[ES] La fabricación de nanopartículas con tamaños por debajo de los 100 nm ha permitido el desarrollo de innovadores nanodispositivos capaces de interactuar de forma directa con sistemas vivos a nivel celular y molecular, convirtiéndose en una parte fundamental dentro del campo de la nanomedicina. Uno de los principales retos a los que se enfrenta la ingeniería de nanopartículas es el desarrollo de nanodispositivos con propiedades físico-químicas bien definidas, ya que de ellas depende el comportamiento y biodistribución de dichos sistemas una vez introducidos en el organismo. No menos importante es el desarrollo de protocolos de síntesis reproducibles y optimizados, indispensables para la fabricación y escalado de nanodispositivos que puedan ser trasladados a futuras aplicaciones biomédicas. El principal objetivo de este proyecto de doctorado es el estudio y fabricación de nanopartículas magnéticas mesoporosas de sílice con estructura "core-shell" para su aplicación como agentes teranósticos en el campo de la nanomedicina. En este estudio se analiza en profundidad la síntesis y caracterización de dichos nanomateriales con el objetivo de producir nanopartículas con unas propiedades físico-químicas bien definidas de forma controlada y reproducible. La obtención de dichas nanopartículas supondría un gran avance de cara al desarrollo de nanodispositivos más complejos y sofisticados. El contenido de la tesis se ha estructurado en distintos capítulos que se detallan brevemente a continuación: ¿El capítulo 1 es una introducción a la nanomedicina, destacando el papel fundamental que tienen las nanopartículas en el desarrollo de nuevas aplicaciones biomédicas. A continuación se presentan las nanopartículas de sílice mesoporosa, mostrando la gran versatilidad de dichos nanomateriales para el desarrollo de dispositivos teranósticos así como sistemas para la liberación controlada de fármacos. Por último, se destaca la importancia de fabricar nanodispositivos con unas propiedades físico-químicas bien definidas como requisito indispensable para la traslación de los resultados experimentales hacia el campo clínico. ¿El capítulo 2 incluye los objetivos principales de la tesis. ¿El capítulo 3 se centra en la síntesis y caracterización de nanopartículas superparamagnéticas de óxido de hierro (USPIONs), siendo estas utilizadas en capítulos posteriores para la síntesis de las nanopartículas mesoporosas tipo "core-shell". Las USPIONs son preparadas a través de un método sencillo de coprecipitación en el que se emplean condiciones de reacción moderadas. Las nanopartículas obtenidas son caracterizadas en profundidad, analizando sus propiedades magnéticas para su aplicación en hipertermia magnética y como agentes de contraste dual en imagen por resonancia magnética (MRI). ¿El capítulo 4 está dedicado a la preparación de nanopartículas magnéticas mesoporosas de sílice con estructura "core-shell". Los conceptos fundamentales relacionados con los mecanismos de formación de este tipo de nanomateriales son ampliamente analizados, así como los parámetros de reacción involucrados en la síntesis. Como punto de partida, se propone un protocolo de síntesis general para la obtención de las nanopartículas tipo "core-shell". A continuación, se analiza en profundidad el efecto que los distintos parámetros de reacción tienen en las propiedades físico-químicas de dichas nanopartículas. Para la fase de optimización se utiliza un modelo semi-empírico como referencia, racionalizando los resultados experimentales observados en base a un posible mecanismo de formación. ¿El capítulo 5 se centra en el análisis y caracterización de la estructura mesoporosa de las nanopartículas tipo "core-shell". Además, se analiza el efecto que los distintos parámetros de reacción tienen sobre la estructura final de las nanopartículas, aportando información adicional sobre su posible mecanismo / [CAT] La fabricació de nanopartícules amb grandàries per davall dels 100 nm ha permés el desenvolupament d'innovadors nanodispositius capaços d'interactuar de forma directa amb sistemes vius a nivell cel¿lular i molecular, convertint-se en una part fonamental dins del camp de la nanomedicina. Un dels principals reptes als quals s'enfronta l'enginyeria de nanopartícules és el desenvolupament de nanodispositius amb propietats físic-químiques ben definides, ja que d'elles depén el comportament i biodistribució d'aquests sistemes una vegada introduïts en l'organisme. No menys important és el desenvolupament de protocols de síntesis reproduïbles i optimitzats, indispensables per a la fabricació a gran escala de nanodispositius que puguen ser utilitzats en futures aplicacions biomèdiques. El principal objectiu d'aquest projecte de doctorat és l'estudi i fabricació de nanopartícules magnètiques mesoporoses de sílice amb estructura "core-shell" per a la seua aplicació com a agents teranòstics en el camp de la nanomedicina. En aquest estudi s'analitza en profunditat la síntesi i caracterització d'aquests nanomaterials amb l'objectiu de produir nanopartícules amb unes propietats físic-químiques ben definides de forma controlada i reproduïble. L'obtenció d'aquestes nanopartícules suposaria un gran avanç de cara al desenvolupament de nanodispositius més complexos i sofisticats. El contingut de la tesi s'ha estructurat en diferents capítols que es detallen breument a continuació: ¿El capítol 1 és una introducció a la nanomedicina, destacant el paper fonamental que tenen les nanopartícules en el desenvolupament de noves aplicacions biomèdiques. A continuació es presenten les nanopartícules de sílice mesoporosa, mostrant la gran versatilitat d'aquests nanomaterials per al desenvolupament de dispositius teranòstics així com sistemes per a l'alliberament controlat de fàrmacs. Finalment, es destaca la importància de fabricar nanodispositius amb unes propietats físic-químiques ben definides com a requisit indispensable per a la translació dels resultats experimentals al camp clínic. ¿El capítol 2 inclou els objectius principals de la tesi així com els objectius específics proposats per a cada capítol de la tesi. ¿El capítol 3 està dedicat a la síntesi i caracterització de nanopartícules superparamagnétiques d'òxid de ferro (USPIONs), sent aquestes utilitzades en capítols posteriors per a la síntesi de les nanopartícules mesoporoses tipus "core-shell". Les USPIONs són preparades a través d'un mètode senzill de coprecipitació en el qual s'empren condicions de reacció moderades. Les nanopartícules obtingudes són caracteritzades en profunditat, analitzant les seues propietats magnètiques per a la seua aplicació en hipertèrmia magnètica i com a agents de contrast dual en imatge per ressonància magnètica (MRI). ¿El capítol 4 està dedicat a la preparació de nanopartícules magnètiques mesoporoses de sílice amb estructura "core-shell". Els conceptes fonamentals relacionats amb els mecanismes de formació d'aquest tipus de nanomaterials són àmpliament analitzats, així com els paràmetres de reacció involucrats en la síntesi. Com a punt de partida, es proposa un protocol de síntesi general per a l'obtenció de les nanopartícules tipus "core-shell". A continuació, s'analitza en profunditat l'efecte que els diferents paràmetres de reacció tenen en les propietats físic-químiques d'aquestes nanopartícules. Per a la fase d'optimització s'utilitza un model semi-empíric com a referència, racionalitzant els resultats experimentals observats sobre la base d'un possible mecanisme de formació. ¿El capítol 5 està dedicat a l'anàlisi i caracterització de l'estructura mesoporosa de les nanopartícules tipus "core-shell". A més, s'analitza l'efecte que els diferents paràmetres de reacció tenen sobre l'estructura final de les nanopartícules, aportant informació / [EN] The fabrication of nanoparticles with sizes below 100 nm has opened the door to the development of innovative nanodevices that directly interact with living systems at the cellular and molecular level, becoming an essential part of nanomedicine. One of the main challenges that nanoparticle engineering is currently facing is the design of nanodevices with well-defined physico-chemical properties, which ultimately determine the fate and function of these systems inside the organism. Similarly, the development of reproducible and versatile synthetic protocols is of great importance for manufacture purposes, a fundamental requirement for an efficient translation of this technology into the clinic. The main objective of this PhD thesis is the study and fabrication of core-shell-type magnetic mesoporous silica nanoparticles (M-MSNs) for their application as theranostic nanodevices in the field of nanomedicine. A comprehensive study about the synthesis and characterization of this type of nanomaterials is presented with the aim of obtaining core-shell M-MSNs with well-defined physico-chemical properties in a robust and reproducible way. The fabrication of such particles would provide a versatile and reliable platform for the development of more complex nanodevices with advanced functionalities. The thesis has been structured into several chapters that are briefly summarized as follows: ¿Chapter 1 is an introduction to the topic of nanomedicine, highlighting the importance of nanoparticles in the development of new biomedical applications. Mesoporous silica nanoparticles are then introduced, showing the great versatility that this nanomaterials offer for the development of theranostic nanodevices and smart drug delivery systems. Finally, the development of nanodevices with well-defined physico-chemical properties is identified as a crucial requirement for overcoming biological barriers and facilitate the translation of nanomedicines from the bench to bedside. ¿Chapter 2 presents the aims of this thesis and the specific objectives that are addressed in the following chapters. ¿Chapter 3 is devoted to the synthesis and characterization of ultrasmall superparamagnetic iron oxide nanoparticles (USPIONs), which are later used as magnetic seeds for the synthesis of core-shell M-MSNs. USPIONs are prepared through a simple coprecipitation method using mild reaction conditions. The obtained nanoparticles are fully characterized and their magnetic properties are analyzed focusing on magnetic hyperthermia and dual MR imaging applications. ¿Chapter 4 is a comprehensive study about the preparation of monodisperse core-shell M-MSNs. The main concepts related to the synthesis and formation mechanisms of this type of nanomaterials are revised, together with the reaction parameters that are expected to have a major contribution on the reaction. As a starting point, a general synthetic protocol for the synthesis of core-shell M-MSNs is presented. Then, specific reaction parameters are investigated in order to understand their effect on the physico-chemical properties of the obtained nanoparticles. The application of a semi-empirical model to the optimization stage is presented in an attempt to provide an adequate reference framework to understand the formation of this complex nanodevices. ¿Chapter 5 presents a detailed analysis about the characterization of mesoporous silica materials and, in particular, the assessment of the mesoporous structure of MSNs with a radial distribution of wormhole-like channels. The effects that specific reaction parameters have on the mesoporous silica structure of core-shell M-MSNs are also analysed, providing additional information about the formation of this type of nanoparticles. ¿Chapter 6 gathers the main conclusions of this thesis. / Sánchez Cabezas, S. (2019). Development of a reproducible and optimized synthetic protocol for the preparation of monodisperse core-shell-type magnetic mesoporous silica nanoparticles [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/129878 / TESIS

The monolithic integration of III-V semiconductors on Si substrates is a part of a long-term technological roadmap for the semiconductor industry towards More-than-Moore technologies. Despite of the different lattice constants and thermal expansion coefficients, research efforts over the last two decades have shown that III-V crystals with a high structural quality can be grown epitaxially in the form of nanowires directly on Si using CMOS-compatible (Au-free) methods. Among other III-V compounds, InxGa1-xAs is of the special interest for the use in infrared photonics and high-speed electronics due to its tunable direct bandgap and low electron effective mass, respectively. For comparison, InxGa1-xAs thin films are typically grown on lattice-matched InP substrates with a limited range of compositions at around x=0.52. The realization of InxGa1-xAs nanowires on Si, though, has been proved challenging owing to the limited In-content when the nanowires are grown Ga-catalyzed or the high density of stacking faults when the nanowires are grown catalyst-free. In this work, the use of highly lattice-mismatched GaAs/InxGa1-xAs and GaAs/InxAl1-xAs core/shell nanowires on Si(111) substrates have been studied as an alternative to InxGa1-xAs nanowires. The core/shell mismatch strain and its accommodation within the nanowires plays an important role in the growth, the structural, and the electronic properties of the nanowires. A key parameter in this work was the unusually small diameter of 20 – 25 nm of the GaAs core. First, the strain-induced bending of the nanowires during the growth of the shell by molecular beam epitaxy was investigated. It was apparent that the nanowires bend as a result of a preferential incorporation of In adatoms on one side of the nanowires. To obtain straight nanowires with symmetric shell composition and thickness around the core, it was necessary to choose relatively low growth temperatures and high growth rates that limited the surface diffusivity of In adatoms. Second, the strain accommodation in straight nanowires was investigated as a function of the shell thickness and composition using a combination of Raman scattering spectroscopy and X-ray diffraction. For a fixed shell composition of x=0.20 and small enough shell thicknesses, the strain in the shell is compressive and decreases progressively as the shell grows thicker. On the other hand, the strain in the core is tensile with hydrostatic character and increases with shell thickness. Finally, for shell thicknesses larger than 40 nm, the shell becomes strain-free, whereas the strain in the core saturates at 3.2% without any dislocations. For a fixed shell thickness of 80 nm, the strain in the core was further increased by increasing the In-content in the shell, reaching values as high as 7% for x=0.54. A plastic relaxation via misfit dislocations was observed only for the next highest In-content of x=0.70. In agreement to theoretical predictions, the tensile strain in the core resulted in a large reduction of the GaAs bandgap (as measured by photoluminescence spectroscopy), up to approximately 40% of the strain-free value. A similar reduction in electron effective mass is also expected. The transport properties of electrons inside the strained GaAs core were assessed by optical-pump terahertz-probe spectroscopy. Quite high mobility values of approximately 6100 cm2/Vs at 300 K for a carrier concentration of 9×1017 cm−3 were measured, which are the highest reported in the literature for GaAs nanowires, but also higher than the values for unstrained bulk GaAs. The importance of the results in this work is two-fold. On the one hand, strain-free InxGa1-xAs nanowire shells were grown on Si substrates with x up to 0.54 and thicknesses well beyond the critical thickness of their thin film counterparts. Such shells could potentially be employed as conduction channels in high electron mobility transistors (HEMTs) integrated in Si platforms. On the other hand, highly tensile-strained GaAs cores with electronic properties like those of InxGa1-xAs thin films were obtained. In this case, the results demonstrate, that GaAs nanowires can be suitable for photonic devices across the near-infrared range, including telecom photonics at 1.3 and potentially 1.55 μm, as well as for high-speed electronics. GaAs as a binary material is expected to be advantageous compared to InxGa1-xAs due to the absence of structural imperfections typically present in ternary alloys. Finally, to explore the potential of the core/shell nanowires as HEMTs, self-consistent Schrödinger-Poisson calculations of two different modulation-doped heterostructures were performed. In the case of a strained GaAs core overgrown by an unstrained InxGa1-xAs shell and an additional unstrained Si-doped InxAl1-xAs shell, the possibility to form a cylindrical-like two-dimensional electron gas inside the InxGa1-xAs shell was found. In the alternative case of a strained GaAs core overgrown by an unstrained Si-doped InxAl1-xAs shell, it was found that it is possible to form a quasi-one-dimensional electron gas at the center of the core. Both structures are the subject of ongoing research.:1 Introduction 1 2 Fundamentals and state-of-the-art 7 2.1 Electronic and structural properties of III-V semiconductors 7 2.2 Growth of III-V nanowires on Si 20 2.3 Core/shell heterostructure nanowires 29 2.4 Strain in epilayers and core/shell nanowires 36 2.5 Strain engineering in core/shell nanowires and its effect on band parameters 46 2.6 Modulation-doped III-V semiconductor heterostructures 56 3 Methods 61 3.1 Optical and electron microscopes 61 3.2 X-ray diffraction 64 3.3 Raman scattering spectroscopy 65 3.4 Photoluminescence spectroscopy 75 3.5 Optical-pump terahertz-probe spectroscopy and photoconductivity in semiconductors 77 3.6 Device processing 82 3.7 Semiconductor nanodevice software “nextnano” 85 3.8 MBE for crystal growth and core/shell nanowire growth 86 4 Results and discussions 91 4.1 Structural, compositional analyses of straight nanowires and coherent growth limit 91 4.2 Bent nanowires 95 4.3 Strain analyses in core/shell nanowires 97 4.3.1 Dependence of strain on shell thickness 97 4.3.2 Dependence of strain on the shell chemical composition 102 4.3.3 Dependence of strain on the core diameter 105 4.4 Strain-induced modification of electronic properties 106 4.5 Strain-enhanced electron mobility of GaAs nanowires higher than the bulk limit 114 4.6 Towards high electron mobility transistors 123 5 Conclusion and outlook 129 Bibliography 131 List of abbreviations I List of Symbols III List of publications VII List of conference contributions VIII Acknowledgements X

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Les nanoparticules métalliques ont la particularité de fritter à des températures bien inférieures que les microparticules. Les pâtes de frittage à base de nanoparticules d'argent (Ag) sont commercialisées pour assembler des puces d'électronique de puissance à leur substrat. L’assemblage se fait classiquement entre 200 et 300°C, sous contrainte. Le joint métallique final obtenu possède d’excellentes propriétés de conductivités électrique et thermique. La température de fusion théorique du joint, une fois densifié, est égale à la température de fusion de l’Ag massif (962°C). Cette propriété fait de ce nanomatériau une excellente alternative dans l’électronique de puissance « haute température ». Le coût de l’argent, qui est un métal précieux, reste un frein à l’utilisation de ces pâtes de frittage. Une alternative pour baisser les coûts est de remplacer les nanoparticules d’argent par des nanoparticules de cuivre. Le cuivre possède des propriétés de conductivités très proches de celles de l’argent. Un obstacle majeur à l’intégration de nanoparticules de cuivre dans des pâtes de frittage est la propension du cuivre à s’oxyder. L’oxydation des nanoparticules empêche le frittage et diminue fortement les propriétés mécaniques ainsi que la conductivité du joint métallique final. En plus de cela, le cuivre, même non oxydé, est moins réactif lors du frittage et nécessite des températures plus élevées pour une bonne densification que l’argent. La stratégie choisie pour protéger les nanoparticules de cuivre de l’oxydation a été de les encapsuler dans un polymère ou avec une fine couche d’argent. L’obtention de systèmes cœur-coquille Cu@Ag, en plus d’augmenter la résistance face à l’oxydation, permet d’améliorer le frittage des joints. Une fois densifiés, les joints à base de nanoparticules Cu@Ag sont capables de résister à des contraintes mécaniques élevées. / Metallic nanoparticles have the particularity to sinter at lower temperatures compared to microparticles. Silver (Ag) nanoparticles based sintering pastes are commercially available for assembling power electronics chips to their substrates. The assembly is performed between 200 and 300°C, generally under pressure (Hot Pressing) and the resulting metallic joint has excellent thermal and electrical conductivity properties. The theoretical melting temperature of the resulting densified joint corresponds to the melting temperature of bulk silver (962°C), making the silver nanoparticles an alternative for "high temperature" power electronics compared to traditional solder. Nevertheless, the cost of Ag, which is a precious metal, remains a barrier to the use of these sintering pastes. The cost can be reduced by replacing the silver nanoparticles with copper (Cu) nanoparticles. Copper has conductive properties very close to silver. The major hurdle to the integration of copper nanoparticles in sintering pastes is the proneness of copper to oxidation. The oxidation of Cu nanoparticles prevents sintering and greatly reduces the mechanical properties and conductivity of the final metallic joint. Moreover, copper is less reactive during sintering and requires higher temperatures to densify. We chose to protect copper nanoparticles by encapsulation. In a first step copper nanoparticles were synthetized at laboratory scale and semi-industrial scale. In a second step the copper nanoparticles were encapsulated either with a polymer or very thin layer of Ag. The oxidation properties of the core-shell nanoparticles were studied. In a third step the Cu@Ag nanoparticles were formulated in a paste in order to obtain metallic joints. The sintering and density properties of the metallic joints were evaluated and positively compared to the joints obtained with a commercial Ag based paste. The Cu@Ag core-shell system prevents oxidation but also improves the sintering process.

Multifunctional superparamagnetic iron oxide nanoparticles (SPIONs) coated with silica are a promising research field for lots of biomedical applications. The scope of this work is a preparation of SPIONs and coating them with silica to form core-shell structured nanoparticles for nanomedicine applications. SPIONs were synthesized by two chemical methods – co-precipitation and thermal decomposition of organic iron precursor. Prepared nanoparticles were carefully characterized –average size, size distribution, morphology, crystallinity, colloidal stability and magnetic properties were studied. After comparing SPIONs synthetized by two routes the most suitable method for biomedical applicable nanoparticles preparation is determined. The nanomedicine requires nanoparticles of the highest quality. The next step was coating SPIONs with silica shell. For this purpose inverse microemulsion method was chosen. TEOS was used as a silica precursor. Mean size, size distribution, magnetic properties, structure of silica shell were studied.

京都大学 / 新制・課程博士 / 博士(医学) / 甲第23602号 / 医博第4789号 / 新制||医||1055(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 長船 健二, 教授 川口 義弥, 教授 大森 孝一 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

Le contrôle optique des propriétés physiques d’un matériau suscite l’intérêt des scientifiques pour des enjeux aussi bien fondamentaux qu’appliqués. L’axe de recherche original que nous avons développé dans le cadre de ce travail de thèse visait à la réalisation et l’étude d’hétérostructures moléculaires photo-magnétiques dans des gammes de température susceptibles d’applications. L’approche proposée consistait à élaborer des hétérostructures de type multiferroïque constituées de deux phases, l’une piézomagnétique et l’autre photo-strictive. L’idée était d’optimiser le couplage, d’origine élastique, entre ces propriétés pour permettre l’observation d’effets photo-magnétiques à des températures plus élevées que celles rapportées pour les matériaux monophasés. La couche photo-strictive peut se déformer sous irradiation lumineuse, générant des contraintes biaxiales dans la couche magnétique. Si celle-ci présente une forte réponse piézomagnétique, son aimantation peut être fortement modifiée, notamment au voisinage du point de Curie, allant jusqu’à un éventuel décalage de la température critique sous contrainte. Les composés moléculaires analogues du Bleu de Prusse, de formule générique AxM[M’(CN)6]y . zH2O (où A est un alcalin et M,M’ des métaux de transition), semblaient particulièrement adaptés à l’élaboration de telles hétérostructures. Nous avons utilisé le composé Rb0,5Co[Fe(CN)6]0,8 . zH2O pour la phase photo-strictive, au coeur, et Rb0,2Ni[Cr(CN)6]0,7 . z’H2O ou K0,2Ni[Cr(CN)6]0,7 . z’H2O pour la phase magnétique, en coquille. Ces deux phases présentent un désaccord paramétrique de 5,3%.L’objectif principal de ce travail de thèse était de comprendre et de contrôler le couplage élastique entre le cœur et la coquille. Nous avons ainsi dans un premier temps mis en évidence l’existence de ce couplage, la présence de la coquille modifiant les propriétés de photo-commutation du cœur et la déformation du réseau cristallin du cœur étant partiellement transmise à la coquille, induisant des modifications structurales et magnétiques de la coquille. Nous nous sommes dans un second temps intéressés à différents paramètres pouvant influence le couplage. D’abord en étudiant des paramètres géométriques, en faisant varier la taille des particules de cœur, l’épaisseur de la coquille et la microstructure de la coquille. Nous avons à cette occasion mis en évidence les facteurs régissant la croissance des particules de cœur et de la coquille. Ces études ont révélé que le rapport volumique entre le cœur et la coquille contrôlait la qualité du couplage, et que des modifications de la microstructure avait une influence à la fois sur les propriétés de photo-commutation du cœur, mais aussi sur la réponse de la coquille. Enfin, nous avons étudié des coquilles de nature chimique différente pour changer le désaccord paramétrique entre le cœur et la coquille. Il en ressort qu’en diminuant le désaccord, on améliore le couplage, mais cela se traduit notamment par une rétroaction de la coquille plus forte. Si cette rétroaction devient trop importante, le réseau du cœur ne peut plus se déformer. Il s’agit donc de trouver un compromis entre force du couplage et force de la rétroaction de la coquille. Finalement, nous avons mis en évidence le fait que l’on ne peut pas simplement associer l’effet de la coquille à un effet de pression hydrostatique, mais que le couplage des réseaux cristallins joue un rôle important dans la synergie entre les deux phases. / The optical control of the physical properties of a material has drawn considerable attention during the past few years for a fundamental point of view and for applications. The originality of the project developed during this thesis was based on the synthesis and the study of photo-magnetic heterostructures in a temperature range convenient for applications. The approach consisted of developing multiferroic-like heterostructures that associate a piezomagnetic phase and a photo-strictive phase. The idea was to exploit the coupling of elastic origin between these properties, to allow the observation of photo-magnetic effects at temperatures higher than those reported for single-phase materials. The photo-strictive phase can deform under light irradiation, generating biaxial strain in the magnetic phase. If the piezomagnetic response of the latter is high enough, its magnetization could be modulated, especially at the vicinity of the Curie temperature, with a possible shift of the critical temperature under stress. In this project, we focused on molecular solids based on polycyanometallates, namely Prussian blue analogues, whose generic formula is AxM[M’(CN)6]y . zH2O (where A is an alkali metal and M,M transition metals). We used the compound Rb0,5Co[Fe(CN)6]0,8 . zH2O for the photo-strictive phase and Rb0,2Ni[Cr(CN)6]0,7 . z’H2O or K0,2Ni[Cr(CN)6]0,7 . z’H2O for the magnetic phase. These two phases have a lattice mismatch of 5.3%The main objective of this work was to understand and to control the elastic coupling between the core and the shell. We first highlighted the existence of this coupling, the presence of the shell changing the photo-switching properties of the core, and the deformation of the crystalline lattice of the core inducing structural and magnetic modifications in the shell. Then, we focused on the study of different parameters which can have an impact on the behavior of the heterostructures under light irradiation. We showed that the volumic ratio between the core and the shell is a key factor to control the efficiency of the coupling. The microstructure of the shell can also play an important role, but is not as well understood. In the end, we studied other Prussian blue analogs shells in order to change the lattice mismatch between the core and the shell. We could evidence that by reducing the lattice mismatch we tend to increase the coupling, but if this coupling is to strong, the retroaction of the shell hinders completely the dilatation of the core lattice. The idea is also to find a compromise between the strength of the coupling and the strength of the shell retroaction. In the end, we proved that we cannot associate the effect of the shell to an hydrostatic pressure, but that the coupling of the crystalline lattices play an important role in the synergy between the two phases.

In recent years, nanostructured materials incorporated with inorganic particles and polymers have attracted attention for simultaneous multifunctional biomedical applications. This thesis summarized three works, which are preparation of mesoporous silica coated superparamagnetic iron oxide (Fe3O4@mSiO2) nanoparticles (NPs) as magnetic resonance imaging T2 contrast agents, polymer grafted Fe3O4@mSiO2 NPs response to temperature change, synthesis and biocompatibility evaluation of high aspect ratio (AR) gold nanorods. Monodisperse Fe3O4@mSiO2 NPs have been prepared through a sol-gel process. The coating thickness and particle sizes can be precisely controlled by varying the synthesis parameters. Impact of surface coatings on magnetometric and relaxometric properties of Fe3O4 NPs is studied. The efficiency of these contrast agents, evaluated by MR relaxivities ratio (r2/r1), is much higher than that of the commercial ones. This coating-thickness dependent relaxation behavior is explained due to the effects of mSiO2 coatings on water exclusion. Multifunctional core-shell composite NPs have been developed by growing thermo-sensitive poly(N-isopropylacrylamide-co-acrylamide) (P(NIPAAm-co-AAm)) on Fe3O4@mSiO2 NPs through free radical polymerization. Their phase transition behavior is studied, and their lower critical solution temperature (LCST) can be subtly tuned from ca. 34 to ca. 42 °C, suitable for further in vivo applications. A seedless surfactant-mediated protocol has been applied for synthesis of high AR gold nanorods with the additive of HNO3. A growth mechanism based on the effect of nitrate ions on surfactant micelle elongation and Ostwald ripening process is proposed. The biocompatibility of high AR nanorods was evaluated on primary human monocyte derived dendritic cells (MDDCs). Their minor effects on viability and immune regulatory markers support further development for medical applications. / QC 20110701

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