0Hc) and persistent (Mr / Ms) if, during the fabrication, a magnetic field is applied or not, therefore showing the orientation (or not) of nanoparticles. This nano-composite is an interesting candidate for the fabrication of circulators even if the concentration and the particle orientation are insufficient. Circulators were designed, modeled and simulated using the HFSS software. Following the interesting results of simulation; a first prototype was fabricated and characterized at high frequencies. The measurement results showed a circulation phenomenon, which is very low due to the small percentage of magnetic nanoparticles in the composite and their imperfect orientation. Technological barriers have been clearly identified and do not allow for the time to achieve an operational circulator

Avec 35 millions de personnes atteintes dans le monde, la maladie d'Alzheimer (MA) est la maladie neurodégénérative la plus répandue. L'une des caractéristiques pathologiques de cette maladie est l'apparition de plaques amyloïdes, composées d'agrégats de peptide beta-amyloïde. Aujourd'hui, le diagnostic repose essentiellement sur des tests neuropsychologiques et sur la mise en évidence de changements dans la structure du cerveau tels que l'atrophie corticale (diminution du volume du cerveau). Cependant les symptômes de cette maladie n'apparaissent qu'à un stade très développé. Ainsi la détection in vivo des dépôts de peptide beta-amyloïde avant le développement de la maladie pourrait conduire à un diagnostic plus précoce et plus probant. Elle pourrait également faciliter le suivi et l'évaluation des effets des interventions thérapeutiques au cours du traitement. Dans ce travail, nous avons développé une méthode de diagnostic précoce innovante, capable de cibler et de détecter les plaques Abeta à la fois par l'imagerie par résonance magnétique et par l'imagerie de fluorescence. Nous avons développé un nouveau type d'agents de contraste intelligents pour l'imagerie multimodale, basé sur des nanoparticules magnétiques sur lesquelles sont greffés les polythiophènes luminescents (LCPs). Les LCPs à la surface des nanoparticules magnétiques se lient aux plaques Abeta de manière sélective et spécifique. Lors de cette liaison, la liberté conformationnelle des polythiophènes se trouve limitée, ce qui conduit à des spectres d'émission spécifiques dépendant de la conformation, et rend pertinent l'usage de l'imagerie par résonance magnétique et de fluorescence des plaques Abeta / Alzheimer's disease is the most common neurodegenerative disorder, affecting around 35 million people worldwide. One of the characteristic pathological hallmarks of AD is amyloid plaques; consist of beta-amyloid peptide aggregates. Today’s diagnosis depends essentially on neuropsychological tests and in highlighting change in brain structure such as cortical atrophy. A major issue is that symptoms appear only at a developed stage of the disease. Then in vivo detection of beta-amyloid deposits at an early stage could lead to earlier and more conclusive diagnosis of AD and help monitoring the effect of therapeutic interventions. In this work, we develop an innovative and early diagnosis method, able to target and detect beta-amyloid deposits aggregates both by magnetic resonance and fluorescence imaging. Thus we develop a new kind of smart contrast agent for multimodal imaging, based on magnetic nanoparticles on which are grafted luminescent conjugated polythiophenes (LCPs). LCPs on the surface of the magnetic nanoparticles bound to beta-amyloid aggregates selectively and specifically. Upon biding to beta-amyloid aggregates the conformational freedom of the backbone is restricted, leading to specific conformation-dependent emission spectra from the LCPs, opening the way for magnetic resonance and fluorescence imaging of the beta-amyloid plaques

L’objectif principal de ce travail de thèse est de formuler un matériau nanocomposite doté de propriétés magnéto-optiques (MO) et photostructurable pour, in fine, réaliser des dispositifs optiques non-réciproques pouvant être intégrés au sein de puces optiques. Le matériau nanocomposite MO est obtenu en dispersant des nanoparticules magnétiques (NP) de ferrite de cobalt dans une matrice sol-gel d’alcoxydes de silicium et de titane. Les NP confèrent au matériau ses propriétés MO. La formulation du matériau est photostructurable en UV profond (193, 266 nm) sans ajout de photoamorceur et se comporte comme une photo-résine négative. La formulation est flexible en termes de ratio molaire Si/Ti et de dopage en NP pouvant atteindre 20 %vol. La photochimie du matériau en films minces a été étudiée par ellipsométrie spectroscopique, FTIR et spectroscopie UV-visible. Les techniques de photolithographies UV interférométriques et par masques binaires ont permis de réaliser des réseaux périodiques de lignes bien définis et couvrant une large gamme de périodes, de 500 nm à 100 µm. Les propriétés optiques et MO (rotation Faraday) du matériau ont été étudiées. En couches minces, l’indice de réfraction peut être modulé entre 1,4 et 1,7 selon la composition du matériau. Il a été établi que l’ensemble des NP introduites dans le matériau contribuent à la rotation Faraday. Des dispositifs microstructurés ont été réalisés en espace libre et en configuration guidée en se basant sur les dimensionnements opto-géométriques déterminés par des simulations optiques et MO. Leurs caractérisations démontrent l’intérêt de ce matériau et son caractère prometteur pour réaliser des dispositifs intégrés. / The main objective of this PhD work is to formulate a nanocomposite material with magneto-optical (MO) properties which is also photostructurable, in order to ultimately create non-reciprocal optical devices that can be integrated into optical chips. The nanocomposite MO material is obtained by homogenously dispersing magnetic nanoparticles (NP) of cobalt ferrite in a sol-gel matrix based on silicon and titanium alkoxides. NP confer the material its MO properties. The material is photostructurable with deep UV wavelengths (193, 266 nm) without any addition of photoinitiator and behaves like a negative photoresist. The formulation is versatile in terms of Si/Ti molar ratio and NP doping, up to 20 %vol. The photochemistry of this material as thin films has been studied by spectroscopic ellipsometry, FTIR and UV-visible spectroscopy. UV photolithography techniques using interferometry setups and binary masks have achieved well-defined periodic lines patterns over a wide range of periods, from 500 nm to 100 microns. The optical and MO (Faraday rotation) properties of the material were studied. In thin layers, the refractive index can be modulated between 1.4 and 1.7 depending on the Si/Ti material stoichiometry and its NP doping. It has been established that all the NP introduced in the material contribute to the Faraday rotation. Micro-structured devices in free space and in guided configuration have been realized using the opto-geometrical features determined using optical and MO simulations. Their characterizations demonstrate the high interest of this material and clearly show its promising character to realize integrated devices.

Cell transplantation and stem cell therapy are promising approaches for regenerative medicine and are of interest to researchers and clinicians worldwide. However, currently, no imaging technique that allows three-dimensional in vivo inspection of therapeutically administered cells in host tissues is available. Therefore, we investigate magnetomotive optical coherence tomography (MM-OCT) of cells labeled with magnetic particles as a potential noninvasive cell tracking method. We develop magnetomotive imaging of mesenchymal stem cells for future cell therapy monitoring. Cells were labeled with fluorescent iron oxide nanoparticles, embedded in tissue-mimicking agar scaffolds, and imaged using a microscope setup with an integrated MM-OCT probe. Magnetic particle-induced motion in response to a pulsed magnetic field of 0.2 T was successfully detected by OCT speckle variance analysis, and cross-sectional and volumetric OCT scans with highlighted labeled cells were obtained. In parallel, fluorescence microscopy and laser speckle reflectometry were applied as two-dimensional reference modalities to image particle distribution and magnetically induced motion inside the sample, respectively. All three optical imaging modalities were in good agreement with each other. Thus, magnetomotive imaging using iron oxide nanoparticles as cellular contrast agents is a potential technique for enhanced visualization of selected cells in OCT.

[pt] Este trabalho pode ser dividido em três etapas principais: síntese das nanopartículas, deposição de filmes finos e litografia por feixe de elétrons. As nanopartículas magnéticas foram sintetizadas pelo método de co-precipitação a partir de sulfato de ferro II (FeSO4), cloreto férrico (FeCl3) e hidróxido de amônia (NH4OH) à temperatura ambiente. Para prevenir a formação de agregados, foi adicionado nitrato de sódio (NaNO3) em pequenas quantidades, que se mostrou bastante eficiente. Em seguida foram produzidos filmes de magnetita utilizando o sistema de pulverização catódica usando fonte de radiofrequência (sputtering RF). Os alvos foram produzidos por compactação das nanopartículas de magnetita produzidas anteriormente. Os filmes finos foram depositados em substrato de silício. A formação de magnetita durante a deposição foi confirmada por difração de raios-x e magnetômetro de amostra vibrante. Uma vez controlados os parâmetros de deposição, foram produzidos arranjos de magnetita. A litografia por feixe de elétrons foi produzida em substrato de silício recoberto com máscara de PMMA (polimetilmetacrilato) de 250 nm de espessura. Foram produzidos arranjos periódicos de formas básicas a modo de testar a técnica de litografia: quadrados de 1 μm e círculos de 1 μm, 500 nm e 250 nm de diâmetro formados de um filme de magnetita de 80 nm de espessura. A espessura do filme, forma, tamanho e separação das figuras que compõem os padrões litografados influenciam na facilidade com que será retirada a mascara de PMMA. / [en] This work can be divided into three main steps: synthesis of nanoparticles, thin film deposition and electron beam lithography. The magnetic nanoparticles were synthesized by co-precipitation method from iron II sulfate (FeSO4), ferric chloride (FeCl3) and ammonium hydroxide (NH4OH) at room temperature. A small amount of sodium nitrate (NaNO3) was added to avoid the cluster formation, which was very efficient. Then the magnetite thin films were produced using the sputtering RF (radio frequency source) system. The targets were produced by compression of magnetite nanoparticles previously produced in the first step. The thin films were deposited on a silicon substrate. The formation of the magnetite after the deposition was confirmed by x-ray diffraction and vibrating sample magnetometer. The arrays of magnetite were made once the deposition parameters were controlled. The electron beam lithography has been produced on silicon substrate covered of PMMA (polymethylmethacrylate) resist 250 nm thick. Were produced periodic arrays of basic forms a way to test the technique of lithography, a square micron circles 1 μm, 500 nm and 250 nm in diameter formed of a magnetite film 80 nm thick. The film thickness, shape, size and separation of the figures which comprise standards lithographed can influence the ease with which the mask is withdrawn from PMMA.