Pendant la première année le microscope à microSQUID était mis en fonctionnement. On a avancé sur le plan cryogenique (dilution) et électronique (programmation de boucles de régulation et d'une détection synchrone). Les composants étaient testés à température ambiante et on est en train de tout tester à basse température. Une méthode était conçu pour déterminer la longueur de pénétration du champ magnétique dans un supraconducteur avec les données qui pourront être fait avec notre microscope. Ceci va être utilisé pour l'échantillon PrOs4Sb12. Il s'agit de trancher le débat sur la nature multibande de la supraconductivité dans ce composé. En deuxième année le developpement a continué, en particulière le microscope était mis à froid. Des différents problèmes due aux basses températures (mouvement de moteur, thermalisation, câblage) ont été resolues. Ensuite on a avancé sur le plan informatique, notamment le contrôle de differents composants. Pendant le deuxième année quelques images magnétique ont été faites, validant le concept. En troisième année on a commence a mésurer des domaines magnetiques d'un supraconducteur ferromagnetique (UCoGe) en Avril - Aout. On a obtenu des resultats tres interessants. Le même dispositif sera ainsi opérationnel pour l'imagerie de domaines dans des bolomètres supraconducteurs. / Pendant cette thèse un microscope à SQUID et AFM à balayage, l'électronique et les logiciels de contrôle ont été conçus. Pour la calibration des mesures sur un film de niobium (avec des motifs) ont été effectuées, montrant la possibilité de faire des image de la topographie at la distribution du champ magnétique au dessus de l'échantillon simultanément. On présent les premières image dans l'espace réel de la structure de domaines dans le ferro supraconducteur UCoGe, un échantillon basé sur l'uranium (fermion lourd) avec un transition supra à environ 0.5K à la pression ambiante. On montre l'évolution de la transition ferromagnétique en fonction de la température. La microscope a été aussi utilisé pour des mésures sur un couche mince de Rhenium, un supraconducteur conventionel. On a obtenu une estimation pour la force de piégeage de vortex on utilisant l'interaction entre SQUID et vortex. En plus, on a déterminé la longueur de pénétration en fonction de la température.

Neste trabalho foi investigada a eletrooxidação de etanol sobre eletrodos nanoparticulados binários Pt-M1 (M1 = Sn ou Re) e ternários Pt-M1-M2 (M1 e M2 = Sn e Re) suportados em carbono. Estes materiais foram preparados pelo método da redução por álcool e foram caracterizados por difração de raios-X e microscopia eletrônica de varredura associada a EDX. Os eletrodos foram montados utilizando-se a técnica de camada ultrafina. Os resultados eletroquímicos mostraram que a adição dos diferentes metais à platina aumentou a atividade catalítica tanto dos eletrodos binários quanto dos ternários. Os testes realizados na célula unitária mostraram que a presença de Sn nos catalisadores binário e de Sn e Re nos catalisadores ternários aumentou significativamente o desempenho da célula quando comparada ao ânodo de Pt pura suportada em carbono, preparado pela metodologia da redução do álcool ou ao comercial da E-TEK. O catalisador Pt70Sn10Re20/C foi o que apresentou a melhor densidade de corrente assim como a melhor densidade de potência com um valor máximo alcançado de aproximadamente 40 mW cm-2 durante a operação da célula a combustível a 90 oC. / In this work was investigated the electrooxidation of ethanol on nanostructured binary Pt-M1 (M1 = Sn or Re) and ternary Pt-M1-M2 (M1 and M2 = Re and Sn) electrodes supported on carbon. These materials were prepared by the alcohol reduction method and were characterized by X-ray diffraction and scanning electron microscopy associated to EDX. The ultra-thin layer technology was used to assemble the electrode. The electrochemical results showed that the addition of different metals to platinum increased the catalytic activity of the binary and ternary electrodes. Tests conducted in unitary fuel cell showed that the presence of Sn in the binary catalysts and Sn and Re in the ternary catalysts increased significantly the performance of the cell when compared to pure Pt anode supported on carbon, prepared by the alcohol methodology or the commercial E-TEK. The catalyst Pt70Sn10Re20/C presented the best current density as well the better power density with a maximum value of ca. 40 mW cm-2 reached during the operation of the fuel cell at 90 oC.

Neste trabalho foi investigada a eletrooxidação de etanol sobre eletrodos nanoparticulados binários Pt-M1 (M1 = Sn ou Re) e ternários Pt-M1-M2 (M1 e M2 = Sn e Re) suportados em carbono. Estes materiais foram preparados pelo método da redução por álcool e foram caracterizados por difração de raios-X e microscopia eletrônica de varredura associada a EDX. Os eletrodos foram montados utilizando-se a técnica de camada ultrafina. Os resultados eletroquímicos mostraram que a adição dos diferentes metais à platina aumentou a atividade catalítica tanto dos eletrodos binários quanto dos ternários. Os testes realizados na célula unitária mostraram que a presença de Sn nos catalisadores binário e de Sn e Re nos catalisadores ternários aumentou significativamente o desempenho da célula quando comparada ao ânodo de Pt pura suportada em carbono, preparado pela metodologia da redução do álcool ou ao comercial da E-TEK. O catalisador Pt70Sn10Re20/C foi o que apresentou a melhor densidade de corrente assim como a melhor densidade de potência com um valor máximo alcançado de aproximadamente 40 mW cm-2 durante a operação da célula a combustível a 90 oC. / In this work was investigated the electrooxidation of ethanol on nanostructured binary Pt-M1 (M1 = Sn or Re) and ternary Pt-M1-M2 (M1 and M2 = Re and Sn) electrodes supported on carbon. These materials were prepared by the alcohol reduction method and were characterized by X-ray diffraction and scanning electron microscopy associated to EDX. The ultra-thin layer technology was used to assemble the electrode. The electrochemical results showed that the addition of different metals to platinum increased the catalytic activity of the binary and ternary electrodes. Tests conducted in unitary fuel cell showed that the presence of Sn in the binary catalysts and Sn and Re in the ternary catalysts increased significantly the performance of the cell when compared to pure Pt anode supported on carbon, prepared by the alcohol methodology or the commercial E-TEK. The catalyst Pt70Sn10Re20/C presented the best current density as well the better power density with a maximum value of ca. 40 mW cm-2 reached during the operation of the fuel cell at 90 oC.

This thesis is focused on analysis of reduction of ammonium perrhenate using less frequent reducing agents. Ascorbic acid and acetylhydrazine were chosen as less common reducing agents. Reductions were observed leveraging capillary zone electrophoresis and UV/Vis spectroscopy. Measurements were carried out both in acidic and in basic environments. Reduction of peak area of ammonium perrhenate was observed using capillary zone electrophoresis after addition of reducing agent. Rate of absorption of ammonium perrhenate was monitored with UV/Vis spectroscopy. Furthermore, the possibility of shifting the equilibrium of the reaction to the benefit of the reduction products was monitored by the addition of the complexing agent. Py- rogallol (benzene-1,2,3-triol) was used as the ligand and acetylhydrazine was selected as the reducing agent. The reduction was monitored by capillary zone electrophoresis. The identity of the resulting complex was confirmed with ESI/MS. Keywords rhenium, rhenium complexes, ascorbic acid, acetylhydrazine, capillary zone electrophore- sis, UV/Vis spectroscopy, mass spectrometry

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

No description available.

This work was initially launched to study the synthesis of low-valent group 13 compounds bearing the bis(imino)pyridine ligand framework. Since its inception, this project has grown beyond the boundaries of group 13 to include low valent tin, silver, and rhenium. Alongside the reports of novel coordination compounds, we utilized computational chemistry to uncover unprecedented interactions which challenge conventional concepts of bonding. Synthesis, characterization, and complimentary computational studies are presented herein. Chapter 1 presents a historical overview of the bis(imino)pyridine ligand as well as our synthetic methodology and characterization of new ligand variants we have contributed to the literature. Chapter 2 presents the synthesis of a series of In(I) and In(III) bis(imino)pyridine complexes with varied sterics. Ligand-metal interaction and effect of ligand steric bulk on complex stability, as well as computational studies highlighting weak covalent interactions will be discussed. Chapter 3 presents the synthesis of Ga(III) bis(imino)pyridine complexes. Reactivity with “GaI” synthon as well as varied-stoichiometry one-pot synthesis attempts to generate low valent Ga-bis(imino)pyridine complexes will be discussed. Chapter 4 presents the synthesis of a series of Tl(I) bis(imino)pyridine complexes with varied sterics analogous to the approach taken with indium(I). Unprecedented weak ligand-metal as well as Tl-arene interactions will be discussed. Chapter 5 presents the synthesis of a series of Sn(II) bis(imino)pyridine complexes with varied sterics and halide substituents. Preferential cation-anion pair formation and attempted reactivity will be discussed. Chapter 6 presents the synthesis of a series of Ag(I) bis(imino)pyridine complexes with varied sterics. Resulting ligand-metal interactions as well as reactivity towards Lewis basic donor ligands will be discussed. Chapter 7 presents the synthesis of first crystallographically authenticated examples of rhenium(I) pincer complexes utilizing the bis(imino)pyridine ligand. Chapter 8 presents a general conclusion to the work.

Esta tese apresenta a síntese e a caracterização de novos complexos de rênio e tecnécio utilizando como agentes complexantes ligantes assimétricos do tipo base de Schiff e ligantes triaminas derivadas da dietilenotriamina. Os ligantes assimétricos foram sintetizados através de reações de condensação entre 2,2\'-dihidroxibenzofenona e as aminas alifáticas etilenodiamina e dietilenotriamina, formando, respectivamente, os ligantes 2,2\'-(((2-aminoetill)imino)metileno)difenol(HL1) e 2,2\'-(((2-((2-aminoetil)amino)etil)imino) metileno)difenol (HL2). Os ligantes simétricos foram sintetizados através de reações de condensação entre benzaldeído, 4-hidroxibenzofenona e 3- e 4-metoxibenzaldeído com a amina alifática dietilenotriamina, formando, respectivamente, os ligantes simétricos tridentados tricloridrato de N1-benzil-N2-(2-(benzilamino)etil)etano-1,2-diamina (HL3), 4,4\'-(((azanodiilbis(etano-2,1-diil))bis- (azanediil))bis(phenilmetileno))difenol (HL4), tricloridrato de N1-(4-metoxibenzil)-N2-(2-((4-metoxibenzil)amino)etil) etano-1,2-diamina (HL5) e tricloridrato de N1-(3-metoxibenzil)-N2-(2-((3-metoxibenzil)amino)etil)etano-1,2-diamina (HL6). Reações de complexação foram conduzidas com os precursores metálicos de ReI eTcI. O complexo [Re(CO)5Br] foi utilizado como precursor de ReI. Foi obtido o complexo neutro do tipo fac-[Re(CO)3(L1)] e complexos catiônicos do tipo fac-[Re(CO)3(HL2,3,4,5,6)]Br. Os ligantes e complexos foram caracterizados por ponto de fusão, análise elementar (CHN), espectroscopia de absorção na região do infravermelho, espectroscopia de absorção na região do ultravioleta visível, espectroscopia de ressonância magnética nuclear de 1H e 13C, espectrometria de massas (MS-ESI) e, no caso dos complexos com os ligantes HL1,2,5,6, difração de raios X pelo método do monocristal. Foi realizada a marcação do ligante HL3 com o complexo fac-[[99mTc](H2O)(CO)3]+, formando o complexo fac-[[99mTc](CO)3(HL3)]Br e outras espécies em solução, que foram separadas por HPLC. Adicionalmente, realizou-se um estudo comparativo entre o método convencional de síntese (aquecimento) com o método de síntese no qual microondas são utilizadas. O complexo de tecnécio foi caracterizado por HPLC e eletroforese em papel. Foram realizados testes de estabilidade em cisteína, histidina e tampão PBS. Os testes de estabilidade mostraram que o complexo apresenta boa estabilidade por período de 3 horas. Foi determinado o coeficiente de partição desse complexo, tendo sido observado o caráter lipofílico do mesmo. Foram também realizados testes biológicos in vitro de captação e extrusão com células B16F10 (melanoma murino), onde as células captaram o complexo fac-[[99mTc](CO)3(HL3)]Br,em torno de 4,2%, e mantiveram retidas em seu interior cerca de 20% do complexo, após 60 minutos de incubação. O teste de viabilidade celular por azul de Tripan, mostrou estabilidade das células, durante os experimentos de captação e extrusão, frente às espécies radioativas, apresentando uma viabilidade celular superior a 90% em todos os casos. / This thesis presents the synthesis and characterization of novel rhenium and technetium complexes using as complexing agents asymmetric ligands (Schiff\'s bases type ligands) and triamines ligands derived from diethylenetriamine. The asymmetric ligands were synthesized by condensation reactions between 2,2\'-dihydroxybenzophenone and the aliphatic amines ethylenediamine and diethylenetriamine, giving rise, respectively, to the ligands 2,2\'-(((2-aminoetill)imino) methylene)diphenol (HL1) and 2,2\'-(((2-((2-aminoethyl)amino)ethyl)imino) methylene) diphenol (HL2). The symmetrical ligands were synthesized by condensation reactions between benzaldehyde, 4-hydroxybenzophenone and 3- and 4-methoxybenzaldehyde with the aliphatic amine diethylenetriamine, resulting in the formation, respectively, of the symmetrical tridentated ligands trihydrochloride N1-benzyl-N2-(2-(benzylamino)ethyl)ethane-1,2-diamine (HL3), 4,4\'-(((azanodiilbis(ethane-2,1-diyl))bis(azanediil))bis(phenilmetileno))diphenol (HL4), trihydrochloride N1-(4-methoxybenzyl)-N2-(2-((4-methoxybenzyl)amino)ethyl)ethane-1,2-diamine (HL5) and trihydrochloride N1-(3-methoxybenzyl)-N2-(2-((3-methoxybenzyl)amino)ethyl)ethane-1,2-diamine (HL6). Complexation reactions were carried out using ReI and TcI as metal precursors. The complex [Re(CO)5Br] was used as ReI precursor. Neutral complexe of the type fac-[Re(CO)3(L1)] and cationic complexes of the type fac-[Re(CO)3(HL2,3,4,5,6)]Br were obtained. The ligands and complexes were characterized by melting point, elemental analysis (CHN), infrared absorption spectroscopy, UV-visible absorption spectroscopy, 1H and 13C nuclear magnetic resonance spectroscopy, mass spectrometry (MS-ESI) and for the complexes with the ligands HL1,2,5,6, single crystal X ray diffraction method. Labeling studies were carried out for the HL3 ligand with the complex fac-[[99mTc](H2O)(CO)3]+, forming the complex fac-[[99mTc](CO)3(HL3)]Br and other species in solution, which were separated by high performance liquid chromatography (HPLC). Additionally, a comparative study was done between the conventional (heating) and the synthesis method using microwaves. The technetium complex was characterized by HPLC and electrophoresis on paper. Stability tests were conducted on cysteine, histidine and PBS buffer. The stability tests showed that the compound presents good stability over a 3 hour period. The lipophilic character of the complex was confirmed by the determination of the partition coefficient. In addition, In vitro biolgical tests of captation and influx were performed on B16F10 cells (murine melanoma). The cells captured around 4.2% of the complex fac-[[99mTc](CO)3(HL3)]Br and retained 20% of the amount inside after 60 minutes of incubation. The Trypan blue exclusion test of cell viability showed stability of the cells during the influx and captation experiments, front of the radioactive species, showing cell viability greater than 90% in all cases.