Esta dissertação apresenta estudos visando à síntese de indanos oticamente ativos, através da contração de anel de 3-alquenóis promovida por tálio(III). Dois novos sais de tálio(III) foram preparados - o (S)-(-)-triacetoxipropionato de tálio (TTAP) e o tripropionato de tálio (TTP) - a partir do triacetato de tálio (TTA) e dos ácidos (S)-(-)-2-acetoxipropiônico e propiônico, respectivamente. A ciclização do isopulegol foi realizada com TTAP e com TTP, em rendimentos similares aos obtidos com TTA e com trinitrato de tálio (TTN). O rearranjo oxidativo do 2-(3,4-diidronaftalen-1-il)-etanol, que é um 3-alquenol, também pôde ser efetuado com o TTAP e com o TTP, embora rendimentos inferiores aos obtidos com TTN, com TTA, ou com trifluoroacetato de tálio (TTFA) tenham sido alcançados. Nestas contrações de anel, fica evidente que a ordem de reatividade segue a força elétron atraente dos ânions ligados ao tálio. Além disso, as melhores condições reacionais obtidas foram as que utilizam como solvente uma mistura de água e do ácido correspondente ao ligante do sal de tálio(III). Finalmente, na reação de contração de anel com o sal de tálio(III) quiral TTAP, o produto de contração de anel foi obtido como uma mistura racêmica. Os testes preliminares de resolução enzimática do 3-hidroxi-1-indan-1-il-propan-1-ona realizados com lipases mostraram-se promissores, abrindo novas perspectivas para a obtenção de indanos oticamente ativos com bom excesso enantiomérico. / This dissertation presents a study toward the synthesis of optically active indans by the thallium(III) promoted ring contraction of 3-alkenols. Two new thallium(III) salts were prepared - thalllium (S)-(-)-triacetoxypropionate (TTAP) and thallium tripropionate (TTP) - from thallium triacetate (TIA) and (S)-(-)-2-acetoxypropionic acid and propionic acid, respectively. The cyclization of isopulegol was performed using TTAP or TTP. The isolated yields for these reactions are similar to that obtained with TTA or with thallium trinitrate (TTN) The oxidative rearrangement of the 2-(3,4-dihydro-naphthalen-1-yl)-ethanol, which is a 3alkenol, could also be performed by TTAP or by TTP, although the isolated yields were lower from that in a similar reaction with TTN, TTA or thallium trifluoroacetate (TTFA). In these ring contractions, the reactivity c1early depends on the eletron-withdrawing ability of the anion bonded to the thallium atom. In addition, the best reaction conditions are those where the solvent is a mixture of H2O and the acid corresponding to the ligand of the thallium(III) salt. Finally, in the reaction using the chiral non-racemic TTAP, the ring contraction product was obtained as a racemic mixture. The preliminary results on the enzymatic resolution of 3-hydroxy-1-indan-1-yl-propan-1-one using lipases show that optically active indan might be obtained in good e.e. using this approach.

The kinetic and mechanistic features of a new series ofplatinum-thallium cyano compounds containing a direct andunsupported by ligands metal-metal bond have been studied insolution, using standard mix–and–measurespectrophotometric technique and stopped–flow method.These reactions are interpreted as oxidative addition of the cspecies to the square planar Pt(CN)42-complex. Each of these processes was found to befirst-order in Pt(CN)42-, the corresponding TIIIIcomplex and a cyanide ion donating species whichacts as a catalyst. Both di- and trinuclear complexes werestudied, and the kinetically significant thallium complexes intheir formation and the catalytically active cyanide sourcesare as follows: [(CN)5PtTl(CN)3]3-: Tl(CN)4–(alkaline region), Tl(CN)3(slightly acidic region) and CN–; [(CN)5Pt–Tl(CN)]–: Tl(CN)2+and Tl(CN)2+; [(CN)5Pt–Tl–Pt(CN)5]3-: [(CN)5Pt–Tl(CN)]–and HCN. Appropriatemechanisms were postulated for the overall reactions in allcases, which include i) metal–metal bond formation stepand ii) coordination of an axial cyanide ion to the platinumcenter. Two experimentally indistinguishable kinetic modelswere proposed for the formation of the dinuclear complexeswhich are different in the sequence of the two steps. In thecase of the trinuclear complex, experimental evidence isavailable to exclude one of the alternative reaction paths, andit was proven that the metal–metal bond formation precedesthe axial cyanide coordination. The cyanide ligands coordinated to TIIIIin the Pt–Tl complexes could be replacedsuccessfully with aminopolycarboxylates e.g.: mimda2-, nta3-, edta4-. The [(CN)5Pt–Tl(edta)]4-complex, with a direct metal–metal bond hasbeen prepared in solution by two different reactions: a)dissolution of [(CN)5Pt–Tl](s) in an aqueous solution of edta, b)directly from Pt(CN)42-and Tl(edta)(CN)2-. The decomposition reaction is greatlyaccelerated by cyanide and significantly inhibited by edta. Itproceeds through the [(CN)5Pt–Tl(CN)3]3-intermediate. The formation of [(CN)5Pt–Tl(edta)]4-can proceed via two different pathways dependingon the ratio of the cyanide to the edta ligand concentrations.The’direct path’at excess of edta means theformation of intermediate[(CN)4Pt···Tl(CN)(edta)]4-, followed by a release of the cyanide from theTl–centre followed by coordination of a cyanide from thebulk to the Pt–centre of the intermediate. The’indirect path’dominates in the absence of extraedta and the formation of the Pt–Tl bond occours betweenPt(CN)42-and Tl(CN)4–. Homoligand MTl(CN)4(M = TlI, K, Na) and, for the first time, Tl(CN)3species have been synthesized in the solid stateand their structures solved by single crystal X–raydiffraction method. Interesting redox processes have been foundbetween TIIIIand CN–in non–aqueous solution and in Tl2O3-CN–aqueous suspension. In the crystal structureof Tl(CN)3·H2O, the thallium(III) ion has a trigonal bypiramidalcoordination geometry with three cyanides in the trigonalplane, while an oxygen atom of the water molecule and anitrogen atom from a cyanide ligand attached to a neighboringthallium complex, form a linear O–Tl–N fragment.Cyanide ligand bridges thallium units forming an infinitezigzag chain structure. Among the thallium(III) tetracyanocompounds, the isostructural M[Tl(CN)4](M = Tl and K) and Na[Tl(CN)4]·3H2O crystallize in different crystal systems, but thethallium(III) ion has in all cases the same tetrahedralgeometry in the [Tl(CN)4]–unit. Three adducts of mercury(II) (isoelectronic with TIIII) (K2PtHg(CN)6·2H2O, Na2PdHg(CN)6·2H2O and K2NiHg(CN)6·2H2O) have been prepared from Hg(CN)2and square planar transition metal cyanides MII(CN)42-and their structure have been studied by singlecrystal X–ray diffraction, XPS and Raman spectroscopy inthe solid state. The structure of (K2PtHg(CN)6·2H2O consists of strictly linear one dimensional wireswith PtIIand HgIIcenters located alternately, dHg–Pt= 3.460 Å. The structure of Na2PdHg(CN)6·2H2O and K2NiHg(CN)6·2H2O can be considered as double salts, the lack ofhetero–metallophilic interaction between both the HgIIand PdIIatoms, dHg–Pd= 4.92 Å, and HgIIand NiIIatoms, dNi–Pd= 4.60 Å, seems obvious. Electronbinding energy values of the metallic centers measured by XPSshow that there is no electron transfer between the metal ionsin all three adducts. In solution, experimental findingsclearly indicate the lack of metal–metal bond formation inall studied HgII–CN-–MII(CN)42-systems (M = Pt, Pd and Ni). It is in contrary tothe platinum–thallium bonded cyanides. KEYWORDS:metal–metal bond, platinum, thallium,kinetics, mechanism, stopped flow, oxidative addition, cyanocomplexes, edta, redox reaction, metal cyanides, X–raydiffraction, Raman, NMR, mercury, palladium, nickel, onedimensional wire

A new family of oligonuclear cyano compounds incorporatingtransition (Pt) and main group (Tl) metals bound with anon-buttressed Pt-Tl bond was synthesised in aqueous solution.The metal-metal linkage is formed in the reaction betweenplatinum and thallium in their stable oxidation forms, Pt(II)and Tl(III), orvice versa: Pt(IV) and Tl(I). Four binuclear complexeswith a general composition [(CN)5Pt-Tl(CN)n(aq)]n-(n = 0-3) and a trinuclear species [(NC)5Pt-Tl-Pt(CN)5]3-were identified and structurally characterised insolution by multinuclear NMR, EXAFS and vibrationalspectroscopy. In aqueous solution the complexes exist inequilibrium. The distribution between the species can bealtered by varying the molar ratio Pt/Tl, cyanide concentrationand pH. Stability constants of the compounds weredetermined. A new compound (NC)5PtTl was also prepared in solid and its crystalstructure solved by a combination of X-ray powder diffractionand EXAFS. Altogether the values of195Pt-205Tl spin-spin coupling constants (25-71 kHz),interatomic Pt-Tl distances (2.598-2.638 Å), and vibrationstretching frequencies v (Pt-Tl) (159-164 cm-1) are fully indicative of a direct and unsupportedPt-Tl bond. The calculated values of Pt-Tl force constants(1.56-1.74 N· cm-1) are characteristic for single metal-metal bond.The oxidation status in the compounds can be viewed asintermediate between II and IV for platinum, and between I andIII for thallium, as reflected by the chemical shifts of195Pt and205Tl nuclei, C≡ N stretching frequencies andelectron binding energies. The compounds are capable to undergo a photoinducedtwo-electron transfer between the coupled hetero-metal ions.Upon irradiation into the metal-to-metal charge transferabsorption band, effective photoredox reaction takes place. Itresults in scission of the Pt-Tl bond and formation of variouscomplexes of oxidised platinum (Pt(III, IV)) and reducedthallium (Tl(I)). The values of photodecomposition quantumyields were determined from a stationary photolysis study ofthe heterometallic complexes. Nanosecond laser flash photolysisof the heteronuclear Pt-Tl cyano compounds was performed in thetimescale range 1· 10-6- 5· 10-2s and several intermediate species were detectedand characterised by optical spectroscopy. The heteronuclear Pt-Tl cyano compounds can be furthermodified in terms of their stability, solubility, and lightabsorption characteristics. It has been found that the platinumpentacyano unit of the [(NC)5Pt-Tl(CN)n(aq)]n-species is inert towards the tested ligands,whereas the thallium "part" of the complexes can be tunedsignificantly. A number of complexes [(NC)5Pt-Tl(L)m]x-(L-ligand) were prepared and characterised insolution. Compounds [(NC)5Pt-Tl(nta)(H2O)]3-, [(NC)5Pt-Tl(bipy)(DMSO)3], and [(NC)5Pt-Tl(bipy)2]have been prepared in solid and their structuresdetermined by single-crystal X-ray diffraction. <b>Keywords:</b>thallium, platinum, cyanide, metal-metal bond,non-buttressed, heterobimetallic, photoinduced, electrontransfer, redox reaction, NMR, chemical shift, spin-spincoupling constant, Raman, EXAFS, X-ray diffraction,equilibrium, oxidation state, oxidative addition,photolysis

<p>A new family of oligonuclear cyano compounds incorporatingtransition (Pt) and main group (Tl) metals bound with anon-buttressed Pt-Tl bond was synthesised in aqueous solution.The metal-metal linkage is formed in the reaction betweenplatinum and thallium in their stable oxidation forms, Pt(II)and Tl(III), or<i>vice versa</i>: Pt(IV) and Tl(I). Four binuclear complexeswith a general composition [(CN)₅Pt-Tl(CN)_n(aq)]^n-(n = 0-3) and a trinuclear species [(NC)₅Pt-Tl-Pt(CN)₅]^3-were identified and structurally characterised insolution by multinuclear NMR, EXAFS and vibrationalspectroscopy. In aqueous solution the complexes exist inequilibrium. The distribution between the species can bealtered by varying the molar ratio Pt/Tl, cyanide concentrationand pH. Stability constants of the compounds weredetermined.</p><p>A new compound (NC)₅PtTl was also prepared in solid and its crystalstructure solved by a combination of X-ray powder diffractionand EXAFS. Altogether the values of¹⁹⁵Pt-²⁰⁵Tl spin-spin coupling constants (25-71 kHz),interatomic Pt-Tl distances (2.598-2.638 Å), and vibrationstretching frequencies v (Pt-Tl) (159-164 cm^-1) are fully indicative of a direct and unsupportedPt-Tl bond. The calculated values of Pt-Tl force constants(1.56-1.74 N· cm^-1) are characteristic for single metal-metal bond.The oxidation status in the compounds can be viewed asintermediate between II and IV for platinum, and between I andIII for thallium, as reflected by the chemical shifts of¹⁹⁵Pt and²⁰⁵Tl nuclei, C≡ N stretching frequencies andelectron binding energies.</p><p>The compounds are capable to undergo a photoinducedtwo-electron transfer between the coupled hetero-metal ions.Upon irradiation into the metal-to-metal charge transferabsorption band, effective photoredox reaction takes place. Itresults in scission of the Pt-Tl bond and formation of variouscomplexes of oxidised platinum (Pt(III, IV)) and reducedthallium (Tl(I)). The values of photodecomposition quantumyields were determined from a stationary photolysis study ofthe heterometallic complexes. Nanosecond laser flash photolysisof the heteronuclear Pt-Tl cyano compounds was performed in thetimescale range 1· 10^-6- 5· 10^-2s and several intermediate species were detectedand characterised by optical spectroscopy.</p><p>The heteronuclear Pt-Tl cyano compounds can be furthermodified in terms of their stability, solubility, and lightabsorption characteristics. It has been found that the platinumpentacyano unit of the [(NC)₅Pt-Tl(CN)_n(aq)]^n-species is inert towards the tested ligands,whereas the thallium "part" of the complexes can be tunedsignificantly. A number of complexes [(NC)₅Pt-Tl(L)_m]^x-(L-ligand) were prepared and characterised insolution. Compounds [(NC)₅Pt-Tl(nta)(H₂O)]^3-, [(NC)₅Pt-Tl(bipy)(DMSO)₃], and [(NC)₅Pt-Tl(bipy)₂]have been prepared in solid and their structuresdetermined by single-crystal X-ray diffraction.</p><p><b>Keywords:</b>thallium, platinum, cyanide, metal-metal bond,non-buttressed, heterobimetallic, photoinduced, electrontransfer, redox reaction, NMR, chemical shift, spin-spincoupling constant, Raman, EXAFS, X-ray diffraction,equilibrium, oxidation state, oxidative addition,photolysis</p>

<p>The kinetic and mechanistic features of a new series ofplatinum-thallium cyano compounds containing a direct andunsupported by ligands metal-metal bond have been studied insolution, using standard mix–and–measurespectrophotometric technique and stopped–flow method.These reactions are interpreted as oxidative addition of the cspecies to the square planar Pt(CN)₄^2-complex. Each of these processes was found to befirst-order in Pt(CN)₄^2-, the corresponding TI^IIIcomplex and a cyanide ion donating species whichacts as a catalyst. Both di- and trinuclear complexes werestudied, and the kinetically significant thallium complexes intheir formation and the catalytically active cyanide sourcesare as follows: [(CN)₅PtTl(CN)₃]^3-: Tl(CN)₄^–(alkaline region), Tl(CN)₃(slightly acidic region) and CN^–; [(CN)₅Pt–Tl(CN)]–: Tl(CN)₂⁺and Tl(CN)₂⁺; [(CN)₅Pt–Tl–Pt(CN)₅]^3-: [(CN)₅Pt–Tl(CN)]–and HCN. Appropriatemechanisms were postulated for the overall reactions in allcases, which include i) metal–metal bond formation stepand ii) coordination of an axial cyanide ion to the platinumcenter. Two experimentally indistinguishable kinetic modelswere proposed for the formation of the dinuclear complexeswhich are different in the sequence of the two steps. In thecase of the trinuclear complex, experimental evidence isavailable to exclude one of the alternative reaction paths, andit was proven that the metal–metal bond formation precedesthe axial cyanide coordination.</p><p>The cyanide ligands coordinated to TI^IIIin the Pt–Tl complexes could be replacedsuccessfully with aminopolycarboxylates e.g.: mimda^2-, nta^3-, edta^4-. The [(CN)₅Pt–Tl(edta)]^4-complex, with a direct metal–metal bond hasbeen prepared in solution by two different reactions: a)dissolution of [(CN)₅Pt–Tl](s) in an aqueous solution of edta, b)directly from Pt(CN)₄^2-and Tl(edta)(CN)^2-. The decomposition reaction is greatlyaccelerated by cyanide and significantly inhibited by edta. Itproceeds through the [(CN)₅Pt–Tl(CN)₃]^3-intermediate. The formation of [(CN)₅Pt–Tl(edta)]^4-can proceed via two different pathways dependingon the ratio of the cyanide to the edta ligand concentrations.The’direct path’at excess of edta means theformation of intermediate[(CN)4Pt···Tl(CN)(edta)]^4-, followed by a release of the cyanide from theTl–centre followed by coordination of a cyanide from thebulk to the Pt–centre of the intermediate. The’indirect path’dominates in the absence of extraedta and the formation of the Pt–Tl bond occours betweenPt(CN)₄^2-and Tl(CN)4^–.</p><p>Homoligand MTl(CN)₄(M = Tl^I, K, Na) and, for the first time, Tl(CN)₃species have been synthesized in the solid stateand their structures solved by single crystal X–raydiffraction method. Interesting redox processes have been foundbetween TI^IIIand CN^–in non–aqueous solution and in Tl₂O₃-CN^–aqueous suspension. In the crystal structureof Tl(CN)₃·H₂O, the thallium(III) ion has a trigonal bypiramidalcoordination geometry with three cyanides in the trigonalplane, while an oxygen atom of the water molecule and anitrogen atom from a cyanide ligand attached to a neighboringthallium complex, form a linear O–Tl–N fragment.Cyanide ligand bridges thallium units forming an infinitezigzag chain structure. Among the thallium(III) tetracyanocompounds, the isostructural M[Tl(CN)₄](M = Tl and K) and Na[Tl(CN)₄]·3H₂O crystallize in different crystal systems, but thethallium(III) ion has in all cases the same tetrahedralgeometry in the [Tl(CN)₄]^–unit.</p><p>Three adducts of mercury(II) (isoelectronic with TI^III) (K₂PtHg(CN)₆·2H₂O, Na₂PdHg(CN)₆·2H₂O and K₂NiHg(CN)₆·2H₂O) have been prepared from Hg(CN)₂and square planar transition metal cyanides M^II(CN)₄^2-and their structure have been studied by singlecrystal X–ray diffraction, XPS and Raman spectroscopy inthe solid state. The structure of (K₂PtHg(CN)₆·2H₂O consists of strictly linear one dimensional wireswith Pt^IIand Hg^IIcenters located alternately, d_Hg–Pt= 3.460 Å. The structure of Na₂PdHg(CN)₆·2H₂O and K₂NiHg(CN)₆·2H₂O can be considered as double salts, the lack ofhetero–metallophilic interaction between both the Hg^IIand Pd^IIatoms, d_Hg–Pd= 4.92 Å, and Hg^IIand Ni^IIatoms, d_Ni–Pd= 4.60 Å, seems obvious. Electronbinding energy values of the metallic centers measured by XPSshow that there is no electron transfer between the metal ionsin all three adducts. In solution, experimental findingsclearly indicate the lack of metal–metal bond formation inall studied Hg^II–CN^-–M^II(CN)4^2-systems (M = Pt, Pd and Ni). It is in contrary tothe platinum–thallium bonded cyanides.</p><p><b>KEYWORDS:</b>metal–metal bond, platinum, thallium,kinetics, mechanism, stopped flow, oxidative addition, cyanocomplexes, edta, redox reaction, metal cyanides, X–raydiffraction, Raman, NMR, mercury, palladium, nickel, onedimensional wire</p>

L'étude du système TIF3-ZrF4 a permis de mettre en évidence deux composes: TI0,67Zr0,33F3,33 et TIZr3F15. Les structures dérivent du type ReO3 par insertion d'anions. La répartition cationique dans les phases MZr3F15 a par ailleurs été précisée en fonction de la taille du cation trivalent. Les fluorostannates des systèmes MF-SnF2 (M = Na, K, Rb, Cs, TI et NH4) ont été étudiés par spectroscopie Mössbauer de 4,2 a 293K. L'interprétation de l'ensemble des paramètres Mössbauer a été assoçiée à la présence du doublet libre de l'étain. Des corrélations entre caractéristiques structurales et spectroscopiques ont été proposées.

Made available in DSpace on 2014-10-09T12:51:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:28Z (GMT). No. of bitstreams: 1 11295.pdf: 3731608 bytes, checksum: 642672d3ddbbe81953275dd174a58822 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:01/09049-5

Made available in DSpace on 2014-10-09T12:51:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:28Z (GMT). No. of bitstreams: 1 11295.pdf: 3731608 bytes, checksum: 642672d3ddbbe81953275dd174a58822 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Neste trabalho, os cristais de TlBr foram crescidos pelo método de Bridgman, a partir de materiais purificados pela técnica de fusão zonal. A eficiência da purificação e avaliação da superfície cristalina em relação ao desempenho como detectores de radiação foi observada. Bons resultados foram obtidos com os aprimoramentos realizados nos processos de purificação, crescimento de cristais e na fabricação dos detectores. A resposta à radiação foi verificada excitando os detectores com fontes de raios gama: 241Am (59 keV), 133Ba (80 e 355 keV), 57Co (122 keV), 22Na (511 keV) e 137Cs (662 keV) à temperatura ambiente. Os valores de resolução em energia mais satisfatórios encontrados nesse trabalho foram a partir de detectores mais puros. Os melhores valores de resolução em energia obtidos foram de 10keV (16%), 12keV (15%), 12keV (10%), 28 keV (8%), 31keV (6%) e 36keV (5%) para as energias de 59, 80, 122, 355, 511 e 662 keV, respectivamente. Também foi realizado um estudo da resposta à detecção a uma temperatura de -20ºC e da estabilidade desses detectores. Nos detectores desenvolvidos não houve diferença significativa na resolução tanto em temperatura ambiente quanto na reduzida. Em relação à estabilidade foi observada uma degradação das características espectrométricas sob operação contínua do detector a temperatura ambiente e esta instabilidade variou para cada detector. Ambas características também foram observadas por outros autores. A viabilidade de utilização do cristal de TlBr como fotodetector para acoplamento em cintiladores também foi estudada neste trabalho. TlBr é um material promissor para ser utilizado como fotodetector devido a sua adequada eficiência quântica na região de 350 a aproximadamente 500 nm. Como uma aplicação para este trabalho foram iniciados estudos para fabricação de sondas cirúrgicas utilizando cristais de TlBr como o meio detector. / Neste trabalho, os cristais de TlBr foram crescidos pelo método de Bridgman, a partir de materiais purificados pela técnica de fusão zonal. A eficiência da purificação e avaliação da superfície cristalina em relação ao desempenho como detectores de radiação foi observada. Bons resultados foram obtidos com os aprimoramentos realizados nos processos de purificação, crescimento de cristais e na fabricação dos detectores. A resposta à radiação foi verificada excitando os detectores com fontes de raios gama: 241Am (59 keV), 133Ba (80 e 355 keV), 57Co (122 keV), 22Na (511 keV) e 137Cs (662 keV) à temperatura ambiente. Os valores de resolução em energia mais satisfatórios encontrados nesse trabalho foram a partir de detectores mais puros. Os melhores valores de resolução em energia obtidos foram de 10keV (16%), 12keV (15%), 12keV (10%), 28 keV (8%), 31keV (6%) e 36keV (5%) para as energias de 59, 80, 122, 355, 511 e 662 keV, respectivamente. Também foi realizado um estudo da resposta à detecção a uma temperatura de -20ºC e da estabilidade desses detectores. Nos detectores desenvolvidos não houve diferença significativa na resolução tanto em temperatura ambiente quanto na reduzida. Em relação à estabilidade foi observada uma degradação das características espectrométricas sob operação contínua do detector a temperatura ambiente e esta instabilidade variou para cada detector. Ambas características também foram observadas por outros autores. A viabilidade de utilização do cristal de TlBr como fotodetector para acoplamento em cintiladores também foi estudada neste trabalho. TlBr é um material promissor para ser utilizado como fotodetector devido a sua adequada eficiência quântica na região de 350 a aproximadamente 500 nm. Como uma aplicação para este trabalho foram iniciados estudos para fabricação de sondas cirúrgicas utilizando cristais de TlBr como o meio detector. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:01/09049-5

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-11-11T13:09:25Z No. of bitstreams: 0 / Made available in DSpace on 2016-11-11T13:09:25Z (GMT). No. of bitstreams: 0 / Neste trabalho, cristais de TlBr foram crescidos e purificados pelo método de Bridgman Repetido, a partir de sais comerciais de TlBr, e caracterizados para serem usados como detectores de radiação à temperatura ambiente. Para avaliar a eficiência de purificação, estudos da diminuição da concentração de impurezas foram feitos após cada crescimento, analisando as impurezas traço por Espectrometria de Massas com Plasma (ICP-MS). Um decréscimo significativo da concentração de impurezas em função do número de purificações foi observado. Os cristais crescidos apresentaram boa qualidade cristalina de acordo com os resultados de análise por Difração de Raios X (DRX), boa qualidade morfológica e estequiometria adequada de acordo com os resultados de análise por MEV(SE) e MEV(EDS). Um modelo matemático definido por equações diferenciais foi desenvolvido para avaliar as concentrações de impurezas no cristal de TlBr e suas segregações em função do número de crescimentos pelo método de Bridgman. Este modelo pode ser usado para calcular o coeficiente de migração das impurezas e mostrou ser útil para prever o número necessário de repetições de crescimento Bridgman para atingir nível de pureza adequado para assegurar a qualidade do cristal como detector de radiação. Os coeficientes se segregação obtidos são parâmetros importantes para análise microestrutural e análise de transporte de cargas nos cristais detectores. Para avaliar os cristais a serem usados como detectores de radiação, medidas de suas resistividades e resposta à incidência de radiação gama das fontes de 241Am (59,5keV) e 133Ba (81 keV) foram realizadas. Essa resposta foi dependente da pureza do cristal. Os detectores apresentaram um avanço significativo na eficiência de coleta de cargas em função da pureza. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Pedro Silva Filho (pfsilva@ipen.br) on 2017-11-22T17:07:51Z No. of bitstreams: 0 / Made available in DSpace on 2017-11-22T17:07:51Z (GMT). No. of bitstreams: 0 / Este trabalho tem como objetivo investigar a concentração de impurezas radioativas gama emissoras presentes nas soluções dos radiofármacos produzidos no Instituto de Pesquisas Energéticas e Nucleares - IPEN em São Paulo. Para que este radiofármaco possa ser utilizado adequadamente, sua qualidade deve ser avaliada de acordo com os procedimentos estabelecidos de acordo com os \"Requisitos Gerais para a Competência de Laboratórios de Teste e Calibração\", ISO / IEC 17025: 2005 e pelas \"Boas Práticas de Fabricação\" (BPF), controladas pela ANVISA (Agência Nacional de Vigilância Sanitária), no Brasil. Para determinar a atividade, dos radiofármacos das impurezas gama emissoras, foi utilizado um espectrômetro gama de alta resolução em duas distâncias fonte-detector; uma de 18 cm e outra de 1,7 cm. Para a distância de 18 cm, o espectrômetro HPGe foi calibrado com energias gama entre 81 kev e 1408 kev, medindo ampolas seladas de 60Co, 133Ba, 137Cs e 152Eu, padronizadas no Laboratório de Metrologia Nuclear (LMN) do IPEN. Para impurezas com baixas atividades, utilizou a distância fontedetector de 1,7 cm. A esta distância, o efeito soma em cascata é muito elevado, tornando difícil a medição das ampolas de calibração padrão, com isso, a curva de eficiência do espectrômetro foi obtida por um código de simulação de Monte Carlo, desenvolvido no IPEN. Neste código, todos os detalhes do sistema de detecção são modelados e as curvas de resposta para raios X e raios gama são calculadas pelo código de transporte de radiação MCNPX. Os espectros gama foram analisados pelo programa Alpino, que aplica o método de integração numérica da área sob os fotopicos de absorção total. Para as impurezas gama emissoras não detectadas visualmente, os limites de detecção foram calculados a partir da taxa de contagem de fundo, sob a área do pico de interesse. As soluções radioativas analisadas foram 67Ga,99Mo, 99mTc, 111In, 131I, 153Sm, 177Lu e 201Tl. Os resultados da relação entre a atividade do radionuclídeo em análise e as impurezas identificadas apresentaram acordo com os certificados de análise dos fabricantes, assim como, com as especificações da ANVISA. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP