A size-selected series of water-soluble luminescent Ag–In–S (AIS) and core/shell AIS/ZnS QDs were produced by a precipitation technique. Up to 10–11 fractions of size-selected AIS (AIS/ZnS) QDs emitting in a broad color range from deep-red to bluish-green were isolated with the photoluminescence (PL) quantum yield reaching 47% for intermediate fractions. The size of the isolated AIS (AIS/ZnS) QDs varied from ~2 nm to ~3.5 nm at a roughly constant chemical compo- sition of the particles throughout the fractions as shown by the X-ray photoelectron spectroscopy. The decrease of the mean AIS QD size in consecutive fractions was accompanied by an increase of the structural QD imperfection/disorder as deduced from a notable Urbach absorption “tail” below the fundamental absorption edge. The Urbach increased from 90–100 meV for the largest QDs up to 350 meV for the smallest QDs, indicating a broadening of the distribution of sub-bandgap states. Both the Urbach energy and the PL bandwidth of the size-selected AIS QDs increased with QD size reduction from 3–4 nm to ~2 nm and a distinct correlation was observed between these parameters. A study of size-selected AIS and AIS/ZnS QDs by UV photoelectron spectroscopy on Au and FTO substrates revealed their valence band level EVB at ~6.6 eV (on Au) and ~7 eV (on FTO) and pinned to the Fermi level of conductive substrates resulting in a masking of any possible size- dependence of the valence band edge position.

A size-selected series of water-soluble luminescent Ag–In–S (AIS) and core/shell AIS/ZnS QDs were produced by a precipitation technique. Up to 10–11 fractions of size-selected AIS (AIS/ZnS) QDs emitting in a broad color range from deep-red to bluish-green were isolated with the photoluminescence (PL) quantum yield reaching 47% for intermediate fractions. The size of the isolated AIS (AIS/ZnS) QDs varied from ~2 nm to ~3.5 nm at a roughly constant chemical compo- sition of the particles throughout the fractions as shown by the X-ray photoelectron spectroscopy. The decrease of the mean AIS QD size in consecutive fractions was accompanied by an increase of the structural QD imperfection/disorder as deduced from a notable Urbach absorption “tail” below the fundamental absorption edge. The Urbach increased from 90–100 meV for the largest QDs up to 350 meV for the smallest QDs, indicating a broadening of the distribution of sub-bandgap states. Both the Urbach energy and the PL bandwidth of the size-selected AIS QDs increased with QD size reduction from 3–4 nm to ~2 nm and a distinct correlation was observed between these parameters. A study of size-selected AIS and AIS/ZnS QDs by UV photoelectron spectroscopy on Au and FTO substrates revealed their valence band level EVB at ~6.6 eV (on Au) and ~7 eV (on FTO) and pinned to the Fermi level of conductive substrates resulting in a masking of any possible size- dependence of the valence band edge position.

Le cadre de cette thèse est l'étude des systèmes contrôlés en réseau sans fil (SCRSF) qui utilise la technologie IEEE 802.15.4. Le premier objectif est d'étudier la pertinence de l'utilisation du réseau de type IEEE 802.15.4 pour les SCRSF puis de proposer et d'évaluer des mécanismes pour garantir la Qualité de Service (QdS) offerte par le réseau au système contrôlé. Nous analysons l'utilisation des slots temporels réservés (GTS) dans le cadre des SCRSF et les contraintes qui en découlent. De plus, nous proposons des mécanismes de gestion de la QdS avec priorité aussi bien pour le mode avec balise que pour le mode sans balise du protocole IEEE 802.15.4. Ces propositions ont été validées par des simulations et une partie de manière analytique. Notre deuxième objectif est de concevoir, d'une manière conjointe, les SCRSF pour pouvoir régler en ligne la QdS offerte par le réseau en fonction de la Qualité de Contrôle (QdC) du système contrôlé. Nous proposons des protocoles d'adaptation en ligne de la QdS du réseau qui prennent en compte la QdC du système contrôlé. Ces protocoles ont été validés par simulations et une implémentation réelle de chacun d'eux est proposée / In this thesis, we study wireless networked control systems (WNCS) which use the IEEE 802.15.4 technology. The first objective is to study the pertinence of the use of the IEEE 802.15.4 for the WNCS, then to propose and evaluate QoS management mechanisms which guarantee the Quality of Service (QoS) offered by network to the controlled system. We analyse the use of the guaranteed temporel slots (GTS) for WNCS and in which conditions it is possible. We propose QoS management mechanisms with priority for both the beacon enabled mode and the non-beacon enabled mode of the IEEE 802.15.4 protocol. These proposals are validated through simulations and partially with analytical approach. The second objective is to design the WNCS so that the QoS offered by the network is adated online depending on the Quality of Control (QoC) on the controlled system. We propose QoS online adaptation protocols which take as parameter the QoC of the system. These protocols are validated through simulations and a realistic implementation of them is proposed

L'évolution des réseaux actuels vise principalement l'amélioration des performances à travers une augmentation importante des débits disponibles. Cependant, les besoins des applications multimédia se situent également dans l'accès à de nouvelles fonctionnalités telles que le multipoint et la garantie de qualité de service (QoS). Pour satisfaire ces besoins, nous proposons d'associer une architecture pour le multipoint avec QoS aux technologies de commutation. Une première instanciation de cette approche nous a amenés à étudier l'intégration de RSVP sur les réseaux ATM, et à proposer une solution palliant l'absence de service multipoint avec QoS capable de soutenir efficacement RSVP. Nous nous intéressons ainsi à CLIP, l'une des techniques d'intégration d'IP sur ATM, pour réaliser l'intégration du modèle RSVP. La contribution repose sur l'utilisation de plusieurs arbres multipoints pour éviter les limitations intrinsèques aux réseaux ATM. Cette approche a été expérimentée sur la plate-forme MIRIHADE à l'aide d'une application vidéo à codage hiérarchique. La commutation associée à une signalisation orientée connexion se prêtant mal à l'intégration des nouvelles fonctionnalités, nous nous sommes orientés vers l'utilisation d'une signalisation en mode non connecté à travers une solution de type ``Commutation par label''. Appliquée à RSVP, nous avons intégré directement la signalisation de la commutation dans celle assurant les nouvelles fonctionnalités pour permettre la commutation directe du trafic de données tout en conservant les fonctionnalités de la couche réseau. Notre solution, appelée ``RSVP Switching'', est en cours d'expérimentation sur la plate-forme SAFIR, pour un projet de simulation interactive distribuée ayant des besoins importants en terme de multipoint avec QoS.

L'objectif de ce travail de thèse dans un premier temps est l'évaluation de performances des modèles de routage multi-chemins pour l'ingénierie de trafic et l'équilibrage de charge sur un réseau de type IP/MPLS (MPLS-TE). Nous comparons la capacité de ces modèles à équilibrer la charge du réseau tout en faisant de la différentiation de trafic. Nous les appliquons sur des grandes topologies générées par le générateur automatique des topologies BRITE, qui s'approchent en forme et en complexité du réseau réel. Nous mesurons ainsi l'impact de leur complexité respective et donc la capacité à les déployer sur des réseaux de grande taille (scalabilité). Dans un second temps, l'objectif est de proposer un concept de modélisation générale d'un réseau à commutations par paquets. Ce modèle est établi sur la base de la théorie différentielle de trafic et la théorie des files d'attente, tout en utilisant des approches graphiques. Le but est d'estimer l'état de charge du réseau et de ses composants (routeurs, liens, chemins). Ensuite, en fonction de ça, nous développons des approches de contrôle de congestion et commande sur l'entrée améliorant les techniques de routage adaptatif et l'équilibrage de charge dans les réseaux IP/MPLS

Nos travaux de thèse ont pour objectif la conception, la mise en Suvre et l'évaluation d'architectures pour la mobilité et la qualité de service (QoS) dans des systèmes satellites DVB-S2/RCS. Ces systèmes peuvent constituer une solution alternative efficace aux réseaux terrestres dans des zones reculées à faible densité de population mais ils doivent pour cela offrir les mêmes services tout en tenant compte de leurs caractéristiques spécifiques, en particulier leur long délai de transmission qui peut s'avérer problématique dans le cadre d'applications multimédias interactives. Notre première contribution a donc été de développer une architecture de QoS adaptée à ce type d'applications, utilisant le modèle DiffServ et se basant essentiellement sur l'interaction entre l'architecture liée au protocole d'initiation de session SIP et différentes entités du système satellite. La QoS peut alors être configurée de façon précise au niveau des STs, par le biais de l'outil TC, en analysant les descripteurs de session SDP compris dans les messages SIP et en déduisant leurs caractéristiques (débit, gigue max, délai max, etc...) soit localement si elles sont connues, soit à partir d'un service Web que nous avons développé. Nous avons ensuite proposé et développé une solution de mobilité basée sur SIP, adaptée au système satellite ainsi qu'à la solution de QoS précédemment décrite. Les performances de cette solution ont alors été comparées, en termes de temps d'interruption et de consommation de ressources, avec celles obtenues par Mobile IPv6 et certaines de ses extensions, démontrant ainsi de réelles améliorations pour le cas des applications multimédias interactives. Enfin, notre dernière contribution a été de développer deux architectures couplant QoS et mobilité, une spécifiquement conçue pour les applications interactives et basée sur la combinaison de notre solution de mobilité SIP avec notre architecture de QoS SIP et une autre basée sur Mobile IPv6 ou FMI Pv6 et sur l'interaction d'un QoS Agent mobile avec les entités de QoS du système satellite. Ces architectures ont été évaluées et comparées sur la plateforme d'émulation PLATINE développée dans le cadre du projet SATSIX.

In this work we investigated fabrication of semiconductor nanomaterials and evaluated their potential for photo-chemical and photovoltaic applications. We investigated different II-VI semiconductor nanomaterial systems; (i) ZnO oriented nanowire arrays non-epitaxially grown from a substrate; and (ii) colloidal CdE (E=Te,Se,S) quantum structures synthesized by solution-based thermal decomposition of organo-metallic precursors. We have studied the synthesis of vertically aligned ZnO nanowire arrays (NWA), by a wet chemical process on various substrates. We have extended this method wherein nanofibers of poly-L-lactide act as a substrate for the radially oriented growth of ZnO nanowires. By combining the large surface area and the flexibility of the PLLA-ZnO hierarchical nanostructure we have shown the proof-of-principle demonstration of a ‘continuous-flow’ water treatment system to decompose known organic pollutants in water, as well as render common waterborne bacteria non-viable. We have studied synthesis of colloidal quantum dots (QD), and show size, morphology and composition tailored nanocrystals for CdE (E=S, Se, Te) compositions. We have studied the influence of crystal growth habits of the nanocrtsyals on the final morphology. Furthermore we have synthesized core-shell, CdSe-CdS QDs with spherical and tetrahedral morphologies by varying the reaction conditions. We show that these core-shell quantum dots show quasi-type II characteristics, and demonstrate with I-V measurements, the spatial localization of the charge carriers in these hetero-nanocrystals. For this purpose, we developed hybrid materials consisting of the core-shell quantum dots with electron acceptors (ZnO nanowires) and hole acceptors (polymeric P3HT nanofibers). In addition we have also compared the synthesis reaction when carried out with conventional heating and microwave-mediated heating. We find that the reaction is enhanced, and the yield is qualitatively better when using microwave induced heating. / QC 20120525

Nos travaux se situent dans le cadre des architectures logicielles dynamiques en tant qu'outil pour l'adaptation des applications à base de services Web, l'objectif étant de proposer des mécanismes d'aide à la gestion de la QdS. Nous proposons une approche de modélisation par le biais d'éléments architecturaux étendant la vue de déploiement d'UML. A partir de la définition de règles de base, issues des techniques de réécriture de graphes, des actions de reconfiguration architecturale sont introduites. Un premier scénario applicatif traite le processus de revue coopérative adapté au cas spécifique d'un système de gestion de conférences. Un deuxième scénario traite le cas d'un magasin en ligne. Nous proposons une classification des cas de dysfonctionnement pour la gestion de la QdS, classification que nous formalisons par le biais d'une ontologie. Notre dernière proposition concerne une architecture de gestion de la QdS, modélisée et validée au moyen de l'outil UML Tau G2.

Submitted by NATHALIA CRISTINA RISSI null (nathaliarissi_farmacia@yahoo.com.br) on 2016-07-04T12:35:43Z No. of bitstreams: 1 Tese Nathalia Cristina Rissi 1.pdf: 3733548 bytes, checksum: bde3d4680fdf9def65256855510fa057 (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-07-07T17:05:40Z (GMT) No. of bitstreams: 1 rissi_nc_dr_arafcf.pdf: 3733548 bytes, checksum: bde3d4680fdf9def65256855510fa057 (MD5) / Made available in DSpace on 2016-07-07T17:05:40Z (GMT). No. of bitstreams: 1 rissi_nc_dr_arafcf.pdf: 3733548 bytes, checksum: bde3d4680fdf9def65256855510fa057 (MD5) Previous issue date: 2016-06-02 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Nos últimos anos, é possível observar um grande interesse no desenvolvimento de sistemas multifuncionais direcionados ao diagnóstico e tratamento do câncer. Estes sistemas também conhecidos como “teranósticos” têm se mostrado interessantes, pois ampliam a capacidade de liberação prolongada de fármacos anticancerígenos em células específicas, além de proporcionar um monitoramento ótico através da luminescência de pontos quânticos. Diante deste contexto, o presente estudo teve como objetivo estabilizar os pontos quânticos a base de óxido de zinco (ZnO) em meio aquoso através da modificação de superfície com o 3-(Glycidyloxypropyl)trimethoxysilane (GPTMS) e também em meio orgânico através da modificação com o Hexadecyltrimethoxysilane (HTMS), permitindo assim a veiculação do mesmo em micelas poliméricas A ligação entre os pontos quânticos e as moléculas dos modificadores ocorreu através das reações de hidrólise e condensação, utilizando como catalisador básico o hidróxido de lítio. Esta reação conduziu a formação de uma camada de siloxano ao redor das nanopartículas e resultou nas ligações covalentes do tipo ZnO-Si-O. Ainda com o objetivo de aumentar a estabilidade do ZnO em meio orgânico e consequentemente suas propriedades luminescentes, foi sintetizado uma bicamada formada entre o Ácido Oleico (AO) e o HTMS. As modificações na superfície do ZnO foram confirmadas pelas técnicas de espectroscopia vibracional na região do infravermelho e também pela espectroscopia de fotoelétrons induzidos por raios-X. O comportamento ótico foi feito através da espectroscopia de absorção na região do UV-Vis. Com está técnica, identificou-se o comprimento de onda limite associado ao pico excitônico do ZnO e através do monitoramento deste pico, observou-se estabilidade em água por um período de 15 dias para a grande maioria das amostras de ZnO modificado pelo GPTMS e também para o ZnO modificado pelo HTMS e pela bicamada de AO/HTMS em clorofórmio. O tamanho final dos pontos quânticos foi analisado pela microscopia de transmissão eletrônica, apresentando um tamanho médio entre 3,5- 4nm para as amostras de ZnO modificado pelo GPTMS e de 4,5 nm para as amostras de ZnO modificado pelo HTMS e pela bicamada de AO/HTMS. Com a técnica de difração de raios-X, identificou-se os picos de difração correspondentes a uma estrutura cristalina do tipo Wurtzita. As medidas de fotoluminescência permitiu a obtenção de informações sobre a intensidade luminescente, assim como as cores emitidas dos pontos quânticos e demostraram a importância das modificações de superfície em relação ao aumento da intensidade luminescente. A veiculação do ZnO estáveis no meio orgânico em micelas poliméricas formadas pelo Pluronic F127 e Pluronic F68, foi realizada com sucesso. Este fato foi observado por meio dos espectros de absorção no UV-vis e também pelas medidas de fotoluminescência. Com a técnica de espalhamento de luz dinâmico, avaliou-se parâmetros relacionados com o tamanho e o índice de polidispersidade das micelas. O teste de citotoxicidade in vitro foi feita através do MTT e apresentou uma boa viabilidade celular para as linhagens celulares de queratinócito humano (HaCat) e de hepatoma humano (HepG2). A quantificação das células em que houve a internalização das micelas contendo os pontos quânticos hidrofóbicos como marcador foi feita através da citometria de fluxo. Diante dos resultados obtidos, conclui-se a existência de um potencial a ser explorado em relação ao ZnO modificado pelo GPTMS em aturar futuramente como sondas biológicas. Já as propriedades hidrofóbicas concedidas ao ZnO modificado pelo HTMS e pela bicamada formada entre o AO/HTMS permitiu a incorporação dos mesmos em sistemas micelares e tem como objetivo auxiliar na aplicação futura desses pontos quânticos através do desenvolvimento de sistemas teranósticos. / In recent years, it is possible to observe a growing interest in the development of multifunctional systems used, that can be used in the diagnosis and treatment of cancer These systems also known as " theranostic " and have gained considerable attention due to their capacity of release anticancer drugs into specific cells, besides to optical monitoring through quantum dots. In this context, the present study was aimed to stabilize the quantum dots of of ZnO in water by modifying with 3-(Glycidyloxypropyl)trimethoxysilane (GPTMS) with and organic medium.by modifying with Hexadecyltrimethoxysilane (HTMS), thus allowing them to be incorporated into polymeric micelles The binding between the quantum dots with the modifiers occurred by hydrolysis and condensation reaction under basic catalysis by lithium hydroxide, thus leading to the formation of siloxane layer and resulted in ZnO-Si-O covalent bond. In order to improve the stability of ZnO-QDs and consequently their photoluminescence properties, was synthesized a coating bilayer by OA and HTMS. The ZnO surface modification was confirmed by infrared spectroscopy and also by X-ray photoelectron spectroscopy. The optical behavior was performed by absorption spectroscopy in the UV-Vis region. With this technique was possible to identify the wavelength limit associated with the excitonic peak and by monitoring of this peak was observed a great stability during 15 days for almost all samples of ZnO modified by GPTMS in water and ZnO modified by HTMS and bilayer AO / HTMS in chloroform. The finale size of quantum dots was analyzed by transmission electron microscopy that showed an average size about 3,5- 4nm for the samples of znO modified by GPTMS, and 4,5 nm by HTMS and AO/HTMS bilayer. By X-ray diffraction, it was possible to identify through the diffraction peak a wurtzite structure. The photoluminescence measurements allowed to obtain information about luminescence intensity, as well as the emitted colors by quantum dots and demonstrated the importance of surface modifications in relation to increase of luminescence intensity. The placement of hydrophobic ZnO into polymeric micelles formed by Pluronic F127 and Pluronic F68 was successful. This fact can be observed by absorption spectroscopy in UV-vis and by photoluminescence measurements. With the dynamic light scattering, it was possible to observe the hydrodynamic size distribution and polydispersity index of the micelles. In vitro cytotoxicity assay was performed by MTT and showed a great cellular viability for human keratinocytes cells (HaCat) and for hepatocellular carcinoma cells (HepG2). The cellular internalization was performed by flow cytometry. Based on these results, it was concluded a potential to be explored in to ZnO modified by GPTMS to acting in the future as biological probes. The hydrophobic properties of ZnO modified by HTMS and the AO / HTMS bilayer allowed the incorporation in micellar systems and aims to assist in the implementation of these quantum dots through the development of systems theranostics.

Nanomaterials have gained great attention for biomedical applications due to their extraordinary physico-chemical and biological properties. The current dissertation presents the design and development of multifunctional nanoparticles for molecular imaging and controlled drug delivery applications which include biodegradable polymeric nanoparticles, superparamagnetic iron oxide nanoparticles (SPION)/polymeric nanocomposite for magnetic resonance imaging (MRI) and drug delivery, manganese-doped zinc sulfide (Mn:ZnS) quantum dots (QDs)/ SPION/ polymeric nanocomposites for fluorescence imaging, MRI and drug delivery.Bioimaging is an important function of multifunctional nanoparticles in this thesis. Imaging probes were made of SPION and Mn:ZnS QDs for in vitro and in vivo imaging. The SPION have been prepared through a high temperature decomposition method to be used as MRI contrast agent. SPION and Mn:ZnS were encapsulated into poly (lactic-co-glycolic) acid (PLGA) nanoparticles during the particles formation. The hydrophobic model drug, busulphan, was loaded in the PLGA vesicles in the composite particles. T2*-weighted MRI of SPION-Mn:ZnS-PLGA phantoms exhibited enhanced negative contrast with r2* relaxivity of 523 mM-1 s-1. SPION-Mn:ZnS-PLGA-NPs have been successfully applied to enhance the contrast of liver in rat model.The biodegradable and biocompatible poly (ethylene glycol)-co-poly (caprolactone) (PEG-PCL) was used as matrix materials for polymeric nanoparticles -based drug delivery system. The PEG-PCL nanoparticles have been constructed to encapsulate SPION and therapeutic agent. The encapsulation efficiency of busulphan was found to be ~ 83 %. PEG-PCL nanoparticles showed a sustained release of the loaded busulphan over a period of 10 h. The SPION-PEG-PCL phantoms showed contrast enhancement in T2*-weighted MRI. Fluorescein-labeled PEG-PCL nanoparticles have been observed in the cytoplasm of the murine macrophage cells (J774A) by fluorescence microscopy. Around 100 % cell viability were noticed for PEG-PCL nanoparticles when incubated with HL60 cell line. The in vivo biodistribution of fluorescent tagged PEG-PCL nanoparticles demonstrated accumulation of PEG-PCL nanoparticles in different tissues including lungs, spleen, liver and kidneys after intravenous administration. / <p>QC 20160516</p>