For the determination of iron (II) and total iron with 2,2'-dipyridyl in mineral waters. Reduction of iron (III) with ascorbic acid [Translation from: Zeitschrift fur Analytische Chemie 209 340-341, 1965]

The determination of bi- and trivalent iron in proximity, in mineral waters has gained in significance, on biological and technical grounds. This short paper describes the procedure of the determination of bivalent iron and total iron in a water sample.

Electrocatalytic reduction of dioxygen at chemically modified electrodes

The kinetics of the reduction of O₂ by Ru(NH₃)₆⁺² as catalyzed by cobalt(II) tetrakis(4-N-methylpyridyl)porphyrin are described both in homogeneous solution and when the reactants are confined to Nafion coatings on graphite electrodes. The catalytic mechanism is determined and the factors that can control the total reduction currents at Nafion-coated electrodes are specified. A kinetic zone diagram for analyzing the behavior of catalyst-mediator-substrate systems at polymer coated electrodes is presented and utilized in identifying the current-limiting processes. Good agreement is demonstrated between calculated and measured reduction currents at rotating disk electrodes. The experimental conditions that will yield the optimum performance of coated electrodes are discussed, and a relationship is derived for the optimal coating thickness.

The relation between the reduction potentials of adsorbed and unadsorbed cobalt(III) tetrakis(4-N-methylpyridyl)porphyrin and those where it catalyzes the electroreduction of dioxygen is described. There is an unusually large change in the formal potential of the Co(III) couple upon the adsorption of the porphyrin on the graphite electrode surface. The mechanism in which the (inevitably) adsorbed porphyrin catalyzes the reduction of O₂ is in accord with a general mechanistic scheme proposed for most monomeric cobalt porphyrins.

Four new dimeric metalloporphyrins (prepared in the laboratory of Professor C. K. Chang) have the two porphyrin rings linked by an anthracene bridge attached to meso positions. The electrocatalytic behavior of the diporphyrins towards the reduction of O₂ at graphite electrodes has been examined for the following combination of metal centers: Co-Cu, Co-Fe, Fe-Fe, Fe-H₂. The Co-Cu diporphyrin catalyzes the reduction of O₂ to H₂O₂ but no further. The other three catalysts all exhibit mixed reduction pathways leading to both H₂O₂ and H₂O. However, the pathways that lead to H₂O do not involve H₂O₂ as an intermediate. A possible mechanistic scheme is offered to account for the observed behavior.

Proton-Coupled Reduction of N2 Facilitated by Molecular Fe Complexes

The activation of Fe-coordinated N₂ via the formal addition of hydrogen atom equivalents is explored in this thesis. These reactions may occur in nitrogenase enzymes during the biological conversion of N₂ to NH₃. To understand these reactions, the N₂ reactivity of a series of molecular Fe(N₂) platforms is investigated. A trigonal pyramidal, carbon-ligated Fe^I complex was prepared that displays a similar geometry to that of the resting state 'belt' Fe atoms of nitrogenase. Upon reduction, this species was shown to coordinate N₂, concomitant with significant weakening of the C-Fe interaction. This hemilability of the axial ligand may play a critical role in mediating the interconversion of Fe(N_xH_y) species during N₂ conversion to NH₃. In fact, a trigonal pyramidal borane-ligated Fe complex was shown to catalyze this transformation, generating up to 8.49 equivalents of NH₃. To shed light on the mechanistic details of this reaction, protonation of a borane-ligated Fe(N₂) complex was investigated and found to give rise to a mixture of species that contains an iron hydrazido(2-) [Fe(NNH₂)] complex. The identification of this species is suggestive of an early N-N bond cleavage event en route to NH₃ production, but the highly-reactive nature of this complex frustrated direct attempts to probe this possibility. A structurally-analogous silyl-ligated Fe(N₂) complex was found to react productively with hydrogen atom equivalents, giving rise to an isolable Fe(NNH₂) species. Spectroscopic and crystallographic studies benefited from the enhanced stability of this complex relative to the borane analogue. One-electron reduction of this species initiates a spontaneous disproportionation reaction with an iron hydrazine [Fe(NH₂NH₂)] complex as the predominant reaction product. This transformation provides support for an Fe-mediated N₂ activation mechanism that proceeds via a late N-N bond cleavage. In hopes of gaining more fundamental insight into these reactions, a series of Fe(CN) complexes were prepared and reacted with hydrogen-atom equivalents. Significant quantities of CH₄ and NH₃ are generated in these reactions as a result of complete C-N bond activation. A series of Fe(CNH_x) were found to be exceptionally stable and may be intermediates in these reactions. The stability of these compounds permitted collection of thermodynamic parameters pertinent to the unique N-H bonds. This data is comparatively discussed with the theoretically-predicted data of the N₂-derived Fe(NNH_x) species. Exceptionally-weak N-H bond enthalpies are found for many of these compounds, and sheds light on their short-lived nature and tendency to evolve H₂. As a whole, these works both establish and provide a means to understand Fe-mediated N₂ activation via the addition of hydrogen atom equivalents.

A vulnerabilidade da vida com HIV/AIDS

Esta tese pretende contribuir para o desenvolvimento de respostas públicas rumo à diminuição do impacto do HIV/Aids nos campos, econômico, político e social tanto no nível coletivo quanto no individual. Discute aspectos téorico-conceituais das noções de risco e vulnerabilidade, mostrando que a atual aplicação e apropriação dessas noções na resposta à essa epidemia dificulta o reconhecimento dos problemas adicionais enfrentados após o diagnóstico. Apresenta as diversas formas de pobreza, desigualdade e exclusão a partir dos indicadores sociais comumente usados e respectivas lógicas construtivas. Questiona as afirmações recentes sobre a queda da desigualdade, da pobreza e da indigência no país; e considera que a desigualdade e a exclusão que afetam a população em geral é a mesma a afetar pessoas que vivem com HIV/Aids. Porém, aponta a existência de vulnerabilidade potencial, conceito desenvolvido nesta tese, na ausência de rede de suporte social. Para identificar e inferir sobre o que ocorre nas vidas das pessoas que vivem em situação de desigualdade ou exclusão após a infecção pelo HIV utiliza dados coletados em pesquisa de survey, discursos, estórias e memórias de casos reais da prática profissional desta autora. O objetivo desta tese é demonstrar que o conceito de vulnerabilidade aplicado após o diagnóstico é importante ferramenta para reconhecer e intervir sobre as dificuldades e problemas adicionais enfrentados. Ressalta a evolução da resposta brasileira à essa epidemia e demonstra as lacunas existentes como desafios a seu aperfeiçoamento. Conclui que o reconhecimento dos problemas adicionais após o diagnóstico e o uso do conceito de vulnerabilidade potencial abre novas possibilidades de enfrentamento do HIV/Aids e exige respostas públicas interligadas e intersetoriais.

Line-width reduction of a laser diode array using an external cavity with two feedback mirrors

A novel Littman-Metcalf external cavity laser diode array with two feedback mirrors is introduced. The line-width broadening effect caused by smile can be reduced by the novel external cavity. At the drive current of 16A, the line-width is narrowed to 0.1nm from free-running width of 1.6nm with output efficiency of 84%.