En chirurgie reconstructive osseuse les biomatériaux remplacent le tissu osseux manquant et dans le cas de pathologies ils peuvent également délivrer des molécules actives. L’élément semi-métallique, gallium (Ga), est utilisé dans le traitement de différentes pathologies liées à la résorption accélérée de l’os dû à son effet inhibiteur sur les ostéoclastes (cellules résorbantes de l’os). Le Ga peut être incorporé dans la structure des biomatériaux osseux et nous nous sommes intéressés aux propriétés biologiques de ces derniers. In vitro, en présence de Ga nous avons mis en évidence une diminution de la différentiation des ostéoclastes, ainsi qu’une sur-expression de plusieurs marqueurs des ostéoblastes (cellules formatrices d’os). In vivo, le modèle murin de comblement du défaut osseux a montré une augmentation de la quantité de tissu osseux néoformé avec un biomatériau chargé en Ga vs. contrôle. Ces données démontrent que les biomatériaux chargés en Ga sont compatibles avec la survie et la prolifération des cellules osseuses et que le Ga peut améliorer la reconstruction osseuse. D’autre part, étant donné que des effets anti-tumoraux du Ga sont largement décrits, nous avons étudié ces effets sur une lignée cellulaire cancéreuse, choisie pour son affinité pour le tissu osseux. Nous avons montré que le Ga réduit la prolifération et probablement le potentiel tumoral de cette lignée, mais aussi la différentiation ostéoclastique induite par les cellules cancéreuses. Ces effets inhibiteurs observés dans un contexte tumoral indiquent que le Ga est un candidat intéressant pour le couplage avec des biomatériaux destinés au comblement osseux après une résection tumorale. / In bone reconstructive surgery biomaterials commonly replace the missing tissue and in case of pathologies can also serve as vectors for drug delivery. The semi-metallic element gallium (Ga) is used for the treatment of several disorders associated with accelerated bone resorption, due to its inhibitory action on bone-resorbing cells (osteoclasts). Since Ga can be incorporated into the structure of bone biomaterials, we embarked on characterising the biological properties of novel Ga-loaded materials. In vitro, we observed a decrease in osteoclast differentiation and the upregulated expression of several osteoblastic markers (bone-forming cells) in the presence of Ga-loaded biomaterial. In vivo, using a rat bone defect model, we showed an increase in newly formed bone tissue in implants filled with Ga-loaded biomaterial vs. control. Taken together, our data indicate that Ga-loaded biomaterials provide biocompatible substrates allowing bone cells survival and improved bone reconstruction in vivo. Taking into account antitumoral effects of Ga, largely described in literature, we also investigated its impact on a bone metastatic model. Using an aggressive human cancer cell line selected for its ability to invade bone tissue, we showed that Ga could reduce cancer cell proliferation and viability and reverse excessive osteoclastogenesis in bone metastatic environment. Moreover, we demonstrated that Ga modulated the expression of several marker genes hindering the tumour-propagating potential of cancer cells. Thus, due to its inhibitory action on cancer cells, Ga could represent an attractive additive to biomaterials used for tissue reconstruction after tumour resection.

Made available in DSpace on 2014-10-09T12:34:44Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:01:14Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:26:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:22Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado Profissionalizante em Lasers em Odontologia) / IPEN/D-MPLO / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP; Faculdade de Odontologia, Universidade de Sao Paulo, Sao Paulo

Made available in DSpace on 2014-10-09T12:34:44Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:01:14Z (GMT). No. of bitstreams: 0 / Há mais de 50 anos os geradores de 68Ge/68Ga vêm sendo desenvolvidos, obtendo o 68Ga sem a necessidade da instalação de um cíclotron próximo à radiofarmácia ou ao centro hospitalar que tenha um PET/CT. O 68Ga é um emissor de pósitron com baixa emissão de fóton (β+, 89%, 1077 keV) e meia vida de 67,7 minutos, compatível com a farmacocinética de moléculas de baixo peso molecular, como peptídeos e fragmentos de anticorpos. Além disso, a química do Ga permite a ligação estável com agentes quelantes acoplados com peptídeos, como o DOTA. Todas estas características do 68Ga aliado a tecnologia PET/CT permitiram avanços em imagem molecular, como no diagnóstico de doenças de origem neuroendócrina. Entretanto, o eluato de 68Ga proveniente dos geradores de 68Ge/68Ga comerciais, ainda contém altos níveis de contaminantes, como o 68Ge e outros metais que competem quimicamente com o 68Ga, como o Fe3+ e Zn2+ e, como consequência, há redução do rendimento de marcação com biomoléculas. Quanto menor a quantidade de impurezas no eluato, a competição entre o peptídeo radiomarcado e peptídeo não marcado será menor e a qualidade de imagem será melhor, por isso existe a necessidade de diminuir a quantidade destes metais. Portanto, os objetivos deste trabalho são avaliar os métodos de purificação do 68Ga para a marcação de biomoléculas, com ênfase no estudo das impurezas químicas presentes nos radioisótopos primários, e desenvolver um método de purificação inédito. Diversos métodos de purificação foram estudados. Na purificação em resina catiônica tradicional e comercial, em que o 68Ga é adsorvido em resina catiônica e eluído em uma solução de acetona/ácido, a resina utilizada não é disponível comercialmente. Várias resinas catiônicas foram testadas simulando o processo comercial, e o uso das menores partículas da resina catiônica AG50W-X4 (200-400 mesh) foi a que apresentou os melhores resultados. Um método inovador foi a cromatografia por extração, onde o éter diisopropílico é adsorvido em resina XAD 16 e o 68Ga eluído em água deionizada. Apesar dos resultados de recuperação do 68Ga e a separação entre o 68Ga e o 65Zn terem sido bons, não houve reprodutibilidade na purificação dos metais. O método mais promissor e inédito foi a purificação do 68Ga em resina catiônica em meio básico que apresentou bons resultados, principalmente em relação à redução do Zn (98 ± 2)%, o contaminante químico encontrado em maior abundância no eluato de 68Ga. A redução total de impurezas foi (95 ± 4)%. Os peptídeos DOTATOC/DOTATATO foram marcados com o 68Ga em três diferentes formas: purificado em meio básico, por extração por solventes e sem a purificação prévia, o melhor resultado de rendimento de marcação do 68Ga DOTATATO foi obtido após a purificação do 68Ga em meio básico, comprovando a eficiência do processo. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:26:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:22Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado Profissionalizante em Lasers em Odontologia) / IPEN/D-MPLO / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP; Faculdade de Odontologia, Universidade de Sao Paulo, Sao Paulo

No description available.

Les gisements de type Mississippi Valley Type (MVT) du centre et de l’est du Tennessee, respectivement MTM (Middle Tennessee Mine) et ETM (East Tennessee Mine), renferment des réserves importantes de zinc sous forme de sphalerite, mais aussi de germanium en substitution du zinc dans la sphalerite. Cependant seuls les gisements du district de MTM contiennent des teneurs économiquement exploitables de germanium. Ces deux districts miniers, observés dans les mêmes formations géologiques et de minéralogies comparables, sont comparés afin de comprendre la distribution du germanium et des autres éléments traces dans les MVT. Les analyses à l’échelle de l’atome par spectroscopie d’absorption X, XANES et EXAFS, ont mis en évidence plusieurs configurations de germanium dans la sphalerite : le germanium peut être en substitution du zinc dans ZnS sous forme 2+ ou 4+, mais il peut aussi être sous forme d’oxyde de germanium en inclusions nanométriques dans la sphalerite. Les analyses à l’échelle du minéral, par microsonde électronique, LA-ICP-MS et spectroscopie Raman, ont mis en évidence deux groupes d’éléments traces : i) le premier composé des éléments Fe et Cd, est préférentiellement incorporé suivant les faces (110) de la sphalerite, ii) le second composé des éléments Cu, Ga et Ge, est préférentiellement incorporé suivant les faces (010) de la sphalerite. Le couplage de la spectroscopie Raman avec l’ablation laser ICP-MS a permis de mettre en évidence un partitionnement des éléments traces entre la forme cubique et hexagonale de ZnS : les éléments Fe et Cd sont plus concentrés dans la forme cubique, alors que les éléments Cu, Ga et Ge sont plus concentrés dans la forme hexagonale de ZnS / Mississippi Valley-type Type deposits (MVT) in central and eastern Tennessee, respectively MTM (Middle Tennessee Mine) and ETM (East Tennessee Mine), contain large reserves of zinc in the form of sphalerite, but also germanium in substitution of zinc in sphalerite. However, only the deposits District MTM contain economic concentrations of germanium. These two mining districts hosted in the same geological formations and with a comparable mineralogy, are compared in order to understand the distribution of germanium and other trace elements in MVT. Analyses at atomic scale by atomic absorption spectroscopy X, XANES and EXAFS, revealed several of germanium configurations in sphalerites: germanium can substituted to zinc in ZnS under 2 + and 4+ form, but it can be under the form of nanoscale inclusions of germanium oxide associated with sphalerite. Analyses at mineral scale by electron microprobe, LA-ICP-MS and Raman spectroscopy showed two groups of trace elements: i) the first group composed by Fe and Cd is preferentially incorporated following (110) faces of sphalerite, ii) the second group composed by Cu, Ga and Ge, is preferably incorporated following (010) faces of sphalerite. The coupling of Raman spectroscopy with laser ablation ICP-MS revealed a partitioning of trace elements between the cubic and hexagonal forms of ZnS: the elements Cd and Fe are more concentrated in the cubic form, while Cu, Ga and Ge are more concentrated in the hexagonal ZnS

The author explores absorptive and refractive optical nonlinearities at 1.06 [mu]m in bulk, semi-insulating, undoped GaAs with a particular emphasis on the influence of the native deep-level defect known as EL2. Picosecond pump-probe experimental technique is used to study the speed, magnitude, and origin of the absorptive and refractive optical nonlinearities and to characterize the dynamics of the optical excitation of EL2 in three distinctly different undoped, semi-insulating GaAs samples. Intense optical excitation of these materials leads to the redistribution of charge among the EL2 states resulting in an absorptive nonlinearity due to different cross sections for electron and hole generation through this level. This absorptive nonlinearity is used in conjunction with the linear optical properties of the material and independent information regarding the EL2 concentration to extract the cross section ratio [sigma][sub p]/[sigma][sub e] [approx equal]0.8, where [sigma][sub p](e) is the absorption cross section for hole (electron) generation from EL2[sup +] (EL2[sup 0]). The picosecond pump-probe technique can be used to determine that EL2/EL2[sup +]density ratio in an arbitrary undoped, semi-insulating GaAs sample. The author describes the use of complementary picosecond pump-probe techniques that are designed to isolate and quantify cumulative and instantaneous absorptive and refractive nonlinear processes. Numerical simulations of the measurements are achieved by solving Maxwell equations with the material equations in a self-consistent manner. The numerical analysis together with the experimental data allows extraction of a set of macroscopic nonlinear optical parameters in undoped GaAs. The nonlinearities in this material have been used to construct three proof-of-principle nonlinear optical devices for use at 1.06 [mu]m: (1) a weak beam amplifier, (2) a polarization rotation optical switch, and (3) optical limiters.

This diploma thesis is focused on deposition Ga and GaN structures on graphene fabricated by method of mechanical exfoliation. For mechanical exfoliation was used new method with using DGL Gel-Film with kinetically controlled adhesion. Ga is deposited by Molecular beam epitaxy with using eusion cell in UHV conditions. GaN was obtained by post-nitridation of Ga islands. These structures were investigated with optical microscope, SEM, Raman spectroscopy and photoluminiscence.

This diploma thesis deals with preparation of graphene samples for depositions of ultrathin layers of gallium and gallium nitride. Graphene substrates were prepared by chemical vapour deposition in home-build high temperature reactor. After graphene transfer to silicon wafers, a series of chemical and thermal treatments were performed. Obtained samples were suitable for the study of growth of ultrathin layers of Ga and GaN. The growth of Ga and GaN was realized in ultra high vacuum conditions. Molecular beam epitaxy technique was used for gallium depositions together with ion source for nitridation. Obtained ultrathin layers were studied with X-ray photoelectron spectroscopy, atomic force microscopy and with scanning electron microscopy.