Les verres de phosphates de zinc et gallium contenant de l’argent ont permis des développements originauxau travers de la structuration d’architectures photoniques multi-échelles innovantes en volume, en surfaceou sur fibre, et également à travers l’ingénierie de composition chimique du matériau. Un taux accru d’oxyded’argent permet de maximiser la quantité de paires au sein de la matrice vitreuse lors de la synthèse dumatériau. Ce dimère favorise les processus d’agrégation conduisant à la formation d’espèces lors del’interaction locale entre le verre et le laser femtoseconde infrarouge. Une étude par spectroscopie RPEmenée sur des échantillons irradiés par des sources ionisantes a permis de montrer que le débit de dose estprépondérant quant au contrôle des processus chimiques. Des centres à électron et à trou sont les espècesmajoritairement stabilisées à faible débit de dose, alors que la formation d’agrégats d’argent luminescentsintervient pour des puissances crête élevées typiques des lasers ultra-courts. Le caractère local de lastructuration par Direct Laser Writing a permis de créer des objets 3D originaux. L’analyse fine de ladistribution chimique au sein d’objets fluorescents a permis de montrer clairement une zone de déplétion enions argent au centre. Les effets de migration d’ions depuis le centre du faisceau laser vers le bord externea ainsi été mis en évidence. Le dopage des verres photosensibles par des ions europium a permis de montrerdes effets de synergie entre agrégats d’argent photo-inscrits et lanthanides trivalent. En effet, une exaltationde l’émission de luminescence de ces derniers à l’endroit des structurations laser a été mesurée. / The silver-containing phosphate glasses allowed original developments throughout the microstructuring ofarchitectures for innovative photonic in the volume, at the surface or in the fibered material. The chemicalengineering of the material plays an important role from this point of view. An increasing silver oxide ratioleads to an important quantity of pairs in the pristine glass matrix. This dimer in favor of the aggregationprocess bringing to the production of species during the interaction between the glass and the infraredfemtosecond laser. A study conducted by EPR spectroscopy on irradiated samples (ionizing sources)demonstrated that the dose rate is predominant for the control of the involved chemical process. Mainly,electron and holes are stabilized at low dose rate whereas the formation of luminescent silver clusters occursfor high peak power typical of ultra-short lasers. The Direct Laser Writing process allows local structuring ofthe matter and resulted in original tridimensional patterns. The fine chemical distribution analysis insideannular fluorescent objects clearly showed a depletion zone of the silver concentration in the center. Ionicmigration effects from the center towards the edges of the laser beam are then highlighted. The Eu3+-dopedphotosensitive glasses emphasized a synergy between photo-induced silver clusters and trivalentlanthanides. Indeed, a luminescence exaltation associated to the europium emission is measured.

As propriedades fotofísicas dos complexos morin-Mg2+ e morin-Ce3+, foram investigadas em solução metanólica, em filmes finos de polímeros e em nanozéolitas por técnicas de fluorescência. A associação do metal ao flavonoide ocorre no sítio da carbonila do anel pirona nas razões estequiométricas de 1:1 e 1:2 (magnésio: morin), e esta associação favorece no aumento considerável da intensidade de fluorescência devido à inibição da transferência intramolecular do próton no estado excitado. Os resultados revelaram que os espectros de emissão do complexo morin-Mg2+ sofreram um pequeno deslocamento hipsocrômico. Os decaimentos de fluorescência do sistema Morin-Mg2+ são triexponenciais para o complexos Morin-Mg2+ formados com tempo de vida máximo de 3 ns. O complexo morin-Ce3+ é pouco fluorescente e a complexação com o metal leva a supressão de fluorescência devido a sua natureza paramagnética. A estequiometria aparente dominante é de um 1:1 e o decaimento possui um componente de tempo de vida longo de 4-5 ns. Na comparação das propriedades de fluorescência do morin-Mg2+ com o indicador magnesium green verificamos que ambos são bons indicadores fluorescentes para a microscopia de fluorescência podendo esses complexos serem usados na detecção de Mg2+ em nanozeólita e outros sistemas / The photophysical properties of the molecular complexes of morin with Mg2+ and Ce3+ cations in methanol solution as well as in thin polymeric films and nanozeolytes have been investigated by using fluorescence spectroscopy and microscopy. The association of morin with Mg2+ occurs at the (4)-carbonyl group of the pyrone ring at 1:1 and 1:2 stoichiometric ratio. The complexes have shown an increase of the emission quantum yield by precluding the excited state deactivation though the intramolecular proton transfer process. The fluorescence decays of the complexes are non exponential due to the presence of more than one emission species and the average decay time found was about 3 ns. On the other hand, the addition of Ce3+ to morin solution resulted in fluorescence quenching ascribed to 1:1 non emissive complex due to the paramagnetic nature of the metal cation. The fluorescence properties of morin-Mg2+ complex have been compared with the standard fluorescence indicator magnesium green. The results pointed out that morin-Mg2+ may be used as an alternative low coast indicator of Mg2+ in homogenous as well as in microheterogeneous media.

La construction de complexes polymétalliques de lanthanides préprogrammés et sophistiqués, de taille nanométrique, pour le développement de matériaux luminescents présentant des propriétés photophysiques nouvelles ou améliorées (double émission, transfert d'énergie intermétallique, etc.) est un des sujets de la chimie supramoléculaire des lanthanides suscitant énormément d'intérêt. La compréhension, le contrôle et la programmation de l'auto-assemblage de complexes de lanthanides est un défi majeur en raison de la difficulté à contrôler l'environnement de coordination de ces ions qui se caractérise par des nombres de coordinations importants et variables et peu de préférences stéréochimiques. Ainsi, la plupart des complexes polynucléaires de lanthanides décrits dans la littérature sont formés de façon fortuite plutôt que par conception rationnelle. Afin d'inclure les ions lanthanides dans des architectures polymétalliques de haute nucléarité tout en améliorant leurs propriétés photophysiques, nous nous sommes concentrés sur des études de complexation de ligands dissymétriques (tridentates anioniques, tétradentates chiraux) permettant de promouvoir la formation des assemblages. Nous avons par ailleurs commencé à explorer le potentiel d'une méthode synthétique originale de clusters oxo par réactivité redox de complexes divalents de lanthanides. Nous présentons ici la synthèse et les propriétés photophysiques de complexes stables émettant dans le proche infrarouge basés sur des ligands anioniques hydroxyquinoléine fonctionnalisé par des groupes carboxylates ou tétrazolates. En outre, nous pouvons montrer que l'utilisation de ligands chiraux possédant un groupement oxazoline favorise l'auto-assemblage diastéréosélectif de complexes de lanthanides homo- et hétéro-polymétalliques énantiopures émettant dans le visible et le proche infrarouge. Un complexe trinucléaire d'europium énantiopure a été caractérisé par cristallographie, celui-ci présentant une forte activité en polarisation circulaire de luminescence (CPL). Le ligand chiral oxazoline a permis d'obtenir une roue heptanucléaire d'europiums, le plus important assemblage polymétallique énantiopure. Enfin, nous avons pu préparer et caractériser des complexes de lanthanides divalents hautement réactifs basés sur un ligand tripode neutre possédant des groupements pyridine (tpa). Des résultats préliminaires montrent que ces complexes peuvent être des précurseurs très utiles pour isoler des clusters oxo polymétalliques. En particulier, la réaction d'un complexe de néodyme hautement réactif a conduit à isoler un cluster oxo volumineux et très intéressant par clivage de THF en présence de tpa. / The construction of preprogrammed, sophisticated and nanoscopic polymetallic lanthanide complexes for the development of luminescent materials that possess new or improved photophysical properties (dual emission, intermetallic energy transfer, etc.) is one of the hot topics in the lanthanide supramolecular chemistry. Understanding, controlling and programming self assembly of lanthanide complexes is a key challenge due to the difficulty in controlling the coordination environment of these ions which display high and variable coordination numbers with little stereochemical preferences. As a result of this, most of the polynuclear lanthanide complexes reported in literature are formed by serendipity rather than rational design. In order to include lanthanide ions in discrete high nuclearity polymetallic architectures with improved photophysical properties we have concentrated on complexation studies with dissymmetric chelating ligands (tridentate anionic ligands, tetradentate chiral ligand) with possibility of promoting assembly formation, and we started to investigate the potential of an original synthetic method using the redox reactivity of divalent lanthanides complexes for the synthesis of oxo clusters. Here we present the synthesis and photophysical properties of NIR emissive stable complexes obtained with hydroxyquinoline based tridentate dianionic ligands functionalised with carboxylic acid and tetrazole groups. Moreover we show that the use of a chiral tetradentate ligand possessing oxazoline ring promotes the diastereoselective self assembly of enantiopure homo- and hetero-polymetallic lanthanide complexes emitting in the visible and NIR range. An original enantiopure trinuclear europium complex was crystallographically characterised and we found that it displays a high circularly polarized luminescence (CPL) activity. The chiral oxazoline based ligand also led to the synthesis of the largest enantiopure polymetallic assembly of europium, a heptanuclear wheel. Finally we were able to prepare and characterize highly reactive complexes of divalent lanthanides with a neutral tripodal pyridine based ligand and very preliminary results show that these complexes can be useful precursors for the isolation of polymetallic oxoclusters. Notably, the reaction of the highly reactive neodymium complex led to the isolation of a very interesting large neodymium oxo cluster by cleavage of THF in the presence of the ligand tpa.

<p>Crystallographic and spectroscopic studies have been performed of structures, coordination and chemical bonding for series of trivalent metal ions solvated by two oxygen-coordinating solvents, water and dimethyl sulfoxide (DMSO). The hydrated scandium(III) and lanthanoid(III) ions, La to Lu, are surrounded by tricapped trigonal prisms of aqua ligands in the isomorphous series of trifluoromethanesulfonates, [M(H₂O)_n](CF₃SO₃)₃. For the smallest ions, M = Er, Tm, Yb, Lu, Sc, the hydration numbers decrease, <i>n</i> = 8.96(5), 8.8(1), 8.7(1), 8.5(1), 8.0(1), respectively, with decreasing size of the ion. The crystal structures at ambient temperature indicate randomly distributed vacancies of the capping oxygen atoms, and ²H solid-state NMR of the diamagnetic [M(H₂O)_n](CF₃SO₃)₃, M = Sc, Lu, Y and La compounds revealed increasing mobility of the water ligands in the coordination sphere with increasing temperature, also for the fully nonahydrated La^III and Y^III ions. The stretching force constants of the Ln-O bonds, evaluated from vibrational spectroscopy, increased from 0.81 to 1.16 N cm^-1 for the Ln-6O trigonal prism in a smooth correlation with the bond distances from La to Lu. For the capping Ln-3O bonds the increase from 0.49 to 0.65 N cm^-1 reflects the increased ligand-ligand repulsion with decreasing ion size. This is also the reason for the water deficiency of the Er, Tm, Yb, Lu and Sc salts, and for [Sc(H₂O)_8.0](CF₃SO₃)₃ the repulsion induced a phase transition at about 185 K that, by low temperature crystallography, was found to distort the coordination of water molecules toward a monocapped trigonal prism around the scandium(III) ion.</p><p>All crystal structures of the octakis(dimethyl sulfoxide)lanthanoid(III) iodides comprise discrete [Ln(dmso)₈]³⁺ complexes surrounded by iodide ions. The lanthanum(III) and praseodymium(III) compounds crystallize in the orthorhombic space group <i>Pbca</i> with more efficient packing than for the heavier and smaller ions in the lanthanoid series, which crystallize in the monoclinic space group <i>P2</i>₁/<i>n</i>. The group 13 metal ions, aluminium(III), gallium(III), indium(III), thallium(III), and also scandium(III) of group 3, form crystalline hexakis(dimethyl sulfoxide) solvates in the space group <i>R</i> 3, with octahedral MO₆ coordination entities, which are increasingly compressed along one threefold axis for increasing ionic size. EXAFS measurements on the solvated ions display similar M-O bond distances in dimethyl sulfoxide solution as in the solid solvates. For all the solid dimethyl sulfoxide solvates the strength and nature of the metal-oxygen bond has been evaluated by normal coordinate analysis of vibrational spectra, and correlated with the S-O stretching vibrational mode.</p><p>Distortions from regular octahedral six coordination are discussed for the hydrated isoelectronic soft mercury(II) and thallium(III) ions in the solid bisaquamercury(II) and trisaquatallium(III) trifluoromethanesulfonates, in terms of pseudo Jahn-Teller effects (PJTE). Mercury(II), generally more strongly influenced by PJTE distortions, displays a 2 + 4 Hg-O coordination forming chains that are held together in sheets by hydrogen bonds and in layers by van der Waals interactions, which explain the fragile structure of the crystals.</p>

Crystallographic and spectroscopic studies have been performed of structures, coordination and chemical bonding for series of trivalent metal ions solvated by two oxygen-coordinating solvents, water and dimethyl sulfoxide (DMSO). The hydrated scandium(III) and lanthanoid(III) ions, La to Lu, are surrounded by tricapped trigonal prisms of aqua ligands in the isomorphous series of trifluoromethanesulfonates, [M(H2O)n](CF3SO3)3. For the smallest ions, M = Er, Tm, Yb, Lu, Sc, the hydration numbers decrease, n = 8.96(5), 8.8(1), 8.7(1), 8.5(1), 8.0(1), respectively, with decreasing size of the ion. The crystal structures at ambient temperature indicate randomly distributed vacancies of the capping oxygen atoms, and 2H solid-state NMR of the diamagnetic [M(H2O)n](CF3SO3)3, M = Sc, Lu, Y and La compounds revealed increasing mobility of the water ligands in the coordination sphere with increasing temperature, also for the fully nonahydrated LaIII and YIII ions. The stretching force constants of the Ln-O bonds, evaluated from vibrational spectroscopy, increased from 0.81 to 1.16 N cm-1 for the Ln-6O trigonal prism in a smooth correlation with the bond distances from La to Lu. For the capping Ln-3O bonds the increase from 0.49 to 0.65 N cm-1 reflects the increased ligand-ligand repulsion with decreasing ion size. This is also the reason for the water deficiency of the Er, Tm, Yb, Lu and Sc salts, and for [Sc(H2O)8.0](CF3SO3)3 the repulsion induced a phase transition at about 185 K that, by low temperature crystallography, was found to distort the coordination of water molecules toward a monocapped trigonal prism around the scandium(III) ion. All crystal structures of the octakis(dimethyl sulfoxide)lanthanoid(III) iodides comprise discrete [Ln(dmso)8]3+ complexes surrounded by iodide ions. The lanthanum(III) and praseodymium(III) compounds crystallize in the orthorhombic space group Pbca with more efficient packing than for the heavier and smaller ions in the lanthanoid series, which crystallize in the monoclinic space group P21/n. The group 13 metal ions, aluminium(III), gallium(III), indium(III), thallium(III), and also scandium(III) of group 3, form crystalline hexakis(dimethyl sulfoxide) solvates in the space group R 3, with octahedral MO6 coordination entities, which are increasingly compressed along one threefold axis for increasing ionic size. EXAFS measurements on the solvated ions display similar M-O bond distances in dimethyl sulfoxide solution as in the solid solvates. For all the solid dimethyl sulfoxide solvates the strength and nature of the metal-oxygen bond has been evaluated by normal coordinate analysis of vibrational spectra, and correlated with the S-O stretching vibrational mode. Distortions from regular octahedral six coordination are discussed for the hydrated isoelectronic soft mercury(II) and thallium(III) ions in the solid bisaquamercury(II) and trisaquatallium(III) trifluoromethanesulfonates, in terms of pseudo Jahn-Teller effects (PJTE). Mercury(II), generally more strongly influenced by PJTE distortions, displays a 2 + 4 Hg-O coordination forming chains that are held together in sheets by hydrogen bonds and in layers by van der Waals interactions, which explain the fragile structure of the crystals.

The goal of this work was to better understand how molybdate and trivalent cations can be used as additives to pH neutral electrolytes to activate the Hydrogen Evolution Reaction (HER). Special emphasis was laid on the chlorate process and therefore also to some of the other effects that the additives may have in that particular process. Cathode films formed from the molybdate and trivalent cations have been investigated with electrochemical and surface analytical methods such as polarization curves, potential sweep, Electrochemical Impedance Spectroscopy (EIS), current efficiency measurements, Scanning Electron Microscope (SEM), Energy-Dispersive X-ray Spectroscopy (EDS), X-ray Photoelectron Spectroscopy (XPS), X-Ray Fluorescence (XRF) and Inductively Coupled Plasma (ICP) analysis. Trivalent cations and molybdate both activate the HER, although in different ways. Ligand water bound to the trivalent cations replaces water as reactant in the HER. Since the ligand water has a lower pKa than free water, it is more easily electrochemically deprotonated than free water and thus catalyzes the HER. Sodium molybdate, on the other hand, is electrochemically reduced on the cathode and form films which catalyze the HER (on cathode materials with poor activity for HER). Molybdate forms films of molybdenum oxides on the electrode surface, while trivalent cation additions form hydroxide films. There is a risk for both types of films that their ohmic resistance increases and the activity of the HER decreases during their growth. Lab-scale experiments show that for films formed from molybdate, these negative effects become less pronounced when the molybdate concentration is reduced. Both types of films can also increase the selectivity of the HER by hindering unwanted side reactions, but none of them as efficiently as the toxic additive Cr(VI) used today in the chlorate process. Trivalent cations are not soluble in chlorate electrolyte and thus not suitable for the chlorate process, whereas molybdate, over a wide pH range, can activate the HER on catalytically poor cathode materials such as titanium. / Målsättningen med detta doktorsarbete har varit att bättre förstå hur trivalenta katjoner och molybdat lösta i elektrolyten kan effektivisera elektrokemisk vätgasproduktion. Tillämpningen av dessa tillsatser i kloratprocessen och eventuella sidoeffekter har undersökts. De filmer som bildas på katoden av tillsatserna har undersökts med både elektrokemiska och fysikaliska ytanalysmetoder: polarisationskurvor, potentialsvep, elektrokemisk impedansspektroskopi (EIS), strömutbytesmätningar, svepelektronmikroskopi (SEM), energidispersiv röntgenspektroskopi (EDS), röntgenfotoelektronspektroskopi (XPS), röntgenfluorensens (XRF) och induktivt kopplat plasma (ICP). Både trivalenta katjoner och molybdat kan aktivera elektrokemisk vätgasutveckling, men på olika sätt. Vatten bundet till trivalenta katjoner ersätter fritt vatten som reaktant vid vätgasutveckling. Eftersom vatten bundet till trivalenta katjoner har lägre pKa-värde, går det lättare att producera vätgas från dessa komplex än från fritt vatten. Natriummolybdat däremot reduceras på katoden och bildar filmer som kan katalysera vätgasutvecklingen på substratmaterial som har låg katalytisk aktivitet för reaktionen. Molybdat bildar molybdenoxider på ytan medan trivalenta katjoner bildar metallhydroxider. Båda typerna av film riskerar att bilda filmer som är resistiva och deaktiverar vätgasutvecklingen. Laboratorieexperiment visar att problemen minskar med minskad molybdathalt. Båda filmerna kan öka selektiviteten för vätgasutveckling genom att hindra sidoreaktioner. Filmerna är dock inte lika effektiva som de filmer som bildas från den ohälsosamma tillsatsen Cr(VI), vilken används i kloratprocessen idag. Trivalenta katjoner är inte lösliga i kloratelektrolyt och är därför inte en lämplig tillsats i kloratprocessen. Molybdat har god löslighet och kan aktivera vätgasutveckling i ett stort pH‑intervall på titan och andra substratmaterial som själva har betydlig sämre aktivitet för vätgasutveckling. / <p>QC 20120530</p> / c6839

Submitted by Vasti Diniz (vastijpa@hotmail.com) on 2017-09-04T14:34:21Z No. of bitstreams: 1 arquivototal.pdf: 3127119 bytes, checksum: 5c890bb880fcbd5cc7d5f5f36f11e4f1 (MD5) / Made available in DSpace on 2017-09-04T14:34:21Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 3127119 bytes, checksum: 5c890bb880fcbd5cc7d5f5f36f11e4f1 (MD5) Previous issue date: 2017-02-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Treatment with antimonials has several limitations, among them the progressive emergence of parasites resistant to these drugs. In this situation, recent evidence suggests that the parameters antimonial resistance and virulence may be correlated in Leishmania sp. have been published in the literature. In this context, this work aimed to investigate whether there is a correlation between virulence and resistance to trivalent antimonial (SbIII) from two clinical isolates of Leishmania (Viannia) braziliensis, named AF and JCTS. Promastigote forms of these parasites resistant to SbIII were selected, obtaining cultures with a resistance level corresponding to 14 and 13 times the wild-type IC50 (sensitive to SbIII) for the isolates AF and JCTS, respectively. When analyzing the stability of the phenotype of acquired resistance, it was verified that both clinical isolates presented an unstable profile, with progressive reversion of resistance after successive passages in drug absence. In morphological analysis, it was observed that two cultures resistant to SbIII presented higher amount of promastigote forms with metacyclic characteristics when compared to sensitive cultures. However, the growth in culture medium was similar for sensitive and resistant cultures of both clinical isolates. In stationary phase of growth, the percentage of serum that caused 50% of cellular lysis (EC50) of the AF culture sensitive to SbIII was 2.3%, whereas the corresponding drug resistant culture presented EC50 9.4%. Similarly, the sensitive and SbIII resistant JCTS cultures showed EC50 2.5% and 18.4%, respectively. Thus, cultures resistant to SbIII from both clinical isolates were more resistant to complement-mediated lysis than drug-sensitive cultures SbIII resistant cultures also showed greater in vitro virulence on murine macrophages when compared to the corresponding sensitive cultures. The infection rate determined for sensitive and resistant SbIII AF was 260 and 593. For sensitive and resistant SbIII JCTS was 115 and 207, respectively. In the model of infection in vivo in swiss mice, no significant virulence was evident in any culture of L. braziliensis. Thus, we conclude that there is a correlation between parameters of in vitro virulence and resistance to SbIII in L. braziliensis. / O tratamento com os antimoniais possui várias limitações, dentre elas o crescente surgimento de parasitos resistentes a estas drogas. Agravando esta situação, recentes evidências de que os parâmetros resistência a antimoniais e virulência possam estar correlacionados em Leishmania sp. têm sido publicadas na literatura. Dentro deste contexto, este trabalho objetivou investigar se existe correlação entre os parâmetros de virulência e resistência ao antimonial trivalente (SbIII) a partir de dois isolados clínicos de Leishmania (Viannia) braziliensis denominados AF e JCTS. Foram selecionadas formas promastigotas destes parasitos resistentes ao SbIII, obtendo-se culturas com um nível de resistência correspondente a 14 e 13 vezes a IC50 da cultura selvagem (sensível ao SbIII) para os isolados AF e JCTS, respectivamente. Ao analisar a estabilidade do fenótipo de resistência adquirido, verificou-se que ambos os isolados clínicos apresentaram um perfil instável, com progressiva reversão da resistência após sucessivos repiques na ausência da droga. Em análise morfológica, foi possível observar que as duas culturas resistentes ao SbIII apresentaram maior quantidade de formas promastigotas com características de metacíclicas quando comparado com as culturas sensíveis. Contudo, o perfil de crescimento em meio de cultivo foi semelhante para as culturas sensíveis e resistentes de ambos os isolados clínicos. Em fase estacionária de crescimento, a porcentagem de soro que causou 50% de lise celular (EC50) da cultura AF sensível ao SbIII foi de 2,3%, enquanto que a correspondente cultura resistente à droga apresentou EC50 de 9,4%. De modo semelhante, as culturas JCTS sensível e resistente ao SbIII apresentaram EC50 de 2,5% e 18,4%, respectivamente. Assim, as culturas resistentes ao SbIII, de ambos os isolados clínicos, foram mais resistentes à lise mediada pelo sistema complemento do que as culturas sensíveis à droga. As culturas resistentes ao SbIII também apresentaram maior virulência in vitro sobre macrófagos murinos quando comparadas às correspondentes culturas sensíveis. O índice de infecção determinado para AF sensível e resistente ao SbIII foi de 260 e 593. Para JCTS sensível e resistente ao SbIII foi de 115 e 207, respectivamente. No modelo de infecção in vivo em camundongos suíços não foi evidenciada virulência significativa em nenhuma das culturas de L. braziliensis. Dessa forma, conclui-se que há uma correlação entre parâmetros de virulência in vitro e resistência ao SbIII em L. braziliensis.

Submitted by Helen Gomes da Silva (helen-277@hotmail.com) on 2018-04-19T16:16:53Z No. of bitstreams: 1 Dissert_Helen.pdf: 519297 bytes, checksum: 5cb7a2e4a99a88a45d87901f4e7476cd (MD5) / Approved for entry into archive by Satie Tagara (satie@marilia.unesp.br) on 2018-04-19T17:33:50Z (GMT) No. of bitstreams: 1 silva_hg_me_mar.pdf: 519297 bytes, checksum: 5cb7a2e4a99a88a45d87901f4e7476cd (MD5) / Made available in DSpace on 2018-04-19T17:33:50Z (GMT). No. of bitstreams: 1 silva_hg_me_mar.pdf: 519297 bytes, checksum: 5cb7a2e4a99a88a45d87901f4e7476cd (MD5) Previous issue date: 2018-02-23 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O professor Newton C. A. da Costa, notável lógico brasileiro, e colaboradores introduziram a noção de quase-verdade no contexto das ciências empíricas, onde há incompletude do conhecimento. Tal abordagem é considerada uma generalização para contextos parciais da proposta de formalização da verdade introduzida por Alfred Tarski. Inspirado nessa noção de quase-verdade, Silvestrini (2011) introduziu uma de nição de quase-verdade através da satisfação pragmática e, no mesmo trabalho apresentou, num sistema axiomático, uma lógica paraconsistente e trivalente, subjacente a essa noção, a qual denominou por Lógica da Verdade Pragmática (LPT- Logic of Pragmatic Truth ). Posteriormente, Feitosa e Silvestrini (2016) apresentaram algumas alterações no conjunto de axiomas de LPT e deram uma demonstração de adequação segundo a semântica matricial da lógica da verdade pragmática. Hoje, sistemas dedutivos alternativos ao axiomático têm sido de grande interesse para a área da teoria da prova e computabilidade, pois esses, em sua maioria, são métodos mais intuitivos. Alguns são caracterizados como algorítmicos, o que possibilita uma fácil implementação do método em computadores. Dentre esses sistemas de provas, destacamos o método dedutivo dos tableaux analíticos, que foi introduzido de uma forma bastante elegante por Smullyan (1968). Neste trabalho, introduzimos um sistema de tableaux analíticos para a Lógica da Verdade Pragmática e veri camos que todos os resultados dedutivos do sistema axiomático da LPT coincidem com os resultados de consequência analítica do sistema de tableaux que aqui introduzimos. / Professor Newton C. A. da Costa, notable Brazilian logician, and collaborators introduced the notion of quasi-truth in the context of the empirical sciences, where there is incompleteness of knowledge. Such an approach is considered a generalization of Tarski's proposal for partial contexts. Inspired by this notion of quasi-truth, Silvestrini (2011) introduced a de nition of quasi-truth through pragmatic satisfaction and, in the same work, presented, in an axiomatic system, a paraconsistent and trivalent logic, underlying this notion, which he called 'Logic of Pragmatic Truth (LPT)'. Later, Feitosa and Silvestrini (2016) presented some changes in the set of axioms of LPT and gave a proof of adequacy according to the trivalent matrix semantics of LPT. Nowadays, alternative axiomatic deductive systems have been of great interest to proof theory and computability, because these are in general intuitive methods. Some of them are characterized as algorithmic, which allows an easy implementation in computers. Among these systems of proof, we highlight the deductive method of analytic tableaux, which was introduced in an elegant way by Smullyan (1968). In this work, we introduce an analytic tableau system for the Logic of Pragmatic Truth and we verify that the results we can develop in the axiomatic system of the LPT coincide with the deductions in this analytic system of tableaux.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This study reports the synthesis, structural and optics characterization of LiSrPO4 pure and doped with Lanthanide ions as Ce3+, Eu3+ or Tb3+. The samples were synthesized via the Sol-gel route. Glucose was chosen as the chelating agent, however, samples were also produced without the use of the chelating agent, with the aim of studying its in uence on the structural and optical properties. Di erent temperatures of syntheses were used in the production of the samples. Samples were produced with stoichiometric variation of Li+ (excess and de ciency) and doped with Ce3+, Eu3+ or Tb3+. The temperature of 1000 C for 2 hours was found as the best condition to obtain the crystalline phase of pure and doped LiSrPO4 . The structural characterization of the samples was performed using X-ray di ractometry and from them it was possible to estimate the mean crystallite size of the samples. The use of glucose allows obtaining crystals of the order of 18 nm, presenting smaller sizes when compared to the route without using the glucose employing the calcination temperature of 1000 C for 2 hours. It was found that the change in temperature of calcination changes the average size of the crystallite in samples pure and doped. Samples produced with stoichiometric variation of Lithium doped have a mean crystallite size higher than pure samples, presenting an average size of 46 nm, 24 nm and 21 nm for samples doped with Ce3+, Eu3+ or Tb3+, respectively. The samples doped with Ce3+ exhibit excitation and emission bands in the UV and near-UV region, respectively. The increase of the Lithium concentration reduces the emission intensity of the samples doped with Ce3+. The samples doped with Eu3+ contains a band of transfer charge (260 nm) with an intensity equivalent to transition 7F0 ! 5L6 (394 nm), both of which were the most intense of the spectrum of excitation. The intensity of the emission of these samples increases with the increase of Li+ concentration, agreeing with the variation of the symmetric factor, in which it is veri ed that the Eu3+ ion is in a site of low symmetry. The high intensity of transitions 5D0 ! 7F2 and 5D0 ! 7F4 provides an emission in the red of the visible spectrum. The samples doped with Tb3+ contain a very intense excitation band in the UV region (219 nm). This high excitation intensity xviii xix results in very intense emission spectra. The increase in the concentration of Li+ reduces the emission intensity of the samples doped with Tb3+. The two peaks with maximum emission refer to transitions 5D3 ! 7F6 (380 nm) and 5D4 ! 7F5 (545 nm), resulting in an emission in the cyan region of the visible spectrum. / Este trabalho relata a s ntese, caracteriza c~ao estrutural e optica do LiSrPO4 puro e dopado com ons terras raras como Ce3+, Eu3+ ou Tb3+. As amostras foram sintetizadas via rota Sol-gel. Foi escolhida como agente quelante a glicose, por em, tamb em foram produzidas amostras sem a utiliza c~ao do agente quelante, com o objetivo de estudar a sua in u^encia nas propriedades estruturais e opticas. Diferentes temperaturas de s nteses foram utilizadas na produ c~ao das amostras. Foram produzidas amostras com varia c~ao estequiom etrica de Li+ (excesso e de ci^encia) e dopados com Ce3+, Eu3+ ou Tb3+. A temperatura de 1000 oC por 2 horas foi encontrada como a melhor condi c~ao para a obten c~ao da fase cristalina do LiSrPO4 puro e dopado. A caracteriza c~ao estrutural das amostras foi realizada utilizando difratometria de raios X e a partir delas foi poss vel estimar o tamanho m edio do cristalito das amostras. A utiliza c~ao da glicose permite obter cristalitos da ordem de 18 nm, apresentando tamanhos menores quando comparado com a rota sem utiliza c~ao da glicose utilizando a temperatura de calcina c~ao de 1000 C por 2 horas. Veri cou-se que a mudan ca na temperatura de calcina c~ao altera o tamanho m edio do cristalito nas amostras puras e dopadas. As amostras produzidas com varia c~ao estequiom etrica de L tio dopada apresentam tamanho m edio de cristalito superior as amostras puras, tendo um tamanho m edio de 46 nm, 24 nm e 21 nm para as amostras dopadas com Ce3+, Tb3+ e Eu3+, respectivamente. As amostras dopadas com Ce3+ apresentam bandas de excita c~ao e emiss~ao na regi~ao do UV e UV pr oximo, respectivamente. O aumento da concentra c~ao de L tio reduz a intensidade de emiss~ao das amostras dopadas com Ce3+. As amostras dopadas com Eu3+ cont em uma banda de transfer^encia de carga (260 nm) com intensidade equivalente a transi c~ao 7F0 ! 5L6 (394 nm), sendo ambas as mais intensas do espectro de excita c~ao. A intensidade da emiss~ao destas amostras aumenta com o incremento da concentra c~ao de Li+, concordando com a varia c~ao do fator de sim etrica, no qual e constatado que o on Eu3+ encontra-se em um s tio de baixa simetria. A alta intensidade das transi c~oes 5D0 ! 7F2 e 5D0 ! 7F4 propicia uma emiss~ao na regi~ao do vermelho do espectro vis vel. As amostras dopadas com Tb3+ cont em uma banda muito intensa de excita c~ao na regi~ao UV (219 nm). Esta alta intensidade de excita c~ao resulta em espectros de emiss~ao bastante intensos. O aumento da concentra c~ao de Li+ reduz a intensidade de emiss~ao das amostras dopadas com Tb3+. Os dois picos com m aximo de emiss~ao referem-se as transi c~oes 5D3 ! 7F6 (380 nm) e 5D4 ! 7F5 (545 nm), resultando em uma emiss~ao na regi~ao do ciano do espectro vis vel. / São Cristóvão, SE

As propriedades fotofísicas dos complexos morin-Mg2+ e morin-Ce3+, foram investigadas em solução metanólica, em filmes finos de polímeros e em nanozéolitas por técnicas de fluorescência. A associação do metal ao flavonoide ocorre no sítio da carbonila do anel pirona nas razões estequiométricas de 1:1 e 1:2 (magnésio: morin), e esta associação favorece no aumento considerável da intensidade de fluorescência devido à inibição da transferência intramolecular do próton no estado excitado. Os resultados revelaram que os espectros de emissão do complexo morin-Mg2+ sofreram um pequeno deslocamento hipsocrômico. Os decaimentos de fluorescência do sistema Morin-Mg2+ são triexponenciais para o complexos Morin-Mg2+ formados com tempo de vida máximo de 3 ns. O complexo morin-Ce3+ é pouco fluorescente e a complexação com o metal leva a supressão de fluorescência devido a sua natureza paramagnética. A estequiometria aparente dominante é de um 1:1 e o decaimento possui um componente de tempo de vida longo de 4-5 ns. Na comparação das propriedades de fluorescência do morin-Mg2+ com o indicador magnesium green verificamos que ambos são bons indicadores fluorescentes para a microscopia de fluorescência podendo esses complexos serem usados na detecção de Mg2+ em nanozeólita e outros sistemas / The photophysical properties of the molecular complexes of morin with Mg2+ and Ce3+ cations in methanol solution as well as in thin polymeric films and nanozeolytes have been investigated by using fluorescence spectroscopy and microscopy. The association of morin with Mg2+ occurs at the (4)-carbonyl group of the pyrone ring at 1:1 and 1:2 stoichiometric ratio. The complexes have shown an increase of the emission quantum yield by precluding the excited state deactivation though the intramolecular proton transfer process. The fluorescence decays of the complexes are non exponential due to the presence of more than one emission species and the average decay time found was about 3 ns. On the other hand, the addition of Ce3+ to morin solution resulted in fluorescence quenching ascribed to 1:1 non emissive complex due to the paramagnetic nature of the metal cation. The fluorescence properties of morin-Mg2+ complex have been compared with the standard fluorescence indicator magnesium green. The results pointed out that morin-Mg2+ may be used as an alternative low coast indicator of Mg2+ in homogenous as well as in microheterogeneous media.