Made available in DSpace on 2014-12-17T15:31:00Z (GMT). No. of bitstreams: 1 BiancaOT.pdf: 2414388 bytes, checksum: aa78504a2ff3ff0a6931a3bf50be0bc3 (MD5) Previous issue date: 2007-04-26 / The rationalization of work in the Dentistry has been taking the professional to work for ways and systems based in the ergonomics, turning their work efficient and less tiring. Since their academic formation, the dentists surgeons are concerned with the high productivity in clinic and with the final result of the work, neglecting the way as it is executed, which reduce their work capacity and exhibits them to occupational diseases that could be minimized and/or forewarned. This research had as the main objective to investigate the knowledge of the Dentistry academics of Rio Grande do Norte Federal University concerning the Noise-induced Hearing Loss (NIHL), relating them at the noise levels that they are exposed, as well as to the preventive measures taken during the clinical activities. Was observed that 95% of the individuals know that the dentist surgeon is a professional in risk for NIHL. Among the causes of NIHL, the one that obtained the largest frequency citation was the high-speed handpieces, reminded by 92,4% of the academics. Among the students which enumerated protective measures for NIHL, 92% mentioned the use of the ear plugs, although 97% of the researched have told do not use any kind of preventive measure related to the noise. Was also observed that 96% of the academics notice the noise during the clinical attendance, what inconvenience 28,1% of them. Related the noise levels, the high-speed handpieces of the academics presented a medium value of 80,5 dB varying from 72,3 to 88,3 dB. The average of the ambient noise observed at the Integrated Clinic was about 74,8 dB. In spite of the noise levels in this research were observed below the established limits of tolerance by the legislation, they can provoke damages to the Dentistry professionals' health, or that suggests the need of an intervention and use of immediate preventive measures able to generate a healthy atmosphere of work and less risky / A racionaliza??o do trabalho na Odontologia tem levado o profissional a trabalhar por meios e sistemas fundamentados na ergonomia, tornando seu trabalho eficiente e menos cansativo. Desde sua forma??o acad?mica, os cirurgi?es dentistas s?o preocupados com a alta produtividade em cl?nica e com o resultado final do trabalho, negligenciando a maneira como este ? executado, o que leva a redu??o de sua capacidade de trabalho e exposi??o a doen?as ocupacionais que poderiam ser minimizadas e/ou prevenidas. Este trabalho teve como objetivo principal investigar o conhecimento de acad?micos de Odontologia de uma Universidade P?blica do Rio Grande do Norte acerca da Perda Auditiva Induzida pelo Ru?do (PAIR), relacionando-o aos n?veis de ru?do a que est?o expostos e ? tomada de medidas preventivas durante as atividades cl?nicas. Foi observado que 95% dos indiv?duos sabem que o cirurgi?o dentista ? um profissional de risco para a PAIR. Dentre as causas da PAIR, a caneta de alta rota??o foi lembrada por 92,4% dos acad?micos. Dos que enumeraram medidas de prote??o para a PAIR, 92% citaram o uso do protetor auricular, embora 97% dos pesquisados tenham relatado n?o usar nenhum tipo de medida preventiva em rela??o ao ru?do. Observou-se tamb?m que 96% dos acad?micos percebem o ru?do durante o atendimento cl?nico, o que chega a incomodar 28,1% deles. Quanto aos n?veis de ru?do, as canetas de alta rota??o dos acad?micos apresentaram um valor m?dio de 80,5 dB variando de 72,3 a 88,3 dB. J? a m?dia do ru?do ambiente observada na Cl?nica Integrada foi de 74,8 dB. Apesar dos n?veis de ru?do observados neste estudo encontrarem-se abaixo dos limites de toler?ncia estabelecidos pela legisla??o, podem provocar preju?zos ? sa?de dos profissionais da Odontologia, o que sugere interven??o e uso de medidas preventivas imediatas capazes de gerar um ambiente ocupacional saud?vel e com menos riscos

The work presented in this thesis has broadly established a few findings about the structure¬hyperpolarizability relation in molecular compounds: First, by measuring βHRS of an organic keto-enol tautomer, benzoylacetanilide in a binary solvent, I have shown that the first hyperpolarizability can be manipulated favourably by changing the composition of the solvent or by altering the pH of the solution. BA which exists in the pure keto form in water and as a keto-enol tautomer in ethanol, co-exists in equilibrium with the keto and enol forms at pH 11 in aqueous solution. The β value of the anion form is 709 x 10¬30 esu , whereas that of the enol is 232 x 10-30 esu and of the keto is 88 x 10-30 esu. There is an enhancement of β by ~ 8 times for the anion and ~3 times for the enol compared to the keto form. This opens up the possibility of finding large nonlinearities in organic molecules by simply ionizing it. Second, in organometallic complexes of divalent Ru, the first hyperpolarizability could be manipulated by altering the valence state of the metal center by oxidation or reduction or by introducing highly polarisable halogen atoms as substitutions in ligands attached to the metal center. The enhancement of first hyperpolarizability was observed in mononuclear [RuII(acac)2(CH3CN)2] complex by 1.7 times when the metal center was oxidized from RuII to RuIII. As it is already known that the complexes like [(acac)2Ru-bptz-Ru(acac)2] produce stable mixed valent compound, the enhancement of β by ~1.6 times is appearing because of that species only. Exploring Large Nonlinearity in Tautomers In this thesis I have taken a linear ketone for studying the effect of structure on β via the enol and anion formation mediated by solvent and pH of the medium. In the present study the proton transfer in BA took place in the ground state of the ketone and the enol or anion are produced in the ground states. The proton transfer reaction (tautomerism) can also happen in the excited state as well in some molecules where there is a substantial barrier to the proton transfer reaction in the ground state. In such systems, once the ketone is excited using ultraviolet light the barrier to proton transfer in the medium is overcome and a proton transfer in the excited state takes place and the enol is produced. Since such a system will be at higher energy, it will be interesting to do a two-laser experiment where the excited state hyperpolarizability is measured in a time resolved manner and the β value is determined in the excited state. Building Molecular Nonlinearity in Step-by-Step Electron Transfer In this thesis, I have dealt with a binuclear complex of Ru(II) which in one-step electrochemical oxidation produced a mixed valence compound which had substantially higher β value compared to the unoxidized complex. In this way it is possible to build a multicentered complex and see if sequential one-electron transfer and subsequent oxidation/reduction of the metal centers produce a mixed-valent metal compound with large molecular nonlinearity. The indication from the present study is that such a scheme should double the β value in each one-electron transfer step. Also the linker group/moiety between the successive metal centers will play an important role in dictating the efficiency of electron transfer. If the metal d-electrons in a multinuclear complex are linked through a π-conjugation, one would expect manifold enhancement of β. Such metal arrays can also be designed in 2 or 3 dimensions. The dimensionality of the multinuclear metal complexes can easily be changed by supramolecular design and synthesis strategy. Such metal networks may or may not generate large β molecules since electronic polarization in such systems may not be superimposable in a coherent fashion and may not add in a positive sense. All these remain to be tested and explored in the future.

Les nanoparticules (NPs) métalliques présentent un grand intérêt dans de nombreuses applications, pour lesquelles un contrôle précis de la taille, de la composition et de la morphologie est requis. Cependant, ce contrôle demeure un défi. Les liquides ioniques (LIs) sont des sels fondus liquides à température ambiante. Ils possèdent des propriétés uniques, à michemin entre le liquide (ce sont des solvants, de bons électrolytes,…) et du solide (ils ne s’évaporent pas). Les LIs sont connus pour être des solvants intelligents, qui permettent, par décomposition de précurseur organométallique, de former des NPs de taille calibrée et contrôlée. Ceci en absence de ligands organiques contrairement aux solvants conventionnels. Cependant, le mécanisme de leur formation reste mal connu. Dans cette thèse, nous identifions les facteurs clés influant sur la taille finale des NPs. Cela permettra de développer des voies de synthèse de NPs de tailles prédéterminées. Par ailleurs, le silicium poreux (PSi) est un matériau prometteur qui peut trouver de multiples utilisations dans les systèmes intégrés ou dans les secteurs photovoltaïque et biomédical. Ses propriétés peuvent être ajustées par l'introduction de métaux dans ses pores. Dans ce cas également, les LIs peuvent être avantageusement utilisés. Dans ce travail, la métallisation de PSi par Cu est réalisée par imprégnation du PSi puis décomposition d’une solution de CuMes dans le LI. En fait, il est observé que c’est le PSi qui décompose le précurseur. Pour cette raison, l’utilisation d’analogues solubles du PSi est étudiée pour remplacer H2 dans la synthèse des NPs. Cela pourrait permettre d’améliorer encore le contrôle de ce procédé / Among nano-objects, metallic nanoparticles (NPs) certainly have a prominent position. This is because they offer a variety of compositions, sizes, shapes and structures that make them suitable for a variety of applications. In the same time, the accurate control of their size, shape and structure is still a challenge, mainly because NPs do not correspond to the thermodynamic stable state of metals. Recently, ionic liquids (ILs) have been shown to stabilize metallic NPs without the need of ligands required in conventional solvents. ILs are liquid molten salt at room temperature. These compounds uniquely combine properties of the liquid (they are good solvents, electrolytes…) and of the solid (they do not evaporate). In the process of decomposing organometallic precursors into metallic NPs, ILs play a central role in controlling the size and ensuring narrow size distribution. However, the corresponding mechanism remains unclear. This PhD work aims at identifying key factors influencing the final size (average and distribution) of metallic NPs chemically formed in ILs. Among nanoporous materials, porous silicon (PSi) is popular due to its exceptional characteristics for microelectronics, integrated optoelectronics, microelectromechanical systems (MEMS), layer transfer technology, solar and fuel cells, biomedicine, etc. Its properties are modified by introducing different materials into its pores. Unique properties of ILs may also be advantageous. In this work, the process used to synthesize metallic NPs is adapted into an easy, efficient, versatile, and safe process to metallise PSi. The metallisation of PSi by Cu is tentatively conducted by impregnation with a solution of CuMes in IL followed by the decomposition of the precursor. In fact, CuMes is shown to be readily decomposed by PSi. Finally, this knowledge is transposed back to the synthesis of metallic NPs, replacing H2 by chemical analogues of PSi as alternative reducing agents. This approach is believed to bring even more control in this process

Dans le cadre de la formation sélective d'oligomères cycliques à partir du cyclo-octène, des matériaux hybrides organiques-inorganiques mésostructurés bien-définis contenant les unités Ru-NHC dissymétriques le long des canaux poreux de leur matrice de silice ont été développés et caractérisés à un niveau moléculaire. Tous les systèmes obtenus ont montré des fortes activités et sélectivités en oligomères cycliques (dimères : 50% et trimères : 25%) en RO-RCM du cyclo-octène, contrairement aux complexes homogènes Ru-NHC analogues symétriques (G-II et GH-II), qui conduisent préférentiellement à la formation de polymères. La variation de la longueur et de la flexibilité des bras espaceurs, dans le cas des catalyseurs hétérogènes, a prouvé que les bras courts et flexibles stabilisent grandement les sites actifs Ru-NHC pendant la réaction de métathèse et ce, grâce à la présence d'interactions entre les sites Ru-NHC catalytiquement actifs et la surface silicique. La présence de telles interactions a été mise en évidence par RMN du phosphore 31 à l'état solide. Des études supplémentaires concernant les performances catalytiques de complexes organométalliques Ru-NHC dissymétriques (analogues aux sites Ru-NHC contenus dans les catalyseurs hétérogènes) et Ru-NHC symétriques (G-II et Nolan) ont clairement montré que le facteur clé influençant la sélectivité en oligomères cycliques est la dissymétrie des ligands NHC. Cette dissymétrie génère la présence de deux sites actifs de configurations différentes au sein même des espèces Ru-NHC. Un des sites favorise la réaction intramoléculaire de fermeture de cycle par métathèse alors que l'autre site permet la réaction intermoléculaire d'ouverture de cycle conduisant ainsi à la formation des oligomères cycliques de petite taille / In the context of the selective formation of cyclic oligomers from cyclooctene, well-defined hybrid organic-inorganic mesoporous materials containing unsymmetrical Ru-NHC units along the pore channel of their silica matrix have been developed and characterized at a molecular level. All systems displayed high activity and selectivity towards the formation of lower cyclic oligomers in the RO-RCM of cyclooctene yielding mainly the dimer and the trimer with 50% and 25% selectivity, respectively, in contrast to classical symmetrical homogeneous analogues (G-II and GH-II), which yield mainly to polymers. Variation of length and flexibility of the tethers showed that flexible short tethers were critical for high stability of the catalysts during metathesis, which is consistent with the stabilization of Ru-NHC active sites by surface functionalities; this surface interaction was further corroborated by the absence of a PCy3 ligand coordinated to Ru when short flexible linkers are used. Further investigations using homogeneous symmetrical (G-II and Nolan) and unsymmetrical (analogues to heterogeneous catalysts) Ru-NHC catalysts clearly showed that the key factor influencing the selectivity towards low cyclic oligomers is the unsymmetrical nature of NHC ligands, which creates dual site configuration in the catalyst architecture thus alternatively favouring one reaction over another, Ring Opening (ROM) vs. Ring Closing (RCM) Metathesis (propagation vs. backbiting), thus leading to the selective tandem RO RCM of cyclooctene. Finally, we have also investigated Grubbs Hoveyda-II (GH-II) type catalysts immobilized on silica support through adsorption, which showed the same product selectivity as that of the well-defined Ru-NHC materials. This result implies that the adsorbed symmetrical GH-II catalyst “becomes unsymmetrical upon adsorption”. Adsorbing unsymmetrical molecular GH II catalysts did not however improve the performances of these types of catalysts. Overall, the unique property of unsymmetrical NHC Ru catalyst, whether supported or not, opens new perspectives in the selective synthesis of macrocycles from other cyclic alkenes via metathesis

No description available.

Thesis advisor: Marc L. Snapper / Tandem processes can have several advantages over multiple single step processes. Non-metathesis transformations of ruthenium alkylidenes were studied and applied to tandem processes. Ruthenium catalyzed tandem RCM/hydroacylation that allows access to tricyclic ring systems from readily available substrates was developed. Mechanistic investigations indicated that this reaction may proceed through a mechanism involving [Ru]-H species. A Ru-catalyzed tandem RCM/olefin isomerization/C-H activation sequence that provides significant advantages in terms of rapid elaboration of simple reaction partners to more complex entities was developed. / Thesis (PhD) — Boston College, 2013. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

A Braquiterapia oftálmica utiliza radionuclídeos, como o Rutênio-106 no tratamento de melanomas uveais e outras neoplasias oculares. Para realização desse procedimento é necessária uma interação da equipe multidisciplinar principalmente entre a Oftalmologia, Oncologia, Radioterapia, Física Médica e Enfermagem, envolvendo estrutura física e profissionais qualificados para garantir os processos e resultados do procedimento. Este estudo tem o objetivo de avaliar os primeiros tratamentos de braquiterapia oftálmica com Rutênio-106 e também estabelecer protocolos e processos para implementação da técnica em um Hospital Geral. Os resultados obtidos para os primeiros 11 casos tratados entre 2015 e 2017, sendo 10 melanomas e 1 hemangioma, evidenciaram baixa toxicidade aguda. Foram analisados 5 pacientes com seguimento de 5 a 13 meses. Houve regressão da lesão em todos os pacientes, com média de 28% no ápice e 12% na base no período de até 12 meses, sendo observado uma regressão progressiva durante o período de avaliação. Os protocolos foram utilizados e validados durante todas as etapas do tratamento. O uso do Ru-106 mostra-se alternativa viável no tratamento de lesões oculares, sendo primordial a capacitação e integração da equipe e seguimento de protocolos para o êxito do tratamento. / Ophthalmic Brachytherapy uses radionuclides, such as Ruthenium-106 in the treatment of uveal melanomas and other ocular tumors. For this procedure is necessary a multidisciplinary interaction between Ophthalmology, Oncology, Radiotherapy, Medical Physics and Nursing, involving physical structure and qualified professionals to guarantee the processes and results of the procedure. This study aims to evaluate the first ophthalmic brachytherapy treatments with ruthenium- 106 and also to establish protocols and processes for the implementation of this service in a General Hospital. The results obtained for the first 11 cases treated between 2015 and 2017, being 10 melanomas and 1 hemangioma, showed low acute toxicity. Five patients were followed up for 5 to 13 months. There was regression of the lesion in all of these patients, with a mean of 28% at the apex and 12% at the base in the period close to 1 year, with a progressive regression during the evaluation period. The protocols were used and validated during all stages of treatment. The use of 106-Ru is a viable alternative in the treatment of ocular tumors, being the team qualification and the correct follow-up of the protocols crucial for the treatment success.

Made available in DSpace on 2016-04-25T20:20:10Z (GMT). No. of bitstreams: 1 Karine Michelle Guirau.pdf: 2806659 bytes, checksum: 39cc0e0ca259bb636829a81a9446f21a (MD5) Previous issue date: 2011-05-13 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / To delimit Indian lands in Brazil is a historically complicated task. And when it comes to the state of Mato Grosso do Sul this task requires twice the challenges. Ñande Ru Marangatu is the land of Kaiowa Indian in the municipality of Antônio João/MS next to Paraguai border. Approved as an Indian land after a long administrative procedure, the Kaiowa from Marangatu witnessed the effects of the ratification decree be suspended by the MS 25463/DF leaving that community to the roadside of MS. Ñande Ru Marangatu is a typical case of racist conduct e negligence by the Brazilian society with regards to the indigenous people in general. This study seeks to understand the intensity of the anti-indigenous speech presented by the anthropological counter report in the administrative procedure of identification and demarcation of Ñande Ru Marangatu and present it as a communicative event that reveals what is beneath the suspension of the effects of the ratification decree / Demarcar terras indígenas no Brasil é tarefa historicamente complicada. Tratando-se do estado do Mato Grosso do Sul é tarefa que dobra em seus desafios. Ñande Ru Marangatu é terra de índio Kaiowa no município de Antônio João/MS junto à fronteira do Paraguai. Homologada como terra indígena depois de um longo procedimento administrativo, os Kaiowa de Marangatu viram ser suspensos os efeitos do decreto homologatório pela MS 25463/DF sobrando àquela comunidade as beiras das estradas de MS. Ñande Ru Marangatu é um típico caso de conduta racista e descaso pela sociedade brasileira frente aos povos indígenas, de forma geral. O presente trabalho busca compreender a intensidade do discurso anti-indígena apresentado pelo contraulado antropológico no procedimento administrativo de identificação e demarcação de Ñande Ru Marangatu e apresentá-lo como um evento comunicativo que revela o que por trás está da suspensão dos efeitos do decreto homologatório

Made available in DSpace on 2016-04-26T14:53:00Z (GMT). No. of bitstreams: 1 Karine Michelle Guirau.pdf: 2806659 bytes, checksum: 39cc0e0ca259bb636829a81a9446f21a (MD5) Previous issue date: 2011-05-13 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / To delimit Indian lands in Brazil is a historically complicated task. And when it comes to the state of Mato Grosso do Sul this task requires twice the challenges. Ñande Ru Marangatu is the land of Kaiowa Indian in the municipality of Antônio João/MS next to Paraguai border. Approved as an Indian land after a long administrative procedure, the Kaiowa from Marangatu witnessed the effects of the ratification decree be suspended by the MS 25463/DF leaving that community to the roadside of MS. Ñande Ru Marangatu is a typical case of racist conduct e negligence by the Brazilian society with regards to the indigenous people in general. This study seeks to understand the intensity of the anti-indigenous speech presented by the anthropological counter report in the administrative procedure of identification and demarcation of Ñande Ru Marangatu and present it as a communicative event that reveals what is beneath the suspension of the effects of the ratification decree / Demarcar terras indígenas no Brasil é tarefa historicamente complicada. Tratando-se do estado do Mato Grosso do Sul é tarefa que dobra em seus desafios. Ñande Ru Marangatu é terra de índio Kaiowa no município de Antônio João/MS junto à fronteira do Paraguai. Homologada como terra indígena depois de um longo procedimento administrativo, os Kaiowa de Marangatu viram ser suspensos os efeitos do decreto homologatório pela MS 25463/DF sobrando àquela comunidade as beiras das estradas de MS. Ñande Ru Marangatu é um típico caso de conduta racista e descaso pela sociedade brasileira frente aos povos indígenas, de forma geral. O presente trabalho busca compreender a intensidade do discurso anti-indígena apresentado pelo contraulado antropológico no procedimento administrativo de identificação e demarcação de Ñande Ru Marangatu e apresentá-lo como um evento comunicativo que revela o que por trás está da suspensão dos efeitos do decreto homologatório

A Braquiterapia oftálmica utiliza radionuclídeos, como o Rutênio-106 no tratamento de melanomas uveais e outras neoplasias oculares. Para realização desse procedimento é necessária uma interação da equipe multidisciplinar principalmente entre a Oftalmologia, Oncologia, Radioterapia, Física Médica e Enfermagem, envolvendo estrutura física e profissionais qualificados para garantir os processos e resultados do procedimento. Este estudo tem o objetivo de avaliar os primeiros tratamentos de braquiterapia oftálmica com Rutênio-106 e também estabelecer protocolos e processos para implementação da técnica em um Hospital Geral. Os resultados obtidos para os primeiros 11 casos tratados entre 2015 e 2017, sendo 10 melanomas e 1 hemangioma, evidenciaram baixa toxicidade aguda. Foram analisados 5 pacientes com seguimento de 5 a 13 meses. Houve regressão da lesão em todos os pacientes, com média de 28% no ápice e 12% na base no período de até 12 meses, sendo observado uma regressão progressiva durante o período de avaliação. Os protocolos foram utilizados e validados durante todas as etapas do tratamento. O uso do Ru-106 mostra-se alternativa viável no tratamento de lesões oculares, sendo primordial a capacitação e integração da equipe e seguimento de protocolos para o êxito do tratamento. / Ophthalmic Brachytherapy uses radionuclides, such as Ruthenium-106 in the treatment of uveal melanomas and other ocular tumors. For this procedure is necessary a multidisciplinary interaction between Ophthalmology, Oncology, Radiotherapy, Medical Physics and Nursing, involving physical structure and qualified professionals to guarantee the processes and results of the procedure. This study aims to evaluate the first ophthalmic brachytherapy treatments with ruthenium- 106 and also to establish protocols and processes for the implementation of this service in a General Hospital. The results obtained for the first 11 cases treated between 2015 and 2017, being 10 melanomas and 1 hemangioma, showed low acute toxicity. Five patients were followed up for 5 to 13 months. There was regression of the lesion in all of these patients, with a mean of 28% at the apex and 12% at the base in the period close to 1 year, with a progressive regression during the evaluation period. The protocols were used and validated during all stages of treatment. The use of 106-Ru is a viable alternative in the treatment of ocular tumors, being the team qualification and the correct follow-up of the protocols crucial for the treatment success.